Catalytic transformation of dinitrogen into ammonia and hydrazine by iron-dinitrogen complexes bearing pincer ligand

PubMed Central

Kuriyama, Shogo; Arashiba, Kazuya; Nakajima, Kazunari; Matsuo, Yuki; Tanaka, Hiromasa; Ishii, Kazuyuki; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

2016-01-01

Synthesis and reactivity of iron-dinitrogen complexes have been extensively studied, because the iron atom plays an important role in the industrial and biological nitrogen fixation. As a result, iron-catalyzed reduction of molecular dinitrogen into ammonia has recently been achieved. Here we show that an iron-dinitrogen complex bearing an anionic PNP-pincer ligand works as an effective catalyst towards the catalytic nitrogen fixation, where a mixture of ammonia and hydrazine is produced. In the present reaction system, molecular dinitrogen is catalytically and directly converted into hydrazine by using transition metal-dinitrogen complexes as catalysts. Because hydrazine is considered as a key intermediate in the nitrogen fixation in nitrogenase, the findings described in this paper provide an opportunity to elucidate the reaction mechanism in nitrogenase. PMID:27435503

Synthesis and reactivity of mononuclear iron models of [Fe]-hydrogenase that contain an acylmethylpyridinol ligand.

PubMed

Hu, Bowen; Chen, Dafa; Hu, Xile

2014-02-03

[Fe]-hydrogenase has a single iron-containing active site that features an acylmethylpyridinol ligand. This unique ligand environment had yet to be reproduced in synthetic models; however the synthesis and reactivity of a new class of small molecule mimics of [Fe]-hydrogenase in which a mono-iron center is ligated by an acylmethylpyridinol ligand has now been achieved. Key to the preparation of these model compounds is the successful C-O cleavage of an alkyl ether moiety to form the desired pyridinol ligand. Reaction of solvated complex [(2-CH2CO-6-HOC5H3N)Fe(CO)2(CH3CN)2](+)(BF4)(-) with thiols or thiophenols in the presence of NEt3 yielded 5-coordinate iron thiolate complexes. Further derivation produced complexes [(2-CH2CO-6-HOC5H3N)Fe(CO)2(SCH2CH2OH)] and [(2-CH2CO-6-HOC5H3N)Fe(CO)2(CH3COO)], which can be regarded as models of FeGP cofactors of [Fe]-hydrogenase extracted by 2-mercaptoethanol and acetic acid, respectively. When the derivative complexes were treated with HBF4 ⋅Et2O, the solvated complex was regenerated by protonation of the thiolate ligands. The reactivity of several models with CO, isocyanide, cyanide, and H2 was also investigated. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organic Complexation of Dissolved Copper and Iron from Shipboard Incubations in the Central California Current System: Investigating the Impacts of Light Conditions and Phytoplankton Growth on Iron- and Copper-Binding Ligand Characteristics

NASA Astrophysics Data System (ADS)

Mellett, T.; Parker, C.; Brown, M.; Coale, T.; Duckham, C.; Chappell, D.; Maldonado, M. T.; Bruland, K. W.; Buck, K. N.

2016-02-01

Two shipboard incubation experiments were carried out in July of 2014 to investigate potential sources and sinks of iron- and copper-binding organic ligands in the surface ocean. Seawater for the experiments was collected from the central California Current System (cCCS) and incubated under varying light conditions and in the presence and absence of natural phytoplankton communities. Incubation treatments were sampled over a period of up to 3 days for measurements of total dissolved copper and iron, and for the concentration and conditional stability constants of copper- and iron-binding organic ligands. Dissolved copper and iron were determined by inductively coupled plasma-mass spectrometry (ICP-MS) following preconcentration on a Nobias PA1 resin. Organic ligand characteristics for iron and copper were determined using a method of competitive ligand exchange-absorptive cathodic stripping voltammetry (CLE-ACSV) with the added competing ligand salicylaldoxime. Trends in ligand concentrations and conditional stability constants across the different treatments and over the course of the incubation experiments will be presented.

Interactions between iron and organic matter may influence the fate of permafrost carbon in the Arctic

NASA Astrophysics Data System (ADS)

Cory, R. M.; Trusiak, A.; Ward, C.; Kling, G. W.; Tfaily, M.; Paša-Tolić, L.; Noel, V.; Bargar, J.

2017-12-01

The ongoing thawing of permafrost soils is the only environmental change that allows tremendous stores of organic carbon (C) to be converted into carbon dioxide (CO2) on decadal time scales, thus providing a positive and accelerating feedback to global warming. Evidence suggests that iron enhances abiotic reactions that convert dissolved organic matter (DOM) to CO2 in dark soils and in sunlit surface waters depending on its redox state and association with DOM (i.e., iron-DOM complexation). However, the complexation of iron in surface waters and soils remains too poorly understood to predict how iron influences the rates of oxidation of DOM to CO2. To address this knowledge gap, we characterized iron-DOM complexation in iron-rich soil and surface waters of the Arctic, in combination with measurements of DOM oxidation to CO2. These waters contain high concentrations of dissolved iron and DOM (up to 1 and 2 mM, respectively), and low concentrations of other potential ligands for iron such as sulfide, carbonate, chloride, or bromide. Ultra-high resolution mass spectrometry (FT-ICR MS) was used to identify ligands for iron within the DOM pool, and synchrotron based X-ray analysis (XAS and EXAFS) was used to assess iron's oxidation state, to detect iron complexation, and to constrain the chemical composition of the complexes. Across a natural gradient of dissolved iron and DOM concentrations, many potential ligands were identified within DOM that are expected to complex with iron (e.g., aromatic acids). EXAFS showed substantial complexation of reduced ferrous iron (Fe(II)) to DOM in arctic soil waters, on the basis of comparison to Fe(II)-DOM reference spectra. Identification of iron complexed to DOM in soil waters is consistent with strongly co-varying iron and DOM concentrations in arctic soil and surface waters, and supports our hypothesis that complexation of iron by DOM influences dark and light redox reactions that oxidize DOM to CO2. Understanding the molecular controls on the biogeochemical reactions that convert permafrost carbon to CO2 is critical for understanding the role of the Arctic in current and future climate change.

Design and synthesis of a tetradentate '3-amine-1-carboxylate' ligand to mimic the metal binding environment at the non-heme iron(II) oxidase active site.

PubMed

Dungan, Victoria J; Ortin, Yannick; Mueller-Bunz, Helge; Rutledge, Peter J

2010-04-07

Non-heme iron(II) oxidases (NHIOs) catalyse a diverse array of oxidative chemistry in Nature. As part of ongoing efforts to realize biomimetic, iron-mediated C-H activation, we report the synthesis of a new 'three-amine-one-carboxylate' ligand designed to complex with iron(II) and mimic the NHIO active site. The tetradentate ligand has been prepared as a single enantiomer in nine synthetic steps from N-Cbz-L-alanine, pyridine-2,6-dimethanol and diphenylamine, using Seebach oxazolidinone chemistry to control the stereochemistry. X-Ray crystal structures are reported for two important intermediates, along with variable temperature NMR experiments to probe the hindered interconversion of conformational isomers of several key intermediates, 2,6-disubstituted pyridine derivatives. The target ligand and an N-Cbz-protected precursor were each then complexed with iron(II) and tested for their ability to promote alkene dihydroxylation, using hydrogen peroxide as the oxidant.

Kinetics of Fe Release from Organic Ligand Complexes: Implications for Fe Isotopes?

NASA Astrophysics Data System (ADS)

Nuester, J.; Liermann, L. J.; Brantley, S. L.

2006-12-01

Although iron is the fourth most abundant element in the earth's surface, its bioavailability is limited by its natural tendency to form insoluble iron (oxyhydr)oxides in terrestrial and marine environments. Paradoxically, iron is an essential nutrient for virtually all living cells, so in order to survive, organisms must develop mechanisms to solubilize iron. To acquire iron, organisms synthesize and release iron-specific chelators called siderophores. These siderophores facilitate the transformation of insoluble crystal-bound iron to organically ligand-bound dissolved iron. The reverse process whereby ferric iron is released from siderophores resulting in the precipitation of iron (oxyhydr)oxides or complexation by other iron chelators is an important but not well studied process in the B-horizon of soils. Fe mobility is documented in soils where Fe is often extracted at the top and precipitated at depth. Both the concentration and isotopic signature of Fe varies with depth due to dissolution, precipitation, sorption, and biological processes. Our study is focused on measurement of isotopic fractionation during this reverse process. In a first approach to understand iron liberation form organic ligands, we mimic this process using a reductive mechanism. We use acetohydroxamic acid (aha), EDTA and desferrioxamine B (DFMB) as test ligands to investigate iron release by sodium ascorbate at varying pH. Our first kinetic measurements showed significant differences in iron release depending on pH and stability of the iron complex. Within one hour all iron is released from aha with a small pH effect in the pH range between 4 and 6. In contrast, the pH has a major influence on the iron release from EDTA and DFMB. Depending on pH, total iron is released from EDTA within 24 hours, while only an incomplete iron release from DFMB could be observed within two weeks. These strong kinetic differences in iron release as a consequence of iron reduction are expected to result in significant iron isotope effects, and we are testing for these effects. For example, we expect to see enrichment of light isotopes in the early released fractions as iron is reduced (like effects observed by Wiederhold et al. (2006) for ligand-controlled and reductive dissolution of goethite). Such kinetic isotope effects should be particularly strong for iron release from siderophores with high Fe affinities like DFMB (log ß_(Fe(III)) = 30.60). We are also investigating other mechanisms to liberate iron from organic ligands including a pathway with extracellular iron reductases.

Molecular Speciation of Trace Metal Organic Complexes in the Pacific Ocean

NASA Astrophysics Data System (ADS)

Repeta, D.; Boiteau, R. M.; Bundy, R. M.; Babcock-Adams, L.

2017-12-01

Microbial production across approximately one third of the surface ocean is limited by extraordinarily low (picomolar) concentrations of dissolved iron, essentially all of which is complexed to strong organic ligands of unknown composition. Other biologically important trace metals (cobalt, copper, zinc, nickel) are also complexed to strong organic ligands, which again have not been extensively characterized. Nevertheless, organic ligands exert a strong influence on metal bioavailability and toxicity. For example, amendment experiments using commercially available siderophores, organic compounds synthesized by microbes to facilitate iron uptake, show these ligands can both facilitate or impede iron uptake depending on the siderophore composition and available uptake pathways. Over the past few years we have developed analytical techniques using high pressure liquid chromatography interfaced with inductively coupled plasma and electrospray ionization mass spectrometry to identify and quantify trace metal organic complexes in laboratory cultures of marine microbes and in seawater. We found siderophores to be widely distributed in the ocean, particularly in regions characterized by low iron concentrations. We also find chemically distinct complexes of copper, zinc, colbalt and nickel that we have yet to fully characterize. We will discuss some of our recent work on trace metal organic speciation in seawater and laboratory cultures, and outline future efforts to better understand the microbial cycling of trace metal organic complexes in the sea.

An iron( ii ) hydride complex of a ligand with two adjacent β-diketiminate binding sites and its reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gehring, Henrike; Metzinger, Ramona; Braun, Beatrice

2016-01-13

After lithiation of PYR-H2 (PYR = [(NC(Me)C(H)C(Me)NC6H3(iPr)2)2(C5H3N)]2-) – the precursor of an expanded β-diketiminato ligand system with two binding pockets – with KN(TMS)2 the reaction of the resulting potassium salt with FeBr2 led to a dinuclear iron(II) bromide complex [(PYR)Fe(μ-Br)2Fe] (1). Through treatment with KHBEt3 the bromide ligands could be replaced by hydrides to yield [PYR)Fe2(μ-H)2] (2), a distorted analogue of known β-diketiminato iron hydride complexes, as evidenced by NMR, Mößbauer and X-ray absorption spectroscopy, as well as by its reactivity: for instance, 2 reacts with the proton source lutidinium triflate via protonation of the hydride ligands to form anmore » iron(II) product [(PYR)Fe2(OTf)2] (4), while CO2 inserts into the Fe–H bonds generating the formate complex [(PYR)Fe2(μ-HCOO)2] (5); in the presence of traces of water partial hydrolysis occurs so that [(PYR)Fe2(μ-OH)(μ-HCOO)] (6) is isolated. Altogether, the iron(II) chemistry supported by the PYR2- ligand is distinctly different from the one of nickel(II), where both, the arrangement of the two binding pockets and the additional pyridyl donor led to diverging features as compared with the corresponding system based on the parent β-diketiminato ligand.« less

Revealing sources and chemical identity of iron ligands across the California Current System

NASA Astrophysics Data System (ADS)

Boiteau, R.; Repeta, D.; Fitzsimmons, J. N.; Parker, C.; Twining, B. S.; Baines, S.

2016-02-01

The California Current System is one of the most productive regions of the ocean, fueled by the upwelling of nutrient rich water. Differences in the supply of micronutrient iron to surface waters along the coast lead to a mosaic of iron-replete and iron-limited conditions across the region, affecting primary production and community composition. Most of the iron in this region is supplied by upwelling of iron from the benthic boundary layer that is complexed by strong organic ligands. However, the source, identity, and bioavailability of these ligands are unknown. Here, we used novel hyphenated chromatography mass spectrometry approaches to structurally characterize organic ligands across the region. With these methods, iron ligands are detected with liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC-ICPMS), and then their mass and fragmentation spectra are determined by high resolution electrospray ionization mass spectrometry (LC-ESIMS). Iron isotopic exchange was used to compare the relative binding strengths of different ligands. Our survey revealed a broad range of ligands from multiple sources. Benthic boundary layers and anoxic sediments were sources of structurally amorphous weak ligands, likely organic degradation products, as well as siderophores, strong iron binding molecules that facilitate iron acquisition. In the euphotic zone, marine microbes and zooplankton grazing produced a wide distribution of other compounds that included known and novel siderophores. This work demonstrates that the chemical nature of ligands from different sources varies substantially and has important implications for iron biogeochemical cycling and availability to members of the microbial community.

Manipulating charge transfer excited state relaxation and spin crossover in iron coordination complexes with ligand substitution

DOE PAGES

Zhang, Wenkai; Kjaer, Kasper S.; Alonso-Mori, Roberto; ...

2016-08-25

Developing light-harvesting and photocatalytic molecules made with iron could provide a cost effective, scalable, and environmentally benign path for solar energy conversion. To date these developments have been limited by the sub-picosecond metal-to-ligand charge transfer (MLCT) electronic excited state lifetime of iron based complexes due to spin crossover – the extremely fast intersystem crossing and internal conversion to high spin metal-centered excited states. We revitalize a 30 year old synthetic strategy for extending the MLCT excited state lifetimes of iron complexes by making mixed ligand iron complexes with four cyanide (CN –) ligands and one 2,2'-bipyridine (bpy) ligand. This enablesmore » MLCT excited state and metal-centered excited state energies to be manipulated with partial independence and provides a path to suppressing spin crossover. We have combined X-ray Free-Electron Laser (XFEL) Kβ hard X-ray fluorescence spectroscopy with femtosecond time-resolved UV-visible absorption spectroscopy to characterize the electronic excited state dynamics initiated by MLCT excitation of [Fe(CN) 4(bpy)] 2–. The two experimental techniques are highly complementary; the time-resolved UV-visible measurement probes allowed electronic transitions between valence states making it sensitive to ligand-centered electronic states such as MLCT states, whereas the Kβ fluorescence spectroscopy provides a sensitive measure of changes in the Fe spin state characteristic of metal-centered excited states. Here, we conclude that the MLCT excited state of [Fe(CN) 4(bpy)] 2– decays with roughly a 20 ps lifetime without undergoing spin crossover, exceeding the MLCT excited state lifetime of [Fe(2,2'-bipyridine) 3] 2+ by more than two orders of magnitude.« less

Iron(II) porphyrins induced conversion of nitrite into nitric oxide: A computational study.

PubMed

Zhang, Ting Ting; Liu, Yong Dong; Zhong, Ru Gang

2015-09-01

Nitrite reduction to nitric oxide by heme proteins was reported as a protective mechanism to hypoxic injury in mammalian physiology. In this study, the pathways of nitrite reduction to nitric oxide mediated by iron(II) porphyrin (P) complexes, which were generally recognized as models for heme proteins, were investigated by using density functional theory (DFT). In view of two type isomers of combination of nitrite and Fe(II)(P), N-nitro- and O-nitrito-Fe(II)-porphyrin complexes, and two binding sites of proton to the different O atoms of nitrite moiety, four main pathways for the conversion of nitrite into nitric oxide mediated by iron(II) porphyrins were proposed. The results indicate that the pathway of N-bound Fe(II)(P)(NO2) isomer into Fe(III)(P)(NO) and water is similar to that of O-bound isomer into nitric oxide and Fe(III)(P)(OH) in both thermodynamical and dynamical aspects. Based on the initial computational studies of five-coordinate nitrite complexes, the conversion of nitrite into NO mediated by Fe(II)(P)(L) complexes with 14 kinds of proximal ligands was also investigated. Generally, the same conclusion that the pathways of N-bound isomers are similar to those of O-bound isomer was obtained for iron(II) porphyrin with ligands. Different effects of ligands on the reduction reactions were also found. It is notable that the negative proximal ligands can improve reactive abilities of N-nitro-iron(II) porphyrins in the conversion of nitrite into nitric oxide compared to neutral ligands. The findings will be helpful to expand our understanding of the mechanism of nitrite reduction to nitric oxide by iron(II) porphyrins. Copyright © 2015 Elsevier Inc. All rights reserved.

Hydrogenation and dehydrogenation iron pincer catalysts capable of metal-ligand cooperation by aromatization/dearomatization.

PubMed

Zell, Thomas; Milstein, David

2015-07-21

The substitution of expensive and potentially toxic noble-metal catalysts by cheap, abundant, environmentally benign, and less toxic metals is highly desirable and in line with green chemistry guidelines. We have recently discovered a new type of metal-ligand cooperation, which is based on the reversible dearomatization/aromatization of different heteroaromatic ligand cores caused by deprotonation/protonation of the ligand. More specifically, we have studied complexes of various transition metals (Ru, Fe, Co, Rh, Ir, Ni, Pd, Pt, and Re) bearing pyridine- and bipyridine-based PNP and PNN pincer ligands, which have slightly acidic methylene protons. In addition, we have discovered long-range metal-ligand cooperation in acridine-based pincer ligands, where the cooperation takes place at the electrophilic C-9 position of the acridine moiety leading to dearomatization of its middle ring. This type of metal-ligand cooperation was used for the activation of chemical bonds, including H-H, C-H (sp(2) and sp(3)), O-H, N-H, and B-H bonds. This unusual reactivity likely takes place in various catalytic hydrogenation, dehydrogenation, and related reactions. In this Account, we summarize our studies on novel bifunctional iron PNP and PNN pincer complexes, which were designed on the basis of their ruthenium congeners. Iron PNP pincer complexes serve as efficient (pre)catalysts for hydrogenation and dehydrogenation reactions under remarkably mild conditions. Their catalytic applications include atom-efficient and industrially important hydrogenation reactions of ketones, aldehydes, and esters to the corresponding alcohols. Moreover, they catalyze the hydrogenation of carbon dioxide to sodium formate in the presence of sodium hydroxide, the selective decomposition of formic acid to carbon dioxide and hydrogen, and the E-selective semihydrogenation of alkynes to give E-alkenes. These catalysts feature, compared to other iron-based catalysts, very high catalytic activities which in some cases can even exceed those of state-of-the-art noble-metal catalysts. For the iron PNP systems, we describe the synthesis of the pyridine- and acridine-based PNP iron complexes and their performances and limitations in catalytic reactions, and we present studies on their reactivity with relevance to their catalytic mechanisms. In the case of the bipyridine-based PNN system, we summarize the synthesis of new complexes and describe studies on the noninnocence of the methylene position, which can be reversibly deprotonated, as well as on the noninnocence of the bipyridine unit. Overall, this Account underlines that the combination of cheap and abundant iron with ligands that are capable of metal-ligand cooperation can result in the development of novel, versatile, and efficient catalysts for atom-efficient catalytic reactions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Seungwoo; Lu, Xiaoyan; Lee, Yong -Min

Here, a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [Fe V(NTs)(TAML)] – (1), was oxidized by one-electron oxidants, affording formation of an iron(V)-imido TAML cation radical species, [Fe V(NTs)(TAML +•)] (2); 2 is a diamagnetic (S = 0) complex, resulting from the antiferromagnetic coupling of the low-spin iron(V) ion (S = 1/2) with the one-electron oxidized ligand (TAML +•). 2 is a competent oxidant in C–H bond functionalization and nitrene transfer reaction, showing that the reactivity of 2 is greater than that of 1.

A Hexanuclear Iron(II) Layer with Two Square-Planar FeO4 Units Spanned by Tetrasiloxide Ligands: Mimicking of Minerals and Catalysts.

PubMed

Manicke, N; Hoof, S; Keck, M; Braun-Cula, B; Feist, M; Limberg, C

2017-07-17

A hexanuclear iron(II) siloxide complex has been prepared by reacting an incompletely condensed silsesquioxane first with NaOMe and then with Fe(OTf) 2 . In the process of product formation, the siloxane framework undergoes a transformation and it was shown that this happens already upon addition of base: Treatment of the ligand precursor with NaOMe leads to a completely condensed silsesquioxane cage with 12 Si atoms that is composed of 2 equiv of the tetrasiloxide ligands found in the product complex. Its iron centers form a two-dimensional array reminiscent of the situations found in minerals and two-dimensional oxide films caused by segregation of FeO x and silica. As the hexairon(II) assembly contains two high-spin square-planar FeO 4 units-suggested to represent the active sites in Fe-zeolites, which react with N 2 O to generate strongly oxidizing sites-it was treated with Me 3 NO. This led to the oxidation of two of the iron centers to the oxidation state +III and elimination of one iron ion, so that a pentanuclear, mixed valent iron siloxide was formed. All complexes were fully characterized.

Trithiocyanurate complexes of iron, manganese and nickel and their anticholinesterase activity.

PubMed

Kopel, Pavel; Dolezal, Karel; Langer, Vratislav; Jun, Daniel; Adam, Vojtech; Kuca, Kamil; Kizek, Rene

2014-04-08

The complexes of Fe(II), Mn(II) and Ni(II) with a combination of a Schiff base, nitrogen-donor ligand or macrocyclic ligand and trithiocyanuric acid (ttcH3) were prepared and characterized by elemental analysis and spectroscopies. Crystal and molecular structures of the iron complex of composition [Fe(L1)](ttcH2)(ClO4)·EtOH·H2O (1), where L1 is Schiff base derived from tris(2-aminoethyl)amine and 2-pyridinecarboxaldehyde, were solved. It was found that the Schiff base is coordinated to the central iron atom by six nitrogens forming deformed octahedral arrangement, whereas trithiocyanurate(1-) anion, perchlorate and solvent molecules are not coordinated. The X-ray structure of the Schiff base sodium salt is also presented and compared with the iron complex. The anticholinesterase activity of the complexes was also studied.

Complexation of iron hexacyanides by cytochrome c. Evidence for electron exchange at the exposed heme edge.

PubMed

Stellwagen, E; Cass, R D

1975-03-25

Electrostatic binding of at least two anionic iron hexacyanides to cationic horse heart cytochrome c was demonstrated by equilibrium dialysis measurements. No binding was detected following trifluoroacetylation of all of the 19 lysine residues. Replacement of the natural heme iron ligand methionine 80 by the alternative intrinsic ligand lysine 79 but not the extrinsic ligand imidazole resulted in the loss of one hexacyanide binding site. It is proposed that this site is located at the exposed heme edge and is functional in electron exchange.

Electronic and Spatial Structures of Water-Soluble Dinitrosyl Iron Complexes with Thiol-Containing Ligands Underlying Their Ability to Act as Nitric Oxide and Nitrosonium Ion Donors

PubMed Central

Vanin, Anatoly F.; Burbaev, Dosymzhan Sh.

2011-01-01

The ability of mononuclear dinitrosyl iron commplexes (M-DNICs) with thiolate ligands to act as NO donors and to trigger S-nitrosation of thiols can be explain only in the paradigm of the model of the [Fe+(NO+)2] core ({Fe(NO)2}7 according to the Enemark-Feltham classification). Similarly, the {(RS−)2Fe+(NO+)2}+ structure describing the distribution of unpaired electron density in M-DNIC corresponds to the low-spin (S = 1/2) state with a d7 electron configuration of the iron atom and predominant localization of the unpaired electron on MO(dz2) and the square planar structure of M-DNIC. On the other side, the formation of molecular orbitals of M-DNIC including orbitals of the iron atom, thiolate and nitrosyl ligands results in a transfer of electron density from sulfur atoms to the iron atom and nitrosyl ligands. Under these conditions, the positive charge on the nitrosyl ligands diminishes appreciably, the interaction of the ligands with hydroxyl ions or with thiols slows down and the hydrolysis of nitrosyl ligands and the S-nitrosating effect of the latter are not manifested. Most probably, the S-nitrosating effect of nitrosyl ligands is a result of weak binding of thiolate ligands to the iron atom under conditions favoring destabilization of M-DNIC. PMID:22505886

Electronic and spatial structures of water-soluble dinitrosyl iron complexes with thiol-containing ligands underlying their ability to act as nitric oxide and nitrosonium ion donors.

PubMed

Vanin, Anatoly F; Burbaev, Dosymzhan Sh

2011-01-01

The ability of mononuclear dinitrosyl iron commplexes (M-DNICs) with thiolate ligands to act as NO donors and to trigger S-nitrosation of thiols can be explain only in the paradigm of the model of the [Fe(+)(NO(+))(2)] core ({Fe(NO)(2)}(7) according to the Enemark-Feltham classification). Similarly, the {(RS(-))(2)Fe(+)(NO(+))(2)}(+) structure describing the distribution of unpaired electron density in M-DNIC corresponds to the low-spin (S = 1/2) state with a d(7) electron configuration of the iron atom and predominant localization of the unpaired electron on MO(d(z2)) and the square planar structure of M-DNIC. On the other side, the formation of molecular orbitals of M-DNIC including orbitals of the iron atom, thiolate and nitrosyl ligands results in a transfer of electron density from sulfur atoms to the iron atom and nitrosyl ligands. Under these conditions, the positive charge on the nitrosyl ligands diminishes appreciably, the interaction of the ligands with hydroxyl ions or with thiols slows down and the hydrolysis of nitrosyl ligands and the S-nitrosating effect of the latter are not manifested. Most probably, the S-nitrosating effect of nitrosyl ligands is a result of weak binding of thiolate ligands to the iron atom under conditions favoring destabilization of M-DNIC.

Mössbauer effect study of iron(III) inidazolidine nitroxyl-free radical ligand complex

NASA Astrophysics Data System (ADS)

Mulaba, A.; Kiremire, E.; Pollak, H.; Boeyens, J.

1999-09-01

A new complex, [Fe(acac)L2], bearing inidazolidine nitroxyl-free radical ligand (L-) was recently synthesised for biological studies. It proved to be biologically active against African sleeping sickness, plasmodium falciparum (malaria), leishmaniasis and chaga disease causative agents. Three ESR well resolved peaks indicated the presence of a free (unpaired) and chemically active electron in the complex. The structural complex ferric iron was found at the centre of two electric gradient whose the biggest is suggested to be initiated by the unpaired charge. No distinction between different cis isomers could be made.

Complexes of horseradish peroxidase with formate, acetate, and carbon monoxide.

PubMed

Carlsson, Gunilla H; Nicholls, Peter; Svistunenko, Dimitri; Berglund, Gunnar I; Hajdu, Janos

2005-01-18

Carbon monoxide, formate, and acetate interact with horseradish peroxidase (HRP) by binding to subsites within the active site. These ligands also bind to catalases, but their interactions are different in the two types of enzymes. Formate (notionally the "hydrated" form of carbon monoxide) is oxidized to carbon dioxide by compound I in catalase, while no such reaction is reported to occur in HRP, and the CO complex of ferrocatalase can only be obtained indirectly. Here we describe high-resolution crystal structures for HRP in its complexes with carbon monoxide and with formate, and compare these with the previously determined HRP-acetate structure [Berglund, G. I., et al. (2002) Nature 417, 463-468]. A multicrystal X-ray data collection strategy preserved the correct oxidation state of the iron during the experiments. Absorption spectra of the crystals and electron paramagnetic resonance data for the acetate and formate complexes in solution correlate electronic states with the structural results. Formate in ferric HRP and CO in ferrous HRP bind directly to the heme iron with iron-ligand distances of 2.3 and 1.8 A, respectively. CO does not bind to the ferric iron in the crystal. Acetate bound to ferric HRP stacks parallel with the heme plane with its carboxylate group 3.6 A from the heme iron, and without an intervening solvent molecule between the iron and acetate. The positions of the oxygen atoms in the bound ligands outline a potential access route for hydrogen peroxide to the iron. We propose that interactions in this channel ensure deprotonation of the proximal oxygen before binding to the heme iron.

Siderophore-based microbial adaptations to iron scarcity across the eastern Pacific Ocean.

PubMed

Boiteau, Rene M; Mende, Daniel R; Hawco, Nicholas J; McIlvin, Matthew R; Fitzsimmons, Jessica N; Saito, Mak A; Sedwick, Peter N; DeLong, Edward F; Repeta, Daniel J

2016-12-13

Nearly all iron dissolved in the ocean is complexed by strong organic ligands of unknown composition. The effect of ligand composition on microbial iron acquisition is poorly understood, but amendment experiments using model ligands show they can facilitate or impede iron uptake depending on their identity. Here we show that siderophores, organic compounds synthesized by microbes to facilitate iron uptake, are a dynamic component of the marine ligand pool in the eastern tropical Pacific Ocean. Siderophore concentrations in iron-deficient waters averaged 9 pM, up to fivefold higher than in iron-rich coastal and nutrient-depleted oligotrophic waters, and were dominated by amphibactins, amphiphilic siderophores with cell membrane affinity. Phylogenetic analysis of amphibactin biosynthetic genes suggests that the ability to produce amphibactins has transferred horizontally across multiple Gammaproteobacteria, potentially driven by pressures to compete for iron. In coastal and oligotrophic regions of the eastern Pacific Ocean, amphibactins were replaced with lower concentrations (1-2 pM) of hydrophilic ferrioxamine siderophores. Our results suggest that organic ligand composition changes across the surface ocean in response to environmental pressures. Hydrophilic siderophores are predominantly found across regions of the ocean where iron is not expected to be the limiting nutrient for the microbial community at large. However, in regions with intense competition for iron, some microbes optimize iron acquisition by producing siderophores that minimize diffusive losses to the environment. These siderophores affect iron bioavailability and thus may be an important component of the marine iron cycle.

Siderophore-based microbial adaptations to iron scarcity across the eastern Pacific Ocean

PubMed Central

Mende, Daniel R.; Hawco, Nicholas J.; McIlvin, Matthew R.; Fitzsimmons, Jessica N.; Saito, Mak A.; Sedwick, Peter N.; DeLong, Edward F.; Repeta, Daniel J.

2016-01-01

Nearly all iron dissolved in the ocean is complexed by strong organic ligands of unknown composition. The effect of ligand composition on microbial iron acquisition is poorly understood, but amendment experiments using model ligands show they can facilitate or impede iron uptake depending on their identity. Here we show that siderophores, organic compounds synthesized by microbes to facilitate iron uptake, are a dynamic component of the marine ligand pool in the eastern tropical Pacific Ocean. Siderophore concentrations in iron-deficient waters averaged 9 pM, up to fivefold higher than in iron-rich coastal and nutrient-depleted oligotrophic waters, and were dominated by amphibactins, amphiphilic siderophores with cell membrane affinity. Phylogenetic analysis of amphibactin biosynthetic genes suggests that the ability to produce amphibactins has transferred horizontally across multiple Gammaproteobacteria, potentially driven by pressures to compete for iron. In coastal and oligotrophic regions of the eastern Pacific Ocean, amphibactins were replaced with lower concentrations (1–2 pM) of hydrophilic ferrioxamine siderophores. Our results suggest that organic ligand composition changes across the surface ocean in response to environmental pressures. Hydrophilic siderophores are predominantly found across regions of the ocean where iron is not expected to be the limiting nutrient for the microbial community at large. However, in regions with intense competition for iron, some microbes optimize iron acquisition by producing siderophores that minimize diffusive losses to the environment. These siderophores affect iron bioavailability and thus may be an important component of the marine iron cycle. PMID:27911777

Bio-inspired computational design of iron catalysts for the hydrogenation of carbon dioxide.

PubMed

Yang, Xinzheng

2015-08-25

Inspired by the active site structure of monoiron hydrogenase, a series of iron complexes are built using experimentally ready-made acylmethylpyridinol and aliphatic PNP pincer ligands. Density functional theory calculations indicate that the newly designed iron complexes are very promising to catalyze the formation of formic acid from H2 and CO2.

Syntheses and structural characterization of iron(II) and copper(II) coordination compounds with the neutral flexible bidentate N-donor ligands

NASA Astrophysics Data System (ADS)

Beheshti, Azizolla; Lalegani, Arash; Bruno, Giuseppe; Rudbari, Hadi Amiri

2014-08-01

Two new coordination compounds [Fe(bib)2(N3)2]n(1) and [Cu2(bpp)2(N3)4] (2) with azide and flexible ligands 1,4-bis(imidazolyl)butane (bib) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp) were prepared and structurally characterized. In the 2D network structure of 1, the iron(II) ion lies on an inversion center and exhibits an FeN6 octahedral arrangement while in the dinuclear structure of 2, the copper(II) ion adopts an FeN5 distorted square pyramid geometry. In the complex 1, each μ2-bib acts as bridging ligand connecting two adjacent iron(II) ions while in the complex 2, the bpp ligand is coordinated to copper(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction. Thermal analysis of polymer 1 was also studied.

Comparison of colorimetry and electrothermal atomic absorption spectroscopy for the quantification of non-transferrin bound iron in human sera.

PubMed

Jittangprasert, Piyada; Wilairat, Prapin; Pootrakul, Pensri

2004-12-01

This paper describes a comparison of two analytical techniques, one employing bathophenanthrolinedisulfonate (BPT), a most commonly-used reagent for Fe (II) determination, as chromogen and an electrothermal atomic absorption spectroscopy (ETAAS) for the quantification of non-transferrin bound iron (NTBI) in sera from thalassemic patients. Nitrilotriacetic acid (NTA) was employed as the ligand for binding iron from low molecular weight iron complexes present in the serum but without removing iron from the transferrin protein. After ultrafiltration the Fe (III)-NTA complex was then quantified by both methods. Kinetic study of the rate of the Fe (II)-BPT complex formation for various excess amounts of NTA ligand was also carried out. The kinetic data show that a minimum time duration (> 60 minutes) is necessary for complete complex formation when large excess of NTA is used. Calibration curves given by colorimetric and ETAAS methods were linear over the range of 0.15-20 microM iron (III). The colorimetric and ETAAS methods exhibited detection limit (3sigma) of 0.13 and 0.14 microM, respectively. The NTBI concentrations from 55 thalassemic serum samples measured employing BPT as chromogen were statistically compared with the results determined by ETAAS. No significant disagreement at 95% confidence level was observed. It is, therefore, possible to select any one of these two techniques for determination of NTBI in serum samples of thalassemic patients. However, the colorimetric procedure requires a longer analysis time because of a slow rate of exchange of NTA ligand with BPT, leading to the slow rate of formation of the colored complex.

Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes

NASA Astrophysics Data System (ADS)

Bhattacharjee, Chira R.; Goswami, Pankaj; Pramanik, Harun A. R.; Paul, Pradip C.; Mondal, Paritosh

2011-05-01

Two new mixed-ligand iron(III) complexes, [Fe(L n)(acac)(C 2H 5OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac) 3] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H 2L 1) or 2-aminobenzoic acid (H 2L 2). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L n)(acac)X] ( n = 1, 2; X = Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, 1H and 13C NMR spectroscopy. Room temperature magnetic susceptibility measurements ( μeff ˜ 5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (Δ Ep > 100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential ( E1/2) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level.

A highly stretchable autonomous self-healing elastomer

NASA Astrophysics Data System (ADS)

Li, Cheng-Hui; Wang, Chao; Keplinger, Christoph; Zuo, Jing-Lin; Jin, Lihua; Sun, Yang; Zheng, Peng; Cao, Yi; Lissel, Franziska; Linder, Christian; You, Xiao-Zeng; Bao, Zhenan

2016-06-01

It is a challenge to synthesize materials that possess the properties of biological muscles—strong, elastic and capable of self-healing. Herein we report a network of poly(dimethylsiloxane) polymer chains crosslinked by coordination complexes that combines high stretchability, high dielectric strength, autonomous self-healing and mechanical actuation. The healing process can take place at a temperature as low as -20 °C and is not significantly affected by surface ageing and moisture. The crosslinking complexes used consist of 2,6-pyridinedicarboxamide ligands that coordinate to Fe(III) centres through three different interactions: a strong pyridyl-iron one, and two weaker carboxamido-iron ones through both the nitrogen and oxygen atoms of the carboxamide groups. As a result, the iron-ligand bonds can readily break and re-form while the iron centres still remain attached to the ligands through the stronger interaction with the pyridyl ring, which enables reversible unfolding and refolding of the chains. We hypothesize that this behaviour supports the high stretchability and self-healing capability of the material.

Azide and acetate complexes plus two iron-depleted crystal structures of the di-iron enzyme delta9 stearoyl-acyl carrier protein desaturase. Implications for oxygen activation and catalytic intermediates.

PubMed

Moche, Martin; Shanklin, John; Ghoshal, Alokesh; Lindqvist, Ylva

2003-07-04

Delta9 stearoyl-acyl carrier protein (ACP) desaturase is a mu-oxo-bridged di-iron enzyme, which belongs to the structural class I of large helix bundle proteins and that catalyzes the NADPH and O2-dependent formation of a cis-double bond in stearoyl-ACP. The crystal structures of complexes with azide and acetate, respectively, as well as the apoand single-iron forms of Delta9 stearoyl-ACP desaturase from Ricinus communis have been determined. In the azide complex, the ligand forms a mu-1,3-bridge between the two iron ions in the active site, replacing a loosely bound water molecule. The structure of the acetate complex is similar, with acetate bridging the di-iron center in the same orientation with respect to the di-iron center. However, in this complex, the iron ligand Glu196 has changed its coordination mode from bidentate to monodentate, the first crystallographic observation of a carboxylate shift in Delta9 stearoyl-ACP desaturase. The two complexes are proposed to mimic a mu-1,2 peroxo intermediate present during catalytic turnover. There are striking structural similarities between the di-iron center in the Delta9 stearoyl-ACP desaturase-azide complex and in the reduced rubrerythrin-azide complex. This suggests that Delta9 stearoyl-ACP desaturase might catalyze the formation of water from exogenous hydrogen peroxide at a low rate. From the similarity in iron center structure, we propose that the mu-oxo-bridge in oxidized desaturase is bound to the di-iron center as in rubrerythrin and not as reported for the R2 subunit of ribonucleotide reductase and the hydroxylase subunit of methane monooxygenase. The crystal structure of the one-iron depleted desaturase species demonstrates that the affinities for the two iron ions comprising the di-iron center are not equivalent, Fe1 being the higher affinity site and Fe2 being the lower affinity site.

Iron Pentapyridyl Complexes as Molecular Water Oxidation Catalysts: Strong Influence of a Chloride Ligand and pH in Altering the Mechanism.

PubMed

Das, Biswanath; Orthaber, Andreas; Ott, Sascha; Thapper, Anders

2016-05-23

The development of molecular water oxidation catalysts based on earth-abundant, non-noble metals is essential for artificial photosynthesis research. Iron, which is the most abundant transition metal in the earth's crust, is a prospective candidate for this purpose. Herein, we report two iron complexes based on the polypyridyl ligand Py5OH (Py5OH=pyridine-2,6-diylbis [di(pyridin-2-yl)methanol]) that can catalyse water oxidation to produce O2 in Ru(III) -induced (at pH 8, highest turnover number (TON)=26.5; turnover frequency (TOF)=2.2 s(-1) ), Ce(IV) -induced (at pH≈1.5 highest TON=16; TOF=0.75 s(-1) ) and photo-induced (at pH 8, highest TON=43.5; TOF=0.6 s(-1) ) reactions. A chloride ligand in one of the iron complexes is shown to affect the activity strongly, improve stability and, thereby, the performance at pH 8 but it inhibits oxygen evolution at pH≈1.5. The observations are consistent with a change in mechanism for catalytic water oxidation with the Fe(Py5OH) complexes between acidic (Ce(IV) ) and near-neutral pH (Ru(III) ). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synergistic effect of reductive and ligand-promoted dissolution of goethite.

PubMed

Wang, Zimeng; Schenkeveld, Walter D C; Kraemer, Stephan M; Giammar, Daniel E

2015-06-16

Ligand-promoted dissolution and reductive dissolution of iron (hydr)oxide minerals control the bioavailability of iron in many environmental systems and have been recognized as biological iron acquisition strategies. This study investigated the potential synergism between ligands (desferrioxamine B (DFOB) or N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid (HBED)) and a reductant (ascorbate) in goethite dissolution. Batch experiments were performed at pH 6 with ligand or reductant alone and in combination, and under both oxic and anoxic conditions. Goethite dissolution in the presence of reductant or ligand alone followed classic surface-controlled dissolution kinetics. Ascorbate alone does not promote goethite dissolution under oxic conditions due to rapid reoxidation of Fe(II). The rate coefficients for goethite dissolution by ligands are closely correlated with the stability constants of the aqueous Fe(III)-ligand complexes. A synergistic effect of DFOB and ascorbate on the rate of goethite dissolution was observed (total rates greater than the sum of the individual rates), and this effect was most pronounced under oxic conditions. For HBED, macroscopically the synergistic effect was hidden due to the inhibitory effect of ascorbate on HBED adsorption. After accounting for the concentrations of adsorbed ascorbate and HBED, a synergistic effect could still be identified. The potential synergism between ligand and reductant for iron (hydr)oxide dissolution may have important implications for iron bioavailability in soil environments.

Arrested α-hydride migration activates a phosphido ligand for C–H insertion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hickey, Anne K.; Muñoz, Salvador B.; Lutz, Sean A.

Bulky tris(carbene)borate ligands provide access to high spin iron(II) phosphido complexes. The complex PhB(MesIm) 3FeP(H)Ph is thermally unstable, and we observed [PPh] group insertion into a C–H bond of the supporting ligand. An arrested α-hydride migration mechanism suggests increased nucleophilicity of the phosphorus atom facilitates [PPh] group transfer reactivity.

Ternary iron(II) complex with an emissive imidazopyridine arm from Schiff base cyclizations and its oxidative DNA cleavage activity.

PubMed

Mukherjee, Arindam; Dhar, Shanta; Nethaji, Munirathinam; Chakravarty, Akhil R

2005-01-21

The ternary iron(II) complex [Fe(L')(L")](PF6)3(1) as a synthetic model for the bleomycins, where L' and L" are formed from metal-mediated cyclizations of N,N'-(2-hydroxypropane-1,3-diyl)bis(pyridine-2-aldimine)(L), is synthesized and structurally characterized by X-ray crystallography. In the six-coordinate iron(ii) complex, ligands L' and L" show tetradentate and bidentate chelating modes of bonding. Ligand L' is formed from an intramolecular attack of the alcoholic OH group of L to one imine moiety leading to the formation of a stereochemically constrained five-membered ring. Ligand L" which is formed from an intermolecular reaction involving one imine moiety of L and pyridine-2-carbaldehyde has an emissive cationic imidazopyridine pendant arm. The complex binds to double-stranded DNA in the minor groove giving a Kapp value of 4.1 x 10(5) M(-1) and displays oxidative cleavage of supercoiled DNA in the presence of H2O2 following a hydroxyl radical pathway. The complex also shows photo-induced DNA cleavage activity on UV light exposure involving formation of singlet oxygen as the reactive species.

Spectroscopic, potentiometric and theoretical studies on the binding properties of a novel tripodal polycatechol-imine ligand towards iron(III)

NASA Astrophysics Data System (ADS)

Kanungo, B. K.; Sahoo, Suban K.; Baral, Minati

2008-12-01

A novel multidentate tripodal ligand, cis, cis-1,3,5-tris[(2,3-dihydroxybenzylidene)aminomethyl]cyclohexane (TDBAC, L) containing one catechol unit in each arms of a tripodal amine, cis, cis-1,3,5-tris(aminomethyl)cyclohexane was investigated as a chelator for iron(III) through potentiometric and spectrophotometric methods in an aqueous medium of 0.1N ionic strength and 25 ± 1 °C as well as in ethanol by continuous variation method. From pH metric in water, three protonation constants characterized for the three-hydroxyl groups of the catechol units at ortho were used as input data to evaluate the stability constants of the complexes. Formation of monomeric complexes FeLH 3, FeLH 2, FeLH and FeL were depicted. In ethanol, formation of complexes FeL, Fe 2L and Fe 3L were characterized. Structures of the complexes were explained by using the experimental evidences and predicted through molecular modeling calculations. The ligand showed potential to coordinate iron(III) through three imine nitrogens and three catecholic oxygens at ortho to form a tris(iminocatecholate) type complex.

Phosphinosilylenes as a novel ligand system for heterobimetallic complexes.

PubMed

Breit, Nora C; Eisenhut, Carsten; Inoue, Shigeyoshi

2016-04-25

A dihydrophosphinosilylene iron complex [LSi{Fe(CO)4}PH2] has been prepared and utilized in the synthesis of novel heterobimetallic complexes. The phosphine moiety in this phosphinosilylene complex allows coordination towards tungsten leading to the iron-tungsten heterobimetallic complex [LSi{Fe(CO)4}PH2{W(CO)5}]. In contrast, the reaction of [LSi{Fe(CO)4}PH2] with ethylenebis(triphenylphosphine)platinum(0) results in the formation of the iron-platinum heterobimetallic complex [LSi{Fe(CO)4}PH{PtH(PPh3)2}] via oxidative addition.

Hydrosilylation of aldehydes and ketones catalyzed by hydrido iron complexes bearing imine ligands.

PubMed

Zuo, Zhenyu; Sun, Hongjian; Wang, Lin; Li, Xiaoyan

2014-08-14

Two new hydrido iron complexes (2 and 4) were synthesized by the reactions of (4-methoxyphenyl)phenylketimine ((4-MeOPh)PhC=NH) with Fe(PMe3)4 or FeMe2(PMe3)4. The molecular structures of complexes 2 and 4 were confirmed by X-ray single crystal diffraction. Using hydrido iron complexes (1-4) as catalysts, the hydrosilylations of aldehydes and ketones were investigated. The four complexes were effective catalysts for this reduction reaction. Complex 1 among them is the best catalyst.

Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

PubMed

Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

2013-03-06

A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

Two Iron Complexes as Homogeneous and Heterogeneous Catalysts for the Chemical Fixation of Carbon Dioxide.

PubMed

Karan, Chandan Kumar; Bhattacharjee, Manish

2018-04-16

Two new bimetallic iron-alkali metal complexes of amino acid (serine)-based reduced Schiff base ligand were synthesized and structurally characterized. Their efficacy as catalysts for the chemical fixation of carbon dioxide was explored. The heterogeneous version of the catalytic reaction was developed by the immobilization of these homogeneous bimetallic iron-alkali metal complexes in an anion-exchange resin. The resin-bound complexes can be used as recyclable catalysts up to six cycles.

Characterization of a tricationic trigonal bipyramidal iron(IV) cyanide complex, with a very high reduction potential, and its iron(II) and iron(III) congeners.

PubMed

England, Jason; Farquhar, Erik R; Guo, Yisong; Cranswick, Matthew A; Ray, Kallol; Münck, Eckard; Que, Lawrence

2011-04-04

Currently, there are only a handful of synthetic S = 2 oxoiron(IV) complexes. These serve as models for the high-spin (S = 2) oxoiron(IV) species that have been postulated, and confirmed in several cases, as key intermediates in the catalytic cycles of a variety of nonheme oxygen activating enzymes. The trigonal bipyramidal complex [Fe(IV)(O)(TMG(3)tren)](2+) (1) was both the first S = 2 oxoiron(IV) model complex to be generated in high yield and the first to be crystallographically characterized. In this study, we demonstrate that the TMG(3)tren ligand is also capable of supporting a tricationic cyanoiron(IV) unit, [Fe(IV)(CN)(TMG(3)tren)](3+) (4). This complex was generated by electrolytic oxidation of the high-spin (S = 2) iron(II) complex [Fe(II)(CN)(TMG(3)tren)](+) (2), via the S = 5/2 complex [Fe(III)(CN)(TMG(3)tren)](2+) (3), the progress of which was conveniently monitored by using UV-vis spectroscopy to follow the growth of bathochromically shifting ligand-to-metal charge transfer (LMCT) bands. A combination of X-ray absorption spectroscopy (XAS), Mössbauer and NMR spectroscopies was used to establish that 4 has a S = 0 iron(IV) center. Consistent with its diamagnetic iron(IV) ground state, extended X-ray absorption fine structure (EXAFS) analysis of 4 indicated a significant contraction of the iron-donor atom bond lengths, relative to those of the crystallographically characterized complexes 2 and 3. Notably, 4 has an Fe(IV/III) reduction potential of ∼1.4 V vs Fc(+/o), the highest value yet observed for a monoiron complex. The relatively high stability of 4 (t(1/2) in CD(3)CN solution containing 0.1 M KPF(6) at 25 °C ≈ 15 min), as reflected by its high-yield accumulation via slow bulk electrolysis and amenability to (13)C NMR at -40 °C, highlights the ability of the sterically protecting, highly basic peralkylguanidyl donors of the TMG(3)tren ligand to support highly charged high-valent complexes.

Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstraction

PubMed Central

Sastri, Chivukula V.; Lee, Jimin; Oh, Kyungeun; Lee, Yoon Jin; Lee, Junghyun; Jackson, Timothy A.; Ray, Kallol; Hirao, Hajime; Shin, Woonsup; Halfen, Jason A.; Kim, Jinheung; Que, Lawrence; Shaik, Sason; Nam, Wonwoo

2007-01-01

The reactivities of mononuclear nonheme iron(IV)–oxo complexes bearing different axial ligands, [FeIV(O)(TMC)(X)]n+ [where TMC is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane and X is NCCH3 (1-NCCH3), CF3COO− (1-OOCCF3), or N3− (1-N3)], and [FeIV(O)(TMCS)]+ (1′-SR) (where TMCS is 1-mercaptoethyl-4,8,11-trimethyl-1,4,8,11-tetraazacyclotetradecane), have been investigated with respect to oxo-transfer to PPh3 and hydrogen atom abstraction from phenol OH and alkylaromatic CH bonds. These reactivities were significantly affected by the identity of the axial ligands, but the reactivity trends differed markedly. In the oxidation of PPh3, the reactivity order of 1-NCCH3 > 1-OOCCF3 > 1-N3 > 1′-SR was observed, reflecting a decrease in the electrophilicity of iron(IV)–oxo unit upon replacement of CH3CN with an anionic axial ligand. Surprisingly, the reactivity order was inverted in the oxidation of alkylaromatic CH and phenol OH bonds, i.e., 1′-SR > 1-N3 > 1-OOCCF3 > 1-NCCH3. Furthermore, a good correlation was observed between the reactivities of iron(IV)–oxo species in H atom abstraction reactions and their reduction potentials, Ep,c, with the most reactive 1′-SR complex exhibiting the lowest potential. In other words, the more electron-donating the axial ligand is, the more reactive the iron(IV)–oxo species becomes in H atom abstraction. Quantum mechanical calculations show that a two-state reactivity model applies to this series of complexes, in which a triplet ground state and a nearby quintet excited-state both contribute to the reactivity of the complexes. The inverted reactivity order in H atom abstraction can be rationalized by a decreased triplet-quintet gap with the more electron-donating axial ligand, which increases the contribution of the much more reactive quintet state and enhances the overall reactivity. PMID:18048327

Kinetic studies on the oxidation of oxyhemoglobin by biologically active iron thiosemicarbazone complexes: relevance to iron-chelator-induced methemoglobinemia.

PubMed

Basha, Maram T; Rodríguez, Carlos; Richardson, Des R; Martínez, Manuel; Bernhardt, Paul V

2014-03-01

The oxidation of oxyhemoglobin to methemoglobin has been found to be facilitated by low molecular weight iron(III) thiosemicarbazone complexes. This deleterious reaction, which produces hemoglobin protein units unable to bind dioxygen and occurs during the administration of iron chelators such as the well-known 3-aminopyridine-2-pyridinecarbaldehyde thiosemicarbazone (3-AP; Triapine), has been observed in the reaction with Fe(III) complexes of some members of the 3-AP structurally-related thiosemicarbazone ligands derived from di-2-pyridyl ketone (HDpxxT series). We have studied the kinetics of this oxidation reaction in vitro using human hemoglobin and found that the reaction proceeds with two distinct time-resolved steps. These have been associated with sequential oxidation of the two different oxyheme cofactors in the α and β protein chains. Unexpected steric and hydrogen-bonding effects on the Fe(III) complexes appear to be the responsible for the observed differences in the reaction rate across the series of HDpxxT ligand complexes used in this study.

Reactivity of tris(acetylacetonato) iron(III) with tridentate [ONO] donor Schiff base as an access to newer mixed-ligand iron(III) complexes.

PubMed

Bhattacharjee, Chira R; Goswami, Pankaj; Pramanik, Harun A R; Paul, Pradip C; Mondal, Paritosh

2011-05-01

Two new mixed-ligand iron(III) complexes, [Fe(L(n))(acac)(C(2)H(5)OH)] incorporating coordinated ethanol from the reaction solvent were accessed from the reaction of [Fe(acac)(3)] with [ONO] donor dibasic tridentate unsymmetrical Schiff base ligands derived from condensation of 2-hydroxy-1-napthaldehyde with 2-aminophenol (H(2)L(1)) or 2-aminobenzoic acid (H(2)L(2)). The thermal study (TGA-DTA) provided evidence for weakly bound ethanol which is readily substituted by neutral N-donor molecule imidazole, benzimidazole or pyridine to produce an array of newer complexes, [Fe(L(n))(acac)X] (n=1, 2; X=Im, Bim, Py). The compounds were characterized by elemental analyses, FT-IR, UV-vis, solution electrical conductivity, FAB mass, (1)H and (13)C NMR spectroscopy. Room temperature magnetic susceptibility measurements (μ(eff)∼5.8 B.M.) are consistent with spin-free octahedral iron(III) complexes. Cyclic voltammetry of ethanol complexes revealed a quasi-reversible one electron redox response (ΔE(p)>100 mV) for the Fe(III)/Fe(II) couple. Low half wave redox potential (E(1/2)) values suggested easy redox susceptibility. The ground state geometries of the ethanol and imidazole complexes have been ascertained to be distorted octahedral by density functional theory using DMol3 program at BLYP/DNP level. Copyright © 2011 Elsevier B.V. All rights reserved.

Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride

DOE PAGES

Martinez, Jorge L.; Lin, Hsiu-Jung; Lee, Wei-Tsung; ...

2017-09-21

The new iron(IV) nitride complex PhB( iPr 2Im) 3Fe≡N reacts with two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB( iPr 2Im) 3Fe(CN)(N 2)(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne iPr 2N-C≡C-N iPr 2. The iron complex is in equilibrium with an N 2- free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C 6F 5) 3 provides the cyanoborane derivative.

Spectrophotometric Determination of Iron(III)-Glycine Formation Constant in Aqueous Medium Using Competitive Ligand Binding

ERIC Educational Resources Information Center

Prasad, Rajendra; Prasad, Surendra

2009-01-01

The formation constant of iron(III) complex with glycine (Gly) ligand in aqueous acidic medium (0.2 M HNO[subscript 3], I = 0.2 M at 28 plus or minus 1 degree C) was determined spectrophotometrically in which a competing color reaction between Fe(III) and SCN[superscript -] was used as an indicator reaction. Under the specified conditions Fe(III)…

A Mononuclear Nonheme Iron(V)-Imido Complex

DOE PAGES

Hong, Seungwoo; Sutherlin, Kyle D.; Vardhaman, Anil Kumar; ...

2017-06-19

Mononuclear nonheme iron(V)-oxo complexes have been reported previously. Herein, we report the first example of a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [(TAML)Fe V(NTs)] – . The spectroscopic characterization of 1 revealed an S = 1/2 Fe(V) oxidation state, an Fe—N bond length of 1.65(4) Å, and an Fe—N vibration at 817 cm –1. In conclusion, the reactivity of 1 was demonstrated in C—H bond functionalization and nitrene transfer reactions.

A Mononuclear Nonheme Iron(V)-Imido Complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hong, Seungwoo; Sutherlin, Kyle D.; Vardhaman, Anil Kumar

Mononuclear nonheme iron(V)-oxo complexes have been reported previously. Herein, we report the first example of a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [(TAML)Fe V(NTs)] – . The spectroscopic characterization of 1 revealed an S = 1/2 Fe(V) oxidation state, an Fe—N bond length of 1.65(4) Å, and an Fe—N vibration at 817 cm –1. In conclusion, the reactivity of 1 was demonstrated in C—H bond functionalization and nitrene transfer reactions.

pH Dependent Spin State Population and 19F NMR Chemical Shift via Remote Ligand Protonation in an Iron(II) Complex (Postprint)

DTIC Science & Technology

2017-12-11

AFRL-RX-WP-JA-2017-0501 pH- DEPENDENT SPIN STATE POPULATION AND 19F NMR CHEMICAL SHIFT VIA REMOTE LIGAND PROTONATION IN AN IRON(II...From - To) 16 November 2017 Interim 24 January 2014 – 16 October 2017 4. TITLE AND SUBTITLE PH- DEPENDENT SPIN STATE POPULATION AND 19F NMR CHEMICAL...dx.doi.org/10.1039/C7CC08099A 14. ABSTRACT (Maximum 200 words) An FeII complex that features a pH- dependent spin state population, by virtue of a

Quercetin-Iron Complex: Synthesis, Characterization, Antioxidant, DNA Binding, DNA Cleavage, and Antibacterial Activity Studies.

PubMed

Raza, Aun; Xu, Xiuquan; Xia, Li; Xia, Changkun; Tang, Jian; Ouyang, Zhen

2016-11-01

Quercetin-iron (II) complex was synthesized and characterized by elemental analysis, ultraviolet-visible spectrophotometry, fourier transform infrared spectroscopy, mass spectrometry, proton nuclear magnetic resonance spectroscopy, thermogravimetry and differential scanning calorimetry, scanning electron micrography and molar conductivity. The low molar conductivity value investigates the non-electrolyte nature of the complex. The elemental analysis and other physical and spectroscopic methods reveal the 1:2 stoichiometric ratio (metal:ligand) of the complex. Antioxidant study of the quercetin and its metal complex against 2, 2-di-phenyl-1-picryl hydrazyl radical showed that the complex has much more radical scavenging activity than free quercetin. The interaction of quercetin-iron (II) complex with DNA was determined using ultraviolet visible spectra, fluorescence spectra and agarose gel electrophoresis. The results showed that quercetin-iron (II) complex can intercalate moderately with DNA, quench a strong intercalator ethidium bromide and compete for the intercalative binding sites. The complex showed significant cleavage of pBR 322 DNA from supercoiled form to nicked circular form and these cleavage effects were dose-dependent. Moreover, the mechanism of DNA cleavage indicated that it was an oxidative cleavage pathway. These results revealed the potential nuclease activity of complex to cleave DNA. In addition, antibacterial activity of complex on E.coli and S. aureus was also investigated. The results showed that complex has higher antibacterial activity than ligand.

Steric modifications tune the regioselectivity of the alkane oxidation catalyzed by non-heme iron complexes.

PubMed

He, Yu; Gorden, John D; Goldsmith, Christian R

2011-12-19

Iron complexes with the tetradentate N-donor ligand N,N'-di(phenylmethyl)-N,N'-bis(2-pyridinylmethyl)-1,2-cyclohexanediamine (bbpc) are reported. Despite the benzyl groups present on the amines, the iron compounds catalyze the oxygenation of cyclohexane to an extent similar to those employing less sterically encumbered ligands. The catalytic activity is strongly dependent on the counterion, with the highest activity and the strongest preference for alkane hydroxylation correlating to the most weakly coordinating anion, SbF(6)(-). The selectivity for the alcohol product over the ketone is amplified when acetic acid is present as an additive. When hydrocarbon substrates with both secondary and tertiary carbons are oxidized by H(2)O(2), the catalyst directs oxidation toward the secondary carbons to a greater degree than other previously reported iron-containing homogeneous catalysts. © 2011 American Chemical Society

Hydrogen production using ammonia borane

DOEpatents

Hamilton, Charles W; Baker, R. Thomas; Semelsberger, Troy A; Shrestha, Roshan P

2013-12-24

Hydrogen ("H.sub.2") is produced when ammonia borane reacts with a catalyst complex of the formula L.sub.nM-X wherein M is a base metal such as iron, X is an anionic nitrogen- or phosphorus-based ligand or hydride, and L is a neutral ancillary ligand that is a neutral monodentate or polydentate ligand.

A rectangular Ni-Fe cluster with unusual cyanide bridges.

PubMed

Krüger, Christoph; Sato, Hiroki; Matsumoto, Takuto; Shiga, Takuya; Newton, Graham N; Renz, Franz; Oshio, Hiroki

2012-10-07

An asymmetric polycyanide iron complex, K(2)[Fe(III)(L1)(CN)(4)](MeOH) (HL1 = 2,2'-(1H-pyrazole-3,5-diyl)bis-pyridine), was synthesized and its complexation compatibility with nickel ions was examined. Two kinds of enantiomeric nickel-iron squares were obtained in the presence of a chiral bidentate capping ligand. The compounds display unusual cyanide bridge geometry and have ferromagnetic interactions between nickel and iron ions.

Decomposition of water-soluble mononitrosyl iron complexes with dithiocarbamates and of dinitrosyl iron complexes with thiol ligands in animal organisms.

PubMed

Serezhenkov, Vladimir A; Timoshin, Alexander A; Orlova, Tsvetina R; Mikoyan, Vasak D; Kubrina, Lioudmila N; Poltorakov, Alexander P; Ruuge, Enno K; Sanina, Natalia A; Vanin, Anatoly F

2008-05-01

EPR studies have shown that water-soluble mononitrosyl iron complexes with N-methyl-d-glucamine dithiocarbamate (MNIC-MGD) (3 micromol) injected to intact mice were decomposed virtually completely within 1h. The total content of MNIC-MGD in animal urine did not exceed 30 nmol/ml. In the liver, a small amount of MNIC-MGD were converted into dinitrosyl iron complexes (30 nmol/g of liver tissue). The same was observed in intact rabbits in which MNIC-MGD formation was induced by endogenous or exogenous NO binding to NO traps, viz., iron complexes with MGD. In mice, the content of MNIC-MGD in urine samples did not change after bacterial lipopolysaccharide-induced expression of iNOS. It was supposed that MNIC-MGD decomposition in intact animals was largely due to the release of NO from the complexes and its further transfer to other specific acceptors. In mice with iNOS expression, the main contribution to MNIC-MGD decomposition was made by superoxide ions whose destructive effect is mediated by an oxidative mechanism. This effect could fully compensate the augmented synthesis of MNIC-MGD involving endogenous NO whose production was supported by iNOS. Water-soluble dinitrosyl iron complexes (DNIC) with various thiol-containing ligands and thiosulfate injected to intact mice were also decomposed; however, in this case the effect was less pronounced than in the case of MNIC-MGD. It was concluded that DNIC decomposition was largely due to the oxidative effect of superoxide ions on these complexes.

Cu(II) removal by Anoxybacillus flavithermus-iron oxide composites during the addition of Fe(II)aq

NASA Astrophysics Data System (ADS)

Franzblau, Rachel E.; Daughney, Christopher J.; Swedlund, Peter J.; Weisener, Christopher G.; Moreau, Magali; Johannessen, Bernt; Harmer, Sarah L.

2016-01-01

There is currently poor understanding of metal removal by composites of bacteria and iron oxide minerals, even though they commonly co-occur and are among the most important sorbents in near-surface fluid-rock environments. This study evaluated Cu removal by composites of Anoxybacillus flavithermus and iron oxide over time during the addition, oxidation, and hydrolysis of Fe(II)aq and precipitation of the mineral, in comparison to Cu removal in the two single-sorbent end-member systems. In the absence of iron oxide, Cu removal by A. flavithermus was well described by a previously published surface complexation model, after inclusion of additional reactions describing aqueous complexation by exudate ligands released by the bacteria. In the absence of bacterial cells, Cu removal by iron oxide synthesized in the presence of the bacterial exudate ligands demonstrated the formation of ternary surface complexes. Removal of Cu by the A. flavithermus-iron oxide composites was ca. 20% greater than the prediction based on assumption of additivity in the two end-member systems. This non-additive behavior was attributed to (1) progressive physical blockage of bacterial surface sites by the iron oxide particles, (2) physical blockage of adsorption sites as a result of self-aggregation of the iron oxide particles, and (3) the reduction of Cu(II) to Cu(I) at the bacterial cell surface, as demonstrated by X-ray absorption spectroscopy. The extent of reduction of Cu(II) to Cu(I) was proportional to the concentration of solid phase Fe(II), suggesting that iron oxidation and copper reduction are linked. This study has shown that Cu removal by bacteria-iron oxide composites is greatly affected by redox processes such as Cu(II) reduction on the cell surface both by other bacterial surface ligands and the oxidation of sorbed Fe(II), as well as Fe(II) redox interactions, and aging effects of the mineral (i.e. surface site masking).

The Importance of Kinetics and Redox in the Biogeochemical Cycling of Iron in the Surface Ocean

PubMed Central

Croot, Peter L.; Heller, Maija I.

2012-01-01

It is now well established that Iron (Fe) is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model and/or its successor the biotic ligand model. Similarly most field work on iron biogeochemistry generally consists of a single profile which is in essence a “snap-shot” in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, dry and wet, are also important perturbations to iron cycling as they bring in new iron to the system and alter the equilibrium between iron species and phases. Here we utilize new field data collected in the open ocean on the complexation kinetics of iron in the surface ocean to identify the important role of weak iron binding ligands (i.e., those that cannot maintain iron in solution indefinitely at seawater pH: αFeL < αFe′) in allowing transient increases in iron solubility in response to iron deposition events. Experiments with the thermal O2- source SOTS-1 also indicate the short term impact of this species on iron solubility also with relevance to the euphotic zone. This data highlights the roles of kinetics, redox, and weaker iron binding ligands in the biogeochemical cycling of iron in the ocean. PMID:22723797

Fe (III), Co(II), Ni(II), Cu(II) and Zn(II) complexes of schiff bases based-on glycine and phenylalanine: Synthesis, magnetic/thermal properties and antimicrobial activity

NASA Astrophysics Data System (ADS)

Sevgi, Fatih; Bagkesici, Ugur; Kursunlu, Ahmed Nuri; Guler, Ersin

2018-02-01

Zinc (II), copper (II), nickel (II), cobalt (II) and iron (III) complexes of Schiff bases (LG, LP) derived from 2-hydroxynaphthaldehyde with glycine and phenylalanine were reported and characterized by 1H NMR, 13C NMR, elemental analyses, melting point, FT-IR, magnetic susceptibility and thermal analyses (TGA). TGA data show that iron and cobalt include to the coordinated water and metal:ligand ratio is 1:2 while the complex stoichiometry for Ni (II), Cu (II) and Zn (II) complexes is 1:1. As expected, Ni (II) and Zn (II) complexes are diamagnetic; Cu (II), Co (II) and Fe (III) complexes are paramagnetic character due to a strong ligand of LG and LP. The LG, LP and their metal complexes were screened for their antimicrobial activities against five Gram-positive (Staphylococcus aureus, Methicillin resistant Staphylococcus aureus (MRSA), Bacillus cereus, Streptococcus mutans and Enterococcus faecalis) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa) and one fungi (Candida albicans) by using broth microdilution techniques. The activity data show that ligands and their metal complexes exhibited moderate to good activity against Gram-positive bacteria and fungi.

Photomagnetic Switching of the Complex [Nd(dmf)[subscript 4](H[subscript 2]O)[subscript 3]([mu]-CN)Fe(CN)[subscript 5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Svendsen, Helle; Overgaard, Jacob; Chevallier, Marie

2009-10-21

Single-crystal XRD experiments (see picture) reveal the excited-state structure of the photomagnetic heterobimetallic title complex. The system shows a decrease in all the iron-ligand bond lengths, suggesting that photoexcitation involves a ligand-to-metal charge transfer or a change in the superexchange coupling between the metal centers.

Reactivity of molecular dioxygen towards a series of isostructural dichloroiron(III) complexes with tripodal tetraamine ligands: general access to mu-oxodiiron(III) complexes and effect of alpha-fluorination on the reaction kinetics.

PubMed

Thallaj, Nasser K; Rotthaus, Olaf; Benhamou, Leila; Humbert, Nicolas; Elhabiri, Mourad; Lachkar, Mohammed; Welter, Richard; Albrecht-Gary, Anne-Marie; Mandon, Dominique

2008-01-01

We have synthesized the mono, di-, and tri-alpha-fluoro ligands in the tris(2-pyridylmethyl)amine (TPA) series, namely, FTPA, F(2)TPA and F(3)TPA, respectively. Fluorination at the alpha-position of these nitrogen-containing tripods shifts the oxidation potential of the ligand by 45-70 mV per added fluorine atom. The crystal structures of the dichloroiron(II) complexes with FTPA and F(2)TPA reveal that the iron center lies in a distorted octahedral geometry comparable to that already found in TPAFeCl(2). All spectroscopic data indicate that the geometry is retained in solution. These three isostructural complexes all react with molecular dioxygen to yield stable mu-oxodiiron(III) complexes. Crystal structure analyses are reported for each of these three mu-oxo compounds. With TPA, a symmetrical structure is obtained for a dicationic compound with the tripod coordinated in the kappa(4)N coordination mode. With FTPA, the compound is a neutral mu-oxodiiron(III) complex with a kappa(3)N coordination mode of the ligand. Oxygenation of the F(2)TPA complex gave a neutral unsymmetrical compound, the structure of which is reminiscent of that already found with the trifluorinated ligand. On reduction, all mu-oxodiiron(III) complexes revert to the starting iron(II) species. The oxygenation reaction parallels the well-known formation of mu-oxo derivatives from dioxygen in the chemistry of porphyrins reported almost three decades ago. The striking feature of the series of iron(II) precursors is the effect of the ligand on the kinetics of oxygenation of the complexes. Whereas the parent complex undergoes 90 % conversion over 40 h, the monofluorinated ligand provides a complex that has fully reacted after 30 h, whereas the reaction time for the complex with the difluorinated ligand is only 10 h. Analysis of the spectroscopic data reveals that formation of the mu-oxo complexes proceeds in two distinct reversible kinetic steps with k(1) approximately 10 k(2). For TPAFeCl(2) and FTPAFeCl(2) only small variations in the k(1) and k(2) values are observed. By contrast, F(2)TPAFeCl(2) exhibits k(1) and k(2) values that are ten times higher. These differences in kinetics are interpreted in the light of structural and electronic effects, especially the Lewis acidity at the metal center. Our results suggest coordination of dioxygen as an initial step in the process leading to formation of mu-oxodiiron(III) compounds, by contrast with an unlikely outer-sphere reduction of dioxygen, which generally occurs at negative potentials.

Human Metabolome-derived Cofactors Are Required for the Antibacterial Activity of Siderocalin in Urine*

PubMed Central

Shields-Cutler, Robin R.; Crowley, Jan R.; Miller, Connelly D.; Stapleton, Ann E.; Cui, Weidong; Henderson, Jeffrey P.

2016-01-01

In human urinary tract infections, host cells release the antimicrobial protein siderocalin (SCN; also known as lipocalin-2, neutrophil gelatinase-associated lipocalin, or 24p3) into the urinary tract. By binding to ferric catechol complexes, SCN can sequester iron, a growth-limiting nutrient for most bacterial pathogens. Recent evidence links the antibacterial activity of SCN in human urine to iron sequestration and metabolomic variation between individuals. To determine whether these metabolomic associations correspond to functional Fe(III)-binding SCN ligands, we devised a biophysical protein binding screen to identify SCN ligands through direct analysis of human urine. This screen revealed a series of physiologic unconjugated urinary catechols that were able to function as SCN ligands of which pyrogallol in particular was positively associated with high urinary SCN activity. In a purified, defined culture system, these physiologic SCN ligands were sufficient to activate SCN antibacterial activity against Escherichia coli. In the presence of multiple SCN ligands, native mass spectrometry demonstrated that SCN may preferentially combine different ligands to coordinate iron, suggesting that availability of specific ligand combinations affects in vivo SCN antibacterial activity. These results support a mechanistic link between the human urinary metabolome and innate immune function. PMID:27780864

Impact on the Fe redox cycling of organic ligands released by Synechococcus PCC 7002, under different iron fertilization scenarios. Modeling approach

NASA Astrophysics Data System (ADS)

Samperio-Ramos, Guillermo; González-Dávila, Melchor; Santana-Casiano, J. Magdalena

2018-06-01

The kinetics of Fe redox transformations are of crucial importance in determining the bioavailability of iron, due to inorganic Fe(II) and Fe weakly organic complexes being the most easily assimilated species by phytoplankton. The role played by the natural organic ligands excreted by the cyanobacteria Synecococcus PCC 7002 on the iron redox chemistry was studied at different stages of growth, considering changes in the organic exudation of the cyanobacteria, associated with growth under two different scenarios of iron availability. The oxidation/reduction processes of iron were studied at nanomolar levels and under different physicochemical conditions of pH (7.2- 8.2), temperature (5- 35 °C) and salinity (10- 37). The presence of natural organic exudates of Synechococcus affected the redox behavior of iron. A pH-dependent and photo-induced Fe(III) reduction process was detected in the presence of exudates produced under Fe-Low conditions. Photolytic reactions also modified the reactivity of those exudates with respect to Fe(II), increasing its lifetime in seawater. Without light mediated processes, organic ligands excreted under iron deficient conditions intensified the Fe(II) oxidation at pH < 7.5. The organic exudates released under High-Fe conditions retarded the Fe(II) oxidation rate, as a function of DOC produced. The changes in the apparent oxidation rate were fitted to polynomial functions for both of the Fe-scenarios considered. A kinetic modeling approach to describe the speciation and the contribution of individual Fe(II) species to the overall oxidation rate was applied, considering the experimental data and delimiting the equilibrium and redox constants between iron and the major ligands present in solution. Two organic type ligands for the exudates of Synechococcus PCC 7002, with different iron-chelation properties were included in the model. The Fe(II) speciation was radically affected when organic ligands were considered. The individual contributions to the overall Fe(II) oxidation rate demonstrated that these organic ligands played a key role in the oxidation process, although their contributions were dependent on the prescribed iron conditions. The study, therefore, suggests that the variability in the composition and nature of organic exudates released, due to iron availability conditions, might determine the redox behaviour of iron in seawater.

The binuclear form of dinitrosyl iron complexes with thiol-containing ligands in animal tissues.

PubMed

Mikoyan, Vasak D; Burgova, Evgeniya N; Borodulin, Rostislav R; Vanin, Anatoly F

2017-01-30

It has been established that treatment of mice with sodium nitrite, S-nitrosoglutathione and the water-soluble nitroglycerine derivative isosorbide dinitrate (ISDN) as NO donors initiates in vivo synthesis of significant amounts of EPR-silent binuclear dinitrosyl iron complexes (B-DNIC) with thiol-containing ligands in the liver and other tissues of experimental mice. This effect is especially apparent if NO donors are administered to mice simultaneously with the Fe 2+ -citrate complex. Similar results were obtained in experiments on isolated liver and other mouse tissues treated with gaseous NО in vitro and during stimulation of endogenous NO synthesis in the presence of inducible NO synthase. B-DNIC appeared in mouse tissues after in vitro treatment of tissue samples with an aqueous solution of diethyldithiocarbamate (DETC), which resulted in the transfer of iron-mononitrosyl fragments from B-DNIC to the thiocarbonyl group of DETC and the formation of EPR-detectable mononitrosyl iron complexes (MNIC) with DETC. EPR-Active MNIC with N-methyl-d-glucamine dithiocarbamate (MGD) were synthesized in a similar way. MNIC-MGD were also formed in the reaction of water-soluble MGD-Fe 2+ complexes with sodium nitrite, S-nitrosoglutathione and ISDN. Copyright © 2016. Published by Elsevier Inc.

Synthesis, spectral and magnetic studies of mono- and bi-nuclear metal complexes of a new bis(tridentate NO2) Schiff base ligand derived from 4,6-diacetylresorcinol and ethanolamine.

PubMed

Shebl, Magdy

2009-07-15

A new bis(tridentate NO2) Schiff base ligand, H(4)L, was prepared by the reaction of the bifunctional carbonyl compound; 4,6-diacetylresorcinol (DAR) with ethanolamine. The ligand reacted with iron(III), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), cerium(III) and uranyl(VI) ions, in absence and in presence of LiOH, to yield mono- and bi-nuclear complexes with different coordinating sites. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. In absence of LiOH, mononuclear complexes (2, 3 and 5-9) as well as binuclear complexes (1 and 4) were obtained. In mononuclear complexes, the ligand acted as a neutral, mono- and di-basic/bi- and tetra-dentate ligand while in binuclear complexes (1 and 4), the ligand acted as a bis(mono- or di-basic/tridentate) ligand. On the other hand, in presence of LiOH, only binuclear complexes (10-15) were obtained in which the ligand acted as a bis(dibasic tridentate) ligand. The metal complexes exhibited different geometrical arrangements such as octahedral, tetrahedral, square planar, square pyramidal and pentagonal bipyramidal arrangements.

Crystal structure of tricarbon­yl(μ-di­phenyl­phosphido-κ2 P:P)(methyl­diphenyl­silyl-κSi)bis(tri­phenyl­phosphane-κP)iron(II)platinum(0)(Fe—Pt)

PubMed Central

Mohamed, Ahmed Said; Jourdain, Isabelle; Knorr, Michael; Rousselin, Yoann; Kubicki, Marek M.

2015-01-01

The title compound, [FePt(C12H10P)(C13H13Si)(C18H15P)2(CO)3]·0.5CH2Cl2, represents an example of a phosphido-bridged heterobimetallic silyl complex; these are inter­esting precursors for the coordination and activation of small unsaturated organic mol­ecules. The μ2-PPh2 ligand spans the iron and platinum atoms, which are connected via a metal–metal bond of 2.7738 (4) Å. In contrast to most other complexes of the [(OC)3Fe(SiR 3)(μ-PR 2)PtL 2] family, where the iron-bound SiR 3 group is trans-arranged with respect to the μ2-PPh2 ligand, the SiPh2Me ligand is roughly collinear with the Fe–Pt vector [Si—Fe—Pt = 169.07 (3)°]. PMID:25878830

A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

NASA Astrophysics Data System (ADS)

Chábera, Pavel; Liu, Yizhu; Prakash, Om; Thyrhaug, Erling; Nahhas, Amal El; Honarfar, Alireza; Essén, Sofia; Fredin, Lisa A.; Harlang, Tobias C. B.; Kjær, Kasper S.; Handrup, Karsten; Ericson, Fredric; Tatsuno, Hideyuki; Morgan, Kelsey; Schnadt, Joachim; Häggström, Lennart; Ericsson, Tore; Sobkowiak, Adam; Lidin, Sven; Huang, Ping; Styring, Stenbjörn; Uhlig, Jens; Bendix, Jesper; Lomoth, Reiner; Sundström, Villy; Persson, Petter; Wärnmark, Kenneth

2017-03-01

Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3‧-dimethyl-1,1‧-bis(p-tolyl)-4,4‧-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

The Organic Complexation of Iron in the Marine Environment: A Review

PubMed Central

Gledhill, Martha; Buck, Kristen N.

2012-01-01

Iron (Fe) is an essential micronutrient for marine organisms, and it is now well established that low Fe availability controls phytoplankton productivity, community structure, and ecosystem functioning in vast regions of the global ocean. The biogeochemical cycle of Fe involves complex interactions between lithogenic inputs (atmospheric, continental, or hydrothermal), dissolution, precipitation, scavenging, biological uptake, remineralization, and sedimentation processes. Each of these aspects of Fe biogeochemical cycling is likely influenced by organic Fe-binding ligands, which complex more than 99% of dissolved Fe. In this review we consider recent advances in our knowledge of Fe complexation in the marine environment and their implications for the biogeochemistry of Fe in the ocean. We also highlight the importance of constraining the dissolved Fe concentration value used in interpreting voltammetric titration data for the determination of Fe speciation. Within the published Fe speciation data, there appear to be important temporal and spatial variations in Fe-binding ligand concentrations and their conditional stability constants in the marine environment. Excess ligand concentrations, particularly in the truly soluble size fraction, seem to be consistently higher in the upper water column, and especially in Fe-limited, but productive, waters. Evidence is accumulating for an association of Fe with both small, well-defined ligands, such as siderophores, as well as with larger, macromolecular complexes like humic substances, exopolymeric substances, and transparent exopolymers. The diverse size spectrum and chemical nature of Fe ligand complexes corresponds to a change in kinetic inertness which will have a consequent impact on biological availability. However, much work is still to be done in coupling voltammetry, mass spectrometry techniques, and process studies to better characterize the nature and cycling of Fe-binding ligands in the marine environment. PMID:22403574

Iron chelates: a challenge to chemists and Mössbauer spectroscopists

NASA Astrophysics Data System (ADS)

Homonnay, Z.; Szilágyi, P. Á.; Vértes, A.; Kuzmann, E.; Sharma, V. K.; Molnár, G.; Bousseksou, A.; Grenèche, J.-M.; Brausam, A.; Meier, R.; van Eldik, R.

2008-02-01

The speciation of iron in aqueous solutions containing Fe3 + and selected chelates such as EDTA, EDDA, CDTA and HEDTA has been studied using transmission 57Fe Mössbauer spectrometry in frozen solutions. The protonation of various complexes as well as binuclear complex formation could be detected as a function of pH. Autoreduction of Fe3 + to Fe2 + was observed in several cases. Reaction with hydrogen peroxide proved to be rather different for the four ligands, while the dihapto complex [XFe( η 2-O2)]3 - had surprisingly identical Mössbauer parameters for X = EDTA, CDTA or HEDTA. Paramagnetic spin relaxation observed in the Mössbauer spectra was found to be strongly influenced by the identity of the chelating ligand, despite the basically spin-spin origin of the phenomenon.

Synthesis, characterization and single crystal x-ray analysis of a complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Sandeep; Andotra, Savit; Kaur, Mandeep

2016-09-15

Complex of iron(II) bis(2,4-dimethylphenyl)dithiophosphate with 4-ethylpyridine [((2,4- (CH{sub 3}){sub 2}C{sub 6}H{sub 3}O)2PS2)2Fe(NC{sub 5}H{sub 4}(C{sub 2}H{sub 5})-4){sub 2}] is synthesized and characterized by elemental analysis, magnetic moment, IR spectroscopy and single crystal X-ray analysis. Complex crystallizes in the monoclinic sp. gr. P2{sub 1}/n, Z = 2. Crystal structure consists of mononuclear units with Fe(II) ion chelated by four S atoms of the two diphenyldithiophosphate ligands in bidentate manner. N atoms from two 4-ethylpyridine ligands are axially coordinated to the Fe(II) atom leading to an octahedral geometry.

A review of the antioxidant mechanisms of polyphenol compounds related to iron binding.

PubMed

Perron, Nathan R; Brumaghim, Julia L

2009-01-01

In this review, primary attention is given to the antioxidant (and prooxidant) activity of polyphenols arising from their interactions with iron both in vitro and in vivo. In addition, an overview of oxidative stress and the Fenton reaction is provided, as well as a discussion of the chemistry of iron binding by catecholate, gallate, and semiquinone ligands along with their stability constants, UV-vis spectra, stoichiometries in solution as a function of pH, rates of iron oxidation by O(2) upon polyphenol binding, and the published crystal structures for iron-polyphenol complexes. Radical scavenging mechanisms of polyphenols unrelated to iron binding, their interactions with copper, and the prooxidant activity of iron-polyphenol complexes are briefly discussed.

Hydroxypyridinone Chelators: From Iron Scavenging to Radiopharmaceuticals for PET Imaging with Gallium-68

PubMed Central

Cusnir, Ruslan; Imberti, Cinzia; Hider, Robert C.; Blower, Philip J.; Ma, Michelle T.

2017-01-01

Derivatives of 3,4-hydroxypyridinones have been extensively studied for in vivo Fe3+ sequestration. Deferiprone, a 1,2-dimethyl-3,4-hydroxypyridinone, is now routinely used for clinical treatment of iron overload disease. Hexadentate tris(3,4-hydroxypyridinone) ligands (THP) complex Fe3+ at very low iron concentrations, and their high affinities for oxophilic trivalent metal ions have led to their development for new applications as bifunctional chelators for the positron emitting radiometal, 68Ga3+, which is clinically used for molecular imaging in positron emission tomography (PET). THP-peptide bioconjugates rapidly and quantitatively complex 68Ga3+ at ambient temperature, neutral pH and micromolar concentrations of ligand, making them amenable to kit-based radiosynthesis of 68Ga PET radiopharmaceuticals. 68Ga-labelled THP-peptides accumulate at target tissue in vivo, and are excreted largely via a renal pathway, providing high quality PET images. PMID:28075350

Hydroxypyridinone Chelators: From Iron Scavenging to Radiopharmaceuticals for PET Imaging with Gallium-68.

PubMed

Cusnir, Ruslan; Imberti, Cinzia; Hider, Robert C; Blower, Philip J; Ma, Michelle T

2017-01-08

Derivatives of 3,4-hydroxypyridinones have been extensively studied for in vivo Fe 3+ sequestration. Deferiprone, a 1,2-dimethyl-3,4-hydroxypyridinone, is now routinely used for clinical treatment of iron overload disease. Hexadentate tris(3,4-hydroxypyridinone) ligands (THP) complex Fe 3+ at very low iron concentrations, and their high affinities for oxophilic trivalent metal ions have led to their development for new applications as bifunctional chelators for the positron emitting radiometal, 68 Ga 3+ , which is clinically used for molecular imaging in positron emission tomography (PET). THP-peptide bioconjugates rapidly and quantitatively complex 68 Ga 3+ at ambient temperature, neutral pH and micromolar concentrations of ligand, making them amenable to kit-based radiosynthesis of 68 Ga PET radiopharmaceuticals. 68 Ga-labelled THP-peptides accumulate at target tissue in vivo, and are excreted largely via a renal pathway, providing high quality PET images.

How does the axial ligand of cytochrome P450 biomimetics influence the regioselectivity of aliphatic versus aromatic hydroxylation?

PubMed

de Visser, Sam P; Tahsini, Laleh; Nam, Wonwoo

2009-01-01

The catalytic activity of high-valent iron-oxo active species of heme enzymes is known to be dependent on the nature of the axial ligand trans to the iron-oxo group. In a similar fashion, experimental studies on iron-oxo porphyrin biomimetic systems have shown a significant axial ligand effect on ethylbenzene hydroxylation, with an axial acetonitrile ligand leading to phenyl hydroxylation products and an axial chloride anion giving predominantly benzyl hydroxylation products. To elucidate the fundamental factors that distinguish this regioselectivity reversal in iron-oxo porphyrin catalysis, we have performed a series of density functional theory calculations on the hydroxylation of ethylbenzene by [Fe(IV)=O(Por(+.))L] (Por = porphyrin; L = NCCH(3) or Cl(-)), which affords 1-phenylethanol and p-ethylphenol products. The calculations confirm the experimentally determined product distributions. Furthermore, a detailed analysis of the electronic differences between the two oxidants shows that their reversed regioselectivity is a result of differences in orbital interactions between the axial ligand and iron-oxo porphyrin system. In particular, three high-lying orbitals (pi*(xz), pi*(yz) and a(2u)), which are singly occupied in the reactant complex, are stabilised with an anionic ligand such as Cl(-), which leads to enhanced HOMO-LUMO energy gaps. As a consequence, reactions leading to cationic intermediates through the two-electron reduction of the metal centre are disfavoured. The aliphatic hydroxylation mechanism, in contrast, is a radical process in which only one electron is transferred in the rate-determining transition state, which means that the effect of the axial ligand on this mechanism is much smaller.

pH-Dependent spin state population and 19F NMR chemical shift via remote ligand protonation in an iron(ii) complex.

PubMed

Gaudette, Alexandra I; Thorarinsdottir, Agnes E; Harris, T David

2017-11-30

An Fe II complex that features a pH-dependent spin state population, by virtue of a variable ligand protonation state, is described. This behavior leads to a highly pH-dependent 19 F NMR chemical shift with a sensitivity of 13.9(5) ppm per pH unit at 37 °C, thereby demonstrating the potential utility of the complex as a 19 F chemical shift-based pH sensor.

Iron(II) cage complexes of N-heterocyclic amide and bis(trimethylsilyl)amide ligands: synthesis, structure, and magnetic properties.

PubMed

Sulway, Scott A; Collison, David; McDouall, Joseph J W; Tuna, Floriana; Layfield, Richard A

2011-03-21

Metallation of hexahydropyrimidopyrimidine (hppH) by [Fe{N(SiMe(3))(2)}(2)] (1) produces the trimetallic iron(II) amide cage complex [{(Me(3)Si)(2)NFe}(2)(hpp)(4)Fe] (2), which contains three iron(II) centers, each of which resides in a distorted tetrahedral environment. An alternative, one-pot route that avoids use of the highly air-sensitive complex 1 is described for the synthesis of the iron(II)-lithium complex [{(Me(3)Si)(2)N}(2)Fe{Li(bta)}](2) (3) (where btaH = benzotriazole), in which both iron(II) centers reside in 3-coordinated pyramidal environments. The structure of 3 is also interpreted in terms of the ring laddering principle developed for alkali metal amides. Magnetic susceptibility measurements reveal that both compounds display very weak antiferromagnetic exchange between the iron(II) centers, and that the iron(II) centers in 2 and 3 possess large negative axial zero-field splittings.

Electrochemistry of Simple Organometallic Models of Iron-Iron Hydrogenases in Organic Solvent and Water.

PubMed

Gloaguen, Frederic

2016-01-19

Synthetic models of the active site of iron-iron hydrogenases are currently the subjects of numerous studies aimed at developing H2-production catalysts based on cheap and abundant materials. In this context, the present report offers an electrochemist's view of the catalysis of proton reduction by simple binuclear iron(I) thiolate complexes. Although these complexes probably do not follow a biocatalytic pathway, we analyze and discuss the interplay between the reduction potential and basicity and how these antagonist properties impact the mechanisms of proton-coupled electron transfer to the metal centers. This question is central to any consideration of the activity at the molecular level of hydrogenases and related enzymes. In a second part, special attention is paid to iron thiolate complexes holding rigid and unsaturated bridging ligands. The complexes that enjoy mild reduction potentials and stabilized reduced forms are promising iron-based catalysts for the photodriven evolution of H2 in organic solvents and, more importantly, in water.

Nitrate reduction by zerovalent iron: effects of formate, oxalate, citrate, chloride, sulfate, borate, and phosphate.

PubMed

Su, Chunming; Puls, Robert W

2004-05-01

Recent studies have shown that zerovalent iron (Fe0) may potentially be used as a chemical medium in permeable reactive barriers (PRBs) for groundwater nitrate remediation; however, the effects of commonly found organic and inorganic ligands in soil and sediments on nitrate reduction by Fe0 have not been well understood. A 25.0 mL nitrate solution of 20.0 mg of N L(-1) (1.43 mM nitrate) was reacted with 1.00 g of Peerless Fe0 at 200 rpm on a rotational shaker at 23 degrees C for up to 120 h in the presence of each of the organic acids (3.0 mM formic, 1.5 mM oxalic, and 1.0 mM citric acids) and inorganic acids (3.0 mM HCl, 1.5 mM H2SO4, 3.0 mM H3BO3, and 1.5 mM H3PO4). These acids provided an initial dissociable H+ concentration of 3.0 mM available for nitrate reduction reactions under conditions of final pH < 9.3. Nitrate reduction rates (pseudo-first-order) increased in the order: H3PO4 < citric acid < H3BO3 < oxalic acid < H2SO4 < formic acid < HCl, ranging from 0.00278 to 0.0913 h(-1), corresponding to surface area normalized rates ranging from 0.126 to 4.15 h(-1) m(-2) mL. Correlation analysis showed a negative linear relationship between the nitrate reduction rates for the ligands and the conditional stability constants for the soluble complexes of the ligands with Fe2+ (R2 = 0.701) or Fe3+ (R2 = 0.918) ions. This sequence of reactivity corresponds also to surface adsorption and complexation of the three organic ligands to iron oxides, which increase in the order formate < oxalate < citrate. The results are also consistent with the sequence of strength of surface complexation of the inorganic ligands to iron oxides, which increases in the order: chloride < sulfate < borate < phosphate. The blockage of reactive sites on the surface of Fe0 and its corrosion products by specific adsorption of the inner-sphere complex forming ligands (oxalate, citrate, sulfate, borate, and phosphate) may be responsible for the decreased nitrate reduction by Fe0 relative to the chloride system.

Transition metal coordination chemistry ofN,N-bis(2-{pyrid-2-ylethyl})hydroxylamine.

PubMed

Belock, Christopher W; Cetin, Anil; Barone, Natalie V; Ziegler, Christopher J

2008-08-18

Although directly relevant to metal mediated biological nitrification as well as the coordination chemistry of peroxide, the metal complexes of hydroxylamines and their functionalized variants remain largely unexplored. The chelating hydroxylamine ligand N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine can be readily generated via a solvent free reaction in high purity; however, the ligand is prone to decomposition which can hamper metal reaction. N,N-bis(2-{pyrid-2-ylethyl})hydroxylamine forms stable complexes with chromium(III), manganese(II), nickel(II), and cadmium(II) ions, coordinating in a side-on mode in the case of chromium and via the nitrogen in the case of the latter three metal ions. The hydroxylamine ligand can also be reduced to form N,N-bis(2-{pyrid-2-ylethyl})amine upon exposure to a stoichiometric amount of the metal salts cobalt(II) nitrate, vanadium(III) chloride, and iron(II) chloride. In the reaction with cobalt nitrate, the reduced ligand then chelates to the metal to form [N,N-bis(2-{pyrid-2-ylethyl})amine]dinitrocobalt(II). Upon reaction with vanadium(III) chloride and iron(III) chloride, the reduced ligand is isolated as the protonated free base, resulting from a metal-mediated decomposition reaction.

Syntheses, crystal and band structures, and optical properties of a selenidoantimonate and an iron polyselenide

NASA Astrophysics Data System (ADS)

Liu, Guang-Ning; Zhu, Wen-Juan; Zhang, Ming-Jian; Xu, Bo; Liu, Qi-Sheng; Zhang, Zhen-Wei; Li, Cuncheng

2014-10-01

A new selenidoantimonate (CH3NH4)[Mn(phen)2](SbSe4)·phen (1, phen=1,10-phenanthroline) and an iron polyselenide [Fe(phen)2](Se4) (2) were obtained under hydro(solvo)thermal conditions. Compound 1 represents the first example of a selenidoantimonate anion as a ligand to a transition-metal π-conjugated ligand complex cation. Compound 2 containing a κ2Se1,Se4 chelating tetraselenide ligand, represents the only example of a tetraselenide ligand to a Fe complex cation. Compounds 1 and 2 exhibit optical gaps of 1.71 and 1.20 eV, respectively and their thermal stabilities have been investigated by thermogravimetric analyses. The electronic band structure along with the density of states calculated by the DFT method indicate that the optical absorptions mainly originate from the charge transitions from the Se 4p and Mn 3d states to the phen p-π* orbital for 1 and the Se 4p and Fe 3d states to the phen p-π* orbital for 2.

Synthesis and reactivity of iron complexes with a new pyrazine-based pincer ligand, and application in catalytic low-pressure hydrogenation of carbon dioxide.

PubMed

Rivada-Wheelaghan, Orestes; Dauth, Alexander; Leitus, Gregory; Diskin-Posner, Yael; Milstein, David

2015-05-04

A novel pincer ligand based on the pyrazine backbone (PNzP) has been synthesized, (2,6-bis(di(tert-butyl)phosphinomethyl)pyrazine), tBu-PNzP. It reacts with FeBr2 to yield [Fe(Br)2(tBu-PNzP)], 1. Treatment of 1 with NaBH4 in MeCN/MeOH gives the hydride complex [Fe(H)(MeCN)2(tBu-PNzP)][X] (X = Br, BH4), 2·X. Counterion exchange and exposure to CO atmosphere yields the complex cis-[Fe(H)(CO)(MeCN)(tBu-PNzP)][BPh4] 4·BPh4, which upon addition of Bu4NCl forms [Fe(H)(Cl)(CO)(tBu-PNzP)] 5. Complex 5, under basic conditions, catalyzes the hydrogenation of CO2 to formate salts at low H2 pressure. Treatment of complex 5 with a base leads to aggregates, presumably of dearomatized species B, stabilized by bridging to another metal center by coordination of the nitrogen at the backbone of the pyrazine pincer ligand. Upon dissolution of compound B in EtOH the crystallographically characterized complex 7 is formed, comprised of six iron units forming a 6-membered ring. The dearomatized species can activate CO2 and H2 by metal-ligand cooperation (MLC), leading to complex 8, trans-[Fe(PNzPtBu-COO)(H)(CO)], and complex 9, trans-[Fe(H)2(CO)(tBu-PNzP)], respectively. Our results point at a very likely mechanism for CO2 hydrogenation involving MLC.

Structure and reactivity of a mononuclear non-haem iron(III)–peroxo complex

PubMed Central

Cho, Jaeheung; Jeon, Sujin; Wilson, Samuel A.; Liu, Lei V.; Kang, Eun A; Braymer, Joseph J.; Lim, Mi Hee; Hedman, Britt; Hodgson, Keith O.; Valentine, Joan Selverstone; Solomon, Edward I.; Nam, Wonwoo

2012-01-01

Oxygen-containing mononuclear iron species—iron(III)–peroxo, iron(III)–hydroperoxo and iron(IV)–oxo—are key intermediates in the catalytic activation of dioxygen by iron-containing metalloenzymes1–7. It has been difficult to generate synthetic analogues of these three active iron–oxygen species in identical host complexes, which is necessary to elucidate changes to the structure of the iron centre during catalysis and the factors that control their chemical reactivities with substrates. Here we report the high-resolution crystal structure of a mononuclear non-haem side-on iron(III)–peroxo complex, [Fe(III)(TMC)(OO)]+. We also report a series of chemical reactions in which this iron(III)–peroxo complex is cleanly converted to the iron(III)–hydroperoxo complex, [Fe(III)(TMC)(OOH)]2+, via a short-lived intermediate on protonation. This iron(III)–hydroperoxo complex then cleanly converts to the ferryl complex, [Fe(IV)(TMC)(O)]2+, via homolytic O–O bond cleavage of the iron(III)–hydroperoxo species. All three of these iron species—the three most biologically relevant iron–oxygen intermediates—have been spectroscopically characterized; we note that they have been obtained using a simple macrocyclic ligand. We have performed relative reactivity studies on these three iron species which reveal that the iron(III)–hydroperoxo complex is the most reactive of the three in the deformylation of aldehydes and that it has a similar reactivity to the iron(IV)–oxo complex in C–H bond activation of alkylaromatics. These reactivity results demonstrate that iron(III)–hydroperoxo species are viable oxidants in both nucleophilic and electrophilic reactions by iron-containing enzymes. PMID:22031443

Characterization of a Tricationic Trigonal Bipyramidal Iron(IV) Cyanide Complex, with a Very High Reduction Potential, and Its Iron(II) and Iron(III) Congeners

PubMed Central

England, Jason; Farquhar, Erik R.; Guo, Yisong; Cranswick, Matthew A.; Ray, Kallol

2011-01-01

Currently, there are only a handful of synthetic S = 2 oxoiron(IV) complexes. These serve as models for the high-spin (S = 2) oxoiron(IV) species that have been postulated, and confirmed in several cases, as key intermediates in the catalytic cycles of a variety of non-heme oxygen activating enzymes. The trigonal bipyramidal complex [FeIV(O)(TMG3tren)]2+ (1) was both the first S = 2 oxoiron(IV) model complex to be generated in high yield and the first to be crystallographically characterized. In this study, we demonstrate that the TMG3tren ligand is also capable of supporting a tricationic cyanoiron(IV) unit, [FeIV(CN)(TMG3tren)]3+ (4). This complex was generated by electrolytic oxidation of the high-spin (S = 2) iron(II) complex [FeII(CN)(TMG3tren)]+ (2), via the S = 5/2 complex [FeIII(CN)(TMG3tren)]2+ (3), the progress of which was conveniently monitored by using UV-Vis spectroscopy to follow the growth of bathochromically shifting LMCT bands. A combination of XAS, Mössbauer and NMR spectroscopies was used to establish that 4 has a S = 0 iron(IV) center. Consistent with its diamagnetic iron(IV) ground state, EXAFS analysis of 4 indicated a significant contraction of the iron-donor atom bond lengths, relative to those of the crystallographically characterized complexes 2 and 3. Notably, 4 has an FeIV/III reduction potential of ~1.4 V vs Fc+/o, the highest value yet observed for a monoiron complex. The relatively high stability of 4 (t1/2 in CD3CN solution containing 0.1 M KPF6 at 25 °C ≈ 15 min), as reflected by its high-yield accumulation via slow bulk electrolysis and amenability to 13C NMR at −40 °C, highlights the ability of the sterically protecting, highly basic peralkylguanidyl donors of the TMG3tren ligand to support highly charged high-valent complexes. PMID:21381646

Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid-Complex Tauto-Conformers.

PubMed

Schäfer, Bernhard; Greisch, Jean-François; Faus, Isabelle; Bodenstein, Tilmann; Šalitroš, Ivan; Fuhr, Olaf; Fink, Karin; Schünemann, Volker; Kappes, Manfred M; Ruben, Mario

2016-08-26

The coordination of iron(II) ions by a homoditopic ligand L with two tridentate chelates leads to the tautomerism-driven emergence of complexity, with isomeric tetramers and trimers as the coordination products. The structures of the two dominant [Fe(II) 4 L4 ](8+) complexes were determined by X-ray diffraction, and the distinctness of the products was confirmed by ion-mobility mass spectrometry. Moreover, these two isomers display contrasting magnetic properties (Fe(II) spin crossover vs. a blocked Fe(II) high-spin state). These results demonstrate how the coordination of a metal ion to a ligand that can undergo tautomerization can increase, at a higher hierarchical level, complexity, here expressed by the formation of isomeric molecular assemblies with distinct physical properties. Such results are of importance for improving our understanding of the emergence of complexity in chemistry and biology. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Modelling the cis-oxo-labile binding site motif of non-heme iron oxygenases. Water exchange and remarkable oxidation reactivity of a novel non-heme iron(IV)-oxo compound bearing a tripodal tetradentate ligand

PubMed Central

Company, Anna; Prat, Irene; Frisch, Jonathan R.; Ballesté, Ruben Mas; Güell, Mireia; Juhász, Gergely; Ribas, Xavi; Münck, Eckard; Luis, Josep M.; Que, Lawrence

2011-01-01

The spectroscopic and chemical characterization of a new synthetic non-heme iron(IV)-oxo species [FeIV(O)(Me,HPytacn)(S)]2+ (2, Me,HPytacn = 1-(2′-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane, S = CH3CN or H2O) is described. 2 has been prepared by reaction of [FeII(CF3SO3)2(Me,HPytacn)] (1) with peracetic acid. Complex 2 bears a tetradentate N4 ligand that leaves two cis- sites available for binding an oxo group and a second external ligand but, unlike related iron(IV)-oxo of tetradentate ligands, it is remarkably stable at room temperature (t1/2 > 2h at 288 K). Its ability to exchange the oxygen atom of the oxo ligand with water has been analyzed in detail by means of kinetic studies, and a mechanism has been proposed on the basis of DFT calculations. Hydrogen-atom abstraction from C-H bonds and oxygen atom transfer to sulfides by 2 have also been studied. Despite its thermal stability, 2 proves to be a very powerful oxidant that is capable of breaking the strong C-H bond of cyclohexane (BDE = 99.3 kcal·mol−1). PMID:21268165

Searching for new aluminium chelating agents: a family of hydroxypyrone ligands.

PubMed

Toso, Leonardo; Crisponi, Guido; Nurchi, Valeria M; Crespo-Alonso, Miriam; Lachowicz, Joanna I; Mansoori, Delara; Arca, Massimiliano; Santos, M Amélia; Marques, Sérgio M; Gano, Lurdes; Niclós-Gutíerrez, Juan; González-Pérez, Josefa M; Domínguez-Martín, Alicia; Choquesillo-Lazarte, Duane; Szewczuk, Zbigniew

2014-01-01

Attention is devoted to the role of chelating agents in the treatment of aluminium related diseases. In fact, in spite of the efforts that have drastically reduced the occurrence of aluminium dialysis diseases, they so far constitute a cause of great medical concern. The use of chelating agents for iron and aluminium in different clinical applications has found increasing attention in the last thirty years. With the aim of designing new chelators, we synthesized a series of kojic acid derivatives containing two kojic units joined by different linkers. A huge advantage of these molecules is that they are cheap and easy to produce. Previous works on complex formation equilibria of a first group of these ligands with iron and aluminium highlighted extremely good pMe values and gave evidence of the ability to scavenge iron from inside cells. On these bases a second set of bis-kojic ligands, whose linkers between the kojic chelating moieties are differentiated both in terms of type and size, has been designed, synthesized and characterized. The aluminium(III) complex formation equilibria studied by potentiometry, electrospray ionization mass spectroscopy (ESI-MS), quantum-mechanical calculations and (1)H NMR spectroscopy are here described and discussed, and the structural characterization of one of these new ligands is presented. The in vivo studies show that these new bis-kojic derivatives induce faster clearance from main organs as compared with the monomeric analog. © 2013.

Gallium(iii) and iron(iii) complexes of quinolone antimicrobials.

PubMed

Mjos, Katja Dralle; Cawthray, Jacqueline F; Polishchuk, Elena; Abrams, Michael J; Orvig, Chris

2016-08-16

Iron is an essential nutrient for many microbes. According to the "Trojan Horse Hypothesis", biological systems have difficulties distinguishing between Fe(3+) and Ga(3+), which constitutes the antimicrobial efficacy of the gallium(iii) ion. Nine novel tris(quinolono)gallium(iii) complexes and their corresponding iron(iii) analogs have been synthesized and fully characterized. Quinolone antimicrobial agents from three drug generations were used in this study: ciprofloxacin, enoxacin, fleroxacin, levofloxacin, lomefloxacin, nalidixic acid, norfloxacin, oxolinic acid, and pipemidic acid. The antimicrobial efficacy of the tris(quinolono)gallium(iii) complexes was studied against E. faecalis and S. aureus (both Gram-positive), as well as E. coli, K. pneumonia, and P. aeruginosa (all Gram-negative) in direct comparison to the tris(quinolono)iron(iii) complexes and the corresponding free quinolone ligands at various concentrations. For the tris(quinolono)gallium(iii) complexes, no combinational antimicrobial effects between Ga(3+) and the quinolone antimicrobial agents were observed.

Multifunctional iron oxide nanoparticles for biomedical applications

NASA Astrophysics Data System (ADS)

Bloemen, M.; Denis, C.; Van Stappen, T.; De Meester, L.; Geukens, N.; Gils, A.; Verbiest, T.

2015-03-01

Multifunctional nanoparticles have attracted a lot of attention since they can combine interesting properties like magnetism, fluorescence or plasmonic effects. As a core material, iron oxide nanoparticles have been the subject of intensive research. These cost-effective and non-toxic particles are used nowadays in many applications. We developed a heterobifunctional PEG ligand that can be used to introduce functional groups (carboxylic acids) onto the surface of the NP. Via click chemistry, a siloxane functionality was added to this ligand, for a subsequent covalent ligand exchange reaction. The functionalized nanoparticles have an excellent colloidal stability in complex environments like buffers and serum or plasma. Antibodies were coupled to the introduced carboxylic acids and these NP-antibody bioconjugates were brought into contact with Legionella bacteria for magnetic separation experiments.

A new hexanuclear iron-selenium nitrosyl cluster: primary exploration of the preparation methods, structure, and spectroscopic and electrochemical properties.

PubMed

Wang, Rongming; Xu, Wei; Zhang, Jian; Li, Lijuan

2010-06-07

A new hexanuclear iron-selenium nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)Se(6)(NO)(6)] (1), and a hexanuclear iron-sulfur nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)S(6)(NO)(6)] (2), were synthesized by the solvent-thermal reactions of [(n-Bu)(4)N][Fe(CO)(3)NO] with selenium or sulfur in methanol, while a tetranuclear iron-sulfur nitrosyl cluster, (Me(4)N)[Fe(4)S(3)(NO)(7)] (3), was also prepared by the solvent-thermal reaction of FeCl(2).4H(2)O with thiourea in the presence of (CH(3))(4)NCl, NaNO(2), and methanol. Complexes 1-3 were characterized by IR, UV-vis, (1)H NMR, electrochemistry, and single-crystal X-ray diffraction analysis. IR spectra of complexes 1 and 2 show the characteristic NO stretching frequencies at 1694 and 1698 cm(-1), respectively, while the absorptions of complex 3 appear at 1799, 1744, and 1710 cm(-1). The UV-vis spectra of complexes 1-3 show different bands in the range of 259-562 nm, which are assigned to the transitions between orbitals delocalized over the Fe-S cluster, the ligand-to-metal charge transfer, pi*(NO)-d(Fe), and the metal-to-ligand charge transfer, d(Fe)-pi*(NO). Single-crystal X-ray structural analysis reveals that complex 1 crystallizes in the monoclinic P2(1)/n space group with two molecules per unit cell. Two parallel "chair-shaped" structures, consisting of three iron and three selenium atoms, are connected by Fe-Se bonds with an average distance of 2.341 A; each iron center is bonded to three selenium atoms and a nitrogen atom from the nitrosyl ligand with a pseudotetrahedral center geometry. Cyclic voltammograms of complexes 1 and 2 display two cathodic and three anodic current peaks with an unusually strong cathodic peak. Further electrochemical investigations demonstrated that the intensity of the unusually strong peak is a result of at least three processes. One is the quasi-reversible reduction, and the other two are from an irreversible electrochemical process, in which the compound goes through a typical electron transfer and chemical reaction mechanism. Compound 3 shows three quasi-reversible reductions.

Probing Ligand Effects on the Redox Energies of [4Fe-4S] Clusters Using Broken-Symmetry Density Functional Theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niu, Shuqiang; Ichiye, Toshiko

A central issue in understanding redox properties of iron-sulfur proteins is determining the factors that tune the reduction potentials of the Fe-S clusters. Recently, Solomon and coworkers have shown that the Fe-S bond covalency of protein analogs measured by %L, the percent ligand character of the Fe 3d orbitals, from ligand K-edge X-ray absorption spectroscopy (XAS) correlates with the electrochemical redox potentials. Also, Wang and coworkers have measured electron detachment energies for iron-sulfur clusters without environmental perturbations by gas-phase photoelectron spectroscopy (PES). Here the correlations of the ligand character with redox energy and %L character are examined in [Fe₄S₄L₄]2⁻ clustersmore » with different ligands by broken symmetry density functional theory (BS-DFT) calculations using the B3LYP functional together with PES and XAS experimental results. These gas-phase studies assess ligand effects independently of environmental perturbations and thus provide essential information for computational studies of iron-sulfur proteins. The B3LYP oxidation energies agree well with PES data, and the %L character obtained from natural bond orbital analysis correlates with XAS values, although it systematically underestimates them because of basis set effects. The results show that stronger electron-donating terminal ligands increase %Lt, the percent ligand character from terminal ligands, but decrease %Sb, the percent ligand character from the bridging sulfurs. Because the oxidized orbital has significant Fe-Lt antibonding character, the oxidation energy correlates well with %Lt. However, because the reduced orbital has varying contributions of both Fe-Lt and Fe-Sb antibonding character, the reduction energy does not correlate with either %Lt or %Sb. Overall, BSDFT calculations together with XAS and PES experiments can unravel the complex underlying factors in the redox energy and chemical bonding of the [4Fe-4S] clusters in iron-sulfur proteins.« less

Iron and its complexation by phenolic cellular metabolites

PubMed Central

Chobot, Vladimir

2010-01-01

Iron is a transition metal that forms chelates and complexes with various organic compounds, also with phenolic plant secondary metabolites. The ligands of iron affect the redox potential of iron. Electrons may be transferred either to hydroxyl radicals, hydrogen peroxide or molecular oxygen. In the first case, oxidative stress is decreased, in the latter two cases, oxidative stress is increased. This milieu-dependent mode of action may explain the non-linear mode of action of juglone and other secondary metabolites. Attention to this phenomenon may help to explain idiosyncratic and often nonlinear effects that result in biological assays. Current chemical assays are discussed that help to explore these aspects of redox chemistry. PMID:20592800

Low-pressure hydrogenation of carbon dioxide catalyzed by an iron pincer complex exhibiting noble metal activity.

PubMed

Langer, Robert; Diskin-Posner, Yael; Leitus, Gregory; Shimon, Linda J W; Ben-David, Yehoshoa; Milstein, David

2011-10-10

A highly active iron catalyst for the hydrogenation of carbon dioxide and bicarbonates works under remarkably low pressures and achieves activities similar to some of the best noble metal catalysts. A mechanism is proposed involving the direct attack of an iron trans-dihydride on carbon dioxide, followed by ligand exchange and dihydrogen coordination. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spectroscopic and Computational Studies of Spin States of Iron(IV) Nitrido and Imido Complexes

DOE PAGES

Bucinsky, Lukas; Breza, Martin; Lee, Wei-Tsung; ...

2017-04-05

High-oxidation state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well as their fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect of the apical multiply bonded ligand on the spin state preferences of three-fold symmetric iron(IV) complexes with tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(Im R) 3}FeN], R = tBu (1), Mes (mesityl, 2) and the related triplet (S = 1) imido complexes, [{PhB(Im R) 3}Fe(NR')] +, R = Mes, R' = Ad (1- adamantyl, 3), tBu (4), have been investigated by electronicmore » absorption and Mössbauer effect spectroscopies. For comparison, two other Fe(IV) nitrido complexes, [(TIMEN Ar)FeN] +, (TIMEN Ar = tris[2-(3-aryl-imidazol-2-ylidene)ethyl]amine; Ar = Xyl (xylyl), Mes), have been investigated by 57Fe Mössbauer spectroscopy, including applied-field measurements. The paramagnetic imido complexes 3 and 4 were also studied by magnetic susceptibility measurements (for 3) and paramagnetic resonance spectroscopy: high-frequency and -field electron paramagnetic resonance (HFEPR) (for 3 and 4) and frequency-domain Fouriertransform (FD-FT) THz EPR (for 3), which reveal their zero-field splitting (zfs) parameters. Experimentally correlated theoretical studies comprising ligand-field theory (LFT) and quantum chemical theory (QCT), the latter including both density functional theory (DFT) and ab initio methods reveal the key role played by the Fe3 d z2 (a1) orbital in these systems: the nature of its interaction with the nitrido or imido ligand dictates the spin state preference of the complex. Lastly, the ability to tune the spin state through the energy and nature of a single orbital has general relevance to the factors controlling spin states in complexes with applicability as single molecule devices.« less

Kinetics of FeII-polyaminocarboxylate oxidation by molecular oxygen

NASA Astrophysics Data System (ADS)

Wilson, Jessica M.; Farley, Kevin J.; Carbonaro, Richard F.

2018-03-01

Complexation of iron by naturally-occurring and synthetic organic ligands has a large effect on iron oxidation and reduction rates which in turn affect the aqueous geochemistry of many other chemical constituents. In this study, the kinetics of FeII oxidation in the presence of the polyaminocarboxylate synthetic chelating agents ethylene glycol tetraacetic acid (EGTA) and trimethylenediamine-N,N,N‧,N‧-tetraacetic acid (TMDTA) was investigated over the pH range 5.50-8.53. Batch oxidation experiments in the presence of molecular oxygen were conducted using a 2:1 M concentration ratio of polyaminocarboxylate (ligand, L) to FeII. The experimental data resembled first order kinetics for the oxidation of FeII-L to FeIII-L and observed rate constants at pH 6.0 were comparable to rate constants for the oxidation of inorganic FeII. Similar to other structurally-similar FeII-polyaminocarboxylate complexes, oxidation rates of FeII-EGTA and FeII-TMDTA decrease with increasing pH, which is the opposite trend for the oxidation of FeII complexed with inorganic ligands. However, the oxidation rates of FeII complexed with EGTA and TMDTA were considerably lower (4-5 orders of magnitude) than FeII complexed to ethylenediaminetetraacetic acid (EDTA). The distinguishing feature of the slower-reacting complexes is that they have a longer backbone between diamine functional groups. An analytical equilibrium model was developed to determine the contributions of the species FeIIL2- and FeII(H)L- to the overall oxidation rate of FeII-L. Application of this model indicated that the protonated FeII(H)L species are more than three orders of magnitude more reactive than FeIIL2-. These rate constants were used in a coupled kinetic equilibrium numerical model where the ligand to iron ratio (TOTL:TOTFe) and pH were varied to evaluate the effect on the FeII oxidation rate. Overall, increasing TOTL:TOTFe for EGTA and TMDTA enhances FeII oxidation rates at lower pH and inhibits FeII oxidation rates at higher pH. Finally, this work demonstrates that the rate of FeII oxidation is very sensitive to the identity and structure of the polyaminocarboxylate chelating agent, which has implications for any metal or organic chemical that reacts either directly or indirectly with iron.

Bimetallic iron–iron and iron–zinc complexes of the redox-active ONO pincer ligand† †Electronic supplementary information (ESI) available: Complete experimental procedures and magnetic measurements and models. CCDC 1417565–1417567. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc03006d Click here for additional data file. Click here for additional data file.

PubMed Central

Wong, Janice L.; Higgins, Robert F.; Bhowmick, Indrani; Cao, David Xi; Szigethy, Géza; Ziller, Joseph W.

2016-01-01

A new bimetallic platform comprising a six-coordinate Fe(ONO)2 unit bound to an (ONO)M (M = Fe, Zn) has been discovered ((ONOcat)H3 = bis(3,5-di-tert-butyl-2-phenol)amine). Reaction of Fe(ONO)2 with either (ONOcat)Fe(py)3 or with (ONOq)FeCl2 under reducing conditions led to the formation of the bimetallic complex Fe2(ONO)3, which includes unique five- and six-coordinate iron centers. Similarly, the reaction of Fe(ONO)2 with the new synthon (ONOsq˙)Zn(py)2 led to the formation of the heterobimetallic complex FeZn(ONO)3, with a six-coordinate iron center and a five-coordinate zinc center. Both bimetallic complexes were characterized by single-crystal X-ray diffraction studies, solid-state magnetic measurements, and multiple spectroscopic techniques. The magnetic data for FeZn(ONO)3 are consistent with a ground state S = 3/2 spin system, generated from a high-spin iron(ii) center that is antiferromagnetically coupled to a single (ONOsq˙)2– radical ligand. In the case of Fe2(ONO)3, the magnetic data revealed a ground state S = 7/2 spin system arising from the interactions of one high-spin iron(ii) center, one high-spin iron(iii) center, and two (ONOsq˙)2– radical ligands. PMID:28808535

Dinitrosyl iron complexes with thiol-containing ligands as a "working form" of endogenous nitric oxide.

PubMed

Vanin, Anatoly F

2016-04-01

The material presented herein is an overview of the results obtained by our research team during the many years' study of biological activities and occurrence of dinitrosyl iron complexes (DNIC) with thiol-containing ligands in human and animal organisms. With regard to their dose dependence and vast diversity of biological activities, DNIC are similar to the system of endogenous NO, one of the most universal regulators of biological processes. The role of biologically active components in DNIC is played by their iron-dinitrosyl fragments, [Fe(NO)2], endowed with the ability to generate neutral NO molecules and nitrosonium ions (NO(+)). Their release is effected by heme-and thiol-containing proteins, which fulfill the function of biological targets and acceptors of NO and NO(+). Beneficial regulatory effects of DNIC on physiological and metabolic processes are numerous and diverse and include, among other things, lowering of arterial pressure and accelerated healing of skin wounds. In the course of fast decomposition of their Fe(NO)2 fragments (e.g., in the presence of iron chelators), DNIC produce adverse (cytotoxic) effects, which can best be exemplified by their ability to suppress the development of experimental endometriosis in animals. In animal tissues, DNIC with thiol-containing ligands are predominantly represented by the binuclear form, which, contrary to mononuclear DNIC detectable by the 2.03 signal, is EPR-silent. The ample body of evidence on biological activities and occurrence of DNIC gained so far clearly demonstrates that in human and animal organisms DNIC with thiol-containing ligands represent a "working form" of the system of endogenous NO responsible for its accumulation and stabilization in animal tissues as well as its further transfer to its biological targets. Copyright © 2016 Elsevier Inc. All rights reserved.

Drug Modulation of Water–Heme Interactions in Low-Spin P450 Complexes of CYP2C9d and CYP125A1

PubMed Central

Conner, Kip P.; Cruce, Alex A.; Krzyaniak, Matthew D.; Schimpf, Alina M.; Frank, Daniel J.; de Montellano, Paul Ortiz; Atkins, William M.; Bowman, Michael K.

2015-01-01

Azoles and pyridines are commonly incorporated into small molecule inhibitor scaffolds that target cytochromes P450 (CYPs) as a strategy to increase drug binding affinity, impart isoform-dependent selectivity, and improve metabolic stability. Optical absorbance spectra of the CYP–inhibitor complex are widely used to infer whether these inhibitors are ligated directly to the heme iron as catalytically inert, low-spin (type II) complexes. Here, we show that the low-spin complex between a drug-metabolizing CYP2C9 variant and 4-(3-phenyl-propyl)-1H-1,2,3-triazole (PPT) retains an axial water ligand despite exhibiting elements of “classic” type II optical behavior. Hydrogens of the axial water ligand are observed by pulsed electron paramagnetic resonance (EPR) spectroscopy for both inhibitor-free and inhibitor-bound species and show that inhibitor binding does not displace the axial water. A 15N label incorporated into PPT is 0.444 nm from the heme iron, showing that PPT is also in the active site. The reverse type I inhibitor, LP10, of CYP125A1 from Mycobacterium tuberculosis, known from X-ray crystal structures to form a low-spin water-bridged complex, is found by EPR and by visible and near-infrared magnetic circular dichroism spectroscopy to retain the axial water ligand in the complex in solution. PMID:25591012

Wavelength-Dependence on the Initiation of Iron-Based Photoactive Explosives

NASA Astrophysics Data System (ADS)

Brown, Kathryn; Myers, Thomas; Clarke, Steven

2017-06-01

Photoactive explosives show promise to be relatively insensitive to impact and friction compared to PETN and other detonator materials, but can be more easily initiated with laser light. Metal-ligand charge transfer (MLCT) complexes have been shown to have tunable explosive properties and absorption profiles, making them strong candidates for laser detonator material. Here, we discuss the synthesis and characterization of several iron-based MLCT complexes, as well as results from recent experiments on their sensitivity to initiation from different wavelengths of laser light.

Ellagic acid inhibits iron-mediated free radical formation

NASA Astrophysics Data System (ADS)

Dalvi, Luana T.; Moreira, Daniel C.; Andrade, Roberto; Ginani, Janini; Alonso, Antonio; Hermes-Lima, Marcelo

2017-02-01

Polyphenols are reported to have some health benefits, which are link to their antioxidant properties. In the case of ellagic acid (EA), there is evidence that it has free radical scavenger properties and that it is able to form complexes with metal ions. However, information on a possible link between the formation of iron-EA complexes and their interference in Haber-Weiss/Fenton reactions was not yet determined. Thus, the present study investigated the in vitro antioxidant mechanism of EA in a system containing ascorbate, Fe(III) and different iron ligands (EDTA, citrate and NTA). Iron-mediated oxidative degradation of 2-deoxyribose was poorly inhibited (by 12%) in the presence of EA (50 μM) and EDTA. When citrate or NTA - which form weak iron complexes - were used, the 2-deoxyribose protection increased to 89-97% and 45%, respectively. EA also presented equivalent inhibitory effects on iron-mediated oxygen uptake and ascorbyl radical formation. Spectral analyses of iron-EA complexes show that EA removes Fe(III) from EDTA within hours, and from citrate within 1 min. This difference in the rate of iron-EA complex formation may explain the antioxidant effects of EA. Furthermore, the EA antioxidant effectiveness was inversely proportional to the Fe(III) concentration, suggesting a competition with EDTA. In conclusion, the results indicate that EA may prevent in vitro free radical formation when it forms a complex with iron ions.

Trace Element Removal in Distributed Drinking Water Treatment Systems by Cathodic H2O2 Production and UV Photolysis

PubMed Central

2017-01-01

As water scarcity intensifies, point-of-use and point-of-entry treatment may provide a means of exploiting locally available water resources that are currently considered to be unsafe for human consumption. Among the different classes of drinking water contaminants, toxic trace elements (e.g., arsenic and lead) pose substantial operational challenges for distributed drinking water treatment systems. Removal of toxic trace elements via adsorption onto iron oxides is an inexpensive and robust treatment method; however, the presence of metal-complexing ligands associated with natural organic matter (NOM) often prevents the formation of iron precipitates at the relatively low concentrations of dissolved iron typically present in natural water sources, thereby requiring the addition of iron which complicates the treatment process and results in a need to dispose of relatively large amounts of accumulated solids. A point-of-use treatment device consisting of a cathodic cell that produced hydrogen peroxide (H2O2) followed by an ultraviolet (UV) irradiation chamber was used to decrease colloid stabilization and metal-complexing capacity of NOM present in groundwater. Exposure to UV light altered NOM, converting ∼6 μM of iron oxides into settable forms that removed between 0.5 and 1 μM of arsenic (As), lead (Pb), and copper (Cu) from solution via adsorption. After treatment, changes in NOM consistent with the loss of iron-complexing carboxylate ligands were observed, including decreases in UV absorbance and shifts in the molecular composition of NOM to higher H/C and lower O/C ratios. Chronoamperometric experiments conducted in synthetic groundwater revealed that the presence of Ca2+ and Mg2+ inhibited intramolecular charge-transfer within photoexcited NOM, leading to substantially increased removal of iron and trace elements. PMID:29240414

Trace Element Removal in Distributed Drinking Water Treatment Systems by Cathodic H2O2 Production and UV Photolysis.

PubMed

Barazesh, James M; Prasse, Carsten; Wenk, Jannis; Berg, Stephanie; Remucal, Christina K; Sedlak, David L

2018-01-02

As water scarcity intensifies, point-of-use and point-of-entry treatment may provide a means of exploiting locally available water resources that are currently considered to be unsafe for human consumption. Among the different classes of drinking water contaminants, toxic trace elements (e.g., arsenic and lead) pose substantial operational challenges for distributed drinking water treatment systems. Removal of toxic trace elements via adsorption onto iron oxides is an inexpensive and robust treatment method; however, the presence of metal-complexing ligands associated with natural organic matter (NOM) often prevents the formation of iron precipitates at the relatively low concentrations of dissolved iron typically present in natural water sources, thereby requiring the addition of iron which complicates the treatment process and results in a need to dispose of relatively large amounts of accumulated solids. A point-of-use treatment device consisting of a cathodic cell that produced hydrogen peroxide (H 2 O 2 ) followed by an ultraviolet (UV) irradiation chamber was used to decrease colloid stabilization and metal-complexing capacity of NOM present in groundwater. Exposure to UV light altered NOM, converting ∼6 μM of iron oxides into settable forms that removed between 0.5 and 1 μM of arsenic (As), lead (Pb), and copper (Cu) from solution via adsorption. After treatment, changes in NOM consistent with the loss of iron-complexing carboxylate ligands were observed, including decreases in UV absorbance and shifts in the molecular composition of NOM to higher H/C and lower O/C ratios. Chronoamperometric experiments conducted in synthetic groundwater revealed that the presence of Ca 2+ and Mg 2+ inhibited intramolecular charge-transfer within photoexcited NOM, leading to substantially increased removal of iron and trace elements.

Selenolate complexes of CYP101 and the heme-bound hHO-1/H25A proximal cavity mutant.

PubMed

Jiang, Yongying; Ortiz de Montellano, Paul R

2008-05-05

Thiolate and selenolate complexes of CYP101 (P450cam) and the H25A proximal cavity mutant of heme-bound human heme oxygenase-1 (hHO-1) have been examined by UV-vis spectroscopy. Both thiolate and selenolate ligands bound to the heme distal side in CYP101 and gave rise to characteristic hyperporphyrin spectra. Thiolate ligands also bound to the proximal side of the heme in the cavity created by the H25A mutation in hHO-1, giving a Soret absorption similar to that of the H25C hHO-1 mutant. Selenolate ligands also bound to this cavity mutant under anaerobic conditions but reduced the heme iron to the ferrous state, as shown by the formation of a ferrous CO complex. Under aerobic conditions, the selenolate ligand but not the thiolate ligand was rapidly oxidized. These results indicate that selenocysteine-coordinated heme proteins will not be stable species in the absence of a redox potential stabilizing effect.

Synthesis and antimalarial activity of metal complexes of cross-bridged tetraazamacrocyclic ligands.

PubMed

Hubin, Timothy J; Amoyaw, Prince N-A; Roewe, Kimberly D; Simpson, Natalie C; Maples, Randall D; Carder Freeman, TaRynn N; Cain, Amy N; Le, Justin G; Archibald, Stephen J; Khan, Shabana I; Tekwani, Babu L; Khan, M O Faruk

2014-07-01

Using transition metals such as manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), several new metal complexes of cross-bridged tetraazamacrocyclic chelators namely, cyclen- and cyclam-analogs with benzyl groups, were synthesized and screened for in vitro antimalarial activity against chloroquine-resistant (W2) and chloroquine-sensitive (D6) strains of Plasmodium falciparum. The metal-free chelators tested showed little or no antimalarial activity. All the metal complexes of the dibenzyl cross-bridged cyclam ligand exhibited potent antimalarial activity. The Mn(2+) complex of this ligand was the most potent with IC50s of 0.127 and 0.157μM against the chloroquine-sensitive (D6) and chloroquine-resistant (W2) P. falciparum strains, respectively. In general, the dibenzyl hydrophobic ligands showed better anti-malarial activity compared to the activity of monobenzyl ligands, potentially because of their higher lipophilicity and thus better cell penetration ability. The higher antimalarial activity displayed by the manganese complex for the cyclam ligand in comparison to that of the cyclen, correlates with the larger pocket of cyclam compared to that of cyclen which produces a more stable complex with the Mn(2+). Few of the Cu(2+) and Fe(2+) complexes also showed improvement in activity but Ni(2+), Co(2+) and Zn(2+) complexes did not show any improvement in activity upon the metal-free ligands for anti-malarial development. Published by Elsevier Ltd.

Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase.

PubMed

Chen, Xiangyang; Jing, Yuanyuan; Yang, Xinzheng

2016-06-20

Inspired by the active-site structure of the [NiFe] hydrogenase, we have computationally designed the iron complex [P(tBu) 2 N(tBu) 2 )Fe(CN)2 CO] by using an experimentally ready-made diphosphine ligand with pendant amines for the hydrogenation of CO2 to methanol. Density functional theory calculations indicate that the rate-determining step in the whole catalytic reaction is the direct hydride transfer from the Fe center to the carbon atom in the formic acid with a total free energy barrier of 28.4 kcal mol(-1) in aqueous solution. Such a barrier indicates that the designed iron complex is a promising low-cost catalyst for the formation of methanol from CO2 and H2 under mild conditions. The key role of the diphosphine ligand with pendent amine groups in the reaction is the assistance of the cleavage of H2 by forming a Fe-H(δ-) ⋅⋅⋅H(δ+) -N dihydrogen bond in a fashion of frustrated Lewis pairs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron silylamide-grafted periodic mesoporous silica.

PubMed

Deschner, Thomas; Törnroos, Karl W; Anwander, Reiner

2011-08-01

The surface chemistry of a series of well-defined metalorganic ferrous and ferric iron complexes on periodic mesoporous silica (PMS) was investigated. In addition to literature known Fe(II)[N(SiMe(3))(2)](2)(THF), Fe(II)[N(SiPh(2)Me(2))(2)](2), and Fe(III)[N(SiMe(3))(2)](2)Cl(THF), the new complexes [Fe(II){N(SiHMe(2))(2)}(2)](2) and Fe(III)[N(SiHMe(2))(2)](3)(μ-Cl)Li(THF)(3) were employed as grafting precursors. Selection criteria for the molecular precursors were the molecular size (monoiron versus diiron species), the oxidation state of the iron center (II versus III), and the functionality of the silylamido ligand (e.g., built-in spectroscopic probes). Hexagonal channel-like MCM-41 and cubic cage-like SBA-1 were chosen as two distinct PMS materials. The highest iron load (12.8 wt %) was obtained for hybrid material [Fe(II){N(SiHMe(2))(2)}(2)](2)@MCM-41 upon stirring the reaction mixture iron silylamide/PMS/n-hexane for 18 h at ambient temperature. Size-selective grafting and concomitantly extensive surface silylation were found to be prominent for cage-like SBA-1. Here, the surface metalation is governed by the type of iron precursor, the pore size, the reaction time, and the solvent. The formation of surface-attached iron-ligand species is discussed on the basis of diffuse reflectance infrared Fourier transform (DRIFT) and electron paramagnetic resonance (EPR) spectroscopy, nitrogen physisorption, and elemental analysis. © 2011 American Chemical Society

Dinitrosyl iron complexes with thiolate ligands: physico-chemistry, biochemistry and physiology.

PubMed

Vanin, Anatoly F

2009-08-01

Some present-day concepts on the origin and functional activities of dinitrosyl iron complexes (DNIC) with thiolate ligands are considered. Nitric oxide (NO) including to DNIC increases its stability and ensures effective targeting of NO to organs and tissues. DNIC have a square-planar structure; unpaired electron is localized on the d(z2) orbital of the d(7) iron atom. The formula of DNIC appears as [(RS(-))(2)Fe(+)(NO(+))(2)....((-)SR)(2)](-); electron spin is S=1/2. Conversion of an originally diamagnetic group, Fe(2+)(NO)(2) with electron configuration d(8), into a paramagnetic Fe(+)(NO(+))(2) group is a result of disproportionation of NO ligands and substitution of newly generated NO(-) for NO. The nitrosonium ions present in DNIC impart to them high nitrosylating activity, e.g., ability to induce S-nitrosylation of thiols. The ability of S-nitrosothiols to form DNIC in a direct reaction with bivalent iron is a prerequisite to effective mutual conversions of DNIC and S-nitrosothiols. In this work, I consider some mechanisms of destructive effects of low-molecular DNIC on active centers of iron-sulfur proteins, ability of DNIC to express certain genes, to activate guanylate cyclase, to exert hypotensive, vasodilator effects, to inhibit platelet aggregation, to accelerate wound healing and to produce potent erective action. Recently a stabilized powder-like polymeric composition based on dimeric glutathione DNIC the water-soluble polymer in which was used as a filling agent was designed. The advantages of this stable DNIC-glutathione preparation include their ability to retain their physico-chemical and functional activities within at least one year. At present, the preparation undergo testing as a base for the design of a wide variety of broad-spectrum drugs.

Synthesis, magnetic, spectral, and antimicrobial studies of Cu(II), Ni(II) Co(II), Fe(III), and UO 2(II) complexes of a new Schiff base hydrazone derived from 7-chloro-4-hydrazinoquinoline

NASA Astrophysics Data System (ADS)

El-Behery, Mostafa; El-Twigry, Haifaa

2007-01-01

A new hydrazone ligand, HL, was prepared by the reaction of 7-chloro-4-hydrazinoquinoline with o-hydroxybenzaldehyde. The ligand behaves as monoprotic bidentate. This was accounted for as the ligand contains a phenolic group and its hydrogen atom is reluctant to be replaced by a metal ion. The ligand reacted with Cu(II), Ni(II), Co(II), Fe(III), and UO 2(II) ions to yield mononuclear complexes. In the case of Fe(III) ion two complexes, mono- and binuclear complexes, were obtained in the absence and presence of LiOH, respectively. Also, mixed ligand complexes were obtained from the reaction of the metal cations Cu(II), Ni(II) and Fe(III) with the ligand (HL) and 8-hydroxyquinoline (8-OHqu) in the presence of LiOH, in the molar ratio 1:1:1:1. It is clear that 8-OHqu behaves as monoprotic bidentate ligand in such mixed ligand complexes. The ligand, HL, and its metal complexes were characterized by elemental analyses, IR, UV-vis, mass, and 1H NMR spectra, as well as magnetic moment, conductance measurements, and thermal analyses. All complexes have octahedral configurations except Cu(II) complex which has an extra square-planar geometry, while Ni(II) mixed complex has also formed a tetrahedral configuration and UO 2(II) complex which formed a favorable pentagonal biprymidial geometry. Magnetic moment of the binuclear Fe(III) complex is quite low compared to calculated value for two iron ions complex and thus shows antiferromagnetic interactions between the two adjacent ferric ions. The HL and metal complexes were tested against one stain Gram positive bacteria ( Staphylococcus aureus), Gram negative bacteria ( Escherichia coli), and fungi ( Candida albicans). The tested compounds exhibited higher antibacterial acivities.

Iron Speciation in the Subtropical Waters East of New Zealand using Multi Detection Window CLE-AdCSV Titrations.

NASA Astrophysics Data System (ADS)

Chandrasekhar, Anoop; Sander, Sylvia; Milnes, Angie; Boyd, Philip

2015-04-01

Iron plays a significant role in the ocean productivity as a micro nutrient that facilitates the growth of marine phytoplankton and microbes. The bioavailability of iron in the ocean depends on it speciation. Iron is bio available in its dissolved form and about 99.9% of dissolved iron in seawater is organically complexed with natural ligands. The competitive ligand equilibration - adsorptive cathodic stripping voltammetry (CLE-AdCSV) is the widely used technique to examine Fe speciation. The method has its own limitations. The analytical window employed in this technique has a distinct impact on Fe speciation results (Buck, Moffett et al. 2012). Recently, (Pizeta, Sander et al. in preparation) have shown that the accuracy of complexometric titrations improve if multiple analytical windows (MAW) are solved as a united dataset. Several programs are now available that enable this approach with the KMS (Kineteql.xls , Hudson 2014), which is based on an Excel application based on speciation calculation (Hudson, Rue et al. 2003, Sander, Hunter et al. 2011), being one of them. In the present work, the unified MAW data analysis method is applied to determine iron speciation by CLE-AdCSV with salicyl aldoxime (SA) (Abualhaija and van den Berg 2014) in real seawater samples from the Spring bloom FeCycle III voyage, which took place in an anticyclonic eddy in subtropical waters east of New Zealand in spring 2012. Two different analytical windows (5 and 15µM SA) were applied to samples from depth profiles taken during this cruise. The data obtained was analysed using the program KMS (Kineteql.xls). Most samples only returned one Fe-binding ligands class. Higher ligand concentrations were observed in the upper water column and the stability constants were above 22 (e.g. 22.25 ± 0.21 for station 63). Our results will be discussed in the context of microbial community distribution as well as other biogeochemical parameters. Abualhaija, M. M. and C. M. G. van den Berg (2014). "Chemical speciation of iron in seawater using catalytic cathodic stripping voltammetry with ligand competition against salicylaldoxime." Marine Chemistry 164(0): 60-74. Buck, K. N., J. Moffett, K. A. Barbeau, R. M. Bundy, Y. Kondo and J. Wu (2012). "The organic complexation of iron and copper: an intercomparison of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques " Limnology and Oceanography: Methods 10: 496-515. Hudson, R. J. M., E. L. Rue and K. W. Bruland (2003). "Modeling Complexometric Titrations of Natural Water Samples." Environ. Sci. Tech. 37: 1553-1562. Pizeta, I., S. G. Sander, O. Baars, K. Buck, R. Bundy, G. Carrasco, P. Croot, C. Garnier, L. Gerringa, M. Gledhill, K. Hirose, D. R. Hudson, Y. Kondo-Jacquot, L. Laglera, D. Omanovic, M. Rijkenberg, B. Twining and M. Wells (in preparation). "Intercomparison of estimating metal binding ligand parameters from simulated titration data using different fitting approaches." for Limnology and Oceanography: Methods. Sander, S. G., K. A. Hunter, H. Harms and M. Wells (2011). "Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability." Environmental Science and Technology 45(15): 6388-6395.

Discrimination of fluorescence light-up effects induced by pH and metal ion chelation on a spirocyclic derivative of rhodamine B.

PubMed

Leite, Andreia; Silva, Ana M G; Cunha-Silva, Luís; de Castro, Baltazar; Gameiro, Paula; Rangel, Maria

2013-05-07

In the present work we describe the structure and the spectroscopic characterization of a spirocyclic derivative of a rhodamine B ligand whose properties allow discrimination of light-up effects induced by metal ion chelation and variation of pH. Distinction of the two effects is important for the use of this type of ligand to detect and monitor metal ions in aqueous solutions. The synthesis of the ligand was performed in two steps, which involve the reaction of rhodamine B with hydrazine hydrate to form rhodamine B hydrazide followed by condensation with 2-pyridinecarboxaldehyde and was successfully optimized using a solvent free approach under microwave irradiation. The ligand was obtained in the expected spirolactam form and was characterized in the solid state by EA, MS and single-crystal X-ray diffraction. The ligand was characterized in solution by NMR and absorption and fluorescence spectroscopies and its properties were found to be sensitive to pH and concentration of iron(III). The study of the fluorescence properties at variable pH shows that the compound is fluorescent in the range 2 < pH < 4 with maximum intensity at pH 3 and allowed the determination of two pK(a) values (pK(a1) = 2.98, pK(a2) = 2.89) and establishment of the corresponding distribution diagram. The very low pK(a) values guarantee that above pH equal to 4 the ligand is mostly present in the fully non-protonated and non-fluorescent form L. The study of the interaction of the ligand with iron(iii) was performed in DMSO and DMSO-H(2)O to exclude the influence of pH and due to the low solubility of the compound. The results indicate that the presence of iron(III) triggers the opening of the spirolactam form of the ligand and the maximum intensity obtained at a metal : ligand ratio of 1 : 2 is consistent with the formation of an iron(III) complex with the tridentate ligand.

Synthesis, characterization and investigation of electrochemical and spectroelectrochemical properties of non-peripherally tetra-5-methyl-1,3,4-thiadiazole substituted copper(II) iron(II) and oxo-titanium (IV) phthalocyanines

NASA Astrophysics Data System (ADS)

Demirbaş, Ümit; Akyüz, Duygu; Akçay, Hakkı Türker; Barut, Burak; Koca, Atıf; Kantekin, Halit

2017-09-01

In this study novel substituted phthalonitrile (3) and non-peripherally tetra 5-Methyl-1,3,4-thiadiazole substituted copper(II) (4), iron(II) (5) and oxo-titanium (IV) (6) phthalocyanines were synthesized. These novel compounds were fully characterized by FT-IR, 1H NMR, UV-vis and MALDI-TOF mass spectroscopic techniques. Voltammetric and in situ spectroelectrochemical measurements were performed for metallo-phthalocyanines (4-6). TiIVOPc and FeIIPc showed metal-based and ligand-based electron transfer reactions while CuIIPc shows only ligand-based electron transfer reaction. Voltammetric measurements indicated that the complexes have reversible, diffusion controlled and one-electron redox reactions. The assignments of the redox processes and color of the electrogenerated species of the complexes were determined with in-situ spectroelectrochemical and electrocolorimetric measurements. These measurements showed that the complexes can be used as the electrochromic materials for various display technologies.

Surface Modification and Nanojunction Fabrication with Molecular Metal Wires

DTIC Science & Technology

2014-02-17

Title: Transition Metal Complexes of a Super Rigid Anthyridine Ligand: Structural, Magnetic and DFT Studies. Transition metal complexes of iron ( II ...Compounds with Masked Diazonium Capping Groups (J. Organomet. Chem. 2013, 745, 93). (3) New Diruthenium( II ,III) Compounds Bearing Terminal Olefin Groups...2012, 36, 2340). (2) Synthesis , Structure, Magnetism, and Single Molecular Conductance of Linear Trinickel String Complexes with Sulfur-Containing

Photoreduction of Terrigenous Fe-Humic Substances Leads to Bioavailable Iron in Oceans.

PubMed

Blazevic, Amir; Orlowska, Ewelina; Kandioller, Wolfgang; Jirsa, Franz; Keppler, Bernhard K; Tafili-Kryeziu, Myrvete; Linert, Wolfgang; Krachler, Rudolf F; Krachler, Regina; Rompel, Annette

2016-05-23

Humic substances (HS) are important iron chelators responsible for the transport of iron from freshwater systems to the open sea, where iron is essential for marine organisms. Evidence suggests that iron complexed to HS comprises the bulk of the iron ligand pool in near-coastal waters and shelf seas. River-derived HS have been investigated to study their transport to, and dwell in oceanic waters. A library of iron model compounds and river-derived Fe-HS samples were probed in a combined X-ray absorption spectroscopy (XAS) and valence-to-core X-ray emission spectroscopy (VtC-XES) study at the Fe K-edge. The analyses performed revealed that iron complexation in HS samples is only dependent on oxygen-containing HS functional groups, such as carboxyl and phenol. The photoreduction mechanism of Fe III -HS in oceanic conditions into bioavailable aquatic Fe II forms, highlights the importance of river-derived HS as an iron source for marine organisms. Consequently, such mechanisms are a vital component of the upper-ocean iron biogeochemistry cycle.

1,2,3-Triazole-Heme Interactions in Cytochrome P450: Functionally Competent Triazole-Water- Heme Complexes

PubMed Central

Conner, Kip P.; Vennam, Preethi; Woods, Caleb M.; Krzyaniak, Matthew D.; Bowman, Michael K.; Atkins, William M.

2012-01-01

In comparison to imidazole (IMZ) and 1,2,4-triazole (1,2,4-TRZ) the isosteric 1,2,3-triazole (1,2,3-TRZ) is unrepresented among CYP inhibitors. This is surprising because 1,2,3-TRZs are easily obtained via ‘click’ chemistry. To understand this underrepresentation of 1,2,3-TRZs among CYP inhibitors, thermodynamic and DFT computational studies were performed with unsusbstituted IMZ, 1,2,4-TRZ, and 1,2,3-TRZ. The results indicate that the lower affinity of 1,2,3-TRZ for the heme iron includes a large unfavorable entropy term likely originating in solvent – 1,2,3-TRZ interactions; the difference is not solely due to differences in the enthalpy of heme – ligand interactions. In addition, the 1,2,3-TRZ fragment was incorporated into a well-established CYP3A4 substrate and mechanism based inactivator, 17-α-ethynylestradiol (17EE), via click chemistry. This derivative, 17-click, yielded optical spectra consistent with low spin ferric heme iron (type II) in contrast to 17EE, which yields a high spin complex (type I). Furthermore, the rate of CYP3A4-mediated metabolism of 17-click was comparable to 17EE, and with different regioselectivity. Surprisingly, CW EPR and HYSCORE EPR spectroscopy indicate that the 17-click does not displace water from the 6th axial ligand position of CYP3A4 as expected for a type II ligand. We propose a binding model where 17-click pendant 1,2,3-TRZ hydrogen bonds with the 6th axial water ligand. The results demonstrate the potential for 1,2,3-TRZ to form metabolically labile water-bridged low spin heme complexes, consistent with recent evidence that nitrogenous type II ligands of CYPs can be efficiently metabolized. The specific case of [CYP3A4•17-click] highlights the risk of interpreting CYP-ligand complex structure on the basis of optical spectra. PMID:22809252

Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

NASA Astrophysics Data System (ADS)

Domagal-Goldman, S.; Kubicki, J. D.

2006-05-01

Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the future analysis of Fe isotope fractionation. Future directions in the theoretical study of metal isotope fractionations will also be discussed, including the modeling of reactions on mineral surfaces.

Reactivity pathways for nitric oxide and nitrosonium with iron complexes in biologically relevant sulfur coordination spheres.

PubMed

Harrop, Todd C; Song, Datong; Lippard, Stephen J

2007-11-01

The interaction of nitric oxide (NO) with iron-sulfur cluster proteins results in the formation of dinitrosyl iron complexes (DNICs) coordinated by cysteine residues from the peptide backbone or with low molecular weight sulfur-containing molecules like glutathione. Such DNICs are among the modes available in biology to store, transport, and deliver NO to its relevant targets. In order to elucidate the fundamental chemistry underlying the formation of DNICs and to characterize possible intermediates in the process, we have investigated the interaction of NO (g) and NO(+) with iron-sulfur complexes having the formula [Fe(SR)(4)](2-), where R=(t)Bu, Ph, or benzyl, chosen to mimic sulfur-rich iron sites in biology. The reaction of NO (g) with [Fe(S(t)Bu)(4)](2-) or [Fe(SBz)(4)](2-) cleanly affords the mononitrosyl complexes (MNICs), [Fe(S(t)Bu)(3)(NO)](-) (1) and [Fe(SBz)(3)(NO)](-) (3), respectively, by ligand displacement. Mononitrosyl species of this kind were previously unknown. These complexes further react with NO (g) to generate the corresponding DNICs, [Fe(SPh)(2)(NO)(2)](-) (4) and [Fe(SBz)(2)(NO)(2)](-) (5), with concomitant reductive elimination of the coordinated thiolate donors. Reaction of [Fe(SR)(4)](2-) complexes with NO(+) proceeds by a different pathway to yield the corresponding dinitrosyl S-bridged Roussin red ester complexes, [Fe(2)(mu-S(t)Bu)(2)(NO)(4)] (2), [Fe(2)(mu-SPh)(2)(NO)(4)] (7) and [Fe(2)(mu-SBz)(2)(NO)(4)] (8). The NO/NO(+) reactivity of an Fe(II) complex with a mixed nitrogen/sulfur coordination sphere was also investigated. The DNIC and red ester species, [Fe(S-o-NH(2)C(6)H(4))(2)(NO)(2)](-) (6) and [Fe(2)(mu-S-o-NH(2)C(6)H(4))(2)(NO)(4)] (9), were generated. The structures of 8 and 9 were verified by X-ray crystallography. The MNIC complex 1 can efficiently deliver NO to iron-porphyrin complexes like [Fe(TPP)Cl], a reaction that is aided by light. Removal of the coordinated NO ligand of 1 by photolysis and addition of elemental sulfur generates higher nuclearity Fe/S clusters.

The preparation and use of metal salen complexes derived from cyclobutane diamine

NASA Astrophysics Data System (ADS)

Patil, Smita

The helix is an important chiral motif in nature, there is increasing development in field of helical transition metal complexes and related supramolecular structures. Hence, the goals of this work are to apply the principles of helicity in order to produce metal complexes with predictable molecular shapes and to study their properties as asymmetric catalysts. Computational studies suggest that the (1R,2 R)-cyclobutyldiamine unit can produce highly twisted salen complexes with a large energy barrier between the M and P helical forms. To test this prediction, the tartrate salt of (1R,2R)-cyclobutyldiamine was synthesized and condensed with a series of saliclaldehydes to produce novel salen ligands. The salicylaldehydes chosen have extended phenanthryl or benz[a]anthryl sidearms to encourage formation of helical coordination complexes. These ligands were metallated with zinc, iron and manganese salts to produce salen metal complexes which were characterized by NMR analysis, high-resolution mass spectrometry, and IR spectroscopy. A second ligand type, neutral bis(pyridine-imine) has also been synthesized from (1R,2R)-cyclobutyldiamine and quinolylaldehydes. The synthesis of bis(pyridine-imine) ligands was conducted using greener method, solvent assisted grinding. These ligands, in-situ with nickel metal salts, showed good catalytic activity for asymmetric Diels-Alder reactions. The third ligand type studied was chiral acid-functionalized Schiff-base ligands. These were synthesized by the condensation of 3-formyl-5-methyl salicylic acid and (1R,2R)-cyclobutyldiamine. With this type of ligand, there is possibility of producing both mono and dinuclear metal complexes. In our studies, we were only able to synthesize mononuclear complexs. These were tested as catalysts for asymmetric direct Mannich-type reaction, but were found to be ineffective.

Synthetic Models for Nickel-Iron Hydrogenase Featuring Redox-Active Ligands.

PubMed

Schilter, David; Gray, Danielle L; Fuller, Amy L; Rauchfuss, Thomas B

2017-05-01

The nickel-iron hydrogenase enzymes efficiently and reversibly interconvert protons, electrons, and dihydrogen. These redox proteins feature iron-sulfur clusters that relay electrons to and from their active sites. Reported here are synthetic models for nickel-iron hydrogenase featuring redox-active auxiliaries that mimic the iron-sulfur cofactors. The complexes prepared are Ni II (μ-H)Fe II Fe II species of formula [(diphosphine)Ni(dithiolate)(μ-H)Fe(CO) 2 (ferrocenylphosphine)] + or Ni II Fe I Fe II complexes [(diphosphine)Ni(dithiolate)Fe(CO) 2 (ferrocenylphosphine)] + (diphosphine = Ph 2 P(CH 2 ) 2 PPh 2 or Cy 2 P(CH 2 ) 2 PCy 2 ; dithiolate = - S(CH 2 ) 3 S - ; ferrocenylphosphine = diphenylphosphinoferrocene, diphenylphosphinomethyl(nonamethylferrocene) or 1,1'-bis(diphenylphosphino)ferrocene). The hydride species is a catalyst for hydrogen evolution, while the latter hydride-free complexes can exist in four redox states - a feature made possible by the incorporation of the ferrocenyl groups. Mixed-valent complexes of 1,1'-bis(diphenylphosphino)ferrocene have one of the phosphine groups unbound, with these species representing advanced structural models with both a redox-active moiety (the ferrocene group) and a potential proton relay (the free phosphine) proximal to a nickel-iron dithiolate.

Distinct Iron-binding Ligands in the Upper Water Column at Station ALOHA

NASA Astrophysics Data System (ADS)

Bundy, R.; Boiteau, R.; Repeta, D.

2016-02-01

The distribution and chemical properties of iron-binding organic ligands at station ALOHA were examined using a combination of solid phase extraction (SPE) followed by high pressure liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICPMS). HPLC-ICPMS ligand measurements were complemented by competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-ACSV) analysis using salicylaldoxime as the added ligand. By HPLC-ICPMS, we find enhanced concentrations of distinct naturally-occurring polar iron-binding ligands present at the surface and in the chlorophyll maximum. Lower concentrations were found in the subsurface, where a suite of non-polar ligands was detected. Siderophores were present at the deepest depths sampled at station ALOHA, down to 400m. Incubation studies provided evidence for the production of iron-binding ligands associated with nutrient amended phytoplankton growth in surface waters, and as a result of microbial particle remineralization in the subsurface water column. Ligands classes identified via SPE were then compared to CLE-ACSV ligand measurements, as well as the conditional stability constants measured from model polar and non-polar siderophores, yielding insight to the sources of iron-binding ligands throughout the water column at station ALOHA.

Metal based pharmacologically active agents: Synthesis, structural characterization, molecular modeling, CT-DNA binding studies and in vitro antimicrobial screening of iron(II) bromosalicylidene amino acid chelates

NASA Astrophysics Data System (ADS)

Abdel-Rahman, Laila H.; El-Khatib, Rafat M.; Nassr, Lobna A. E.; Abu-Dief, Ahmed M.; Ismael, Mohamed; Seleem, Amin Abdou

2014-01-01

In recent years, great interest has been focused on Fe(II) Schiff base amino acid complexes as cytotoxic and antitumor drugs. Thus a series of new iron(II) complexes based on Schiff bases amino acids ligands have been designed and synthesized from condensation of 5-bromosalicylaldehyde (bs) and α-amino acids (L-alanine (ala), L-phenylalanine (phala), L-aspartic acid (aspa), L-histidine (his) and L-arginine (arg)). The structure of the investigated iron(II) complexes was elucidated using elemental analyses, infrared, ultraviolet-visible, thermogravimetric analysis, as well as conductivity and magnetic susceptibility measurements. Moreover, the stoichiometry and the stability constants of the prepared complexes have been determined spectrophotometrically. The results suggest that 5-bromosalicylaldehyde amino acid Schiff bases (bs:aa) behave as dibasic tridentate ONO ligands and coordinate to Fe(II) in octahedral geometry according to the general formula [Fe(bs:aa)2]ṡnH2O. The conductivity values between 37 and 64 ohm-1 mol-1 cm2 in ethanol imply the presence of nonelectrolyte species. The structure of the complexes was validated using quantum mechanics calculations based on accurate DFT methods. Geometry optimization of the Fe-Schiff base amino acid complexes showed that all complexes had octahedral coordination. In addition, the interaction of these complexes with (CT-DNA) was investigated at pH = 7.2, by using UV-vis absorption, viscosity and agarose gel electrophoresis measurements. Results indicated that the investigated complexes strongly bind to calf thymus DNA via intercalative mode and showed a different DNA binding according to the sequence: bsari > bshi > bsali > bsasi > bsphali. Moreover, the prepared compounds are screened for their in vitro antibacterial and antifungal activity against three types of bacteria, Escherichia coli, Pseudomonas aeruginosa and Bacillus cereus and three types of anti fungal cultures, Penicillium purpurogenium, Aspergillus flavus and Trichotheium rosium. The results of these studies indicated that the metal complexes exhibit a stronger antibacterial and antifungal efficiency than their corresponding Schiff base amino acid ligands.

Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-Producing Catalysts.

PubMed

Weber, Katharina; Weyhermüller, Thomas; Bill, Eckhard; Erdem, Özlen F; Lubitz, Wolfgang

2015-07-20

Diamagnetic iron chloro compounds [(P(Ph)2N(Ph)2)FeCp*Cl] [1Cl] and [(P(Cy)2N(Ph)2)FeCp*Cl] [2Cl] and the corresponding hydrido complexes [(P(Ph)2N(Ph)2)FeCp*H] [1H] and [(P(Cy)2N(Ph)2)FeCp*H] [2H] have been synthesized and characterized by NMR spectroscopy, electrochemical studies, electronic absorption, and (57)Fe Mössbauer spectroscopy (P(Ph)2N(Ph)2 = 1,3,5,7-tetraphenyl-1,5-diphospha-3,7-diazacyclooctane, P(Cy)2N(Ph)2 = 1,5-dicyclohexyl-3,7-diphenyl-1,5-diphospha-3,7-diazacyclooctane, Cp* = pentamethylcyclopentadienyl). Molecular structures of [2Cl], [1H], and [2H], derived from single-crystal X-ray diffraction, revealed that these compounds have a typical piano-stool geometry. The results show that the electronic properties of the hydrido complexes are strongly influenced by the substituents at the phosphorus donor atoms of the P(R)2N(Ph)2 ligand, whereas those of the chloro complexes are less affected. These results illustrate that the hydride is a strong-field ligand, as compared to chloride, and thus leads to a significant degree of covalent character of the iron hydride bonds. This is important in the context of possible catalytic intermediates of iron hydrido species, as proposed for the catalytic cycle of [FeFe] hydrogenases and other synthetic catalysts. Both hydrido compounds [1H] and [2H] show enhanced catalytic currents in cyclic voltammetry upon addition of the strong acid trifluoromethanesulfonimide [NHTf2] (pKa(MeCN) = 1.0). In contrast to the related complex [(P(tBu)N(Bn))2FeCp(C6F5)H], which was reported by Liu et al. (Nat. Chem. 2013, 5, 228-233) to be an electrocatalyst for hydrogen splitting, the here presented hydride complexes [1H] and [2H] show the tendency for electrocatalytic hydrogen production. Hence, the catalytic direction of this class of monoiron compounds can be reversed by specific ligand modifications.

A diketiminate-bound diiron complex with a bridging carbonate ligand

PubMed Central

Sadique, Azwana R.; Brennessel, William W.; Holland, Patrick L.

2009-01-01

Reduction of carbon dioxide by a diiron(I) complex gives μ-carbonato-κ3 O:O′,O′′-bis­{[2,2,6,6-tetra­methyl-3,5-bis­(2,4,6-triisopropyl­phenyl)heptane-2,5-diiminate(1−)-κ2 N,N′]iron(II)} toluene disolvate, [Fe2(C41H65N)2(CO3)]·2C7H8, a diiron(II) species with a bridging carbonate ligand. The asymmetric unit contains one diiron complex and two cocrystallized toluene solvent mol­ecules that are distributed over three sites, one with atoms in general positions and two in crystallographic sites. Both FeII atoms are η2-coordinated to diketiminate ligands, but η1- and η2-coordinated to the bridging carbonate ligand. Thus, one FeII center is three-coordinate and the other is four-coordinate. The bridging carbonate ligand is nearly perpendicular to the iron–diketiminate plane of the four-coordinate FeII center and parallel to the plane of the three-coordinate FeII center. PMID:19407402

Synthesis, structure, biochemical, and docking studies of a new dinitrosyl iron complex [Fe2(μ-SC4H3SCH2)2(NO)4

NASA Astrophysics Data System (ADS)

Davidovich, P. B.; Fischer, A. I.; Korchagin, D. V.; Panchuk, V. V.; Shchukarev, A. V.; Garabadzhiu, A. V.; Belyaev, A. N.

2015-07-01

A new dinitrosyl iron complex of binuclear structure [Fe2(μ-S-2-methylthiophene)2(NO)4] was first synthesized and structurally characterized by XRD and theoretical methods. Using caspase-3 as an example it was shown that [Fe2(μ-S-2-methylthiophene)2(NO)4] and its analog [Fe2(μ-S-2-methylfurane)2(NO)4] can inhibit the action of active site cysteine proteins; the difference in inhibitory activity was explained by molecular docking studies. Biochemical and in silico studies give grounds that the biological activity of dinitrosyl iron complexes is a μ-SR bridging ligand structure function. Thus the rational design strategy of [Fe2(μ-SR)2(NO)4] complexes can be applied to make NO prodrugs with high affinity to therapeutically significant targets involved in cancer and inflammation.

Thermodynamic studies of iron chelation with doxycycline in acidic medium

NASA Astrophysics Data System (ADS)

Javed, Javeria; Zahir, Erum

2017-06-01

Doxycycline (DOX) is a broad-spectrum tetracycline antibiotic synthetically derived from oxytetracycline. The complex formation of this drug with iron(III) was studied using spectrophotometry. The thermodynamic parameters of the systems were calculated using the changes in the absorption spectra which occur due to hydrogen bond or complex formation. Thermodynamic parameters of the formation of iron(III) complex with doxycycline (Δ H, Δ G, Δ S, and stability constants) were determined spectrophotometrically at a wavelength corresponding to absorption maximum (374.5 nm) at three different temperatures (22, 35, and 45°C). The obtained data show that the complex has metal to ligand molar ratio of 1: 2 at pH 2-3. The stability constants were calculated to be 13.99 × 106, 7.06 × 105, and 1.29 × 106 by mole ratio method at 22, 35, and 45°C, respectively.

Selenolate Complexes of CYP101 and the Heme-bound hHO-1/H25A Proximal Cavity Mutant

PubMed Central

Jiang, Yongying; Ortiz de Montellano, Paul R.

2009-01-01

Thiolate and selenolate complexes of CYP101 (P450cam) and the H25A proximal cavity mutant of heme-bound human heme oxygenase-1 (hHO-1) have been examined by UV-visible spectroscopy. Both thiolate and selenolate ligands bound to the heme distal side in CYP101 and gave rise to characteristic hyperporphyrin spectra. Thiolate ligands also bound to the proximal side of the heme in the cavity created by the H25A mutation in hHO-1, giving a Soret absorption similar to that of the H25C hHO-1 mutant. Selenolate ligands also bound to this cavity mutant under anaerobic conditions, but reduced the heme iron to the ferrous state as shown by formation of a ferrous-CO complex. Under aerobic conditions, the selenolate but not thiolate ligand was rapidly oxidized. These results indicate that selenocysteine-coordinated heme proteins will not be stable species in the absence of a redox potential stabilizing effect. PMID:18376820

Bonding coordination requirements induce antiferromagnetic coupling between m-phenylene bridged o-iminosemiquinonato diradicals.

PubMed

Dei, Andrea; Gatteschi, Dante; Sangregorio, Claudio; Sorace, Lorenzo; Vaz, Maria G F

2003-03-10

Triply bridged bis-iminodioxolene dinuclear metal complexes of general formula M(2)(diox-diox)(3), with M = Co, Fe, have been synthesized using the bis-bidentate ligand N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,3-phenylenediamine. These complexes were characterized by means of X-ray, HF-EPR, and magnetic measurements. X-ray structures clearly show that both complexes can be described as containing three bis-iminosemiquinonato ligands acting in a bis-bidentate manner toward tripositive metal ions. The magnetic data show that both of these complexes have singlet ground states. The observed experimental behavior indicates the existence of intraligand antiferromagnetic interactions between the three pairs of m-phenylene units linked iminosemiquinonato radicals (J = 21 cm(-)(1) for the cobalt complex and J = 11 cm(-)(1) for the iron one). It is here suggested that the conditions for the ferromagnetic coupling that is expected to characterize the free diradical ligand are no longer satisfied because of the severe torsional distortion induced by the metal coordination.

Iron-Induced Virulence of Salmonella enterica Serovar Typhimurium at the Intestinal Epithelial Interface Can Be Suppressed by Carvacrol

PubMed Central

Kortman, Guus A. M.; Roelofs, Rian W. H. M.; Swinkels, Dorine W.; de Jonge, Marien I.; Burt, Sara A.

2014-01-01

Oral iron therapy can increase the abundance of bacterial pathogens, e.g., Salmonella spp., in the large intestine of African children. Carvacrol is a natural compound with antimicrobial activity against various intestinal bacterial pathogens, among which is the highly prevalent Salmonella enterica serovar Typhimurium. This study aimed to explore a presumed interaction between carvacrol and bacterial iron handling and to assess the potential of carvacrol in preventing the increase of bacterial pathogenicity during high iron availability. S. Typhimurium was cultured with increasing concentrations of iron and carvacrol to study the effects of these combined interventions on growth, adhesion to intestinal epithelial cells, and iron uptake/influx in both bacterial and epithelial cells. In addition, the ability of carvacrol to remove iron from the high-affinity ligand transferrin and an Fe-dye complex was examined. Carvacrol retarded growth of S. Typhimurium at all iron conditions. Furthermore, iron-induced epithelial adhesion was effectively reduced by carvacrol at high iron concentrations. The reduction of growth and virulence by carvacrol was not paralleled by a change in iron uptake or influx into S. Typhimurium. In contrast, bioavailability of iron for epithelial cells was moderately decreased under these conditions. Further, carvacrol was shown to lack the properties of an iron binding molecule; however, it was able to weaken iron-ligand interactions by which it may possibly interfere with bacterial virulence. In conclusion, our in vitro data suggest that carvacrol has the potential to serve as a novel dietary supplement to prevent pathogenic overgrowth and colonization in the large intestine during oral iron therapy. PMID:24379194

Synthesis and spectroscopic studies of binuclear metal complexes of a tetradentate N2O2 Schiff base ligand derived from 4,6-diacetylresorcinol and benzylamine.

PubMed

Shebl, Magdy

2008-09-01

A tetradentate N2O2 donor Schiff base ligand, H2L, was synthesized by the condensation of 4,6-diacetylresorcinol with benzylamine. The structure of the ligand was elucidated by elemental analyses, IR, 1H NMR, electronic and mass spectra. Reaction of the Schiff base ligand with nickel(II), cobalt(II), iron(III), cerium(III), vanadyl(IV) and uranyl(VI) ions in 1:2 molar ratio afforded binuclear metal complexes. Also, reaction of the ligand with several copper(II) salts, including Cl-, NO3-, AcO-, ClO4- and SO42- afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO(4)(-) anion as compared to the strongly coordinating power of SO42- and Cl- anions. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, 1H NMR, electronic, mass and ESR spectra as well as magnetic susceptibility measurements. The metal complexes exhibited different geometrical arrangements such as square planar, octahedral, square pyramidal and pentagonal bipyramidal arrangements. The variety in the geometrical arrangements depends on the nature of both the anion and the metal ion.

Characteristics Of Bridging Oxo And Sulfido Groups In Multinuclear Iron Proteins

NASA Astrophysics Data System (ADS)

Loehr, Thomas M.

1989-07-01

The presence of oxo-bridged dinuclear iron clusters has been established in the respiratory protein, hemerythrin (Hr), and in the DNA-biosynthesis regulatory enzyme, ribonucleotide reductase (Rr). For the iron proteins uteroferrin and purple acid phosphatase (PAP) evidence for μ-oxo-bridged centers is less clear. Resonance Raman (RR) spectra obtained by excitation into an 0(2-) --> Fe(III) CT band may show strong symmetric and weak antisymmetric Fe-0-Fe vibrational modes. We have investigated the spectra of a variety of μ-oxo-bridged Fe(III) complexes to establish the dependence of Raman scattering intensities upon structural parameters. Intensities were found to relate to the nature of the ligand trans to the oxo group: nitrogen ligands with unsaturation (e.g., pyrazole and imidazole) lead to strong scattering, whereas saturated ligands provide only poor scattering. The Fe-0 bonds in Hr and Rr are strong scatterers; the former is known from x-ray crystallography to have a histidyl ligand trans to the μ-oxo group. On this basis, a similar ligand structure is likely in the reductase. In contrast, PAP shows no oxo-bridge with UV and near-UV excitation. We propose that a different structural framework is necessary to account for this result. Hydrogen bonding of protein side chains to oxo and sulfido ligands is proposed to explain changes in frequencies for samples dissolved in water vs. D20. Differences in hydrogen-bond strengths between 0...(D) and S...(D) systems are transferred to the observed Fe-0 and Fe-S bond vibrations.

Dinitrosyl iron complexes with glutathione as NO and NO⁺ donors.

PubMed

Borodulin, Rostislav R; Kubrina, Lyudmila N; Mikoyan, Vasak D; Poltorakov, Alexander P; Shvydkiy, Vyacheslav О; Burbaev, Dosymzhan Sh; Serezhenkov, Vladimir A; Yakhontova, Elena R; Vanin, Anatoly F

2013-02-28

It has been found that heating of solutions of the binuclear form of dinitrosyl iron complexes (B-DNIC) with glutathione in a degassed Thunberg apparatus (рН 1.0, 70°С, 6 h) results in their decomposition with a concomitant release of four gaseous NO molecules per one B-DNIC. Further injection of air into the Thunberg apparatus initiates fast oxidation of NO to NO₂ and formation of two GS-NO molecules per one B-DNIC. Under similar conditions, the decomposition of B-DNIC solutions in the Thunberg apparatus in the presence of air is complete within 30-40 min and is accompanied by formation of four GS-NO molecules per one B-DNIC. It is suggested that the latter events are determined by oxidation of B-DNIC iron and concominant release of four nitrosonium ions (NO⁺) from each complex. Binding of NO⁺ to thiol groups of glutathione provokes GS-NO synthesis. At neutral рН, decomposition of B-DNIC is initiated by strong iron chelators, viz., о-phenanthroline and N-methyl-d-glucamine dithiocarbamate (MGD). In the former case, the reaction occurs under anaerobic conditions (degassed Thunberg apparatus) and is accompanied by a release of four NO molecules from B-DNIC. Under identical conditions, MGD-induced decomposition of B-DNIC gives two EPR-active mononuclear mononitrosyl iron complexes with MGD (MNIC-MGD) able to incorporate two iron molecules and two NO molecules from each B-DNIC. The other two NO molecules released from B-DNIC (most probably, in the form of nitrosonium ions) bind to thiol groups of MGD to give corresponding S-nitrosothiols. Acidification of test solutions to рН 1.0 initiates hydrolysis of MGD and, as a consequence, decomposition of MNIC-MGD and the S-nitrosated form of MGD; the gaseous phase contains four NO molecules (as calculated per each B-DNIC). The data obtained testify to the ability of B-DNIC with glutathione (and, probably, of B-DNIC with other thiol-containing ligands) to release both NO molecules and nitrosonium ions upon their decomposition. As far as nitrosyl iron complexes with non-thiol-containing ligands predominantly represented by the mononuclear mononitrosyl iron form (MNIC) are concerned, their decomposition yields exclusively NO molecules. Copyright © 2012 Elsevier Inc. All rights reserved.

A Comparative Study of Iron Uptake Mechanisms in Marine Microalgae: Iron Binding at the Cell Surface Is a Critical Step1[W][OA

PubMed Central

Sutak, Robert; Botebol, Hugo; Blaiseau, Pierre-Louis; Léger, Thibaut; Bouget, François-Yves; Camadro, Jean-Michel; Lesuisse, Emmanuel

2012-01-01

We investigated iron uptake mechanisms in five marine microalgae from different ecologically important phyla: the diatoms Phaeodactylum tricornutum and Thalassiosira pseudonana, the prasinophyceae Ostreococcus tauri and Micromonas pusilla, and the coccolithophore Emiliania huxleyi. Among these species, only the two diatoms were clearly able to reduce iron, via an inducible (P. tricornutum) or constitutive (T. pseudonana) ferrireductase system displaying characteristics similar to the yeast (Saccharomyces cerevisiae) flavohemoproteins proteins. Iron uptake mechanisms probably involve very different components according to the species, but the species we studied shared common features. Regardless of the presence and/or induction of a ferrireductase system, all the species were able to take up both ferric and ferrous iron, and iron reduction was not a prerequisite for uptake. Iron uptake decreased with increasing the affinity constants of iron-ligand complexes and with increasing ligand-iron ratios. Therefore, at least one step of the iron uptake mechanism involves a thermodynamically controlled process. Another step escapes to simple thermodynamic rules and involves specific and strong binding of ferric as well as ferrous iron at the cell surface before uptake of iron. Binding was paradoxically increased in iron-rich conditions, whereas uptake per se was induced in all species only after prolonged iron deprivation. We sought cell proteins loaded with iron following iron uptake. One such protein in O. tauri may be ferritin, and in P. tricornutum, Isip1 may be involved. We conclude that the species we studied have uptake systems for both ferric and ferrous iron, both involving specific iron binding at the cell surface. PMID:23033141

Revisiting the Electronic Structure of FeS Monomers Using ab Initio Ligand Field Theory and the Angular Overlap Model.

PubMed

Chilkuri, Vijay Gopal; DeBeer, Serena; Neese, Frank

2017-09-05

Iron-sulfur (FeS) proteins are universally found in nature with actives sites ranging in complexity from simple monomers to multinuclear sites from two up to eight iron atoms. These sites include mononuclear (rubredoxins), dinuclear (ferredoxins and Rieske proteins), trinuclear (e.g., hydrogenases), and tetranuclear (various ferredoxins and high-potential iron-sulfur proteins). The electronic structure of the higher-nuclearity clusters is inherently extremely complex. Hence, it is reasonable to take a bottom-up approach in which clusters of increasing nuclearity are analyzed in terms of the properties of their lower nuclearity constituents. In the present study, the first step is taken by an in-depth analysis of mononuclear FeS systems. Two different FeS molecules with phenylthiolate and methylthiolate as ligands are studied in their oxidized and reduced forms using modern wave function-based ab initio methods. The ab initio electronic spectra and wave function are presented and analyzed in detail. The very intricate electronic structure-geometry relationship in these systems is analyzed using ab initio ligand field theory (AILFT) in conjunction with the angular overlap model (AOM) parametrization scheme. The simple AOM model is used to explain the effect of geometric variations on the electronic structure. Through a comparison of the ab initio computed UV-vis absorption spectra and the available experimental spectra, the low-energy part of the many-particle spectrum is carefully analyzed. We show ab initio calculated magnetic circular dichroism spectra and present a comparison with the experimental spectrum. Finally, AILFT parameters and the ab initio spectra are compared with those obtained experimentally to understand the effect of the increased covalency of the thiolate ligands on the electronic structure of FeS monomers.

Nitric oxide activation by distal redox modulation in tetranuclear iron nitrosyl complexes.

PubMed

de Ruiter, Graham; Thompson, Niklas B; Lionetti, Davide; Agapie, Theodor

2015-11-11

A series of tetranuclear iron complexes displaying a site-differentiated metal center was synthesized. Three of the metal centers are coordinated to our previously reported ligand, based on a 1,3,5-triarylbenzene motif with nitrogen and oxygen donors. The fourth (apical) iron center is coordinatively unsaturated and appended to the trinuclear core through three bridging pyrazolates and an interstitial μ4-oxide moiety. Electrochemical studies of complex [LFe3(PhPz)3OFe][OTf]2 revealed three reversible redox events assigned to the Fe(II)4/Fe(II)3Fe(III) (-1.733 V), Fe(II)3Fe(III)/Fe(II)2Fe(III)2 (-0.727 V), and Fe(II)2Fe(III)2/Fe(II)Fe(III)3 (0.018 V) redox couples. Combined Mössbauer and crystallographic studies indicate that the change in oxidation state is exclusively localized at the triiron core, without changing the oxidation state of the apical metal center. This phenomenon is assigned to differences in the coordination environment of the two metal sites and provides a strategy for storing electron and hole equivalents without affecting the oxidation state of the coordinatively unsaturated metal. The presence of a ligand-binding site allowed the effect of redox modulation on nitric oxide activation by an Fe(II) metal center to be studied. Treatment of the clusters with nitric oxide resulted in binding of NO to the apical iron center, generating a {FeNO}(7) moiety. As with the NO-free precursors, the three reversible redox events are localized at the iron centers distal from the NO ligand. Altering the redox state of the triiron core resulted in significant change in the NO stretching frequency, by as much as 100 cm(-1). The increased activation of NO is attributed to structural changes within the clusters, in particular, those related to the interaction of the metal centers with the interstitial atom. The differences in NO activation were further shown to lead to differential reactivity, with NO disproportionation and N2O formation performed by the more electron-rich cluster.

Ligand Exchange Kinetics of Environmentally Relevant Metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Panasci, Adele Frances

2014-07-15

The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb tomore » mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.« less

Mössbauer study of novel iron(II) complexes synthesized with Schiff bases

NASA Astrophysics Data System (ADS)

Várhelyi, Cs.; Lengyel, A.; Homonnay, Z.; Szalay, R.; Pokol, Gy.; Szilágyi, I.-M.; Huszthy, P.; Papp, J.; Goga, F.; Golban, L.-M.; Várhelyi, M.; Tomoaia-Cotisel, M.; Szőke, Á.; Kuzmann, E.

2017-11-01

Novel [Fe(4-benzyl-2-hydroxyphenyl-propylidene)2ethylene-diamine], and [Fe (2,4,6-trihydroxy-benzyl-4-metoxiphenyl-methylidene)2ethylene-diamine] complexes were synthesized by reacting FeII salt with the indicated Schiff-base ligands. The compounds were characterized by57Fe Mössbauer spectroscopy, FTIR, UV-VIS, TG-DTA-DTG, MS, AFM, XRD, cyclic voltammetry and biological activity measurements. 295 K and 78 K Mössbauer spectra revealed that iron is dominantly in high spin FeII state in both complexes while simultaneously a minor low spin FeII was also present in both complexes, furthermore a minor high spin FeIII was observed in [Fe(2,4,6-trihydroxy-benzyl-4-metoxiphenyl- methylidene) 2ethylene-diamine], too.

What is the best bonding model of the (σ-H-BR) species bound to a transition metal? Bonding analysis in complexes [(H)2Cl(PMe3)2M(σ-H-BR)] (M = Fe, Ru, Os).

PubMed

Pandey, Krishna K

2012-03-21

Density Functional Theory calculations have been performed for the σ-hydroboryl complexes of iron, ruthenium and osmium [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] (M = Fe, Ru, Os; R = OMe, NMe(2), Ph) at the BP86/TZ2P/ZORA level of theory in order to understand the interactions between metal and HBR ligands. The calculated geometries of the complexes [(H)(2)Cl(PMe(3))(2)Ru(HBNMe(2))], [(H)(2)Cl(PMe(3))(2)Os(HBR)] (R = OMe, NMe(2)) are in excellent agreement with structurally characterized complexes [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))], [(H)(2)Cl(P(i)Pr(3))(2)Os{σ-H-BOCH(2)CH(2)OB(O(2)CH(2)CH(2))}] and [(H)(2)Cl(P(i)Pr(3))(2)Os(σ-H-BNMe(2))]. The longer calculated M-B bond distance in complex [(H)(2)Cl(PMe(3))(2)M(σ-H-BNMe(2))] are due to greater B-N π bonding and as a result, a weaker M-B π-back-bonding. The B-H2 bond distances reveal that (i) iron complexes contain bis(σ-borane) ligand, (ii) ruthenium complexes contain (σ-H-BR) ligands with a stretched B-H2 bond, and (iii) osmium complexes contain hydride (H2) and (σ-H-BR) ligands. The H-BR ligands in osmium complexes are a better trans-directing ligand than the Cl ligand. Values of interaction energy, electrostatic interaction, orbital interaction, and bond dissociation energy for interactions between ionic fragments are very large and may not be consistent with M-(σ-H-BR) bonding. The EDA as well as NBO and AIM analysis suggest that the best bonding model for the M-σ-H-BR interactions in the complexes [(H)(2)Cl(PMe(3))(2)M(σ-H-BR)] is the interaction between neutral fragments [(H)(2)Cl(PMe(3))(2)M] and [σ-H-BR]. This becomes evident from the calculated values for the orbital interactions. The electron configuration of the fragments which is shown for C in Fig. 1 experiences the smallest change upon the M-σ-H-BR bond formation. Since model C also requires the least amount of electronic excitation and geometry changes of all models given by the ΔE(prep) values, it is clearly the most appropriate choice of interacting fragments. The π-bonding contribution is 14-22% of the total orbital contribution.

Efficient Hydrogenation of Ketones and Aldehydes Catalyzed by Well-Defined Iron(II) PNP Pincer Complexes: Evidence for an Insertion Mechanism

PubMed Central

2014-01-01

We have prepared and structurally characterized a new class of Fe(II) PNP pincer hydride complexes [Fe(PNP-iPr)(H)(CO)(L)]n (L = Br–, CH3CN, pyridine, PMe3, SCN–, CO, BH4–; n = 0, +1) based on the 2,6-diaminopyridine scaffold where the PiPr2 moieties of the PNP ligand are connected to the pyridine ring via NH and/or NMe spacers. Complexes [Fe(PNP-iPr)(H)(CO)(L)]n with labile ligands (L = Br–, CH3CN, BH4–) and NH spacers are efficient catalysts for the hydrogenation of both ketones and aldehydes to alcohols under mild conditions, while those containing inert ligands (L = pyridine, PMe3, SCN–, CO) are catalytically inactive. Interestingly, complex [Fe(PNPMe-iPr)(H)(CO)(Br)], featuring NMe spacers, is an efficient catalyst for the chemoselective hydrogenation of aldehydes. The first type of complexes involves deprotonation of the PNP ligand as well as heterolytic dihydrogen cleavage via metal-alkoxide cooperation, but no reversible aromatization/deprotonation of the PNP ligand. In the case of the N-methylated complex the mechanism remains unclear, but obviously does not allow bifunctional activation of dihydrogen. The experimental results complemented by DFT calculations strongly support an insertion of the C=O bond of the carbonyl compound into the Fe–H bond. PMID:27642211

A model of Fe speciation and biogeochemistry at the Tropical Eastern North Atlantic Time-Series Observatory site

NASA Astrophysics Data System (ADS)

Ye, Y.; Völker, C.; Wolf-Gladrow, D. A.

2009-10-01

A one-dimensional model of Fe speciation and biogeochemistry, coupled with the General Ocean Turbulence Model (GOTM) and a NPZD-type ecosystem model, is applied for the Tropical Eastern North Atlantic Time-Series Observatory (TENATSO) site. Among diverse processes affecting Fe speciation, this study is focusing on investigating the role of dust particles in removing dissolved iron (DFe) by a more complex description of particle aggregation and sinking, and explaining the abundance of organic Fe-binding ligands by modelling their origin and fate. The vertical distribution of different particle classes in the model shows high sensitivity to changing aggregation rates. Using the aggregation rates from the sensitivity study in this work, modelled particle fluxes are close to observations, with dust particles dominating near the surface and aggregates deeper in the water column. POC export at 1000 m is a little higher than regional sediment trap measurements, suggesting further improvement of modelling particle aggregation, sinking or remineralisation. Modelled strong ligands have a high abundance near the surface and decline rapidly below the deep chlorophyll maximum, showing qualitative similarity to observations. Without production of strong ligands, phytoplankton concentration falls to 0 within the first 2 years in the model integration, caused by strong Fe-limitation. A nudging of total weak ligands towards a constant value is required for reproducing the observed nutrient-like profiles, assuming a decay time of 7 years for weak ligands. This indicates that weak ligands have a longer decay time and therefore cannot be modelled adequately in a one-dimensional model. The modelled DFe profile is strongly influenced by particle concentration and vertical distribution, because the most important removal of DFe in deeper waters is colloid formation and aggregation. Redissolution of particulate iron is required to reproduce an observed DFe profile at TENATSO site. Assuming colloidal iron is mainly composed of inorganic colloids, the modelled colloidal to soluble iron ratio is lower that observations, indicating the importance of organic colloids.

Heme versus non-heme iron-nitroxyl {FeN(H)O}⁸ complexes: electronic structure and biologically relevant reactivity.

PubMed

Speelman, Amy L; Lehnert, Nicolai

2014-04-15

Researchers have completed extensive studies on heme and non-heme iron-nitrosyl complexes, which are labeled {FeNO}(7) in the Enemark-Feltham notation, but they have had very limited success in producing corresponding, one-electron reduced, {FeNO}(8) complexes where a nitroxyl anion (NO(-)) is formally bound to an iron(II) center. These complexes, and their protonated iron(II)-NHO analogues, are proposed key intermediates in nitrite (NO2(-)) and nitric oxide (NO) reducing enzymes in bacteria and fungi. In addition, HNO is known to have a variety of physiological effects, most notably in the cardiovascular system. HNO may also serve as a signaling molecule in mammals. For these functions, iron-containing proteins may mediate the production of HNO and serve as receptors for HNO in vivo. In this Account, we highlight recent key advances in the preparation, spectroscopic characterization, and reactivity of ferrous heme and non-heme nitroxyl (NO(-)/HNO) complexes that have greatly enhanced our understanding of the potential biological roles of these species. Low-spin (ls) heme {FeNO}(7) complexes (S = 1/2) can be reversibly reduced to the corresponding {FeNO}(8) species, which are stable, diamagnetic compounds. Because the reduction is ligand (NO) centered in these cases, it occurs at extremely negative redox potentials that are at the edge of the biologically feasible range. Interestingly, the electronic structures of ls-{FeNO}(7) and ls-{FeNO}(8) species are strongly correlated with very similar frontier molecular orbitals (FMOs) and thermodynamically strong Fe-NO bonds. In contrast, high-spin (hs) non-heme {FeNO}(7) complexes (S = 3/2) can be reduced at relatively mild redox potentials. Here, the reduction is metal-centered and leads to a paramagnetic (S = 1) {FeNO}(8) complex. The increased electron density at the iron center in these species significantly decreases the covalency of the Fe-NO bond, making the reduced complexes highly reactive. In the absence of steric bulk, monomeric high-spin {FeNO}(8) complexes decompose rapidly. Notably, in a recently prepared, dimeric [{FeNO}(7)]2 species, we observed that reduction leads to rapid N-N bond formation and N2O generation, which directly models the reactivity of flavodiiron NO reductases (FNORs). We have also made key progress in the preparation and stabilization of corresponding HNO complexes, {FeNHO}(8), using both heme and non-heme ligand sets. In both cases, we have taken advantage of sterically bulky coligands to stabilize these species. ls-{FeNO}(8) complexes are basic and easily form corresponding ls-{FeNHO}(8) species, which, however, decompose rapidly via disproportionation and H2 release. Importantly, we recently showed that we can suppress this reaction via steric protection of the bound HNO ligand. As a result, we have demonstrated that ls-{FeNHO}(8) model complexes are stable and amenable to spectroscopic characterization. Neither ls-{FeNO}(8) nor ls-{FeNHO}(8) model complexes are active for N-N coupling, and hence, seem unsuitable as reactive intermediates in nitric oxide reductases (NORs). Hs-{FeNO}(8) complexes are more basic than their hs-{FeNO}(7) precursors, but their electronic structure and reactivity is not as well characterized.

Multiconfiguration Pair-Density Functional Theory Predicts Spin-State Ordering in Iron Complexes with the Same Accuracy as Complete Active Space Second-Order Perturbation Theory at a Significantly Reduced Computational Cost.

PubMed

Wilbraham, Liam; Verma, Pragya; Truhlar, Donald G; Gagliardi, Laura; Ciofini, Ilaria

2017-05-04

The spin-state orderings in nine Fe(II) and Fe(III) complexes with ligands of diverse ligand-field strength were investigated with multiconfiguration pair-density functional theory (MC-PDFT). The performance of this method was compared to that of complete active space second-order perturbation theory (CASPT2) and Kohn-Sham density functional theory. We also investigated the dependence of CASPT2 and MC-PDFT results on the size of the active-space. MC-PDFT reproduces the CASPT2 spin-state ordering, the dependence on the ligand field strength, and the dependence on active space at a computational cost that is significantly reduced as compared to CASPT2.

Interaction of Triapine and related thiosemicarbazones with iron(III)/(II) and gallium(III): a comparative solution equilibrium study†

PubMed Central

Enyedy, Éva A.; Primik, Michael F.; Kowol, Christian R.; Arion, Vladimir B.; Kiss, Tamás; Keppler, Bernhard K.

2012-01-01

Stoichiometry and stability of GaIII, FeIII, FeII complexes of Triapine and five related α-N heterocyclic thiosemicarbazones with potential antitumor activity have been determined by pH-potentiometry, UV-vis spectrophotometry, 1H NMR spectroscopy, and spectrofluorimetry in aqueous solution (with 30% DMSO), together with the characterization of the proton dissociation processes. Additionally, the redox properties of the iron complexes were studied by cyclic voltammetry at various pH values. Formation of high stability bis-ligand complexes was found in all cases, which are predominant at physiological pH with FeIII/FeII, whilst only at the acidic pH range with GaIII. The results show that among the thiosemicarbazones with various substituents the N-terminal dimethylation does not exert a measurable effect on the redox potential, but has the highest impact on the stability of the complexes as well as the cytotoxicity, especially in the absence of a pyridine-NH2 group in the molecule. In addition the fluorescence properties of the ligands in aqueous solution and their changes caused by GaIII were studied. PMID:21523301

Synthesis, Structure, and Physical Properties for a Series of Monomeric Iron(III) Hydroxo Complexes with Varying Hydrogen-Bond Networks

PubMed Central

Mukherjee, Jhumpa; Lucas, Robie L.; Zart, Matthew K.; Powell, Douglas R.; Day, Victor W.; Borovik, A. S.

2013-01-01

Mononuclear iron(III) complexes with terminal hydroxo ligands are proposed to be important species in several metalloproteins, but they have been difficult to isolate in synthetic systems. Using a series of amidate/ureido tripodal ligands, we have prepared and characterized monomeric FeIIIOH complexes with similar trigonal-bipyramidal primary coordination spheres. Three anionic nitrogen donors define the trigonal plane, and the hydroxo oxygen atom is trans to an apical amine nitrogen atom. The complexes have varied secondary coordination spheres that are defined by intramolecular hydrogen bonds between the FeIIIOH unit and the urea NH groups. Structural trends were observed between the number of hydrogen bonds and the Fe–Ohydroxo bond distances: the more intramolecular hydrogen bonds there were, the longer the Fe–O bond became. Spectroscopic trends were also found, including an increase in the energy of the O–H vibrations with a decrease in the number of hydrogen bonds. However, the FeIII/II reduction potentials were constant throughout the series (∼2.0 V vs [Cp2Fe]0/+1), which is ascribed to a balancing of the primary and secondary coordination-sphere effects. PMID:18498155

Analysis of Heme Iron Coordination in DGCR8: The Heme-Binding Component of the Microprocessor Complex.

PubMed

Girvan, Hazel M; Bradley, Justin M; Cheesman, Myles R; Kincaid, James R; Liu, Yilin; Czarnecki, Kazimierz; Fisher, Karl; Leys, David; Rigby, Stephen E J; Munro, Andrew W

2016-09-13

DGCR8 is the RNA-binding partner of the nuclease Drosha. Their complex (the "Microprocessor") is essential for processing of long, primary microRNAs (pri-miRNAs) in the nucleus. Binding of heme to DGCR8 is essential for pri-miRNA processing. On the basis of the split Soret ultraviolet-visible (UV-vis) spectrum of ferric DGCR8, bis-thiolate sulfur (cysteinate, Cys(-)) heme iron coordination of DGCR8 heme iron was proposed. We have characterized DGCR8 heme ligation using the Δ276 DGCR8 variant and combined electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), electron nuclear double resonance, resonance Raman, and electronic absorption spectroscopy. These studies indicate DGCR8 bis-Cys heme iron ligation, with conversion from bis-thiolate (Cys(-)/Cys(-)) axial coordination in ferric DGCR8 to bis-thiol (CysH/CysH) coordination in ferrous DGCR8. Pri-miRNA binding does not perturb ferric DGCR8's optical spectrum, consistent with the axial ligand environment being separated from the substrate-binding site. UV-vis absorption spectra of the Fe(II) and Fe(II)-CO forms indicate discrete species exhibiting peaks with absorption coefficients substantially larger than those for ferric DGCR8 and that previously reported for a ferrous form of DGCR8. Electron-nuclear double resonance spectroscopy data exclude histidine or water as axial ligands for ferric DGCR8 and favor bis-thiolate coordination in this form. UV-vis MCD and near-infrared MCD provide data consistent with this conclusion. UV-vis MCD data for ferrous DGCR8 reveal features consistent with bis-thiol heme iron coordination, and resonance Raman data for the ferrous-CO form are consistent with a thiol ligand trans to the CO. These studies support retention of DGCR8 cysteine coordination upon reduction, a conclusion distinct from those of previous studies of a different ferrous DGCR8 isoform.

Differences and Comparisons of the Properties and Reactivities of Iron(III)–hydroperoxo Complexes with Saturated Coordination Sphere

PubMed Central

Faponle, Abayomi S; Quesne, Matthew G; Sastri, Chivukula V; Banse, Frédéric; de Visser, Sam P

2015-01-01

Heme and nonheme monoxygenases and dioxygenases catalyze important oxygen atom transfer reactions to substrates in the body. It is now well established that the cytochrome P450 enzymes react through the formation of a high-valent iron(IV)–oxo heme cation radical. Its precursor in the catalytic cycle, the iron(III)–hydroperoxo complex, was tested for catalytic activity and found to be a sluggish oxidant of hydroxylation, epoxidation and sulfoxidation reactions. In a recent twist of events, evidence has emerged of several nonheme iron(III)–hydroperoxo complexes that appear to react with substrates via oxygen atom transfer processes. Although it was not clear from these studies whether the iron(III)–hydroperoxo reacted directly with substrates or that an initial O–O bond cleavage preceded the reaction. Clearly, the catalytic activity of heme and nonheme iron(III)–hydroperoxo complexes is substantially different, but the origins of this are still poorly understood and warrant a detailed analysis. In this work, an extensive computational analysis of aromatic hydroxylation by biomimetic nonheme and heme iron systems is presented, starting from an iron(III)–hydroperoxo complex with pentadentate ligand system (L52). Direct C–O bond formation by an iron(III)–hydroperoxo complex is investigated, as well as the initial heterolytic and homolytic bond cleavage of the hydroperoxo group. The calculations show that [(L52)FeIII(OOH)]2+ should be able to initiate an aromatic hydroxylation process, although a low-energy homolytic cleavage pathway is only slightly higher in energy. A detailed valence bond and thermochemical analysis rationalizes the differences in chemical reactivity of heme and nonheme iron(III)–hydroperoxo and show that the main reason for this particular nonheme complex to be reactive comes from the fact that they homolytically split the O–O bond, whereas a heterolytic O–O bond breaking in heme iron(III)–hydroperoxo is found. PMID:25399782

Iron-catalyzed halogenation of alkanes: modeling of nonheme halogenases by experiment and DFT calculations.

PubMed

Comba, Peter; Wunderlich, Steffen

2010-06-25

When the dichloroiron(II) complex of the tetradentate bispidine ligand L=3,7-dimethyl-9-oxo-2,4-bis(2-pyridyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate methyl ester is oxidized with H(2)O(2), tBuOOH, or iodosylbenzene, the high-valent Fe=O complex efficiently oxidizes and halogenates cyclohexane. Kinetic D isotope effects and the preference for the abstraction of tertiary over secondary carbon-bound hydrogen atoms (quantified in the halogenation of adamantane) indicate that C-H activation is the rate-determining step. The efficiencies (yields in stoichiometric and turnover numbers in catalytic reactions), product ratios (alcohol vs. bromo- vs. chloroalkane), and kinetic isotope effects depend on the oxidant. These results suggest different pathways with different oxidants, and these may include iron(IV)- and iron(V)-oxo complexes as well as oxygen-based radicals.

Advanced X-ray Spectroscopic Methods for Studying Iron-Sulfur-Containing Proteins and Model Complexes.

PubMed

DeBeer, Serena

2018-01-01

In this chapter, a brief overview of X-ray spectroscopic methods that may be utilized to obtain insight into the geometric and electronic structure of iron-sulfur proteins is provided. These methods include conventional methods, such as metal and ligand K-edge X-ray absorption, as well as more advanced methods including nonresonant and resonant X-ray emission. In each section, the basic information content of the spectra is highlighted and important experimental considerations are discussed. Throughout the chapter, recent applications to iron-sulfur-containing models and proteins are highlighted. © 2018 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Toczydlowska, Diana; Kedra-Krolik, Karolina; Nejbert, Krzysztof

The role of surface electrostatics on the reductive dissolution of iron (III) oxides is poorly understood, despite its importance in controlling the amount of mobilized iron. We report the potentiometric titration of the a; y -Fe2O3 oxides exposed to reductants and complexing ligands (Fe(II), ascorbate, oxalate, malonate). We monitored in situ surface and potentials, the ratio of mobilized ferric to ferrous ions, and periodically analyzed nanoparticle crystal structure using X-ray diffraction. We found that addition of Fe2+ ions produces a response consistent with the iron solubilityactivity curve, whereas the presence of ascorbate significantly decreases the amount of mobilized Fe(III) duemore » to reduction to Fe(II). In addition, XRD analysis proved that y-Fe2O3 particles remain structurally unchanged along the titration pathway despite iron cycling between aqueous and solid reservoirs. Our studies, suggest that the surface redoxactivity of iron oxides is primarily governed by the balance between Fe(III) and Fe(II) ions in aqueous phase, which may be easily altered by complexing and reducing agents.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kleinlein, Claudia; Zheng, Shao-Liang; Betley, Theodore A.

Three ferric dipyrromethene complexes featuring different ancillary ligands were synthesized by one electron oxidation of ferrous precursors. Four-coordinate iron complexes of the type ( ArL)FeX 2 [ ArL = 1,9-(2,4,6-Ph 3C 6H 2) 2-5-mesityldipyrromethene] with X = Cl or tBuO were prepared and found to be high-spin (S = 5/2), as determined by superconducting quantum interference device magnetometry, electron paramagnetic resonance, and 57Fe Mössbauer spectroscopy. The ancillary ligand substitution was found to affect both ground state and excited properties of the ferric complexes examined. While each ferric complex displays reversible reduction and oxidation events, each alkoxide for chloride substitution resultsmore » in a nearly 600 mV cathodic shift of the Fe III/II couple. The oxidation event remains largely unaffected by the ancillary ligand substitution and is likely dipyrrin-centered. While the alkoxide substituted ferric species largely retain the color of their ferrous precursors, characteristic of dipyrrin-based ligand-to-ligand charge transfer (LLCT), the dichloride ferric complex loses the prominent dipyrrin chromophore, taking on a deep green color. Time-dependent density functional theory analyses indicate the weaker-field chloride ligands allow substantial configuration mixing of ligand-to-metal charge transfer into the LLCT bands, giving rise to the color changes observed. Furthermore, the higher degree of covalency between the alkoxide ferric centers is manifest in the observed reactivity. Delocalization of spin density onto the tert-butoxide ligand in ( ArL)FeCl(O tBu) is evidenced by hydrogen atom abstraction to yield ( ArL)FeCl and HOtBu in the presence of substrates containing weak C–H bonds, whereas the chloride ( ArL)FeCl 2 analogue does not react under these conditions.« less

Spectroscopic investigation and direct comparison of the reactivities of iron pyridyl oxidation catalysts

NASA Astrophysics Data System (ADS)

Song, Yang; Mayes, Howard G.; Queensen, Matthew J.; Bauer, Eike B.; Dupureur, Cynthia M.

2017-03-01

The growing interest in green chemistry has fueled attention to the development and characterization of effective iron complex oxidation catalysts. A number of iron complexes are known to catalyze the oxidation of organic substrates utilizing peroxides as the oxidant. Their development is complicated by a lack of direct comparison of the reactivities of the iron complexes. To begin to correlate reactivity with structural elements, we compare the reactivities of a series of iron pyridyl complexes toward a single dye substrate, malachite green (MG), for which colorless oxidation products are established. Complexes with tetradentate, nitrogen-based ligands with cis open coordination sites were found to be the most reactive. While some complexes reflect sensitivity to different peroxides, others are similarly reactive with either H2O2 or tBuOOH, which suggests some mechanistic distinctions. [Fe(S,S-PDP)(CH3CN)2](SbF6)2 and [Fe(OTf)2(tpa)] transition under the oxidative reaction conditions to a single intermediate at a rate that exceeds dye degradation (PDP = bis(pyridin-2-ylmethyl) bipyrrolidine; tpa = tris(2-pyridylmethyl)amine). For the less reactive [Fe(OTf)2(dpa)] (dpa = dipicolylamine), this reaction occurs on a timescale similar to that of MG oxidation. Thus, the spectroscopic method presented herein provides information about the efficiency and mechanism of iron catalyzed oxidation reactions as well as about potential oxidative catalyst decomposition and chemical changes of the catalyst before or during the oxidation reaction.

Synthesis of polymers containing 3-hydroxypyridin-4-one bidentate ligands for treatment of iron overload

PubMed Central

Saghaie, Lotfollah; Liu, Dy; Hider, Robert C

2015-01-01

Iron overload is a clinical problem which can be prevented by using iron chelating agents. An alternative method of relieving iron overload is to reduce iron absorption from the intestine by administering specific iron chelating agents, which can bind iron to form nonabsorbable complexes. Based on this strategy, a series of polymeric ligands containing the chelating moiety 3-hydroxypyridin-4-ones (HPOs) were synthesized. The synthetic route involves the benzylation of hydroxyl group of (2-methyl-3-hydroxypyran-4-one (maltol) and conversion of benzylated maltol to 3-benzyloxypyridin-4-one derivatives by using three suitable primary amines (2,6-diaminohexanoic acid (lysine) and 1,6-diaminohexane and 5-aminopentanol). The resulted compounds incorporated into polymer by copolymerization with acryloyl chloride using 2, 2’-azobisisobutyronitrile (AIBN) as the initiator. Finally, the benzyl groups of polymers were removed by catalytic hydrogenation (Pd/C). In this work, three final polymers of HPO derivatives namely poly-2-propylamido-6-(3- hydroxy -1,4-dihydro-2-methy-4-oxopyrid-1-yl) hexanoic acid, 6-(3-hydroxy-1, 4-dihydro-2-methyl-4-oxopyrid-1-yl) hexyl-1-polypropylamide and 5-(3-hydroxy-1-,4-dihydro-2-methyl-4-oxopyrid-1-yl)-1-polyacrylate pentane were synthesized. Identification and structural elucidation of compounds were achieved by proton nuclear magnetic resonance (1H NMR), carbon nuclear magnetic resonance (13C NMR) and infrared (IR) spectroscopy. PMID:26600863

An investigation of siderophore production by oceanic Synechococcus

NASA Astrophysics Data System (ADS)

Wisniewski, R. J.; Webb, E. A.; Moffett, J. W.

2003-04-01

Cyanobacteria are significant contributors to global primary production. They can be found in warm high-nutrient, low-chlorophyll regions where low concentrations of iron are thought to limit primary productivity. Determining how these organisms obtain iron is critical to understanding the biogeochemical cycle of iron and its role as a determinant of marine primary production. Siderophore production has been observed in halotolerant freshwater cyanobacteria (see C.G. Trick and co-authors) and marine heterotrophic bacteria (see A. Butler, M.G. Haygood and co-authors), but to date, siderophore production in truly marine cyanobacteria has not been demonstrated. We examined the response of two marine Synechococcus species (WH7803 and WH8102) to iron stress. Axenic cultures of both Synechococcus species were grown under iron-stressed and iron-replete conditions. The supernatants of these cultures were examined using competitive ligand exchange-cathodic stripping voltammetry (CLE-CSV), a sensitive method of quantitative ligand detection. Observing ligand accumulation in culture is an analytical challenge due to the low cell densities and reduced growth rates of iron stressed marine cyanobacteria. Preliminary results suggest the presence of an iron-binding ligand in the iron-stressed cultures which was not present under iron-replete conditions. The amount of ligand produced by Synechococcus was approximately 1 × 10-18 mol/cell, comparable with the amount produced by marine heterotrophic bacteria (K. Barbeau, pers. comm.).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinez, Jorge L.; Lin, Hsiu-Jung; Lee, Wei-Tsung

The new iron(IV) nitride complex PhB( iPr 2Im) 3Fe≡N reacts with two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB( iPr 2Im) 3Fe(CN)(N 2)(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne iPr 2N-C≡C-N iPr 2. The iron complex is in equilibrium with an N 2- free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C 6F 5) 3 provides the cyanoborane derivative.

Spin-crossover in an iron(III)-bispidine-alkylperoxide system.

PubMed

Bautz, Jochen; Comba, Peter; Que, Lawrence

2006-09-04

The iron(II) complex of a tetradentate bispidine ligand with two tertiary amines and two pyridine groups (L = dimethyl [3,7-dimethyl-9,9'-dihydroxy-2,4-di-(2-pyridyl)-3,7-diazabicyclo nonan-1,5-dicaboxylate]) is oxidized with tert-butyl hydroperoxide to the corresponding end-on tert-butylperoxo complex [Fe(III)(L)(OOtBu)(X)]n+ (X = solvent, anion). UV-vis, resonance Raman, and EPR spectroscopy, as a function of the solvent, show that this is a spin-crossover compound. The experimentally observed Raman vibrations for both low-spin and high-spin isomers are in good agreement with those computed by DFT.

Antimicrobial and mutagenic activity of some carbono- and thiocarbonohydrazone ligands and their copper(II), iron(II) and zinc(II) complexes.

PubMed

Bacchi, A; Carcelli, M; Pelagatti, P; Pelizzi, C; Pelizzi, G; Zani, F

1999-06-15

Several mono- and bis- carbono- and thiocarbonohydrazone ligands have been synthesised and characterised; the X-ray diffraction analysis of bis(phenyl 2-pyridyl ketone) thiocarbonohydrazone is reported. The coordinating properties of the ligands have been studied towards Cu(II), Fe(II), and Zn(II) salts. The ligands and the metal complexes were tested in vitro against Gram positive and Gram negative bacteria, yeasts and moulds. In general, the bisthiocarbonohydrazones possess the best antimicrobial properties and Gram positive bacteria are the most sensitive microorganisms. Bis(ethyl 2-pyridyl ketone) thiocarbonohydrazone, bis(butyl 2-pyridyl ketone)thiocarbonohydrazone and Cu(H2nft)Cl2 (H2nft, bis(5-nitrofuraldehyde)thiocarbonohydrazone) reveal a strong activity with minimum inhibitory concentrations of 0.7 microgram ml-1 against Bacillus subtilis and of 3 micrograms ml-1 against Staphylococcus aureus. Cu(II) complexes are more effective than Fe(II) and Zn(II) ones. All bisthiocarbono- and carbonohydrazones are devoid of mutagenic properties, with the exception of the compounds derived from 5-nitrofuraldehyde. On the contrary a weak mutagenicity, that disappears in the copper complexes, is exhibited by monosubstituted thiocarbonohydrazones.

Photochemistry of iron citrates initiated by UV-VIS light

NASA Astrophysics Data System (ADS)

Corral Arroyo, Pablo; Dou, Jing; Alpert, Peter; Krieger, Ulrich; Ammann, Markus

2017-04-01

Aerosol aging refers to the multitude of physical and chemical transformation atmospheric particles undergo, which play an important role in the impact of aerosols on climate, air quality and health. Aging processes may be started by chromophores, which act as photocatalysts that induce the oxidation of non-absorbing molecules [1]. Iron (Fe(III)) carboxylate complexes absorb light below about 500 nm, which is followed by ligand to metal charge transfer (LMCT) resulting in the reduction of iron to Fe(II) and oxidation of the carboxylate ligands, a process that represents an important sink of organic acids in the troposphere [2]. Our goal is to investigate how these photochemical processes contribute to the change of chemical and physical properties of the aerosol particles. To achieve this scope, we carry out coated wall flow tube experiments, exposing films with iron citrate to UV light, which will give information about the radical and LVOC production (connecting the CWFT to a Chemiluminescent Detector or PTR-TOF-MS respectively). From extracting and analyzing the films after irradiation with UV light, we obtain a profile of low-volatility products evolving from the photochemistry of iron citrates. By Scanning Transmission X-Ray Microspectroscopy (STXM) we analyze changes in the C K-edge and Fe L-edge in particles loaded with iron citrate upon exposure to light and follow their chemical and structural evolution upon photochemical oxidation in situ to investigate the degradation kinetics under varying environmental conditions. [1] George G., Ammann M., D'Anna B., Donaldson D. J., Nizkorodov S. A., Heterogeneous photochemistry in the Atmosphere, Chem. Rev., 2015, 115 (10), pp 4218-4258 [2] Weller, C., Horn, S., and Herrmann, H.: Photolysis of Fe(III) carboxylate complexes: Fe(II) quantum yields and reaction mechanisms, Photochemistry and Photobiology A: Chemistry, 268, 24-36, 2013.

Polyaminoquinoline iron chelators for vectorization of antiproliferative agents: design, synthesis, and validation.

PubMed

Corcé, Vincent; Morin, Emmanuelle; Guihéneuf, Solène; Renault, Eric; Renaud, Stéphanie; Cannie, Isabelle; Tripier, Raphaël; Lima, Luís M P; Julienne, Karine; Gouin, Sébastien G; Loréal, Olivier; Deniaud, David; Gaboriau, François

2012-09-19

Iron chelation in tumoral cells has been reported as potentially useful during antitumoral treatment. Our aim was to develop new polyaminoquinoline iron chelators targeting tumoral cells. For this purpose, we designed, synthesized, and evaluated the biological activity of a new generation of iron chelators, which we named Quilamines, based on an 8-hydroxyquinoline (8-HQ) scaffold linked to linear polyamine vectors. These were designed to target tumor cells expressing an overactive polyamine transport system (PTS). A set of Quilamines bearing variable polyamine chains was designed and assessed for their ability to interact with iron. Quilamines were also screened for their cytostatic/cytotoxic effects and their selective uptake by the PTS in the CHO cell line. Our results show that both the 8-HQ moiety and the polyamine part participate in the iron coordination. HQ1-44, the most promising Quilamine identified, presents a homospermidine moiety and was shown to be highly taken up by the PTS and to display an efficient antiproliferative activity that occurred in the micromolar range. In addition, cytotoxicity was only observed at concentrations higher than 100 μM. We also demonstrated the high complexation capacity of HQ1-44 with iron while much weaker complexes were formed with other cations, indicative of a high selectivity. We applied the density functional theory to study the binding energy and the electronic structure of prototypical iron(III)-Quilamine complexes. On the basis of these calculations, Quilamine HQ1-44 is a strong tridentate ligand for iron(III) especially in the form of a 1:2 complex.

Synthesis of thin film containing 4-amino-1,2,4-triazole iron(II) complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Onggo, Djulia, E-mail: djulia@Chem.itb.ac.id

The Iron(II) complex with 4-amino-1,2,4 triazole (NH{sub 2}-trz) ligand has potential applications as smart material since the compounds show a distinct color change from lilac at low temperature to colorless at high temperature. The lilac color of the complex represent the diamagnetic low spin state while the colorless correspond to the paramagnetic high spin state of iron(II). The transition between the two states could be tuned by changing the anionic group. Generally, the complex was synthesized directly from aqueous solution of iron(II) salt with considerable amounts of NH{sub 2}-trz solution produced solid powder compound. For application as an electronic molecularmore » device, the complex should be obtained as a thin film. The transparent [Fe(NH{sub 2}trz){sub 3}]-Nafion film has been successfully obtained, however, no anion variation can be produced since the nafion is an anionic resin. In this work, the [Fe(NH{sub 2}trz){sub 3}]-complexes with several anions have been synthesized inside nata de coco membrane that commonly used as a medium for deposition metal nano-particles. After drying the membrane containing the complex became a thin film. At room temperature, the film containing iron(II) complexes of sulphate and nitrate salts show lilac color, similar to that of the original complexes in the powder form. On heating, the color of the complex film changed to colorless and this color change was observed reversibly. In contrast, the films containing perchlorate and tetrafluoroborate iron(II) complexes are colorless at room temperature and changed to lilac on cooling. The significant color changing of the iron(II)complexes in the nata de coco film can be used for demonstration thermo chromic effect of smart materials with relatively small amount of the compounds.« less

Highly selective biaryl cross-coupling reactions between aryl halides and aryl Grignard reagents: a new catalyst combination of N-heterocyclic carbenes and iron, cobalt, and nickel fluorides.

PubMed

Hatakeyama, Takuji; Hashimoto, Sigma; Ishizuka, Kentaro; Nakamura, Masaharu

2009-08-26

Combinations of N-heterocyclic carbenes (NHCs) and fluoride salts of the iron-group metals (Fe, Co, and Ni) have been shown to be excellent catalysts for the cross-coupling reactions of aryl Grignard reagents (Ar(1)MgBr) with aryl and heteroaryl halides (Ar(2)X) to give unsymmetrical biaryls (Ar(1)-Ar(2)). Iron fluorides in combination with SIPr, a saturated NHC ligand, catalyze the biaryl cross-coupling between various aryl chlorides and aryl Grignard reagents in high yield and high selectivity. On the other hand, cobalt and nickel fluorides in combination with IPr, an unsaturated NHC ligand, exhibit interesting complementary reactivity in the coupling of aryl bromides or iodides; in contrast, with these substrates the iron catalysts show a lower selectivity. The formation of homocoupling byproducts is suppressed markedly to less than 5% in most cases by choosing the appropriate metal fluoride/NHC combination. The present catalyst combinations offer several synthetic advantages over existing methods: practical synthesis of a broad range of unsymmetrical biaryls without the use of palladium catalysts and phosphine ligands. On the basis of stoichiometric control experiments and theoretical studies, the origin of the unique catalytic effect of the fluoride counterion can be ascribed to the formation of a higher-valent heteroleptic metalate [Ar(1)MF(2)]MgBr as the key intermediate in our proposed catalytic cycle. First, stoichiometric control experiments revealed the stark differences in chemical reactivity between the metal fluorides and metal chlorides. Second, DFT calculations indicate that the initial reduction of di- or trivalent metal fluoride in the wake of transmetalation with PhMgCl is energetically unfavorable and that formation of a divalent heteroleptic metalate complex, [PhMF(2)]MgCl (M = Fe, Co, Ni), is dominant in the metal fluoride system. The heteroleptic ate-complex serves as a key reactive intermediate, which undergoes oxidative addition with PhCl and releases the biaryl cross-coupling product Ph-Ph with reasonable energy barriers. The present cross-coupling reaction catalyzed by iron-group metal fluorides and an NHC ligand provides a highly selective and practical method for the synthesis of unsymmetrical biaryls as well as the opportunity to gain new mechanistic insights into the metal-catalyzed cross-coupling reactions.

Synthesis, chemical and biological studies on new Fe(3+)-glycosilated beta-diketo complexes for the treatment of iron deficiency.

PubMed

Arezzini, Beatrice; Ferrali, Marco; Ferrari, Erika; Frassineti, Chiara; Lazzari, Sandra; Marverti, Gaetano; Spagnolo, Ferdinando; Saladini, Monica

2008-11-01

A simple synthetic pathway to obtain glycosilated beta-diketo derivatives is proposed. These compounds show a good iron(III) affinity therefore we may suggest the use of their Fe(3+)-complexes as oral iron supplements in the treatment of anaemia. The glycosilated compounds (6-GlcH, 6-GlcOH and 6-GlcOCH(3)) are characterized by means of spectroscopic (UV, (1)H and (13)C NMR) and potentiometric techniques; they have a good water solubility, are kinetically stable in physiological condition (t(1/2)>100h) and show a low cytotoxicity also in high concentrations (IC(50)>400 microM). They are able to bind Fe(3+) ion in acid condition (pH approximately 2) forming complex species thermodynamically more stable than those of other ligands commonly used in the treatment of iron deficiency. The iron complexes show also a good kinetic stability both in acidic and physiological pH and have a good lypophilicity (logP>-0.7) that suggests an efficient gastrointestinal absorption in view of their possible use in oral therapy. In addition they demonstrate a poor affinity for competitive biological metal ion such as Ca(2+), and in particular 6-GlcOCH(3) is able to inhibit lipid peroxidation.

A Tertiary Carbon–Iron Bond as an Fe I Cl Synthon and the Reductive Alkylation of Diphosphine-Supported Iron(II) Chloride Complexes to Low-Valent Iron

DOE PAGES

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

2016-05-23

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

PubMed

Shul'pin, Georgiy B

2013-09-28

This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2 fragment. This provokes the O-O bond rupture in the hydrogen peroxide molecule as is assumed for the role of Fe(2+) ions in the Fenton system.

Oxoiron(IV) Tetramethylcyclam Complexes with Axial Carboxylate Ligands: Effect of Tethering the Carboxylate on Reactivity.

PubMed

Bigelow, Jennifer O; England, Jason; Klein, Johannes E M N; Farquhar, Erik R; Frisch, Jonathan R; Martinho, Marlène; Mandal, Debasish; Münck, Eckard; Shaik, Sason; Que, Lawrence

2017-03-20

Oxoiron(IV) species are implicated as reactive intermediates in nonheme monoiron oxygenases, often acting as the agent for hydrogen-atom transfer from substrate. A histidine is the most likely ligand trans to the oxo unit in most enzymes characterized thus far but is replaced by a carboxylate in the case of isopenicillin N synthase. As the effect of a trans carboxylate ligand on the properties of the oxoiron(IV) unit has not been systematically studied, we have synthesized and characterized four oxoiron(IV) complexes supported by the tetramethylcyclam (TMC) macrocycle and having a carboxylate ligand trans to the oxo unit. Two complexes have acetate or propionate axial ligands, while the other two have the carboxylate functionality tethered to the macrocyclic ligand framework by one or two methylene units. Interestingly, these four complexes exhibit substrate oxidation rates that differ by more than 100-fold, despite having E p,c values for the reduction of the Fe═O unit that span a range of only 130 mV. Eyring parameters for 1,4-cyclohexadiene oxidation show that reactivity differences originate from differences in activation enthalpy between complexes with tethered carboxylates and those with untethered carboxylates, in agreement with computational results. As noted previously for the initial subset of four complexes, the logarithms of the oxygen atom transfer rates of 11 complexes of the Fe IV (O)TMC(X) series increase linearly with the observed E p,c values, reflecting the electrophilicity of the Fe═O unit. In contrast, no correlation with E p,c values is observed for the corresponding hydrogen atom transfer (HAT) reaction rates; instead, the HAT rates increase as the computed triplet-quintet spin state gap narrows, consistent with Shaik's two-state-reactivity model. In fact, the two complexes with untethered carboxylates are among the most reactive HAT agents in this series, demonstrating that the axial ligand can play a key role in tuning the HAT reactivity in a nonheme iron enzyme active site.

Low- and high-spin iron (II) complexes studied by effective crystal field method combined with molecular mechanics.

PubMed

Darkhovskii, M B; Pletnev, I V; Tchougréeff, A L

2003-11-15

A computational method targeted to Werner-type complexes is developed on the basis of quantum mechanical effective Hamiltonian crystal field (EHCF) methodology (previously proposed for describing electronic structure of transition metal complexes) combined with the Gillespie-Kepert version of molecular mechanics (MM). It is a special version of the hybrid quantum/MM approach. The MM part is responsible for representing the whole molecule, including ligand atoms and metal ion coordination sphere, but leaving out the effects of the d-shell. The quantum mechanical EHCF part is limited to the metal ion d-shell. The method reproduces with reasonable accuracy geometry and spin states of the Fe(II) complexes with monodentate and polydentate aromatic ligands with nitrogen donor atoms. In this setting a single set of MM parameters set is shown to be sufficient for handling all spin states of the complexes under consideration. Copyright 2003 Wiley Periodicals, Inc.

Synthesis and Properties of Ortho-Nitro-Fe Complex

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mishra, A.; Mishra, Niyati; Sharma, R.

2011-07-15

Ortho-Nitro-Fe complex (Transition metal complex) has synthesized by chemical route method and properties of made complex has characterized by X-Ray diffraction (XRD), Moessbauer spectroscopy, Fourier transformation infra-red spectroscopy (FTIR) and X-Ray photoelectron spectroscopy (XPS). XRD analysis shows that sample is crystalline in nature and having particle size in the range of few nano meters. Moessbauer spectroscopy at room temperature shows the oxidation state of Iron (central metal ion) after complaxasion. FTIR spectra of the complex confirms the coordination of metal ion with ligand.

Mechanism of Ferric Oxalate Photolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr

Iron(III) oxalate, Fe 3+(C 2O 4) 3 3–, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2O and H 2O up to 3 ns following photoexcitation. We find that intramolecularmore » electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2(aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.« less

Mechanism of Ferric Oxalate Photolysis

DOE PAGES

Mangiante, David. M.; Schaller, Richard D.; Zarzycki, Piotr; ...

2017-06-08

Iron(III) oxalate, Fe 3+(C 2O 4) 3 3–, is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO 2 is not well understood for any system. Here, we employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D 2O and H 2O up to 3 ns following photoexcitation. We find that intramolecularmore » electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO 2(aq) and a species inferred to be CO 2 •– based on the appearance of a new vibrational absorption band and ab initio simulation. Our work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.« less

Synthetic Models for Nickel–Iron Hydrogenase Featuring Redox-Active Ligands*

PubMed Central

Schilter, David; Gray, Danielle L.; Fuller, Amy L.; Rauchfuss, Thomas B.

2017-01-01

The nickel–iron hydrogenase enzymes efficiently and reversibly interconvert protons, electrons, and dihydrogen. These redox proteins feature iron–sulfur clusters that relay electrons to and from their active sites. Reported here are synthetic models for nickel–iron hydrogenase featuring redox-active auxiliaries that mimic the iron–sulfur cofactors. The complexes prepared are NiII(μ-H)FeIIFeII species of formula [(diphosphine)Ni(dithiolate)(μ-H)Fe(CO)2(ferrocenylphosphine)]+ or NiIIFeIFeII complexes [(diphosphine)Ni(dithiolate)Fe(CO)2(ferrocenylphosphine)]+ (diphosphine = Ph2P(CH2)2PPh2 or Cy2P(CH2)2PCy2; dithiolate = −S(CH2)3S−; ferrocenylphosphine = diphenylphosphinoferrocene, diphenylphosphinomethyl(nonamethylferrocene) or 1,1′-bis(diphenylphosphino)ferrocene). The hydride species is a catalyst for hydrogen evolution, while the latter hydride-free complexes can exist in four redox states – a feature made possible by the incorporation of the ferrocenyl groups. Mixed-valent complexes of 1,1′-bis(diphenylphosphino)ferrocene have one of the phosphine groups unbound, with these species representing advanced structural models with both a redox-active moiety (the ferrocene group) and a potential proton relay (the free phosphine) proximal to a nickel–iron dithiolate. PMID:28819328

Theoretical study of novel complexed structures for methoxy derivatives of scytonemin: potential biomarkers in iron-rich stressed environments.

PubMed

Varnali, Tereza; Edwards, Howell G M

2013-09-01

Scytonemin is a cyanobacterial sheath pigment with potent UV (UVA, UVB, and UVC) absorbing properties. Di- and tetramethoxy derivatives of scytonemin have also been found and described in the literature. The importance of these biomolecules is their photoprotective function, which is one of the major survival strategies adopted by extremophiles in environmentally stressed conditions. Also, iron compounds [particularly iron(III) oxides] offer an additional UV-protecting facility to subsurface endolithic biological colonization; hence, banded iron formations (accompanied by zones of depletion of iron) in rock matrices have attracted attention with special interest in the method of transportation of iron compounds through the rock. Di- and tetramethoxyscytonemin and their iron(III) complexes have been modeled and studied computationally by using density functional theory calculations at the level of B3LYP/6-31G** methodology. We propose new structures that could feature in survival strategy and facilitate the movement of iron through the rock especially for iron-rich stressed terrestrial environments exemplified by the Río Tinto system with the added potential of subsurface Mars exploration. This study represents a continuation of our previous work on scytonemin. The calculated Raman spectra of the proposed iron complexes are compared with those of their parent compounds and discussed in relation to structural changes effected in the parent ligand upon complexation. This information leads to new insights to be gained by experimental Raman spectroscopists and the characterization of spectroscopic biosignatures for the database being compiled for the remote Raman analytical interrogation of the martian surface and subsurface being proposed for the ESA ExoMars mission planned for launch in 2018.

Oxidative degradation stability and hydrogen sulfide removal performance of dual-ligand iron chelate of Fe-EDTA/CA.

PubMed

Miao, Xinmei; Ma, Yiwen; Chen, Zezhi; Gong, Huijuan

2017-09-05

Catalytic oxidation desulfurization using chelated iron catalyst is an effective method to remove H 2 S from various gas streams including biogas. However, the ligand of ethylenediaminetetraacetic acid (EDTA), which is usually adopted to prepare chelated iron catalyst, is liable to be oxidative degraded, and leads to the loss of desulfurization performance. In order to improve the degradation stability of the iron chelate, a series of iron chelates composed of two ligands including citric acid (CA) and EDTA were prepared and the oxidative degradation stability as well as desulfurization performance of these chelated iron catalysts were studied. Results show that the iron chelate of Fe-CA is more stable than Fe-EDTA, while for the desulfurization performance, the situation is converse. For the dual-ligand iron chelates of Fe-EDTA/CA, with the increase of mol ratio of CA to EDTA in the iron chelate solution, the oxidative degradation stability increased while the desulfurization performance decreased. The results of this work showed that Fe-EDTA/CA with a mol ratio of CA:EDTA = 1:1 presents a relative high oxidative degradation stability and an acceptable desulfurization performance with over 90% of H 2 S removal efficiency.

Ligand-Centered Electron-Transfer Redox Processes for Manganese, Iron, and Cobalt Complexes in Relation to Selected Catalytic Systems

DTIC Science & Technology

1989-05-01

of Fe(acac)3 exhibits oxidation features common to acac- and its complexes. Table VIH (b) summarizes the EI/ 2 values for the oxidations of a number of...Data supplied by Dr. Pablo Cofr6 of the Universidad Cat6lica de Chile . 141. Chin, D.-H.; Chiericato, G., Jr.; Nanni, E. J., Jr.; Sawyer, D. T. 1. Am

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cances, Benjamin; Benedetti, Marc; Farges, Francois

2007-02-02

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxy-hydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au LIII-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl)4), with dominantly OH ligands atmore » pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution - MUlti SIte Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

Adsorption Mechanisms of Trivalent Gold onto Iron Oxy-Hydroxides: From the Molecular Scale to the Model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cances, Benjamin; /Marne La Vallee U.; Benedetti, Marc

2006-12-13

Gold is a highly valuable metal that can concentrate in iron-rich exogenetic horizons such as laterites. An improved knowledge of the retention mechanisms of gold onto highly reactive soil components such as iron oxyhydroxides is therefore needed to better understand and predict the geochemical behavior of this element. In this study, we use EXAFS information and titration experiments to provide a realistic thermochemical description of the sorption of trivalent gold onto iron oxy-hydroxides. Analysis of Au L{sub III}-edge XAFS spectra shows that aqueous Au(III) adsorbs from chloride solutions onto goethite surfaces as inner-sphere square-planar complexes (Au(III)(OH,Cl){sub 4}), with dominantly OHmore » ligands at pH > 6 and mixed OH/Cl ligands at lower pH values. In combination with these spectroscopic results, Reverse Monte Carlo simulations were used to constraint the possible sorption sites on the surface of goethite. Based on this structural information, we calculated sorption isotherms of Au(III) on Fe oxy-hydroxides surfaces, using the CD-MUSIC (Charge Distribution--Multi Site Complexation) model. The various Au(III)-sorbed species were identified as a function of pH, and the results of these EXAFS+CD-MUSIC models are compared with titration experiments. The overall good agreement between the predicted and measured structural models shows the potential of this combined approach to better model sorption processes of transition elements onto highly reactive solid surfaces such as goethite and ferrihydrite.« less

Acenaphthenequinone thiosemicarbazone and its transition metal complexes: synthesis, structure, and biological activity.

PubMed

Rodriguez-Argüelles, M C; Belicchi Ferrari, M; Gasparri Fava, G; Pelizzi, C; Pelosi, G; Albertini, R; Bonati, A; Dall'Aglio, P P; Lunghi, P; Pinelli, S

1997-04-01

The reaction of iron, nickel, copper, and zinc chlorides or acetates with acenaphthenequinone thiosemicarbazone, Haqtsc leads to the formation of novel complexes that have been characterized by spectroscopic studies (NMR, IR) and biological properties. The crystal structures of the free ligand Haqtsc 1 and of the compound [Ni(aqtsc)2].DMF 2, have also been determined by X-ray methods from diffractometer data. In 1, the conformation of the two nonequivalent molecules is governed by intramolecular hydrogen bonds, while an intermolecular hydrogen bond is responsible for dimer-like groups formation. In 2, the coordination geometry about nickel is distorted octahedral, and the two ligand molecules are terdentate monodeprotonated. Biological studies have shown that, for the first time at least up the used doses, a free ligand is active both in the inhibition of cell proliferation and in the induced differentiation on Friend erythroleukemia cells (FLC).

Siderophores in Cloud Waters and Potential Impact on Atmospheric Chemistry: Photoreactivity of Iron Complexes under Sun-Simulated Conditions.

PubMed

Passananti, Monica; Vinatier, Virginie; Delort, Anne-Marie; Mailhot, Gilles; Brigante, Marcello

2016-09-06

In the present work, the photoreactivity of a mixture of iron(III)–pyoverdin (Fe(III)–Pyo) complexes was investigated under simulated cloud conditions. Pyoverdins are expected to complex ferric ions naturally present in cloudwater, thus modifying their availability and photoreactivity. The spectroscopic properties and photoreactivity of Fe(III)-Pyo were investigated, with particular attention to their fate under solar irradiation, also studied through simulations. The photolysis of the Fe(III)–Pyo complex leads to the generation of Fe(II), with rates of formation (RFe(II)f) of 6.98 and 3.96 × 10–9 M s–1 at pH 4.0 and 6.0, respectively. Interestingly, acetate formation was observed during the iron-complex photolysis, suggesting that fragmentation can occur after the ligand-to-metal charge transfer (LMCT) via a complex reaction mechanism. Moreover, photogenerated Fe(II) represent an important source of hydroxyl radical via the Fenton reaction in cloudwater. This reactivity might be relevant for the estimation of the rates of formation and steady-state concentrations of the hydroxyl radical by cloud chemistry models and for organic matter speciation in the cloud aqueous phase. In fact, the conventional models, which describe the iron photoreactivity in terms of iron–aqua and oxalate complexes, are not in accordance with our results.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

NASA Astrophysics Data System (ADS)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Reactivity of food phenols with iron and copper ions: binding, dioxygen activation and oxidation mechanisms.

PubMed

Nkhili, Ezzohra; Loonis, Michèle; Mihai, Simona; El Hajji, Hakima; Dangles, Olivier

2014-06-01

In this work, the affinity of common dietary phenols (gallic acid, caffeic acid, catechin, and rutin) for iron and copper ions was quantitatively investigated in neutral phosphate buffer as well as the reactivity of the complexes toward dioxygen. Contrasting behaviors were observed: because of the competing phosphate ions, Fe(III) binding is much slower than Fe(II) binding, which is rapidly followed by autoxidation of Fe(II) into Fe(III). With both ions, O2 consumption and H2O2 production are modest and the phenolic ligands are only slowly oxidized. By contrast, metal-phenol binding is fast with both Cu(I) and Cu(II). With Cu(I), O2 consumption and H2O2 production are very significant and the phenolic ligands are rapidly oxidized into a complex mixture of oligomers. The corresponding mechanism with Cu(II) is hampered by the preliminary rate-determining step of Cu(II) reduction by the phenols. The consequences of these findings for the stability and antioxidant activity of plant phenols are discussed.

Neutral and anionic duality of 1,2,4-triazole α-amino acid scaffold in 1D coordination polymers

NASA Astrophysics Data System (ADS)

Naik, Anil D.; Dîrtu, Marinela M.; Garcia, Yann

2012-03-01

A tiny supramolecular synthon, 4H-1,2,4-triazol-4-yl acetic acid (HGlytrz) which is bifunctional by design having an electronic asymmetry and conformational flexibility has been introduced to synthesize iron(II) complexes. Having 1,2,4-triazole or carboxylic extremities on the same framework HGlytrz could display dual functionality by acting as a neutral as well as anionic ligand based on the possibility of deprotonation of carboxylic group. Four new iron(II) HGlytrz complexes with ClO4- ( 1), NO3- ( 2), BF4- ( 3) and CF3SO3- ( 4) anions were prepared. Formulation of their composition which is complicated due to ligand deprotonation is discussed. Unlike its ester protected counterpart ethyl-4H-1,2,4-triazol-4-yl-acetate ( αGlytrz) which show hysteretic room temperature spin crossover, 1- 4 remain in the high-spin state as revealed by 57Mössbauer spectroscopy. Prospects of such 1D coordination polymers with dangling unbounded carboxylic entities in the realm of self-assembled monolayer (SAM) are discussed.

Iron piano-stool complexes containing NHC ligands outfitted with pendent arms: synthesis, characterization, and screening for catalytic transfer hydrogenation

Treesearch

Parthapratim Das; Thomas Elder; William W. Brennessel; Stephen C. Chmely

2016-01-01

Catalysis is a fundamental technology that is widely used in the food, petrochemical, pharmaceutical, and agricultural sectors to produce chemical products on an industrial scale. Well-defined molecular organometallic species are a cornerstone of catalytic methodology, and the activity and selectivity of these complexes can be modulated by judicious choice of metal and...

Two zinc(II) coordination complexes based on an asymmetric multidentate ligand: syntheses, structures, selective fluorescence sensing of iron(III) ions and thermal analyses.

PubMed

Liu, Yaru; Liu, Lan; Zhang, Xiao; Liang, Guorui; Gong, Xuebing

2018-01-01

The rational selection of ligands is vitally important in the construction of coordination complexes. Two novel Zn II complexes, namely bis(acetato-κO)bis[1-(1H-benzotriazol-1-ylmethyl)-2-propyl-1H-imidazole-κN 3 ]zinc(II) monohydrate, [Zn(C 13 H 15 N 5 ) 2 (C 2 H 3 O 2 ) 2 ]·H 2 O, (1), and bis(azido-κN 1 )bis[1-(1H-benzotriazol-1-ylmethyl)-2-propyl-1H-imidazole-κN 3 ]zinc(II), [Zn(C 13 H 15 N 5 ) 2 (N 3 ) 2 ], (2), constructed from the asymmetric multidentate imidazole ligand, have been synthesized under mild conditions and characterized by elemental analyses, IR spectroscopy and single-crystal X-ray diffraction analysis. Both complexes exhibit a three-dimensional supramolecular network directed by different intermolecular interactions between discrete mononuclear units. The complexes were also investigated by fluorescence and thermal analyses. The experimental results show that (1) is a promising fluorescence sensor for detecting Fe 3+ ions and (2) is effective as an accelerator of the thermal decomposition of ammonium perchlorate.

Synthesis, spectroscopic, molecular orbital calculation, cytotoxic, molecular docking of DNA binding and DNA cleavage studies of transition metal complexes with N-benzylidene-N'-salicylidene-1,1-diaminopropane

NASA Astrophysics Data System (ADS)

Al-Mogren, Muneerah M.; Alaghaz, Abdel-Nasser M. A.; Elbohy, Salwa A. H.

2013-10-01

Eight mononuclear chromium(III), manganese(II), iron(III), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes of Schiff's base ligand were synthesized and determined by different physical techniques. The complexes are insoluble in common organic solvents but soluble in DMF and DMSO. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytic in nature. All the eight metal complexes have been fully characterized with the help of elemental analyses, molecular weights, molar conductance values, magnetic moments and spectroscopic data. The analytical data helped to elucidate the structure of the metal complexes. The Schiff base is found to act as tridentate ligand using N2O donor set of atoms leading to an octahedral geometry for the complexes around all the metal ions. Quantum chemical calculations were performed with semi-empirical method to find the optimum geometry of the ligand and its complexes. Additionally in silico, the docking studies and the calculated pharmacokinetic parameters show promising futures for application of the ligand and complexes as high potency agents for DNA binding activity. The interaction of the complexes with calf thymus DNA (CT-DNA) has been investigated by UV absorption method, and the mode of CT-DNA binding to the complexes has been explored. Furthermore, the DNA cleavage activity by the complexes was performed. The Schiff base and their complexes have been screened for their antibacterial activity against bacterial strains [Staphylococcus aureus (RCMB010027), Staphylococcus epidermidis (RCMB010024), Bacillis subtilis (RCMB010063), Proteous vulgaris (RCMB 010085), Klebsiella pneumonia (RCMB 010093) and Shigella flexneri (RCMB 0100542)] and fungi [(Aspergillus fumigates (RCMB 02564), Aspergillus clavatus (RCMB 02593) and Candida albicans (RCMB05035)] by disk diffusion method. All the metal complexes have potent biocidal activity than the free ligand.

CW EPR parameters reveal cytochrome P450 ligand binding modes.

PubMed

Lockart, Molly M; Rodriguez, Carlo A; Atkins, William M; Bowman, Michael K

2018-06-01

Cytochrome P450 (CYP) monoxygenses utilize heme cofactors to catalyze oxidation reactions. They play a critical role in metabolism of many classes of drugs, are an attractive target for drug development, and mediate several prominent drug interactions. Many substrates and inhibitors alter the spin state of the ferric heme by displacing the heme's axial water ligand in the resting enzyme to yield a five-coordinate iron complex, or they replace the axial water to yield a nitrogen-ligated six-coordinate iron complex, which are traditionally assigned by UV-vis spectroscopy. However, crystal structures and recent pulsed electron paramagnetic resonance (EPR) studies find a few cases where molecules hydrogen bond to the axial water. The water-bridged drug-H 2 O-heme has UV-vis spectra similar to nitrogen-ligated, six-coordinate complexes, but are closer to "reverse type I" complexes described in older liteature. Here, pulsed and continuous wave (CW) EPR demonstrate that water-bridged complexes are remarkably common among a range of nitrogenous drugs or drug fragments that bind to CYP3A4 or CYP2C9. Principal component analysis reveals a distinct clustering of CW EPR spectral parameters for water-bridged complexes. CW EPR reveals heterogeneous mixtures of ligated states, including multiple directly-coordinated complexes and water-bridged complexes. These results suggest that water-bridged complexes are under-represented in CYP structural databases and can have energies similar to other ligation modes. The data indicates that water-bridged binding modes can be identified and distinguished from directly-coordinated binding by CW EPR. Copyright © 2018 Elsevier Inc. All rights reserved.

Dinitrosyl iron complexes and S-nitrosothiols are two possible forms for stabilization and transport of nitric oxide in biological systems.

PubMed

Vanin, A F

1998-07-01

The physicochemical properties, mechanisms of synthesis and decomposition of dinitrosyl iron complexes (DNICs) with thiol-containing ligands and of S-nitrosothiols (RS-NO), and the potential role of these compounds in storage and transport of NO in biological systems are reviewed. Special attention is given to the phenomenon of mutual transformation of DNIC and RS-NO catalyzed by Fe2+. Each Fe2+ binds two neutral NO molecules in the DNICs, catalyzes their mutual oxidation--reduction with formation of nitrous oxide and nitrosonium ions appearing in the DNICs. These ions S-nitrosate thiol-compounds with RS-NO formation. Fe2+ binds two RS-NO molecules and catalyzes their mutual oxidation--reduction followed by decomposition of the resulting molecules. Mutual conversion of DNICs and RS-NO regulated by iron, thiol, and NO levels is suggested to provide NO transport in cells and tissues.

1H NMR study of the effect of variable ligand on heme oxygenase electronic and molecular structure

PubMed Central

Ma, Li-Hua; Liu, Yangzhong; Zhang, Xuhong; Yoshida, Tadashi; La Mar, Gerd N.

2009-01-01

Heme oxygenase carries out stereospecific catabolism of protohemin to yield iron, CO and biliverdin. Instability of the physiological oxy complex has necessitated the use of model ligands, of which cyanide and azide are amenable to solution NMR characterization. Since cyanide and azide are contrasting models for bound oxygen, it is of interest to characterize differences in their molecular and/or electronic structures. We report on detailed 2D NMR comparison of the azide and cyanide substrate complexes of heme oxygenase from Neisseria meningitidis, which reveals significant and widespread differences in chemical shifts between the two complexes. To differentiate molecular from electronic structural changes between the two complexes, the anisotropy and orientation of the paramagnetic susceptibility tensor were determined for the azide complex for comparison with those for the cyanide complex. Comparison of the predicted and observed dipolar shifts reveals that shift differences are strongly dominated by differences in electronic structure and do not provide any evidence for detectable differences in molecular structure or hydrogen bonding except in the immediate vicinity of the distal ligand. The readily cleaved C-terminus interacts with the active site and saturation-transfer allows difficult heme assignments in the high-spin aquo complex. PMID:18976815

Ribonucleotide reductase inhibition by metal complexes of Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone): A combined experimental and theoretical study

PubMed Central

Popović-Bijelić, Ana; Kowol, Christian R.; Lind, Maria E.S.; Luo, Jinghui; Himo, Fahmi; Enyedy, Éva A.; Arion, Vladimir B.; Gräslund, Astrid

2012-01-01

Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone, 3-AP) is currently the most promising chemotherapeutic compound among the class of α-N-heterocyclic thiosemicarbazones. Here we report further insights into the mechanism(s) of anticancer drug activity and inhibition of mouse ribonucleotide reductase (RNR) by Triapine. In addition to the metal-free ligand, its iron(III), gallium(III), zinc(II) and copper (II) complexes were studied, aiming to correlate their cytotoxic activities with their effects on the diferric/tyrosyl radical center of the RNR enzyme in vitro. In this study we propose for the first time a potential specific binding pocket for Triapine on the surface of the mouse R2 RNR protein. In our mechanistic model, interaction with Triapine results in the labilization of the diferric center in the R2 protein. Subsequently the Triapine molecules act as iron chelators. In the absence of external reductants, and in presence of the mouse R2 RNR protein, catalytic amounts of the iron(III)–Triapine are reduced to the iron(II)–Triapine complex. In the presence of an external reductant (dithiothreitol), stoichiometric amounts of the potently reactive iron (II)–Triapine complex are formed. Formation of the iron(II)–Triapine complex, as the essential part of the reaction outcome, promotes further reactions with molecular oxygen, which give rise to reactive oxygen species (ROS) and thereby damage the RNR enzyme. Triapine affects the diferric center of the mouse R2 protein and, unlike hydroxyurea, is not a potent reductant, not likely to act directly on the tyrosyl radical. PMID:21955844

Structure of the Ni(II) complex of Escherichia coli peptide deformylase and suggestions on deformylase activities depending on different metal(II) centres.

PubMed

Yen, Ngo Thi Hai; Bogdanović, Xenia; Palm, Gottfried J; Kühl, Olaf; Hinrichs, Winfried

2010-02-01

Crystal structures of polypeptide deformylase (PDF) of Escherichia coli with nickel(II) replacing the native iron(II) have been solved with chloride and formate as metal ligands. The chloro complex is a model for the correct protonation state of the hydrolytic hydroxo ligand and the protonated status of the Glu133 side chain as part of the hydrolytic mechanism. The ambiguity that recently some PDFs have been identified with Zn(2+) ion as the active-site centre whereas others are only active with Fe(2+) (or Co(2+), Ni(2+) is discussed with respect to Lewis acid criteria of the metal ion and substrate activation by the CD loop.

Manganese(II), iron(II), cobalt(II), and copper(II) complexes of an extended inherently chiral tris-bipyridyl cage.

PubMed

Perkins, David F; Lindoy, Leonard F; McAuley, Alexander; Meehan, George V; Turner, Peter

2006-01-17

Manganese(II), iron(II), cobalt(II), and copper(II) derivatives of two inherently chiral, Tris(bipyridyl) cages (L and L') of type [ML]-(PF(6))(2)(solvent)(n) and [FeL'](ClO(4))(2) are reported, where L is the hexa-tertiary butyl-substituted derivative of L'. These products were obtained by using the free cage and metal template procedures; the latter involved the reductive amination of the respective Tris-dialdehyde precursor complexes of iron(II), cobalt(II), or nickel(II). Electrochemical, EPR, and NMR studies have been used to probe the nature of the individual complexes. X-ray structures of the manganese(II), iron(II), and copper(II) complexes of L and the iron(II) complex of L' are presented; these are compared with the previously reported structures of the corresponding nickel(II) complex and metal-free cage (L). In each complex the metal cation occupies the cage's central cavity and is coordinated to six nitrogens from the three bipyridyl groups. The cations [MnL](2+) and [FeL](2+) are isostructural but both exhibit a different arrangement of the bound cage to that observed in the corresponding nickel(II) and copper(II) complexes. The latter have an exo-exo arrangement of the bridgehead nitrogen lone pairs, with the metal inducing a triple helical twist that extends approximately 22 A along the axial length of each complex. In contrast, [MnL](2+) and [FeL](2+) have their terminal nitrogen lone pairs directed endo, causing a significant change in the configuration of the bound ligand. In [FeL'](2+), the cage has both bridgehead nitrogen lone pairs orientated exo. Semiempirical calculations indicate that the observed endo-endo and exo-exo arrangements are of comparable energy.

The synthesis of PNP-supported low-spin nitro manganese(I) carbonyl complexes

DOE PAGES

Tondreau, Aaron M.; Boncella, James M.

2016-09-01

In this study, the coordination chemistry of Mn(CO) 5Br was investigated with a series of PNP-pincer ligands. The ligands iPrPONOP ( iPrPONOP = 2,6-bis(diisopropylphosphinito)pyridine) and iPrPN HP ( iPrPN HP = HN{CH 2CH 2(PiPr 2)} 2) gave the desired organometallic manganese complexes ( iPrPONOP)Mn(CO) 2Br and ( iPrPN HP)Mn(CO) 2Br, respectively, upon chelation to Mn(CO) 5Br. The reactivity of iPrPNNNP ( iPrPNNNP = N,N'-bis(diisopropylphosphino)-2,6-diaminopyridine) with Mn(CO) 5Br yielded a pair of products, [( iPrPNNNP)Mn(CO) 3][Br] and ( iPrPNNNCO)Mn(CO) 3. The formation of the asymmetric chelate arises from a formal loss of iPr 2PBr and C–N bond formation from a carbonylmore » ligand and NH, yielding a Mn(I) amide core. The nitration reactions of ( iPrPONOP)Mn(CO) 2Br and ( iPrPN HP)Mn(CO) 2Br were carried out using silver nitrite, yielding the nitro compounds ( iPrPONOP)Mn(CO) 2(NO 2) and ( iPrPN HP)Mn(CO) 2(NO 2), respectively. The analogous iron complex ( iPrPONOP)Fe(CO)Cl 2 was nitrated under the same conditions to yield the salt pair [( iPrPONOP)Fe(CO) 2][FeCl 3NO]. This reactivity underlines the difference between iso-valent iron and manganese centers. The manganese complexes ( iPrPONOP)Mn(CO) 2(NO 2) and ( iPrPN HP)Mn(CO) 2(NO 2) were ineffective as oxygen atom transfer reagents for a variety of substrates.« less

Synthesis, structural, optical band gap and biological studies on iron (III), nickel (II), zinc (II) and mercury (II) complexes of benzyl α-monoxime pyridyl thiosemicarbazone

NASA Astrophysics Data System (ADS)

Bedier, R. A.; Yousef, T. A.; Abu El-Reash, G. M.; El-Gammal, O. A.

2017-07-01

New ligand, (E)-2-((E)-2-(hydroxyimino)-1,2-diphenylethylidene)-N-(pyridin-2 yl) hydrazinecarbothioamide (H2DPPT) and its complexes [Fe(DPPT)Cl(H2O)], [Ni(H2DPPT)2Cl2], [Zn(HDPPT)(OAc)] and [Hg(HDPPT)Cl](H2O)4 were isolated and characterized by various of physico-chemical techniques. IR spectra show that H2DPPT coordinates to the metal ions as neutral NN bidentate, mononegative NNS tridentate and binegative NNSN tetradentate, respectively. From the modeling studies, the bond length, bond angle, HOMO, LUMO and dipole moment had been calculated to confirm the geometry of the ligands and their investigated complexes. The thermal studies showed the type of water molecules involved in metal complexes Furthermore, the kinetic and thermodynamic parameters for the different decomposition steps were calculated using the Coats-Redfern and Horowitz-Metzger methods. Also, the optical band gap (Eg) has been calculated to elucidate the conductivity of the isolated complexes. The optical transition energy (Eg) is direct and equals 3.34 and 3.44 ev for Ni and Fe complexes, respectively. The ligand and their metal complexes were screened for antibacterial activity against the following bacterial species, Bacillus thuringiensis, Staphylococcus aureus, Pseudomonas aeuroginosa and Escherichia coli. The results revealed that the metal complexes have more potent antibacterial compared with the ligand. Also, the degradation effect of the investigated compounds was tested showing that, Ni complex exhibited powerful and complete degradation effect on DNA.

Oxoiron(IV) complexes as synthons for the assembly of heterobimetallic centers such as the Fe/Mn active site of Class Ic ribonucleotide reductases.

PubMed

Zhou, Ang; Crossland, Patrick M; Draksharapu, Apparao; Jasniewski, Andrew J; Kleespies, Scott T; Que, Lawrence

2018-01-01

Nonheme oxoiron(IV) complexes can serve as synthons for generating heterobimetallic oxo-bridged dimetal complexes by reaction with divalent metal complexes. The formation of Fe III -O-Cr III and Fe III -O-Mn III complexes is described herein. The latter complexes may serve as models for the Fe III -X-Mn III active sites of an emerging class of Fe/Mn enzymes represented by the Class 1c ribonucleotide reductase from Chlamydia trachomatis and the R2-like ligand-binding oxidase (R2lox) found in Mycobacterium tuberculosis. These synthetic complexes have been characterized by UV-Vis, resonance Raman, and X-ray absorption spectroscopy, as well as electrospray mass spectrometry. The Fe III -O-Cr III complexes exhibit a three-band UV-Vis pattern that differs from the simpler features associated with Fe III -O-Fe III complexes. The positions of these features are modulated by the nature of the supporting polydentate ligand on the iron center, and their bands intensify dramatically in two examples upon the binding of an axial cyanate or thiocyanate ligand trans to the oxo bridge. In contrast, the Fe III -O-Mn III complexes resemble Fe III -O-Fe III complexes more closely. Resonance Raman characterization of the Fe III -O-M III complexes reveals an 18 O-sensitive vibration in the range of 760-890 cm -1 . This feature has been assigned to the asymmetric Fe III -O-M III stretching mode and correlates reasonably with the Fe-O bond distance determined by EXAFS analysis. The likely binding of an acetate as a bridging ligand to the Fe III -O-Mn III complex 12 lays the foundation for further efforts to model the heterobimetallic active sites of Fe/Mn enzymes.

Ligand-controlled Fe mobilization catalyzed by adsorbed Fe(II) on Fe(hydr)oxides

NASA Astrophysics Data System (ADS)

Kang, Kyounglim; Biswakarma, Jagannath; Borowski, Susan C.; Hug, Stephan J.; Hering, Janet G.; Schenkeveld, Walter D. C.; Kraemer, Stephan M.

2017-04-01

Dissolution of Fe(hydr)oxides is a key process in biological iron acquisition. Due to the low solubility of iron oxides in environments with a circumneutral pH, organisms may exude organic compounds catalyzing iron mobilization by reductive and ligand controlled dissolution mechanisms. Recently, we have shown synergistic effects between reductive dissolution and ligand-controlled dissolution that may operate in biological iron acquisition. The synergistic effects were observed in Fe mobilization from single goethite suspensions as well as in suspensions containing calcareous soil[1],[2]. However, how the redox reaction accelerates Fe(hydr)oxide dissolution by ligands is not studied intensively. In our study, we hypothesized that electron transfer to structural Fe(III) labilizes the Fe(hydr)oxide structure, and that this can accelerate ligand controlled dissolution. Systematical batch dissolution experiments were carried out under anoxic conditions at environmentally relevant pH values in which various Fe(hydr)oxides (goethite, hematite, lepidocrocite) interacted with two different types of ligand (desferrioxamine B (DFOB) and N,N'-Di(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid monohydrochloride (HBED)). Electron transfer to the structure was induced by adsorbing Fe(II) to the mineral surface at various Fe(II) concentrations. Our results show a distinct catalytic effect of adsorbed Fe(II) on ligand controlled dissolution, even at submicromolar Fe(II) concentrations. We observed the effect for a range of iron oxides, but it was strongest in lepidocrocite, most likely due to anisotropy in conductivity leading to higher near-surface concentration of reduced iron. Our results demonstrate that the catalytic effect of reductive processes on ligand controlled dissolution require a very low degree of reduction making this an efficient process for biological iron acquisition and a potentially important effect in natural iron cycling. References 1. Wang, Z. M.; Schenkeveld, W. D. C.; Kraemer, S. M.; Giammar, D. E. Environ. Sci. Technol. 2015, 49, (12), 7236-7244. 2. Schenkeveld, W. D. C.; Wang, Z. M.; Giammar, D. E.; Kraemer, S. M. Environ. Sci. Technol. 2016, 50, (12), 6381-6388.

Nitrate-to-nitrite-to-nitric oxide conversion modulated by nitrate-containing {Fe(NO)2}9 dinitrosyl iron complex (DNIC).

PubMed

Tsai, Fu-Te; Lee, Yu-Ching; Chiang, Ming-Hsi; Liaw, Wen-Feng

2013-01-07

Nitrosylation of high-spin [Fe(κ(2)-O(2)NO)(4)](2-) (1) yields {Fe(NO)}(7) mononitrosyl iron complex (MNIC) [(κ(2)-O(2)NO)(κ(1)-ONO(2))(3)Fe(NO)](2-) (2) displaying an S = 3/2 axial electron paramagnetic resonance (EPR) spectrum (g(⊥) = 3.988 and g(∥) = 2.000). The thermally unstable nitrate-containing {Fe(NO)(2)}(9) dinitrosyl iron complex (DNIC) [(κ(1)-ONO(2))(2)Fe(NO)(2)](-) (3) was exclusively obtained from reaction of HNO(3) and [(OAc)(2)Fe(NO)(2)](-) and was characterized by IR, UV-vis, EPR, superconducting quantum interference device (SQUID), X-ray absorption spectroscopy (XAS), and single-crystal X-ray diffraction (XRD). In contrast to {Fe(NO)(2)}(9) DNIC [(ONO)(2)Fe(NO)(2)](-) constructed by two monodentate O-bound nitrito ligands, the weak interaction between Fe(1) and the distal oxygens O(5)/O(7) of nitrato-coordinated ligands (Fe(1)···O(5) and Fe(1)···O(7) distances of 2.582(2) and 2.583(2) Å, respectively) may play important roles in stabilizing DNIC 3. Transformation of nitrate-containing DNIC 3 into N-bound nitro {Fe(NO)}(6) [(NO)(κ(1)-NO(2))Fe(S(2)CNEt(2))(2)] (7) triggered by bis(diethylthiocarbamoyl) disulfide ((S(2)CNEt(2))(2)) implicates that nitrate-to-nitrite conversion may occur via the intramolecular association of the coordinated nitrate and the adjacent polarized NO-coordinate ligand (nitrosonium) of the proposed {Fe(NO)(2)}(7) intermediate [(NO)(2)(κ(1)-ONO(2))Fe(S(2)CNEt(2))(2)] (A) yielding {Fe(NO)}(7) [(NO)Fe(S(2)CNEt(2))(2)] (6) along with the release of N(2)O(4) (·NO(2)) and the subsequent binding of ·NO(2) to complex 6. The N-bound nitro {Fe(NO)}(6) complex 7 undergoes Me(2)S-promoted O-atom transfer facilitated by imidazole to give {Fe(NO)}(7) complex 6 accompanied by release of nitric oxide. This result demonstrates that nitrate-containing DNIC 3 acts as an active center to modulate nitrate-to-nitrite-to-nitric oxide conversion.

Electrochemistry of 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene ligands: free phosphines, metal complexes, and chalcogenides.

PubMed

Mandell, Chelsea L; Kleinbach, Shannon S; Dougherty, William G; Kassel, W Scott; Nataro, Chip

2010-10-18

The oxidative electrochemistries of a series of chiral bisphosphinoferrocene ligands, 1,1'-bis(2,4-dialkylphosphetanyl)ferrocene (FerroTANE) and 1,1'-bis(2,5-dialkylphospholanyl)ferrocene (FerroLANE), were examined. The reversibility of the oxidation is sensitive to the steric bulk of the alkyl groups. New transition metal compounds and phosphine chalcogenides of these ligands were prepared and characterized. X-ray crystal structures of 10 of these compounds are reported. The percent buried volume (%V(bur)) is a recently developed measurement based on crystallographic data that examines the steric bulk of N-heterocyclic carbene and phosphine ligands. The %V(bur) for the FerroTANE and FerroLANE structures with methyl or ethyl substituents suggests these ligands are similar in steric properties to 1,1'-bis(diphenylphosphino)ferrocene (dppf). In addition the %V(bur) has been found to correlate well with the Tolman cone angle for phosphine chalcogenides. The oxidative electrochemistries of the transition metal complexes occur at more positive potentials than the free ligands. While a similar positive shift is seen for the oxidative electrochemistries of the phosphine chalcogenides, the oxidation of the phosphine selenides does not occur at the iron center, but rather oxidation occurs at the selenium atoms.

Synthesis and Ligand Non-Innocence of Thiolate-Ligated (N4S) Iron(II) and Nickel(II) Bis(imino)pyridine Complexes

PubMed Central

Widger, Leland R.; Jiang, Yunbo; Siegler, Maxime; Kumar, Devesh; Latifi, Reza; de Visser, Sam P.; Jameson, Guy N.L.; Goldberg, David P.

2013-01-01

The known iron(II) complex [FeII(LN3S)(OTf)] (1) was used as starting material to prepare the new biomimetic (N4S(thiolate)) iron(II) complexes [FeII(LN3S)(py)](OTf) (2) and [FeII(LN3S)(DMAP)](OTf) (3), where LN3S is a tetradentate bis(imino)pyridine (BIP) derivative with a covalently tethered phenylthiolate donor. These complexes were characterized by X-ray crystallography, UV-vis, 1H NMR, and Mössbauer spectroscopy, as well as electrochemistry. A nickel(II) analogue, [NiII(LN3S)](BF4) (5), was also synthesized and characterized by structural and spectroscopic methods. Cyclic voltammetric studies showed 1 – 3 and 5 undergo a single reduction process with E1/2 between −0.9 to −1.2 V versus Fc+/Fc. Treatment of 3 with 0.5% Na/Hg amalgam gave the mono-reduced complex [Fe(LN3S)(DMAP)]0 (4), which was characterized by X-ray crystallography, UV-vis, EPR (g = [2.155, 2.057, 2.038]) and Mössbauer (δ = 0.33 mm s−1; ΔEQ = 2.04 mm s−1) spectroscopies. Computational methods (DFT) were employed to model complexes 3 – 5. The combined experimental and computational studies show that 1 – 3 are 5-coordinate, high-spin (S = 2) FeII complexes, whereas 4 is best described as a 5-coordinate, intermediate-spin (S = 1) FeII complex antiferromagnetically coupled to a ligand radical. This unique electronic configuration leads to an overall doublet spin (Stotal = ½) ground state. Complexes 2 and 3 are shown to react with O2 to give S-oxygenated products, as previously reported for 1. In contrast, the mono-reduced 4 appears to react with O2 to give a mixture of S- and Fe-oxygenates. The nickel(II) complex 5 does not react with O2, and even when the mono-reduced nickel complex is produced, it appears to undergo only outer-sphere oxidation with O2. PMID:23992096

Relevance of peat-draining rivers for the riverine input of dissolved iron into the ocean.

PubMed

Krachler, Regina; Krachler, Rudolf F; von der Kammer, Frank; Süphandag, Altan; Jirsa, Franz; Ayromlou, Shahram; Hofmann, Thilo; Keppler, Bernhard K

2010-05-01

Peat bogs have the ability to produce strong chelate ligands (humic and fulvic acids) which enhance the weathering rates of iron-silicate minerals and greatly increase the solubility of the essential trace metal iron in river water. Fluvial networks link peat bogs with the ocean, and thus terrestrial-derived fulvic-iron complexes fuel the ocean's biological productivity and biological carbon pump, but understanding this role is constrained by inconsistent observations regarding the behaviour of riverine iron in the estuarine mixing zone, where precipitation reactions remove iron from the water column. We applied a characterization of the colloidal iron carriers in peatland-draining rivers in North Scotland, using field-flow fractionation (FFF), in combination with end-member mixing experiments of river water sampled near the river mouth and coastal seawater using a (59)Fe radiotracer method. According to our results, the investigated river contributed "truly dissolved" Fe concentrations of about 3300nmolL(-1) to the ocean which is nearly two orders of magnitude higher than the dissolved iron contribution of the "average world" river ( approximately 40nmolL(-1)). Thus we conclude that peatland-draining rivers are important sources of dissolved iron to the ocean margins. We propose highly electrostatic and sterical stabilized iron-organic matter complexes in the size range of <2kDa to be responsible for iron transport across the estuarine mixing zone. Copyright 2010 Elsevier B.V. All rights reserved.

Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

PubMed

Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui

2016-03-23

C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

Homoleptic 2,2'-bipyridine metalates(-I) of iron and cobalt, one cocrystallized with an anthracene radical anion and the other with neutral anthracene.

PubMed

Brennessel, William W; Ellis, John E

2014-08-01

Homoleptic 2,2'-bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2'-bipyridine)ferrate(-I) anthracene(-I), [K(C18H36N2O6)]2[Fe(C10H8N2)3](C14H10), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2'-bipyridine)cobaltate(-I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C18H36N2O6)][Co(C10H8N2)2]·0.5C14H10·2C4H8O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry-related bipy ligands such that aromatic donor-acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined component mass ratio of 0.412 (4):0.387 (3):0.201 (3).

Quaternary ammonium oxidative demethylation: X-ray crystallographic, resonance Raman, and UV-visible spectroscopic analysis of a Rieske-type demethylase.

PubMed

Daughtry, Kelly D; Xiao, Youli; Stoner-Ma, Deborah; Cho, Eunsun; Orville, Allen M; Liu, Pinghua; Allen, Karen N

2012-02-08

Herein, the structure resulting from in situ turnover in a chemically challenging quaternary ammonium oxidative demethylation reaction was captured via crystallographic analysis and analyzed via single-crystal spectroscopy. Crystal structures were determined for the Rieske-type monooxygenase, stachydrine demethylase, in the unliganded state (at 1.6 Å resolution) and in the product complex (at 2.2 Å resolution). The ligand complex was obtained from enzyme aerobically cocrystallized with the substrate stachydrine (N,N-dimethylproline). The ligand electron density in the complex was interpreted as proline, generated within the active site at 100 K by the absorption of X-ray photon energy and two consecutive demethylation cycles. The oxidation state of the Rieske iron-sulfur cluster was characterized by UV-visible spectroscopy throughout X-ray data collection in conjunction with resonance Raman spectra collected before and after diffraction data. Shifts in the absorption band wavelength and intensity as a function of absorbed X-ray dose demonstrated that the Rieske center was reduced by solvated electrons generated by X-ray photons; the kinetics of the reduction process differed dramatically for the liganded complex compared to unliganded demethylase, which may correspond to the observed turnover in the crystal.

Electronic structure and reactivity of high-spin iron--alkyl- and--pterinperoxo complexes.

PubMed

Lehnert, Nicolai; Fujisawa, Kiyoshi; Solomon, Edward I

2003-01-27

The spectroscopic properties and electronic structure of the four-coordinate high-spin [FeIII(L3)(OOtBu)]+ complex (1; L3 = hydrotris(3-tert-butyl-5-isopropyl-1-pyrazolyl)borate; tBu = tert-butyl) are investigated and compared to the six-coordinated high-spin [Fe(6-Me3TPA)(OHx)(OOtBu)]x+ system (TPA = tris(2-pyridylmethyl)amine, x = 1 or 2) studied earlier [Lehnert, N.; Ho, R. Y. N.; Que, L., Jr.; Solomon, E. I. J. Am. Chem. Soc. 2001, 123, 12802-12816]. Complex 1 is characterized by Raman features at 889 and 830 cm-1 which are assigned to the O-O stretch (mixed with the symmetric C-C stretch) and a band at 625 cm-1 that corresponds to nu(Fe-O). The UV-vis spectrum shows a charge-transfer (CT) transition at 510 nm from the alkylperoxo pi v* (v = vertical to C-O-O plane) to a d orbital of Fe(III). A second CT is identified from MCD at 370 nm that is assigned to a transition from pi h* (h = horizontal to C-O-O plane) to an Fe(III) d orbital. For the TPA complex the pi v* CT is at 560 nm while the pi h* CT is to higher energy than 250 nm. These spectroscopic differences between four- and six-coordinate Fe(III)-OOR complexes are interpreted on the basis of their different ligand fields. In addition, the electronic structure of Fe-OOPtn complexes with the biologically relevant pterinperoxo ligand are investigated. Substitution of the tert-butyl group in 1 by pterin leads to the corresponding Fe(III)-OOPtn species (2), which shows a stronger electron donation from the peroxide to Fe(III) than 1. This is related to the lower ionization potential of pterin. Reduction of 2 by one electron leads to the Fe(II)-OOPtn complex (3), which is relevant as a model for potential intermediates in pterin-dependent hydroxylases. However, in the four-coordinate ligand field of 3, the additional electron is located in a nonbonding d orbital of iron. Hence, the pterinperoxo ligand is not activated for heterolytic cleavage of the O-O bond in this system. This is also evident from the calculated reaction energies that are endothermic by at least 20 kcal/mol.

Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]-: formation pathway of dinitrosyl iron complexes (DNICs) from nitrosylation of biomimetic rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et).

PubMed

Lu, Tsai-Te; Chiou, Show-Jen; Chen, Chun-Yu; Liaw, Wen-Feng

2006-10-16

Nitrosylation of the biomimetic reduced- and oxidized-form rubredoxin [Fe(SR)4]2-/1- (R = Ph, Et) in a 1:1 stoichiometry led to the formation of the extremely air- and light-sensitive mononitrosyl tris(thiolate) iron complexes (MNICs) [Fe(NO)(SR)3]- along with byproducts [SR]- or (RS)2. Transformation of [Fe(NO)(SR)3]- into dinitrosyl iron complexes (DNICs) [(RS)2Fe(NO)2]- and Roussin's red ester [Fe2(mu-SR)2(NO)4] occurs rapidly under addition of 1 equiv of NO(g) and [NO]+, respectively. Obviously, the mononitrosyl tris(thiolate) complex [Fe(NO)(SR)3]- acts as an intermediate when the biomimetic oxidized- and reduced-form rubredoxin [Fe(SR)4]2-/1- exposed to NO(g) were modified to form dinitrosyl iron complexes [(RS)2Fe(NO)2]-. Presumably, NO binding to the electron-deficient [Fe(III)(SR)4]- and [Fe(III)(NO)(SR)3]- complexes triggers reductive elimination of dialkyl/diphenyl disulfide, while binding of NO radical to the reduced-form [Fe(II)(SR)4]2- induces the thiolate-ligand elimination. Protonation of [Fe(NO)(SEt)3]- yielding [Fe(NO)(SPh)3]- by adding 3 equiv of thiophenol and transformation of [Fe(NO)(SPh)3]- to [Fe(NO)(SEt)3]- in the presence of 3 equiv of [SEt]-, respectively, demonstrated that complexes [Fe(NO)(SPh)3]- and [Fe(NO)(SEt)3]- are chemically interconvertible. Mononitrosyl tris(thiolate) iron complex [Fe(NO)(SPh)3]- and dinitrosyl iron complex [(EtS)2Fe(NO)2]- were isolated and characterized by X-ray diffraction. The mean NO bond distances of 1.181(7) A (or 1.191(7) A) in complex [(EtS)2Fe(NO)2]- are nearly at the upper end of the 1.178(3)-1.160(6) A for the anionic {Fe(NO)2}9 DNICs, while the mean FeN(O) distances of 1.674(6) A (or 1.679(6) A) exactly fall in the range of 1.695(3)-1.661(4) A for the anionic {Fe(NO)2}9 DNICs.

New method for the direct determination of dissolved Fe(III) concentration in acid mine waters

USGS Publications Warehouse

To, T.B.; Nordstrom, D. Kirk; Cunningham, K.M.; Ball, J.W.; McCleskey, R. Blaine

1999-01-01

A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II) >> Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), AI(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2 ??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.A new method for direct determination of dissolved Fe(III) in acid mine water has been developed. In most present methods, Fe(III) is determined by computing the difference between total dissolved Fe and dissolved Fe(II). For acid mine waters, frequently Fe(II)???Fe(III); thus, accuracy and precision are considerably improved by determining Fe(III) concentration directly. The new method utilizes two selective ligands to stabilize Fe(III) and Fe(II), thereby preventing changes in Fe reduction-oxidation distribution. Complexed Fe(II) is cleanly removed using a silica-based, reversed-phase adsorbent, yielding excellent isolation of the Fe(III) complex. Iron(III) concentration is measured colorimetrically or by graphite furnace atomic absorption spectrometry (GFAAS). The method requires inexpensive commercial reagents and simple procedures that can be used in the field. Calcium(II), Ni(II), Pb(II), Al(III), Zn(II), and Cd(II) cause insignificant colorimetric interferences for most acid mine waters. Waters containing >20 mg of Cu/L could cause a colorimetric interference and should be measured by GFAAS. Cobalt(II) and Cr(III) interfere if their molar ratios to Fe(III) exceed 24 and 5, respectively. Iron(II) interferes when its concentration exceeds the capacity of the complexing ligand (14 mg/L). Because of the GFAAS elemental specificity, only Fe(II) is a potential interferent in the GFAAS technique. The method detection limit is 2/??g/L (40 nM) using GFAAS and 20 ??g/L (0.4 ??M) by colorimetry.

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory.

PubMed

Zhang, Yu; Mukamel, Shaul; Khalil, Munira; Govind, Niranjan

2015-12-08

Valence-to-core (VtC) X-ray emission spectroscopy (XES) has emerged as a powerful technique for the structural characterization of complex organometallic compounds in realistic environments. Since the spectrum represents electronic transitions from the ligand molecular orbitals to the core holes of the metal centers, the approach is more chemically sensitive to the metal-ligand bonding character compared with conventional X-ray absorption techniques. In this paper we study how linear-response time-dependent density functional theory (LR-TDDFT) can be harnessed to simulate K-edge VtC X-ray emission spectra reliably. LR-TDDFT allows one to go beyond the single-particle picture that has been extensively used to simulate VtC-XES. We consider seven low- and high-spin model complexes involving chromium, manganese, and iron transition metal centers. Our results are in good agreement with experiment.

The position 68(E11) side chain in myoglobin regulates ligand capture, bond formation with heme iron, and internal movement into the xenon cavities.

PubMed

Dantsker, David; Roche, Camille; Samuni, Uri; Blouin, George; Olson, John S; Friedman, Joel M

2005-11-18

After photodissociation, ligand rebinding to myoglobin exhibits complex kinetic patterns associated with multiple first-order geminate recombination processes occurring within the protein and a simpler bimolecular phase representing second-order ligand rebinding from the solvent. A smooth transition from cryogenic-like to solution phase properties can be obtained by using a combination of sol-gel encapsulation, addition of glycerol as a bathing medium, and temperature tuning (-15 --> 65 degrees C). This approach was applied to a series of double mutants, myoglobin CO (H64L/V68X, where X = Ala, Val, Leu, Asn, and Phe), which were designed to examine the contributions of the position 68(E11) side chain to the appearance and disappearance of internal rebinding phases in the absence of steric and polar interactions with the distal histidine. Based on the effects of viscosity, temperature, and the stereochemistry of the E11 side chain, the three major phases, B --> A, C --> A, and D --> A, can be assigned, respectively, to ligand rebinding from the following: (i) the distal heme pocket, (ii) the xenon cavities prior to large amplitude side chain conformational relaxation, and (iii) the xenon cavities after significant conformational relaxation of the position 68(E11) side chain. The relative amplitudes of the B --> A and C --> A phases depend markedly on the size and shape of the E11 side chain, which regulates sterically both ligand return to the heme iron atom and ligand migration to the xenon cavities. The internal xenon cavities provide a transient docking site that allows side chain relaxations and the entry of water into the vacated distal pocket, which in turn slows ligand recombination markedly.

Influence of Organic Ligands on the Surface Oxidation State and Magnetic Properties of Iron Oxide Particles

NASA Astrophysics Data System (ADS)

Goroncy, Christian; Saloga, Patrick E. J.; Gruner, Mathias; Schmudde, Madlen; Vonnemann, Jonathan; Otero, Edwige; Haag, Rainer; Graf, Christina

2018-05-01

For the application of iron oxide nanoparticles from thermal decomposition approaches as contrast agents in magnetic resonance imaging (MRI), their initial hydrophobic ligands have to be replaced by hydrophilic ones. This exchange can influence the surface oxidation state and the magnetic properties of the particles. Here, the effect of the anchor group of three organic ligands, citric acid and two catechols, dihydrocaffeic acid and its nitrated derivative nitro dihydrocaffeic acid on iron oxide nanoparticles is evaluated. The oleate ligands of Fe3O4/γ-Fe2O3 nanoparticles prepared by the thermal decomposition of iron oleate were exchanged against the hydrophilic ligands. X-ray absorption spectroscopy, especially X-ray magnetic circular dichroism (XMCD) measurements in the total electron yield (TEY) mode was used to investigate local magnetic and electronic properties of the particles' surface region before and after the ligand exchange. XMCD was combined with charge transfer multiplet calculations which provide information on the contributions of Fe2+ and Fe3+ at different lattice sites, i.e. either in tetrahedral or octahedral environment. The obtained data demonstrate that nitro hydrocaffeic acid leads to least reduction of the magnetizability of the surface region of the iron oxide nanoparticles compared to the two other ligands. For all hydrophilic samples, the proportion of Fe3+ ions in octahedral sites increases at the expense of the Fe2+ in octahedral sites whereas the percentage of Fe3+ in tetrahedral sites hardly changes. These observations suggest that an oxidation process took place, but a selective decrease of the Fe2+ ions in octahedral sites ions due to surface dissolution processes is unlikely. The citrate ligand has the least oxidative effect, whereas the degree of oxidation was similar for both catechol ligands regardless of the nitro group. Twenty-four hours of incubation in isotonic saline has nearly no influences on the magnetic properties of the nanoparticles, the least on those with the nitrated hydrocaffeic acid ligand.

A dithiolate-bridged (CN)2(CO)Fe-Ni complex reproducing the IR bands of [NiFe] hydrogenase.

PubMed

Tanino, Soichiro; Li, Zilong; Ohki, Yasuhiro; Tatsumi, Kazuyuki

2009-03-16

A dithiolate-bridged dinuclear Fe-Ni complex, which has the desired fac-(CN)(2)(CO) ligand set at iron, has been synthesized. Its CN/CO bands in the IR spectrum reproduce those of the Ni-A, Ni-B, and Ni-SU states, which indicate that these octahedral Fe(II) centers have similar electronic properties. This result verifies the assignment of a (CN)(2)(CO)Fe(II) moiety in the active site of [NiFe] hydrogenase.

EHPG iron(III) complexes as potential contrast contrast agents for MRI.

PubMed

Kuźnik, Nikodem; Jewuła, Paweł; Oczek, Lidia; Kozłowicz, Sylwia; Grucela, Artur; Domagała, Wojciech

2014-01-01

A series of EHPG ligands and complexes were obtained. The derivatives of choice were p-OMe, 3,4-dimethyl, p-NHAc and p-Ph substituted ones. The complexes were characterized by NMR relaxation decay (T1), EPR and cyclic voltammetry (CV). r1 Relaxivity of the Fe-EHPG-OMe, Fe-EHPG-Ph derivatives was found higher than that of Fe-EHPG. EPR measurements at liquid nitrogen temperature indicate a typical rhombohedral structure for both rac- and meso-diastereoisomers of the EHPG complexes. CV revealed the redox inactivity of the Fe-EHPG complexes at physiological conditions. Interpretation and discussion of the results is presented.

Experimental and theoretical vibrational spectroscopy studies of acetohydroxamic acid and desferrioxamine B in aqueous solution: Effects of pH and iron complexation

NASA Astrophysics Data System (ADS)

Edwards, David C.; Nielsen, Steen B.; Jarzęcki, Andrzej A.; Spiro, Thomas G.; Myneni, Satish C. B.

2005-07-01

The deprotonation and iron complexation of the hydroxamate siderophore, desferrioxamine B (desB), and a model hydroxamate ligand, acetohydroxamic acid (aHa), were studied using infrared, resonance Raman and UV-vis spectroscopy. The experimental spectra were interpreted by a comparison with DFT calculated spectra of aHa (partly hydrated) and desB (reactive groups of unhydrated molecule) at the B3LYP/6-31G* level of theory. The ab initio models include three water molecules surrounding the deprotonation site of aHa to account for partial hydration. Experiments and calculations were also conducted in D 2O to verify spectral assignments. These studies of aHa suggest that the cis-keto-aHa is the dominant form, and its deprotonation occurs at the oxime oxygen atom in aqueous solutions. The stable form of iron-complexed aHa is identified as Fe(aHa) 3 for a wide range of pH conditions. The spectral information of aHa and an ab initio model of desB were used to interpret the chemical state of different functional groups in desB. Vibrational spectra of desB indicate that the oxime and amide carbonyl groups can be identified unambiguously. Vibrational spectral analysis of the oxime carbonyl after deprotonation and iron complexation of desB indicates that the conformational changes between anion and the iron-complexed anion are small. Enhanced electron delocalization in the oxime group of Fe-desB when compared to that of Fe(aHa) 3 may be responsible for higher stability constant of the former.

Ligand-Enhanced Abiotic Iron Oxidation and the Effects of Chemical versus Biological Iron Cycling in Anoxic Environments

PubMed Central

2013-01-01

This study introduces a newly isolated, genetically tractable bacterium (Pseudogulbenkiania sp. strain MAI-1) and explores the extent to which its nitrate-dependent iron-oxidation activity is directly biologically catalyzed. Specifically, we focused on the role of iron chelating ligands in promoting chemical oxidation of Fe(II) by nitrite under anoxic conditions. Strong organic ligands such as nitrilotriacetate and citrate can substantially enhance chemical oxidation of Fe(II) by nitrite at circumneutral pH. We show that strain MAI-1 exhibits unambiguous biological Fe(II) oxidation despite a significant contribution (∼30–35%) from ligand-enhanced chemical oxidation. Our work with the model denitrifying strain Paracoccus denitrificans further shows that ligand-enhanced chemical oxidation of Fe(II) by microbially produced nitrite can be an important general side effect of biological denitrification. Our assessment of reaction rates derived from literature reports of anaerobic Fe(II) oxidation, both chemical and biological, highlights the potential competition and likely co-occurrence of chemical Fe(II) oxidation (mediated by microbial production of nitrite) and truly biological Fe(II) oxidation. PMID:23402562

Iron-Virus Interactions in the Oceans

NASA Astrophysics Data System (ADS)

Bonnain, C. C.; Buck, K. N.; Breitbart, M.

2016-02-01

Iron is an essential nutrient in the oceans, with the sub-nanomolar concentrations found in open ocean surface waters often insufficient for supporting biological activity. More than 99.9% of dissolved iron is bound to organic ligands, yet identifying the sources of these ligands in seawater remains a major challenge. A significant portion of iron-binding ligands fall into the colloidal fraction, which is operationally defined as the fraction collected between a 0.02 µm and a 0.45 µm filter. Among the organic ligands in this fraction persists an extremely abundant biological candidate: viruses. On average there are 107 viruses per milliliter of seawater, most of which are phages (viruses that infect bacteria). The impact of viruses on ocean biogeochemistry is often evoked purely through the act of lysing hosts and very few studies have considered the geochemical potential of the viral particles themselves. Recent work in non-marine model systems has revealed the presence of iron atoms within the structure of diverse phages infecting Escherichia coli. Combined with the small size and sheer abundance of phages in the oceans, the inclusion of iron in phage structures would translate into a major factor for cycling of this important trace metal. In addition, iron is so critical for growth that bacteria have evolved multiple uptake systems for assimilating iron, such as siderophores. Certain outer membrane proteins serve a dual function in siderophore uptake and as a phage receptor, suggesting that some of the strategies utilized for iron acquisition make bacteria vulnerable to phage infection. Given the constant arms race between bacteria and phages to develop resistance and counter-resistance, respectively, it is not surprising that phage would have evolved to utilize critical regions of surface-exposed proteins which are indispensable for bacterial growth as receptors. The research presented here explores the potential of marine phages to serve as iron-binding ligands and discusses the implications for both trace metal biogeochemistry and marine phage-host interactions.

Fate of the nitrilotriacetic acid-Fe(III) complex during photodegradation and biodegradation by Rhodococcus rhodochrous.

PubMed

Bunescu, Andrei; Besse-Hoggan, Pascale; Sancelme, Martine; Mailhot, Gilles; Delort, Anne-Marie

2008-10-01

Aminopolycarboxylic acids are ubiquitous in natural waters and wastewaters. They have the ability to form very stable water-soluble complexes with many metallic di- or trivalent ions. The iron complex nitrilotriacetic acid-Fe(III) (FeNTA) has been previously shown to increase drastically the rate of photo- and biodegradation of 2-aminobenzothiazole, an organic pollutant, by Rhodococcus rhodochrous. For this paper, the fate of FeNTA was investigated during these degradation processes. First, it was shown, using in situ (1)H nuclear magnetic resonance, that the complex FeNTA was biodegraded by Rhodococcus rhodochrous cells, but the ligand (NTA) alone was not. This result indicates that FeNTA was transported and biotransformed inside the cell. The same products, including iminodiacetic acid, glycine, and formate, were obtained during the photo- and biodegradation processes of FeNTA, likely because they both involve oxidoreduction mechanisms. When the results of the different experiments are compared, the soluble iron, measured by spectrophotometry, was decreasing when microbial cells were present. About 20% of the initial iron was found inside the cells. These results allowed us to propose detailed mechanistic schemes for FeNTA degradation by solar light and by R. rhodochrous.

Fate of the Nitrilotriacetic Acid-Fe(III) Complex during Photodegradation and Biodegradation by Rhodococcus rhodochrous▿

PubMed Central

Bunescu, Andrei; Besse-Hoggan, Pascale; Sancelme, Martine; Mailhot, Gilles; Delort, Anne-Marie

2008-01-01

Aminopolycarboxylic acids are ubiquitous in natural waters and wastewaters. They have the ability to form very stable water-soluble complexes with many metallic di- or trivalent ions. The iron complex nitrilotriacetic acid-Fe(III) (FeNTA) has been previously shown to increase drastically the rate of photo- and biodegradation of 2-aminobenzothiazole, an organic pollutant, by Rhodococcus rhodochrous. For this paper, the fate of FeNTA was investigated during these degradation processes. First, it was shown, using in situ 1H nuclear magnetic resonance, that the complex FeNTA was biodegraded by Rhodococcus rhodochrous cells, but the ligand (NTA) alone was not. This result indicates that FeNTA was transported and biotransformed inside the cell. The same products, including iminodiacetic acid, glycine, and formate, were obtained during the photo- and biodegradation processes of FeNTA, likely because they both involve oxidoreduction mechanisms. When the results of the different experiments are compared, the soluble iron, measured by spectrophotometry, was decreasing when microbial cells were present. About 20% of the initial iron was found inside the cells. These results allowed us to propose detailed mechanistic schemes for FeNTA degradation by solar light and by R. rhodochrous. PMID:18757580

Development of a C3-symmetric benzohydroxamate tripod: Trimetallic complexation with Fe(III), Cr(III) and Al(III)

NASA Astrophysics Data System (ADS)

Baral, Minati; Gupta, Amit; Kanungo, B. K.

2016-06-01

The design, synthesis and physicochemical characterization of a C3-symmetry Benzene-1,3,5-tricarbonylhydroxamate tripod, noted here as BTHA, are described. The chelator was built from a benzene as an anchor, symmetrically extended by three hydroxamate as ligating moieties, each bearing O, O donor sites. A combination of absorption spectrophotometry, potentiometry and theoretical investigations are used to explore the complexation behavior of the ligand with some trivalent metal ions: Fe(III), Cr(III), and Al(III). Three protonation constants were calculated for the ligand in a pH range of 2-11 in a highly aqueous medium (9:1 H2O: DMSO). A high rigidity in the molecular structure restricts the formation of 1:1 (M/L) metal encapsulation but shows a high binding efficiency for a 3:1 metal ligand stoichiometry giving formation constant (in β unit) 28.73, 26.13 and 19.69 for [M3L]; Mdbnd Fe(III), Al(III) and Cr(III) respectively, and may be considered as an efficient Fe-carrier. The spectrophotometric study reveals of interesting electronic transitions occurred during the complexation. BTHA exhibits a peak at 238 nm in acidic pH and with the increase of pH, a new peak appeared at 270 nm. A substantial shifting in both of the peaks in presence of the metal ions implicates a s coordination between ligand and metal ions. Moreover, complexation of BTHA with iron shows three distinct colors, violet, reddish orange and yellow in different pH, enables the ligand to be considered for the use as colorimetric sensor.

Synthesis of silyl iron hydride via Si-H activation and its dual catalytic application in the hydrosilylation of carbonyl compounds and dehydration of benzamides.

PubMed

Ren, Shishuai; Xie, Shangqing; Zheng, Tingting; Wang, Yangyang; Xu, Shilu; Xue, Benjing; Li, Xiaoyan; Sun, Hongjian; Fuhr, Olaf; Fenske, Dieter

2018-03-28

The hydrido silyl iron complex (o-Ph 2 PC 6 H 4 SiMe 2 )Fe(PMe 3 ) 3 H (2) was obtained via the activation of the Si-H bond of the bidentate silyl ligand o-Ph 2 P(C 6 H 4 )SiMe 2 H (1) by Fe(PMe 3 ) 4 . 2 showed good to excellent catalytic activity in both the reduction of aldehydes/ketones and the dehydration of benzamide. In addition, with complex 2 as a catalyst, α,β-unsaturated carbonyls could be selectively reduced to the corresponding α,β-unsaturated alcohols. The mechanisms of the formation of 2 and the catalytic dehydration process are proposed and partly experimentally verified.

Ammonia formation by a thiolate-bridged diiron amide complex as a nitrogenase mimic

NASA Astrophysics Data System (ADS)

Li, Yang; Li, Ying; Wang, Baomin; Luo, Yi; Yang, Dawei; Tong, Peng; Zhao, Jinfeng; Luo, Lun; Zhou, Yuhan; Chen, Si; Cheng, Fang; Qu, Jingping

2013-04-01

Although nitrogenase enzymes routinely convert molecular nitrogen into ammonia under ambient temperature and pressure, this reaction is currently carried out industrially using the Haber-Bosch process, which requires extreme temperatures and pressures to activate dinitrogen. Biological fixation occurs through dinitrogen and reduced NxHy species at multi-iron centres of compounds bearing sulfur ligands, but it is difficult to elucidate the mechanistic details and to obtain stable model intermediate complexes for further investigation. Metal-based synthetic models have been applied to reveal partial details, although most models involve a mononuclear system. Here, we report a diiron complex bridged by a bidentate thiolate ligand that can accommodate HN=NH. Following reductions and protonations, HN=NH is converted to NH3 through pivotal intermediate complexes bridged by N2H3- and NH2- species. Notably, the final ammonia release was effected with water as the proton source. Density functional theory calculations were carried out, and a pathway of biological nitrogen fixation is proposed.

Decoupling of Iron and Phosphate in the Global Ocean

NASA Technical Reports Server (NTRS)

Parekh, Payal

2003-01-01

Iron is an essential micronutrient for marine phytoplankton, limiting their growth in high nutrient, low chlorophyll regions of the ocean. I use a hierarchy of ocean circulation and biogeochemistry models to understand controls on global iron distribution. I formulate a mechanistic model of iron cycling which includes scavenging onto sinking particles and complexation with an organic ligand. The iron cycle is coupled to a phosphorus cycling model. Iron's aeolian source is prescribed. In the context of a highly idealized multi-box model scheme, the model can be brought into consistency with the relatively sparse ocean observations of iron in the oceans. This biogeochemical scheme is also implemented in a coarse resolution ocean general circulation model. This model also successfully reproduces the broad regional patterns of iron and phosphorus. In particular, the high macronutrient concentrations of the Southern Ocean result from iron limitation in the model. Due to the potential ability of iron to change the efficiency of the carbon pump in the remote Southern Ocean, I study Southern Ocean surface phosphate response to increased aeolian dust flux. My box model and GCM results suggest that a global ten fold increase in dust flux can support a phosphate drawdown of 0.25-0.5 micromolar.

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

DOE PAGES

Ganguly, Sumit; Giles, Logan J.; Thomas, Kolle E.; ...

2017-10-06

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3, H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2(μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2O,more » and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV-like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III-like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.« less

Mineral stimulation of subsurface microorganisms: release of limiting nutrients from silicates

USGS Publications Warehouse

Roger, Jennifer Roberts; Bennett, Philip C.

2004-01-01

Microorganisms play an important role in the weathering of silicate minerals in many subsurface environments, but an unanswered question is whether the mineral plays an important role in the microbial ecology. Silicate minerals often contain nutrients necessary for microbial growth, but whether the microbial community benefits from their release during weathering is unclear. In this study, we used field and laboratory approaches to investigate microbial interactions with minerals and glasses containing beneficial nutrients and metals. Field experiments from a petroleum-contaminated aquifer, where silicate weathering is substantially accelerated in the contaminated zone, revealed that phosphorus (P) and iron (Fe)-bearing silicate glasses were preferentially colonized and weathered, while glasses without these elements were typically barren of colonizing microorganisms, corroborating previous studies using feldspars. In laboratory studies, we investigated microbial weathering of silicates and the release of nutrients using a model ligand-promoted pathway. A metal-chelating organic ligand 3,4 dihydroxybenzoic acid (3,4 DHBA) was used as a source of chelated ferric iron, and a carbon source, to investigate mineral weathering rate and microbial metabolism.In the investigated aquifer, we hypothesize that microbes produce organic ligands to chelate metals, particularly Fe, for metabolic processes and also form stable complexes with Al and occasionally with Si. Further, the concentration of these ligands is apparently sufficient near an attached microorganism to destroy the silicate framework while releasing the nutrient of interest. In microcosms containing silicates and glasses with trace phosphate mineral inclusions, microbial biomass increased, indicating that the microbial community can use silicate-bound phosphate inclusions. The addition of a native microbial consortium to microcosms containing silicates or glasses with iron oxide inclusions correlated to accelerated weathering and release of Si into solution as well as the accelerated degradation of the model substrate 3,4 DHBA. We propose that silicate-bound P and Fe inclusions are bioavailable, and microorganisms may use organic ligands to dissolve the silicate matrix and access these otherwise limiting nutrients.

Systemic combinatorial peptide selection yields a non-canonical iron-mimicry mechanism for targeting tumors in a mouse model of human glioblastoma

PubMed Central

Staquicini, Fernanda I.; Ozawa, Michael G.; Moya, Catherine A.; Driessen, Wouter H.P.; Barbu, E. Magda; Nishimori, Hiroyuki; Soghomonyan, Suren; Flores, Leo G.; Liang, Xiaowen; Paolillo, Vincenzo; Alauddin, Mian M.; Basilion, James P.; Furnari, Frank B.; Bogler, Oliver; Lang, Frederick F.; Aldape, Kenneth D.; Fuller, Gregory N.; Höök, Magnus; Gelovani, Juri G.; Sidman, Richard L.; Cavenee, Webster K.; Pasqualini, Renata; Arap, Wadih

2010-01-01

The management of CNS tumors is limited by the blood-brain barrier (BBB), a vascular interface that restricts the passage of most molecules from the blood into the brain. Here we show that phage particles targeted with certain ligand motifs selected in vivo from a combinatorial peptide library can cross the BBB under normal and pathological conditions. Specifically, we demonstrated that phage clones displaying an iron-mimic peptide were able to target a protein complex of transferrin and transferrin receptor (TfR) through a non-canonical allosteric binding mechanism and that this functional protein complex mediated transport of the corresponding viral particles into the normal mouse brain. We also showed that, in an orthotopic mouse model of human glioblastoma, a combination of TfR overexpression plus extended vascular permeability and ligand retention resulted in remarkable brain tumor targeting of chimeric adeno-associated virus/phage particles displaying the iron-mimic peptide and carrying a gene of interest. As a proof of concept, we delivered the HSV thymidine kinase gene for molecular-genetic imaging and targeted therapy of intracranial xenografted tumors. Finally, we established that these experimental findings might be clinically relevant by determining through human tissue microarrays that many primary astrocytic tumors strongly express TfR. Together, our combinatorial selection system and results may provide a translational avenue for the targeted detection and treatment of brain tumors. PMID:21183793

Ligand binding to the Fe(III)-protoporphyrin IX complex of phosphodiesterase from Escherichia coli (Ec DOS) markedly enhances catalysis of cyclic di-GMP: roles of Met95, Arg97, and Phe113 of the putative heme distal side in catalytic regulation and ligand binding.

PubMed

Tanaka, Atsunari; Shimizu, Toru

2008-12-16

Phosphodiesterase (Ec DOS) from Escherichia coli is a gas-sensor enzyme in which binding of gas molecules, such as O(2), CO, and NO, to the Fe(II)-protoporphyrin IX complex in the sensor domain stimulates phosphodiesterase activity toward cyclic-di-GMP. In this study, we report that external axial ligands, such as cyanide or imidazole, bind to Fe(III)-protoporphyrin IX in the sensor domain and induce a 10- to 11-fold increase (from 8.1 up to 86 min(-1)) in catalysis, which is more substantial than that (6.3 to 7.2-fold) observed for other gas-stimulated Fe(II) heme-bound enzymes. Catalytic activity (50 min(-1)) of the heme-free mutant, H77A, was comparable to that of the ligand-stimulated enzymes. Accordingly, we propose that the heme at the sensor domain inhibits catalysis and that ligand binding to the heme iron complex releases this catalytic suppression. Furthermore, mutations of Met95, Arg97, and Phe113 at the putative heme distal side suppressed the ligand effects on catalysis. The rate constants (19,000 x 10(-5) microM(-1)min(-1)) for cyanide binding to the M95A and M95L mutants of the full-length enzyme were 633-fold higher than that to wild-type Ec DOS (30 x 10(-5) microM(-1)min(-1)). The absorption spectrum of the F113Y mutant suggests that the Tyr O(-) group directly coordinates to the Fe(III) complex and that the cyanide binding rate to the mutant is very slow, compared with those of the wild-type and other mutant proteins. We observed a similar trend in the binding behavior of imidazole to full-length mutant enzymes. Therefore, while Met95 and Phe113 are not direct axial ligands for the Fe(III) complex, catalytic, spectroscopic, and ligand binding evidence suggests that these residues are located in the vicinity of the heme.

Covalent heme attachment to the protein in human heme oxygenase-1 with selenocysteine replacing the His25 proximal iron ligand

PubMed Central

Jiang, Yongying; Trnka, Michael J.; Medzihradszky, Katalin F.; Ouellet, Hugues; Wang, Yongqiang; Ortiz de Montellano, Paul R.

2009-01-01

To characterize heme oxygenase with a selenocysteine (SeCys) as the proximal iron ligand, we have expressed truncated human heme oxygenase-1 (hHO-1) His25Cys, in which Cys-25 is the only cysteine, in the Escherichia coli cysteine auxotroph strain BL21(DE3)cys. Selenocysteine incorporation into the protein was demonstrated by both intact protein mass measurement and mass spectrometric identification of the selenocysteine-containing tryptic peptide. One selenocysteine was incorporated into approximately 95% of the expressed protein. Formation of an adduct with Ellman's reagent (DTNB) indicated that the selenocysteine in the expressed protein was in the reduced state. The heme-His25SeCys hHO-1 complex could be prepared by either (a) supplementing the overexpression medium with heme, or (b) reconstituting the purified apoprotein with heme. Under reducing conditions in the presence of imidazole, a covalent bond is formed by addition of the selenocysteine residue to one of the heme vinyl groups. No covalent bond is formed when the heme is replaced by mesoheme, in which the vinyls are replaced by ethyl groups. These results, together with our earlier demonstration that external selenolate ligands can transfer an electron to the iron (Jiang, Y., Ortiz de Montellano, P.R., Inorg. Chem., 47, 3480-3482 (2008)), indicate that a selenyl radical is formed in the hHO1 His25SeCys mutant that adds to a heme vinyl group. PMID:19135260

Covalent heme attachment to the protein in human heme oxygenase-1 with selenocysteine replacing the His25 proximal iron ligand.

PubMed

Jiang, Yongying; Trnka, Michael J; Medzihradszky, Katalin F; Ouellet, Hugues; Wang, Yongqiang; Ortiz de Montellano, Paul R

2009-03-01

To characterize heme oxygenase with a selenocysteine (SeCys) as the proximal iron ligand, we have expressed truncated human heme oxygenase-1 (hHO-1) His25Cys, in which Cys-25 is the only cysteine, in the Escherichia coli cysteine auxotroph strain BL21(DE3)cys. Selenocysteine incorporation into the protein was demonstrated by both intact protein mass measurement and mass spectrometric identification of the selenocysteine-containing tryptic peptide. One selenocysteine was incorporated into approximately 95% of the expressed protein. Formation of an adduct with Ellman's reagent (DTNB) indicated that the selenocysteine in the expressed protein was in the reduced state. The heme-His25SeCys hHO-1 complex could be prepared by either (a) supplementing the overexpression medium with heme, or (b) reconstituting the purified apoprotein with heme. Under reducing conditions in the presence of imidazole, a covalent bond is formed by addition of the selenocysteine residue to one of the heme vinyl groups. No covalent bond is formed when the heme is replaced by mesoheme, in which the vinyls are replaced by ethyl groups. These results, together with our earlier demonstration that external selenolate ligands can transfer an electron to the iron [Y. Jiang, P.R. Ortiz de Montellano, Inorg. Chem. 47 (2008) 3480-3482 ], indicate that a selenyl radical is formed in the hHO-1 His25SeCys mutant that adds to a heme vinyl group.

Assessing the impact of electronic and steric tuning of the ligand in the spin state and catalytic oxidation ability of the Fe(II)(Pytacn) family of complexes.

PubMed

Prat, Irene; Company, Anna; Corona, Teresa; Parella, Teodor; Ribas, Xavi; Costas, Miquel

2013-08-19

A family of iron complexes with the general formula [Fe(II)((R,R)'Pytacn)(X)2](n+) is described, where (R,R)'Pytacn is the tetradentate ligand 1-[(4-R'-6-R-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, R refers to the group at the α-position of the pyridine, R' corresponds to the group at the γ-position, and X denotes CH3CN or CF3SO3. Herein, we study the influence of the pyridine substituents R and R' on the electronic properties of the coordinated iron center by a combination of structural and spectroscopic characterization using X-ray diffraction, (1)H NMR and UV-vis spectroscopies, and magnetic susceptibility measurements. The electronic properties of the substituent in the γ-position of the pyridine ring (R') modulate the strength of the ligand field, as shown by magnetic susceptibility measurements in CD3CN solution, which provide a direct indication of the population of the magnetically active high-spin S = 2 ferrous state. Indeed, a series of complexes [Fe(II)((H,R)'Pytacn)(CD3CN)2](2+) exist as mixtures of high-spin (S = 2) and low-spin (S = 0) complexes, and their effective magnetic moment directly correlates with the electron-releasing ability of R'. On the other hand, the substitution of the hydrogen atom in the α-position of the pyridine by a methyl, chlorine, or fluorine group favors the high-spin state. The whole family of complexes has been assayed in catalytic C-H and C═C oxidation reactions with H2O2. These catalysts exhibit excellent efficiency in the stereospecific hydroxylation of alkanes and in the oxidation of olefins. Remarkably, R'-substituents have little influence on the efficiency and chemoselectivity of the catalytic activity of the complexes, but the selectivity toward olefin cis-dihydroxylation is enhanced for complexes with R = Me, F, or Cl. Isotopic labeling studies in the epoxidation and cis-dihydroxylation reactions show that R has a definitive role in dictating the origin of the oxygen atom that is transferred in the epoxidation reaction.

Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.

PubMed

McCracken, John; Cappillino, Patrick J; McNally, Joshua S; Krzyaniak, Matthew D; Howart, Michael; Tarves, Paul C; Caradonna, John P

2015-07-06

Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.

Organic Exudates Enhance Iron Bioavailability to Trichodesmium (IMS101) by Modifying Fe Speciation

NASA Astrophysics Data System (ADS)

Tohidi Farid, H.; Rose, A.; Schulz, K.

2016-02-01

Although ferrous iron (Fe (II)) is believed to be the most readily absorbed form of Fe by cells, under alkaline and oxygenated conditions typical of marine environments, the thermodynamically stable Fe(III) state dominates. In marine environments, this Fe(III) is primarily presents as organic Fe(III)L complexes whose bioavailability is highly variable. However, it has been demonstrated that some eukaryotic marine algae are able to release organic ligands into their surrounding environments that change Fe bioavailability through complexation and/or redox reactions. Nevertheless, it is unclear how Fe(II) oxidation and Fe(III) reduction rates might be modified by these exudates and how this might increase or decrease iron bioavailability to microorganisms. Here, the role of natural organic ligands excreted by the cyanobacterium Trichodesmium erythraeum on the oxidation kinetics of Fe(II) was studied using the luminol chemiluminescence technique. The oxidation kinetics of Fe(II) were examined at nanomolar Fe concentrations in presence of different concentrations of EDTA and dissolved organic carbon exuded by Trichodesmium cells. The results indicated that an increase in the concentration of exuded organic matter, and consequently L:Fe(II) ratio, resulted in decreasing rates of Fe(II) oxidation by oxygen, primarily due to formation of Fe(II) complexes. Moreover, the results demonstrated that the exudates from Trichodesmium may be able to reduce Fe(III) to the more bioavailable Fe(II) state under some circumstances. This study therefore supports the ability of microorganisms to manipulate Fe bioavailability by releasing organic compounds into the extracellular environment that retard Fe(II) oxidation rates or reducing Fe(III) species to Fe(II). It also provides new insight into the potential mechanism(s) by which Trichdesmium may acquire Fe under conditions where Fe bioavailability is otherwise limited.

The Preparation of an Ultrastable Mesoporous Cr(III)-MOF via Reductive Labilization

DTIC Science & Technology

2015-09-02

of metal clusters from a template MOF with a known structure. Fe(III)-MOFs can serve as practical structural templates because iron resembles chromium ...clusters in PCN-333 are able to accommodate both di- and trivalent metal ions by varying the charges of the terminal ligands, the bridging oxygen atoms, and...molecules in trivalent aqua complexes27 Inert complexes Labile complexes M(OH2) Cr(OH2)6 3+ Ir(OH2)6 3+ V(OH2)6 3+ Fe(OH2)6 3+ Ti(OH2)6 3+ k (s1) 2.4 10

New Chemical and Stereochemical Applications of Organoiron Complexes

PubMed Central

Fatiadi, Alexander J.

1991-01-01

The objective of this review is to provide a current overview of the rapidly developing chemistry of organometallic complexes and particularly organoiron complexes useful in asymmetric and stereoselective reactions. Also covered are stereoselective reactions of α, β-unsaturated acyl ligands bound to the chiral auxiliary [(η5-C5H5) Fe(CO)(PPh3)] and new applications of organoiron complexes in the synthesis of natural products. The mechanistic aspects and stabilizing effects of the Fe(CO)3 group for alkenes or conjugated dienes are discussed. A brief summary of recent work on the special role of iron in biological reactions is also included. PMID:28184103

Expanding the Therapeutic Potential of the Iron Chelator Deferasirox in the Development of Aqueous Stable Ti(IV) Anticancer Complexes.

PubMed

Loza-Rosas, Sergio A; Vázquez-Salgado, Alexandra M; Rivero, Kennett I; Negrón, Lenny J; Delgado, Yamixa; Benjamín-Rivera, Josué A; Vázquez-Maldonado, Angel L; Parks, Timothy B; Munet-Colón, Charlene; Tinoco, Arthur D

2017-07-17

The recent X-ray structure of titanium(IV)-bound human serum transferrin (STf) exhibiting citrate as a synergistic anion reveals a difference in Ti(IV) coordination versus iron(III), the metal endogenously delivered by the protein to cells. This finding enriches our bioinspired drug design strategy for Ti(IV)-based anticancer therapeutics, which applies a family of Fe(III) chelators termed chemical transferrin mimetic (cTfm) ligands to inhibit Fe bioavailability in cancer cells. Deferasirox, a drug used for iron overload disease, is a cTfm ligand that models STf coordination to Fe(III), favoring Fe(III) binding versus Ti(IV). This metal affinity preference drives deferasirox to facilitate the release of cytotoxic Ti(IV) intracellularly in exchange for Fe(III). An aqueous speciation study performed by potentiometric titration from pH 4 to 8 with micromolar levels of Ti(IV) deferasirox at a 1:2 ratio reveals exclusively Ti(deferasirox) 2 in solution. The predominant complex at pH 7.4, [Ti(deferasirox) 2 ] 2- , exhibits the one of the highest aqueous stabilities observed for a potent cytotoxic Ti(IV) species, demonstrating little dissociation even after 1 month in cell culture media. UV-vis and 1 H NMR studies show that the stability is unaffected by the presence of biomolecular Ti(IV) binders such as citrate, STf, and albumin, which have been shown to induce dissociation or regulate cellular uptake and can alter the activity of other antiproliferative Ti(IV) complexes. Kinetic studies on [Ti(deferasirox) 2 ] 2- transmetalation with Fe(III) show that a labile Fe(III) source is required to induce this process. The initial step of this process occurs on the time scale of minutes, and equilibrium for the complete transmetalation is reached on a time scale of hours to a day. This work reveals a mechanism to deliver Ti(IV) compounds into cells and trigger Ti(IV) release by a labile Fe(III) species. Cellular studies including other cTfm ligands confirm the Fe(III) depletion mechanism of these compounds and show their ability to induce early and late apoptosis.

Efficient Nitrogen Fixation via a Redox-Flexible Single-Iron Site with Reverse-Dative Iron → Boron σ Bonding.

PubMed

Lu, Jun-Bo; Ma, Xue-Lu; Wang, Jia-Qi; Liu, Jin-Cheng; Xiao, Hai; Li, Jun

2018-05-10

Model systems of the FeMo cofactor of nitrogenase have been explored extensively in catalysis to gain insights into their ability for nitrogen fixation that is of vital importance to the human society. Here we investigate the trigonal pyramidal borane-ligand Fe complex by first-principles calculations, and find that the variation of oxidation state of Fe along the reaction path correlates with that of the reverse-dative Fe → B bonding. The redox-flexibility of the reverse-dative Fe → B bonding helps to provide an electron reservoir that buffers and stabilizes the evolution of Fe oxidation state, which is essential for forming the key intermediates of N 2 activation. Our work provides insights for understanding and optimizing homogeneous and surface single-atom catalysts with reverse-dative donating ligands for efficient dinitrogen fixation. The extension of this kind of molecular catalytic active center to heterogeneous catalysts with surface single-clusters is also discussed.

Galline Ex-FABP is an Antibacterial Siderocalin and a Lysophosphatidic Acid Sensor Functioning through Dual Ligand Specificities

PubMed Central

Correnti, Colin; Clifton, Matthew C.; Abergel, Rebecca J.; Allred, Ben; Hoette, Trisha M.; Ruiz, Mario; Cancedda, Ranieri; Raymond, Kenneth N.; Descalzi, Fiorella; Strong, Roland K.

2011-01-01

SUMMARY Galline Ex-FABP was identified as another candidate antibacterial, catecholate siderophore binding lipocalin (siderocalin) based on structural parallels with the family archetype, mammalian Siderocalin. Binding assays show that Ex-FABP retains iron in a siderophore-dependent manner in both hypertrophic and dedifferentiated chondrocytes, where Ex-FABP expression is induced after treatment with proinflammatory agents, and specifically binds ferric complexes of enterobactin, parabactin, bacillibactin and, unexpectedly, monoglucosylated enterobactin, which does not bind to Siderocalin. Growth arrest assays functionally confirm the bacteriostatic effect of Ex-FABP in vitro under iron-limiting conditions. The 1.8Å crystal structure of Ex-FABP explains the expanded specificity, but also surprisingly reveals an extended, multi-chambered cavity extending through the protein and encompassing two separate ligand specificities, one for bacterial siderophores (as in Siderocalin) at one end and one specifically binding co-purified lysophosphatidic acid, a potent cell signaling molecule, at the other end, suggesting Ex-FABP employs dual functionalities to explain its diverse endogenous activities. PMID:22153502

Iron oxide nanoparticles stabilized with dendritic polyglycerols as selective MRI contrast agents

NASA Astrophysics Data System (ADS)

Nordmeyer, Daniel; Stumpf, Patrick; Gröger, Dominic; Hofmann, Andreas; Enders, Sven; Riese, Sebastian B.; Dernedde, Jens; Taupitz, Matthias; Rauch, Ursula; Haag, Rainer; Rühl, Eckart; Graf, Christina

2014-07-01

Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI.Monodisperse small iron oxide nanoparticles functionalized with dendritic polyglycerol (dPG) or dendritic polyglycerol sulfate (dPGS) are prepared. They are highly stable in aqueous solutions as well as physiological media. In particular, oleic acid capped iron oxide particles (core diameter = 11 +/- 1 nm) were modified by a ligand exchange process in a one pot synthesis with dPG and dPGS bearing phosphonate as anchor groups. Dynamic light scattering measurements performed in water and different biological media demonstrate that the hydrodynamic diameter of the particles is only slightly increased by the ligand exchange process resulting in a final diameter of less than 30 nm and that the particles are stable in these media. It is also revealed by magnetic resonance studies that their magnetic relaxivity is reduced by the surface modification but it is still sufficient for high contrast magnetic resonance imaging (MRI). Additionally, incubation of dPGS functionalized iron oxide nanoparticles with human umbilical vein endothelial cells showed a 50% survival at 85 nM (concentration of nanoparticles). Surface plasmon resonance (SPR) studies demonstrate that the dPGS functionalized iron oxide nanoparticles inhibit L-selectin ligand binding whereas the particles containing only dPG do not show this effect. Experiments in a flow chamber with human myelogenous leukemia cells confirmed L-selectin inhibition of the dPGS functionalized iron oxide nanoparticles and with that the L-selectin mediated leukocyte adhesion. These results indicate that dPGS functionalized iron oxide nanoparticles are a promising contrast agent for inflamed tissue probed by MRI. Electronic supplementary information (ESI) available: A detailed description of the synthesis of the ligands as well as the preparation and functionalization of the iron oxide nanoparticles including their physico-chemical characterization are presented. Further, details of the cell experiments and the SPR experiments are given. Two representative movies are provided showing leukocyte rolling on the ligand coated surface of the flow chamber. See DOI: 10.1039/c3nr04793h

Experimental study of iron-chloride complexing in hydrothermal fluids

USGS Publications Warehouse

Fein, J.B.; Hemley, J.J.; d'Angelo, W. M.; Komninou, A.; Sverjensky, D.A.

1992-01-01

Mineral assemblage solubilities were measured in cold-seal pressure vessels as a function of pressure, temperature, and potassium chloride concentration in order to determine the nature and thermodynamic properties of iron-chloride complexes under hydrothermal conditions. The assemblage pyritepyrrhotite-magnetite was used to buffer f{hook}S2 and f{hook}O2, and K+ H+ ratios were buffered at reasonable geologic values using the assemblage potassium feldspar-muscovite (or andalusite)-quartz. The pressure-temperature ranges were 0.5-2.0 kbar and 300-600??C, and initial fluid compositions ranged from 0.01-2.0 molal KCl. With all other factors constant, the concentration of iron in solution increases with increasing temperature, with decreasing pressure, and with increasing total potassium chloride concentration. Changes in iron concentrations as a function of KCl concentration, in conjunction with charge balance, mass action, and mass balance constraints on the system, place constraints on the stoichiometry of the important iron-chloride complexes under each of the experimental conditions. Using least-squared linear regression fits to determine these slopes, the calculations yield values for the average ligand numbers that are in the range 1.2-1.9, with uncertainties ranging from ??0.1-0.6 at the several PT conditions considered. The slopes of the regressed fits to the data suggest that both FeCl+ and FeCl20 are important in the experimental fluids, with FeCl20 becoming dominant at the higher temperatures. Theoretical calculations, however, indicate that FeCl+ does not contribute significantly to the solubility. Because of the large uncertainties associated with some of the calculated average ligand numbers, we base our data analysis on the theoretical calculations. A statistical analysis is applied to the solubility data in order to determine the values and uncertainties of the dissociation constant for FeCl20 that best fit the data at each of the experimental pressures and temperatures. The calculated stability of FeCl20 increases with increasing temperature and total chloride concentration, and with decreasing pressure. The values of the dissociation constant of FeCl20that are calculated in this study are in moderately good agreement with FeCl20dissociation constants from other studies of iron-chloride complexing in supercritical fluids. Differences are likely due to different assumptions made concerning activity coefficients of aqueous species. Log kd values for full dissociation of FeCl20 at 0.5 kbar-300??C-and at 1 kbar-400, 500, and 600??C, respectively-are -3.75 ?? 0.40, -6.25 ?? 0.10, -9.19 ?? 0.44, and -13.29 ?? 0.09. ?? 1992.

Linking phytoplankton and bacterioplankton community dynamics to iron-binding ligand production in a microcosm experiment

NASA Astrophysics Data System (ADS)

Hogle, S. L.; Bundy, R.; Barbeau, K.

2016-02-01

Several significant lines of evidence implicate heterotrophic bacterioplankton as agents of iron cycling and sources of iron-binding ligands in seawater, but direct and mechanistic linkages have mostly remained elusive. Currently, it is unknown how microbial community composition varies during the course of biogenic particle remineralization and how shifts in community structure are related to sources and sinks of Fe-binding ligands. In order to simulate the rise, decline, and ultimate remineralization of a phytoplankton bloom, we followed the production of different classes of Fe-binding ligands as measured by electrochemical techniques, Fe concentrations, and macronutrient concentrations in a series of iron-amended whole seawater incubations over a period of six days during a California Current Ecosystem Long Term Ecological Research (CCE-LTER) process cruise. At the termination of the experiment phytoplankton communities were similar across iron treatments, but high iron conditions generated greater phytoplankton biomass and increased nutrient drawdown suggesting that phytoplankton communities were in different phases of bloom development. Strikingly, L1 ligands akin to siderophores in binding strength were only observed in high iron treatments implicating phytoplankton bloom phase as an important control. Using high-throughput 16S rRNA gene surveys, we observed that the abundance of transiently dominant copiotroph bacteria were strongly correlated with L1 concentrations. However, incubations with similar L1 concentrations and binding strengths produced distinct copiotroph community profiles dominated by a few strains. We suggest that phytoplankton bloom maturity influences algal-associated heterotrophic community succession, and that L1 production is either directly or indirectly tied to the appearance and eventual dominance of rarely abundant copiotroph bacterial strains.

Synthesis and Mossbauer spectroscopy of macrocyclic complexes of iron(III)

NASA Astrophysics Data System (ADS)

Mishra, A.; Sura, Kamaljeet S.; Sharma, P.

2016-10-01

The article deals with a fresh series of the complexes of the type: [Fe(III)(TML)Cl]Cl2; where TML is a tetra-dentate macrocyclic ligand; has been synthesized by condensation of o-phenylenediamine, diethyl malonate and diazonium ion in the ethanolic medium, through refluxing with FeCl3.The synthesized metal complexes were characterized by Mossbauer spectroscopy. Mossbauer measurements were carried out using standard PC-based spectrometer equipped with Weissel velocity drive operating in the constant acceleration mode. Mossbauer study interprets paramagnetic nature of complexes. Mossbauer measurement of complex 1 and 2 has been taken to find out the value of isomer shift and quadrapole splitting and oxidation state after complaxsation.

Iron behaving badly: inappropriate iron chelation as a major contributor to the aetiology of vascular and other progressive inflammatory and degenerative diseases

PubMed Central

Kell, Douglas B

2009-01-01

Background The production of peroxide and superoxide is an inevitable consequence of aerobic metabolism, and while these particular 'reactive oxygen species' (ROSs) can exhibit a number of biological effects, they are not of themselves excessively reactive and thus they are not especially damaging at physiological concentrations. However, their reactions with poorly liganded iron species can lead to the catalytic production of the very reactive and dangerous hydroxyl radical, which is exceptionally damaging, and a major cause of chronic inflammation. Review We review the considerable and wide-ranging evidence for the involvement of this combination of (su)peroxide and poorly liganded iron in a large number of physiological and indeed pathological processes and inflammatory disorders, especially those involving the progressive degradation of cellular and organismal performance. These diseases share a great many similarities and thus might be considered to have a common cause (i.e. iron-catalysed free radical and especially hydroxyl radical generation). The studies reviewed include those focused on a series of cardiovascular, metabolic and neurological diseases, where iron can be found at the sites of plaques and lesions, as well as studies showing the significance of iron to aging and longevity. The effective chelation of iron by natural or synthetic ligands is thus of major physiological (and potentially therapeutic) importance. As systems properties, we need to recognise that physiological observables have multiple molecular causes, and studying them in isolation leads to inconsistent patterns of apparent causality when it is the simultaneous combination of multiple factors that is responsible. This explains, for instance, the decidedly mixed effects of antioxidants that have been observed, since in some circumstances (especially the presence of poorly liganded iron) molecules that are nominally antioxidants can actually act as pro-oxidants. The reduction of redox stress thus requires suitable levels of both antioxidants and effective iron chelators. Some polyphenolic antioxidants may serve both roles. Understanding the exact speciation and liganding of iron in all its states is thus crucial to separating its various pro- and anti-inflammatory activities. Redox stress, innate immunity and pro- (and some anti-)inflammatory cytokines are linked in particular via signalling pathways involving NF-kappaB and p38, with the oxidative roles of iron here seemingly involved upstream of the IkappaB kinase (IKK) reaction. In a number of cases it is possible to identify mechanisms by which ROSs and poorly liganded iron act synergistically and autocatalytically, leading to 'runaway' reactions that are hard to control unless one tackles multiple sites of action simultaneously. Some molecules such as statins and erythropoietin, not traditionally associated with anti-inflammatory activity, do indeed have 'pleiotropic' anti-inflammatory effects that may be of benefit here. Conclusion Overall we argue, by synthesising a widely dispersed literature, that the role of poorly liganded iron has been rather underappreciated in the past, and that in combination with peroxide and superoxide its activity underpins the behaviour of a great many physiological processes that degrade over time. Understanding these requires an integrative, systems-level approach that may lead to novel therapeutic targets. PMID:19133145

Synthesis, structural characterization and conversion of dinuclear iron-sulfur clusters containing the disulfide ligand: [Cp*Fe(μ-η2:η2-bdt)(cis-μ-η1:η1-S2)FeCp*], [Cp*Fe(μ-S(C6H4S2))(cis-μ-η1:η1-S2)FeCp*], and [{Cp*Fe(bdt)}2(trans-μ-η1:η1-S2)].

PubMed

Ji, Xiaoxiao; Tong, Peng; Yang, Dawei; Wang, Baomin; Zhao, Jinfeng; Li, Yang; Qu, Jingping

2017-03-21

The treatment of [Cp*Fe(μ-η 2 :η 4 -bdt)FeCp*] (1, Cp* = η 5 -C 5 Me 5 , bdt = benzene-1,2-dithiolate) with 1/4 equiv. of elemental sulfur (S 8 ) gave a dinuclear iron-sulfur cluster [Cp*Fe(μ-η 2 :η 2 -bdt)(cis-μ-η 1 :η 1 -S 2 )FeCp*] (2), which contains a cis-1,2-disulfide ligand. When complex 2 further interacted with 1/8 equiv. of S 8 , another sulfur atom inserted into an Fe-S bond to give a rare product [Cp*Fe(μ-S(C 6 H 4 S 2 ))(cis-μ-η 1 :η 1 -S 2 )FeCp*] (3). Unexpectedly, a trans-1,2 disulfide-bridged diiron complex [{Cp*Fe(bdt)} 2 (trans-μ-η 1 :η 1 -S 2 )] (4) was isolated from the reaction of complex 1 with 1/2 equiv. of S 8 , which represents a structural isomer of [2Fe-2S] ferredoxin-type clusters. In addition, cis-1,2-disulfide-bridged complex 3 can slowly convert into trans-1,2-disulfide-bridged complex 4 and the complex [Cp*Fe(μ-η 2 :η 2 -S 2 )(cis-μ-η 1 :η 1 -S 2 )FeCp*] (5) by self-assembly reaction at ambient temperature, which is evidenced by time-dependent 1 H NMR spectroscopy.

Iron uptake in Mycelia sterilia EP-76.

PubMed Central

Adjimani, J P; Emery, T

1987-01-01

The cyclic trihydroxamic acid, N,N',N''-triacetylfusarinine C, produced by Mycelia sterilia EP-76, was shown to be a ferric ionophore for this organism. The logarithm of the association constant k for the ferric triacetylfusarinine C chelate was determined to be 31.8. Other iron-chelating agents, such as rhodotorulic acid, citric acid, and the monomeric subunit of triacetylfusarinine C, N-acetylfusarinine, delivered iron to the cells by an indirect mechanism involving iron exchange into triacetylfusarinine C. In vitro ferric ion exchange was found to be rapid with triacetylfusarinine C. Gallium uptake rates comparable to those of iron were observed with the chelating agents that transport iron into the cell. Ferrichrome, but not ferrichrome A, was also capable of delivering iron and gallium to this organism, but not by an exchange mechanism. Unlike triacetylfusarinine C, the 14C-ligand of ferrichrome was retained by the cell. A midpoint potential of -690 mV with respect to the saturated silver chloride electrode was obtained for the ferric triacetylfusarinine C complex, indicating that an unfavorable reduction potential was not the reason for the use of a hydrolytic mechanism of intracellular iron release from the ferric triacetylfusarinine C chelate. PMID:3611025

a Moessbauer Effect and Fenske-Hall Molecular Orbital Study of the Electronic Properties of Organoiron Clusters.

NASA Astrophysics Data System (ADS)

Buhl, Margaret Linn

The electronic properties of trinuclear iron, tetranuclear iron butterfly, iron-cobalt, and iron-copper clusters have been studied experimentally at 78K by the Mossbauer effect and theoretically by Fenske-Hall molecular orbital calculations. The Mossbauer effect isomer shift is very sensitive to the differences in the iron s-electron densities in these clusters and, as expected, decreases as the sum of the iron 4s Mulliken population and the Clementi and Raimondi effective nuclear charge increases. The molecular orbital wave functions and the Mulliken atomic charges are used to calculate the electric field gradient at the metal nuclei and the iron Mossbauer effect quadrupole splittings. The valence contribution was found to be the major component of the electric field gradient in all the clusters studied. In general the calculated value of Delta E_ {Q} is larger than the observed value, as a result of neglect of the valence Sternheimer factor, R. The metal charge depends upon its electronegativity and upon the nature of its Lewis base ligands. The carbonyl ligand carbon charge becomes more positive as the metal electronegativity increases. The oxygen charge becomes more negative as the anionic cluster charge increases, and in so doing, yields the maximum anionic charge separation. The electronic properties of the terminal carbonyl ligands are similar to those of carbon monoxide, whereas the electronic properties of the bridging carbonyl ligands are similar to those of the carbonyl group found in aldehydes and ketones.

A Six-Coordinate Peroxynitrite Low-Spin Iron(III) Porphyrinate Complex—The Product of the Reaction of Nitrogen Monoxide (·NO (g)) with a Ferric-Superoxide Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Savita K.; Schaefer, Andrew W.; Lim, Hyeongtaek

Peroxynitrite ( –OON=O, PN) is a reactive nitrogen species (RNS) which can effect deleterious nitrative or oxidative (bio)chemistry. It may derive from reaction of superoxide anion (O 2 •–) with nitric oxide (·NO) and has been suggested to form an as-yet unobserved bound heme-iron-PN intermediate in the catalytic cycle of nitric oxide dioxygenase (NOD) enzymes, which facilitate a ·NO homeostatic process, i.e., its oxidation to the nitrate anion. Here, a discrete six-coordinate low-spin porphyrinate-Fe III complex [(P Im)Fe III( –OON=O)] (P Im; a porphyrin moiety with a covalently tethered imidazole axial “base” donor ligand) has been identified and characterized bymore » various spectroscopies (UV–vis, NMR, EPR, XAS, resonance Raman) and DFT calculations, following its formation at –80 °C by addition of ·NO (g) to the heme-superoxo species, [(P Im)Fe III(O 2 •–)]. DFT calculations confirm that is a six-coordinate low-spin species with the PN ligand coordinated to iron via its terminal peroxidic anionic O atom with the overall geometry being in a cis-configuration. Complex thermally transforms to its isomeric low-spin nitrato form [(P Im)Fe III(NO 3 –)]. While previous (bio)chemical studies show that phenolic substrates undergo nitration in the presence of PN or PN-metal complexes, in the present system, addition of 2,4-di- tert-butylphenol ( 2,4DTBP) to complex does not lead to nitrated phenol; the nitrate complex still forms. Furthermore, DFT calculations reveal that the phenolic H atom approaches the terminal PN O atom (farthest from the metal center and ring core), effecting O–O cleavage, giving nitrogen dioxide (·NO 2) plus a ferryl compound [(P Im)Fe IV=O] (7); this rebounds to give [(P Im)Fe III(NO 3 –)].The generation and characterization of the long sought after ferriheme peroxynitrite complex has been accomplished.« less

A Six-Coordinate Peroxynitrite Low-Spin Iron(III) Porphyrinate Complex—The Product of the Reaction of Nitrogen Monoxide (·NO (g)) with a Ferric-Superoxide Species

DOE PAGES

Sharma, Savita K.; Schaefer, Andrew W.; Lim, Hyeongtaek; ...

2017-11-01

Peroxynitrite ( –OON=O, PN) is a reactive nitrogen species (RNS) which can effect deleterious nitrative or oxidative (bio)chemistry. It may derive from reaction of superoxide anion (O 2 •–) with nitric oxide (·NO) and has been suggested to form an as-yet unobserved bound heme-iron-PN intermediate in the catalytic cycle of nitric oxide dioxygenase (NOD) enzymes, which facilitate a ·NO homeostatic process, i.e., its oxidation to the nitrate anion. Here, a discrete six-coordinate low-spin porphyrinate-Fe III complex [(P Im)Fe III( –OON=O)] (P Im; a porphyrin moiety with a covalently tethered imidazole axial “base” donor ligand) has been identified and characterized bymore » various spectroscopies (UV–vis, NMR, EPR, XAS, resonance Raman) and DFT calculations, following its formation at –80 °C by addition of ·NO (g) to the heme-superoxo species, [(P Im)Fe III(O 2 •–)]. DFT calculations confirm that is a six-coordinate low-spin species with the PN ligand coordinated to iron via its terminal peroxidic anionic O atom with the overall geometry being in a cis-configuration. Complex thermally transforms to its isomeric low-spin nitrato form [(P Im)Fe III(NO 3 –)]. While previous (bio)chemical studies show that phenolic substrates undergo nitration in the presence of PN or PN-metal complexes, in the present system, addition of 2,4-di- tert-butylphenol ( 2,4DTBP) to complex does not lead to nitrated phenol; the nitrate complex still forms. Furthermore, DFT calculations reveal that the phenolic H atom approaches the terminal PN O atom (farthest from the metal center and ring core), effecting O–O cleavage, giving nitrogen dioxide (·NO 2) plus a ferryl compound [(P Im)Fe IV=O] (7); this rebounds to give [(P Im)Fe III(NO 3 –)].The generation and characterization of the long sought after ferriheme peroxynitrite complex has been accomplished.« less

Modulation of protein function by exogenous ligands in protein cavities: CO binding to a myoglobin cavity mutant containing unnatural proximal ligands.

PubMed

Decatur, S M; DePillis, G D; Boxer, S G

1996-04-02

A variety of heterocyclic ligands can be exchanged into the proximal cavity of sperm whale myoglobin mutant H93G, providing a simple method for introduction of the equivalent of unnatural amino acid side chains into a functionally critical location in this protein. These modified proteins bind CO on the distal side. 1H NMR data on H93G(Im)CO, where Im is imidazole, demonstrate that the structure of the distal heme pocket in H93G(Im)CO is very similar to that of wild type; thus, the effects of the proximal ligand's properties on CO binding can be studied with minimal perturbation of distal pocket structure. The exogenous proximal ligands used in this study include imidazole (Im), 4-methylimidazole (4-MeIm), 4-bromoimidazole (4-BrIm), N-methylimidazole (N-MeIm), pyridine (Pyr), and 3-fluoropyridine (3-FPyr). Substitution of the proximal ligand is found to produce substantial changes in the CO on and off rates, the equilibrium binding constant, and the vibrational stretch frequency of CO. Many of the changes are as large as those reported for distal pocket mutants prepared by site-directed mutagenesis. The ability to systematically vary the nature of the proximal ligand is exploited to test the effects of particular properties of the proximal ligand on CO binding. For example, 4-MeIm and 4-BrIm are similar in size and shape but differ significantly in pKa. The same relationship is true for Pyr and 3-FPyr. By comparison of the IR spectra and CO recombination kinetics of these complexes, the effects of proximal ligand pKa on the CO binding are assessed. Likewise, N-MeIm and 4-MeIm are similar in size and pKa but differ in their ability to hydrogen bond to amino acid residues in the proximal cavity. Comparisons of IR spectra and CO binding kinetics in these complexes reveal that proximal ligand conformation and hydrogen bonding affect the kinetics of CO binding. The mechanism of proximal ligand exchange between solution and the proximal cavity in CO complexes was investigated by obtaining the 19F NMR spectrum of H93G(3-FPyr)CO, whose 19F signal can be observed without interference from resonances of the protein. The proximal ligand is found to exchange within a few seconds by saturation transfer. This exchange rate is about 2 orders of magniture faster than what is observed for the isoelectronic metcyano complex [Decatur, S. M., & Boxer, S. G. (1995) Biochemistry 34, 2122-2129]; in both the ferrous CO and ferric cyano complexes, the proximal ligand exchange rate is independent of ligand concentration. These results suggest that the rate-limiting step in proximal ligand exchange is breakage of the iron-ligand bond, followed by rapid diffusion of the ligand through the protein to bulk solution.

Chelating agents related to ethylenediamine bis(2-hydroxyphenyl)acetic acid (EDDHA): synthesis, characterization, and equilibrium studies of the free ligands and their Mg2+, Ca2+, Cu2+, and Fe3+ chelates.

PubMed

Yunta, Felipe; García-Marco, Sonia; Lucena, Juan J; Gómez-Gallego, Mar; Alcázar, Roberto; Sierra, Miguel A

2003-08-25

Iron chelates such as ethylenediamine-N,N'-bis(2-hydroxyphenyl)acetic acid (EDDHA) and their analogues are the most efficient soil fertilizers to treat iron chlorosis in plants growing in calcareous soils. EDDHA, EDDH4MA (ethylenediamine-N,N'-bis(2-hydroxy-4-methylphenyl)acetic acid), and EDDCHA (ethylenediamine-N,N'-bis(2-hydroxy-5-carboxyphenyl)acetic acid) are allowed by the European directive, but also EDDHSA (ethylenediamine-N,N'-bis(2-hydroxy-5-sulfonylphenyl)acetic acid) and EDDH5MA (ethylenediamine-N,N'-bis(2-hydroxy-5-methylphenyl)acetic acid) are present in several commercial iron chelates. In this study, these chelating agents as well as p,p-EDDHA (ethylenediamine-N,N'-bis(4-hydroxyphenyl)acetic acid) and EDDMtxA (ethylenediamine-N,N'-bis(2-metoxyphenyl)acetic acid) have been obtained following a new synthetic pathway. Their chemical behavior has been studied to predict the effect of the substituents in the benzene ring on their efficacy as iron fertilizers for soils above pH 7. The purity of the chelating agents has been determined using a novel methodology through spectrophotometric titration at 480 nm with Fe(3+) as titrant to evaluate the inorganic impurities. The protonation constants were determined by both spectrophotometric and potentiometric methods, and Ca(2+) and Mg(2+) stability constants were determined from potentiometric titrations. To establish the Fe(3+) and Cu(2+) stability constants, a new spectrophotometric method has been developed, and the results were compared with those reported in the literature for EDDHA and EDDHMA and their meso- and rac-isomers. pM values have been also determined to provide a comparable basis to establish the relative chelating ability of these ligands. The purity obtained for the ligands is higher than 87% in all cases and is comparable with that obtained by (1)H NMR. No significant differences have been found among ligands when their protonation and stability constants were compared. As expected, no Fe(3+) complexation was observed for p,p-EDDHA and EDDMtxA. The presence of sulfonium groups in EDDHSA produces an increase in acidity that affects their protonation and stability constants, although the pFe values suggest that EDDHSA could be also effective to correct iron chlorosis in plants.

Reactivity of catecholamine-driven Fenton reaction and its relationships with iron(III) speciation.

PubMed

Melin, Victoria; Henríquez, Adolfo; Freer, Juanita; Contreras, David

2015-03-01

Fenton reaction is the main source of free radicals in biological systems. The reactivity of this reaction can be modified by several factors, among these iron ligands are important. Catecholamine (dopamine, epinephrine, and norepinephrine) are able to form Fe(III) complexes whose extension in the coordination number depends upon the pH. Fe(III)-catecholamine complexes have been related with the development of several pathologies. In this work, the ability of catecholamines to enhance the oxidative degradation of an organic substrate (veratryl alcohol, VA) through Fenton and Fenton-like reactions was studied. The initial VA degradation rate at different pH values and its relationship to the different iron species present in solution were determined. Furthermore, the oxidative degradation of VA after 24 hours of reaction and its main oxidation products were also determined. The catecholamine-driven Fenton and Fenton-like systems showed higher VA degradation compared to unmodified Fenton or Fenton-like systems, which also showed an increase in the oxidation state of the VA degradation product. All of this oxidative degradation takes place at pH values lower than 5.50, where the primarily responsible species would be the Fe(III) mono-complex. The presence of Fe(III) mono-complex is essential in the ability of catecholamines to increase the oxidative capacity of Fenton systems.

Syntheses, crystal structures, and magnetic properties of the oxalato-bridged mixed-valence complexes (FeII(bpm)3]2[FeIII2(ox)5].8H2O and FeII(bpm)3Na(H2O)2Fe(ox)(3).4H2O (bpm = 2,2'-bipyrimidine).

PubMed

Armentano, D; De Munno, G; Faus, J; Lloret, F; Julve, M

2001-02-12

The preparation and crystal structures of two oxalato-bridged FeII-FeIII mixed-valence compounds, [FeII(bpm)3]2[FeIII2(ox)5].8H2O (1) and FeII(bpm)3Na(H2O)2FeIII(ox)(3).4H2O (2) (bpm = 2,2'-bipyrimidine; ox = oxalate dianion) are reported here. Complex 1 crystallizes in the triclinic system, space group P1, with a = 10.998(2) A, b = 13.073(3) A, c = 13.308(3) A, alpha = 101.95(2) degrees, beta = 109.20(2) degrees, gamma = 99.89(2) degrees, and Z = 1. Complex 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 12.609(2) A, b = 19.670(5) A, c = 15.843(3) A, beta = 99.46(1) degrees, and Z = 4. The structure of complex 1 consists of centrosymmetric oxalato-bridged dinuclear high-spin iron(III) [Fe2(ox)5]2- anions, tris-chelated low-spin iron(II) [Fe(bpm)3]2+ cations, and lattice water molecules. The iron atoms are hexacoordinated: six oxygen atoms (iron(III)) from two bidentate and one bisbidentate oxalato ligands and six nitrogen atoms (iron(II)) from three bidentate bpm groups. The Fe(III)-O(ox) and Fe(II)-N(bpm) bond distances vary in the ranges 1.967(3)-2.099(3) and 1.967(4)-1.995(3) A, respectively. The iron(III)-iron(III) separation across the bridging oxalato is 5.449(2) A, whereas the shortest intermolecular iron(III)-iron(II) distance is 6.841(2) A. The structure of complex 2 consists of neutral heterotrinuclear Fe(bpm)2Na(H2O)2Fe(ox)3 units and water molecules of crystallization. The tris-chelated low-spin iron(II) ([Fe(bpm)3]2+) and high-spin iron(III) ([Fe(ox)3]3-) entities act as bidentate ligands (through two bpm-nitrogen and two oxalato-oxygen atoms, respectively) toward the univalent sodium cation, yielding the trinuclear (bpm)2Fe(II)-bpm-Na(I)-ox-Fe(III)(ox)2 complex. Two cis-coordinated water molecules complete the distorted octahedral surrounding of the sodium atom. The ranges of the Fe(II)-N(bpm) and Fe(III)-O(ox) bond distances [1.968(6)-1.993(5) and 1.992(6)-2.024(6) A, respectively] compare well with those observed in 1. The Na-N(bpm) bond lengths (2.548(7) and 2.677(7) A) are longer than those of Na-O(ox) (2.514(7) and 2.380(7) A) and Na-O(water) (2.334(15) and 2.356(12) A). The intramolecular Fe(II)...Fe(III) separation is 6.763(2) A, whereas the shortest intermolecular Fe(II)...Fe(II) and Fe(III)...Fe(III) distances are 8.152(2) and 8.992(2) A, respectively. Magnetic susceptibility measurements in the temperature range 2.0-290 K for 1 reveal that the high-spin iron(III) ions are antiferromagnetically coupled (J = -6.6 cm-1, the Hamiltonian being defined as H = -JS1.S2). The magnitude of the antiferromagnetic coupling through the bridging oxalato in the magneto-structurally characterized family of formula [M2(ox)5](2m-10)+ (M = Fe(III) (1), Cr(III), and Ni(II)) is analyzed and discussed by means of a simple orbital model.

Electron transfer function versus oxygen delivery: a comparative study for several hexacoordinated globins across the animal kingdom.

PubMed

Kiger, Laurent; Tilleman, Lesley; Geuens, Eva; Hoogewijs, David; Lechauve, Christophe; Moens, Luc; Dewilde, Sylvia; Marden, Michael C

2011-01-01

Caenorhabditis elegans globin GLB-26 (expressed from gene T22C1.2) has been studied in comparison with human neuroglobin (Ngb) and cytoglobin (Cygb) for its electron transfer properties. GLB-26 exhibits no reversible binding for O(2) and a relatively low CO affinity compared to myoglobin-like globins. These differences arise from its mechanism of gaseous ligand binding since the heme iron of GLB-26 is strongly hexacoordinated in the absence of external ligands; the replacement of this internal ligand, probably the E7 distal histidine, is required before binding of CO or O(2) as for Ngb and Cygb. Interestingly the ferrous bis-histidyl GLB-26 and Ngb, another strongly hexacoordinated globin, can transfer an electron to cytochrome c (Cyt-c) at a high bimolecular rate, comparable to those of inter-protein electron transfer in mitochondria. In addition, GLB-26 displays an unexpectedly rapid oxidation of the ferrous His-Fe-His complex without O(2) actually binding to the iron atom, since the heme is oxidized by O(2) faster than the time for distal histidine dissociation. These efficient mechanisms for electron transfer could indicate a family of hexacoordinated globin which are functionally different from that of pentacoordinated globins.

Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jay, Raphael M.; Norell, Jesper; Eckert, Sebastian

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by themore » metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.« less

Disentangling Transient Charge Density and Metal–Ligand Covalency in Photoexcited Ferricyanide with Femtosecond Resonant Inelastic Soft X-ray Scattering

DOE PAGES

Jay, Raphael M.; Norell, Jesper; Eckert, Sebastian; ...

2018-06-11

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by themore » metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jay, Raphael M.; Norell, Jesper; Eckert, Sebastian

Soft X-ray spectroscopies are ideal probes of the local valence electronic structure of photocatalytically active metal sites. Here, we apply the selectivity of time-resolved resonant inelastic X-ray scattering at the iron L-edge to the transient charge distribution of an optically excited charge-transfer state in aqueous ferricyanide. Through comparison to steady-state spectra and quantum chemical calculations, the coupled effects of valence-shell closing and ligand-hole creation are experimentally and theoretically disentangled and described in terms of orbital occupancy, metal–ligand covalency, and ligand field splitting, thereby extending established steady-state concepts to the excited-state domain. π-Back-donation is found to be mainly determined by themore » metal site occupation, whereas the ligand hole instead influences σ-donation. Here, our results demonstrate how ultrafast resonant inelastic X-ray scattering can help characterize local charge distributions around catalytic metal centers in short-lived charge-transfer excited states, as a step toward future rationalization and tailoring of photocatalytic capabilities of transition-metal complexes.« less

Kinetics of acid hydrolysis and reactivity of some antibacterial hydrophilic iron(II) imino-complexes

NASA Astrophysics Data System (ADS)

Shaker, Ali Mohamed; Nassr, Lobna Abdel-Mohsen Ebaid; Adam, Mohamed Shaker Saied; Mohamed, Ibrahim Mohamed Abdelhalim

2015-05-01

Kinetic study of acid hydrolysis of some hydrophilic Fe(II) Schiff base amino acid complexes with antibacterial properties was performed using spectrophotometry. The Schiff base ligands were derived from sodium 2-hydroxybenzaldehyde-5-sulfonate and glycine, L-alanine, L-leucine, L-isoleucine, DL-methionine, DL-serine, or L-phenylalanine. The reaction was studied in aqueous media under conditions of pseudo-first order kinetics. Moreover, the acid hydrolysis was studied at different temperatures and the activation parameters were calculated. The general rate equation was suggested as follows: rate = k obs [Complex], where k obs = k 2 [H+]. The evaluated rate constants and activation parameters are consistent with the hydrophilicity of the investigated complexes.

Heme-Coordinating Inhibitors of Neuronal Nitric Oxide Synthase. Iron-Thioether Coordination is Stabilized by Hydrophobic Contacts Without Increased Inhibitor Potency

PubMed Central

Martell, Jeffrey D.; Li, Huiying; Doukov, Tzanko; Martásek, Pavel; Roman, Linda J.; Soltis, Michael; Poulos, Thomas L.; Silverman, Richard B.

2010-01-01

The heme-thioether ligand interaction often occurs between heme iron and native methionine ligands, but thioether-based heme-coordinating (type II) inhibitors are uncommon due to the difficulty in stabilizing the Fe-S bond. Here, a thioether-based inhibitor (3) of neuronal nitric oxide synthase (nNOS) was designed, and its binding was characterized by spectrophotometry and crystallography. A crystal structure of inhibitor 3 coordinated to heme iron was obtained, representing, to our knowledge, the first crystal structure of a thioether inhibitor complexed to any heme enzyme. A series of related potential inhibitors (4-8) also were evaluated. Compounds 4-8 were all found to be type I (non-heme-coordinating) inhibitors of ferric nNOS, but 4 and 6-8 were found to switch to type II upon heme reduction to the ferrous state, reflecting the higher affinity of thioethers for ferrous heme than for ferric heme. Contrary to what has been widely thought, thioether-heme ligation was found not to increase inhibitor potency, illustrating the intrinsic weakness of the thioether-ferric heme linkage. Subtle changes in the alkyl groups attached to the thioether sulfur caused drastic changes in binding conformation, indicating that hydrophobic contacts play a crucial role in stabilizing the thioether-heme coordination. PMID:20014790

The insecticide target in the PSST subunit of complex I.

PubMed

Schuler, F; Casida, J E

2001-10-01

Current insecticides have been selected by sifting and winnowing hundreds of thousands of synthetic chemicals and natural products to obtain commercial preparations of optimal effectiveness and safety. This process has often ended up with compounds of high potency as inhibitors of the electron transport chain and more specifically of complex I (NADH:ubiquinone oxidoreductase). Many classes of chemicals are involved and the enzyme is one of the most complicated known, with 43 subunits catalyzing electron transfer from NADH to ubiquinone through flavin mononucleotide and up to eight iron-sulfur clusters. We used a potent photoaffinity ligand, (trifluoromethyl)diazirinyl[3H]pyridaben, to localize the insecticide target to a single high-affinity site in the PSST subunit that couples electron transfer from iron-sulfur cluster N2 to ubiquinone. Most importantly, all of the potent complex I-inhibiting pesticides, despite their great structural diversity, compete for this same specific binding domain in PSST. Finding their common mode of action and target provides insight into shared toxicological features and potential selection for resistant pests.

Desferrithiocin: A Search for Clinically Effective Iron Chelators

PubMed Central

2015-01-01

The successful search for orally active iron chelators to treat transfusional iron-overload diseases, e.g., thalassemia, is overviewed. The critical role of iron in nature as a redox engine is first described, as well as how primitive life forms and humans manage the metal. The problems that derive when iron homeostasis in humans is disrupted and the mechanism of the ensuing damage, uncontrolled Fenton chemistry, are discussed. The solution to the problem, chelator-mediated iron removal, is clear. Design options for the assembly of ligands that sequester and decorporate iron are reviewed, along with the shortcomings of the currently available therapeutics. The rationale for choosing desferrithiocin, a natural product iron chelator (a siderophore), as a platform for structure–activity relationship studies in the search for an orally active iron chelator is thoroughly developed. The study provides an excellent example of how to systematically reengineer a pharmacophore in order to overcome toxicological problems while maintaining iron clearing efficacy and has led to three ligands being evaluated in human clinical trials. PMID:25207964

Crystal Structure of the Ectoine Hydroxylase, a Snapshot of the Active Site*

PubMed Central

Höppner, Astrid; Widderich, Nils; Lenders, Michael; Bremer, Erhard; Smits, Sander H. J.

2014-01-01

Ectoine and its derivative 5-hydroxyectoine are compatible solutes that are widely synthesized by bacteria to cope physiologically with osmotic stress. They also serve as chemical chaperones and maintain the functionality of macromolecules. 5-Hydroxyectoine is produced from ectoine through a stereo-specific hydroxylation, an enzymatic reaction catalyzed by the ectoine hydroxylase (EctD). The EctD protein is a member of the non-heme-containing iron(II) and 2-oxoglutarate-dependent dioxygenase superfamily and is evolutionarily well conserved. We studied the ectoine hydroxylase from the cold-adapted marine ultra-microbacterium Sphingopyxis alaskensis (Sa) and found that the purified SaEctD protein is a homodimer in solution. We determined the SaEctD crystal structure in its apo-form, complexed with the iron catalyst, and in a form that contained iron, the co-substrate 2-oxoglutarate, and the reaction product of EctD, 5-hydroxyectoine. The iron and 2-oxoglutarate ligands are bound within the EctD active site in a fashion similar to that found in other members of the dioxygenase superfamily. 5-Hydroxyectoine, however, is coordinated by EctD in manner different from that found in high affinity solute receptor proteins operating in conjunction with microbial import systems for ectoines. Our crystallographic analysis provides a detailed view into the active site of the ectoine hydroxylase and exposes an intricate network of interactions between the enzyme and its ligands that collectively ensure the hydroxylation of the ectoine substrate in a position- and stereo-specific manner. PMID:25172507

Abrupt spin transition with thermal hysteresis of iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine).

PubMed

Fujinami, Takeshi; Koike, Masataka; Matsumoto, Naohide; Sunatsuki, Yukinari; Okazawa, Atsushi; Kojima, Norimichi

2014-02-17

The solvent-free spin crossover iron(III) complex [Fe(III)(Him)2(hapen)]AsF6 (Him = imidazole, H2hapen = N,N'-bis(2-hydroxyacetophenylidene)ethylenediamine), exhibiting thermal hysteresis, was synthesized and characterized. The Fe(III) ion has an octahedral coordination geometry, with N2O2 donor atoms of the planar tetradentate ligand (hapen) and two nitrogen atoms of two imidazoles at the axial positions. One of two imidazoles is hydrogen-bonded to the phenoxo oxygen atom of hapen of the adjacent unit to give a hydrogen-bonded one-dimensional chain, while the other imidazole group is free from hydrogen bonding. The temperature dependencies of the magnetic susceptibilities and Mössbauer spectra revealed an abrupt spin transition between the high-spin (S = 5/2) and low-spin (S = 1/2) states, with thermal hysteresis.

Spectroscopic studies of uranium species for environmental decontamination applications

NASA Astrophysics Data System (ADS)

Eng, Charlotte

After the Cold War, Department of Energy began to concentrate its efforts on cleanup of former nuclear material processing facilities, especially uranium-contaminated groundwater and soil. This research aims to study uranium association to both organic and inorganic compounds found in the contaminated environment in the hopes that the information gathered can be applied to the development and optimization of cost-effective remediation techniques. Spectroscopic and electrochemical methods will be employed to examine the behavior of uranium in given conditions to further our understanding of its impact on the environment. Uranium found in groundwater and soil bind with various ligands, especially organic ligands present in the environment due to natural sources (e.g. metabolic by-products or degradation of plants and animals) or man-made sources (e.g. chelating agents used in operating or cleanup of uranium processing facilities). We selected reasonable analogs of naturally occurring matter and studied their structure, chemical and electrochemical behavior and found that the structure of uranyl complexes depends heavily on the nature of the ligand and environmental factors such as pH. Association of uranium-organic complexes with anaerobic bacteria, Clostridium sp. was studied to establish if the bacteria can effectively bioreduce uranium while going through normal bacterial activity. It was found that the nature of the organic ligand affected the bioavailability and toxicity of the uranium on the bacteria. In addition, we have found that the type of iron corrosion products and uranyl species present on the surface of corroded steel depended on various environmental factors, which subsequently affected the removal rate of uranium by a citric acid/hydrogen peroxide/deionized water cleaning process. The method was found to remove uranium from only the topmost corrosion layers and residual uranium could be found (a) deeper in the corrosion layers where it is occluded by the steel corrosion products or (b) in areas where the dissolved uranium/iron species, the products generated by the dissolution power of citric acid, was not properly rinsed away.

Facile synthesis, cytotoxicity and bioimaging of Fe(3+) selective fluorescent chemosensor.

PubMed

Saleem, Muhammad; Abdullah, Razack; Ali, Anser; Park, Bong Joo; Choi, Eun Ha; Hong, In Seok; Lee, Ki Hwan

2014-04-01

The designing and development of fluorescent chemosensors have recently been intensively explored for sensitive and specific detection of environmentally and biologically relevant metal ions in aqueous solution and living cells. Herein, we report the photophysical results of alanine substituted rhodamine B derivative 3 having specific binding affinity toward Fe(3+) with micro molar concentration level. Through fluorescence titration at 599nm, we were confirmed that ligand 3 exhibited ratiometric fluorescence response with remarkable enhancement in emission intensity by complexation between 3 and Fe(3+) while it appeared no emission in case of the competitive ions (Sc(3+), Yb(3+), In(3+), Ce(3+), Sm(3+), Cr(3+), Sn(2+), Pb(2+), Ni(2+), Co(2+), Cu(2+), Ba(2+), Ca(2+), Mg(2+), Ag(+), Cs(+), Cu(+), K(+)) in aqueous/methanol (60:40, v/v) at neutral pH. However, the fluorescence as well as colorimetric response of ligand-iron complex solution was quenched by addition of KCN which snatches the Fe(3+) from complex and turn off the sensor confirming the recognition process was reversible. Furthermore, bioimaging studies against L-929 cells (mouse fibroblast cells) and BHK-21 (hamster kidney fibroblast), through confocal fluorescence microscopic experiment indicated that ligand showed good permeability and minimum toxicity against the tested cell lines. Copyright © 2014 Elsevier Ltd. All rights reserved.

High Valent Manganese and Cobalt Complexes of Oxidatively Robust Nitrogen and Oxygen Donor Ligands.

NASA Astrophysics Data System (ADS)

Gordon-Wylie, Scott Wallace

1995-01-01

The focus of this thesis is to extend the range of ligands that satisfy the Collins criteria through a program of organic synthesis, and to apply the resulting high valent metal ligand complexes to the solution of current problems in structural inorganic chemistry, solid state chemistry (with a particular emphasis on magnetic interactions in solids) and to homogeneous and heterogeneous catalysis. Notable achievements along these directions to date are: (i) A streamlined synthesis of diamide dialkoxide and diamide diphenoxide acyclic ligands which allows for a wide range of both electron withdrawing and electron donating substituents to be incorporated into the ligand framework. (ii) The first example of a LMn(V)O species stable enough to be crystallographically characterized was obtained, utilizing the acyclic ligands of (i). (iii) Catalytic O-atom transfer oxidations utilizing acyclic ligands from (i) have been performed. Planar Co(III) complexes of these ligands can catalyze O-atom transfers, ^1 with 30-50 turnovers, including enantioselective ones,^2 implicating that the ligands remain at least partially intact during the catalytic process. (iv) Unusual magnetic ordering has been observed in an infinite linear chain of S = 2 LMn(III) centers, in collaboration with Edmund P. Day. (v) Ferromagnetic exchange has been obtained in a ((LCo(III)) _3Co(II)) ^{-} complex^4 Magnetic model building in collaboration with Gordon Yee and Emile Bominaar has led to an understanding of the magnetic data suitable for publication.^5 (vi) Adaptation of a range of electronic substituents (see (i)) into a macrocyclic framework^7 allows for the preparation of hydrolytically and oxidatively stable high valent metal complexes. The presence of a range of electronic substituents further allows redox potentials for a single (LM) ^{rm n+}/(LM) ^{(rm n+1)+ } oxidation process to be tuned over a range that spans ca. 1 V. (vii) Initial linear syntheses for these macrocycles involved the use of organic azide intermediates. (viii) A new macrocyclic switching ligand has been synthesized utilizing (vii), that allows H^{+} or other lewis acids to act at the secondary site as electron withdrawing groups from the metal. In the structurally characterized switching (Co(III)( kappa^4-L)) ^{ -} complex, there is a bidentate switching site consisting of a pyridine-N and an adjacent amide-O donor. It has been found that the cobalt(II) derivative (CO(II)(kappa^4-L)) ^{-} readily reduces O _2 by an outer sphere (presumably by 1 e ^{-}) process. (ix) Robust homogeneous metalloredox-active oxidants are an important strategic goal for primary pollution prevention, or what is often called "green chemistry". Use of (vii) provides access to quantities of a macrocyclic ligand, that is derivatized in such a way that it can be attached to a solid polymer support. (x) C-H bond activation has been observed in iron systems^{15} in collaboration with Mike Bartos (the principal investigator) where use of (vii) has allowed quantities of ligand to be synthesized and burned in reaction chemistry with nitriles and oxidants. (xi) Macrocyclic ligands with organic solubilizing groups have been prepared utilizing (vii) and metal complexes with substantial alkane solubility result. (Abstract shortened by UMI.).

Metal ion binding to iron oxides

NASA Astrophysics Data System (ADS)

Ponthieu, M.; Juillot, F.; Hiemstra, T.; van Riemsdijk, W. H.; Benedetti, M. F.

2006-06-01

The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

Electrochemical behavior of meso-substituted iron porphyrins in alkaline aqueous media

NASA Astrophysics Data System (ADS)

Berezina, N. M.; Bazanov, M. I.; Maksimova, A. A.; Semeikin, A. S.

2017-12-01

The effect meso-substitution in iron porphyrin complexes has on their redox behavior in alkaline aqueous solutions is studied via cyclic voltammetry. The voltammetric features of the reduction of iron pyridylporphyrins suggest that the sites of electron transfer lie at the ligand, the metal ion, and the pyridyl moieties. The electron transfer reactions between the different forms of these compounds, including the oxygen reduction reaction they mediate, are outlined to show the sequence and potential ranges in which they occur in alkaline aqueous media. Under our experimental conditions, the iron porphyrins exist as μ-oxo dimmers whose activity for the electrocatalytic reduction of oxygen displays a considerable dependence on the nature of the substitutents and nitrogen isomerization (for pyridylporphyrins) and grows in the order (Fe( ms-Ph)4P)2O, (Fe[ ms-(Py-3)Ph3]P)2O, (Fe[ ms-(Py-4)4]P)2O, and (Fe[ ms-(Py-3)4]P)2O.

Towards a unifying, systems biology understanding of large-scale cellular death and destruction caused by poorly liganded iron: Parkinson’s, Huntington’s, Alzheimer’s, prions, bactericides, chemical toxicology and others as examples

PubMed Central

2010-01-01

Exposure to a variety of toxins and/or infectious agents leads to disease, degeneration and death, often characterised by circumstances in which cells or tissues do not merely die and cease to function but may be more or less entirely obliterated. It is then legitimate to ask the question as to whether, despite the many kinds of agent involved, there may be at least some unifying mechanisms of such cell death and destruction. I summarise the evidence that in a great many cases, one underlying mechanism, providing major stresses of this type, entails continuing and autocatalytic production (based on positive feedback mechanisms) of hydroxyl radicals via Fenton chemistry involving poorly liganded iron, leading to cell death via apoptosis (probably including via pathways induced by changes in the NF-κB system). While every pathway is in some sense connected to every other one, I highlight the literature evidence suggesting that the degenerative effects of many diseases and toxicological insults converge on iron dysregulation. This highlights specifically the role of iron metabolism, and the detailed speciation of iron, in chemical and other toxicology, and has significant implications for the use of iron chelating substances (probably in partnership with appropriate anti-oxidants) as nutritional or therapeutic agents in inhibiting both the progression of these mainly degenerative diseases and the sequelae of both chronic and acute toxin exposure. The complexity of biochemical networks, especially those involving autocatalytic behaviour and positive feedbacks, means that multiple interventions (e.g. of iron chelators plus antioxidants) are likely to prove most effective. A variety of systems biology approaches, that I summarise, can predict both the mechanisms involved in these cell death pathways and the optimal sites of action for nutritional or pharmacological interventions. PMID:20967426

M≡E and M=E Complexes of Iron and Cobalt that Emphasize Three-fold Symmetry (E = O, N, NR)

PubMed Central

Saouma, Caroline T.; Peters, Jonas C.

2011-01-01

Mid-to-late transition metal complexes that feature terminal, multiply bonded ligands such as oxos, imides, and nitrides have been invoked as intermediates in several catalytic transformations of synthetic and biological significance. Until about ten years ago, isolable examples of such species were virtually unknown. Over the past decade or so, numerous chemically well-defined examples of such species have been discovered. In this context, the presentreview summarizes the development of 4- and 5-coordinate Fe(E) and Co(E) species under local three-fold symmetry. PMID:21625302

Filling the Gap in Extended Metal Atom Chains: Ferromagnetic Interactions in a Tetrairon(II) String Supported by Oligo-α-pyridylamido Ligands.

PubMed

Nicolini, Alessio; Galavotti, Rita; Barra, Anne-Laure; Borsari, Marco; Caleffi, Matteo; Luo, Guangpu; Novitchi, Ghenadie; Park, Kyungwha; Ranieri, Antonio; Rigamonti, Luca; Roncaglia, Fabrizio; Train, Cyrille; Cornia, Andrea

2018-05-07

The stringlike complex [Fe 4 (tpda) 3 Cl 2 ] (2; H 2 tpda = N 2 , N 6 -bis(pyridin-2-yl)pyridine-2,6-diamine) was obtained as the first homometallic extended metal atom chain based on iron(II) and oligo-α-pyridylamido ligands. The synthesis was performed under strictly anaerobic and anhydrous conditions using dimesityliron, [Fe 2 (Mes) 4 ] (1; HMes = mesitylene), as both an iron source and a deprotonating agent for H 2 tpda. The four lined-up iron(II) ions in the structure of 2 (Fe···Fe = 2.94-2.99 Å, Fe···Fe···Fe = 171.7-168.8°) are wrapped by three doubly deprotonated twisted ligands, and the chain is capped at its termini by two chloride ions. The spectroscopic and electronic properties of 2 were investigated in dichloromethane by UV-vis-NIR absorption spectroscopy, 1 H NMR spectroscopy, and cyclic voltammetry. The electrochemical measurements showed four fully resolved, quasi-reversible one-electron-redox processes, implying that 2 can adopt five oxidation states in a potential window of only 0.8 V. Direct current (dc) magnetic measurements indicate dominant ferromagnetic coupling at room temperature, although the ground state is only weakly magnetic. On the basis of density functional theory and angular overlap model calculations, this magnetic behavior was explained as being due to two pairs of ferromagnetically coupled iron(II) ions ( J = -21 cm -1 using JŜ i ·Ŝ j convention) weakly antiferromagnetically coupled with each other. Alternating-current susceptibility data in the presence of a 2 kOe dc field and at frequencies up to 1.5 kHz revealed the onset of slow magnetic relaxation below 2.8 K, with the estimated energy barrier U eff / k B = 10.1(1.3) K.

3D Motions of Iron in Six-Coordinate {FeNO} 7 Hemes by Nuclear Resonance Vibration Spectroscopy [3-D Motions of Iron in Six-coordinate {FeNO} 7 Hemes by NRVS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Qian; Pavlik, Jeffrey W.; Silvernail, Nathan J.

The vibrational spectrum of a six-coordinate nitrosyl iron porphyrinate, monoclinic [Fe(T pFPP)(1-MeIm)(NO)] (T pFPP = tetra- para-fluorophenylporphyrin; 1-MeIm=1-methylimidazole), has been studied by oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS). The crystal was oriented to give spectra perpendicular to the porphyrin plane and two in-plane spectra perpendicular or parallel to the projection of the FeNO plane. These enable assignment of the FeNO bending and stretching modes. The measurements reveal that the two in-plane spectra have substantial differences that result from the strongly bonded axial NO ligand. The direction of the in-plane iron motion is found to be largely parallel and perpendicularmore » to the projection of the bent FeNO on the porphyrin plane. The out-of-plane Fe-N-O stretching and bending modes are strongly mixed with each other, as well as with porphyrin ligand modes. The stretch is mixed with v 50 as was also observed for dioxygen complexes. The frequency of the assigned stretching mode of eight Fe-X-O (X= N, C, and O) complexes is correlated with the Fe XO bond lengths. The nature of highest frequency band at ≈560 cm -1 has also been examined in two additional new derivatives. Previously assigned as the Fe NO stretch (by resonance Raman), it is better described as the bend, as the motion of the central nitrogen atom of the FeNO group is very large. There is significant mixing of this mode. In conclusion, the results emphasize the importance of mode mixing; the extent of mixing must be related to the peripheral phenyl substituents.« less

3D Motions of Iron in Six-Coordinate {FeNO} 7 Hemes by Nuclear Resonance Vibration Spectroscopy [3-D Motions of Iron in Six-coordinate {FeNO} 7 Hemes by NRVS

DOE PAGES

Peng, Qian; Pavlik, Jeffrey W.; Silvernail, Nathan J.; ...

2016-03-21

The vibrational spectrum of a six-coordinate nitrosyl iron porphyrinate, monoclinic [Fe(T pFPP)(1-MeIm)(NO)] (T pFPP = tetra- para-fluorophenylporphyrin; 1-MeIm=1-methylimidazole), has been studied by oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS). The crystal was oriented to give spectra perpendicular to the porphyrin plane and two in-plane spectra perpendicular or parallel to the projection of the FeNO plane. These enable assignment of the FeNO bending and stretching modes. The measurements reveal that the two in-plane spectra have substantial differences that result from the strongly bonded axial NO ligand. The direction of the in-plane iron motion is found to be largely parallel and perpendicularmore » to the projection of the bent FeNO on the porphyrin plane. The out-of-plane Fe-N-O stretching and bending modes are strongly mixed with each other, as well as with porphyrin ligand modes. The stretch is mixed with v 50 as was also observed for dioxygen complexes. The frequency of the assigned stretching mode of eight Fe-X-O (X= N, C, and O) complexes is correlated with the Fe XO bond lengths. The nature of highest frequency band at ≈560 cm -1 has also been examined in two additional new derivatives. Previously assigned as the Fe NO stretch (by resonance Raman), it is better described as the bend, as the motion of the central nitrogen atom of the FeNO group is very large. There is significant mixing of this mode. In conclusion, the results emphasize the importance of mode mixing; the extent of mixing must be related to the peripheral phenyl substituents.« less

Multidentate oligomeric ligands to enhance the biocompatibility of iron oxide and other metal nanoparticles

NASA Astrophysics Data System (ADS)

Wang, Wentao; Palui, Goutam; Ji, Xin; Aldeek, Fadi; Mattoussi, Hedi

2014-03-01

We prepared a set of multi-coordinating and reactive amphiphilic polymer ligands and used them for surface-functionalizing magnetic iron oxide nanoparticles. The amphiphilic oligomers were prepared by coupling (via one step nucleophilic addition) several dopamine anchoring groups, polyethylene glycol moieties and reactive groups onto a poly(isobutylene-alt-maleic anhydride) chain. The availability of several anchoring groups in the same ligand greatly enhances the ligand affinity to the nanoparticle surfaces, via multiplecoordination, while the hydrophilic and reactive groups promote colloidal stability in buffer media and allow subsequent conjugation to target biomolecules. The hydrophilic nanoparticles capped with these polymers maintain compact size and exhibit great long term colloidal stability.

Modeling the active site of [NiFe] hydrogenases and the [NiFeu] subsite of the C-cluster of carbon monoxide dehydrogenases: low-spin iron(II) versus high-spin iron(II).

PubMed

Weber, Katharina; Erdem, Özlen F; Bill, Eckhard; Weyhermüller, Thomas; Lubitz, Wolfgang

2014-06-16

A series of four [S2Ni(μ-S)2FeCp*Cl] compounds with different tetradentate thiolate/thioether ligands bound to the Ni(II) ion is reported (Cp* = C5Me5). The {S2Ni(μ-S)2Fe} core of these compounds resembles structural features of the active site of [NiFe] hydrogenases. Detailed analyses of the electronic structures of these compounds by Mössbauer and electron paramagnetic resonance spectroscopy, magnetic measurements, and density functional theory calculations reveal the oxidation states Ni(II) low spin and Fe(II) high spin for the metal ions. The same electronic configurations have been suggested for the Cred1 state of the C-cluster [NiFeu] subsite in carbon monoxide dehydrogenases (CODH). The Ni-Fe distance of ∼3 Å excludes a metal-metal bond between nickel and iron, which is in agreement with the computational results. Electrochemical experiments show that iron is the redox active site in these complexes, performing a reversible one-electron oxidation. The four complexes are discussed with regard to their similarities and differences both to the [NiFe] hydrogenases and the C-cluster of Ni-containing CODH.

Bis(2,3,5,6-tetra-2-pyridylpyrazine-κ3 N 2,N 1,N 6)iron(II) bis­(dicyanamidate) 4.5-hydrate

PubMed Central

Callejo, L.; De la Pinta, N.; Madariaga, G.; Fidalgo, M.L.; Cortés, R.

2010-01-01

In the title compound, [Fe(C24H16N6)2][N(CN)2]2·4.5H2O, the central iron(II) ion is hexa­coordinated by six N atoms of two tridentate 2,3,5,6-tetra-2-pyridylpyrazine (tppz) ligands. Two dicyanamide anions [dca or N(CN)2 −] act as counter-ions, and 4.5 water mol­ecules act as solvation agents. The structure contains isolated cationic iron(II)–tppz complexes and the final neutrality is obtained with the two dicyanamide anions. One of the dicyanamide anions and a water mol­ecule are disordered with an occupancy ratio of 0.614 (8):0.386 (8). O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds involving dca, water and tppz mol­ecules are observed. PMID:21580205

(18-Crown-6)potassium [(1,2,5,6-η)-cyclo-octa-1,5-diene][(1,2,3,4-η)-naph-tha-lene]-ferrate(-I).

PubMed

Brennessel, William W; Ellis, John E

2012-10-01

The title salt, [K(C(12)H(24)O(6))][Fe(C(8)H(12))(C(10)H(8))], is the only known naphthalene complex containing iron in a formally negative oxidation state. Each (naphthalene)(1,5-cod)ferrate(-I) anion is in contact with one (18-crown-6)potassium cation via K⋯C contacts to the outer four carbon atoms of the naphthalene ligand (cod = 1,5-cyclo-octa-diene, 18-crown-6 = 1,4,7,10,13,16-hexa-oxacyclo-octa-deca-ne). When using the midpoints of the coordinating olefin bonds, the overall geometry of the coordination sphere around iron can be best described as distorted tetra-hedral. The naphthalene fold angle between the plane of the iron-coordinating butadiene unit and the plane containing the exo-benzene moiety is 19.2 (1)°.

Mixed-valent dicobalt and iron-cobalt complexes with high-spin configurations and short metal-metal bonds.

PubMed

Zall, Christopher M; Clouston, Laura J; Young, Victor G; Ding, Keying; Kim, Hyun Jung; Zherebetskyy, Danylo; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C

2013-08-19

Cobalt-cobalt and iron-cobalt bonds are investigated in coordination complexes with formally mixed-valent [M2](3+) cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co2(DPhF)3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L(Ph)), the isolation of a dicobalt homobimetallic and an iron-cobalt heterobimetallic are demonstrated. The new [Co2](3+) and [FeCo](3+) cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal-metal bond distances of 2.29 Å for Co-Co and 2.18 Å for Fe-Co; the latter is the shortest distance for an iron-cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL(Ph) is more precisely described as (Fe0.94(1)Co0.06(1))(Co0.95(1)Fe0.05(1))L(Ph). The iron-cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe2(DPhF)3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M2](3+) cores are fully delocalized.

Interactions of human hemoglobin with charged ligand-functionalized iron oxide nanoparticles and effect of counterions

NASA Astrophysics Data System (ADS)

Ghosh, Goutam; Panicker, Lata

2014-12-01

Human hemoglobin is an important metalloprotein. It has tetrameric structure with each subunit containing a `heme' group which carries oxygen and carbon dioxide in blood. In this work, we have investigated the interactions of human hemoglobin (Hb) with charged ligand-functionalized iron oxide nanoparticles and the effect of counterions, in aqueous medium. Several techniques like DLS and ζ-potential measurements, UV-vis, fluorescence, and CD spectroscopy have been used to characterize the interaction. The nanoparticle size was measured to be in the range of 20-30 nm. Our results indicated the binding of Hb with both positively as well as negatively charged ligand-functionalized iron oxide nanoparticles in neutral aqueous medium which was driven by the electrostatic and the hydrophobic interactions. The electrostatic binding interaction was not seen in phosphate buffer at pH 7.4. We have also observed that the `heme' groups of Hb remained unaffected on binding with charged nanoparticles, suggesting the utility of the charged ligand-functionalized nanoparticles in biomedical applications.

Photomagnetic switching of heterometallic complexes [M(dmf)4(H2O)3(mu-CN)Fe(CN)5].H2O (M=Nd, La, Gd, Y) analyzed by single-crystal X-ray diffraction and ab initio theory.

PubMed

Svendsen, Helle; Overgaard, Jacob; Chevallier, Marie A; Collet, Eric; Chen, Yu-Sheng; Jensen, Frank; Iversen, Bo B

2010-06-25

Single-crystal X-ray diffraction measurements have been carried out on [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (1; dmf=dimethylformamide), [Nd(dmf)(4)(H(2)O)(3)(mu-CN)Co(CN)(5)].H(2)O (2), [La(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (3), [Gd(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (4), and [Y(dmf)(4)(H(2)O)(3)(mu-CN)Fe(CN)(5)].H(2)O (5), at 15(2) K with and without UV illumination of the crystals. Significant changes in unit-cell parameters were observed for all the iron-containing complexes, whereas 2 showed no response to UV illumination. Photoexcited crystal structures have been determined for 1, 3, and 4 based on refinements of two-conformer models, and excited-state occupancies of 78.6(1), 84(6), and 86.6(7)% were reached, respectively. Significant bond-length changes were observed for the Fe-ligand bonds (up to 0.19 A), the cyano bonds (up to 0.09 A), and the lanthanide-ligand bonds (up to 0.10 A). Ab initio theoretical calculations were carried out for the experimental ground-state geometry of 1 to understand the electronic structure changes upon UV illumination. The calculations suggest that UV illumination gives a charge transfer from the cyano groups on the iron atom to the lanthanide ion moiety, {Nd(dmf)(4)(H(2)O)(3)}, with a distance of approximately 6 A from the iron atom. The charge transfer is accompanied by a reorganization of the spin state on the {Fe(CN)(6)} complex, and a change in geometry that produces a metastable charge-transfer state with an increased number of unpaired electrons, thus accounting for the observed photomagnetic effect.

First-Principles Fe L 2,3 -Edge and O K-Edge XANES and XMCD Spectra for Iron Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sassi, Michel; Pearce, Carolyn I.; Bagus, Paul S.

X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) spectroscopies are tools in widespread use for providing detailed local atomic structure, oxidation state, and magnetic structure information for materials and organometallic complexes. The analysis of these spectra for transition-metal L-edges is routinely performed on the basis of ligand-field multiplet theory because one- and two-particle mean-field ab initio methods typically cannot describe the multiplet structure. Here we show that multireference configuration interaction (MRCI) calculations can satisfactorily reproduce measured XANES spectra for a range of complex iron oxide materials including hematite and magnetite. MRCI Fe L2,3-edge XANES and XMCD spectramore » of Fe(II)O6, Fe(III)O6, and Fe(III)O4 in magnetite are found to be in very good qualitative agreement with experiment and multiplet calculations. Point-charge embedding and small distortions of the first-shell oxygen ligands have only small effects. Oxygen K-edge XANES/XMCD spectra for magnetite investigated by a real-space Green’s function approach complete the very good qualitative agreement with experiment. Material-specific differences in local coordination and site symmetry are well reproduced, making the approach useful for assigning spectral features to specific oxidation states and coordination environments.« less

Subpicosecond oxygen trapping in the heme pocket of the oxygen sensor FixL observed by time-resolved resonance Raman spectroscopy.

PubMed

Kruglik, Sergei G; Jasaitis, Audrius; Hola, Klara; Yamashita, Taku; Liebl, Ursula; Martin, Jean-Louis; Vos, Marten H

2007-05-01

Dissociation of oxygen from the heme domain of the bacterial oxygen sensor protein FixL constitutes the first step in hypoxia-induced signaling. In the present study, the photodissociation of the heme-O2 bond was used to synchronize this event, and time-resolved resonance Raman (TR(3)) spectroscopy with subpicosecond time resolution was implemented to characterize the heme configuration of the primary photoproduct. TR(3) measurements on heme-oxycomplexes are highly challenging and have not yet been reported. Whereas in all other known six-coordinated heme protein complexes with diatomic ligands, including the oxymyoglobin reported here, heme iron out-of-plane motion (doming) occurs faster than 1 ps after iron-ligand bond breaking; surprisingly, no sizeable doming is observed in the oxycomplex of the Bradyrhizobium japonicum FixL sensor domain (FixLH). This assessment is deduced from the absence of the iron-histidine band around 217 cm(-1) as early as 0.5 ps. We suggest that efficient ultrafast oxygen rebinding to the heme occurs on the femtosecond time scale, thus hindering heme doming. Comparing WT oxy-FixLH, mutant proteins FixLH-R220H and FixLH-R220Q, the respective carbonmonoxy-complexes, and oxymyoglobin, we show that a hydrogen bond of the terminal oxygen atom with the residue in position 220 is responsible for the observed behavior; in WT FixL this residue is arginine, crucially implicated in signal transmission. We propose that the rigid O2 configuration imposed by this residue, in combination with the hydrophobic and constrained properties of the distal cavity, keep dissociated oxygen in place. These results uncover the origin of the "oxygen cage" properties of this oxygen sensor protein.

An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

PubMed Central

Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

1982-01-01

Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

Integration of ligand and structure based approaches for identification of novel MbtI inhibitors in Mycobacterium tuberculosis and molecular dynamics simulation studies.

PubMed

Maganti, Lakshmi; Grandhi, Pradeep; Ghoshal, Nanda

2016-11-01

Mycobacterium tuberculosis is an obligate pathogen of mammals and is responsible for more than two million deaths annually. The ability to acquire iron from the extracellular environment is a key determinant of pathogenicity in mycobacteria. M. tuberculosis acquires iron exclusively through the siderophores. Several lines of evidence suggest that siderophores have a critical role in bacterial growth and virulence. Hence, in the present study, we have used a combined ligand and structure-based drug design approach for identification of novel inhibitors against salicylate synthase MbtI, a unique and essential enzyme for the biosynthesis of siderophores in M. tuberculosis. We have generated the ligand based and structure based pharmacophores and validated exhaustively. From the validation results it was found that GH (Goodness of Hit) scores for the selected ligand based and structure based pharmacophore models were 0.89 and 0.97, respectively, which indicate that the quality of the pharmacophore models are acceptable as GH value is >0.7. The validated pharmacophores were used for screening the ZINC database. A total of 73 hits, obtained through various insilico screening techniques, were further enriched to 17 hits using docking studies. Molecular dynamics simulations were carried out to compare the binding mode and stability of complexes of MbtI bound with substrate, known inhibitors, and three top ranked hits. The results obtained in this study gave assurance about the identified hits as prospective inhibitors of MbtI. Copyright © 2016 Elsevier Inc. All rights reserved.

Effects of citrate on hexavalent chromium reduction by structural Fe(II) in nontronite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Xiaolei; Dong, Hailiang; Yang, Xuewei

Iron-bearing clay minerals and organic matter are two important components in natural environments that influence hexavalent chromium (Cr(VI)) reduction. Previous studies have shown that organic ligands could influence Cr(VI) reduction by aqueous Fe2+ and pyrite. However, the effects of organic ligands on Cr(VI) reduction by structural Fe(II) in clays are not well understood. In this study, the effects of citrate on Cr(VI) reduction by nontronite (NAu-2) were investigated under near neutral pH condition (pH=6). Our results showed that the presence of citrate decreased the rate but increased the amount of Cr(VI) reduction by structural Fe(II) in NAu-2. The decreased reactionmore » rate was likely due to competitive sorption of citrate and polyanionic dichromate (Cr2O7- ), because sorption of dichromate appeared to be the first step for subsequent Cr(VI) reduction. The increased amount of Cr(VI) reduction in the presence of citrate was likely because citrate provided additional reducing power through ligand-metal electron transfer in the presence of soluble Fe 3+ derived from dissolution of reduced NAu-2. Soluble Cr(III)-citrate complex was the possible form of reduced chromium when citrate was present. In contrast, nanometer-sized Cr2O3 particles were the product of Cr(VI) reduction by reduced NAu-2 without citrate. Our study highlights the importance of organic ligands on Cr(VI) reduction and immobilization when iron-bearing clay minerals are applied to treat Cr(VI) contaminant in organic matter rich environments.« less

Production and Isolation of Amphibactin siderophores in Iron-stressed cultures of the marine bacteria Vibrio spp.

NASA Astrophysics Data System (ADS)

McLean, C.; Boiteau, R.; Bundy, R.; Gauglitz, J.; Repeta, D.

2016-02-01

Iron is an important micronutrient for marine microbes. Low concentrations of dissolved iron limit production in much of the ocean, putting pressure on microbial communities to develop efficient iron acquisition strategies. One such strategy is the production of siderophores, high affinity iron binding ligands, to facilitate iron uptake to meet their physiological iron quota. Recently, our lab has shown that amphibactins, siderophores with lipid side chains, are present in iron-deficient regions of the ocean. However, little is known about which organisms can utilize amphibactin bound iron. Here we describe a method to isolate amphibactins from laboratory cultures in order to identify the conditional stability constants and uptake rates of purified amphibactin compounds. We searched the National Center for Biotechnology Information database to identify microbial genomes containing homologous to the known amphibactin biosynthesis genes. Several of these strains were screened with high performance reverse-phase liquid chromatography electrospray ionization mass spectrometry (HPLC-ESIMS) to confirm amphibactin production. We then optimized amphibactin production for the strain Vibrio cyclitrophicus 1F53 under different shaking speeds and iron concentrations, using a chrome azurol S (CAS) assay to screen for siderophore abundance. Maximum production was found after 38 hours of shaking at 150-rpm, and with the addition of 10nM of desferrioxamine B to induce iron limitation. Amphibactins were extracted from the media by solid phase extraction and purified by reverse phase HPLC. The conditional stability constants for several amphibactins were then measured in seawater using competitive ligand exchange absorptive cathodic stripping voltammetry with salicylaldoxime as the added ligand. Future work will determine the uptake rates of these compounds by natural communities of marine bacteria, and give insight on the bioavailability of amphibactins in the marine environment.

Crystal structure of bis-(benzyl-amine-κN)[5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinato-κ(4) N]iron(II) n-hexane monosolvate.

PubMed

Dhifaoui, Selma; Harhouri, Wafa; Bujacz, Anna; Nasri, Habib

2016-01-01

In the title compound, [Fe(II)(C44H24Cl4N4)(C6H5CH2NH2)2]·C6H14 or [Fe(II)(TPP-Cl)(BzNH2)2]·n-hexane [where TPP-Cl and BzNH2 are 5,10,15,20-tetra-kis-(4-chloro-phen-yl)porphyrinate and benzyl-amine ligands, respectively], the Fe(II) cation lies on an inversion centre and is octa-hedrally coordinated by the four pyrrole N atoms of the porphyrin ligand in the equatorial plane and by two amine N atoms of the benzyl-amine ligand in the axial sites. The crystal structure also contains one inversion-symmetric n-hexane solvent mol-ecule per complex mol-ecule. The average Fe-Npyrrole bond length [1.994 (3) Å] indicates a low-spin complex. The crystal packing is sustained by N-H⋯Cl and C-H⋯Cl hydrogen-bonding inter-actions and by C-H⋯π inter-molecular inter-actions, leading to a three-dimensional network structure.

Combined MCD/DFT/TDDFT Study of the Electronic Structure of Axially Pyridine Coordinated Metallocorroles.

PubMed

Rhoda, Hannah M; Crandall, Laura A; Geier, G Richard; Ziegler, Christopher J; Nemykin, Victor N

2015-05-18

A series of metallocorroles were investigated by UV-vis and magnetic circular dichroism spectroscopies. The diamagnetic distorted square-pyramidal main-group corrole Ga(tpfc)py (2), the diamagnetic distorted octahedral transition-metal adduct Co(tpfc)(py)2 (3), and paramagnetic distorted octahedral transition-metal complex Fe(tpfc)(py)2 (4) [H3tpfc = tris(perfluorophenyl)corrole] were studied to investigate similarities and differences in the electronic structure and spectroscopy of the closed- and open-shell metallocorroles. Similar to the free-base H3tpfc (1), inspection of the MCD Faraday B-terms for all of the macrocycles presented in this report revealed that a ΔHOMO < ΔLUMO [ΔHOMO is the energy difference between two highest energy corrole-centered π-orbitals and ΔLUMO is the energy difference between two lowest energy corrole-centered π*-orbitals originating from ML ± 4 and ML ± 5 pairs of perimeter] condition is present for each complex, which results in an unusual sign-reversed sequence for π-π* transitions in their MCD spectra. In addition, the MCD spectra of the cobalt and the iron complexes were also complicated by a number of charge-transfer states in the visible region. Iron complex 4 also exhibits a low-energy absorption in the NIR region (1023 nm). DFT and TDDFT calculations were used to elaborate the electronic structures and provide band assignments in UV-vis and MCD spectra of the metallocorroles. DFT and TDDFT calculations predict that the orientation of the axial pyridine ligand(s) has a very minor influence on the calculated electronic structures and absorption spectra in the target systems.

A combined experimental and theoretical study of dinitrosyl iron complexes containing chelating bis(diphenyl)phosphinoX (X = benzene, propane and ethylene): X-ray crystal structures and properties influenced by the presence or absence of π-bonds in chelating ligands

PubMed Central

Holloway, Lauren R.; Clough, Andrew J.; Li, Jessica Y.; Tao, Emily L.; Tao, Fu-Ming; Li, Lijuan

2014-01-01

Recent discoveries involving the roles of nitric oxide in humans have stimulated intense interest in transition metal nitrosyl complexes. A series of dinitrosyl iron complexes with the formula [(DPPX)Fe(NO)2], {DPPX = 1,2-bis(diphenylphosphino)benzene (1), 1,3-bis(diphenylphosphino)propane (2), and cis-1,2-bis(diphenylphosphino)ethylene (3)} has been prepared and characterized through a combination of FT-IR, NMR, UV-vis, X-ray crystallography, and electrochemical techniques. Infrared spectroscopy showed NO shifts to the region of 1723 and 1674 cm−1 for complexes 1 and 3, and 1708 and 1660 cm−1 for 2, indicating that ligand 2 acts as a stronger σ–donor. The X-ray crystallographic data showed that 1 and 3 possess the rare repulso conformation while 2 has the attracto conformation. CV studies on compounds 1, 2 and 3 display two quasi-reversible oxidations with the E°1/2 values at 0.101 and 0.186 V, 0.121 and 0.184 V, and 0.019 and 0.342 V, respectively. The larger ΔE value for compound 2 compared with that of 1 and 3 is attributed to the lack of π-bonds between the two phosphorus atoms. Theoretical calculations using density functional theory were carried out on the synthesized compounds and model compounds and the results are consistent with the experimental data. The calculated HOMO-LUMO gaps for compounds 1, 2 and 3 are 3.736, 4.060, and 3.669 eV, respectively, which supports the stronger back-donation for compound 2 than that of compounds 1 and 3. PMID:24860235

Effects of molecular composition of natural organic matter on ferric iron complexation at circumneutral pH.

PubMed

Fujii, Manabu; Imaoka, Akira; Yoshimura, Chihiro; Waite, T D

2014-04-15

Thermodynamic and kinetic parameters for ferric iron (Fe[III]) complexation by well-characterized humic substances (HS) from various origins were determined by a competitive ligand method with 5-sulfosalicylic acid at circumneutral pH (6.0-8.0) and an ionic strength of ∼0.06 M. The measured Fe binding properties including conditional stability constants and complexation capacities ranged over more than 2 orders of magnitude, depending on the origin and the particular operationally defined fraction of HS examined. Statistical comparison of the complexation parameters to a range of chemical properties of the HS indicated a strong positive correlation between Fe(III) complexation capacity and aromatic carbon content in the HS at all pHs examined. In contrast, the complexation capacity was determined to be up to a few orders of magnitude smaller than the concentration of carboxylic and phenolic groups present. Therefore, specific functional groups including those resident in the proximity of aromatic structures within the HS are likely preferable for Fe(III) coordination under the conditions examined. Overall, our results suggest that the concentration of dissolved Fe(III) complexes in natural waters is substantially influenced by variation in HS characteristics in addition to other well-known factors such as HS concentration and nature and concentration of competing cations present.

Bis(hydroxylamino)triazines: High Selectivity and Hydrolytic Stability of Hydroxylamine-Based Ligands for Uranyl Compared to Vanadium(V) and Iron(III).

PubMed

Hadjithoma, Sofia; Papanikolaou, Michael G; Leontidis, Epameinondas; Kabanos, Themistoklis A; Keramidas, Anastasios D

2018-06-08

The development of ligands with high selectivity and affinity for uranium is critical in the extraction of uranium from human body, radioactive waste, and seawater. A scientific challenge is the improvement of the selectivity of chelators for uranium over other heavy metals, including iron and vanadium. Flat ligands with hard donor atoms that satisfy the geometric and electronic requirements of the U VI O 2 2+ exhibit high selectivity for the uranyl moiety. The bis(hydroxylamino)(triazine) ligand, 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H 2 bihyat), a strong binder for hard metal ions (Fe III , Ti IV , V V , and Mo VI ), reacted with [U VI O 2 (NO 3 ) 2 (H 2 O) 2 ]·4H 2 O in aqueous solution and resulted in the isolation of the complexes [U VI O 2 (bihyat)(H 2 O)], [U VI O 2 (bihyat) 2 ] 2- , and {[U VI O 2 (bihyat)(μ-OH)]} 2 2- . These three species are in equilibrium in aqueous solution, and their abundance varies with the concentration of H 2 bihyat and the pH. Reaction of H 2 bihyat with [U VI O 2 (NO 3 ) 2 (H 2 O) 2 ]·4H 2 O in CH 3 CN gave the trinuclear complex [U VI 3 O 6 (bihyat) 2 (μ-bihyat) 2 ] 2- , which is the major species in organic solvents. The dynamics between the U VI O 2 2+ and the free ligand H 2 bihyat in aqueous and dimethyl sulfoxide solutions; the metal binding ability of the H 2 bihyat over pyridine-2,6-dicarboxylic acid (H 2 dipic) or glutarimidedioxime for U VI O 2 2+ , and the selectivity of the H 2 bihyat to bind U VI O 2 2+ in comparison to V V O 4 3- and Fe III in either U VI O 2 2+ /V V O 4 3- or U VI O 2 2+ /Fe III solutions were examined by NMR and UV-vis spectroscopies. The results revealed that H 2 bihyat is a superior ligand for U VI O 2 2+ with high selectivity compared to Fe III and V V O 4 3- , which increases at higher pHs. Thus, this type of ligand might find applications in the extraction of uranium from the sea and its removal from the environment and the human body.

Spin state switching in iron coordination compounds

PubMed Central

Gaspar, Ana B; Garcia, Yann

2013-01-01

Summary The article deals with coordination compounds of iron(II) that may exhibit thermally induced spin transition, known as spin crossover, depending on the nature of the coordinating ligand sphere. Spin transition in such compounds also occurs under pressure and irradiation with light. The spin states involved have different magnetic and optical properties suitable for their detection and characterization. Spin crossover compounds, though known for more than eight decades, have become most attractive in recent years and are extensively studied by chemists and physicists. The switching properties make such materials potential candidates for practical applications in thermal and pressure sensors as well as optical devices. The article begins with a brief description of the principle of molecular spin state switching using simple concepts of ligand field theory. Conditions to be fulfilled in order to observe spin crossover will be explained and general remarks regarding the chemical nature that is important for the occurrence of spin crossover will be made. A subsequent section describes the molecular consequences of spin crossover and the variety of physical techniques usually applied for their characterization. The effects of light irradiation (LIESST) and application of pressure are subjects of two separate sections. The major part of this account concentrates on selected spin crossover compounds of iron(II), with particular emphasis on the chemical and physical influences on the spin crossover behavior. The vast variety of compounds exhibiting this fascinating switching phenomenon encompasses mono-, oligo- and polynuclear iron(II) complexes and cages, polymeric 1D, 2D and 3D systems, nanomaterials, and polyfunctional materials that combine spin crossover with another physical or chemical property. PMID:23504535

Iron L-edge X-ray Absorption Spectroscopy of Oxy-Picket Fence Porphyrin: Experimental Insight into Fe-O2 Bonding

PubMed Central

Wilson, Samuel A.; Kroll, Thomas; Decreau, Richard A.; Hocking, Rosalie K.; Lundberg, Marcus; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

2013-01-01

The electronic structure of the Fe–O2 center in oxy-hemoglobin and oxy-myoglobin is a long-standing issue in the field of bioinorganic chemistry. Spectroscopic studies have been complicated by the highly delocalized nature of the porphyrin and calculations require interpretation of multi-determinant wavefunctions for a highly covalent metal site. Here, iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction (VBCI) multiplet model, is applied to directly probe the electronic structure of the iron in the biomimetic Fe–O2 heme complex [Fe(pfp)(1-MeIm)O2] (pfp = meso-tetra(α,α,α,α-o-pivalamidophenyl) porphyrin or TpivPP). This method allows separate estimates of σ-donor, π-donor, and π-acceptor interactions through ligand to metal charge transfer (LMCT) and metal to ligand charge transfer (MLCT) mixing pathways. The L-edge spectrum of [Fe(pfp)(1-MeIm)O2] is further compared to those of [FeII(pfp)(1-MeIm)2], [FeII(pfp)], and [FeIII(tpp)(ImH)2]Cl (tpp = meso-tetraphenylporphyrin) which have FeII S = 0, FeII S = 1 and FeIII S = 1/2 ground states, respectively. These serve as references for the three possible contributions to the ground state of oxy-pfp. The Fe–O2 pfp site is experimentally determined to have both significant σ-donation and a strong π-interaction of the O2 with the iron, with the latter having implications with respect to the spin polarization of the ground state. PMID:23259487

Comprehensive analysis of organic ligands in whole root exudates using nuclear magnetic resonance and gas chromatography-mass spectrometry.

PubMed

Fan, T W; Lane, A N; Pedler, J; Crowley, D; Higashi, R M

1997-08-15

Root exudates in the rhizosphere are vital to the normal life cycle of plants. A key factor is phytometallophores, which function in the nutritional acquisition of iron and zinc and are likely to be important in the uptake of pollutant metals by plants. Unraveling the biochemistry of these compounds is tedious using traditional analyses, which also fall short in providing the overall chemical composition or in detecting unknown or unexpected organic ligands in the exudates. Here, we demonstrate a comprehensive analysis of the exudate composition directly by 1H and 13C multidimensional NMR and silylation GC-MS. The advantages are (a) minimal sample preparation, with no loss of unknown compounds, and reduced net analysis time; (b) structure-based analysis for universal detection and identification; and (c) simultaneous analysis of a large number of constituents in a complex mixture. Using barley root exudates, a large number of common organic and amino acids were identified. Three derivatives of mugineic acid phytosiderophores were also determined, the major one being 3-epihydroxymugineic acid, for which complete 1H and 13C NMR assignments were obtained. Quantification of all major components using these methods revealed a sevenfold increase in total exudation under moderate iron deficiency, with 3-epihydroxymugineic acid comprising approximately 22% of the exudate mixture. As iron deficiency increased, total quantities of exudate per gram of root remained unchanged, but the relative quantity of carbon allocated to phytosiderophore increased to approximately 50% of the total exudate in response to severe iron deficiency.

Stabilities of thiomolybdate complexes of iron; implications for retention of essential trace elements (Fe, Cu, Mo) in sulfidic waters.

PubMed

Helz, George R; Erickson, Britt E; Vorlicek, Trent P

2014-06-01

In aquatic ecosystems, availabilities of Fe, Mo and Cu potentially limit rates of critical biological processes, including nitrogen fixation, nitrate assimilation and N2O decomposition. During long periods in Earth's history when large parts of the ocean were sulfidic, what prevented these elements' quantitative loss from marine habitats as insoluble sulfide phases? They must have been retained by formation of soluble complexes. Identities of the key ligands are poorly known but probably include thioanions. Here, the first determinations of stability constants for Fe(2+)-[MoS4](2-) complexes in aqueous solution are reported based on measurements of pyrrhotite (hexagonal FeS) solubility under mildly alkaline conditions. Two linear complexes, [FeO(OH)MoS4](3-) and [(Fe2S2)(MoS4)2](4-), best explain the observed solubility variations. Complexes that would be consistent with cuboid cluster structures were less successful, implying that such clusters probably are minor or absent in aqueous solution under the conditions studied. The new data, together with prior data on stabilities of Cu(+)-[MoS4](2-) complexes, are used to explore computationally how competition of Fe(2+) and Cu(+) for [MoS4](2-), as well as competition of [MoS4](2-) and HS(-) for both metals would be resolved in solutions representative of sulfidic natural waters. Thiomolybdate complexes will be most important at sulfide concentrations near the [MoO4](2-)-[MoS4](2-) equivalence point. At lower sulfide concentrations, thiomolybdates are insufficiently stable to be competitive ligands in natural waters and at higher sulfide concentrations HS(-) ligands out-compete thiomolybdates.

Ligand-hole localization in oxides with unusual valence Fe

PubMed Central

Chen, Wei-Tin; Saito, Takashi; Hayashi, Naoaki; Takano, Mikio; Shimakawa, Yuichi

2012-01-01

Unusual high-valence states of iron are stabilized in a few oxides. A-site-ordered perovskite-structure oxides contain such iron cations and exhibit distinct electronic behaviors at low temperatures, e.g. charge disproportionation (4Fe4+ → 2Fe3+ + 2Fe5+) in CaCu3Fe4O12 and intersite charge transfer (3Cu2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+) in LaCu3Fe4O12. Here we report the synthesis of solid solutions of CaCu3Fe4O12 and LaCu3Fe4O12 and explain how the instabilities of their unusual valence states of iron are relieved. Although these behaviors look completely different from each other in simple ionic models, they can both be explained by the localization of ligand holes, which are produced by the strong hybridization of iron d and oxygen p orbitals in oxides. The localization behavior in the charge disproportionation of CaCu3Fe4O12 is regarded as charge ordering of the ligand holes, and that in the intersite charge transfer of LaCu3Fe4O12 is regarded as a Mott transition of the ligand holes. PMID:22690318

Analytical Interference in Serum Iron Determination Reveals Iron Versus Gadolinium Transmetallation With Linear Gadolinium-Based Contrast Agents

PubMed Central

Fretellier, Nathalie; Poteau, Nathalie; Factor, Cécile; Mayer, Jean-François; Medina, Christelle; Port, Marc; Idée, Jean-Marc; Corot, Claire

2014-01-01

Objectives The purposes of this study were to evaluate the risk for analytical interference with gadolinium-based contrast agents (GBCAs) for the colorimetric measurement of serum iron (Fe3+) and to investigate the mechanisms involved. Materials and Methods Rat serum was spiked with several concentrations of all molecular categories of GBCAs, ligands, or “free” soluble gadolinium (Gd3+). Serum iron concentration was determined by 2 different colorimetric methods at pH 4.0 (with a Vitros DT60 analyzer or a Cobas Integra 400 analyzer). Secondly, the cause of interference was investigated by (a) adding free soluble Gd3+ or Mn2+ to serum in the presence of gadobenic acid or gadodiamide and (b) electrospray ionization mass spectrometry. Results Spurious decrease in serum Fe3+ concentration was observed with all linear GBCAs (only with the Vitros DT60 technique occurring at pH 4.0) but not with macrocyclic GBCAs or with free soluble Gd3+. Spurious hyposideremia was also observed with the free ligands present in the pharmaceutical solutions of the linear GBCAs gadopentetic acid and gadodiamide (ie, diethylene triamine pentaacetic acid and calcium-diethylene triamine pentaacetic acid bismethylamide, respectively), suggesting the formation of Fe-ligand chelate. Gadobenic acid-induced interference was blocked in a concentration-dependent fashion by adding a free soluble Gd3+ salt. Conversely, Mn2+, which has a lower affinity than Gd3+ and Fe3+ for the ligand of gadobenic acid (ie, benzyloxypropionic diethylenetriamine tetraacetic acid), was less effective (interference was only partially blocked), suggesting an Fe3+ versus Gd3+ transmetallation phenomenon at pH 4.0. Similar results were observed with gadodiamide. Mass spectrometry detected the formation of Fe-ligand with all linear GBCAs tested in the presence of Fe3+ and the disappearance of Fe-ligand after the addition of free soluble Gd3+. No Fe-ligand chelate was found in the case of the macrocyclic GBCA gadoteric acid. Conclusions Macrocyclic GBCAs induced no interference with colorimetric methods for iron determination, whereas negative interference was observed with linear GBCAs using a Vitros DT60 analyzer. This interference of linear GBCAs seems to be caused by the excess of ligand and/or an Fe3+ versus Gd3+ transmetallation phenomenon. PMID:24943092

Comparison of ligand migration and binding in heme proteins of the globin family

NASA Astrophysics Data System (ADS)

Karin, Nienhaus; Ulrich Nienhaus, G.

2015-12-01

The binding of small diatomic ligands such as carbon monoxide or dioxygen to heme proteins is among the simplest biological processes known. Still, it has taken many decades to understand the mechanistic aspects of this process in full detail. Here, we compare ligand binding in three heme proteins of the globin family, myoglobin, a dimeric hemoglobin, and neuroglobin. The combination of structural, spectroscopic, and kinetic experiments over many years by many laboratories has revealed common properties of globins and a clear mechanistic picture of ligand binding at the molecular level. In addition to the ligand binding site at the heme iron, a primary ligand docking site exists that ensures efficient ligand binding to and release from the heme iron. Additional, secondary docking sites can greatly facilitate ligand escape after its dissociation from the heme. Although there is only indirect evidence at present, a preformed histidine gate appears to exist that allows ligand entry to and exit from the active site. The importance of these features can be assessed by studies involving modified proteins (via site-directed mutagenesis) and comparison with heme proteins not belonging to the globin family.

Magnetic blocking in a linear iron(I) complex.

PubMed

Zadrozny, Joseph M; Xiao, Dianne J; Atanasov, Mihail; Long, Gary J; Grandjean, Fernande; Neese, Frank; Long, Jeffrey R

2013-07-01

Single-molecule magnets that contain one spin centre may represent the smallest possible unit for spin-based computational devices. Such applications, however, require the realization of molecules with a substantial energy barrier for spin inversion, achieved through a large axial magnetic anisotropy. Recently, significant progress has been made in this regard by using lanthanide centres such as terbium(III) and dysprosium(III), whose anisotropy can lead to extremely high relaxation barriers. We contend that similar effects should be achievable with transition metals by maintaining a low coordination number to restrict the magnitude of the d-orbital ligand-field splitting energy (which tends to hinder the development of large anisotropies). Herein we report the first two-coordinate complex of iron(I), [Fe(C(SiMe3)3)2](-), for which alternating current magnetic susceptibility measurements reveal slow magnetic relaxation below 29 K in a zero applied direct-current field. This S =  complex exhibits an effective spin-reversal barrier of Ueff = 226(4) cm(-1), the largest yet observed for a single-molecule magnet based on a transition metal, and displays magnetic blocking below 4.5 K.

Synthesis of low cost organometallic-type catalysts for their application in microbial fuel cell technology.

PubMed

Zerrouki, A; Salar-García, M J; Ortiz-Martínez, V M; Guendouz, S; Ilikti, H; de Los Ríos, A P; Hernández-Fernández, F J; Kameche, M

2018-03-05

Microbial fuel cells (MFCs) are a promising technology that generates electricity from several biodegradable substrates and wastes. The main drawback of these devices is the need of using a catalyst for the oxygen reduction reaction at the cathode, which makes the process relatively expensive. In this work, two low cost materials are tested as catalysts in MFCs. A novel iron complex based on the ligand n-phenyledenparaethoxy aniline has been synthesized and its performance as catalyst in single chamber MFCs containing ionic liquids has been compared with a commercial inorganic material such as Raney nickel. The results show that both materials are suitable for bioenergy production and wastewater treatment in the systems. Raney nickel cathodes allow MFCs to reach a maximum power output of 160 mW.m -3 anode , while the iron complex offers lower values. Regarding the wastewater treatment capacity, MFCs working with Raney nickel-based cathodes reach higher values of chemical oxygen demand removal (76%) compared with the performance displayed by the cathodes based on Fe-complex (56%).

Efficient catalytic cycloalkane oxidation employing a "helmet" phthalocyaninato iron(III) complex.

PubMed

Brown, Elizabeth S; Robinson, Jerome R; McCoy, Aaron M; McGaff, Robert W

2011-06-14

We have examined the catalytic activity of an iron(III) complex bearing the 14,28-[1,3-diiminoisoindolinato]phthalocyaninato (diiPc) ligand in oxidation reactions with three substrates (cyclohexane, cyclooctane, and indan). This modified metallophthalocyaninato complex serves as an efficient and selective catalyst for the oxidation of cyclohexane and cyclooctane, and to a far lesser extent indan. In the oxidations of cyclohexane and cyclooctane, in which hydrogen peroxide is employed as the oxidant under inert atmosphere, we have observed turnover numbers of 100.9 and 122.2 for cyclohexanol and cyclooctanol, respectively. The catalyst shows strong selectivity for alcohol (vs. ketone) formation, with alcohol to ketone (A/K) ratios of 6.7 and 21.0 for the cyclohexane and cyclooctane oxidations, respectively. Overall yields (alcohol + ketone) were 73% for cyclohexane and 92% for cyclooctane, based upon the total hydrogen peroxide added. In the catalytic oxidation of indan under similar conditions, the TON for 1-indanol was 10.1, with a yield of 12% based upon hydrogen peroxide. No 1-indanone was observed in the product mixture.

Demetalation of Fe, Mn, and Cu chelates and complexes: application to the NMR analysis of micronutrient fertilizers.

PubMed

López-Rayo, Sandra; Lucena, Juan J; Laghi, Luca; Cremonini, Mauro A

2011-12-28

The application of nuclear magnetic resonance (NMR) for the quality control of fertilizers based on Fe(3+), Mn(2+), and Cu(2+) chelates and complexes is precluded by the strong paramagnetism of metals. Recently, a method based on the use of ferrocyanide has been described to remove iron from commercial iron chelates based on the o,o-EDDHA [ethylenediamine-N,N'bis(2-hydroxyphenylacetic)acid] chelating agent for their analysis and quantification by NMR. The present work extended that procedure to other paramagnetic ions, manganese and copper, and other chelating, EDTA (ethylenediaminetetraacetic acid), IDHA [N-(1,2-dicarboxyethyl)-d,l-aspartic acid], and complexing agents, gluconate and heptagluconate. Results showed that the removal of the paramagnetic ions was complete, allowing us to obtain (1)H NMR spectra characterized by narrow peaks. The quantification of the ligands by NMR and high-performance liquid chromatography showed that their complete recovery was granted. The NMR analysis enabled detection and quantification of unknown impurities without the need of pure compounds as internal standards.

CO synthesized from the central one-carbon pool as source for the iron carbonyl in O2-tolerant [NiFe]-hydrogenase

PubMed Central

Bürstel, Ingmar; Siebert, Elisabeth; Zebger, Ingo; Friedrich, Bärbel

2016-01-01

Hydrogenases are nature’s key catalysts involved in both microbial consumption and production of molecular hydrogen. H2 exhibits a strongly bonded, almost inert electron pair and requires transition metals for activation. Consequently, all hydrogenases are metalloenzymes that contain at least one iron atom in the catalytic center. For appropriate interaction with H2, the iron moiety demands for a sophisticated coordination environment that cannot be provided just by standard amino acids. This dilemma has been overcome by the introduction of unprecedented chemistry—that is, by ligating the iron with carbon monoxide (CO) and cyanide (or equivalent) groups. These ligands are both unprecedented in microbial metabolism and, in their free form, highly toxic to living organisms. Therefore, the formation of the diatomic ligands relies on dedicated biosynthesis pathways. So far, biosynthesis of the CO ligand in [NiFe]-hydrogenases was unknown. Here we show that the aerobic H2 oxidizer Ralstonia eutropha, which produces active [NiFe]-hydrogenases in the presence of O2, employs the auxiliary protein HypX (hydrogenase pleiotropic maturation X) for CO ligand formation. Using genetic engineering and isotope labeling experiments in combination with infrared spectroscopic investigations, we demonstrate that the α-carbon of glycine ends up in the CO ligand of [NiFe]-hydrogenase. The α-carbon of glycine is a building block of the central one-carbon metabolism intermediate, N10-formyl-tetrahydrofolate (N10-CHO-THF). Evidence is presented that the multidomain protein, HypX, converts the formyl group of N10-CHO-THF into water and CO, thereby providing the carbonyl ligand for hydrogenase. This study contributes insights into microbial biosynthesis of metal carbonyls involving toxic intermediates. PMID:27930319

Molecular and electronic structures of mononuclear iron complexes using strongly electron-donating ligands and their oxidized forms.

PubMed

Strautmann, Julia B H; George, Serena DeBeer; Bothe, Eberhard; Bill, Eckhard; Weyhermüller, Thomas; Stammler, Anja; Bögge, Hartmut; Glaser, Thorsten

2008-08-04

The ligand L (2-) (H 2L = N, N'-dimethyl- N, N'-bis(3,5-di- t-butyl-2-hydroxybenzyl)-1,2-diaminoethane) has been employed for the synthesis of two mononuclear Fe (III) complexes, namely, [LFe(eta (2)-NO 3)] and [LFeCl]. L (2-) is comprised of four strongly electron-donating groups (two tert-amines and two phenolates) that increase the electron density at the coordinated ferric ions. This property should facilitate oxidation of the complexes, that is, stabilization of the oxidized species. The molecular structures in the solid state have been established by X-ray diffraction studies. [LFeCl] is five-coordinate in a square-pyramidal coordination environment with the ligand adopting a trans-conformation, while [LFe(eta (2)-NO 3)] is six-coordinate in a distorted octahedral environment with the ligand in a beta-cis conformation. The electronic structures have been studied using magnetization, EPR, Mossbauer (with and without applied field), UV-vis-NIR, and X-ray absorption spectroscopies, which demonstrate highly anisotropic covalency from the strong sigma- and pi-donating phenolates. This analysis is supported by DFT calculations on [LFeCl]. The variations of the well-understood spectroscopic data in the solid state to the spectroscopic data in solution have been used to obtain insight in the molecular structure of the two complexes in solution. While the molecular structures of the solid states are retained in solutions of nonpolar aprotic solvents, there is, however, one common molecular structure in all protic polar solvents. The analysis of the LMCT transitions and the rhombicity E/ D clearly establish that both compounds exhibit a beta-cis conformation in these protic polar solvents. These two open coordination sites, cis to each other, allow access for two potential ligands in close proximity. Electrochemical analysis establishes two reversible oxidation waves for [LFeCl] at +0.55 V and +0.93 V vs Fc (+)/Fc and one reversible oxidation wave at +0.59 V with an irreversible oxidation at +1.07 V vs Fc (+)/Fc for [LFe(eta (2)-NO 3)]. The one- and the two-electron oxidations of [LFeCl] by chronoamperometry have been followed spectroscopically. The increase of a strong band centered at 420 nm indicates the formulation of [LFeCl] (+) as a Fe (III) monophenoxyl radical complex and of [LFeCl] (2+) as a Fe (III) bisphenoxyl radical complex. These studies imply that the ligand L (2-) is capable of providing a flexible coordination geometry with two binding sites for substrates and the allocation of two oxidation equivalents on the ligand.

The crystal structures of iron and cobalt pyridine (py)–sulfates, [Fe(SO4)(py)4]n and [Co3(SO4)3(py)11]n

PubMed Central

Pham, Duyen N. K.; Roy, Mrittika; Kreider-Mueller, Ava; Golen, James A.; Manke, David R.

2018-01-01

The solid-state structures of two metal–pyridine–sulfate compounds, namely catena-poly[[tetra­kis­(pyridine-κN)iron(II)]-μ-sulfato-κ2 O:O′], [Fe(SO4)(C5H5N)4]n, (1), and catena-poly[[tetra­kis­(pyridine-κN)cobalt(II)]-μ-sulfato-κ2 O:O′-[tetra­kis­(pyridine-κN)cobalt(II)]-μ-sulfato-κ3 O,O′:O′′-[tris­(pyridine-κN)cobalt(II)]-μ-sulfato-κ2 O:O′], [Co3(SO4)3(C5H5N)11]n, (2), are reported. The iron compound (1) displays a polymeric structure, with infinite chains of FeII atoms adopting octa­hedral N4O2 coordination environments that involve four pyridine ligands and two bridging sulfate ligands. The cobalt compound (2) displays a polymeric structure, with infinite chains of CoII atoms. Two of the three Co centers have an octa­hedral N4O2 coordination environment that involves four pyridine ligands and two bridging sulfate ligands. The third Co center has an octa­hedral N3O3 coordination environment that involves three pyridine ligands, and two bridging sulfate ligands with one sulfate chelating the cobalt atom.

Structural studies of Proteus mirabilis catalase in its ground state, oxidized state and in complex with formic acid.

PubMed

Andreoletti, Pierre; Pernoud, Anaïs; Sainz, Germaine; Gouet, Patrice; Jouve, Hélène Marie

2003-12-01

The structure of Proteus mirabilis catalase in complex with an inhibitor, formic acid, has been solved at 2.3 A resolution. Formic acid is a key ligand of catalase because of its ability to react with the ferric enzyme, giving a high-spin iron complex. Alternatively, it can react with two transient oxidized intermediates of the enzymatic mechanism, compounds I and II. In this work, the structures of native P. mirabilis catalase (PMC) and compound I have also been determined at high resolution (2.0 and 2.5 A, respectively) from frozen crystals. Comparisons between these three PMC structures show that a water molecule present at a distance of 3.5 A from the haem iron in the resting state is absent in the formic acid complex, but reappears in compound I. In addition, movements of solvent molecules are observed during formation of compound I in a cavity located away from the active site, in which a glycerol molecule is replaced by a sulfate. These results give structural insights into the movement of solvent molecules, which may be important in the enzymatic reaction.

Promoted Iron Nanocrystals Obtained via Ligand Exchange as Active and Selective Catalysts for Synthesis Gas Conversion

PubMed Central

2017-01-01

Colloidal synthesis routes have been recently used to fabricate heterogeneous catalysts with more controllable and homogeneous properties. Herein a method was developed to modify the surface composition of colloidal nanocrystal catalysts and to purposely introduce specific atoms via ligands and change the catalyst reactivity. Organic ligands adsorbed on the surface of iron oxide catalysts were exchanged with inorganic species such as Na2S, not only to provide an active surface but also to introduce controlled amounts of Na and S acting as promoters for the catalytic process. The catalyst composition was optimized for the Fischer–Tropsch direct conversion of synthesis gas into lower olefins. At industrially relevant conditions, these nanocrystal-based catalysts with controlled composition were more active, selective, and stable than catalysts with similar composition but synthesized using conventional methods, possibly due to their homogeneity of properties and synergic interaction of iron and promoters. PMID:28824820

Spectroscopic studies on two mono nuclear iron (III) complexes derived from a schiff base and an azodye

NASA Astrophysics Data System (ADS)

Mini, S.; Sadasivan, V.; Meena, S. S.; Bhatt, Pramod

2014-10-01

Two new mono nuclear Fe(III) complexes of an azodye (ANSN) and a Schiff base (FAHP) are reported. The azodye is prepared by coupling diazotized 1-amino-2-naphthol-4-sulphonicacid with 2-naphthol and the Schiff base is prepared by condensing 2-amino-3-hydroxy pyridine with furfural. The complexes were synthesized by the reaction of FeCl3˙2H2O with respective ligands. They were characterized on the basis of elemental analysis and spectral studies like IR, NMR, Electronic and M.ssbauer. Magnetic susceptibility and Molar conductance of complexes at room temperature were studied. Based on the spectroscopic evidences and other analytical data the complexes are formulated as[Fe(ANSN)Cl(H2O)2] and [Fe(FAHP)Cl2(H2O)2].

Ligand versus metal protonation of an iron hydrogenase active site mimic.

PubMed

Eilers, Gerriet; Schwartz, Lennart; Stein, Matthias; Zampella, Giuseppe; de Gioia, Luca; Ott, Sascha; Lomoth, Reiner

2007-01-01

The protonation behavior of the iron hydrogenase active-site mimic [Fe2(mu-adt)(CO)4(PMe3)2] (1; adt=N-benzyl-azadithiolate) has been investigated by spectroscopic, electrochemical, and computational methods. The combination of an adt bridge and electron-donating phosphine ligands allows protonation of either the adt nitrogen to give [Fe2(mu-Hadt)(CO)4(PMe3)2]+ ([1 H]+), the Fe-Fe bond to give [Fe2(mu-adt)(mu-H)(CO)4(PMe3)2]+ ([1 Hy]+), or both sites simultaneously to give [Fe2(mu-Hadt)(mu-H)(CO)4(PMe3)2]2+ ([1 HHy]2 +). Complex 1 and its protonation products have been characterized in acetonitrile solution by IR, (1)H, and (31)P NMR spectroscopy. The solution structures of all protonation states feature a basal/basal orientation of the phosphine ligands, which contrasts with the basal/apical structure of 1 in the solid state. Density functional calculations have been performed on all protonation states and a comparison between calculated and experimental spectra confirms the structural assignments. The ligand protonated complex [1 H]+ (pKa=12) is the initial, metastable protonation product while the hydride [1 Hy]+ (pKa=15) is the thermodynamically stable singly protonated form. Tautomerization of cation [1 H]+ to [1 Hy]+ does not occur spontaneously. However, it can be catalyzed by HCl (k=2.2 m(-1) s(-1)), which results in the selective formation of cation [1 Hy]+. The protonations of the two basic sites have strong mutual effects on their basicities such that the hydride (pK(a)=8) and the ammonium proton (pK(a)=5) of the doubly protonated cationic complex [1 HHy]2+ are considerably more acidic than in the singly protonated analogues. The formation of dication [1 HHy]2+ from cation [1 H]+ is exceptionally slow with perchloric or trifluoromethanesulfonic acid (k=0.15 m(-1) s(-1)), while the dication is formed substantially faster (k>10(2) m(-1) s(-1)) with hydrobromic acid. Electrochemically, 1 undergoes irreversible reduction at -2.2 V versus ferrocene, and this potential shifts to -1.6, -1.1, and -1.0 V for the cationic complexes [1 H]+, [1 Hy]+, and [1 HHy]2+, respectively, upon protonation. The doubly protonated form [1 HHy]2+ is reduced at less negative potential than all previously reported hydrogenase models, although catalytic proton reduction at this potential is characterized by slow turnover.

Iron dissolution of dust source materials during simulated acidic processing: the effect of sulfuric, acetic, and oxalic acids.

PubMed

Chen, Haihan; Grassian, Vicki H

2013-09-17

Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.

Assessing bioavailability levels of metals in effluent-affected rivers: effect of Fe(III) and chelating agents on the distribution of metal speciation.

PubMed

Han, Shuping; Naito, Wataru; Masunaga, Shigeki

To assess the effects of Fe(III) and anthropogenic ligands on the bioavailability of Ni, Cu, Zn, and Pb, concentrations of bioavailable metals were measured by the DGT (diffusive gradients in thin films) method in some urban rivers, and were compared with concentrations calculated by a chemical equilibrium model (WHAM 7.0). Assuming that dissolved Fe(III) (<0.45 μm membrane filtered) was in equilibrium with colloidal iron oxide, the WHAM 7.0 model estimated that bioavailable concentrations of Ni, Cu, and Zn were slightly higher than the corresponding values estimated assuming that dissolved Fe(III) was absent. In contrast, lower levels of free Pb were predicted by the WHAM 7.0 model when dissolved Fe(III) was included. Estimates showed that most of the dissolved Pb was present as colloidal iron-Pb complex. Ethylene-diamine-tetra-acetic acid (EDTA) concentrations at sampling sites were predicted from the relationship between EDTA and the calculated bioavailable concentration of Zn. When both colloidal iron and predicted EDTA concentrations were included in the WHAM 7.0 calculations, dissolved metals showed a strong tendency to form EDTA complexes, in the order Ni > Cu > Zn > Pb. With the inclusion of EDTA, bioavailable concentrations of Ni, Cu, and Zn predicted by WHAM 7.0 were different from those predicted considering only humic substances and colloidal iron.

FAST TRACK COMMUNICATION Tuning the spin state of iron phthalocyanine by ligand adsorption

NASA Astrophysics Data System (ADS)

Isvoranu, C.; Wang, B.; Schulte, K.; Ataman, E.; Knudsen, J.; Andersen, J. N.; Bocquet, M. L.; Schnadt, J.

2010-12-01

The future use of single-molecule magnets in applications will require the ability to control and manipulate the spin state and magnetization of the magnets by external means. There are different approaches to this control, one being the modification of the magnets by adsorption of small ligand molecules. In this paper we use iron phthalocyanine supported by an Au(111) surface as a model compound and demonstrate, using x-ray photoelectron spectroscopy and density functional theory, that the spin state of the molecule can be tuned to different values (S ~ 0, \\case {1}{2} , 1) by adsorption of ammonia, pyridine, carbon monoxide or nitric oxide on the iron ion. The interaction also leads to electronic decoupling of the iron phthalocyanine from the Au(111) support.

Anti-Plasmodial Activity of Aroylhydrazone and Thiosemicarbazone Iron Chelators: Effect on Erythrocyte Membrane Integrity, Parasite Development and the Intracellular Labile Iron Pool

PubMed Central

Walcourt, Asikiya; Kurantsin-Mills, Joseph; Kwagyan, John; Adenuga, Babafemi B.; Kalinowski, Danuta S.; Lovejoy, David B.; Lane, Darius J. R.; Richardson, Des R.

2013-01-01

Iron chelators inhibit the growth of the malaria parasite, Plasmodium falciparum, in culture and in animal and human studies. We previously reported the anti-plasmodial activity of the chelators, 2-hydroxy-1-naphthylaldehyde isonicotinoyl hydrazone (311), 2-hydroxy-1-naphthylaldehyde 4-methyl-3-thiosemicarbazone (N4mT), and 2-hydroxy-1-naphthylaldehyde 4-phenyl-3-thiosemicarbazone (N4pT). In fact, these ligands showed greater growth inhibition of chloroquine-sensitive (3D7) and chloroquine-resistant (7G8) strains of P. falciparum in culture compared to desferrioxamine (DFO). The present study examined the effects of 311, N4mT and N4pT on erythrocyte membrane integrity and asexual parasite development. While the characteristic biconcave disk shape of the erythrocytes was unaffected, the chelators caused very slight hemolysis at IC50 values that inhibited parasite growth. The chelators 311, N4mT and N4pT affected all stages of the intra-erythrocytic development cycle (IDC) of P. falciparum in culture. However, while these ligands primarily affected the ring-stage, DFO inhibited primarily trophozoite and schizont-stages. Ring, trophozoite and schizont-stages of the IDC were inhibited by significantly lower concentrations of 311, N4mT, and N4pT (IC50 = 4.45 ± 1.70, 10.30 ± 4.40, and 3.64 ± 2.00 μM, respectively) than DFO (IC50 = 23.43 ± 3.40 μM). Complexation of 311, N4mT and N4pT with iron reduced their anti-plasmodial activity. Estimation of the intracellular labile iron pool (LIP) in erythrocytes showed that the chelation efficacy of 311, N4mT and N4pT corresponded to their anti-plasmodial activity, suggesting that the LIP may be a potential source of non-heme iron for parasite metabolism within the erythrocyte. This study has implications for malaria chemotherapy that specifically disrupts parasite iron utilization. PMID:24028863

Complexation of Arsenite with Humic Acid in the Presence of Ferric Iron

PubMed Central

Liu, Guangliang; Fernandez, Aymara; Cai, Yong

2011-01-01

In the presence of iron (Fe), dissolved organic matter (DOM) may bind considerable amounts of arsenic (As), through formation of Fe-bridged As-Fe-DOM complexes and surface complexation of As on DOM-stabilized Fe-colloids (collectively referred to as As-Fe-DOM complexation). However, direct (e.g., chromatographic and spectroscopic) evidence and fundamental kinetic and stability constants have been rarely reported for this As-Fe-DOM complexation. Using a size exclusion chromatography (SEC)-UV-inductively coupled plasma mass spectrometry (ICP-MS) technique, arsenite (AsIII)-Fe-DOM complexation was investigated after adding AsIII into the priorly prepared Fe-DOM. A series of evidence, including coelution of As, Fe, and DOM from the SEC column and coretention of As, Fe, and DOM by 3 kDa MWCO centrifugal filtration membrane, demonstrated the occurrence of AsIII-Fe-DOM complexation. The kinetic data of AsIII-Fe-DOM complexation were well described by a pseudo-first order rate equation (R2 = 0.95), with the rate constant (k′) being 0.17±0.04 1/h. Stability of AsIII-Fe-DOM complexation was characterized by apparent stability constant (Ks) derived from two-site ligand binding model, with log Ks ranging from 4.4±0.2 to 5.6±0.4. Considering the kinetics (within hours) and stability (similar to typical metal-humates) of AsIII-Fe-DOM complexation, this complexation needs to be included when evaluating As mobility in Fe and DOM rich environments. PMID:21322632

The therapeutic potential of iron-targeting gallium compounds in human disease: From basic research to clinical application.

PubMed

Chitambar, Christopher R

2017-01-01

Gallium, group IIIa metal, shares certain chemical characteristics with iron which enable it to function as an iron mimetic that can disrupt iron-dependent tumor cell growth. Gallium may also display antimicrobial activity by disrupting iron homeostasis in certain bacteria and fungi. Gallium's action on iron homeostasis leads to inhibition of ribonucleotide reductase, mitochondrial function, and changes in proteins of iron transport and storage. In addition, gallium induces an increase in mitochondrial reactive oxygen species in cells which triggers downstream upregulation of metallothionein and hemoxygenase-1. Early clinical trials evaluated the efficacy of the simple gallium salts, gallium nitrate and gallium chloride. However, newer gallium-ligands such as Tris(8-quinolinolato)gallium(III) (KP46) and gallium maltolate have been developed and are undergoing clinical evaluation. Additional gallium-ligands that demonstrate antitumor activity in preclinical studies have emerged. Their mechanisms of action and their spectrum of antitumor activity may extend beyond the earlier generations of gallium compounds and warrant further investigation. This review will focus on the evolution and potential of gallium-based therapeutics. Copyright © 2016 Elsevier Ltd. All rights reserved.

(18-Crown-6)potassium [(1,2,5,6-η)-cyclo­octa-1,5-diene][(1,2,3,4-η)-naph­tha­lene]­ferrate(−I)

PubMed Central

Brennessel, William W.; Ellis, John E.

2012-01-01

The title salt, [K(C12H24O6)][Fe(C8H12)(C10H8)], is the only known naphthalene complex containing iron in a formally negative oxidation state. Each (naphthalene)(1,5-cod)ferrate(−I) anion is in contact with one (18-crown-6)potassium cation via K⋯C contacts to the outer four carbon atoms of the naphthalene ligand (cod = 1,5-cyclo­octa­diene, 18-crown-6 = 1,4,7,10,13,16-hexa­oxacyclo­octa­deca­ne). When using the midpoints of the coordinating olefin bonds, the overall geometry of the coordination sphere around iron can be best described as distorted tetra­hedral. The naphthalene fold angle between the plane of the iron-coordinating butadiene unit and the plane containing the exo-benzene moiety is 19.2 (1)°. PMID:23125569

Coupling of the Distal H-bond Network to the Exogenous Ligand in Substrate-bound, Resting State Human Heme Oxygenase ‡

PubMed Central

Peng, Dungeng; Ogura, Hiroshi; Zhu, Wenfeng; Ma, Li-Hua; Evans, John P.; Ortiz de Montellano, Paul R.; La Mar, Gerd N.

2010-01-01

Mammalian heme oxygenase, HO, possesses catalytically implicated distal ordered water molecules within an extended H-bond network, with one of the ordered water molecules (#1) providing a bridge between the iron-coordinated ligand and the catalytically critical Asp140, that, in turn, serves as an acceptor for the Tyr58 OH H-bond. The degree of H-bonding by the ligated water molecule and the coupling of this water molecule to the H-bond network are of current interest and are herein investigated by 1H NMR. 2D NMR allowed sufficient assignments to provide both the H-bond strength and hyperfine shifts, the latter of which were used to quantify the magnetic anisotropy in both the ferric high-spin aquo and low-spin hydroxo complexes. The anisotropy in the aquo complex indicates that the H-bond donation to water #1 is marginally stronger than in a bacterial HO, while the anisotropy for the hydroxo complex reveals a conventional (dxz, dyz)1 ground state indicative of only moderate to weak H-bond acceptance by the ligated hydroxide. Mapping out the changes of the H-bond strengths in the network during the ligated water → hydroxide conversion by correcting for the effects of magnetic anisotropy, reveals a very substantial change in H-bond strength for Tyr58 OH, and lesser effects on nearby H-bonds. The effect of pH on the H-bonding network in human HO is much larger and transmitted much further from the iron than in a pathogenic bacterial HO. The implications for the HO mechanism of the H-bond of Tyr58 to Asp140 are discussed. PMID:19842713

Dissociation kinetics of Fe(III)- and Al(III)-natural organic matter complexes at pH 6.0 and 8.0 and 25 °C

NASA Astrophysics Data System (ADS)

Jones, Adele M.; Pham, A. Ninh; Collins, Richard N.; Waite, T. David

2009-05-01

The rate at which iron- and aluminium-natural organic matter (NOM) complexes dissociate plays a critical role in the transport of these elements given the readiness with which they hydrolyse and precipitate. Despite this, there have only been a few reliable studies on the dissociation kinetics of these complexes suggesting half-times of some hours for the dissociation of Fe(III) and Al(III) from a strongly binding component of NOM. First-order dissociation rate constants are re-evaluated here at pH 6.0 and 8.0 and 25 °C using both cation exchange resin and competing ligand methods for Fe(III) and a cation exchange resin method only for Al(III) complexes. Both methods provide similar results at a particular pH with a two-ligand model accounting satisfactorily for the dissociation kinetics results obtained. For Fe(III), half-times on the order of 6-7 h were obtained for dissociation of the strong component and 4-5 min for dissociation of the weak component. For aluminium, the half-times were on the order of 1.5 h and 1-2 min for the strong and weak components, respectively. Overall, Fe(III) complexes with NOM are more stable than analogous complexes with Al(III), implying Fe(III) may be transported further from its source upon dilution and dispersion.

Saccharides enhance iron bioavailability to Southern Ocean phytoplankton

PubMed Central

Hassler, Christel S.; Nichols, Carol Mancuso; Butler, Edward C. V.; Boyd, Philip W.

2011-01-01

Iron limits primary productivity in vast regions of the ocean. Given that marine phytoplankton contribute up to 40% of global biological carbon fixation, it is important to understand what parameters control the availability of iron (iron bioavailability) to these organisms. Most studies on iron bioavailability have focused on the role of siderophores; however, eukaryotic phytoplankton do not produce or release siderophores. Here, we report on the pivotal role of saccharides—which may act like an organic ligand—in enhancing iron bioavailability to a Southern Ocean cultured diatom, a prymnesiophyte, as well as to natural populations of eukaryotic phytoplankton. Addition of a monosaccharide (>2 nM of glucuronic acid, GLU) to natural planktonic assemblages from both the polar front and subantarctic zones resulted in an increase in iron bioavailability for eukaryotic phytoplankton, relative to bacterioplankton. The enhanced iron bioavailability observed for several groups of eukaryotic phytoplankton (i.e., cultured and natural populations) using three saccharides, suggests it is a common phenomenon. Increased iron bioavailability resulted from the combination of saccharides forming highly bioavailable organic associations with iron and increasing iron solubility, mainly as colloidal iron. As saccharides are ubiquitous, present at nanomolar to micromolar concentrations, and produced by biota in surface waters, they also satisfy the prerequisites to be important constituents of the poorly defined “ligand soup,” known to weakly bind iron. Our findings point to an additional type of organic ligand, controlling iron bioavailability to eukaryotic phytoplankton—a key unknown in iron biogeochemistry. PMID:21169217

Mobilization of soil-borne arsenic by three common organic acids: Dosage and time effects.

PubMed

Onireti, Olaronke O; Lin, Chuxia

2016-03-01

A batch experiment was conducted to investigate the mobilization of soil-borne arsenic by three common low-molecular-weight organic acids with a focus on dosage and time effects. The results show that oxalic acid behaved differently from citric acid and malic acid in terms of mobilizing As that was bound to iron compounds. At an equivalent molar concentration, reactions between oxalic acid and soil-borne Fe were kinetically more favourable, as compared to those between either citric acid or malic acid and the soil-borne Fe. It was found that reductive dissolution of soil-borne Fe played a more important role in liberating As, as compared to non-reductive reactions. Prior to the 7th day of the experiment, As mobility increased with increasing dose of oxalic acid while there was no significant difference (P > 0.05) in mobilized As among the treatments with different doses of citric acid or malic acid. The dosage effect on soil-borne As mobilization in the citric acid and malic acid treatments became clear only after the 7th day of the experiment. Soluble Ca present in the soils could cause re-immobilization of As by competing with solution-borne Fe for available organic ligands to form practically insoluble organic compounds of calcium (i.e. calcium oxalate). This resulted in transformation of highly soluble organic complexes of iron (i.e. iron oxalate complexes) into slightly soluble organic compounds of iron (i.e. iron oxalate) or free ferric ion, which then reacted with the solution-borne arsenate ions to form practically insoluble iron arsenates in the latter part of the experiment. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ligand Displacement Reaction Paths in a Diiron Hydrogenase Active Site Model Complex.

PubMed

Blank, Jan H; Moncho, Salvador; Lunsford, Allen M; Brothers, Edward N; Darensbourg, Marcetta Y; Bengali, Ashfaq A

2016-08-26

The mechanism and energetics of CO, 1-hexene, and 1-hexyne substitution from the complexes (SBenz)2 [Fe2 (CO)6 ] (SBenz=SCH2 Ph) (1-CO), (SBenz)2 [Fe2 (CO)5 (η(2) -1-hexene)] (1-(η(2) -1-hexene)), and (SBenz)2 [Fe2 (CO)5 (η(2) -1-hexyne)] (1-(η(2) -1-hexyne)) were studied by using time-resolved infrared spectroscopy. Exchange of both CO and 1-hexyne by P(OEt)3 and pyridine, respectively, proceeds by a bimolecular mechanism. As similar activation enthalpies are obtained for both reactions, the rate-determining step in both cases is assumed to be the rotation of the Fe(CO)2 L (L=CO or 1-hexyne) unit to accommodate the incoming ligand. The kinetic profile for the displacement of 1-hexene is quite different than that for the alkyne and, in this case, both reaction channels, that is, dissociative (SN 1) and associative (SN 2), were found to be competitive. Because DFT calculations predict similar binding enthalpies of alkene and alkyne to the iron center, the results indicate that the bimolecular pathway in the case of the alkyne is lower in free energy than that of the alkene. In complexes of this type, subtle changes in the departing ligand characteristics and the nature of the mercapto bridge can influence the exchange mechanism, such that more than one reaction pathway is available for ligand substitution. The difference between this and the analogous study of (μ-pdt)[Fe(CO)3 ]2 (pdt=S(CH2 )3 S) underscores the unique characteristics of a three-atom S-S linker in the active site of diiron hydrogenases. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystallographic Analysis of Active Site Contributions to Regiospecificity in the Diiron Enzyme Toluene 4-Monooxygenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bailey, Lucas J.; Acheson, Justin F.; McCoy, Jason G.

Crystal structures of toluene 4-monooxygenase hydroxylase in complex with reaction products and effector protein reveal active site interactions leading to regiospecificity. Complexes with phenolic products yield an asymmetric {mu}-phenoxo-bridged diiron center and a shift of diiron ligand E231 into a hydrogen bonding position with conserved T201. In contrast, complexes with inhibitors p-NH{sub 2}-benzoate and p-Br-benzoate showed a {mu}-1,1 coordination of carboxylate oxygen between the iron atoms and only a partial shift in the position of E231. Among active site residues, F176 trapped the aromatic ring of products against a surface of the active site cavity formed by G103, E104 andmore » A107, while F196 positioned the aromatic ring against this surface via a {pi}-stacking interaction. The proximity of G103 and F176 to the para substituent of the substrate aromatic ring and the structure of G103L T4moHD suggest how changes in regiospecificity arise from mutations at G103. Although effector protein binding produced significant shifts in the positions of residues along the outer portion of the active site (T201, N202, and Q228) and in some iron ligands (E231 and E197), surprisingly minor shifts (<1 {angstrom}) were produced in F176, F196, and other interior residues of the active site. Likewise, products bound to the diiron center in either the presence or absence of effector protein did not significantly shift the position of the interior residues, suggesting that positioning of the cognate substrates will not be strongly influenced by effector protein binding. Thus, changes in product distributions in the absence of the effector protein are proposed to arise from differences in rates of chemical steps of the reaction relative to motion of substrates within the active site channel of the uncomplexed, less efficient enzyme, while structural changes in diiron ligand geometry associated with cycling between diferrous and diferric states are discussed for their potential contribution to product release.« less

Metal-ligand Covalency of Iron Complexes from High-Resolution Resonant Inelastic X-ray Scattering

PubMed Central

Lundberg, Marcus; Kroll, Thomas; DeBeer, Serena; Bergmann, Uwe; Wilson, Samuel A.; Glatzel, Pieter; Nordlund, Dennis; Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.

2013-01-01

Data from Kα resonant inelastic X-ray scattering (RIXS) have been used to extract electronic structure information, i.e., the covalency of metal-ligand bonds, for four iron complexes using an experimentally based theoretical model. Kα RIXS involves resonant 1s → 3d excitation and detection of the 2p → 1s (Kα) emission. This two-photon process reaches similar final states as single-photon L-edge (2p → 3d) X-ray absorption spectroscopy (XAS), but involves only hard X-rays and can therefore be used to get high-resolution L-edge-like spectra for metal proteins, solution catalysts and their intermediates. To analyze the information content of Kα RIXS spectra, data have been collected for four characteristic σ-donor and π-backdonation complexes; ferrous tacn [FeII(tacn)2]Br2, ferrocyanide [FeII(CN)6]K4, ferric tacn [FeIII(tacn)2]Br3 and ferricyanide [FeIII(CN)6]K3. From these spectra metal-ligand covalencies can be extracted using a charge-transfer multiplet model, without previous information from the L-edge XAS experiment. A direct comparison of L-edge XAS and Kα RIXS spectra show that the latter reaches additional final states, e.g., when exciting into the eg (σ*) orbitals, and the splitting between final states of different symmetry provides an extra dimension that makes Kα RIXS a more sensitive probe of σ-bonding. Another key difference between L-edge XAS and Kα RIXS is the π-backbonding features in ferro- and ferricyanide that are significantly more intense in L-edge XAS compared to Kα RIXS. This shows that two methods are complimentary in assigning electronic structure. The Kα RIXS approach can thus be used as a stand-alone method, in combination with L-edge XAS for strongly covalent systems that are difficult to probe by UV/Vis spectroscopy, or as an extension to conventional absorption spectroscopy for a wide range of transition metal enzymes and catalysts. PMID:24131028

Synthesis, structure and catechol-oxidase activity of copper(II) complexes of 17-hydroxy-16-(N-3-oxo-prop-1-enyl)amino steroids.

PubMed

Wegner, Rainer; Dubs, Manuela; Görls, Helmar; Robl, Christian; Schönecker, Bruno; Jäger, Ernst-G

2002-09-01

Copper is next to iron the most important element in the biological transport, storage and in redox reactions of dioxygen. A bioanalogous activation of dioxygen with copper complexes is used for catalytical epoxidation, allylic hydroxylation and oxidative coupling of aromatic substrates, for example. With stereochemical information in form of chiral ligands, enantioselective reactions may be possible. Another aspect of interest on copper catalyzed reactions with dioxygen is that the exact mechanism and biological function of some enzymes (especially catechol oxidase) is yet not fully clear. For studies mimicking the copper-containing catechol oxidase appropriate chiral steroid ligands with defined stereochemistry and conformation have been synthesized. The four diastereomeric 16,17-aminoalcohols of the 3-methoxy-estra-1,3,5(10)-triene series have been condensed with salicylic aldehyde and different beta-ketoenols to the chiral ligand types 1-5. These compounds with different steric and electronic properties and different arrangements of the neighboring hydroxy and nitrogen functions were reacted with copper(II) acetate to copper complexes. The structure of these complexes will be discussed. The bioanalogous oxidation of 3,5-di-tbutyl-catechol (dtbc) to the corresponding quinone was catalyzed by most of the complexes, indicating their ability to activate dioxygen. The trans configurations c and d showed an activity one magnitude higher than the cis configurations a and b. Comparing compounds with the same diastereomeric configuration, the main influence was that of the peripheral R(1-3) substituents at the beta-ketoenaminic group which are useful for the fine-tuning of the properties of the copper atoms like redox potential and Lewis acidity.

A Solomon link through an interwoven molecular grid.

PubMed

Beves, Jonathon E; Danon, Jonathan J; Leigh, David A; Lemonnier, Jean-François; Vitorica-Yrezabal, Iñigo J

2015-06-22

A molecular Solomon link was synthesized through the assembly of an interwoven molecular grid consisting of four bis(benzimidazolepyridyl)benzthiazolo[5,4-d]thiazole ligands and four zinc(II), iron(II), or cobalt(II) cations, followed by ring-closing olefin metathesis. NMR spectroscopy, mass spectrometry, and X-ray crystallography confirmed the doubly interlocked topology, and subsequent demetalation afforded the wholly organic Solomon link. The synthesis, in which each metal ion defines the crossing point of two ligand strands, suggests that interwoven molecular grids should be useful scaffolds for the rational construction of other topologically complex structures. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

Synthesis, physicochemical studies, embryos toxicity and DNA interaction of some new Iron(II) Schiff base amino acid complexes

NASA Astrophysics Data System (ADS)

Abdel-Rahman, Laila H.; El-Khatib, Rafat M.; Nassr, Lobna A. E.; Abu-Dief, Ahmed M.

2013-05-01

New Fe(II) Schiff base amino acid complexes derived from the condensation of o-hydroxynaphthaldehyde with L-alanine, L-phenylalanine, L-aspartic acid, L-histidine and L-arginine were synthesized and characterized by elemental analysis, IR, electronic spectra, and conductance measurements. The stoichiometry and the stability constants of the complexes were determined spectrophotometrically. The investigated Schiff bases exhibited tridentate coordination mode with the general formulae [Fe(HL)2]·nH2O for all amino acids except L-histidine. But in case of L-histidine, the ligand acts as tetradentate ([FeL(H2O)2]·2H2O), where HL = mono anion and L = dianion of the ligand. The structure of the prepared complexes is suggested to be octahedral. The prepared complexes were tested for their toxicity on chick embryos and found to be safe until a concentration of 100 μg/egg with full embryos formation. The interaction between CT-DNA and the investigated complexes were followed by spectrophotometry and viscosity measurements. It was found that, the prepared complexes bind to DNA via classical intercalative mode and showed a different DNA cleavage activity with the sequence: nhi > nari > nali > nasi > nphali. The thermodynamic Profile of the binding of nphali complex and CT-DNA was constructed by analyzing the experimental data of absorption titration and UV melting studies with the McGhee equation, van't Hoff's equation, and the Gibbs-Helmholtz equation.

The nitroxide Tempo inhibits hydroxyl radical production from the Fenton-like reaction of iron(II)-citrate with hydrogen peroxide.

PubMed

Shi, Fengqiang; Zhang, Peifeng; Mao, Yujia; Wang, Can; Zheng, Meiqing; Zhao, Zhongwei

2017-01-29

In vivo physiological ligand citrate can bind iron(II) ions to form the iron(II)-citrate complex. Inhibition of hydroxyl radical (OH) production from the Fenton-like reaction of iron(II)-citrate with H 2 O 2 is biologically important, as this reaction may account for one of the mechanisms of the labile iron pool in vivo to induce oxidative stress and pathological conditions. Nitroxides have promising potentials as therapeutic antioxidants. However, there are controversial findings indicating that they not only act as antioxidants but also as pro-oxidants when engaged in Fenton reactions. Although the underlying mechanisms are proposed to be the inhibition or enhancement of the OH production by nitroxides, the proposed elucidations are only based on assessing biological damages and not demonstrated directly by measuring the OH production in the presence of nitroxides. In this study, therefore, we employed EPR and fluorescence spectroscopies to show direct evidence that nitroxide 2,2,6,6-tetramethyl-piperidine-1-oxyl (Tempo) inhibited OH production from the Fenton-like reaction of iron(II)-citrate with H 2 O 2 by up to 90%. We also demonstrated spectrophotometrically, for the first time, that this inhibition was due to oxidation of the iron(II)-citrate by Tempo with a stoichiometry of Tempo:Iron(III)-citrate = 1.1:1.0. A scheme was proposed to illustrate the roles of nitroxides engaged in Fenton/Fenton-like reactions. Copyright © 2016 Elsevier Inc. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tondreau, Aaron M.; Scott, Brian L.; Boncella, James M.

We explored ligand-induced reduction of ferrous alkyl complexes via homolytic cleavage of the alkyl fragment with simple chelating diphosphines. The reactivities of the sodium salts of diphenylmethane, phenyl(trimethylsilyl)methane, or diphenyl(trimethylsilyl)methane were explored in their reactivity with (py) 4FeCl 2. Furthermore, we prepared a series of monoalkylated salts of the type (py) 2FeRCl and characterized from the addition of 1 equiv of the corresponding alkyl sodium species. These complexes are isostructural and have similar magnetic properties. The double alkylation of (py) 4FeCl 2 resulted in the formation of tetrahedral high-spin iron complexes with the sodium salts of diphenylmethane and phenyl(trimethylsilyl)methane thatmore » readily decomposed. A bis(cyclohexadienyl) sandwich complex was formed with the addition of 2 equiv of the tertiary alkyl species sodium diphenyl(trimethylsilyl)methane. The addition of chelating phosphines to (py) 2FeRCl resulted in the overall transfer of Fe(I) chloride concurrent with loss of pyridine and alkyl radical. (dmpe) 2FeCl was synthesized via addition of 1 equiv of sodium diphenyl(trimethylsilyl)methane, whereas the addition of 2 equiv of the sodium compound to (dmpe) 2FeCl 2 gave the reduced Fe(0) nitrogen complex (dmpe) 2Fe(N 2). Our results demonstrate that iron–alkyl homolysis can be used to afford clean, low-valent iron complexes without the use of alkali metals.« less

Metal ion complex formation in small lakes of the Western Siberian Arctic zone

NASA Astrophysics Data System (ADS)

Kremleva, Tatiana; Dinu, Marina

2017-04-01

The paper is based on joint investigation of the Tyumen State University (Russia, Tyumen) and the Geochemistry and Analytical Chemistry Vernadsky Institute of Russian Academy of Sciences (Moscow, Russia) during 2012-2014 period. It presents the results of research of chemical composition of about 70 small lakes located in the area of tundra and northern taiga of West Siberia (Russia, Yamal-Nenets and Khanty-Mansi Autonomous Districts of the Tyumen region). The investigation includes determination of different parameters of natural water samples: • content of trace elements (Al, Fe, Mn, Cr, Cu, Ni, Zn, Cd, Co, Pb, etc., total more than 60 elements) by emission method with an inductively coupled plasma (ICP-MS) using mass spektrometrometre Element 2 equipment; • content of inorganic and total carbon (TIC and TC) by elemental analysis and the difference between the total and inorganic carbon gives the organic carbon content (TOC); • pH value by potentiometric method; • content of basic ions (Na+, Ca2+, K+, Mg2+, NH4+, Cl-, SO42-, NO3-, PO43-) by ion chromatography. Determination of the chemical composition of samples was conducted in the accredited laboratory according to standard procedures with regular quality control of results. Heavy metals in natural waters can exist in various forms: free (hydrated) ions bound in complexes with organic or inorganic ligands, as well as in the form of suspensions. The form of metal existence has a significant influence on their availability to transport in aquatic organisms. Metal ions associated in stable complexes with organic substances are considered less toxic. From the previous investigations state that the most stable complexes are ligands with organic ions Fe3+, Al3+. The main conclusion of the present research states that if the total content of aluminum, iron and manganese ions (meq/dm3) is equal to or greater than the concentration of dissolved organic carbon (TOC, mg/dm3) in lakes water other heavy metals will be predominantly in free, ionic or bound form with inorganic ligands. This state means paradox consequence that the increase of dissolved Fe content will lead to toxicity rise of other elements having less affinity to organic material. For surface waters of Western Siberian Arctic zone this situation is quite common. The total concentration of iron and aluminum ions in most lakes of tundra and northern taiga zones is approximately equal to water complexing ability. From the other side humic substances participation in inactivation of other more toxic metals (Cu, Pb, Cd, Cr, Ni et al.) will be poor. Arctic part of Western Siberia undergoes significant anthropogenic load due to extensive oil and gas recovery in this zone. Surface waters of Western Siberia are characterized by high natural content of iron, aluminum and copper ions and anthropogenic load of heavy metals makes the situation more serious.

Macrocyclic metal complexes for metalloenzyme mimicry and sensor development.

PubMed

Joshi, Tanmaya; Graham, Bim; Spiccia, Leone

2015-08-18

Examples of proteins that incorporate one or more metal ions within their structure are found within a broad range of classes, including oxidases, oxidoreductases, reductases, proteases, proton transport proteins, electron transfer/transport proteins, storage proteins, lyases, rusticyanins, metallochaperones, sporulation proteins, hydrolases, endopeptidases, luminescent proteins, iron transport proteins, oxygen storage/transport proteins, calcium binding proteins, and monooxygenases. The metal coordination environment therein is often generated from residues inherent to the protein, small exogenous molecules (e.g., aqua ligands) and/or macrocyclic porphyrin units found, for example, in hemoglobin, myoglobin, cytochrome C, cytochrome C oxidase, and vitamin B12. Thus, there continues to be considerable interest in employing macrocyclic metal complexes to construct low-molecular weight models for metallobiosites that mirror essential features of the coordination environment of a bound metal ion without inclusion of the surrounding protein framework. Herein, we review and appraise our research exploring the application of the metal complexes formed by two macrocyclic ligands, 1,4,7-triazacyclononane (tacn) and 1,4,7,10-tetraazacyclododecane (cyclen), and their derivatives in biological inorganic chemistry. Taking advantage of the kinetic inertness and thermodynamic stability of their metal complexes, these macrocyclic scaffolds have been employed in the development of models that aid the understanding of metal ion-binding natural systems, and complexes with potential applications in biomolecule sensing, diagnosis, and therapy. In particular, the focus has been on "coordinatively unsaturated" metal complexes that incorporate a kinetically inert and stable metal-ligand moiety, but which also contain one or more weakly bound ligands, allowing for the reversible binding of guest molecules via the formation and dissociation of coordinate bonds. With regards to mimicking metallobiosites, examples are presented from our work on tacn-based complexes developed as simplified structural models for multimetallic enzyme sites. In particular, structural comparisons are made between multinuclear copper(II) complexes formed by such ligands and multicopper enzymes featuring type-2 and type-3 copper centers, such as ascorbate oxidase (AO) and laccase (Lc). Likewise, with the aid of relevant examples, we highlight the importance of cooperativity between either multiple metal centers or a metal center and a proximal auxiliary unit appended to the macrocyclic ligand in achieving efficient phosphate ester cleavage. Finally, the critical importance of the Zn(II)-imido and Zn(II)-phosphate interactions in Zn-cyclen-based systems for delivering highly sensitive electrochemical and fluorescent chemosensors is also showcased. The Account additionally highlights some of the factors that limit the performance of these synthetic nucleases and the practical application of the biosensors, and then identifies some avenues for the development of more effective macrocyclic constructs in the future.

CD and MCD of CytC3 and taurine dioxygenase: role of the facial triad in alpha-KG-dependent oxygenases.

PubMed

Neidig, Michael L; Brown, Christina D; Light, Kenneth M; Fujimori, Danica Galonić; Nolan, Elizabeth M; Price, John C; Barr, Eric W; Bollinger, J Martin; Krebs, Carsten; Walsh, Christopher T; Solomon, Edward I

2007-11-21

The alpha-ketoglutarate (alpha-KG)-dependent oxygenases are a large and diverse class of mononuclear non-heme iron enzymes that require FeII, alpha-KG, and dioxygen for catalysis with the alpha-KG cosubstrate supplying the additional reducing equivalents for oxygen activation. While these systems exhibit a diverse array of reactivities (i.e., hydroxylation, desaturation, ring closure, etc.), they all share a common structural motif at the FeII active site, termed the 2-His-1-carboxylate facial triad. Recently, a new subclass of alpha-KG-dependent oxygenases has been identified that exhibits novel reactivity, the oxidative halogenation of unactivated carbon centers. These enzymes are also structurally unique in that they do not contain the standard facial triad, as a Cl- ligand is coordinated in place of the carboxylate. An FeII methodology involving CD, MCD, and VTVH MCD spectroscopies was applied to CytC3 to elucidate the active-site structural effects of this perturbation of the coordination sphere. A significant decrease in the affinity of FeII for apo-CytC3 was observed, supporting the necessity of the facial triad for iron coordination to form the resting site. In addition, interesting differences observed in the FeII/alpha-KG complex relative to the cognate complex in other alpha-KG-dependent oxygenases indicate the presence of a distorted 6C site with a weak water ligand. Combined with parallel studies of taurine dioxygenase and past studies of clavaminate synthase, these results define a role of the carboxylate ligand of the facial triad in stabilizing water coordination via a H-bonding interaction between the noncoordinating oxygen of the carboxylate and the coordinated water. These studies provide initial insight into the active-site features that favor chlorination by CytC3 over the hydroxylation reactions occurring in related enzymes.

One-pot synthesis of water soluble iron nanoparticles using rationally-designed peptides and ligand release.

PubMed

Papst, Stefanie; Cheong, Soshan; Banholzer, Moritz J; Brimble, Margaret A; Williams, David E; Tilley, Richard D

2013-05-18

Herein we report the rational design of new phosphopeptides for control of nucleation, growth and aggregation of water-soluble, superparamagnetic iron-iron oxide core-shell nanoparticles. The use of the designed peptides enables a one-pot synthesis that avoids utilizing unstable or toxic iron precursors, organic solvents, and the need for exchange of capping agent after synthesis of the NPs.

Quantum mechanical/molecular mechanical and docking study of the novel analogues based on hybridization of common pharmacophores as potential anti-breast cancer agents

PubMed Central

Asadi, Parvin; Khodarahmi, Ghadamali; Farrokhpour, Hossein; Hassanzadeh, Farshid; Saghaei, Lotfollah

2017-01-01

In an attempt to identify some new potential leads as anti-breast cancer agents, novel hybrid compounds were designed by molecular hybridization approach. These derivatives were structurally derived from hybrid benzofuran–imidazole and quinazolinone derivatives, which had shown good cytotoxicity against the breast cancer cell line (MCF-7). Since aromatase enzyme (CYP19) is highly expressed in the MCF-7 cell line, the binding of these novel hybrid compounds to aromatase was investigated using the docking method. In this study, due to the positive charge on the imidazole ring of the designed ligands and also, the presence of heme iron in the active site of the enzyme, it was decided to optimize the ligand inside the protein to obtain more realistic atomic charges for it. Quantum mechanical/molecular mechanical (QM/MM) method was used to obtain more accurate atomic charges of ligand for docking calculations by considering the polarization effects of CYP19 on ligands. It was observed that the refitted charge improved the binding energy of the docked compounds. Also, the results showed that these novel hybrid compounds were adopted properly within the aromatase binding site, thereby suggesting that they could be potential inhibitors of aromatase. The main binding modes in these complexes were through hydrophobic and H bond interactions showing agreement with the basic physicochemical features of known anti aromatase compounds. Finally, the complex structures obtained from the docking study were used for single point QM/MM calculations to obtain more accurate electronic interaction energy, considering the electronic polarization of the ligand by its protein environment. PMID:28626481

Iron-[S,S']-EDDS (FeEDDS) Chelate as an Iron Source for Horticultural Crop Production: Marigold Growth and Nutrition, Spectral Properties, and Photodegradation

USDA-ARS?s Scientific Manuscript database

Aminopolycarboxylic acid (APCA) complexones, commonly referred to as ligands or chelating agents, like ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) are commonly used in soluble fertilizers to supply copper (Cu), iron (Fe), manganese (Mn), and/or zinc (Zn) to p...

Axial vs. Equatorial Ligand Rivalry in Controlling the Reactivity of Iron(IV)-Oxo Species: Single-State vs. Two-State Reactivity.

PubMed

Kumar, Ravi; Ansari, Azaj; Rajaraman, Gopalan

2018-05-07

High-valent iron-oxo species are known for their very high reactivity, and this aspect has been studied in detail over the years. The role of axial ligands in fine-tuning the reactivity of the iron(IV)-oxo species has been particularly well studied. The corresponding role of equatorial ligands, however, has rarely been explored, and is of prime importance in the development of non-heme chemistry. Here, we have undertaken detailed DFT calculations on [(L NHC )Fe IV (O)(CH 3 CN)] 2+ (1; L NHC =3,9,14,20-tetraaza1,6,12,17-tetraazoniapenta-cyclohexacosane-1(23),4,6(26),10,12(25),15,17(24),21-octaene) in comparison to compound II of cytochrome P450 [(porphyrin)Fe IV (O)(SH)] - (2) to probe this aspect. The electronic structures of 1 and 2 are found to vary significantly, implying a large variation in their reactivities. In particular, the strong equatorial ligand present in 1 significantly destabilizes the quintet states as compared to species 2. To fully understand the reactivity pattern of these species, we have modelled the hydroxylation of methane by both 1 and 2. Our calculations reveal that 1 reacts via a low-lying S=1 π pathway, and that the generally available S=2 σ pathway is not energetically accessible. In addition to having a significant barrier for C-H bond activation, the -OH rebound step is also computed to have a large barrier height, leading to a marked difference in reactivity between these two species. Of particular relevance here is the observation of pure triplet-state reactivity for 1. We have also attempted to test the role of axial ligands in fine-tuning the reactivity of 1, and our results demonstrate that, in contrast to heme systems, the axial ligands in 1 do not significantly influence the reactivity. This highlights the importance of designing equatorial ligands to fine-tune reactivity of high-valent iron(IV)-oxo species. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of natural organic matter and iron binding capacity in fen samples

NASA Astrophysics Data System (ADS)

Kügler, Stefan; Cooper, Rebecca E.; Frieder Mohr, Jan; Wichard, Thomas; Küsel, Kirsten

2017-04-01

Natural organic matter (NOM) plays an important role in ecosystem processes such as soil carbon stabilization, nutrient availability and metal complexation. Iron-NOM-complexes, for example, are known to increase the solubility and, as a result, the bioavailability of iron in natural environments leading to several effects on the microbial community. Due to the various functions of NOM in natural environments, there is a high level of interest in the characterization of the molecular composition. The complexity of NOM presents a significant challenge in the elucidation of its composition. However, the development and utilization of high resolution mass spectrometry (HR-MS) as a tool to detect single compounds in complex samples has spearheaded the effort to elucidate the composition of NOM. Over the past years, the accuracy of ion cyclotron- or Orbitrap mass spectrometers has increased dramatically resulting in the possibility to obtain a mass differentiation of the large number of compounds in NOM. Together these tools provide significant and powerful insight into the molecular composition of NOM. In the current study, we aim to understand abiotic and biotic interactions between NOM and metals, such as iron, found in the Schlöppnerbrunnen fen (Fichtelgebirge, Germany) and how these interactions impact the microbial consortia. We characterized the dissolved organic matter (DOM) as well as basic chemical parameters in the iron-rich (up to 20 mg (g wt peat)-1), slightly acidic (pH 4.8) fen to gain more information about DOM-metal interactions. This minerotrophic peatland connected to the groundwater has received Fe(II) released from the surrounding soils in the Lehstenbach catchment. Absorption spectroscopy (AAS), differential pulse polarography (DPP) and high resolution electrospray ionization mass spectrometry (HR-ESI-Orbitrap-MS) was applied to characterize the molecular composition of DOM in the peat water extract (PWE). We identified typical patterns for DOM illustrated by van Krevelen plots, which indicate the presence of different substance classes including condensed aromatics, lignins and tannins known to complex iron. Our results indicate a variety of potential Fe-DOM-complexes present in the PWE samples when iron is incorporated into the elemental composition search. Using DPP we determine the complexation capacity of iron in the natural matrix of the fen along with the identification of ligands in order to estimate the iron bioavailability for bacteria. As the microbial redox system of the fen is impacted by other metals in the environment, we perform comprehensive analysis of the entirety of metal ions and concentrations in the water samples. Dialysis chambers are currently installed in the iron-rich fen from which pore water samples will be collected at 1 cm increments between 0-20 cm depth to determine the depth profiles of Fe(II)- and Fe(III)-concentration and evaluate the influence of the depth profiles on the interplay between microorganism comprising the natural microbial redox system of the fen. We have shown that metal-DOM-pH interactions affect the bioavailable metal concentration in fen water systems. This information will pave the way for a better understanding of the bacterial recruitment of trace elements and microbial redox reactions.

The Impact of Polyether Chain Length on the Iron Clearing Efficiency and Physiochemical Properties of Desferrithiocin Analogues

PubMed Central

Bergeron, Raymond J.; Bharti, Neelam; Wiegand, Jan; McManis, James S.; Singh, Shailendra; Abboud, Khalil A.

2010-01-01

(S)-2-(2,4-Dihydroxyphenyl)-4,5-dihydro-4-methyl-4-thiazolecarboxylic acid (2) was abandoned in clinical trials as an iron chelator for the treatment of iron overload disease because of its nephrotoxicity. However, subsequent investigations revealed that replacing the 4′-(HO) of 2 with a 3,6,9-trioxadecyloxy group, ligand 4, increased iron clearing efficiency (ICEa) and ameliorated the renal toxicity of 2. This compelled a closer look at additional polyether analogues, the subject of this work. The 3,6,9,12-tetraoxatridecyloxy analogue of 4, chelator 5, an oil, had twice the ICE in rodents of 4, although its ICE in primates was reduced relative to 4. The corresponding 3,6-dioxaheptyloxy analogue of 2, 6 (a crystalline solid), had high ICEs in both the rodent and primate models. It significantly decorporated hepatic, renal, and cardiac iron, with no obvious histopathologies. These findings suggest that polyether chain length has a profound effect on ICE, tissue iron decorporation, and ligand physiochemical properties. PMID:20232803

Part I. Cobalt thiolate complexes modeling the active site of cobalt nitrile hydratase. Part II. Formation of inorganic nanoparticles on protein scaffolding in Escherichia coli glutamine synthetase

NASA Astrophysics Data System (ADS)

Kung, Irene Yuk Man

Part I. A series of novel cobalt dithiolate complexes with mixed imine/amine ligand systems is presented here as electronic and structural models for the active site in the bacterial enzyme class, nitrile hydratase (NHase). Pentadentate cobalt(II) complexes with S2N 3 ligand environments are first studied as precursors to the more relevant cobalt(III) complexes. Adjustment of the backbone length by removal of a methylene group increases the reactivity of the system; whereas reduction of the two backbone imine bonds to allow free rotation about those bonds may decrease reactivity. Reactivity change due to the replacement of the backbone amine proton with a more sterically challenging methyl group is not yet clear. Upon oxidation, the monocationic pentadentate cobalt(III) complex, 1b, shows promising reactivity similar to that of NHase. The metal's open coordination site allows reversible binding of the endogenous, monoanionic ligands, N 3- and NCS-. Oxygenation of the thiolate sulfur atoms by exposure to O2 and H2O 2 produces sulfenate and sulfinate ligands in complex 8, which resembles the crystal structure of "deactivated" Fe NHase. However, its lack of reactivity argues against the oxygenated enzyme structure as the active form. Six-coordinate cobalt(III) complexes with S2N4 amine/amine ligand systems are also presented as analogues of previously reported iron(III) compounds, which mimic the spectroscopic properties of Fe NHase. The cobalt complexes do not seem to similarly model Co NHase. However, the S = 0 cobalt(III) center can be spectroscopically silent and difficult to detect, making comparison with synthetic models using common techniques hard. Part II. Dodecameric Escherichia coli glutamine synthetase mutant, E165C, stacks along its six-fold axis to produce tubular nanostructures in the presence of some divalent metal ions, as does the wild type enzyme. The centrally located, engineered Cys-165 residues appear to bind to various species and may serve as scaffolding for inorganic mineralization. US nanoclusters of discreet size seem to grow in the presence of E165C in aqueous solution spontaneously. Commercially available mono(maleimido)undecagold seem to bind only to E165C through the reactive cysteine side chains. Reduction of Au3+ to elemental gold in solution with E165C, generates long, linear structures of approximately 100-nm diameter.

Experimental determination and modeling of arsenic complexation with humic and fulvic acids.

PubMed

Fakour, Hoda; Lin, Tsair-Fuh

2014-08-30

The complexation of humic acid (HA) and fulvic acid (FA) with arsenic (As) in water was studied. Experimental results indicate that arsenic may form complexes with HA and FA with a higher affinity for arsenate than for arsenite. With the presence of iron oxide based adsorbents, binding of arsenic to HA/FA in water was significantly suppressed, probably due to adsorption of As and HA/FA. A two-site ligand binding model, considering only strong and weak site types of binding affinity, was successfully developed to describe the complexation of arsenic on the two natural organic fractions. The model showed that the numbers of weak sites were more than 10 times those of strong sites on both HA and FA for both arsenic species studied. The numbers of both types of binding sites were found to be proportional to the HA concentrations, while the apparent stability constants, defined for describing binding affinity between arsenic and the sites, are independent of the HA concentrations. To the best of our knowledge, this is the first study to characterize the impact of HA concentrations on the applicability of the ligand binding model, and to extrapolate the model to FA. The obtained results may give insights on the complexation of arsenic in HA/FA laden groundwater and on the selection of more effective adsorption-based treatment methods for natural waters. Copyright © 2014 Elsevier B.V. All rights reserved.

Activation of Dioxygen by Iron and Manganese Complexes: A Heme and Nonheme Perspective

PubMed Central

Sahu, Sumit; Goldberg, David P.

2016-01-01

The rational design of well-defined, first-row transition metal complexes that can activate dioxygen has been a challenging goal for the synthetic inorganic chemist. The activation of O2 is important in part because of its central role in the functioning of metalloenzymes, which utilize O2 to perform a number of challenging reactions including the highly selective oxidation of various substrates. There is also great interest in utilizing O2, an abundant and environmentally benign oxidant, in synthetic catalytic oxidation systems. This Perspective brings together recent examples of biomimetic Fe and Mn complexes that can activate O2 in heme or nonheme-type ligand environments. The use of oxidants such as hypervalent iodine (e.g., ArIO), peracids (e.g., m-CPBA), peroxides (e.g., H2O2) or even superoxide is a popular choice for accessing well-characterized metal–superoxo, metal–peroxo, or metal–oxo species, but the instances of biomimetic Fe/Mn complexes that react with dioxygen to yield such observable metal–oxygen species are surprisingly few. This Perspective focuses on mononuclear Fe and Mn complexes that exhibit reactivity with O2 and lead to spectroscopically observable metal–oxygen species, and/or oxidize biologically relevant substrates. Analysis of these examples reveals that solvent, spin state, redox potential, external co-reductants, and ligand architecture can all play important roles in the O2 activation process. PMID:27576170

Iron complexes of dendrimer-appended carboxylates for activating dioxygen and oxidizing hydrocarbons.

PubMed

Zhao, Min; Helms, Brett; Slonkina, Elena; Friedle, Simone; Lee, Dongwhan; Dubois, Jennifer; Hedman, Britt; Hodgson, Keith O; Fréchet, Jean M J; Lippard, Stephen J

2008-04-02

The active sites of metalloenzymes are often deeply buried inside a hydrophobic protein sheath, which protects them from undesirable hydrolysis and polymerization reactions, allowing them to achieve their normal functions. In order to mimic the hydrophobic environment of the active sites in bacterial monooxygenases, diiron(II) compounds of the general formula [Fe2([G-3]COO)4(4-RPy)2] were prepared, where [G-3]COO- is a third-generation dendrimer-appended terphenyl carboxylate ligand and 4-RPy is a pyridine derivative. The dendrimer environment provides excellent protection for the diiron center, reducing its reactivity toward dioxygen by about 300-fold compared with analogous complexes of terphenyl carboxylate ([G-1]COO-) ligands. An FeIIFeIII intermediate was characterized by electronic, electron paramagnetic resonance, Mössbauer, and X-ray absorption spectroscopic analyses following the oxygenation of [Fe2([G-3]COO)4(4-PPy)2], where 4-PPy is 4-pyrrolidinopyridine. The results are consistent with the formation of a superoxo species. This diiron compound, in the presence of dioxygen, can oxidize external substrates.

Iron Complexes of Dendrimer-Appended Carboxylates for Activating Dioxygen and Oxidizing Hydrocarbons

PubMed Central

Zhao, Min; Helms, Brett; Slonkina, Elena; Friedle, Simone; Lee, Dongwhan; DuBois, Jennifer; Hedman, Britt; Hodgson, Keith O.; Fréchet, Jean M. J.; Lippard, Stephen J.

2008-01-01

The active sites of metalloenzymes are often deeply buried inside a hydrophobic protein sheath, which protects them from undesirable hydrolysis and polymerization reactions, allowing them to achieve their normal functions. In order to mimic the hydrophobic environment of the active sites in bacterial monooxygenases, diiron(II) compounds of the general formula [Fe2([G-3]COO)4(4-RPy)2] were prepared, where [G-3]COO− is a third-generation dendrimer-appended terphenyl carboxylate ligand and 4-RPy is a pyridine derivative. The dendrimer environment provides excellent protection for the diiron center, reducing its reactivity toward dioxygen by about 300-fold compared with analogous complexes of terphenyl carboxylate ([G-1]COO−) ligands. An FeIIFeIII intermediate was characterized by electronic, electron paramagnetic resonance, Mössbauer, and X-ray absorption spectroscopic analyses following the oxygenation of [Fe2−([G-3]COO)4(4-PPy)2], where 4-PPy is 4-pyrrolidinopyridine. The results are consistent with the formation of a superoxo species. This diiron compound, in the presence of dioxygen, can oxidize external substrates. PMID:18331028

Exchange Interactions on the Highest-Spin Reported Molecule: the Mixed-Valence Fe42 Complex

NASA Astrophysics Data System (ADS)

Aravena, Daniel; Venegas-Yazigi, Diego; Ruiz, Eliseo

2016-04-01

The finding of high-spin molecules that could behave as conventional magnets has been one of the main challenges in Molecular Magnetism. Here, the exchange interactions, present in the highest-spin molecule published in the literature, Fe42, have been analysed using theoretical methods based on Density Functional Theory. The system with a total spin value S = 45 is formed by 42 iron centres containing 18 high-spin FeIII ferromagnetically coupled and 24 diamagnetic low-spin FeII ions. The bridging ligands between the two paramagnetic centres are two cyanide ligands coordinated to the diamagnetic FeII cations. Calculations were performed using either small Fe4 or Fe3 models or the whole Fe42 complex, showing the presence of two different ferromagnetic couplings between the paramagnetic FeIII centres. Finally, Quantum Monte Carlo simulations for the whole system were carried out in order to compare the experimental and simulated magnetic susceptibility curves from the calculated exchange coupling constants with the experimental one. This comparison allows for the evaluation of the accuracy of different exchange-correlation functionals to reproduce such magnetic properties.

Axial iron coordination and spin state change in a heme c upon electrostatic protein-SAM interaction.

PubMed

Di Rocco, Giulia; Ranieri, Antonio; Bortolotti, Carlo Augusto; Battistuzzi, Gianantonio; Bonifacio, Alois; Sergo, Valter; Borsari, Marco; Sola, Marco

2013-08-28

A bacterial di-heme cytochrome c binds electrostatically to a gold electrode surface coated with a negatively charged COOH-terminated SAM adopting a sort of 'perpendicular' orientation. Cyclic voltammetry, Resonance Raman and SERRS spectroscopies indicate that the high-potential C-terminal heme center proximal to the SAM's surface undergoes an adsorption-induced swapping of one axial His ligand with a water molecule, which is probably lost in the reduced form, and a low- to high-spin transition. This coordination change for a bis-His ligated heme center upon an electrostatically-driven molecular recognition is as yet unprecedented, as well as the resulting increase in reduction potential. We discuss it in comparison with the known methionine ligand lability in monoheme cytochromes c occurring upon interaction with charged molecular patches. One possible implication of this finding in biological ET is that mobile redox partners do not behave as rigid and invariant bodies, but in the ET complex are subjected to molecular changes and structural fluctuations that affect in a complex way the thermodynamics and the kinetics of the process.

Altered expression of CD1d molecules and lipid accumulation in the human hepatoma cell line HepG2 after iron loading.

PubMed

Cabrita, Marisa; Pereira, Carlos F; Rodrigues, Pedro; Cardoso, Elsa M; Arosa, Fernando A

2005-01-01

Iron overload in the liver may occur in clinical conditions such as hemochromatosis and nonalcoholic steatohepatitis, and may lead to the deterioration of the normal liver architecture by mechanisms not well understood. Although a relationship between the expression of ICAM-1, and classical major histocompatibility complex (MHC) class I molecules, and iron overload has been reported, no relationship has been identified between iron overload and the expression of unconventional MHC class I molecules. Herein, we report that parameters of iron metabolism were regulated in a coordinated-fashion in a human hepatoma cell line (HepG2 cells) after iron loading, leading to increased cellular oxidative stress and growth retardation. Iron loading of HepG2 cells resulted in increased expression of Nor3.2-reactive CD1d molecules at the plasma membrane. Expression of classical MHC class I and II molecules, ICAM-1 and the epithelial CD8 ligand, gp180 was not significantly affected by iron. Considering that intracellular lipids regulate expression of CD1d at the cell surface, we examined parameters of lipid metabolism in iron-loaded HepG2 cells. Interestingly, increased expression of CD1d molecules by iron-loaded HepG2 cells was associated with increased phosphatidylserine expression in the outer leaflet of the plasma membrane and the presence of many intracellular lipid droplets. These data describe a new relationship between iron loading, lipid accumulation and altered expression of CD1d, an unconventional MHC class I molecule reported to monitor intracellular and plasma membrane lipid metabolism, in the human hepatoma cell line HepG2.

A complementary set of electrochemical and X-ray synchrotron techniques to determine the passivation mechanism of iron treated in a new corrosion inhibitor solution specifically developed for the preservation of metallic artefacts

NASA Astrophysics Data System (ADS)

Mirambet, F.; Reguer, S.; Rocca, E.; Hollner, S.; Testemale, D.

2010-05-01

Metallic artefacts of the cultural heritage are often stored in uncontrolled environmental conditions. They are very sensitive to atmospheric corrosion caused by a succession of wet and dry periods due to variations of relative humidity and temperature. To avoid the complete degradation of the metallic artefacts, new preventive strategies must be developed. In this context, we have studied new compounds based on sodium carboxylates solutions CH3(CH2) n-2COO-, Na+ hereafter called NaC n . They allow the formation of a passive layer at the metallic surface composed of a metal-carboxylate complex. To understand the action of those inhibitors in the passivation process of iron we have performed electrochemical measurements and surface characterisation. Moreover, to monitor in real time the growth of the coating, in situ X-ray absorption spectroscopy (XAS) experiments at iron K-edge were carried out in an electrochemical cell. These analyses have shown that in the case of NaC10 solution, the protection of iron surface is correlated to the precipitation of a well-organised layer of FeC10. These experiments confirmed that this compound is a fully oxidised trinuclear Fe(III) complex containing decanoate anions as ligands. Such information concerning the passive layer is a key factor to evaluate its stability and finally the long-term efficiency of the protection treatment.

Mechanism of ubiquinol oxidation by the bc(1) complex: role of the iron sulfur protein and its mobility.

PubMed

Crofts, A R; Guergova-Kuras, M; Huang, L; Kuras, R; Zhang, Z; Berry, E A

1999-11-30

Native structures of ubihydroquinone:cytochrome c oxidoreductase (bc(1) complex) from different sources, and structures with inhibitors in place, show a 16-22 A displacement of the [2Fe-2S] cluster and the position of the C-terminal extrinsic domain of the iron sulfur protein. None of the structures shows a static configuration that would allow catalysis of all partial reactions of quinol oxidation. We have suggested that the different conformations reflect a movement of the subunit necessary for catalysis. The displacement from an interface with cytochrome c(1) in native crystals to an interface with cytochrome b is induced by stigmatellin or 5-n-undecyl-6-hydroxy-4,7-dioxobenzothiazole (UHDBT) and involves ligand formation between His-161 of the [2Fe-2S] binding cluster and the inhibitor. The movement is a rotational displacement, so that the same conserved docking surface on the iron sulfur protein interacts with cytochrome c(1) and with cytochrome b. The mobile extrinsic domain retains essentially the same tertiary structure, and the anchoring N-terminal tail remains in the same position. The movement occurs through an extension of a helical segment in the short linking span. We report details of the protein structure for the two main configurations in the chicken heart mitochondrial complex and discuss insights into mechanism provided by the structures and by mutant strains in which the docking at the cytochrome b interface is impaired. The movement of the iron sulfur protein represents a novel mechanism of electron transfer, in which a tethered mobile head allows electron transfer through a distance without the entropic loss from free diffusion.

Dioxygen Reactivity of Biomimetic Fe(II) Complexes with Noninnocent Catecholate, o-Aminophenolate, and o-Phenylenediamine Ligands

PubMed Central

2015-01-01

This study describes the O2 reactivity of a series of high-spin mononuclear Fe(II) complexes each containing the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine (Ph2TIP) ligand and one of the following bidentate, redox-active ligands: 4-tert-butylcatecholate (tBuCatH–), 4,6-di-tert-butyl-2-aminophenolate (tBu2APH–), or 4-tert-butyl-1,2-phenylenediamine (tBuPDA). The preparation and X-ray structural characterization of [Fe2+(Ph2TIP)(tBuCatH)]OTf, [3]OTf and [Fe2+(Ph2TIP)(tBuPDA)](OTf)2, [4](OTf)2 are described here, whereas [Fe2+(Ph2TIP)(tBu2APH)]OTf, [2]OTf was reported in our previous paper [Bittner et al., Chem.—Eur. J.2013,19, 9686–9698]. These complexes mimic the substrate-bound active sites of nonheme iron dioxygenases, which catalyze the oxidative ring-cleavage of aromatic substrates like catechols and aminophenols. Each complex is oxidized in the presence of O2, and the geometric and electronic structures of the resulting complexes were examined with spectroscopic (absorption, EPR, Mössbauer, resonance Raman) and density functional theory (DFT) methods. Complex [3]OTf reacts rapidly with O2 to yield the ferric-catecholate species [Fe3+(Ph2TIP)(tBuCat)]+ (3ox), which undergoes further oxidation to generate an extradiol cleavage product. In contrast, complex [4]2+ experiences a two-electron (2e–), ligand-based oxidation to give [Fe2+(Ph2TIP)(tBuDIBQ)]2+ (4ox), where DIBQ is o-diiminobenzoquinone. The reaction of [2]+ with O2 is also a 2e– process, yet in this case both the Fe center and tBu2AP ligand are oxidized; the resulting complex (2ox) is best described as [Fe3+(Ph2TIP)(tBu2ISQ)]+, where ISQ is o-iminobenzosemiquinone. Thus, the oxidized complexes display a remarkable continuum of electronic structures ranging from [Fe3+(L2–)]+ (3ox) to [Fe3+(L•–)]2+ (2ox) to [Fe2+(L0)]2+ (4ox). Notably, the O2 reaction rates vary by a factor of 105 across the series, following the order [3]+ > [2]+ > [4]2+, even though the complexes have similar structures and Fe3+/2+ redox potentials. To account for the kinetic data, we examined the relative abilities of the title complexes to bind O2 and participate in H-atom transfer reactions. We conclude that the trend in O2 reactivity can be rationalized by accounting for the role of proton transfer(s) in the overall reaction. PMID:24697567

Facile deferration of commercial fertilizers containing iron chelates for their NMR analysis.

PubMed

Laghi, Luca; Alcañiz, Sara; Cerdán, Mar; Gomez-Gallego, Mar; Sierra, Miguel Angel; Placucci, Giuseppe; Cremonini, Mauro Andrea

2009-06-24

Ethylenediamine-N,N'-bis(o-hydroxyphenylacetic) acid (o,o-EDDHA) is widely used in commercial formulations as a Fe(3+) chelating agent to remedy iron shortage in calcareous and alkaline soils. Commercially available o,o-EDDHA-Fe(3+) formulations contain a mixture of EDDHA regioisomers (o,p-EDDHA and p,p-EDDHA), together with other, still uncharacterized, products. NMR spectroscopy can be applied to their study as long as iron is accurately removed prior to the observation. This paper shows that it is possible to obtain a deferrated solution of the organic ligands present in commercial fertilizers containing the EDDHA-Fe(3+) chelate by treating the chelate with ferrocyanide, thus forming Prussian Blue that can be easily removed by centrifugation. This iron removal process does not cause significant losses of the o,o-EDDHA ligand or its minor structural isomers.

Simultaneous preconcentration and removal of iron, chromium, nickel with N,N'-etylenebis-(ethane sulfonamide) ligand on activated carbon in aqueous solution and determination by ICP-OES.

PubMed

Karacan, Mehmet Sayim; Aslantaş, Neslihan

2008-07-15

In this study, Fe, Cr and Ni have been preconcentrated and removed by using N,N'-ethylenebis (ethane sulfonamide), (ESEN) ligand on activated carbon (AC) in aqueous solution. For this purpose, complexes between these metals and ligands have been investigated and used in preconcentration and removal studies. Factors which have affected adsorption of metals on activated carbon have been optimized. Adsorbed metals have been preconcentrated 10-fold and determined by ICP-OES. Interferences of Ca, Mg and K to this process have been investigated. The proposed method has been applied to the tap water and Ankara Creek water in order to Fe, Cr, and Ni remediation and preconcentration. Determination of metals by ICP-OES has been checked with standard reference material (NIST 1643e). The proposed method provides the recoveries of 87%, 108% and 106% for Fe, Cr and Ni, respectively, in preconcentration. It also provides the removal of Fe, Cr and Ni by 93%, 100% and 100% removal from waters, respectively.

Iron catalyzed conversion of NO into nitrosonium (NO+) and nitroxyl (HNO/NO-) species.

PubMed

Stojanović, Srdjan; Stanić, Dragana; Nikolić, Milan; Spasić, Mihailo; Niketić, Vesna

2004-11-01

The conversion of NO into its congeners, nitrosonium (NO+) and nitroxyl (HNO/NO-) species, has important consequences in NO metabolism. Dinitrosyl iron complex (DNIC) combined with thiol ligands was shown to catalyze the conversion of NO into NO+, resulting in the synthesis of S-nitrosothiols (RSNO) both in vitro and in vivo. The formation mechanism of DNIC was proposed to involve the intermediate release of nitroxyl. Since the detection of hydroxylamine (as the product of a rapid reaction of HNO/NO- with thiols) is taken as the evidence for nitroxyl generation, we examined the formation of hydroxylamine, RSNO, and nitrite (the product of a rapid reaction of NO+ with water) in neutral solutions containing iron ions and thiols exposed to NO under anaerobic conditions. Hydroxylamine was detected in NO treated solutions of iron ions in the presence of cysteine, but not glutathione (GSH). The addition of urate, a major "free" iron-binding agent in humans, to solutions of GSH and iron ions, and the subsequent treatment of these solutions with NO increased the synthesis of GSNO and resulted in the formation of hydroxylamine. This caused a loss of urate and yielded a novel nitrosative/nitration product. GSH attenuated the urate decomposition to such a degree that it could be reflected as the function of GSH:urate. Results described here contribute to the understanding of the role of iron ions in catalyzing the conversion of NO into HNO/NO- and point to the role of uric acid not previously described.

Characterization of the Terminal Iron(IV) Imides {[PhBPtBu2(pz’)]FeIV≡NAd}+

PubMed Central

Thomas, Christine M.; Mankad, Neal P.; Peters, Jonas C.

2008-01-01

New hybrid bis(phosphine)(pyrazole)borate tripodal ligands ([PhBPtBu2(pz’)]−) are reported that support pseudotetrahedral iron in the oxidation states +1, +2, +3, and +4. The higher oxidation states are stabilized by a terminal Fe≡NR linkage. Of particular interest is the generation and thorough characterization of an S = 1 FeIV≡NR+ imide cation using this new ligand system. The latter species can be observed electrochemically and spectroscopically, and its solid-state crystal structure is reported. PMID:16608321

Iron, copper, and manganese complexes with in vitro superoxide dismutase and/or catalase activities that keep Saccharomyces cerevisiae cells alive under severe oxidative stress.

PubMed

Ribeiro, Thales P; Fernandes, Christiane; Melo, Karen V; Ferreira, Sarah S; Lessa, Josane A; Franco, Roberto W A; Schenk, Gerhard; Pereira, Marcos D; Horn, Adolfo

2015-03-01

Due to their aerobic lifestyle, eukaryotic organisms have evolved different strategies to overcome oxidative stress. The recruitment of some specific metalloenzymes such as superoxide dismutases (SODs) and catalases (CATs) is of great importance for eliminating harmful reactive oxygen species (hydrogen peroxide and superoxide anion). Using the ligand HPClNOL {1-[bis(pyridin-2-ylmethyl)amino]-3-chloropropan-2-ol}, we have synthesized three coordination compounds containing iron(III), copper(II), and manganese(II) ions, which are also present in the active site of the above-noted metalloenzymes. These compounds were evaluated as SOD and CAT mimetics. The manganese and iron compounds showed both SOD and CAT activities, while copper showed only SOD activity. The copper and manganese in vitro SOD activities are very similar (IC50~0.4 μmol dm(-3)) and about 70-fold higher than those of iron. The manganese compound showed CAT activity higher than that of the iron species. Analyzing their capacity to protect Saccharomyces cerevisiae cells against oxidative stress (H2O2 and the O2(•-) radical), we observed that all compounds act as antioxidants, increasing the resistance of yeast cells mainly due to a reduction of lipid oxidation. Especially for the iron compound, the data indicate complete protection when wild-type cells were exposed to H2O2 or O2(•-) species. Interestingly, these compounds also compensate for both superoxide dismutase and catalase deficiencies; their antioxidant activity is metal ion dependent, in the order iron(III)>copper(II)>manganese(II). The protection mechanism employed by the complexes proved to be independent of the activation of transcription factors (such as Yap1, Hsf1, Msn2/Msn4) and protein synthesis. There is no direct relation between the in vitro and the in vivo antioxidant activities. Copyright © 2014 Elsevier Inc. All rights reserved.

Complexation- and ligand-induced metal release from 316L particles: importance of particle size and crystallographic structure.

PubMed

Hedberg, Yolanda; Hedberg, Jonas; Liu, Yi; Wallinder, Inger Odnevall

2011-12-01

Iron, chromium, nickel, and manganese released from gas-atomized AISI 316L stainless steel powders (sized <45 and <4 μm) were investigated in artificial lysosomal fluid (ALF, pH 4.5) and in solutions of its individual inorganic and organic components to determine its most aggressive component, elucidate synergistic effects, and assess release mechanisms, in dependence of surface changes using atomic absorption spectroscopy, Raman, XPS, and voltammetry. Complexation is the main reason for metal release from 316L particles immersed in ALF. Iron was mainly released, while manganese was preferentially released as a consequence of the reduction of manganese oxide on the surface. These processes resulted in highly complexing media in a partial oxidation of trivalent chromium to hexavalent chromium on the surface. The extent of metal release was partially controlled by surface properties (e.g., availability of elements on the surface and structure of the outermost surface) and partially by the complexation capacity of the different metals with the complexing agents of the different media. In general, compared to the coarse powder (<45 μm), the fine (<4 μm) powder displayed significantly higher released amounts of metals per surface area, increased with increased solution complexation capacity, while less amounts of metals were released into non-complexing solutions. Due to the ferritic structure of lower solubility for nickel of the fine powder, more nickel was released into all solutions compared with the coarser powder.

The effect of post-synthesis aging on the ligand exchange activity of iron oxide nanoparticles.

PubMed

Davis, Kathleen; Vidmar, Michael; Khasanov, Airat; Cole, Brian; Ghelardini, Melanie; Mayer, Justin; Kitchens, Christopher; Nath, Amar; Powell, Brian A; Mefford, O Thompson

2018-02-01

Ligand exchange is a widely-used method of controlling the surface chemistry of nanomaterials. Exchange is dependent on many factors including the age of the core particle being modified. Aging of the particles can impact surface structure and composition, which in turn can affect ligand binding. To quantify the effects of aging on ligand exchange, we employed a technique to track the exchange of radiolabeled 14 C-oleic acid with unlabeled, oleic acid bound to iron oxide nanoparticles. Liquid scintillation counting (LSC) was used to determine the amount of 14 C-oleic acid adsorbing to the particles throughout the duration of the exchange for particles aged for 2days, 7days, and 30days. Results revealed an increase in the total amount of ligands exchanged with aging up to 30days. Kinetic analysis of these results revealed a significant decrease in the overall rate of ligand exchange between 2 and 30days. The change in extent of adsorption with age could suggest increased availability of free binding sites. A follow-up study comparing exchange with oxidized and unoxidized particles suggested this increase in ligand adsorption may be due to changes in the Fe 2+ /Fe 3+ ratio on the surface as the particles aged. Copyright © 2017 Elsevier Inc. All rights reserved.

Formation of metal-nicotianamine complexes as affected by pH, ligand exchange with citrate and metal exchange. A study by electrospray ionization time-of-flight mass spectrometry.

PubMed

Rellán-Alvarez, Rubén; Abadía, Javier; Alvarez-Fernández, Ana

2008-05-01

Nicotianamine (NA) is considered as a key element in plant metal homeostasis. This non-proteinogenic amino acid has an optimal structure for chelation of metal ions, with six functional groups that allow octahedral coordination. The ability to chelate metals by NA is largely dependent on the pK of the resulting complex and the pH of the solution, with most metals being chelated at neutral or basic pH values. In silico calculations using pKa and pK values have predicted the occurrence of metal-NA complexes in plant fluids, but the use of soft ionization techniques (e.g. electrospray), together with high-resolution mass spectrometers (e.g. time-of-flight mass detector), can offer direct and metal-specific information on the speciation of NA in solution. We have used direct infusion electrospray ionization mass spectrometry (time-of-flight) ESI-MS(TOF) to study the complexation of Mn, Fe(II), Fe(III), Ni, Cu by NA. The pH dependence of the metal-NA complexes in ESI-MS was compared to that predicted in silico. Possible exchange reactions that may occur between Fe-NA and other metal micronutrients as Zn and Cu, as well as between Fe-NA and citrate, another possible Fe ligand candidate in plants, were studied at pH 5.5 and 7.5, values typical of the plant xylem and phloem saps. Metal-NA complexes were generally observed in the ESI-MS experiments at a pH value approximately 1-2 units lower than that predicted in silico, and this difference could be only partially explained by the estimated error, approximately 0.3 pH units, associated with measuring pH in organic solvent-containing solutions. Iron-NA complexes are less likely to participate in ligand- and metal-exchange reactions at pH 7.5 than at pH 5.5. Results support that NA may be the ligand chelating Fe at pH values usually found in phloem sap, whereas in the xylem sap NA is not likely to be involved in Fe transport, conversely to what occurs with other metals such as Cu and Ni. Some considerations that need to be addressed when studying metal complexes in plant compartments by ESI-MS are also discussed.

Heteroatom-free arene-cobalt and arene-iron catalysts for hydrogenations.

PubMed

Gärtner, Dominik; Welther, Alice; Rad, Babak Rezaei; Wolf, Robert; Jacobi von Wangelin, Axel

2014-04-01

75 years after the discovery of hydroformylation, cobalt catalysts are now undergoing a renaissance in hydrogenation reactions. We have evaluated arene metalates in which the low-valent metal species is--conceptually different from heteroatom-based ligands--stabilized by π coordination to hydrocarbons. Potassium bis(anthracene)cobaltate 1 and -ferrate 2 can be viewed as synthetic precursors of quasi-"naked" anionic metal species; their aggregation is effectively impeded by (labile) coordination to the various π acceptors present in the hydrogenation reactions of unsaturated molecules (alkenes, arenes, carbonyl compounds). Kinetic studies, NMR spectroscopy, and poisoning studies of alkene hydrogenations support the formation of a homogeneous catalyst derived from 1 which is stabilized by the coordination of alkenes. This catalyst concept complements the use of complexes with heteroatom donor ligands for reductive processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NRVS and EPR Spectroscopy of 57Fe-enriched [FeFe] Hydrogenase Indicate Stepwise Assembly of the H-cluster†

PubMed Central

Kuchenreuther, Jon M.; Guo, Yisong; Wang, Hongxin; Myers, William K.; George, Simon J.; Boyke, Christine A.; Yoda, Yoshitaka; Alp, E. Ercan; Zhao, Jiyong; Britt, R. David; Swartz, James R.; Cramer, Stephen P.

2013-01-01

The [FeFe] hydrogenase from Clostridium pasteurianum (CpI) harbors four Fe–S clusters that facilitate electron transfer to the H-cluster, a ligand-coordinated six-iron prosthetic group that catalyzes the redox interconversion of protons and H2. Here, we have used 57Fe nuclear resonance vibrational spectroscopy (NRVS) to study the iron centers in CpI, and we compare our data to that for a [4Fe–4S] ferredoxin as well as a model complex resembling the [2Fe]H catalytic domain of the H-cluster. In order to enrich the hydrogenase with 57Fe nuclei, we used cell-free methods to post-translationally mature the enzyme. Specifically, inactive CpI apoprotein with 56Fe-labeled Fe–S clusters was activated in vitro using 57Fe-enriched maturation proteins. This approach enabled us to selectively label the [2Fe]H subcluster with 57Fe, which NRVS confirms by detecting 57Fe–CO and 57Fe–CN normal modes from the H-cluster nonprotein ligands. The NRVS and iron quantification results also suggest that the hydrogenase contains a second 57Fe–S cluster. EPR spectroscopy indicates that this 57Fe-enriched metal center is not the [4Fe– 4S]H subcluster of the H-cluster. This finding demonstrates that the CpI hydrogenase retained an 56Fe-enriched [4Fe–4S]H cluster during in vitro maturation, providing unambiguous evidence for stepwise assembly of the H-cluster. In addition, this work represents the first NRVS characterization of [FeFe] hydrogenases. PMID:23249091

Metal isotope coded profiling of organic ligands by mass spectrometry in aquatic environments

NASA Astrophysics Data System (ADS)

Wichard, Thomas; Deicke, Michael; Frieder Mohr, Jan; Klein, Martin

2017-04-01

Metal isotope coded profiling (MICP) introduces a universal discovery platform for metal chelating natural products that act as metallophores, ion buffers or sequestering agents. The detection of cation and oxoanion complexing ligands is facilitated by the identification of unique isotopic signatures created by the application of isotopically pure metals. We present a targeted analysis of low-molecular-weight organic ligands based on fast UHPLC-ESI-MS measurements. Replacement of, for example, natural iron or molybdenum with isotopically pure 54Fe/58Fe (ratio 1:1) or 95Mo/98Mo (ratio 1:1) causes easily detectable unique isotopic signatures in the mass spectra of potential metal-complexing ligands. This can be achieved under laboratory conditions not only in growth media, but also by spiking directly aqueous samples or solid-phase extracts. Importantly, as the relative affinity of the metallophores for e.g., Mo or Fe is dependent on the pH, all experiments needs to be conducted under pH-controlled conditions. The improved ionization efficiency of some metal complexes helps to enhance the signal-to-noise ratio compared to the free ligand at the same chromatographic conditions. The methodology does not necessarily depend on HR-ESI-MS measurements (e.g., Q-Exactive Orbitrap) and can be applied to any mass spectrometer. With MICP, two birds can be killed with one stone: (i) the identification of metallophores (e.g., siderophores, molybdophores) for metal uptake by any organism and (ii) organic ligands which solely work as metal buffer in dissolved organic matter (DOM). We currently address following two main research lines: First, DOM has often been used as a proxy for bio-productivity in terms of a carbon source; however, the specific impact of DOM as a "metal buffer" for biological processes is still under-investigated. Upon the administration of individual isotopes or isotopic pairs, for example, 54Fe/58Fe, 63Cu/65Cu, 66Zn/68Zn, or 95Mo/98Mo and subsequent measurements by mass spectrometry, organic ligands can be identified that contribute potentially to the regulation of bioavailability and toxicity of metals in the water column. Secondly, metal acquisition by ligand exchange processes is vital for macroalgae-bacteria interactions. Both alga and bacteria contribute to the "soup of organic ligands" which potentially increases the bioavailability of metals due to various ligand exchanges with DOM. In particular, we will outline the analytical process resulting in the identification of ligands in the chemosphere of the marine macroalga Ulva (Chlorophyta) and its associated bacteria. In summary, the identification of metal organic ligands in natural samples will pave the way for understanding the organic ligand-mediated metal acquisition shuttled from DOM to alga. (References: Wichard T. (2016) Front. Mar. Sci. 3:131; Deicke M., Mohr J.M., Wichard T. (2014) Analyst, 139, 6096-6099)

Comprehensive Fe-ligand vibration identification in {FeNO} 6 Hemes

DOE PAGES

Li, Jianfeng; Peng, Qian; Oliver, Allen G.; ...

2014-12-09

Oriented single-crystal nuclear resonance vibrational spectroscopy (NRVS) has been used to obtain all iron vibrations in two {FeNO} 6 porphyrinate complexes, five-coordinate [Fe(OEP)(NO)]ClO 4 and six-coordinate [Fe(OEP)(2-MeHIm)(NO)]ClO 4. A new crystal structure was required for measurements of [Fe(OEP)(2-MeHIm)(NO)]ClO 4, and the new structure is reported herein. Single crystals of both complexes were oriented to be either parallel or perpendicular to the porphyrin plane and/or axial imidazole ligand plane. Thus, the FeNO bending and stretching modes can now be unambiguously assigned; the pattern of shifts in frequency as a function of coordination number can also be determined. The pattern is quitemore » distinct from those found for CO or {FeNO} 7 heme species. This is the result of unchanging Fe–N NO bonding interactions in the {FeNO} 6 species, in distinct contrast to the other diatomic ligand species. DFT calculations were also used to obtain detailed predictions of vibrational modes. Predictions were consistent with the intensity and character found in the experimental spectra. The NRVS data allow the assignment and observation of the challenging to obtain Fe–Im stretch in six-coordinate heme derivatives. Furthermore, NRVS data for this and related six-coordinate hemes with the diatomic ligands CO, NO, and O 2 reveal a strong correlation between the Fe–Im stretch and Fe–N Im bond distance that is detailed for the first time.« less

Enhanced ferrihydrite dissolution by a unicellular, planktonic cyanobacterium: a biological contribution to particulate iron bioavailability.

PubMed

Kranzler, Chana; Kessler, Nivi; Keren, Nir; Shaked, Yeala

2016-12-01

Iron (Fe) bioavailability, as determined by its sources, sinks, solubility and speciation, places severe environmental constraints on microorganisms in aquatic environments. Cyanobacteria are a widespread group of aquatic, photosynthetic microorganisms with especially high iron requirements. While iron exists predominantly in particulate form, little is known about its bioavailability to cyanobacteria. Some cyanobacteria secrete iron solubilizing ligands called siderophores, yet many environmentally relevant strains do not have this ability. This work explores the bioavailability of amorphous synthetic Fe-oxides (ferrihydrite) to the non-siderophore producing, unicellular cyanobacterium, Synechocystis sp PCC 6803. Iron uptake assays with 55 ferrihydrite established dissolution as a critical prerequisite for iron transport. Dissolution assays with the iron binding ligand, desferrioxamine B, demonstrated that Synechocystis 6803 enhances ferrihydrite dissolution, exerting siderophore-independent biological influence on ferrihydrite bioavailability. Dissolution mechanisms were studied using a range of experimental conditions; both cell-particle physical proximity and cellular electron flow were shown to be important determinants of bio-dissolution by Synechocystis 6803. Finally, the effects of ferrihydrite stability on bio-dissolution rates and cell physiology were measured, integrating biological and chemical aspects of ferrihydrite bioavailability. Collectively, these findings demonstrate that Synechocystis 6803 actively dissolves ferrihydrite, highlighting a significant biological component to mineral phase iron bioavailability in aquatic environments. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Simultaneous spectrophotometric determination of copper, cobalt, nickel and iron in foodstuffs and vegetables with a new bis thiosemicarbazone ligand using chemometric approaches.

PubMed

Rohani Moghadam, Masoud; Poorakbarian Jahromi, Sayedeh Maria; Darehkordi, Ali

2016-02-01

A newly synthesized bis thiosemicarbazone ligand, (2Z,2'Z)-2,2'-((4S,5R)-4,5,6-trihydroxyhexane-1,2-diylidene)bis(N-phenylhydrazinecarbothioamide), was used to make a complex with Cu(2+), Ni(2+), Co(2+) and Fe(3+) for their simultaneous spectrophotometric determination using chemometric methods. By Job's method, the ratio of metal to ligand in Ni(2+) was found to be 1:2, whereas it was 1:4 for the others. The effect of pH on the sensitivity and selectivity of the formed complexes was studied according to the net analyte signal (NAS). Under optimum conditions, the calibration graphs were linear in the ranges of 0.10-3.83, 0.20-3.83, 0.23-5.23 and 0.32-8.12 mg L(-1) with the detection limits of 2, 3, 4 and 10 μg L(-1) for Cu(2+), Co(2+), Ni(2+) and Fe(3+) respectively. The OSC-PLS1 for Cu(2+) and Ni(2+), the PLS1 for Co(2+) and the PC-FFANN for Fe(3+) were selected as the best models. The selected models were successfully applied for the simultaneous determination of elements in some foodstuffs and vegetables. Copyright © 2015 Elsevier Ltd. All rights reserved.

From iron coordination compounds to metal oxide nanoparticles.

PubMed

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel; Cazacu, Maria

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe 2 III Fe II O(CH 3 COO) 6 (H 2 O) 3 ]·2H 2 O (FeAc1), μ 3 -oxo trinuclear iron(III) acetate, [Fe 3 O(CH 3 COO) 6 (H 2 O) 3 ]NO 3 ∙4H 2 O (FeAc2), iron furoate, [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeF), iron chromium furoate, FeCr 2 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

From iron coordination compounds to metal oxide nanoparticles

PubMed Central

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2 IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), μ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles. PMID:28144555

Connecting [NiFe]- and [FeFe]-Hydrogenases: Mixed-Valence Nickel-Iron Dithiolates With Rotated Structures

PubMed Central

Schilter, David; Rauchfuss, Thomas B.; Stein, Matthias

2012-01-01

A series of mixed-valence iron-nickel dithiolates is described that exhibits structures similar to those of mixed-valence diiron dithiolates. Interaction of tricarbonyl salt [(dppe)Ni(pdt)Fe(CO)3]BF4 ([1]BF4, dppe = Ph2PCH2CH2PPh2, pdtH2 = HSCH2CH2CH2SH) with P-donor ligands (L) afforded the substituted derivatives [(dppe)Ni(pdt)Fe(CO)2L]BF4 incorporating L = PHCy2 ([1a]BF4), PPh(NEt2)2 ([1b]BF4), P(NMe2)3 ([1c]BF4), P(i-Pr)3 ([1d]BF4) and PCy3 ([1e]BF4). The related precursor [(dcpe)Ni(pdt)Fe(CO)3]BF4 ([2]BF4, dcpe = Cy2PCH2CH2PCy2) gave the more electron-rich family of compounds [(dcpe)Ni(pdt)Fe(CO)2L]BF4 for L = PPh2(2-pyridyl) ([2a]BF4), PPh3 ([2b]BF4) and PCy3 ([2c]BF4). For bulky and strongly basic monophosphorus ligands, the salts feature distorted Fe coordination geometries: crystallographic analyses of [1e]BF4 and [2c]BF4 showed they adopt ‘rotated’ Fe(I) centers, in which PCy3 occupies a basal site and one CO ligand partially bridges the Ni and Fe centers. Like the undistorted mixed-valence derivatives, the new class of complexes are described as Ni(II)Fe(I) (S = ½) systems according to EPR spectroscopy, although with attenuated 31P hyperfine interactions. DFT calculations using the BP86, B3LYP, and PBE0 exchange-correlation functionals agree with the structural and spectroscopic data, suggesting that the spin for [1e]+ is localized in a Fe(I)-centered d(z2) orbital, orthogonal to the Fe-P bond. The PCy3 complexes, rare examples of species featuring ‘rotated’ Fe centers, both structurally and spectroscopically resemble mixed-valence diiron dithiolates. Also reproducing the NiS2Fe core of the [NiFe]-H2ase active site, the hybrid models incorporate key features of the two major classes of H2ase. Furthermore, cyclic voltammetry experiments suggest that the highly basic phosphine ligands enable a second oxidation corresponding to the couple [(dxpe)Ni(pdt)Fe(CO)2L]+/2+. The resulting unsaturated 32e− dications represent the closest approach to modeling the highly electrophilic Ni-SIa state. In the case of L = PPh2(2-pyridyl) chelation of this ligand accompanies the second oxidation. PMID:22838645

Electrochemistry of mixed-metal bimetallic complexes containing the pentacyanoferrate(II) or pentaammineruthenium(II) metal center

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, K.J.; Lee, L.; Mabbott, G.A.

1983-03-30

The electrochemistry of a series of mixed-metal bimetallic complexes of the type B/sub 5/MLM'B'/sub 5/, where B/sub 5/M = (CNN)/sub 5/Fe/sup II/ or (NH/sub 3/)/sub 5/Ru/sup II/, L = pyrazine, 4,4'-bipyridine, or 4-cyanopyridine, M'B'/sub 5/ = Rh/sup III/(NH/sub 3/)/sub 5/ or Co/sup III/(CN)/sub 5/, is reported. The bimetallic complexes all have metal-to-ligand charge-transfer (MLCT) bands associated with the M-B unit (d/sub ..pi../M ..-->.. p/sub ..pi../*L). The effect of the remote metal center, M'B'/sub 5/, is to function as a Lewis acid, shifting the MLCT maximum to lower energy and shifting the M/sup III///sup II/ reduction potential more positive with respectmore » to free B/sub 5/ML. The remote metal influence is attenuated by longer bridging ligands and by reduced ..pi..-overlap. A comparison of the electrochemical data of the mixed-valence Fe(II)/Fe(III) and Ru(II)/Ru(III) complexes to the mixed-metal Fe(II)/Co(III) and Ru(II)/Rh(III) complexes has enabled a quantitative measure of the stabilization due to electron delocalization in the mixed-valence complexes. The results show that electron delocalization is greater for the ruthenium complexes than for the iron complexes, is a small contributor to the total stabilization of the mixed-valence state, and even in ruthenium drops off rapidly as the length of the bridge increases.« less

COMPARATIVE ASSESSMENT OF THE COMPOSITION AND CHARGE STATE OF NITROGENASE FeMo-COFACTOR

PubMed Central

Harris, Travis V.; Szilagyi, Robert K.

2011-01-01

A significant limitation in our understanding of the molecular mechanism of biological nitrogen fixation is the uncertain composition of the FeMo-cofactor (FeMo-co) of nitrogenase. In this study we present a systematic, density functional theory-based evaluation of spin coupling schemes, iron oxidation states, ligand protonation states, and interstitial ligand composition using a wide range of experimental criteria. The employed functionals and basis sets were validated with molecular orbital information from X-ray absorption spectroscopic data of relevant iron-sulfur clusters. Independently from the employed level of theory, the electronic structure with the greatest number of antiferromagnetic interactions corresponds to the lowest energy state for a given charge and oxidation state distribution of the iron ions. The relative spin state energies of resting and oxidized FeMo-co already allowed the exclusion of certain iron oxidation state distributions and interstitial ligand compositions. Geometry optimized FeMo-co structures of several models further eliminated additional states and compositions, while reduction potentials indicated a strong preference for the most likely charge state of FeMo-co. Mössbauer and ENDOR parameter calculations were found to be remarkably dependent on the employed training set, density functional and basis set. Overall, we found that a more oxidized [MoIV-2FeII-5FeIII-9S2−-C4−] composition with a hydroxyl-protonated homocitrate ligand satisfies all of the available experimental criteria, and is thus favored over the currently preferred composition of [MoIV-4FeII-3FeIII-9S2−-N3−] from the literature. PMID:21545160

Influence of Analyte Concentration on Stability Constant Values Determined by Capillary Electrophoresis.

PubMed

Sursyakova, Viktoria V; Burmakina, Galina V; Rubaylo, Anatoly I

2016-08-01

The influence of analyte concentration when compared with the concentration of a charged ligand in background electrolyte (BGE) on the measured values of electrophoretic mobilities and stability constants (association, binding or formation constants) is studied using capillary electrophoresis (CE) and a dynamic mathematical simulator of CE. The study is performed using labile complexes (with fast kinetics) of iron (III) and 5-sulfosalicylate ions (ISC) as an example. It is shown that because the ligand concentration in the analyte zone is not equal to that in BGE, considerable changes in the migration times and electrophoretic mobilities are observed, resulting in systematic errors in the stability constant values. Of crucial significance is the slope of the dependence of the electrophoretic mobility decrease on the ligand equilibrium concentration. Without prior information on this dependence to accurately evaluate the stability constants for similar systems, the total ligand concentration must be at least >50-100 times higher than the total concentration of analyte. Experimental ISC peak fronting and the difference between the direction of the experimental pH dependence of the electrophoretic mobility decrease and the mathematical simulation allow assuming the presence of capillary wall interaction. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Zinc Pyrithione Inhibits Yeast Growth through Copper Influx and Inactivation of Iron-Sulfur Proteins▿†

PubMed Central

Reeder, Nancy L.; Kaplan, Jerry; Xu, Jun; Youngquist, R. Scott; Wallace, Jared; Hu, Ping; Juhlin, Kenton D.; Schwartz, James R.; Grant, Raymond A.; Fieno, Angela; Nemeth, Suzanne; Reichling, Tim; Tiesman, Jay P.; Mills, Tim; Steinke, Mark; Wang, Shuo L.; Saunders, Charles W.

2011-01-01

Zinc pyrithione (ZPT) is an antimicrobial material with widespread use in antidandruff shampoos and antifouling paints. Despite decades of commercial use, there is little understanding of its antimicrobial mechanism of action. We used a combination of genome-wide approaches (yeast deletion mutants and microarrays) and traditional methods (gene constructs and atomic emission) to characterize the activity of ZPT against a model yeast, Saccharomyces cerevisiae. ZPT acts through an increase in cellular copper levels that leads to loss of activity of iron-sulfur cluster-containing proteins. ZPT was also found to mediate growth inhibition through an increase in copper in the scalp fungus Malassezia globosa. A model is presented in which pyrithione acts as a copper ionophore, enabling copper to enter cells and distribute across intracellular membranes. This is the first report of a metal-ligand complex that inhibits fungal growth by increasing the cellular level of a different metal. PMID:21947398

Targeting cancer by binding iron: Dissecting cellular signaling pathways

PubMed Central

Lui, Goldie Y.L.; Kovacevic, Zaklina; Richardson, Vera; Merlot, Angelica M.; Kalinowski, Danuta S.; Richardson, Des R.

2015-01-01

Newer and more potent therapies are urgently needed to effectively treat advanced cancers that have developed resistance and metastasized. One such strategy is to target cancer cell iron metabolism, which is altered compared to normal cells and may facilitate their rapid proliferation. This is supported by studies reporting the anti-neoplastic activities of the clinically available iron chelators, desferrioxamine and deferasirox. More recently, ligands of the di-2-pyridylketone thiosemicarbazone (DpT) class have demonstrated potent and selective anti-proliferative activity across multiple cancer-types in vivo, fueling studies aimed at dissecting their molecular mechanisms of action. In the past five years alone, significant advances have been made in understanding how chelators not only modulate cellular iron metabolism, but also multiple signaling pathways implicated in tumor progression and metastasis. Herein, we discuss recent research on the targeting of iron in cancer cells, with a focus on the novel and potent DpT ligands. Several key studies have revealed that iron chelation can target the AKT, ERK, JNK, p38, STAT3, TGF-β, Wnt and autophagic pathways to subsequently inhibit cellular proliferation, the epithelial-mesenchymal transition (EMT) and metastasis. These developments emphasize that these novel therapies could be utilized clinically to effectively target cancer. PMID:26125440

Heterobimetallic Complexes Featuring Fe(CO)5 as a Ligand on Gold.

PubMed

Wang, Guocang; Ponduru, Tharun T; Wang, Qing; Zhao, Lili; Frenking, Gernot; Dias, H V Rasika

2017-12-06

Iron(0) pentacarbonyl complexes of gold(I), [Mes 3 PAu-Fe(CO) 5 ][SbF 6 ] (1) and [(IPr*)Au-Fe(CO) 5 ][SbF 6 ] (2) (Mes=2,4,6-trimethylphenyl; IPr*=1,3-bis(2,6-bis(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene) have been synthesized using Mes 3 PAuCl and (IPr*)AuCl as the gold(I) precursor, AgSbF 6 halide ion abstractor, and the Lewis base Fe(CO) 5 . The Au-Fe bond lengths of these metal-only Lewis pair complexes are significantly shorter than the sum of the experimentally derived covalent radii of Au and Fe. The v̄(CO) bands of the molecules show a notable blueshift relative to those observed for free Fe(CO) 5 , indicating a substantial reduction in Fe→CO backbonding upon its coordination to gold(I) with either Mes 3 P or IPr* supporting ligands (L). The analysis of the electronic structure with quantum chemical method suggests that the Au-Fe bond consists mainly of [LAu] + ←Fe(CO) 5 σ-donation and weaker [LAu] + →Fe(CO) 5 π-backdonation. The donor strength of Fe(CO) 5 is similar to that of CO. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cation Distribution and Local Configuration of Fe 2+ Ions in Structurally Nonequivalent Lattice Sites of Heterometallic Fe(II)/ M(II) ( M = Mn, Co, Ni, Cu, Zn) Diaquadiformato Complexes

NASA Astrophysics Data System (ADS)

Devillers, M.; Ladrière, J.

1993-03-01

57Fe Mössbauer investigations are carried out on a wide series of heterometallic diaquadiformato Fe(II)/ M(II) complexes with M = Mn, Co, Ni, Cu, and Zn to provide a local picture of the coordination environment of the 57Fe 2+ ions as a function of (i) the nature of the host cation and (ii) the relative amounts of both metals in the matrix (between 50 and 0.25 at.% Fe). Information is obtained on the quantitative distribution of both metals between the two structurally nonequivalent lattice sites and on the local geometry around the dopant atom in each crystal site. In the mixed Fe-Cu complexes. Fe 2+ ions are preferentially incorporated in the tetrahydrated site; in Cu-rich Fe xCu 1- x(HCO 2) 2· 2H 2O, the 57Fe 2+ ions located in the hexaformato-coordinated site are surrounded by an axially compressed octahedron of formate ligands which contrasts with the elongated configuration observed in the pure iron compound and in the other mixed systems. Semiquantitative estimations of the tetragonal field splitting and of the extent of metal-ligand interactions are proposed from the temperature dependence of the quadrupole splitting values.

Surface anisotropy of iron oxide nanoparticles and slabs from first principles: Influence of coatings and ligands as a test of the Heisenberg model

NASA Astrophysics Data System (ADS)

Brymora, Katarzyna; Calvayrac, Florent

2017-07-01

We performed ab initio computations of the magnetic properties of simple iron oxide clusters and slabs. We considered an iron oxide cluster functionalized by a molecule or glued to a gold cluster of the same size. We also considered a magnetite slab coated by cobalt oxide or a mixture of iron oxide and cobalt oxide. The changes in magnetic behavior were explored using constrained magnetic calculations. A possible value for the surface anisotropy was estimated from the fit of a classical Heisenberg model on ab initio results. The value was found to be compatible with estimations obtained by other means, or inferred from experimental results. The addition of a ligand, coating, or of a metallic nanoparticle to the systems degraded the quality of the description by the Heisenberg Hamiltonian. Proposing a change in the anisotropies allowing for the proportion of each transition atom we could get a much better description of the magnetism of series of hybrid cobalt and iron oxide systems.

Effects of formate binding on the quinone-iron electron acceptor complex of photosystem II.

PubMed

Sedoud, Arezki; Kastner, Lisa; Cox, Nicholas; El-Alaoui, Sabah; Kirilovsky, Diana; Rutherford, A William

2011-02-01

EPR was used to study the influence of formate on the electron acceptor side of photosystem II (PSII) from Thermosynechococcus elongatus. Two new EPR signals were found and characterized. The first is assigned to the semiquinone form of Q(B) interacting magnetically with a high spin, non-heme-iron (Fe²(+), S=2) when the native bicarbonate/carbonate ligand is replaced by formate. This assignment is based on several experimental observations, the most important of which were: (i) its presence in the dark in a significant fraction of centers, and (ii) the period-of-two variations in the concentration expected for Q(B)(•-) when PSII underwent a series of single-electron turnovers. This signal is similar but not identical to the well-know formate-modified EPR signal observed for the Q(A)(•-)Fe²(+) complex (W.F.J. Vermaas and A.W. Rutherford, FEBS Lett. 175 (1984) 243-248). The formate-modified signals from Q(A)(•-)Fe²(+) and Q(B)(•-)Fe²(+) are also similar to native semiquinone-iron signals (Q(A)(•-)Fe²(+)/Q(B)(•-)Fe²(+)) seen in purple bacterial reaction centers where a glutamate provides the carboxylate ligand to the iron. The second new signal was formed when Q(A)(•-) was generated in formate-inhibited PSII when the secondary acceptor was reduced by two electrons. While the signal is reminiscent of the formate-modified semiquinone-iron signals, it is broader and its main turning point has a major sub-peak at higher field. This new signal is attributed to the Q(A)(•-)Fe²(+) with formate bound but which is perturbed when Q(B) is fully reduced, most likely as Q(B)H₂ (or possibly Q(B)H(•-) or Q(B)(²•-)). Flash experiments on formate-inhibited PSII monitoring these new EPR signals indicate that the outcome of charge separation on the first two flashes is not greatly modified by formate. However on the third flash and subsequent flashes, the modified Q(A)(•-)Fe²(+)Q(B)H₂ signal is trapped in the EPR experiment and there is a marked decrease in the quantum yield of formation of stable charge pairs. The main effect of formate then appears to be on Q(B)H₂ exchange and this agrees with earlier studies using different methods. Copyright © 2010 Elsevier B.V. All rights reserved.

Stabilization of higher-valent states of iron porphyrin by hydroxide and methoxide ligands: electrochemical generation of iron(IV)-oxo porphyrins.

PubMed Central

Lee, W A; Calderwood, T S; Bruice, T C

1985-01-01

An electrochemical study of hydroxide- and methoxide-ligated iron(III) tetraphenylporphyrins possessing ortho-phenyl substituents that block mu-oxo dimer formation has been carried out. Ligation by these strongly basic oxyanions promotes the formation of iron(IV)-oxo porphyrins upon one-electron oxidation. Further one-electron oxidation of the latter provides the iron(IV)-oxo porphyrin pi-cation radical. These results are discussed in terms of chemical model studies and the enzymatic intermediate compounds I and II of the peroxidases. PMID:3859865

Identification of the iron-sulfur center of spinach ferredoxin-nitrite reductase as a tetranuclear center, and preliminary EPR studies of mechanism.

PubMed

Lancaster, J R; Vega, J M; Kamin, H; Orme-Johnson, N R; Orme-Johnson, W H; Krueger, R J; Siegel, L M

1979-02-25

EPR spectroscopic and chemical analyses of spinach nitrite reductase show that the enzyme contains one reducible iron-sulfur center, and one site for binding either cyanide or nitrite, per siroheme. The heme is nearly all in the high spin ferric state in the enzyme as isolated. The extinction coefficient of the enzyme has been revised to E386 = 7.6 X 10(4) cm-1 (M heme)-1. The iron-sulfur center is reduced with difficulty by agents such as reduced methyl viologen (equilibrated with 1 atm of H2 at pH 7.7 in the presence of hydrogenase) or dithionite. Complexation of the enzyme with CO (a known ligand for nitrite reductase heme) markedly increases the reducibility of the iron-sulfur center. New chemical analyses and reinterpretation of previous data show that the enzyme contains 6 mol of iron and 4 mol of acid-labile S2-/mol of siroheme. The EPR spectrum of reduced nitrite reductase in 80% dimethyl sulfoxide establishes clearly that the enzyme contains a tetranuclear iron-sulfur (Fe4S4) center. The ferriheme and Fe4S4 centers are reduced at similar rates (k = 3 to 4 s-1) by dithionite. The dithionite-reduced Fe4S4 center is rapidly (k = 100 s-1) reoxidized by nitrite. These results indicate a role for the Fe4S4 center in catalysis.

Nuclear magnetic resonance studies of high-spin ferric hemoproteins.

PubMed

Morishmima, I; Ogawa, S; Inubushi, T; Iizuka, T

1978-01-01

220 MHz proton Fourier transform (FT) NMR with quadrature phase detection (QPD) technique is applied to observe largely hyperfine-shifted signals of various hemoproteins and hemoenzymes in ferric high-spin state. The binding of F-, OCN-, SCN-, and CH3OH to the ferric heme iron in high-spin state in various hemoproteins has been studied by the use of FT/QPD technique at 220 MHz. The binding of formate ion to metmyoglobin (metMb) has also been studied. The spectrum of the formate complex was compared with that of hemoglobin M Milwaukee where carboxylate groups are bound to the hemes of the beta subunits. The acid-base transition of ferric myoglobin (Mb) was confirmed by monitoring the pH-dependent shift of the heme side methyl signals with the reflection point at pH 9.1. This finding is analyzed on the basis of rapid exchange between alkaline (low spin) and acidic (high spin) forms accompanied by the dissociation and association of one proton in the ferric Mb. The structure of the heme environment of ferric horseradish peroxidase (HRP) was studied. The pH-dependent features of NMR spectra of the ferric enzyme and its complexes with cyanide and azide were discussed in terms of heme environmental structures, comparing with the case of metMb. The results were interpreted as follows: There exists an ionizable amino group near the heme responsible for the ligand binding reactions of the enzyme, which modulates the entry of external azide to the heme iron through protolytic equilibrium of this group. The pK value of this group was determined to be 5.9 by monitoring the pH-dependent shift of the heme peripheral methyl signals of the native enzyme, indicating that the group is probably a histidyl residue. Acid-alkaline transition of metMb was confirmed to associate with the proton dissociation of an iron-bound water molecule, whereas in HRP, pH-dependent spin state change characterized by pK 11 is attributed not to the simple protolytic reaction of the iron-bound water but to the direct coordination of an amino acid residue of the polypeptide chain to the ferric heme iron. Histidyl imidazole is a possible candidate for the new sixth iron ligand in alkaline peroxidase above pH 11. Interaction of HRP with electron donor(indolepropionic acid, IPA) was also studied. The hyperfine-shifted proton signals of the heme peripheral groups of the enzyme showed a small but significant shift with stepwise additions of IPA, indicating that the donor binds at a specific site of HRP. There results are interpreted in terms of the interaction between the enzyme and the donor at the heme edge site.

Topography of tyrosine residues and their involvement in peroxidation of polyunsaturated cardiolipin in cytochrome c/cardiolipin peroxidase complexes

PubMed Central

Kapralov, Alexandr A.; Yanamala, Naveena; Tyurina, Yulia Y.; Castro, Laura; Arias, Alejandro Samhan; Vladimirov, Yuri A.; Maeda, Akihiro; Weitz, Andrew A.; Peterson, Jim; Mylnikov, Danila; Demicheli, Verónica; Tortora, Verónica; Klein-Seetharaman, Judith; Radi, Rafael; Kagan, Valerian E.

2011-01-01

Formation of cytochrome c (cyt c)/cardiolipin (CL) peroxidase complex selective towards peroxidation of polyunsaturated CLs is a pre-requisite for mitochondrial membrane permeabilization. Tyrosine residues – via the generation of tyrosyl radicals (Tyr•) - are likely reactive intermediates of the peroxidase cycle leading to CL peroxidation. We used mutants of horse heart cyt c in which each of the four Tyr residues was substituted for Phe and assessed their contribution to the peroxidase catalysis. Tyr67Phe mutation was associated with a partial loss of the oxygenase function of the cyt c/CL complex and the lowest concentration of H2O2-induced Tyr radicals in electron paramagnetic resonance (EPR) spectra. Our MS experiments directly demonstrated decreased production of CL-hydroperoxides (CL-OOH) by Tyr67Phe mutant. Similarly, oxidation of a phenolic substrate, Amplex Red, was affected to a greater extent in Tyr67Phe than in three other mutants. Tyr67Phe mutant exerted high resistance to H2O2-induced oligomerization. Measurements of Tyr fluorescence, hetero-nuclear magnetic resonance (NMR) and computer simulations position Tyr67 in close proximity to the porphyrin ring heme iron and one of the two axial heme-iron ligand residues, Met80. Thus, the highly conserved Tyr67 is a likely electron-donor (radical acceptor) in the oxygenase half-reaction of the cyt c/CL peroxidase complex. PMID:21550335

A new efficient iron catalyst for olefin epoxidation with hydrogen peroxide.

PubMed

Mikhalyova, Elena A; Makhlynets, Olga V; Palluccio, Taryn D; Filatov, Alexander S; Rybak-Akimova, Elena V

2012-01-18

A new aminopyridine ligand derived from bipiperidine (the product of full reduction of bipyridine, bipy) coordinates to iron(II) in a cis-α fashion, yielding a new selective catalyst for olefin epoxidation with H(2)O(2) under limiting substrate conditions.

Design of a Hole Trapping Ligand

DOE PAGES

La Croix, Andrew D.; O’Hara, Andrew; Reid, Kemar R.; ...

2017-01-18

A new ligand that covalently attaches to the surface of colloidal CdSe/ CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate$-$bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic$-$organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer frommore » the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV$-$vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Lastly, theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolved photoluminescence« less

Design of a Hole Trapping Ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

La Croix, Andrew D.; O’Hara, Andrew; Reid, Kemar R.

A new ligand that covalently attaches to the surface of colloidal CdSe/ CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate$-$bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic$-$organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer frommore » the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV$-$vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Lastly, theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolved photoluminescence« less

Electron-paramagnetic-resonance studies of the mechanism of leaf nitrite reductase. Signals from the iron-sulphur centre and haem under turnover conditions.

PubMed

Cammack, R; Hucklesby, D P; Hewitt, E J

1978-06-01

Low-temperature e.p.r. spectra are presented of nitrite reductase purified from leaves of vegetable marrow (Cucurbita pepo). The oxidized enzyme showed a spectrum at g=6.86, 4.98 and 1.95 corresponding to high-spin Fe(3+) in sirohaem, which disappeared slowly on treatment with nitrite. The midpoint potential of the sirohaem was estimated to be -120mV. On reduction with Na(2)S(2)O(4) or Na(2)S(2)O(4)+Methyl Viologen a spectrum at g=2.038, 1.944 and 1.922 was observed, due to a reduced iron-sulphur centre. The midpoint potential of this centre was very low, about -570mV at pH8.1, decreasing with increasing pH. On addition of cyanide, which binds to haem, and Na(2)S(2)O(4), the iron-sulphur centre became further reduced. We think that this is due to an increased midpoint potential of the iron-sulphur centre. Other ligands to haem, such as CO and the reaction product NH(3), had similar but less pronounced effects, and also changed the lineshape of the iron-sulphur signal. Samples were prepared of the enzyme frozen during the reaction with nitrite, Methyl Viologen and Na(2)S(2)O(4) in various proportions. Signals were interpreted as due to the reduced iron-sulphur centre (with slightly different g values), a haem-NO complex and reduced Methyl Viologen. In the presence of an excess of nitrite, the haem-NO spectrum was more intense, whereas in the presence of an excess of Na(2)S(2)O(4) it was weaker, and disappeared at the end of the reaction. A reaction sequence is proposed for the enzyme, in which the haem-NO complex is an intermediate, followed by other e.p.r.-silent states, leading to the production of NH(4) (+).

Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole-iron(V)-oxo species and 1.6 × 106 M−1 s−1 for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions. PMID:18278877

Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.

Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids

NASA Astrophysics Data System (ADS)

Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi; Sakthinathan, Subramanian

2015-05-01

The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2]3+ (1), cis-[Co(dp)2(C12H25NH2)2]3+ (2), cis-[Co(trien)(C12H25NH2)2]3+ (3), cis-[Co(bpy)2(C12H25NH2)2]3+ (4) and cis-[Co(phen)2(C12H25NH2)2]3+ (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2‧-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe2+ ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323 K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ΔH‡ and entropy of activation ΔS‡) of the reaction have been calculated which substantiate the kinetics of the reaction.

Carbon-supported iron complexes as electrocatalysts for the cogeneration of hydroxylamine and electricity in a NO-H2 fuel cell: A combined electrochemical and density functional theory study

NASA Astrophysics Data System (ADS)

Sheng, Xia; Alvarez-Gallego, Yolanda; Dominguez-Benetton, Xochitl; Baert, Kitty; Hubin, Annick; Zhao, Hailiang; Mihaylov, Tzvetan T.; Pierloot, Kristine; Vankelecom, Ivo F. J.; Pescarmona, Paolo P.

2018-06-01

Carbon-supported iron complexes were investigated as electrocatalysts for the reduction of nitric oxide (NO) in a H2-NO fuel cell conceived for the production of hydroxylamine (NH2OH) with concomitant generation of electricity. Two types of iron complexes with tetradentate ligands, namely bis(salicylidene)ethylenediimine (Salen) and phthalocyanine (Pc), supported on activated carbon or graphite were prepared and evaluated as electrocatalysts, either without further treatment or after pyrolysis at 700 °C. The performance in the reduction of NO of gas diffusion cathodes based on these electrocatalysts was investigated in an electrochemical half cell (3-electrode configuration) using linear sweep voltammetry (LSV). The most promising electrocatalysts were studied further by chronoamperometric experiments in a H2-NO fuel cell, which allowed comparison in terms of power output and hydroxylamine production. Depending on the concentration of the NO feed (6 or 18%), the best electrocatalytic performance was delivered either by FePc or FeSalen. The gas diffusion electrode based on FeSalen supported on activated carbon with 0.3 wt% Fe-loading provided the highest current density (86 A/m2) and the best current efficiency (43%) towards the desired NH2OH when operating at the higher NO concentration (18%). Moreover, FeSalen offers the advantage of being cheaper than FePc. The experimental work was complemented by density functional theory (DFT) calculations, which allowed to shed more light on the reaction mechanism for the reduction of nitric oxide at the atomistic level.

Radiochemical studies of 99mTc complexes of modified cysteine ligands and bifunctional chelating agents.

PubMed

Pillai, M R; Kothari, K; Banerjee, S; Samuel, G; Suresh, M; Sarma, H D; Jurisson, S

1999-07-01

The synthesis of four novel ligands using the amino-acid cysteine and its ethyl carboxylate derivative is described. The synthetic method involves a two-step procedure, wherein the intermediate Schiff base formed by the condensation of the amino group of the cysteine substrate and salicylaldehyde is reduced to give the target ligands. The intermediates and the final products were characterized by high resolution nuclear magnetic resonance spectroscopy. Complexation studies of the ligands with 99mTc were optimized using stannous tartrate as the reducing agent under varying reaction conditions. The complexes were characterized using standard quality control techniques such as thin layer chromatography, paper electrophoresis, and paper chromatography. Lipophilicities of the complexes were estimated by solvent extraction into chloroform. Substantial changes in net charge and lipophilicity of the 99mTc complexes were observed on substituting the carboxylic acid functionality in ligands I and II with the ethyl carboxylate groups (ligands II and IV). All the ligands formed 99mTc complexes in high yield. Whereas the complexes with ligands I and II were observed to be hydrophilic in nature and not extractable into CHCl3, ligands III and IV resulted in neutral and lipophilic 99mTc complexes. The 99mTc complex with ligand II was not stable and on storage formed a hydrophilic and nonextractable species. The biodistribution of the complexes of ligands I and II showed that they cleared predominantly through the kidneys, whereas the complexes with ligands III and IV were excreted primarily through the hepatobiliary system. No significant brain uptake was observed with the 99mTc complexes with ligands III and IV despite their favorable properties of neutrality, lipophilicity, and conversion into a hydrophilic species. These ligands offer potential for use as bifunctional chelating agents.

Monomeric Yeast Frataxin is an Iron-Binding Protein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook,J.; Bencze, K.; Jankovic, A.

Friedreich's ataxia, an autosomal cardio- and neurodegenerative disorder that affects 1 in 50 000 humans, is caused by decreased levels of the protein frataxin. Although frataxin is nuclear-encoded, it is targeted to the mitochondrial matrix and necessary for proper regulation of cellular iron homeostasis. Frataxin is required for the cellular production of both heme and iron-sulfur (Fe-S) clusters. Monomeric frataxin binds with high affinity to ferrochelatase, the enzyme involved in iron insertion into porphyrin during heme production. Monomeric frataxin also binds to Isu, the scaffold protein required for assembly of Fe-S cluster intermediates. These processes (heme and Fe-S cluster assembly)more » share requirements for iron, suggesting that monomeric frataxin might function as the common iron donor. To provide a molecular basis to better understand frataxin's function, we have characterized the binding properties and metal-site structure of ferrous iron bound to monomeric yeast frataxin. Yeast frataxin is stable as an iron-loaded monomer, and the protein can bind two ferrous iron atoms with micromolar binding affinity. Frataxin amino acids affected by the presence of iron are localized within conserved acidic patches located on the surfaces of both helix-1 and strand-1. Under anaerobic conditions, bound metal is stable in the high-spin ferrous state. The metal-ligand coordination geometry of both metal-binding sites is consistent with a six-coordinate iron-(oxygen/nitrogen) based ligand geometry, surely constructed in part from carboxylate and possibly imidazole side chains coming from residues within these conserved acidic patches on the protein. On the basis of our results, we have developed a model for how we believe yeast frataxin interacts with iron.« less

Monomeric Yeast Frataxin is an Iron Binding Protein†

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cook, J.; Bencze, K; Jankovic, A

Friedreich's ataxia, an autosomal cardio- and neurodegenerative disorder that affects 1 in 50000 humans, is caused by decreased levels of the protein frataxin. Although frataxin is nuclear-encoded, it is targeted to the mitochondrial matrix and necessary for proper regulation of cellular iron homeostasis. Frataxin is required for the cellular production of both heme and iron-sulfur (Fe-S) clusters. Monomeric frataxin binds with high affinity to ferrochelatase, the enzyme involved in iron insertion into porphyrin during heme production. Monomeric frataxin also binds to Isu, the scaffold protein required for assembly of Fe-S cluster intermediates. These processes (heme and Fe-S cluster assembly) sharemore » requirements for iron, suggesting that monomeric frataxin might function as the common iron donor. To provide a molecular basis to better understand frataxin's function, we have characterized the binding properties and metal-site structure of ferrous iron bound to monomeric yeast frataxin. Yeast frataxin is stable as an iron-loaded monomer, and the protein can bind two ferrous iron atoms with micromolar binding affinity. Frataxin amino acids affected by the presence of iron are localized within conserved acidic patches located on the surfaces of both helix-1 and strand-1. Under anaerobic conditions, bound metal is stable in the high-spin ferrous state. The metal-ligand coordination geometry of both metal-binding sites is consistent with a six-coordinate iron-(oxygen/nitrogen) based ligand geometry, surely constructed in part from carboxylate and possibly imidazole side chains coming from residues within these conserved acidic patches on the protein. On the basis of our results, we have developed a model for how we believe yeast frataxin interacts with iron.« less

[The sources of inorganic sulfur in the process of cluster protein Fnr[4Fe-4S]2+ reconstruction in Escherichia coli cells cultivated with NO-donating agents].

PubMed

Vasil'eva, S V; Strel'tsova, D A; Vlaskina, A V; Mikoian, V D; Vanin, A F

2012-01-01

Dinitrosyl iron complexes (DNICs) with thiol ligands--binuclear and mononuclear--inhibited aidB gene expression in E. coli cells. This process is due to the nitrosylation of the active center in iron-sulfur protein Fnr [4Fe-4S]2+ by low-molecular DNICs. The next step is transformation of the above DNICs into the DNICs with the thiol groups in the apo-form of Fnr protein. These nitrosylated proteins are characterized by the EPR signal with g perpendicular = 2.04 and g parallel 1 = 2,014. An addition of sulfur containing L-Cys or N-A-L-Cys as well as Na2S to the cells lead to the increasing in the aidB gene expression simultaneously with an appearance of the EPR signal with g perpendicular = 2.04 and g parallel = 2.02 as the characteristics of the DNICs with persulfide (R-S-S-) ligands. We suppose that the recovery of the aidB gene activity was due to the accumulation of inorganic sulfur in the cells and reconstruction of the active center in Fnr[4Fe-4S]2+. It appears that the above process is the function of L-cysteine-desulfurase protein which repaired the active center of Fnr[4Fe-4S]2+ protein using the sulfur from L-Cys or N-A-L-Cys after its deacetylation. On the other side the ions of inorganic sulfur being reacted with SH-groups led to the transformation of DNIC with thiol ligands into the persulfides. Na2S was the most potent activator of the aidB gene expression in our experiments.

Simulations of iron K pre-edge X-ray absorption spectra using the restricted active space method.

PubMed

Guo, Meiyuan; Sørensen, Lasse Kragh; Delcey, Mickaël G; Pinjari, Rahul V; Lundberg, Marcus

2016-01-28

The intensities and relative energies of metal K pre-edge features are sensitive to both geometric and electronic structures. With the possibility to collect high-resolution spectral data it is important to find theoretical methods that include all important spectral effects: ligand-field splitting, multiplet structures, 3d-4p orbital hybridization, and charge-transfer excitations. Here the restricted active space (RAS) method is used for the first time to calculate metal K pre-edge spectra of open-shell systems, and its performance is tested against on six iron complexes: [FeCl6](n-), [FeCl4](n-), and [Fe(CN)6](n-) in ferrous and ferric oxidation states. The method gives good descriptions of the spectral shapes for all six systems. The mean absolute deviation for the relative energies of different peaks is only 0.1 eV. For the two systems that lack centrosymmetry [FeCl4](2-/1-), the ratios between dipole and quadrupole intensity contributions are reproduced with an error of 10%, which leads to good descriptions of the integrated pre-edge intensities. To gain further chemical insight, the origins of the pre-edge features have been analyzed with a chemically intuitive molecular orbital picture that serves as a bridge between the spectra and the electronic structures. The pre-edges contain information about both ligand-field strengths and orbital covalencies, which can be understood by analyzing the RAS wavefunction. The RAS method can thus be used to predict and rationalize the effects of changes in both the oxidation state and ligand environment in a number of hard X-ray studies of small and medium-sized molecular systems.

Redox reactions of [FeFe]-hydrogenase models containing an internal amine and a pendant phosphine.

PubMed

Zheng, Dehua; Wang, Mei; Chen, Lin; Wang, Ning; Sun, Licheng

2014-02-03

A diiron dithiolate complex with a pendant phosphine coordinated to one of the iron centers, [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe2(CO)5}] (1), was prepared and structurally characterized. The pendant phosphine is dissociated together with a CO ligand in the presence of excess PMe3, to afford [(μ-SCH2)2N(CH2C6H4-o-PPh2){Fe(CO)2(PMe3)}2] (2). Redox reactions of 2 and related complexes were studied in detail by in situ IR spectroscopy. A series of new Fe(II)Fe(I) ([3](+) and [6](+)), Fe(II)Fe(II) ([4](2+)), and Fe(I)Fe(I) (5) complexes relevant to Hox, Hox(CO), and Hred states of the [FeFe]-hydrogenase active site were detected. Among these complexes, the molecular structures of the diferrous complex [4](2+) with the internal amine and the pendant phosphine co-coordinated to the same iron center and the triphosphine diiron complex 5 were determined by X-ray crystallography. To make a comparison, the redox reactions of an analogous complex, [(μ-SCH2)2N(CH2C6H5){Fe(CO)2(PMe3)}2] (7), were also investigated by in situ IR spectroscopy in the absence or presence of extrinsic PPh3, which has no influence on the oxidation reaction of 7. The pendant phosphine in the second coordination sphere makes the redox reaction of 2 different from that of its analogue 7.

Origins of the different metal preferences of Escherichia coli peptide deformylase and Bacillus thermoproteolyticus thermolysin: a comparative quantum mechanical/molecular mechanical study.

PubMed

Dong, Minghui; Liu, Haiyan

2008-08-21

The Escherichia coli peptide deformylase (PDF) and Bacillus thermoproteolyticus thermolysin (TLN) are two representative metal-requiring peptidases having remarkably similar active centers but distinctively different metal preferences. Zinc is a competent catalytic cofactor for TLN but not for PDF. Reaction pathways and the associated energetics for both enzymes were determined using combined semiempirical and ab initio quantum mechanical/molecular mechanical modeling, without presuming reaction coordinates. The results confirmed that both enzymes catalyze via the same chemical steps, and reproduced their different preferences for zinc or iron as competent cofactors. Further analyses indicated that different feasibility of the nucleophilic attack step leads to different metal preferences of the two enzymes. In TLN, the substrate is strongly activated and can serve as the fifth coordination ligand of zinc prior to the chemical steps. In PDF, the substrate carbonyl is activated by the chemical step itself, and becomes the fifth coordination partner of zinc only in a later stage of the nucleophilic attack. These leads to a much more difficult nucleophilic attack in PDF than in TLN. Different from some earlier suggestions, zinc has no difficulty in accepting an activated substrate as the fifth ligand to switch from tetra- to penta-coordination in either PDF or TLN. When iron replaces zinc, its stronger interaction with the hydroxide ligand may lead to higher activation barrier in TLN. In PDF, the stronger interactions of iron with ligands allow iron-substrate coordination to take place either before or at a very early stage of the chemical step, leading to effective catalysis. Our calculations also show combined semiempirical and ab initio quantum mechanical modeling can be efficient approaches to explore complicated reaction pathways in enzyme systems.

Role of the Iron Axial Ligands of Heme Carrier HasA in Heme Uptake and Release*

PubMed Central

Caillet-Saguy, Célia; Piccioli, Mario; Turano, Paola; Lukat-Rodgers, Gudrun; Wolff, Nicolas; Rodgers, Kenton R.; Izadi-Pruneyre, Nadia; Delepierre, Muriel; Lecroisey, Anne

2012-01-01

The hemophore protein HasA from Serratia marcescens cycles between two states as follows: the heme-bound holoprotein, which functions as a carrier of the metal cofactor toward the membrane receptor HasR, and the heme-free apoprotein fishing for new porphyrin to be taken up after the heme has been delivered to HasR. Holo- and apo-forms differ for the conformation of the two loops L1 and L2, which provide the axial ligands of the iron through His32 and Tyr75, respectively. In the apo-form, loop L1 protrudes toward the solvent far away from loop L2; in the holoprotein, closing of the loops on the heme occurs upon establishment of the two axial coordination bonds. We have established that the two variants obtained via single point mutations of either axial ligand (namely H32A and Y75A) are both in the closed conformation. The presence of the heme and one out of two axial ligands is sufficient to establish a link between L1 and L2, thanks to the presence of coordinating solvent molecules. The latter are stabilized in the iron coordination environment by H-bond interactions with surrounding protein residues. The presence of such a water molecule in both variants is revealed here through a set of different spectroscopic techniques. Previous studies had shown that heme release and uptake processes occur via intermediate states characterized by a Tyr75-iron-bound form with open conformation of loop L1. Here, we demonstrate that these states do not naturally occur in the free protein but can only be driven by the interaction with the partner proteins. PMID:22700962

Uranyl-Peroxide Clusters Incorporating Iron Trimers and Bridging by Bisphosphonate- and Carboxylate-Containing Ligands.

PubMed

Qiu, Jie; Dong, Sining; Szymanowski, Jennifer E S; Dobrowolska, Malgorzata; Burns, Peter C

2017-04-03

A hybrid uranium-iron cage nanocluster, [(UO 2 ) 24 (FeOH) 24 (O 2 ) 24 (PO 4 ) 8 (CH(COO)(PO 3 ) 2 ) 24 ] 96- (U 24 Fe 24 ), was synthesized using bridging ligands containing bisphosphonate and carboxylate groups. U 24 Fe 24 contains six tetramers of uranyl hexagonal bipyramids and eight iron trimers, each of which consists of three corner-sharing Fe 3+ octahedra and is stabilized by in situ formed phosphate and 2,2-bis(phosphonato)acetate (C 2 P 2 ) groups. Tetramers and trimers are bridged by 24 C 2 P 2 groups into a cage cluster. Crystals of U 24 Fe 24 present a paramagnetic-like behavior. X-ray scattering showed that U 24 Fe 24 forms in the reactant solution prior to crystallization and is stable upon dissolution in water.

Exchange Interactions on the Highest-Spin Reported Molecule: the Mixed-Valence Fe42 Complex

PubMed Central

Aravena, Daniel; Venegas-Yazigi, Diego; Ruiz, Eliseo

2016-01-01

The finding of high-spin molecules that could behave as conventional magnets has been one of the main challenges in Molecular Magnetism. Here, the exchange interactions, present in the highest-spin molecule published in the literature, Fe42, have been analysed using theoretical methods based on Density Functional Theory. The system with a total spin value S = 45 is formed by 42 iron centres containing 18 high-spin FeIII ferromagnetically coupled and 24 diamagnetic low-spin FeII ions. The bridging ligands between the two paramagnetic centres are two cyanide ligands coordinated to the diamagnetic FeII cations. Calculations were performed using either small Fe4 or Fe3 models or the whole Fe42 complex, showing the presence of two different ferromagnetic couplings between the paramagnetic FeIII centres. Finally, Quantum Monte Carlo simulations for the whole system were carried out in order to compare the experimental and simulated magnetic susceptibility curves from the calculated exchange coupling constants with the experimental one. This comparison allows for the evaluation of the accuracy of different exchange-correlation functionals to reproduce such magnetic properties. PMID:27033418

THE EFFECT OF PRESSURE ON THE OXIDATION STATE OF IRON, IV. THIOCYANATE AND ISOTHIOCYANATE LIGANDS*

PubMed Central

Fung, S. C.; Drickamer, H. G.

1969-01-01

The effect of pressure on the Mössbauer resonance spectra of Fe(III) with thiocyanate (M-SCN) and isothiocyanate (M-NCS) ligands has been studied. Fe(NCS)3·6H2O, which has the isothiocyanate structure, reduces with increasing pressure, reversibly, and with a pressure dependence for the conversion very similar to that shown by a wide variety of ionic ferric compounds. K3Fe(SCN)6 has the thiocyanate structure. At low pressures, it exhibits a significantly larger reduction than the Fe(NCS)3. With increasing pressure the thiocyanate complexes isomerize, each complex apparently exhibiting about the same degree of conversion at a given pressure. At 150 kb the isomerization is essentially complete. The reduction of the Fe(III) to Fe(II) is reversible but the isomerization is not, and the sample, when powdered and reloaded in the high-pressure cell, exhibits the isomer shift, quadrupole splitting, and Fe(III) to Fe(II) conversion characteristic of an isothiocyanate. Heating the thiocyanate to 110°C at 5 kb yields a mixture of thiocyanate and isothiocyanate that converts with pressure completely to the isothiocyanate. PMID:16591728

Iron-catalyzed, directed oxidative arylation of olefins with organozinc and Grignard reagents.

PubMed

Ilies, Laurean; Okabe, Jun; Yoshikai, Naohiko; Nakamura, Eiichi

2010-06-18

Chelation-controlled arylation of olefins with organozinc or Grignard reagents proceeds in the presence of an iron catalyst, under mild conditions and typically without the need of external ligands, to afford substituted olefins in high yield and with complete regio- and stereocontrol.

Investigations of ultrafast ligand rebinding to heme and heme proteins using temperature and strong magnetic field perturbations

NASA Astrophysics Data System (ADS)

Zhang, Zhenyu

This thesis is written to summarize investigations of the mechanisms that underlie the kinetics of diatomic ligand rebinding to the iron atom of the heme group, which is chelated inside heme proteins. The family of heme proteins is a major object of studies for several branches of scientific research activity. Understanding the ligand binding mechanisms and pathways is one of the major goals for biophysics. My interests mainly focus on the physics of this ligand binding process. Therefore, to investigate the problem, isolated from the influence of the protein matrix, Fe-protophorphyrin IX is chosen as the prototype system in my studies. Myoglobin, the most extensively and intensively studied protein, is another ideal system that allows coupling the protein polypeptide matrix into the investigation. A technique to synchro-lock two laser pulse trains electronically is applied to our pump-probe spectroscopic studies. Based on this technique, a two color, fs/ps pump-probe system is developed which extends the temporal window for our investigation to 13ns and fills a gap existing in previous pump-probe investigations. In order to apply this newly-developed pump-probe laser system to implement systematic studies on the kinetics of diatomic ligand (NO, CO, O2) rebinding to heme and heme proteins, several experimental setups are utilized. In Chapter 1, the essential background knowledge, which helps to understand the iron-ligand interaction, is briefly described. In Chapter 2, in addition to a description of the preparation protocols of protein samples and details of the method for data analysis, three home-made setups are described, which include: a picosecond laser regenerative amplifier, a pump-probe application along the bore (2-inch in diameter) of a superconducting magnet and a temperature-controllable cryostat for spinning sample cell. Chapter 3 presents high magnetic field studies of several heme-ligand or protein-ligand systems. Pump-probe spectroscopy is used to study the ligand recombination after photolysis. No magnetic field induced rate changes are observed in any of these ligand recombination processes within the experimental detection limit. A magnetic field dependent CO rebinding behavior is observed for the FePPIX-CO sample in 80%glycerol/20%water environment. Careful data analysis indicates that this magnetic field induced change is due to the amplitude difference of a "fast" (<10ps) response with and without the magnetic field application (the amplitude changes from ˜55% at 0 Tesla to ˜45% at 10 Tesla). Kinetics of CO rebinding to FePPIX in 80%glycerol at the extremes of the magnetic field intensities (0Tesla vs. 10 Tesla) can be decomposed into a ligand rebinding process plus two 5ps decays heme cooling with different amplitudes. It leads to suggest a magnetic field induced change of a short-lived heme cooling response after photolysis. Also, CO rebinding kinetics to different heme compounds demonstrates a wide range for the Arrhenius pre-factors. This work reveals that the "spin-selection rule" does not play a key role in the recombination process of CO to heme iron. In Appendix 1, the recombination of oxymyoglobin and its mutants is investigated in the temperature range from 275K to 318K, using a home-made cryostat. Quite surprisingly, the O2 molecule rebinds to heme iron inside myoglobin with dramatically different behavior as the temperature is varied, depending on the protein environment. It shows little dependence (Mb), no dependence (V68W Mb mutant) and large dependence (L29W Mb mutant) in this 40K temperature window. To expand this temperature window, since the motor inside the cryostat is capable to work as low as 230K, glycerol is introduced into the protein preparation. It is observed that protein samples in a glycerol/water mixture, even with only 20% glycerol (in weight), the temperature dependences of the O2 rebinding to heme iron are dramatically altered. The O 2 rebinding behavior also shows a high dependence on the glycerol concentration in the solution. In Appendix 2, the absorption spectra of Fe-protoporphyrin IX in different monomeric complexes are investigated and compared. This work may suggest that, inside the CTAB micelles, ferrous Fe-PPIX exists in an equilibrium state of different species, CO probably can bind to FeII-PPIX with different trans ligand (H2O or OH-), and the trans effect, exhibiting while NO binds to H93G Mb mutants might also happen when NO binds to FeII-PPIX inside CTAB micelles. In Appendix 3, several ultrafast kinetics studies of CO rebinding to FePPIX are listed. They might be helpful for future studies on such systems. In Appendix 4, a series of systematic studies of the NO recombination to FeIIPPIX is performed with temperature and environment variation. A four-state model is proposed to explain the kinetics of NO-FeIIPPIX after photolysis. (Abstract shortened by UMI.)

Reactivity and effectiveness of traditional and novel ligands for multi-micronutrient fertilization in a calcareous soil

PubMed Central

López-Rayo, Sandra; Nadal, Paloma; Lucena, Juan J.

2015-01-01

This study compares the effectiveness of multi-micronutrient formulations containing iron (Fe), manganese (Mn), and zinc (Zn) with traditional (EDTA, DTPA, HEEDTA, and EDDHAm) or novel chelates (o,p-EDDHA, S,S-EDDS, and IDHA) and natural complexing agents (gluconate and lignosulfonate). The stability and reactivity of the formulations were studied on batch experiments with calcareous soil and by speciation modeling. Formulations containing traditional ligands maintained higher Mn but lower Zn concentration in soil solution than the novel ligands. The gluconate and lignosulfonate maintained low concentrations of both Mn and Zn in soil solution. Selected formulations were applied into calcareous soil and their efficacy was evaluated in a pot experiment with soybean. The formulation containing DTPA led to the highest Zn concentration in plants, as well as the formulation containing S,S-EDDS in the short-term, which correlated with its biodegradability. The application of traditional or novel ligands in formulations did not result in sufficient plant Mn concentrations, which was related to the low Mn stability observed for all formulations under moderate oxidation conditions. The results highlight the need to consider the effect of metals and ligands interactions in multi-nutrient fertilization and the potential of S,S-EDDS to be used for Zn fertilization. Furthermore, it is necessary to explore new sources of Mn fertilization for calcareous soils that have greater stability and efficiency, or instead to use foliar fertilization. PMID:26442065

Reactivity and effectiveness of traditional and novel ligands for multi-micronutrient fertilization in a calcareous soil.

PubMed

López-Rayo, Sandra; Nadal, Paloma; Lucena, Juan J

2015-01-01

This study compares the effectiveness of multi-micronutrient formulations containing iron (Fe), manganese (Mn), and zinc (Zn) with traditional (EDTA, DTPA, HEEDTA, and EDDHAm) or novel chelates (o,p-EDDHA, S,S-EDDS, and IDHA) and natural complexing agents (gluconate and lignosulfonate). The stability and reactivity of the formulations were studied on batch experiments with calcareous soil and by speciation modeling. Formulations containing traditional ligands maintained higher Mn but lower Zn concentration in soil solution than the novel ligands. The gluconate and lignosulfonate maintained low concentrations of both Mn and Zn in soil solution. Selected formulations were applied into calcareous soil and their efficacy was evaluated in a pot experiment with soybean. The formulation containing DTPA led to the highest Zn concentration in plants, as well as the formulation containing S,S-EDDS in the short-term, which correlated with its biodegradability. The application of traditional or novel ligands in formulations did not result in sufficient plant Mn concentrations, which was related to the low Mn stability observed for all formulations under moderate oxidation conditions. The results highlight the need to consider the effect of metals and ligands interactions in multi-nutrient fertilization and the potential of S,S-EDDS to be used for Zn fertilization. Furthermore, it is necessary to explore new sources of Mn fertilization for calcareous soils that have greater stability and efficiency, or instead to use foliar fertilization.

Kinetic behavior of Fe(o,o-EDDHA)-humic substance mixtures in several soil components and in calcareous soils.

PubMed

Cerdán, Mar; Alcañiz, Sara; Juárez, Margarita; Jordá, Juana D; Bermúdez, Dolores

2007-10-31

Ferric ethylenediamine- N, N'-bis-(o-hydroxyphenylacetic)acid chelate (Fe(o, o-EDDHA)) is one of the most effective Fe fertilizers in calcareous soils. However, humic substances are occasionally combined with iron chelates in drip irrigation systems in order to lower costs. The reactivity of iron chelate-humic substance mixtures in several soil components and in calcareous soils was investigated through interaction tests, and their behavior was compared to the application of iron chelates and humic substances separately. Two commercial humic substances and two Fe(o, o-EDDHA) chelates (one synthesized in the laboratory and one commercial) were used to prepare iron chelate-humic substance mixtures at 50% (w/w). Various soil components (calcium carbonate, gibbsite, amorphous iron oxide, hematite, tenorite, zincite, amorphous Mn oxide, and peat) and three calcareous soils were shaken for 15 days with the mixtures and with iron chelate and humic substance solutions. The kinetic behavior of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) (Fe bonded to (o,p-EDDHA) and other polycondensated ligands) and of the different nutrients solubilized after the interaction assay was determined. The results showed that the mixtures did not significantly reduce the retention of Fe(o, o-EDDHA) and Fe non-(o,o-EDDHA) in the soil components and the calcareous soils compared to the iron chelate solutions, but they did produce changes in the retention rate. Moreover, the competition between humic substances and synthetic chelating agents for complexing metal cations limited the effectiveness of the mixtures to mobilize nutrients from the substrates. The presence of Fe(o, p-EDDHA) and other byproducts in the commercial iron chelate had an important effect on the evolution of Fe(o, o-EDDHA) and the nutrient solubilization process.

Collision-induced dissociation of [4Fe-4S] cubane cluster complexes: [Fe4S4Cl4 - x(SC2H5)x]2-/1- (x = 0-4)

NASA Astrophysics Data System (ADS)

Fu, You-Jun; Laskin, Julia; Wang, Lai-Sheng

2006-09-01

Collision-induced dissociation (CID) experiments on a series of [4Fe-4S] cluster ions, [Fe4S4Cl4 - x(SC2H5)x]2-/1- (x = 0-4), revealed that their fragmentation channels change with the coordination environment. Among the three Coulomb repulsion related channels for the doubly charged species, the collision induced electron detachment channel was found to become more significant from x = 0 to 4 due to the decreasing electron binding energies and the magnitude of repulsion Coulomb barrier, while both the ligand detachment of Cl- and the fission of the [Fe4S4]2+ core became more and more significant with the increase of the Cl- coordination, and eventually became the dominant channel at x = 0. From the parents containing the SC2H5 ligand, neutral losses of HSC2H5 (62 u) and/or HSCHCH2 (60 u) were observed. It was proposed that inter- and intra-ligand proton transfer could happen during the CID process, resulting in hydrogen coordination to the [4Fe-4S] cluster. In the presence of O2, [Fe4S4Cl3(SC2H5)]2- and [Fe4S4Cl4]2- can form the O2-substituted products [Fe4S4Cl2(SC2H5)O2]- and [Fe4S4Cl3O2]-, respectively. It was shown that the O2 complexation occurs by coordination to the empty iron site of the [4Fe-4S] cubane core after dissociation of one Cl- ligand.

Unusual Synthetic Pathway for an {Fe(NO) 2} 9 Dinitrosyl Iron Complex (DNIC) and Insight into DNIC Electronic Structure via Nuclear Resonance Vibrational Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Speelman, Amy L.; Zhang, Bo; Silakov, Alexey

2016-06-06

Dinitrosyl iron complexes (DNICs) are among the most abundant NO-derived cellular species. Monomeric DNICs can exist in the {Fe(NO) 2} 9 or {Fe(NO) 2} 10 oxidation state (in the Enemark -Feltham notation). However, experimental studies of analogous DNICs in both oxidation states are rare, which prevents a thorough understanding of the di ff erences in the electronic structures of these species. Here, the {Fe(NO) 2} 9 DNIC [Fe(dmp)(NO) 2](OTf) ( 1 ; dmp = 2,9-dimethyl-1,10- phenanthroline) is synthesized from a ferrous precursor via an unusual pathway, involving disproportionation of an {FeNO} 7 complex to yield the {Fe(NO) 2} 9 DNICmore » and a ferric species, which is subsequently reduced by NO gas to generate a ferrous complex that re-enters the reaction cycle. In contrast to most {Fe(NO) 2} 9 DNICs with neutral N-donor ligands, 1 exhibits high solution stability and can be characterized structurally and spectroscopically. Reduction of 1 yields the corresponding {Fe(NO) 2} 10 DNIC [Fe(dmp)(NO) 2](2). The Mo ssbauer isomer shift of 2 is 0.08 mm/s smaller than that of 1 , which indicates that the iron center is slightly more oxidized in the reduced complex. The nuclear resonance vibrational spectra (NRVS) of 1 and 2 are distinct and provide direct experimental insight into di ff erences in bonding in these complexes. In particular, the symmetric out-of-plane Fe -N - O bending mode is shifted to higher energy by 188 cm -1 in 2 in comparison to 1 . Using quantum chemistry centered normal coordinate analysis (QCC-NCA), this is shown to arise from an increase in Fe - NO bond order and a sti ff ening of the Fe(NO) 2 unit upon reduction of 1 to 2 . DFT calculations demonstrate that the changes in bonding arise from an iron- centered reduction which leads to a distinct increase in Fe - NO π -back-bonding in {Fe(NO) 2} 10 DNICs in comparison to the corresponding {Fe(NO) 2} 9 complexes, in agreement with all experimental findings. Finally, the implications of the electronic structure of DNICs for their reactivity are discussed, especially with respect to N-N bond formation in NO reductases.« less

Analysis of macromolecules, ligands and macromolecule-ligand complexes

DOEpatents

Von Dreele, Robert B [Los Alamos, NM

2008-12-23

A method for determining atomic level structures of macromolecule-ligand complexes through high-resolution powder diffraction analysis and a method for providing suitable microcrystalline powder for diffraction analysis are provided. In one embodiment, powder diffraction data is collected from samples of polycrystalline macromolecule and macromolecule-ligand complex and the refined structure of the macromolecule is used as an approximate model for a combined Rietveld and stereochemical restraint refinement of the macromolecule-ligand complex. A difference Fourier map is calculated and the ligand position and points of interaction between the atoms of the macromolecule and the atoms of the ligand can be deduced and visualized. A suitable polycrystalline sample of macromolecule-ligand complex can be produced by physically agitating a mixture of lyophilized macromolecule, ligand and a solvent.

The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: implications for the enzyme mechanism.

PubMed

Ogura, Hiroshi; Evans, John P; Peng, Dungeng; Satterlee, James D; Ortiz de Montellano, Paul R; La Mar, Gerd N

2009-04-14

The active site electronic structure of the azide complex of substrate-bound human heme oxygenase 1 (hHO) has been investigated by (1)H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. Two-dimensional (1)H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts that places the lone iron pi-spin in the d(xz) orbital, rather than the d(yz) orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy, and magnetic susceptibilities argues for a low-spin, (d(xy))(2)(d(yz),d(xz))(3), ground state in both azide and cyanide complexes. The switch from singly occupied d(yz) for the cyanide to d(xz) for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide pi-plane in the latter complex, which is approximately 90 degrees in-plane rotated from that of the imidazole pi-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicates that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 --> Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed.

The orbital ground state of the azide-substrate complex of human heme oxygenase is an indicator of distal H-bonding: Implications for the enzyme mechanism‡

PubMed Central

Ogura, Hiroshi; Evans, John P.; Peng, Dungeng; Satterlee, James D.; de Montellano, Paul R. Ortiz; Mar, Gerd N. La

2009-01-01

The active site electronic structure of the azide complex of substrate-bound human heme oxygenase-1, (hHO) has been investigated by 1H NMR spectroscopy to shed light on the orbital/spin ground state as an indicator of the unique distal pocket environment of the enzyme. 2D 1H NMR assignments of the substrate and substrate-contact residue signals reveal a pattern of substrate methyl contact shifts, that places the lone iron π-spin in the dxz orbital, rather than the dyz orbital found in the cyanide complex. Comparison of iron spin relaxivity, magnetic anisotropy and magnetic susceptibilities argues for a low-spin, (dxy)2(dyz,dxz)3, ground state in both azide and cyanide complexes. The switch from singly-occupied dyz for the cyanide to dxz for the azide complex of hHO is shown to be consistent with the orbital hole determined by the azide π-plane in the latter complex, which is ∼90° in-plane rotated from that of the imidazole π-plane. The induction of the altered orbital ground state in the azide relative to the cyanide hHO complex, as well as the mean low-field bias of methyl hyperfine shifts and their paramagnetic relaxivity relative to those in globins, indicate that azide exerts a stronger ligand field in hHO than in the globins, or that the distal H-bonding to azide is weaker in hHO than in globins. The Asp140 → Ala hHO mutant that abolishes activity retains the unusual WT azide complex spin/orbital ground state. The relevance of our findings for other HO complexes and the HO mechanism is discussed. PMID:19243105

Preparation of highly-oxidized starch using hydrogen peroxide and its application as a novel ligand for zirconium tanning of leather.

PubMed

Yu, Yue; Wang, Ya-Nan; Ding, Wei; Zhou, Jianfei; Shi, Bi

2017-10-15

A series of highly-oxidized starch (HOS) were prepared using H 2 O 2 and a copper-iron catalyst as a desired ligand for zirconium tanning of leather. The effects of catalyst and H 2 O 2 dosages, and reaction temperature on the oxidation degree (OD, represented as the amount of carbonyl and carboxyl groups derived) of starch were investigated. The OD reached 76.2% when oxidation was conducted using 60% H 2 O 2 and 0.015% catalyst at 98°C for 2h. 13 C NMR and FT-IR illustrated carbonyl and carboxyl groups were formed in HOS after oxidation. GPC and laser particle size analyses indicated the decrease of HOS molecular size with increasing H 2 O 2 dosage and OD. HOS with moderate OD and molecular weight was able to coordinate with zirconium and remarkably improve tanning process. Leather tanned by Zr complexes using HOS-60 (60% H 2 O 2 , Mn 3516g/mol) as ligand presented considerably better physical and organoleptic properties than those of traditional Zr-tanned leather. Copyright © 2017 Elsevier Ltd. All rights reserved.

Reactivity and dynamics of H2S, NO, and O2 interacting with hemoglobins from Lucina pectinata.

PubMed

Ramos-Alvarez, Cacimar; Yoo, Byung-Kuk; Pietri, Ruth; Lamarre, Isabelle; Martin, Jean-Louis; Lopez-Garriga, Juan; Negrerie, Michel

2013-10-08

Hemoglobin HbI from the clam Lucina pectinata is involved in H2S transport, whereas homologous heme protein HbII/III is involved in O2 metabolism. Despite similar tertiary structures, HbI and HbII/III exhibit very different reactivity toward heme ligands H2S, O2, and NO. To investigate this reactivity at the heme level, we measured the dynamics of ligand interaction by time-resolved absorption spectroscopy in the picosecond to nanosecond time range. We demonstrated that H2S can be photodissociated from both ferric and ferrous HbI. H2S geminately rebinds to ferric and ferrous out-of-plane iron with time constants (τgem) of 12 and 165 ps, respectively, with very different proportions of photodissociated H2S exiting the protein (24% in ferric and 80% in ferrous HbI). The Gln(E7)His mutation considerably changes H2S dynamics in ferric HbI, indicating the role of Gln(E7) in controling H2S reactivity. In ferric HbI, the rate of diffusion of H2S from the solvent into the heme pocket (kentry) is 0.30 μM(-1) s(-1). For the HbII/III-O2 complex, we observed mainly a six-coordinate vibrationally excited heme-O2 complex with O2 still bound to the iron. This explains the low yield of O2 photodissociation and low koff from HbII/III, compared with those of HbI and Mb. Both isoforms behave very differently with regard to NO and O2 dynamics. Whereas the amplitude of geminate rebinding of O2 to HbI (38.5%) is similar to that of myoglobin (34.5%) in spite of different distal heme sites, it appears to be much larger for HbII/III (77%). The distal Tyr(B10) side chain present in HbII/III increases the energy barrier for ligand escape and participates in the stabilization of bound O2 and NO.

Heterometallic molecular precursors for a lithium-iron oxide material: synthesis, solid state structure, solution and gas-phase behaviour, and thermal decomposition.

PubMed

Han, Haixiang; Wei, Zheng; Barry, Matthew C; Filatov, Alexander S; Dikarev, Evgeny V

2017-05-02

Three heterometallic single-source precursors with a Li : Fe = 1 : 1 ratio for a LiFeO 2 oxide material are reported. Heterometallic compounds LiFeL 3 (L = tbaoac (1), ptac (2), and acac(3)) have been obtained on a large scale, in nearly quantitative yields by one-step reactions that employ readily available reagents. The heterometallic precursor LiFe(acac) 3 (3) with small, symmetric substituents on the ligand (acac = pentane-2,4-dionate), maintains a 1D polymeric structure in the solid state that limits its volatility and prevents solubility in non-coordinating solvents. The application of the unsymmetrical ligands, tbaoac (tert-butyl acetoacetate) and ptac (1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionate), that exhibit different bridging properties at the two ends of the ligand, allowed us to change the connectivity pattern within the heterometallic assembly. The latter was demonstrated by structural characterization of heterometallic complexes LiFe(tbaoac) 3 (1) and LiFe(ptac) 3 (2) that consist of discrete heterocyclic tetranuclear molecules Li 2 Fe 2 L 6 . The compounds are highly volatile and exhibit a congruent sublimation character. DART mass spectrometric investigation revealed the presence of heterometallic molecules in the gas phase. The positive mode spectra are dominated by the presence of [M - L] + peaks (M = Li 2 Fe 2 L 6 ). In accord with their discrete molecular structure, complexes 1 and 2 are highly soluble in nearly all common solvents. In order to test the retention of the heterometallic structure in solution, the diamagnetic analog of 1, LiMg(tbaoac) 3 (4), has been isolated. Its tetranuclear molecular structure was found to be isomorphous to that of the iron counterpart. 1 H and 7 Li NMR spectroscopy unambiguously confirmed the presence of heterometallic molecules in solutions of non-coordinating solvents. The heterometallic precursor 1 was shown to exhibit clean thermal decomposition in air that results in phase-pure α-modification of layered oxide LiFeO 2 , the prospective cathode material for lithium ion batteries.

Metal–organic complexation in the marine environment

PubMed Central

Luther, George W; Rozan, Timothy F; Witter, Amy; Lewis, Brent

2001-01-01

We discuss the voltammetric methods that are used to assess metal–organic complexation in seawater. These consist of titration methods using anodic stripping voltammetry (ASV) and cathodic stripping voltammetry competitive ligand experiments (CSV-CLE). These approaches and a kinetic approach using CSV-CLE give similar information on the amount of excess ligand to metal in a sample and the conditional metal ligand stability constant for the excess ligand bound to the metal. CSV-CLE data using different ligands to measure Fe(III) organic complexes are similar. All these methods give conditional stability constants for which the side reaction coefficient for the metal can be corrected but not that for the ligand. Another approach, pseudovoltammetry, provides information on the actual metal–ligand complex(es) in a sample by doing ASV experiments where the deposition potential is varied more negatively in order to destroy the metal–ligand complex. This latter approach gives concentration information on each actual ligand bound to the metal as well as the thermodynamic stability constant of each complex in solution when compared to known metal–ligand complexes. In this case the side reaction coefficients for the metal and ligand are corrected. Thus, this method may not give identical information to the titration methods because the excess ligand in the sample may not be identical to some of the actual ligands binding the metal in the sample. PMID:16759421

NITRATE REDUCTION BY ZEROVALENT IRON: EFFECTS OF FORMATE, OXALATE, CITRATE, CHLORIDE, SULFATE, BORATE, AND PHOSPHATE

EPA Science Inventory

Recent studies have shown that zerovalent iron (Fe0) may potentially be used as a chemical medium in permeable reactive barriers (PRBs) for nitrate remediation in groundwater; however, the effects of commonly found organic and inorganic ligands in soil and sediments on nitrate re...

Identification of an Isothiocyanate on the HypEF Complex Suggests a Route for Efficient Cyanyl–Group Channeling during [NiFe]–Hydrogenase Cofactor Generation

PubMed Central

Stripp, Sven T.; Lindenstrauss, Ute; Sawers, R. Gary; Soboh, Basem

2015-01-01

[NiFe]–hydrogenases catalyze uptake and evolution of H2 in a wide range of microorganisms. The enzyme is characterized by an inorganic nickel/ iron cofactor, the latter of which carries carbon monoxide and cyanide ligands. In vivo generation of these ligands requires a number of auxiliary proteins, the so–called Hyp family. Initially, HypF binds and activates the precursor metabolite carbamoyl phosphate. HypF catalyzes removal of phosphate and transfers the carbamate group to HypE. In an ATP–dependent condensation reaction, the C–terminal cysteinyl residue of HypE is modified to what has been interpreted as thiocyanate. This group is the direct precursor of the cyanide ligands of the [NiFe]–hydrogenase active site cofactor. We present a FT–IR analysis of HypE and HypF as isolated from E. coli. We follow the HypF–catalyzed cyanation of HypE in vitro and screen for the influence of carbamoyl phosphate and ATP. To elucidate on the differences between HypE and the HypEF complex, spectro–electrochemistry was used to map the vibrational Stark effect of naturally cyanated HypE. The IR signature of HypE could ultimately be assigned to isothiocyanate (–N=C=S) rather than thiocyanate (–S–C≡N). This has important implications for cyanyl–group channeling during [NiFe]–hydrogenase cofactor generation. PMID:26186649

A structural mechanism for bacterial autotransporter glycosylation by a dodecameric heptosyltransferase family

PubMed Central

Yao, Qing; Lu, Qiuhe; Wan, Xiaobo; Song, Feng; Xu, Yue; Hu, Mo; Zamyatina, Alla; Liu, Xiaoyun; Huang, Niu; Zhu, Ping; Shao, Feng

2014-01-01

A large group of bacterial virulence autotransporters including AIDA-I from diffusely adhering E. coli (DAEC) and TibA from enterotoxigenic E. coli (ETEC) require hyperglycosylation for functioning. Here we demonstrate that TibC from ETEC harbors a heptosyltransferase activity on TibA and AIDA-I, defining a large family of bacterial autotransporter heptosyltransferases (BAHTs). The crystal structure of TibC reveals a characteristic ring-shape dodecamer. The protomer features an N-terminal β-barrel, a catalytic domain, a β-hairpin thumb, and a unique iron-finger motif. The iron-finger motif contributes to back-to-back dimerization; six dimers form the ring through β-hairpin thumb-mediated hand-in-hand contact. The structure of ADP-D-glycero-β-D-manno-heptose (ADP-D,D-heptose)-bound TibC reveals a sugar transfer mechanism and also the ligand stereoselectivity determinant. Electron-cryomicroscopy analyses uncover a TibC–TibA dodecamer/hexamer assembly with two enzyme molecules binding to one TibA substrate. The complex structure also highlights a high efficient hyperglycosylation of six autotransporter substrates simultaneously by the dodecamer enzyme complex. DOI: http://dx.doi.org/10.7554/eLife.03714.001 PMID:25310236

Mechanisms of Mitochondrial Holocytochrome c Synthase and the Key Roles Played by Cysteines and Histidine of the Heme Attachment Site, Cys-XX-Cys-His*

PubMed Central

Babbitt, Shalon E.; San Francisco, Brian; Mendez, Deanna L.; Lukat-Rodgers, Gudrun S.; Rodgers, Kenton R.; Bretsnyder, Eric C.; Kranz, Robert G.

2014-01-01

Mitochondrial cytochrome c assembly requires the covalent attachment of heme by thioether bonds between heme vinyl groups and a conserved CXXCH motif of cytochrome c/c1. The enzyme holocytochrome c synthase (HCCS) binds heme and apocytochrome c substrate to catalyze this attachment, subsequently releasing holocytochrome c for proper folding to its native structure. We address mechanisms of assembly using a functional Escherichia coli recombinant system expressing human HCCS. Human cytochrome c variants with individual cysteine, histidine, double cysteine, and triple cysteine/histidine substitutions (of CXXCH) were co-purified with HCCS. Single and double mutants form a complex with HCCS but not the triple mutant. Resonance Raman and UV-visible spectroscopy support the proposal that heme puckering induced by both thioether bonds facilitate release of holocytochrome c from the complex. His-19 (of CXXCH) supplies the second axial ligand to heme in the complex, the first axial ligand was previously shown to be from HCCS residue His-154. Substitutions of His-19 in cytochrome c to seven other residues (Gly, Ala, Met, Arg, Lys, Cys, and Tyr) were used with various approaches to establish other roles played by His-19. Three roles for His-19 in HCCS-mediated assembly are suggested: (i) to provide the second axial ligand to the heme iron in preparation for covalent attachment; (ii) to spatially position the two cysteinyl sulfurs adjacent to the two heme vinyl groups for thioether formation; and (iii) to aid in release of the holocytochrome c from the HCCS active site. Only H19M is able to carry out these three roles, albeit at lower efficiencies than the natural His-19. PMID:25170082

Exposure to nitric oxide increases the nitrosyl-iron complexes content in sorghum embryonic axes.

PubMed

Simontacchi, Marcela; Buet, Agustina; Lamattina, Lorenzo; Puntarulo, Susana

2012-02-01

This work was aimed to investigate nitrosyl-Fe complexes formation by reaction of endogenous ligands and Fe, in sorghum embryonic axes exposed to NO-donors. Electron paramagnetic resonance (EPR) was employed to detect the presence of nitrosyl-Fe complexes in plant embryos, as well as changes in labile iron pool (LIP). Nitrosyl-Fe complexes formation was detected in sorghum embryonic axes homogenates incubated in vitro in the presence of 1 mM of NO donors: diethylenetriamine NONOate (DETA NONOate), S-nitrosoglutathione (GSNO) and sodium nitroprusside (SNP). In axes isolated from seeds incubated in vivo in the presence of 1 mM SNP for 24 h, the content of NO was increased by 2-fold, and the EPR spectrum from mononitrosyl-Fe complexes (MNIC) was observed with a concomitant increase in the fresh weight of sorghum axes. The simultaneous exposure to deferoxamine and the NO donor precluded the increase in fresh weight observed in the presence of excess NO. While total Fe content in the axes isolated from seeds exposed to 1mM SNP was not significantly affected as compared to control axes, the LIP was increased by over 2-fold.The data reported suggest a critical role for the generation of complexes between Fe and NO when cells faced a situation leading to a significant increase in NO content. Moreover, demonstrate the presence of MNICs as one of the important components of the LIP, which could actively participate in Fe cellular mobilization. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron.

PubMed

Zhang, Xianlan; Deng, Baolin; Guo, Jing; Wang, Yang; Lan, Yeqing

2011-04-01

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT. Copyright © 2010 Elsevier Ltd. All rights reserved.

Magnetic circular dichroism and computational study of mononuclear and dinuclear iron(iv) complexes† †Electronic supplementary information (ESI) available: VT MCD spectra, VT and VTVH MCD intensity analysis of complex 1, energies, S x, S z values and Boltzmann populations of S = 1 magnetic sublevels as a function of the applied magnetic field, derivation of the excited states arising from the 1b2 → 2b1 transition, determination of the C-term sign of band 1 and the E(2e → 2a1) transitions for complex 1, VTVH MCD spectra, VTVH simulations and the computed MCD spectrum of complex 2. See DOI: 10.1039/c4sc03268c Click here for additional data file.

PubMed Central

Xue, Genqiang; Krivokapic, Itana; Petrenko, Taras

2015-01-01

High-valent iron(iv)-oxo species are key intermediates in the catalytic cycles of a range of O2-activating iron enzymes. This work presents a detailed study of the electronic structures of mononuclear ([FeIV(O)(L)(NCMe)]2+, 1, L = tris(3,5-dimethyl-4-methoxylpyridyl-2-methyl)amine) and dinuclear ([(L)FeIV(O)(μ-O)FeIV(OH)(L)]3+, 2) iron(iv) complexes using absorption (ABS), magnetic circular dichroism (MCD) spectroscopy and wave-function-based quantum chemical calculations. For complex 1, the experimental MCD spectra at 2–10 K are dominated by a broad positive band between 12 000 and 18 000 cm–1. As the temperature increases up to ∼20 K, this feature is gradually replaced by a derivative-shaped signal. The computed MCD spectra are in excellent agreement with experiment, which reproduce not only the excitation energies and the MCD signs of key transitions but also their temperature-dependent intensity variations. To further corroborate the assignments suggested by the calculations, the individual MCD sign for each transition is independently determined from the corresponding electron donating and accepting orbitals. Thus, unambiguous assignments can be made for the observed transitions in 1. The ABS/MCD data of complex 2 exhibit ten features that are assigned as ligand-field transitions or oxo- or hydroxo-to-metal charge transfer bands, based on MCD/ABS intensity ratios, calculated excitation energies, polarizations, and MCD signs. In comparison with complex 1, the electronic structure of the FeIV 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O site is not significantly perturbed by the binding to another iron(iv) center. This may explain the experimental finding that complexes 1 and 2 have similar reactivities toward C–H bond activation and O-atom transfer. PMID:26417426

Hydrogen storage and delivery: the carbon dioxide - formic acid couple.

PubMed

Laurenczy, Gábor

2011-01-01

Carbon dioxide and the carbonates, the available natural C1 sources, can be easily hydrogenated into formic acid and formates in water; the rate of this reduction strongly depends on the pH of the solution. This reaction is catalysed by ruthenium(II) pre-catalyst complexes with a large variety of water-soluble phosphine ligands; high conversions and turnover numbers have been realised. Although ruthenium(II) is predominant in these reactions, the iron(II) - tris[(2-diphenylphosphino)-ethyl]phosphine (PP3) complex is also active, showing a new perspective to use abundant and inexpensive iron-based compounds in the CO2 reduction. In the catalytic hydrogenation cycles the in situ formed metal hydride complexes play a key role, their structures with several other intermediates have been proven by multinuclear NMR spectroscopy. In the other hand safe and convenient hydrogen storage and supply is the fundamental question for the further development of the hydrogen economy; and carbon dioxide has been recognised to be a viable H2 vector. Formic acid--containing 4.4 weight % of H2, that is 53 g hydrogen per litre--is suitable for H2 storage; we have shown that in aqueous solutions it can be selectively decomposed into CO-free (CO < 10 ppm) CO2 and H2. The reaction takes place under mild experimental conditions and it is able to generate high pressure H2 (up to 600 bar). The cleavage of HCOOH is catalysed by several hydrophilic Ru(II) phosphine complexes (meta-trisulfonated triphenylphosphine, mTPPTS, being the most efficient one), either in homogeneous systems or as immobilised catalysts. We have also shown that the iron(II)--hydrido tris[(2-diphenylphosphino)ethyl]phosphine complex catalyses with an exceptionally high rate and efficiency (turnover frequency, TOF = 9425 h(-1)mol(-1); turnover number, TON = 92400) the formic acid cleavage, in environmentally friendly propylene carbonate solution, opening the way to use cheap, non-noble metal based catalysts for this reaction, too.

Bio-inspired nitrile hydration by peptidic ligands based on L-cysteine, L-methionine or L-penicillamine and pyridine-2,6-dicarboxylic acid.

PubMed

Byrne, Cillian; Houlihan, Kate M; Devi, Prarthana; Jensen, Paul; Rutledge, Peter J

2014-12-12

Nitrile hydratase (NHase, EC 4.2.1.84) is a metalloenzyme which catalyses the conversion of nitriles to amides. The high efficiency and broad substrate range of NHase have led to the successful application of this enzyme as a biocatalyst in the industrial syntheses of acrylamide and nicotinamide and in the bioremediation of nitrile waste. Crystal structures of both cobalt(III)- and iron(III)-dependent NHases reveal an unusual metal binding motif made up from six sequential amino acids and comprising two amide nitrogens from the peptide backbone and three cysteine-derived sulfur ligands, each at a different oxidation state (thiolate, sulfenate and sulfinate). Based on the active site geometry revealed by these crystal structures, we have designed a series of small-molecule ligands which integrate essential features of the NHase metal binding motif into a readily accessible peptide environment. We report the synthesis of ligands based on a pyridine-2,6-dicarboxylic acid scaffold and L-cysteine, L-S-methylcysteine, L-methionine or L-penicillamine. These ligands have been combined with cobalt(III) and iron(III) and tested as catalysts for biomimetic nitrile hydration. The highest levels of activity are observed with the L-penicillamine ligand which, in combination with cobalt(III), converts acetonitrile to acetamide at 1.25 turnovers and benzonitrile to benzamide at 1.20 turnovers.

Evolution reversed: the ability to bind iron restored to the N-lobe of the murine inhibitor of carbonic anhydrase by strategic mutagenesis.

PubMed

Mason, Anne B; Judson, Gregory L; Bravo, Maria Cristina; Edelstein, Andrew; Byrne, Shaina L; James, Nicholas G; Roush, Eric D; Fierke, Carol A; Bobst, Cedric E; Kaltashov, Igor A; Daughtery, Margaret A

2008-09-16

The murine inhibitor of carbonic anhydrase (mICA) is a member of the superfamily related to the bilobal iron transport protein transferrin (TF), which binds a ferric ion within a cleft in each lobe. Although the gene encoding ICA in humans is classified as a pseudogene, an apparently functional ICA gene has been annotated in mice, rats, cows, pigs, and dogs. All ICAs lack one (or more) of the amino acid ligands in each lobe essential for high-affinity coordination of iron and the requisite synergistic anion, carbonate. The reason why ICA family members have lost the ability to bind iron is potentially related to acquiring a new function(s), one of which is inhibition of certain carbonic anhydrase (CA) isoforms. A recombinant mutant of the mICA (W124R/S188Y) was created with the goal of restoring the ligands required for both anion (Arg124) and iron (Tyr188) binding in the N-lobe. Absorption and fluorescence spectra definitively show that the mutant binds ferric iron in the N-lobe. Electrospray ionization mass spectrometry confirms the presence of both ferric iron and carbonate. At the putative endosomal pH of 5.6, iron is released by two slow processes indicative of high-affinity coordination. Induction of specific iron binding implies that (1) the structure of mICA resembles those of other TF family members and (2) the N-lobe can adopt a conformation in which the cleft closes when iron binds. Because the conformational change in the N-lobe indicated by metal binding does not impact the inhibitory activity of mICA, inhibition of CA was tentatively assigned to the C-lobe. Proof of this assignment is provided by limited trypsin proteolysis of porcine ICA.

Trichlorido[(meth­yl{2-[meth­yl(2-pyridyl­meth­yl)amino]eth­yl}amino)acetonitrile]iron(III) methanol hemisolvate

PubMed Central

Nielsen, Anne; McKenzie, Christine J.; Bond, Andrew D.

2009-01-01

The title compound, [FeCl3(C12H18N4)]·0.5CH3OH, contains an FeIII ion in a distorted octa­hedral coordination environment. The neutral N,N′,N′′-tridentate ligand adopts a fac coordination mode, and chloride ligands lie trans to each of the three coordinated N atoms. In the crystal, the complexes form columns extending parallel to the approximate local threefold axes of the FeN3Cl3 octa­hedra, and the columns are arranged so that the uncoordinated nitrile groups align in an anti­parallel manner and the pyridyl rings form offset face-to-face arrangements [inter­planar separations = 2.95 (1) and 3.11 (1) Å; centroid–centroid distances = 5.31 (1) and 4.92 (1) Å]. The methanol solvent mol­ecule is disordered about a twofold rotation axis. PMID:21578169

Indirect Redox Transformations of Iron, Copper, and Chromium Catalyzed by Extremely Acidophilic Bacteria

PubMed Central

Johnson, D. Barrie; Hedrich, Sabrina; Pakostova, Eva

2017-01-01

Experiments were carried out to examine redox transformations of copper and chromium by acidophilic bacteria (Acidithiobacillus, Leptospirillum, and Acidiphilium), and also of iron (III) reduction by Acidithiobacillus spp. under aerobic conditions. Reduction of iron (III) was found with all five species of Acidithiobacillus tested, grown aerobically on elemental sulfur. Cultures maintained at pH 1.0 for protracted periods displayed increasing propensity for aerobic iron (III) reduction, which was observed with cell-free culture liquors as well as those containing bacteria. At. caldus grown on hydrogen also reduced iron (III) under aerobic conditions, confirming that the unknown metabolite(s) responsible for iron (III) reduction were not (exclusively) sulfur intermediates. Reduction of copper (II) by aerobic cultures of sulfur-grown Acidithiobacillus spp. showed similar trends to iron (III) reduction in being more pronounced as culture pH declined, and occurring in both the presence and absence of cells. Cultures of Acidithiobacillus grown anaerobically on hydrogen only reduced copper (II) when iron (III) (which was also reduced) was also included; identical results were found with Acidiphilium cryptum grown micro-aerobically on glucose. Harvested biomass of hydrogen-grown At. ferridurans oxidized iron (II) but not copper (I), and copper (I) was only oxidized by growing cultures of Acidithiobacillus spp. when iron (II) was also included. The data confirmed that oxidation and reduction of copper were both mediated by acidophilic bacteria indirectly, via iron (II) and iron (III). No oxidation of chromium (III) by acidophilic bacteria was observed even when, in the case of Leptospirillum spp., the redox potential of oxidized cultures exceeded +900 mV. Cultures of At. ferridurans and A. cryptum reduced chromium (VI), though only when iron (III) was also present, confirming an indirect mechanism and contradicting an earlier report of direct chromium reduction by A. cryptum. Measurements of redox potentials of iron, copper and chromium couples in acidic, sulfate-containing liquors showed that these differed from situations where metals are not complexed by inorganic ligands, and supported the current observations of indirect copper oxido-reduction and chromium reduction mediated by acidophilic bacteria. The implications of these results for both industrial applications of acidophiles and for exobiology are discussed. PMID:28239375

Nano iron oxide impregnated in chitosan bead as a highly efficient sorbent for Cr(VI) removal from water.

PubMed

Lu, Jianbo; Xu, Kai; Yang, Jinmei; Hao, Yarong; Cheng, Fang

2017-10-01

Using Fe(III) salts and chitosan, nano iron oxide impregnated in chitosan bead (NIOC) was successfully synthesized for aqueous Cr(VI) detoxification via sol-gel technique without any additional crosslinking agent. NIOC characterization demonstrated that the iron in NIOC mainly existed as nano akaganeite (β-FeOOH) and complex with chitosan. Intraparticle diffusion was the major rate-limiting step. The maximal adsorption capacity was 69.8mg/g (pH 5.0, 20°C). Normal concentration of coexisting anions (SO 4 2- , CO 3 2- , SiO 3 2 -) showed insignificant competition, whereas PO 4 3- suppressed the Cr(VI) sorption. Cr(VI)-loaded NIOC could be effectively regenerated by alkaline solutions. Column adsorption runs using granular NIOC could effectively treat about 1600 bed volumes of Cr(VI) solution (from 3.7mg Cr/L in influent to <0.5mg Cr/L in effluent). The Cr(VI) removal mechanisms involved the direct sorption of Cr(VI) (electrostatic attraction and ligand exchange), reduction of Cr(VI) into Cr(III) and re-sorption of Cr(III) via chelation on NIOC surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Dinitrosyl iron complexes with glutathione recover rats with experimental endometriosis].

PubMed

Adamian, L V; Burgova, E N; Tkachev, N A; Mikoian, V D; Stepanian, A A; Sonova, M M; Vanin, A F

2013-01-01

The effect of binuclear dinitrosyl iron complexes (DNIC) with glutathione on endometrioid tumors in rats with experimental endometriosis has been studied. The latter was induced by an autotransplantation model, where two fragments of endometrium with myometrium (2 x 2 mm) from the left uterine horn was grafted to the inner surface of the anterior abdominal wall. The test animals received intraperitoneal injections of 0.5 ml DNIC-glutathione at the dose of 12.5 micromole per kg daily for 12 days 28 days after operation. The injections resulted in more than a 2-fold decrease in the total volume of both large tumors formed from grafts and small additive tumors formed nearby grafts. The disappearance of the additive tumors was also observed in test animals. The EPR signal with g(av) = 2.03 characteristic of protein bound DNIC with thiol-containing ligands was recorded in livers, graft and additive tumors of test and control animals pointing out intensive generation of nitric oxide in rats with experimental endometriosis. Ribonucleotide reductase activation discovered by doublet the EPR signal at g = 2.0 with 2.3 mT hyperfine structure splitting was found in small tumors. The cytotoxic effect of DNIC-glutathione on endometrioid tumors was suggested to be due to DNIC degradation nearby the tumors induced by iron chelating compounds released from the tumors. The degradation resulted in release of a high amount of nitric oxide molecules and nitrosonium ions from DNICs affecting the tumors by way of the cytotoxic effect.

Mössbauer spectroscopic characterization of iron methyl pyropheophorbide a and its derivatives

NASA Astrophysics Data System (ADS)

Inoue, H.; Soeda, K.; Akahori, H.; Nonomura, Y.; Yoshioka, N.

1994-12-01

Two kinds of iron chlorophylls, i.e. (methyl pyropheophorbide a)iron(III) chloride and its bis-pyridine adduct, were prepared and characterized by57Fe Mössbauer spectroscopy. (Methyl pyropheophorbide a)iron(III) chloride gave an asymmetric quadrupole-split doublet typical of high-spin iron(III) chlorophylls, while its bis-pyridine adduct showed a symmetric quadrupole-split doublet characteristic of low-spin iron(II) chlorophylls. The isomer shift and quadrupole splitting obtained for (methyl pyropheophorbide a)iron(III) chloride and its bis-pyridine adduct have led to the following conclusions. The substitution of the bulky phytyl group for the methyl group hardly affects the electronic state of the iron(II,III) ion, but the elimination of the methoxycarbonyl group increases the planarity of the macrocyclic chlorin ligand.

Structural insight into the substrate- and dioxygen-binding manner in the catalytic cycle of rieske nonheme iron oxygenase system, carbazole 1,9a-dioxygenase.

PubMed

Ashikawa, Yuji; Fujimoto, Zui; Usami, Yusuke; Inoue, Kengo; Noguchi, Haruko; Yamane, Hisakazu; Nojiri, Hideaki

2012-06-24

Dihydroxylation of tandemly linked aromatic carbons in a cis-configuration, catalyzed by multicomponent oxygenase systems known as Rieske nonheme iron oxygenase systems (ROs), often constitute the initial step of aerobic degradation pathways for various aromatic compounds. Because such RO reactions inherently govern whether downstream degradation processes occur, novel oxygenation mechanisms involving oxygenase components of ROs (RO-Os) is of great interest. Despite substantial progress in structural and physicochemical analyses, no consensus exists on the chemical steps in the catalytic cycles of ROs. Thus, determining whether conformational changes at the active site of RO-O occur by substrate and/or oxygen binding is important. Carbazole 1,9a-dioxygenase (CARDO), a RO member consists of catalytic terminal oxygenase (CARDO-O), ferredoxin (CARDO-F), and ferredoxin reductase. We have succeeded in determining the crystal structures of oxidized CARDO-O, oxidized CARDO-F, and both oxidized and reduced forms of the CARDO-O: CARDO-F binary complex. In the present study, we determined the crystal structures of the reduced carbazole (CAR)-bound, dioxygen-bound, and both CAR- and dioxygen-bound CARDO-O: CARDO-F binary complex structures at 1.95, 1.85, and 2.00 Å resolution. These structures revealed the conformational changes that occur in the catalytic cycle. Structural comparison between complex structures in each step of the catalytic mechanism provides several implications, such as the order of substrate and dioxygen bindings, the iron-dioxygen species likely being Fe(III)-(hydro)peroxo, and the creation of room for dioxygen binding and the promotion of dioxygen binding in desirable fashion by preceding substrate binding. The RO catalytic mechanism is proposed as follows: When the Rieske cluster is reduced, substrate binding induces several conformational changes (e.g., movements of the nonheme iron and the ligand residue) that create room for oxygen binding. Dioxygen bound in a side-on fashion onto nonheme iron is activated by reduction to the peroxo state [Fe(III)-(hydro)peroxo]. This state may react directly with the bound substrate, or O-O bond cleavage may occur to generate Fe(V)-oxo-hydroxo species prior to the reaction. After producing a cis-dihydrodiol, the product is released by reducing the nonheme iron. This proposed scheme describes the catalytic cycle of ROs and provides important information for a better understanding of the mechanism.

Synthesis, spectroscopic, and antibacterial activity of tetraazamacrocyclic complexes of trivalent chromium, manganese, and iron.

PubMed

Singh, D P; Malik, Vandna; Kumar, Ramesh; Singh, Jitender

2009-10-01

A new series of macrocyclic complexes of type [M(TML)X]X(2), where M = Cr(III), Mn(III), or Fe(III), TML is tetradentate macrocyclic ligand, and X = Cl(-), NO(3)(-), CH(3)COO(-) for Cr(III), Fe(III) and X = CH(3)COO(-) for Mn (III), has been synthesized by condensation of benzil and succinyldihydrazide in the presence of metal salt. The complexes have been so formulated due to the 1:2 electrolytic nature of these complexes as shown by conductivity measurements. The complexes have been characterized with the help of various physicochemical techniques such as elemental analysis, molar conductance, electronic and infrared spectral studies, and magnetic susceptibility. On the basis of these studies, a five-coordinate distorted square pyramidal geometry, in which two nitrogens and two carbonyl oxygen atoms are suitably placed for coordination toward the metal ion, has been proposed for all the complexes. The complexes have been tested for their in vitro antibacterial activity. Some of the complexes show remarkable antibacterial activities against some selected bacterial strains. The minimum inhibitory concentrations shown by these complexes have been compared with those shown by some standard antibiotics such as linezolid and cefaclor.

Tris(1,10-phenanthroline-κ2 N,N′)iron(II) bis­(1,1-dicyano-2-eth­oxy-2-oxoethanide)

PubMed Central

Cai, Zhan-Mao; Zhan, Shu-Zhong

2012-01-01

The title compound, [Fe(C12H8N2)3](C6H5N2O2)2, consists of one [Fe(phen)3]2+ cation (phen = 1,10-phenanthroline) and two 1,1-dicyano-2-eth­oxy-2-oxoethanide anions. Five atoms of the anion are disordered over two positions [site occupancy = 0.521 (13) for the major component]. In the complex cation, the FeII atom is coordinated by six N atoms from three phen ligands in a distorted octa­hedral geometry. Two intra­molecular C—H⋯N hydrogen bonds occur in the complex cation. The crystal structure is mainly stabilized by Coulombic inter­actions. Weak intermolecular C—H⋯N inter­actions are also observed. PMID:22807778

Conformational Transitions upon Ligand Binding: Holo-Structure Prediction from Apo Conformations

PubMed Central

Seeliger, Daniel; de Groot, Bert L.

2010-01-01

Biological function of proteins is frequently associated with the formation of complexes with small-molecule ligands. Experimental structure determination of such complexes at atomic resolution, however, can be time-consuming and costly. Computational methods for structure prediction of protein/ligand complexes, particularly docking, are as yet restricted by their limited consideration of receptor flexibility, rendering them not applicable for predicting protein/ligand complexes if large conformational changes of the receptor upon ligand binding are involved. Accurate receptor models in the ligand-bound state (holo structures), however, are a prerequisite for successful structure-based drug design. Hence, if only an unbound (apo) structure is available distinct from the ligand-bound conformation, structure-based drug design is severely limited. We present a method to predict the structure of protein/ligand complexes based solely on the apo structure, the ligand and the radius of gyration of the holo structure. The method is applied to ten cases in which proteins undergo structural rearrangements of up to 7.1 Å backbone RMSD upon ligand binding. In all cases, receptor models within 1.6 Å backbone RMSD to the target were predicted and close-to-native ligand binding poses were obtained for 8 of 10 cases in the top-ranked complex models. A protocol is presented that is expected to enable structure modeling of protein/ligand complexes and structure-based drug design for cases where crystal structures of ligand-bound conformations are not available. PMID:20066034

Dinitrosyl iron complexes with natural thiol-containing ligands in aqueous solutions: Synthesis and some physico-chemical characteristics (A methodological review).

PubMed

Vanin, Anatoly F; Borodulin, Rostislav R; Mikoyan, Vasak D

2017-06-01

Two approaches to the synthesis of dinitrosyl iron complexes (DNIC) with glutathione and l-cysteine in aqueous solutions based on the use of gaseous NO and appropriate S-nitrosothiols, viz., S-nitrosoglutathione (GS-NO) or S-nitrosocysteine (Cys-NO), respectively, are considered. A schematic representation of a vacuum unit for generation and accumulation of gaseous NO purified from the NO 2 admixture and its application for obtaining aqueous solutions of DNIC in a Thunberg apparatus is given. To achieve this, a solution of bivalent iron in distilled water is loaded into the upper chamber of the Thunberg apparatus, while the thiol solution in an appropriate buffer (рН 7.4) is loaded into its lower chamber. Further steps, which include degassing, addition of gaseous NO, shaking of both solutions and formation of the Fe 2+ -thiol mixture, culminate in the synthesis of DNIC. The second approach consists in a stepwise addition of Fe 2+ salts and nitrite to aqueous solutions of glutathione or cysteine. In the presence of Fe 2+ and after the increase in рН to the physiological level, GS-NO or Cys-NO generated at acid media (pH < 4) are converted into DNIC with glutathione or cysteine. Noteworthy, irrespective of the procedure used for their synthesis DNIC with glutathione manifest much higher stability than DNIC with cysteine. The pattern of spin density distribution in iron-dinitrosyl fragments of DNIC characterized by the d 7 electronic configuration of the iron atom and described by the formula Fe + (NO + ) 2 is unique in that it provides a plausible explanation for the ability of DNIC to generate NO and nitrosonium ions (NO + ) and the peculiar characteristics of the EPR signal of their mononuclear form (M-DNIC). Copyright © 2017. Published by Elsevier Inc.

The Multifaceted Roles of Neutrophil Gelatinase Associated Lipocalin (NGAL) In Inflammation and Cancer

PubMed Central

Chakraborty, Subhankar; Kaur, Sukhwinder; Guha, Sushovan; Batra, Surinder K.

2012-01-01

Neutrophil gelatinase associated lipocalin (NGAL), also known as oncogene 24p3, uterocalin, siderocalin or lipocalin 2, is a 24 kDa secreted glycoprotein originally purified from a culture of mouse kidney cells infected with simian virus 40 (SV-40). Subsequent investigations have revealed that it is a member of the lipocalin family of proteins that transport small, hydrophobic ligands. Since then, NGAL expression has been reported in several normal tissues where it serves to provide protection against bacterial infection and modulate oxidative stress. Its expression is also dysregulated in several benign and malignant diseases. Its small size, secreted nature and relative stability have led to it being investigated as a diagnostic and prognostic biomarker in numerous diseases including inflammation and cancer. Functional studies, conducted primarily on lipocalin 2 (Lcn2), the mouse homologue of human NGAL have revealed that Lcn2 has a strong affinity for iron complexed to both bacterial siderophores (iron binding proteins) and certain human proteins like norepinephrine. By sequestering iron-laden siderophores, Lcn2 deprives bacteria of a vital nutrient and thus inhibits their growth (bacteriostatic effect). In malignant cells, its proposed functions range from inhibiting apoptosis (in thyroid cancer cells), invasion and angiogenesis (in pancreatic cancer) to increasing proliferation and metastasis (in breast and colon cancer). Ectopic expression of Lcn2 also promotes BCR-ABL induced chronic myelogenous leukemia in murine models. By transporting iron into and out of the cell, NGAL also regulates iron responsive genes. Further, it stabilizes the proteolytic enzyme matrix metalloprotease-9 (MMP-9) by forming a complex with it, and thereby prevents its autodegradation. The factors regulating NGAL expression are numerous and range from pro-inflammatory cytokines like interleukins, tumor necrosis factor-α and interferons to vitamins like retinoic acid. The purpose of this review article is to examine the expression, structure, regulation and biological role of NGAL and critically assess its potential as a novel diagnostic and prognostic marker in both benign and malignant human diseases. PMID:22513004

Synthesis, crystal structure, fluorescence and electrochemical studies of a new tridentate Schiff base ligand and its nickel(II) and palladium(II) complexes

NASA Astrophysics Data System (ADS)

Shafaatian, Bita; Soleymanpour, Ahmad; Kholghi Oskouei, Nasim; Notash, Behrouz; Rezvani, Seyyed Ahmad

2014-07-01

A new unsymmetrical tridentate Schiff base ligand was derived from the 1:1 M condensation of ortho-vanillin with 2-mercaptoethylamine. Nickel and palladium complexes were obtained by the reaction of the tridentate Schiff base ligand with nickel(II) acetate tetrahydrate and palladium(II) acetate in 2:1 M ratio. In nickel and palladium complexes the ligand was coordinated to metals via the imine N and enolic O atoms. The S groups of Schiff bases were not coordinated to the metals and S-S coupling was occured. The complexes have been found to possess 1:2 Metal:Ligand stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The complexes exhibited octahedral coordination geometry. The emission spectra of the ligand and its complexes were studied in methanol. Electrochemical properties of the ligand and its metal complexes were investigated in the CH3CN solvent at the 100 mV s-1 scan rate. The ligand and metal complexes showed both reversible and quasi-reversible processes at this scan rate. The Schiff base and its complexes have been characterized by IR, 1H NMR, UV/Vis, elemental analyses and conductometry. The crystal structure of nickel complex has been determined by single crystal X-ray diffraction.

Structures of the Substrate-free and Product-bound Forms of HmuO, a Heme Oxygenase from Corynebacterium diphtheriae

PubMed Central

Unno, Masaki; Ardèvol, Albert; Rovira, Carme; Ikeda-Saito, Masao

2013-01-01

Heme oxygenase catalyzes the degradation of heme to biliverdin, iron, and carbon monoxide. Here, we present crystal structures of the substrate-free, Fe3+-biliverdin-bound, and biliverdin-bound forms of HmuO, a heme oxygenase from Corynebacterium diphtheriae, refined to 1.80, 1.90, and 1.85 Å resolution, respectively. In the substrate-free structure, the proximal and distal helices, which tightly bracket the substrate heme in the substrate-bound heme complex, move apart, and the proximal helix is partially unwound. These features are supported by the molecular dynamic simulations. The structure implies that the heme binding fixes the enzyme active site structure, including the water hydrogen bond network critical for heme degradation. The biliverdin groups assume the helical conformation and are located in the heme pocket in the crystal structures of the Fe3+-biliverdin-bound and the biliverdin-bound HmuO, prepared by in situ heme oxygenase reaction from the heme complex crystals. The proximal His serves as the Fe3+-biliverdin axial ligand in the former complex and forms a hydrogen bond through a bridging water molecule with the biliverdin pyrrole nitrogen atoms in the latter complex. In both structures, salt bridges between one of the biliverdin propionate groups and the Arg and Lys residues further stabilize biliverdin at the HmuO heme pocket. Additionally, the crystal structure of a mixture of two intermediates between the Fe3+-biliverdin and biliverdin complexes has been determined at 1.70 Å resolution, implying a possible route for iron exit. PMID:24106279

Effect of Atmospheric Organics on Bioavailable Fe Lifetime in the Oceans

NASA Technical Reports Server (NTRS)

Meskhidze, Nicholas; Hurley, David; Royalty, Taylor Michael; Johnson, Matthew S.

2016-01-01

The deposition of atmospheric aerosols is an important supply pathway of soluble iron (sol-Fe) to the global oceans influencing marine ecosystem processes and climate. Previous studies have shown that natural and anthropogenic acidic trace gases, when mixed with mineral dust, can lead to production of sol-Fe, leading to considerable increase in dust-Fe solubility. Recent studies have further highlighted the importance of atmospheric organic compounds/ligands in the production of sol-Fe during atmospheric transport and transformation of mineral aerosols. However, the actual scope of this aerosol sol-Fe for stimulating the primary productivity in the oceans is determined by both: the total atmospheric fluxes of sol-Fe and the lifetime of sol-Fe after its deposition to the ocean. In this study several atmospheric organic ligands were investigated for their effect on the lifetime of sol-Fe after mixing with seawater. Organic ligands were selected based on their abundance in the marine boundary layer and rainwater and their ability to form bidentate complexes with Fe. The results reveal that the tested organics had minor influence on Fe(II) lifetime in seawater. However, results also show that some organic acid considerably extended the lifetime of colloidal and aqueous Fe(III). Using these results we simulate aerosol sol-Fe lifetime in the ocean for different mineral dust deposition events in the presence and the absence of atmospheric organic ligands. The calculations suggest that when a large dust plume is assumed to contain Fe(II) alone, less than 15% of aerosol sol-Fe gets complexed with marine organic ligands. However, this fraction increases to over 90% when atmospheric Fe is allowed to bond with atmospheric organic acids prior to deposition to the oceans. Calculations also show that for the conditions when seawater organic ligands get titrated by Fe released from dust aerosol particles, retention of sol-Fe in the ocean depends on surface ocean mixing, i.e., replenishing rates for Fe-bonding ligands from below. This study suggests that in future ocean biogeochemistry models more attention should be devoted to better quantification of the role of atmospheric organic acids in the lifetime of aerosol sol-Fe after its deposition to the ocean and the improvements of upper ocean turbulence parameterizations.

An iron-iron hydrogenase mimic with appended electron reservoir for efficient proton reduction in aqueous media

PubMed Central

Becker, René; Amirjalayer, Saeed; Li, Ping; Woutersen, Sander; Reek, Joost N. H.

2016-01-01

The transition from a fossil-based economy to a hydrogen-based economy requires cheap and abundant, yet stable and efficient, hydrogen production catalysts. Nature shows the potential of iron-based catalysts such as the iron-iron hydrogenase (H2ase) enzyme, which catalyzes hydrogen evolution at rates similar to platinum with low overpotential. However, existing synthetic H2ase mimics generally suffer from low efficiency and oxygen sensitivity and generally operate in organic solvents. We report on a synthetic H2ase mimic that contains a redox-active phosphole ligand as an electron reservoir, a feature that is also crucial for the working of the natural enzyme. Using a combination of (spectro)electrochemistry and time-resolved infrared spectroscopy, we elucidate the unique redox behavior of the catalyst. We find that the electron reservoir actively partakes in the reduction of protons and that its electron-rich redox states are stabilized through ligand protonation. In dilute sulfuric acid, the catalyst has a turnover frequency of 7.0 × 104 s−1 at an overpotential of 0.66 V. This catalyst is tolerant to the presence of oxygen, thereby paving the way for a new generation of synthetic H2ase mimics that combine the benefits of the enzyme with synthetic versatility and improved stability. PMID:26844297

Synthesis, characterization, single crystal X-ray determination, fluorescence and electrochemical studies of new dinuclear nickel(II) and oxovanadium(IV) complexes containing double Schiff base ligands

NASA Astrophysics Data System (ADS)

Shafaatian, Bita; Ozbakzaei, Zahra; Notash, Behrouz; Rezvani, S. Ahmad

2015-04-01

A series of new bimetallic complexes of nickel(II) and vanadium(IV) have been synthesized by the reaction of the new double bidentate Schiff base ligands with nickel acetate and vanadyl acetylacetonate in 1:1 M ratio. In nickel and also vanadyl complexes the ligands were coordinated to the metals via the imine N and enolic O atoms. The complexes have been found to possess 1:1 metals to ligands stoichiometry and the molar conductance data revealed that the metal complexes were non-electrolytes. The nickel and vanadyl complexes exhibited distorted square planar and square pyramidal coordination geometries, respectively. The emission spectra of the ligands and their complexes were studied in methanol. Electrochemical properties of the ligands and their metal complexes were also investigated in DMSO solvent at 150 mV s-1 scan rate. The ligands and metal complexes showed both quasi-reversible and irreversible processes at this scan rate. The Schiff bases and their complexes have been characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis and conductometry. The crystal structure of the nickel complex has been determined by single crystal X-ray diffraction.

Perturbation-response scanning reveals ligand entry-exit mechanisms of ferric binding protein.

PubMed

Atilgan, Canan; Atilgan, Ali Rana

2009-10-01

We study apo and holo forms of the bacterial ferric binding protein (FBP) which exhibits the so-called ferric transport dilemma: it uptakes iron from the host with remarkable affinity, yet releases it with ease in the cytoplasm for subsequent use. The observations fit the "conformational selection" model whereby the existence of a weakly populated, higher energy conformation that is stabilized in the presence of the ligand is proposed. We introduce a new tool that we term perturbation-response scanning (PRS) for the analysis of remote control strategies utilized. The approach relies on the systematic use of computational perturbation/response techniques based on linear response theory, by sequentially applying directed forces on single-residues along the chain and recording the resulting relative changes in the residue coordinates. We further obtain closed-form expressions for the magnitude and the directionality of the response. Using PRS, we study the ligand release mechanisms of FBP and support the findings by molecular dynamics simulations. We find that the residue-by-residue displacements between the apo and the holo forms, as determined from the X-ray structures, are faithfully reproduced by perturbations applied on the majority of the residues of the apo form. However, once the stabilizing ligand (Fe) is integrated to the system in holo FBP, perturbing only a few select residues successfully reproduces the experimental displacements. Thus, iron uptake by FBP is a favored process in the fluctuating environment of the protein, whereas iron release is controlled by mechanisms including chelation and allostery. The directional analysis that we implement in the PRS methodology implicates the latter mechanism by leading to a few distant, charged, and exposed loop residues. Upon perturbing these, irrespective of the direction of the operating forces, we find that the cap residues involved in iron release are made to operate coherently, facilitating release of the ion.

A mixed valence zinc dithiolene system with spectator metal and reactor ligands.

PubMed

Ratvasky, Stephen C; Mogesa, Benjamin; van Stipdonk, Michael J; Basu, Partha

2016-08-16

Neutral complexes of zinc with N,N'-diisopropylpiperazine-2,3-dithione ( i Pr 2 Dt 0 ) and N,N'-dimethylpiperazine-2,3-dithione (Me 2 Dt 0 ) with chloride or maleonitriledithiolate (mnt 2- ) as coligands have been synthesized and characterized. The molecular structures of these zinc complexes have been determined using single crystal X-ray diffractometry. Complexes recrystallize in monoclinic P type systems with zinc adopting a distorted tetrahedral geometry. Two zinc complexes with mixed-valent dithiolene ligands exhibit ligand-to-ligand charge transfer bands. Optimized geometries, molecular vibrations and electronic structures of charge-transfer complexes were calculated using density functional theory (B3LYP/6-311G+(d,p) level). Redox orbitals are shown to be almost exclusively ligand in nature, with a HOMO based heavily on the electron-rich maleonitriledithiolate ligand, and a LUMO comprised mostly of the electron-deficient dithione ligand. Charge transfer is thus believed to proceed from dithiolate HOMO to dithione LUMO, showing ligand-to-ligand redox interplay across a d 10 metal.

De novo design, synthesis and characterisation of MP3, a new catalytic four-helix bundle hemeprotein.

PubMed

Faiella, Marina; Maglio, Ornella; Nastri, Flavia; Lombardi, Angela; Lista, Liliana; Hagen, Wilfred R; Pavone, Vincenzo

2012-12-07

A new artificial metalloenzyme, MP3 (MiniPeroxidase 3), designed by combining the excellent structural properties of four-helix bundle protein scaffolds with the activity of natural peroxidases, was synthesised and characterised. This new hemeprotein model was developed by covalently linking the deuteroporphyrin to two peptide chains of different compositions to obtain an asymmetric helix-loop-helix/heme/helix-loop-helix sandwich arrangement, characterised by 1) a His residue on one chain that acts as an axial ligand to the iron ion; 2) a vacant distal site that is able to accommodate exogenous ligands or substrates; and 3) an Arg residue in the distal site that should assist in hydrogen peroxide activation to give an HRP-like catalytic process. MP3 was synthesised and characterised as its iron complex. CD measurements revealed the high helix-forming propensity of the peptide, confirming the appropriateness of the model procedure; UV/Vis, MCD and EPR experiments gave insights into the coordination geometry and the spin state of the metal. Kinetic experiments showed that Fe(III)-MP3 possesses peroxidase-like activity comparable to R38A-hHRP, highlighting the possibility of mimicking the functional features of natural enzymes. The synergistic application of de novo design methods, synthetic procedures, and spectroscopic characterisation, described herein, demonstrates a method by which to implement and optimise catalytic activity for an enzyme mimetic. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic spectra and photophysics of platinum(II) complexes with alpha-diimine ligands - Solid-state effects. I - Monomers and ligand pi dimers

NASA Technical Reports Server (NTRS)

Miskowski, Vincent M.; Houlding, Virginia H.

1989-01-01

Two types of emission behavior for Pt(II) complexes containing alpha-diimine ligands have been observed in dilute solution. If the complex also has weak field ligands such as chloride, ligand field (d-d) excited states become the lowest energy excited states. If only strong field ligands are present, a diimine 3(pi-pi/asterisk/) state becomes the lowest. In none of the cases studied did metal-to-ligand charge transfer excited state lie lowest.

Isocyanide or nitrosyl complexation to hemes with varying tethered axial base ligand donors: synthesis and characterization.

PubMed

Sharma, Savita K; Kim, Hyun; Rogler, Patrick J; A Siegler, Maxime; Karlin, Kenneth D

2016-09-01

A series of ferrous-heme 2,6-dimethylphenyl isocyanide (DIMPI) and ferrous-heme mononitrosyl complexes have been synthesized and characterized. The heme portion of the complexes studied is varied with respect to the nature of the axial ligand, including complexes, where it is covalently tethered to the porphyrinate periphery. Reduced heme complexes, [(F8)Fe(II)], [(P(Py))Fe(II)], [(P(Im))Fe(II)], and [(P(ImH))Fe(II)], where F8 = tetrakis(2,6-difluorophenyl)-porphyrinate and P(Py), P(Im), and P(ImH) are partially fluorinated tetraaryl porphyrinates with covalently appended axial base pyridyl/imidazolyl or histamine moieties, were employed; P(ImH) is a new construct. Room temperature addition of DIMPI to these iron(II) complexes affords the bis-isocyanide species [(F8)Fe(II)-(DIMPI)2] in the case of [(F8)Fe(II)], while for the other hemes, mono-DIMPI compounds are obtained, [(P(Py))Fe(II)-(DIMPI)] [(2)-DIMPI], [(P(Im))Fe(II)-(DIMPI)] [(3)-DIMPI], and [(P(ImH))Fe(II)-(DIMPI)] [(4)-DIMPI]. The structures of complexes (3)-DIMPI and (4)-DIMPI have been determined by single crystal X-ray crystallography, where interesting H…F(porphryinate aryl group) interactions are observed. (19)F-NMR spectra determined for these complexes suggest that H…F(porphyrinate aryl groups) attractions also occur in solution, the H atom coming either from the DIMPI methyl groups or from a porphyinate axial base imidazole or porphyrinate pyrrole. Similarly, we have used nitrogen monoxide to generate ferrous-nitrosyl complexes, a five-coordinate species for F8, [(F8)Fe(II)-(NO)], or low-spin six-coordinate compounds [(P(Py))Fe(II)-(NO)], [(P(Im))Fe(II)-(NO)], and [(P(ImH))Fe(II)-(NO)]. The DIMPI and mononitrosyl complexes have also been characterized using UV-Vis, IR, (1)H-NMR, and EPR spectroscopies.

Whey Peptide-Iron Complexes Increase the Oxidative Stability of Oil-in-Water Emulsions in Comparison to Iron Salts.

PubMed

Caetano-Silva, Maria Elisa; Barros Mariutti, Lilian Regina; Bragagnolo, Neura; Bertoldo-Pacheco, Maria Teresa; Netto, Flavia Maria

2018-02-28

Food fortification with iron may favor lipid oxidation in both food matrices and the human body. This study aimed at evaluating the effect of peptide-iron complexation on lipid oxidation catalyzed by iron, using oil-in-water (O/W) emulsions as a model system. The extent of lipid oxidation of emulsions containing iron salts (FeSO 4 or FeCl 2 ) or iron complexes (peptide-iron complexes or ferrous bisglycinate) was evaluated during 7 days, measured as primary (peroxide value) and secondary products (TBARS and volatile compounds). Both salts catalyzed lipid oxidation, leading to peroxide values 2.6- to 4.6-fold higher than the values found for the peptide-iron complexes. The addition of the peptide-iron complexes resulted in the formation of lower amounts of secondary volatiles of lipid oxidation (up to 78-fold) than those of iron salts, possibly due to the antioxidant activity of the peptides and their capacity to keep iron apart from the lipid phase, since the iron atom is coordinated and takes part in a stable structure. The peptide-iron complexes showed potential to reduce the undesirable sensory changes in food products and to decrease the side effects related to free iron and the lipid damage of cell membranes in the organism, due to the lower reactivity of iron in the complexed form.

Mixed ligand complexation of some transition metal ions in solution and solid state: Spectral characterization, antimicrobial, antioxidant, DNA cleavage activities and molecular modeling

NASA Astrophysics Data System (ADS)

Shobana, Sutha; Dharmaraja, Jeyaprakash; Selvaraj, Shanmugaperumal

2013-04-01

Equilibrium studies of Ni(II), Cu(II) and Zn(II) mixed ligand complexes involving a primary ligand 5-fluorouracil (5-FU; A) and imidazoles viz., imidazole (him), benzimidazole (bim), histamine (hist) and L-histidine (his) as co-ligands(B) were carried out pH-metrically in aqueous medium at 310 ± 0.1 K with I = 0.15 M (NaClO4). In solution state, the stoichiometry of MABH, MAB and MAB2 species have been detected. The primary ligand(A) binds the central M(II) ions in a monodentate manner whereas him, bim, hist and his co-ligands(B) bind in mono, mono, bi and tridentate modes respectively. The calculated Δ log K, log X and log X' values indicate higher stability of the mixed ligand complexes in comparison to binary species. Stability of the mixed ligand complex equilibria follows the Irving-Williams order of stability. In vitro biological evaluations of the free ligand(A) and their metal complexes by well diffusion technique show moderate activities against common bacterial and fungal strains. Oxidative cleavage interaction of ligand(A) and their copper complexes with CT DNA is also studied by gel electrophoresis method in the presence of oxidant. In vitro antioxidant evaluations of the primary ligand(A), CuA and CuAB complexes by DPPH free radical scavenging model were carried out. In solid, the MAB type of M(II)sbnd 5-FU(A)sbnd his(B) complexes were isolated and characterized by various physico-chemical and spectral techniques. Both the magnetic susceptibility and electronic spectral analysis suggest distorted octahedral geometry. Thermal studies on the synthesized mixed ligand complexes show loss of coordinated water molecule in the first step followed by decomposition of the organic residues subsequently. XRD and SEM analysis suggest that the microcrystalline nature and homogeneous morphology of MAB complexes. Further, the 3D molecular modeling and analysis for the mixed ligand MAB complexes have also been carried out.

Quantum mechanics study of repulsive π-π interaction and flexibility of phenyl moiety in the iron azodioxide complex

NASA Astrophysics Data System (ADS)

Liu, Yuemin; Liu, Yucheng; Murru, Siva; Tzeng, Nianfeng; Srivastava, Radhey S.

2015-10-01

In this study, repulsive π-π interactions within iron azodioxide complex Fe[Ph(O)NN(O)Ph]3 were quantum mechanically characterized using DFT, MP2 and CCSD(T) methods. Flexibility of six phenyl moieties in this complex structure was also investigated by structural optimization approach using the DFT methods. Our MP2 and CCSD(T) calculations of the closest pair provided interaction energy of 6.62 and 8.29 kcal/mol respectively, which indicate a strongest repulsion among these intra-molecular π-π interactions. Interaction energy of the particular π-π pair calculated from 24 hybrid DFT methods ranges from 4.56 kcal/mol from BHandH method to 15.15 kcal/mol from O3LYP method. Cares should be exercised when interpreting interaction energy and geometry optimization from DFT simulation of systems containing π-π interaction. Comparison between the DFT results and the benchmark CCSD(T) results shows that the DFT calculations of π-π interaction are reasonable but still need to be interpreted with caution. Furthermore, MP2 interaction energy of -44.69 kcal/mol between two substituted π systems/phenyl rings Ph(O)N-moieties suggested that above energetically unfavorable π-π interaction can be compensated by the covalent bond N-N in a single ligand Ph(O)NN(O)Ph, which allows for a reasonable stability across the complex molecules. Optimizations of the entire complex molecule using B3LYP and M06HF methods produced a large variation of π-π distances and orientations, which implied that the complex molecule may perform catalysis at room temperature.

Aluminum and Fenton reaction: how can the reaction be modulated by speciation? A computational study using citrate as a test case.

PubMed

Mujika, Jon I; Dalla Torre, Gabriele; Lopez, Xabier

2018-06-13

The pro-oxidant ability of aluminum is behind many of the potential toxic effects of this exogenous element in the human organism. Although the overall process is still far from being understood at the molecular level, the well known ability of aluminum to promote the Fenton reaction is mediated through the formation of stable aluminum-superoxide radical complexes. However, the properties of metal complexes are highly influenced by the speciation of the metal. In this paper, we investigate the effect that speciation could have on the pro-oxidant activity of aluminum. We choose citrate as a test case, because it is the main low-molecular-mass chelator of aluminum in blood serum, forming very stable aluminum-citrate complexes. The influence of citrate in the interaction of aluminum with the superoxide radical is investigated, determining how the formation of aluminum-citrate complexes affects the promotion of the Fenton reaction. The results indicate that citrate increases the stability of the aluminum-superoxide complexes through the formation of ternary compounds, and that the Fenton reaction is even more favorable when aluminum is chelated to citrate. Nevertheless, our results demonstrate that overall, citrate may prevent the pro-oxidant activity of aluminum: on one hand, in an excess of citrate, the formation of 1 : 2 aluminum-citrate complexes is expected. On the other hand, the chelation of iron by citrate makes the reduction of iron thermodynamically unfavorable. In summary, the results suggest that citrate can have both a promotion and protective role, depending on subtle factors, such as initial concentration, non-equilibrium behavior and the exchange rate of ligands in the first shell of the metals.

Aquatic photolysis: photolytic redox reactions between goethite and adsorbed organic acids in aqueous solutions

USGS Publications Warehouse

Goldberg, M.C.; Cunningham, K.M.; Weiner, Eugene R.

1993-01-01

Photolysis of mono and di-carboxylic acids that are adsorbed onto the surface of the iron oxyhydroxide (goethite) results in an oxidation of the organic material and a reduction from Fe(III) to Fe(II) in the iron complex. There is a subsequent release of Fe2+ ions into solution. At constant light flux and constant solution light absorption, the factors responsible for the degree of photolytic reaction include: the number of lattice sites that are bonded by the organic acid; the rate of acid readsorption to the surface during photolysis; the conformation and structure of the organic acid; the degree of oxidation of the organic acid; the presence or absence of an ??-hydroxy group on the acid, the number of carbons in the di-acid chain and the conformation of the di-acid. The ability to liberate Fe(III) at pH 6.5 from the geothite lattice is described by the lyotropic series: tartrate>citrate> oxalate > glycolate > maleate > succinate > formate > fumarate > malonate > glutarate > benzoate = butanoate = control. Although a larger amount of iron is liberated, the series is almost the same at pH 5.5 except that oxalate > citrate and succinate > maleate. A set of rate equations are given that describe the release of iron from the goethite lattice. It was observed that the pH of the solution increases during photolysis if the solutions are not buffered. There is evidence to suggest the primary mechanism for all these reactions is an electron transfer from the organic ligand to the Fe(III) in the complex. Of all the iron-oxyhydroxide materials, crystalline goethite is the least soluble in water; yet, this study indicates that in an aqueous suspension, iron can be liberated from the goethite lattice. Further, it has been shown that photolysis can occur in a multiphase system at the sediment- water interface which results in an oxidation of the organic species and release of Fe2+ to solution where it becomes available for further reaction. ?? 1993.

Method and apparatus for dissociating metals from metal compounds extracted into supercritical fluids

DOEpatents

Wai, Chien M.; Hunt, Fred H.; Smart, Neil G.; Lin, Yuehe

2000-01-01

A method for dissociating metal-ligand complexes in a supercritical fluid by treating the metal-ligand complex with heat and/or reducing or oxidizing agents is described. Once the metal-ligand complex is dissociated, the resulting metal and/or metal oxide form fine particles of substantially uniform size. In preferred embodiments, the solvent is supercritical carbon dioxide and the ligand is a .beta.-diketone such as hexafluoroacetylacetone or dibutyldiacetate. In other preferred embodiments, the metals in the metal-ligand complex are copper, silver, gold, tungsten, titanium, tantalum, tin, or mixtures thereof. In preferred embodiments, the reducing agent is hydrogen. The method provides an efficient process for dissociating metal-ligand complexes and produces easily-collected metal particles free from hydrocarbon solvent impurities. The ligand and the supercritical fluid can be regenerated to provide an economic, efficient process.

Aminopyridinate-FI hybrids, their hafnium and titanium complexes, and their application in the living polymerization of 1-hexene.

PubMed

Haas, Isabelle; Dietel, Thomas; Press, Konstantin; Kol, Moshe; Kempe, Rhett

2013-10-11

Based on two well-established ligand systems, the aminopyridinato (Ap) and the phenoxyimine (FI) ligand systems, new Ap-FI hybrid ligands were developed. Four different Ap-FI hybrid ligands were synthesized through a simple condensation reaction and fully characterized. The reaction of hafnium tetrabenzyl with all four Ap-FI hybrid ligands exclusively led to mono(Ap-FI) complexes of the type [(Ap-FI)HfBn2 ]. The ligands acted as tetradentate dianionic chelates. Upon activation with tris(pentafluorophenyl)borane, the hafnium-dibenzyl complexes led to highly active catalysts for the polymerization of 1-hexene. Ultrahigh molecular weights and extremely narrow polydispersities support the living nature of this polymerization process. A possible deactivation product of the hafnium catalysts was characterized by single-crystal X-ray analysis and is discussed. The coordination modes of these new ligands were studied with the help of model titanium complexes. The reaction of titanium(IV) isopropoxide with ligand 1 led to a mono(Ap-FI) complex, which showed the desired fac-mer coordination mode. Titanium (IV) isopropoxide reacted with ligand 4 to give a complex of the type [(ApH-FI)2 Ti(OiPr)2 ], which featured the ligand in its monoanionic form. The two titanium complexes were characterized by X-ray crystal-structure analysis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Repulsive Guidance Molecule is a structural bridge between Neogenin and Bone Morphogenetic Protein

PubMed Central

Healey, Eleanor G.; Bishop, Benjamin; Elegheert, Jonathan; Bell, Christian H.; Padilla-Parra, Sergi; Siebold, Christian

2015-01-01

Repulsive guidance molecules (RGMs) control crucial processes spanning cell motility, adhesion, immune cell regulation and systemic iron metabolism. RGMs signal via two fundamental signaling cascades: the Neogenin (NEO1) and the Bone Morphogenetic Protein (BMP) pathways. Here, we report crystal structures of the N-terminal domains of all human RGM family members in complex with the BMP ligand BMP2, revealing a novel protein fold and a conserved BMP-binding mode. Our structural and functional data suggest a pH-linked mechanism for RGM-activated BMP signaling and offer a rationale for RGM mutations causing juvenile hemochromatosis. We also determined the ternary BMP2–RGM–NEO1 complex crystal structure, which combined with solution scattering and live-cell super-resolution fluorescence microscopy, indicates BMP-induced clustering of the RGM–NEO1 complex. Our results show how RGM acts as the central hub linking BMP and NEO1 and physically connecting these fundamental signaling pathways. PMID:25938661

Spectroscopic definition of the biferrous and biferric sites in de novo designed four-helix bundle DFsc peptides: implications for O2 reactivity of binuclear non-heme iron enzymes.

PubMed

Bell, Caleb B; Calhoun, Jennifer R; Bobyr, Elena; Wei, Pin-Pin; Hedman, Britt; Hodgson, Keith O; Degrado, William F; Solomon, Edward I

2009-01-13

DFsc is a single chain de novo designed four-helix bundle peptide that mimics the core protein fold and primary ligand set of various binuclear non-heme iron enzymes. DFsc and the E11D, Y51L, and Y18F single amino acid variants have been studied using a combination of near-IR circular dichroism (CD), magnetic circular dichroism (MCD), variable temperature variable field MCD (VTVH MCD), and X-ray absorption (XAS) spectroscopies. The biferrous sites are all weakly antiferromagnetically coupled with mu-1,3 carboxylate bridges and one 4-coordinate and one 5-coordinate Fe, very similar to the active site of class I ribonucleotide reductase (R2) providing open coordination positions on both irons for dioxygen to bridge. From perturbations of the MCD and VTVH MCD the iron proximal to Y51 can be assigned as the 4-coordinate center, and XAS results show that Y51 is not bound to this iron in the reduced state. The two open coordination positions on one iron in the biferrous state would become occupied by dioxygen and Y51 along the O(2) reaction coordinate. Subsequent binding of Y51 functions as an internal spectral probe of the O(2) reaction and as a proton source that would promote loss of H(2)O(2). Coordination by a ligand that functions as a proton source could be a structural mechanism used by natural binuclear iron enzymes to drive their reactions past peroxo biferric level intermediates.

Spectroscopic definition of the biferrous and biferric sites of de novo designed 4-helix bundle DFsc peptides: Implications for O2 reactivity of binuclear non-heme iron enzymes

PubMed Central

Bell, Caleb B.; Calhoun, Jennifer R.; Bobyr, Elena; Wei, Pin-pin; Hedman, Britt; Hodgson, Keith O.; DeGrado, William F.; Solomon, Edward I.

2009-01-01

DFsc is a single chain de novo designed 4-helix bundle peptide that mimics the core protein fold and primary ligand set of various binuclear non-heme iron enzymes. DFsc and the E11D, Y51L and Y18F single amino acid variants have been studied using a combination of near-IR circular dichroism (CD), magnetic circular dichroism (MCD), variable temperature variable field MCD (VTVH MCD) and x-ray absorption (XAS) spectroscopies. The biferrous sites are all weakly antiferromagnetically coupled with μ-1,3 carboxylate bridges and one 4-coordinate and one 5-coordinate Fe, very similar to the active site of Class I ribonucleotide reductase (R2) providing open coordination positions on both irons for dioxygen to bridge. From perturbations of the MCD and VTVH MCD the iron proximal to Y51 can be assigned as the 4-coordinate center and XAS results show that Y51 is not bound to this iron in the reduced state. The two open coordination positions on one iron in the biferrous state would become occupied by dioxygen and Y51 along the O2 reaction coordinate. Subsequent binding of Y51 functions as an internal spectral probe of the O2 reaction and as a proton source that would promote loss of H2O2. Coordination by a ligand that functions as a proton source could be a structural mechanism used by natural binuclear iron enzymes to drive their reactions past peroxo biferric level intermediates. PMID:19090676

Trace element uptake and distribution in plants.

PubMed

Graham, Robin D; Stangoulis, James C R

2003-05-01

There are similarities between mammals and plants in the absorption and transport of trace elements. The chemistry of trace element uptake from food sources in both cases is based on the thermodynamics of adsorption on charged solid surfaces embedded in a solution phase of charged ions and metal-binding ligands together with redox systems in the case of iron and some other elements. Constitutive absorption systems function in nutrient uptake during normal conditions, and inducible "turbo" systems increase the supply of a particular nutrient during deficiency. Iron uptake is the most studied of the micronutrients, and divides the plant kingdom into two groups: dicotyledonous plants have a turbo system that is an upregulated version of the constitutive system, which consists of a membrane-bound reductase and an ATP-driven hydrogen ion extrusion pump; and monocotyledonous plants have a constitutive system similar to that of the dicots, but with an inducible system remarkably different that uses the mugeneic acid class of phytosiderophores (PS). The PS system may in fact be an important port of entry for iron from an iron-rich but exceedingly iron-insoluble lithosphere into the iron-starved biosphere. Absorption of trace metals in these graminaceous plants is normally via divalent ion channels after reduction in the plasma membrane. Once absorbed, iron can be stored in plants as phytoferritin or transported to active sites by transport-specific ligands. The transport of iron and zinc into seeds is dominated by the phloem sap system, which has a high pH that requires chelation of heavy metals. Loading into grains involves three or four genes each that control chelation, membrane transport and deposition as phytate.

L-Edge X-ray Absorption Spectroscopic Investigation of {FeNO} 6: Delocalization vs Antiferromagnetic Coupling

DOE PAGES

Yan, James J.; Gonzales, Margarita A.; Mascharak, Pradip K.; ...

2016-12-22

NO is a classic non-innocent ligand, and iron nitrosyls can have different electronic structure descriptions depending on their spin state and coordination environment. These highly covalent ligands are found in metalloproteins and are also used as models for Fe–O 2 systems. Here, this study utilizes iron L-edge X-ray absorption spectroscopy (XAS), interpreted using a valence bond configuration interaction multiplet model, to directly experimentally probe the electronic structure of the S = 0 {FeNO} 6 compound [Fe(PaPy 3)NO] 2+ (PaPy 3 = N,N-bis(2-pyridylmethyl)amine-N-ethyl-2-pyridine-2-carboxamide) and the S = 0 [Fe(PaPy 3)CO] + reference compound. This method allows separation of the σ-donation andmore » π-acceptor interactions of the ligand through ligand-to-metal and metal-to-ligand charge-transfer mixing pathways. The analysis shows that the {FeNO} 6 electronic structure is best described as Fe III–NO(neutral), with no localized electron in an NO π* orbital or electron hole in an Fe dπ orbital. This delocalization comes from the large energy gap between the Fe–NO π-bonding and antibonding molecular orbitals relative to the exchange interactions between electrons in these orbitals. This study demonstrates the utility of L-edge XAS in experimentally defining highly delocalized electronic structures.« less

In vitro molecular magnetic resonance imaging detection and measurement of apoptosis using superparamagnetic iron oxide + antibody as ligands for nucleosomes

NASA Astrophysics Data System (ADS)

Rapley, P. L.; Witiw, C.; Rich, K.; Niccoli, S.; Tassotto, M. L.; Th'ng, J.

2012-11-01

Recent research in cell biology as well as oncology research has focused on apoptosis or programmed cell death as a means of quantifying the induced effects of treatment. A hallmark of late-stage apoptosis is nuclear fragmentation in which DNA is degraded to release nucleosomes with their associated histones. In this work, a method was developed for detecting and measuring nucleosome concentration in vitro with magnetic resonance imaging (MRI). The indirect procedure used a commercially available secondary antibody-superparamagnetic iron oxide (SPIO) particle complex as a contrast agent that bound to primary antibodies against nucleosomal histones H4, H2A and H2B. Using a multiple-echo spin-echo sequence on a 1.5 T clinical MRI scanner, significant T2 relaxation enhancement as a function of in vitro nucleosomal concentration was measured. In addition, clustering or aggregation of the contrast agent was demonstrated with its associated enhancement in T2 effects. The T2 clustering enhancement showed a complex dependence on relative concentrations of nucleosomes, primary antibody and secondary antibody + SPIO. The technique supports the feasibility of using MRI measurements of nucleosome concentration in blood as a diagnostic, prognostic and predictive tool in the management of cancer.

Dissolved iron anomaly in the deep tropical-subtropical Pacific: Evidence for long-range transport of hydrothermal iron

NASA Astrophysics Data System (ADS)

Wu, Jingfeng; Wells, Mark L.; Rember, Robert

2011-01-01

Dissolved iron profiles along a north-south transect along 158°W in the tropical Pacific show evidence of two deepwater anomalies. The first extends from Station ALOHA (22.78°N) to the equator at ˜1000-1500 m and lies below the maximum apparent oxygen utilization and nutrient (N, P) concentrations. The feature is not supported by vertical export processes, but instead corresponds with the lateral dilution field of δ 3He derived from the Loihi seamount, Hawaii, though a sediment source associated with the Hawaiian Island Chain cannot be entirely ruled out. The second, deeper (2000-3000 m) anomaly occurs in tropical South Pacific waters (7°S) and also does not correlate with the depths of maximum nutrient concentrations or apparent oxygen utilization, but it does coincide closely with δ 3He emanating from the East Pacific Rise, more than 5000 km to the east. We hypothesize that these anomalies represent the long-range (>2000 km) transport of hydrothermal iron residuals, stabilized against scavenging by complexation with excess organic ligands in the plume source regions. Such trace leakage of hydrothermal iron to distal plume regions would have been difficult to identify in most hydrothermal vent mapping studies because low analytical detection limits were not needed for the proximal plume regions. These findings suggest that hydrothermal activity may represent a major source of dissolved iron throughout the South Pacific deep basin today, as well as other regions having high mid-ocean spreading rates in the geologic past. In particular, we hypothesize that high spreading rates along the South Atlantic and Southern Ocean mid-oceanic ridges, combined with the upwelling ventilation of these distal hydrothermal plumes, may have increased ocean productivity and carbon export in the Southern Ocean. Assessing the magnitude and persistence of dissolved hydrothermal iron in basin scale deep waters will be important for understanding the marine biogeochemistry of iron and, potentially, on ocean productivity and climate change during the geologic past.

Synthesis, structural elucidation, biological, antioxidant and nuclease activities of some 5-Fluorouracil-amino acid mixed ligand complexes

NASA Astrophysics Data System (ADS)

Shobana, Sutha; Subramaniam, Perumal; Mitu, Liviu; Dharmaraja, Jeyaprakash; Arvind Narayan, Sundaram

2015-01-01

Some biologically active mixed ligand complexes (1-9) have been synthesized from 5-Fluorouracil (5-FU; A) and amino acids (B) such as glycine (gly), L-alanine (ala) and L-valine (val) with Ni(II), Cu(II) and Zn(II) ions. The synthesized mixed ligand complexes (1-9) were characterized by various physico-chemical, spectral, thermal and morphological studies. 5-Fluorouracil and its mixed ligand complexes have been tested for their in vitro biological activities against some pathogenic bacterial and fungal species by the agar well diffusion method. The in vitro antioxidant activities of 5-Fluorouracil and its complexes have also been investigated by using the DPPH assay method. The results demonstrate that Cu(II) mixed ligand complexes (4-6) exhibit potent biological as well as antioxidant activities compared to 5-Fluorouracil and Ni(II) (1-3) and Zn(II) (7-9) mixed ligand complexes. Further, the cleaving activities of CT DNA under aerobic conditions show moderate activity with the synthesized Cu(II) and Ni(II) mixed ligand complexes (1-6) while no activity is seen with Zn(II) complexes (7-9). Binding studies of CT DNA with these complexes show a decrease in intensity of the charge transfer band to the extent of 5-15% along with a minor red shift. The free energy change values (Δ‡G) calculated from intrinsic binding constants indicate that the interaction between mixed ligand complex and DNA is spontaneous.

Unifying Exchange Sensitivity in Transition-Metal Spin-State Ordering and Catalysis through Bond Valence Metrics.

PubMed

Gani, Terry Z H; Kulik, Heather J

2017-11-14

Accurate predictions of spin-state ordering, reaction energetics, and barrier heights are critical for the computational discovery of open-shell transition-metal (TM) catalysts. Semilocal approximations in density functional theory, such as the generalized gradient approximation (GGA), suffer from delocalization error that causes them to overstabilize strongly bonded states. Descriptions of energetics and bonding are often improved by introducing a fraction of exact exchange (e.g., erroneous low-spin GGA ground states are instead correctly predicted as high-spin with a hybrid functional). The degree of spin-splitting sensitivity to exchange can be understood based on the chemical composition of the complex, but the effect of exchange on reaction energetics within a single spin state is less well-established. Across a number of model iron complexes, we observe strong exchange sensitivities of reaction barriers and energies that are of the same magnitude as those for spin splitting energies. We rationalize trends in both reaction and spin energetics by introducing a measure of delocalization, the bond valence of the metal-ligand bonds in each complex. The bond valence thus represents a simple-to-compute property that unifies understanding of exchange sensitivity for catalytic properties and spin-state ordering in TM complexes. Close agreement of the resulting per-metal-organic-bond sensitivity estimates, together with failure of alternative descriptors demonstrates the utility of the bond valence as a robust descriptor of how differences in metal-ligand delocalization produce differing relative energetics with exchange tuning. Our unified description explains the overall effect of exact exchange tuning on the paradigmatic two-state FeO + /CH 4 reaction that combines challenges of spin-state and reactivity predictions. This new descriptor-sensitivity relationship provides a path to quantifying how predictions in transition-metal complex screening are sensitive to the method used.

Ultrafast Spin Crossover in [FeII (bpy)3 ]2+ : Revealing Two Competing Mechanisms by Extreme Ultraviolet Photoemission Spectroscopy.

PubMed

Moguilevski, Alexandre; Wilke, Martin; Grell, Gilbert; Bokarev, Sergey I; Aziz, Saadullah G; Engel, Nicholas; Raheem, Azhr A; Kühn, Oliver; Kiyan, Igor Yu; Aziz, Emad F

2017-03-03

Photoinduced spin-flip in Fe II complexes is an ultrafast phenomenon that has the potential to become an alternative to conventional processing and magnetic storage of information. Following the initial excitation by visible light into the singlet metal-to-ligand charge-transfer state, the electronic transition to the high-spin quintet state may undergo different pathways. Here we apply ultrafast XUV (extreme ultraviolet) photoemission spectroscopy to track the low-to-high spin dynamics in the aqueous iron tris-bipyridine complex, [Fe(bpy) 3 ] 2+ , by monitoring the transient electron density distribution among excited states with femtosecond time resolution. Aided by first-principles calculations, this approach enables us to reveal unambiguously both the sequential and direct de-excitation pathways from singlet to quintet state, with a branching ratio of 4.5:1. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, characterization and biological investigations of novel Schiff base ligands containing imidazoline moiety and their Co(II) and Cu(II) complexes

NASA Astrophysics Data System (ADS)

Radha, V. P.; Jone Kirubavathy, S.; Chitra, S.

2018-08-01

Novel imidazoline based Schiff base ligands L1 and L2 were synthesized from o-phenylenediamine/o-aminophenol with creatinine. The ligands were complexed with Co(II) and Cu(II) by direct reaction with metal salts. The synthesized ligands and the metal complexes were characterized by elemental analysis, FT-IR, 1H NMR, mass, electronic, thermal analyses, conductivity and magnetic susceptibility measurements. The conductivity measurements showed the non-electrolytic nature of the complexes. The thermogravimetric analyses confirmed the presence of lattice and coordinated water molecules in the complexes. The DFT calculations were carried out at B3LYP/6-31G(d,p) level for the determination of the optimized structure of the ligands. The synthesized ligands and the metal complexes were screened for their antimicrobial activity against two gram positive bacteria (Staphylococcus aureus and Bacillus subtilis) and two gram negative bacteria (Escherichia coli and Pseudomonas aeruginosa) and two fungal strains (Aspergillus niger and Candida albicans). The outcomes revealed that the metal complexes showed pronounced activity than the ligands.

Distinct Siderophores Contribute to Iron Cycling in the Mesopelagic at Station ALOHA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bundy, Randelle M.; Boiteau, Rene M.; McLean, Craig

The distribution of dissolved iron (Fe), total organic Fe-binding ligands, and siderophores were measured between the surface and 400 m at Station ALOHA, a long term ecological study site in the North Pacific Subtropical Gyre. Dissolved Fe concentrations were low throughout the water column and strong organic Fe-binding ligands exceeded dissolved Fe at all depths; varying from 0.9 nmol L -1 in the surface to 1.6 nmol L -1 below 150 m. Although Fe does not appear to limit microbial production, we nevertheless found siderophores at nearly all depths, indicating some populations of microbes were responding to Fe stress. Ferrioxaminemore » siderophores were most abundant in the upper water column, with concentrations between 0.1-2 pmol L -1, while a suite of amphibactins were found below 200 m with concentrations between 0.8-11 pmol L -1. The distinct vertical distribution of ferrioxamines and amphibactins may indicate disparate strategies for acquiring Fe from dust in the upper water column and recycled organic matter in the lower water column. Amphibactins were found to have conditional stability constants (log ) ranging from 12.0-12.5, while ferrioxamines had much stronger conditional stability constants ranging from 14.0-14.4, within the range of observed L1 ligands by voltammetry. We used our data to calculate equilibrium Fe speciation at Station ALOHA to compare the relative concentration of inorganic and siderophore complexed Fe. The results indicate that the concentration of Fe bound to siderophores was up to two orders of magnitude higher than inorganic Fe, suggesting that even if less bioavailable, siderophores were nevertheless a viable pathway for Fe acquisition by microbes at our study site. Finally, we observed rapid production of ferrioxamine E by particle-associated bacteria during incubation of freshly collected sinking organic matter. Fe-limitation may therefore be a factor in regulating carbon metabolism and nutrient regeneration in the mesopelagic.« less

How do local and remote processes affect the distribution of iron in the Atlantic Ocean?

NASA Astrophysics Data System (ADS)

Tagliabue, A.; Boyd, P.; Rijkenberg, M. J. A.; Williams, R. G.

2016-02-01

Iron (Fe) plays an important role in governing the magnitudes and patterns of primary productivity, nitrogen fixation and phytoplankton community composition across the Atlantic Ocean. Variations in the supply of Fe to surface waters across the mixed layer interface, over seasonal to annual to decadal scales, are underpinned by it's vertical profile. Traditionally, nutrient profiles are understood in terms of surface depletion and subsurface regeneration, but for Fe this is more complicated due to the role of scavenging and organic complexation by ligands, as well as subsurface sources. This means that the Fe profile may be controlled locally, by sinking, regeneration and scavenging or remotely, by the upstream conditions of subducted water masses. Subduction drives the transfer of Fe across the interface between winter mixed layer and the ocean interior, but has received little attention thus far. Via the subduction of watermasses with distinct biogeochemical signatures to low latitudes, remote processes can regulate the Atlantic Ocean Fe distribution at local scales. Specifically, the formation of mode waters with excess Fe binding ligands (positive L*) enable these waters to stabilise any Fe flux from regeneration that would otherwise be lost by scavenging. The pattern of mode water ventilation then highlights those regions of the ocean where local processes are able to influence the Fe profile. Local process that augment L*, such as the production of ligands during particle regeneration, can also interact with the larger scale ventilation signature but do not alter the main trends. By applying our framework to recent GEOTRACES datasets over the Atlantic Ocean we are able to highlight regions where the Fe profile is forced locally or remotely, thereby providing an important process-based constraint on the biogeochemical models we rely on for future projections. Furthermore, we are able to appraise how the varying influence of local and remote processes drives the degree of agreement in the vertical profiles of Fe and macronutrients, which then sets the degree of surface water Fe limitation.

Distinct Siderophores Contribute to Iron Cycling in the Mesopelagic at Station ALOHA

DOE PAGES

Bundy, Randelle M.; Boiteau, Rene M.; McLean, Craig; ...

2018-03-01

The distribution of dissolved iron (Fe), total organic Fe-binding ligands, and siderophores were measured between the surface and 400 m at Station ALOHA, a long term ecological study site in the North Pacific Subtropical Gyre. Dissolved Fe concentrations were low throughout the water column and strong organic Fe-binding ligands exceeded dissolved Fe at all depths; varying from 0.9 nmol L -1 in the surface to 1.6 nmol L -1 below 150 m. Although Fe does not appear to limit microbial production, we nevertheless found siderophores at nearly all depths, indicating some populations of microbes were responding to Fe stress. Ferrioxaminemore » siderophores were most abundant in the upper water column, with concentrations between 0.1-2 pmol L -1, while a suite of amphibactins were found below 200 m with concentrations between 0.8-11 pmol L -1. The distinct vertical distribution of ferrioxamines and amphibactins may indicate disparate strategies for acquiring Fe from dust in the upper water column and recycled organic matter in the lower water column. Amphibactins were found to have conditional stability constants (log ) ranging from 12.0-12.5, while ferrioxamines had much stronger conditional stability constants ranging from 14.0-14.4, within the range of observed L1 ligands by voltammetry. We used our data to calculate equilibrium Fe speciation at Station ALOHA to compare the relative concentration of inorganic and siderophore complexed Fe. The results indicate that the concentration of Fe bound to siderophores was up to two orders of magnitude higher than inorganic Fe, suggesting that even if less bioavailable, siderophores were nevertheless a viable pathway for Fe acquisition by microbes at our study site. Finally, we observed rapid production of ferrioxamine E by particle-associated bacteria during incubation of freshly collected sinking organic matter. Fe-limitation may therefore be a factor in regulating carbon metabolism and nutrient regeneration in the mesopelagic.« less

Coordination modes of tyrosinate-ligated catalase-type heme enzymes: magnetic circular dichroism studies of Plexaura homomalla allene oxide synthase, Mycobacterium avium ssp. paratuberculosis protein-2744c, and bovine liver catalase in their ferric and ferrous states.

PubMed

Bandara, D M Indika; Sono, Masanori; Bruce, Grant S; Brash, Alan R; Dawson, John H

2011-12-01

Bovine liver catalase (BLC), catalase-related allene oxide synthase (cAOS) from Plexaura homomalla, and a recently isolated protein from the cattle pathogen Mycobacterium avium ssp. paratuberculosis (MAP-2744c (MAP)) are all tyrosinate-ligated heme enzymes whose crystal structures have been reported. cAOS and MAP have low (<20%) sequence similarity to, and significantly different catalytic functions from, BLC. cAOS transforms 8R-hydroperoxy-eicosatetraenoic acid to an allene epoxide, whereas the MAP protein is a putative organic peroxide-dependent peroxidase. To elucidate factors influencing the functions of these and related heme proteins, we have investigated the heme iron coordination properties of these tyrosinate-ligated heme enzymes in their ferric and ferrous states using magnetic circular dichroism and UV-visible absorption spectroscopy. The MAP protein shows remarkable spectral similarities to cAOS and BLC in its native Fe(III) state, but clear differences from ferric proximal heme ligand His93Tyr Mb (myoglobin) mutant, which may be attributed to the presence of an Arg(+)-N(ω)-H···¯O-Tyr (proximal heme axial ligand) hydrogen bond in the first three heme proteins. Furthermore, the spectra of Fe(III)-CN¯, Fe(III)-NO, Fe(II)-NO (except for five-coordinate MAP), Fe(II)-CO, and Fe(II)-O(2) states of cAOS and MAP, but not H93Y Mb, are also similar to the corresponding six-coordinate complexes of BLC, suggesting that a tyrosinate (Tyr-O¯) is the heme axial ligand trans to the bound ligands in these complexes. The Arg(+)-N(ω)-H to ¯O-Tyr hydrogen bond would be expected to modulate the donor properties of the proximal tyrosinate oxyanion and, combined with the subtle differences in the catalytic site structures, affect the activities of cAOS, MAP and BLC. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis of [Fe(Leq)(Lax)] n coordination polymer nanoparticles using blockcopolymer micelles.

PubMed

Göbel, Christoph; Klimm, Ottokar; Puchtler, Florian; Rosenfeldt, Sabine; Förster, Stephan; Weber, Birgit

2017-01-01

Spin-crossover compounds are a class of materials that can change their spin state from high spin (HS) to low spin (LS) by external stimuli such as light, pressure or temperature. Applications demand compounds with defined properties concerning the size and switchability that are maintained when the compound is integrated into composite materials. Here, we report the synthesis of [Fe(L eq )(L ax )] n coordination polymer (CP) nanoparticles using self-assembled polystyrene- block -poly(4-vinylpyridine) (PS- b -P4VP) block copolymer (BCP) micelles as template. Variation of the solvent (THF and toluene) and the rigidity of the axial ligand L ax (L ax = 1,2-di(pyridin-4-yl)ethane) (bpea), trans -1,2-di(pyridin-4-yl)ethene (bpee), and 1,2-di(pyridin-4-yl)ethyne) (bpey); L eq = 1,2-phenylenebis(iminomethylidyne)-bis(2,4-pentanedionato)(2-)) allowed the determination of the preconditions for the selective formation of nanoparticles. A low solubility of the CP in the used solvent and a high stability of the Fe-L bond with regard to ligand exchange are necessary for the formation of composite nanoparticles where the BCP micelle is filled with the CP, as in the case of the [FeL eq (bpey)] n @BCP. Otherwise, in the case of more flexible ligands or ligands that lead to high spin complexes, the formation of microcrystals next to the CP-BCP nanoparticles is observed above a certain concentration of [Fe(L eq )(L ax )] n . The core of the nanoparticles is about 45 nm in diameter due to the templating effect of the BCP micelle, independent of the used iron complex and [Fe(L eq )(L ax )] n concentration. The spin-crossover properties of the composite material are similar to those of the bulk for FeL eq (bpea)] n @BCP while pronounced differences are observed in the case of [FeL eq (bpey)] n @BCP nanoparticles.

Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some binuclear transition metal complexes of bicompartmental ONO donor ligands containing benzo[b]thiophene moiety

NASA Astrophysics Data System (ADS)

Mahendra Raj, K.; Vivekanand, B.; Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

2014-02-01

A series of new binucleating Cu(II), Co(II), Ni(II) and Zn(II) complexes of bicompartmental ligands with ONO donor were synthesized. The ligands were obtained by the condensation of 3-chloro-6-substituted benzo[b]thiophene-2-carbohydrazides and 4,6-diacetylresorcinol. The synthesized ligands and their complexes were characterized by elemental analysis and various spectroscopic techniques. Elemental analysis, IR, 1H NMR, ESI-mass, UV-Visible, TG-DTA, magnetic measurements, molar conductance and powder-XRD data has been used to elucidate their structures. The bonding sites are the oxygen atom of amide carbonyl, azomethine nitrogen and phenolic oxygen for ligands 1 and 2. The binuclear nature of the complexes was confirmed by ESR spectral data. TG-DTA studies for some complexes showed the presence of coordinated water molecules and the final product is the metal oxide. All the complexes were investigated for their electrochemical activity, only the Cu(II) complexes showed the redox property. Cu(II) complexes were square planar, whereas Co(II), Ni(II) and Zn(II) complexes were octahedral. Powder-XRD pattern have been studied in order to test the degree of crystallinity of the complexes and unit cell calculations were made. In order to evaluate the effect of antimicrobial activity of metal ions upon chelation, both the ligands and their metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The results showed that the metal complexes were found to be more active than free ligands. The DNA cleaving capacities of all the complexes were analyzed by agarose gel electrophoresis method against supercoiled plasmid DNA. Among the compounds tested for antioxidant capacity, ligand 1 displayed excellent activity than its metal complexes.

Sulfide Oxidation by O2: Synthesis, Structure and Reactivity of Novel Sulfide-Incorporated Fe(II) Bis(imino)pyridine Complexes

PubMed Central

Widger, Leland R.; Siegler, Maxime A.

2013-01-01

The unsymmetrical iron(II) bis(imino)pyridine complexes [FeII(LN3SMe)(H2O)3](OTf)2 (1), and [FeII(LN3SMe)Cl2] (2) were synthesized and their reactivity with O2 was examined. Complexes 1 and 2 were characterized by single crystal X-ray crystallography, LDI-MS, 1H-NMR and elemental analysis. The LN3SMe ligand was designed to incorporate a single sulfide donor and relies on the bis(imino)pyridine scaffold. This scaffold was selected for its ease of synthesis and its well-precedented ability to stabilize Fe(II) ions. Complexes 1 and 2 ware prepared via a metal-assisted template reaction from the unsymmetrical pyridyl ketone precursor 2-(O=CMe)-6-(2,6-(iPr2-C6H3N=CMe)-C5H3N. Reaction of 1 with O2 was shown to afford the S-oxygenated sulfoxide complex [Fe(LN3S(O)Me)(OTf)]2+(3), whereas compound 2, under the same reaction conditions, afforded the corresponding sulfone complex [Fe(LN3S(O2)Me)Cl]2+ (4). PMID:23878411

Kinetic and equilibrium studies of acrylonitrile binding to cytochrome c peroxidase and oxidation of acrylonitrile by cytochrome c peroxidase compound I.

PubMed

Chinchilla, Diana; Kilheeney, Heather; Vitello, Lidia B; Erman, James E

2014-01-03

Ferric heme proteins bind weakly basic ligands and the binding affinity is often pH dependent due to protonation of the ligand as well as the protein. In an effort to find a small, neutral ligand without significant acid/base properties to probe ligand binding reactions in ferric heme proteins we were led to consider the organonitriles. Although organonitriles are known to bind to transition metals, we have been unable to find any prior studies of nitrile binding to heme proteins. In this communication we report on the equilibrium and kinetic properties of acrylonitrile binding to cytochrome c peroxidase (CcP) as well as the oxidation of acrylonitrile by CcP compound I. Acrylonitrile binding to CcP is independent of pH between pH 4 and 8. The association and dissociation rate constants are 0.32±0.16 M(-1) s(-1) and 0.34±0.15 s(-1), respectively, and the independently measured equilibrium dissociation constant for the complex is 1.1±0.2 M. We have demonstrated for the first time that acrylonitrile can bind to a ferric heme protein. The binding mechanism appears to be a simple, one-step association of the ligand with the heme iron. We have also demonstrated that CcP can catalyze the oxidation of acrylonitrile, most likely to 2-cyanoethylene oxide in a "peroxygenase"-type reaction, with rates that are similar to rat liver microsomal cytochrome P450-catalyzed oxidation of acrylonitrile in the monooxygenase reaction. CcP compound I oxidizes acrylonitrile with a maximum turnover number of 0.61 min(-1) at pH 6.0. Copyright © 2013 Elsevier Inc. All rights reserved.

Kinetic and equilibrium studies of acrylonitrile binding to cytochrome c peroxidase and oxidation of acrylonitrile by cytochrome c peroxidase compound I

PubMed Central

Chinchilla, Diana; Kilheeney, Heather; Vitello, Lidia B.; Erman, James E.

2013-01-01

Ferric heme proteins bind weakly basic ligands and the binding affinity is often pH dependent due to protonation of the ligand as well as the protein. In an effort to find a small, neutral ligand without significant acid/base properties to probe ligand binding reactions in ferric heme proteins we were led to consider the organonitriles. Although organonitriles are known to bind to transition metals, we have been unable to find any prior studies of nitrile binding to heme proteins. In this communication we report on the equilibrium and kinetic properties of acrylonitrile binding to cytochrome c peroxidase (CcP) as well as the oxidation of acrylonitrile by CcP compound I. Acrylonitrile binding to CcP is independent of pH between pH 4 and 8. The association and dissociation rate constants are 0.32 ± 0.16 M−1s−1 and 0.34 ± 0.15 s−1, respectively, and the independently measured equilibrium dissociation constant for the complex is 1.1 ± 0.2 M. We have demonstrated for the first time that acrylonitrile can bind to a ferric heme protein. The binding mechanism appears to be a simple, one-step association of the ligand with the heme iron. We have also demonstrated that CcP can catalyze the oxidation of acrylonitrile, most likely to 2-cyanoethylene oxide in a “peroxygenase”-type reaction, with rates that are similar to rat liver microsomal cytochrome P450-catalyzed oxidation of acrylonitrile in the monooxygenase reaction. CcP compound I oxidizes acrylonitrile with a maximum turnover number of 0.61 min−1 at pH 6.0. PMID:24291498

River-derived humic substances as iron chelators in seawater

PubMed Central

Krachler, Regina; Krachler, Rudolf F.; Wallner, Gabriele; Hann, Stephan; Laux, Monika; Cervantes Recalde, Maria F.; Jirsa, Franz; Neubauer, Elisabeth; von der Kammer, Frank; Hofmann, Thilo; Keppler, Bernhard K.

2015-01-01

The speciation of iron(III) in oxic seawater is dominated by its hydrolysis and sedimentation of insoluble iron(III)-oxyhydroxide. As a consequence, many oceanic areas have very low iron levels in surface seawater which leads to iron deficiency since phytoplankton require iron as a micronutrient in order to grow. Fortunately, iron solubility is not truly as low as Fe(III) solubility measurements in inorganic seawater would suggest, since oceanic waters contain organic molecules which tend to bind the iron and keep it in solution. Various iron-binding organic ligands which combine to stabilize dissolved iron have been detected and thoroughly investigated in recent years. However, the role of iron-binding ligands from terrestrial sources remains poorly constrained. Blackwater rivers supply large amounts of natural organic material (NOM) to the ocean. This NOM (which consists mainly of vascular plant-derived humic substances) is able to greatly enhance iron bioavailability in estuaries and coastal regions, however, breakdown processes lead to a rapid decrease of river-derived NOM concentrations with increasing distance from land. It has therefore been argued that the influence of river-derived NOM on iron biogeochemistry in offshore seawater does not seem to be significant. Here we used a standard method based on 59Fe as a radiotracer to study the solubility of Fe(III)-oxyhydroxide in seawater in the presence of riverine NOM. We aimed to address the question how effective is freshwater NOM as an iron chelator under open ocean conditions where the concentration of land-derived organic material is about 3 orders of magnitude smaller than in coastal regions, and does this iron chelating ability vary between NOM from different sources and between different size fractions of the river-borne NOM. Our results show that the investigated NOM fractions were able to substantially enhance Fe(III)-oxyhydroxide solubility in seawater at concentrations of the NOM ≥ 5 μg L− 1. Terrigenous NOM concentrations ≥ 5 μg L− 1 are in no way unusual in open ocean surface waters especially of the Arctic and the North Atlantic Oceans. River-derived humic substances could therefore play a greater role as iron carriers in the ocean than previously thought. PMID:26412934

Chemodynamics of aquatic metal complexes: from small ligands to colloids.

PubMed

Van Leeuwen, Herman P; Buffle, Jacques

2009-10-01

Recent progress in understanding the formation/dissociation kinetics of aquatic metal complexes with complexants in different size ranges is evaluated and put in perspective, with suggestions for further studies. The elementary steps in the Eigen mechanism, i.e., diffusion and dehydration of the metal ion, are reviewed and further developed. The (de)protonation of both the ligand and the coordinating metal ion is reconsidered in terms of the consequences for dehydration rates and stabilities of the various outer-sphere complexes. In the nanoparticulate size range, special attention is given to the case of fulvic ligands, for which the impact of electrostatic interactions is especially large. In complexation with colloidal ligands (hard, soft, and combination thereof) the diffusive transport of metal ions is generally a slower step than in the case of complexation with small ligands in a homogeneous solution. The ensuing consequences for the chemodynamics of colloidal complexes are discussed in detail and placed in a generic framework, encompassing the complete range of ligand sizes.

Synthesis, spectroscopic, DFT studies and biological activity of some ruthenium carbonyl derivatives of bis-(salicylaldehyde)phenylenediimine Schiff base ligand

NASA Astrophysics Data System (ADS)

Ramadan, Ramadan M.; Abu Al-Nasr, Ahmad K.; Ali, Omayma A. M.

2018-06-01

Bis-(salicylaldehyde)phenylenediimine Schiff base (H2salphen) reacted oxidatively with the triruthenium dodecacarbonyl complex, [Ru3(CO)12] to give the dicarbonyl derivative [Ru(CO)2(salphen)], 1. In presence of a secondary ligand L (L = pyridine, triphenyl phosphine, 2-aminobenzimidazole or thiourea), the monocarbonyl derivatives [Ru(CO)(salphen)L], 2-5, were isolated. When the bipyridine (bpy) ligand was used as a secondary ligand, the dicarbonyl complex [Ru(CO)2(Hsalphen)(bpy)], 6, was obtained. In complexes 1-5, the Schiff base ligand acted as a tetradentate, while it coordinated as a bidentate in complex 6. The structure and stoichiometry of the complexes were investigated by the conventional analytical and spectroscopic techniques, which revealed that they have several structural arrangements. The structures of ligand and complexes were verified by theoretical calculations based on accurate DFT approximations. The relative reactivities were estimated using chemical descriptors analysis. Biological activities of the complexes against the Escherchia coli and Staphylococcus aureus bacteria were screened.

Optical spectroscopy of nanoscale and heterostructured oxides

NASA Astrophysics Data System (ADS)

Senty, Tess R.

Through careful analysis of a material's properties, devices are continually getting smaller, faster and more efficient each day. Without a complete scientific understanding of material properties, devices cannot continue to improve. This dissertation uses optical spectroscopy techniques to understand light-matter interactions in several oxide materials with promising uses mainly in light harvesting applications. Linear absorption, photoluminescence and transient absorption spectroscopy are primarily used on europium doped yttrium vanadate nanoparticles, copper gallium oxide delafossites doped with iron, and cadmium selenide quantum dots attached to titanium dioxide nanoparticles. Europium doped yttrium vanadate nanoparticles have promising applications for linking to biomolecules. Using Fourier-transform infrared spectroscopy, it was shown that organic ligands (benzoic acid, 3-nitro 4-chloro-benzoic acid and 3,4-dihydroxybenzoic acid) can be attached to the surface of these molecules using metal-carboxylate coordination. Photoluminescence spectroscopy display little difference in the position of the dominant photoluminescence peaks between samples with different organic ligands although there is a strong decrease in their intensity when 3,4-dihydroxybenzoic acid is attached. It is shown that this strong quenching is due to the presence of high-frequency hydroxide vibrational modes within the organic linker. Ultraviolet/visible linear absorption measurements on delafossites display that by doping copper gallium oxide with iron allows for the previously forbidden fundamental gap transition to be accessed. Using tauc plots, it is shown that doping with iron lowers the bandgap from 2.8 eV for pure copper gallium oxide, to 1.7 eV for samples with 1 -- 5% iron doping. Using terahertz transient absorption spectroscopy measurements, it was also determined that doping with iron reduces the charge mobility of the pure delafossite samples. A comparison of cadmium selenide quantum dots, both with and without capping ligands, attached to titanium dioxide nanoparticles is performed using a new transient absorption analysis technique. Multiple exponential fit models were applied to the system and compared with the new inversion analysis technique. It is shown how the new inversion analysis can map out the charge carrier dynamics, providing carrier recombination rates and lifetimes as a function of carrier concentration, where the multiple exponential fit technique is not dependent on the carrier concentration. With the inversion analysis technique it is shown that capping ligands allow for increased charge transfer due to traps being passivated on the quantum dot surface.

Bioactive ruthenium(II)-arene complexes containing modified 18β-glycyrrhetinic acid ligands.

PubMed

Kong, Yaqiong; Chen, Feng; Su, Zhi; Qian, Yong; Wang, Fang-Xin; Wang, Xiuxiu; Zhao, Jing; Mao, Zong-Wan; Liu, Hong-Ke

2018-05-01

Metal-arene complexes containing bioactive natural-product derived ligands can have new and unusual properties. We report the synthesis, characterization and antiproliferative activity of two new Ru(II) arene complexes with imidazole (dichlorido complex 1) or bipyridyl (chlorido complex 2) ligands conjugated to 18β-glycyrrhetinic acid, an active triterpenoid metabolite of Glycyrrhiza glabra. In general, the conjugated ligands and complexes showed only moderate activity against HeLa (cervical), MCF-7 (breast) and A2780 (ovarian) cancer cells, although the activity of complex 2 in the former two cell lines approached that of the drug cisplatin. Complex 2 (in contrast to complex 1) also exhibited significant activity towards both Gram-positive S. aureus and Gram-negative E. coil bacteria. Complex 2 can induce condensation of DNA and enhances the generation of intracellular reactive oxygen species (ROS). The conjugation of natural products to ligands in organometallic half-sandwich complexes provides a strategy to enhance their biological activities. Copyright © 2018 Elsevier Inc. All rights reserved.

Synthesis and photoluminescence properties of novel Schiff base type polymer-rare earth complexes containing furfural-based bidentate Schiff base ligands

NASA Astrophysics Data System (ADS)

Gao, Baojiao; Zhang, Dandan; Li, Yanbin

2018-03-01

Luminescent polymer-rare earth complexes are an important class of photoluminescence and electroluminescence materials. Via molecular design, two furfural-based bidentate Schiff base ligands, furfural-aniline (FA) type ligand and furfural-cyclohexylamine (FC) type ligand, were bonded on the side chains of polysulfone (PSF), respectively, forming two functionalized macromolecules, PSF-FA and PSF-FC. And then through respective coordination reactions of the two functionalized macromolecules with Eu(Ⅲ) ion and Tb(Ⅲ) ion, novel luminescent binary and ternary (with 1,10-phenanthroline as the second ligand) polymer-rare earth complexes were synthesized. For these complexes, on basis of the characterization of their chemical structures, they photoluminescence properties were main researched, and the relationship between their luminescent properties and structures was explored. The experimental results show that the complexes coming from PSF-FA and Eu(Ⅲ) ion including binary and ternary complexes emit strong red luminescence, indicating that the bonded bidentate Schiff base ligand FA can sensitize the fluorescence emission of Eu(III) ion. While the complexes coming from PSF-FC and Tb(Ⅲ) ion produce green luminescence, displaying that the bonded bidentate Schiff base ligand FC can sensitize the fluorescence emission of Tb(Ⅲ) ion. The fluorescence emission intensities of the ternary complexes were stronger than that of binary complexes, reflecting the important effect of the second ligand. The fluorescence emission of the solid film of complexes is much stronger than that of the solutions of complexes. Besides, by comparison, it is found that the furfural (as a heteroaromatic compound)-based Schiff base type polymer-rare earth complexes have stronger fluorescence emission and higher energy transfer efficiency than salicylaldehyde (as a common aromatic compound)-based Schiff base type polymer-rare earth complexes.

Investigation of the Iron(II) Release Mechanism of Human H-Ferritin as a Function of pH.

PubMed

Sala, Davide; Ciambellotti, Silvia; Giachetti, Andrea; Turano, Paola; Rosato, Antonio

2017-09-25

We investigated the kinetics of the release of iron(II) ions from the internal cavity of human H-ferritin as a function of pH. Extensive molecular dynamics simulations of the entire 24-mer ferritin provided atomic-level information on the release mechanism. Double protonation of His residues at pH 4 facilitates the removal of the iron ligands within the C3 channel through the formation of salt bridges, resulting in a significantly lower release energy barrier than pH 9.

Impact of iron chelators on short-term dissolution of basaltic glass

NASA Astrophysics Data System (ADS)

Perez, Anne; Rossano, Stéphanie; Trcera, Nicolas; Verney-Carron, Aurélie; Huguenot, David; van Hullebusch, Eric D.; Catillon, Gilles; Razafitianamaharavo, Angelina; Guyot, François

2015-08-01

Although microorganisms seem to play an important role in the alteration processes of basaltic glasses in solution, the elementary mechanisms involved remain unclear in particular with regard to the role of organic ligands excreted by the cells. Two glasses, one with Fe and one without Fe were synthesized to model basaltic glass compositions. Fe in the glass was mostly Fe(III) for enhancing interaction with siderophores, yet with small but significant amounts of Fe(II) (between 10% and 30% of iron). The prepared samples were submitted to abiotic alteration experiments in buffered (pH 6.4) diluted solutions of metal-specific ligands, namely oxalic acid (OA, 10 mM), desferrioxamine (DFA, 1 mM) or 2,2‧-bipyridyl (BPI, 1 mM). Element release from the glass into the solution after short term alteration (maximum 1 week) was measured by ICP-OES, and normalized mass losses and relative release ratios (with respect to Si) were evaluated for each element in each experimental condition. The presence of organic ligands had a significant effect on the dissolution of both glasses. Trivalent metals chelators (OA, DFA) impacted on the release of Fe3+ and Al3+, and thus on the global dissolution of both glasses, enhancing all release rates and dissolution stoichiometry (release rates were increased up to 7 times for Al or Fe). As expected, the mostly divalent metal chelator BPI interacted preferentially with Ca2+, Mg2+ and Fe2+. This study thus allows to highlight the central roles of iron and aluminium in interaction with some organic ligands in the alteration processes of basaltic glasses. It thus provides a step toward understanding the biological contribution of this fundamental geological process.

Synthesis of ligand-stabilized metal oxide nanocrystals and epitaxial core/shell nanocrystals via a lower-temperature esterification process.

PubMed

Ito, Daisuke; Yokoyama, Shun; Zaikova, Tatiana; Masuko, Keiichiro; Hutchison, James E

2014-01-28

The properties of metal oxide nanocrystals can be tuned by incorporating mixtures of matrix metal elements, adding metal ion dopants, or constructing core/shell structures. However, high-temperature conditions required to synthesize these nanocrystals make it difficult to achieve the desired compositions, doping levels, and structural control. We present a lower temperature synthesis of ligand-stabilized metal oxide nanocrystals that produces crystalline, monodisperse nanocrystals at temperatures well below the thermal decomposition point of the precursors. Slow injection (0.2 mL/min) of an oleic acid solution of the metal oleate complex into an oleyl alcohol solvent at 230 °C results in a rapid esterification reaction and the production of metal oxide nanocrystals. The approach produces high yields of crystalline, monodisperse metal oxide nanoparticles containing manganese, iron, cobalt, zinc, and indium within 20 min. Synthesis of tin-doped indium oxide (ITO) can be accomplished with good control of the tin doping levels. Finally, the method makes it possible to perform epitaxial growth of shells onto nanocrystal cores to produce core/shell nanocrystals.

Tantallacyclopentadiene as a unique metal-containing diene ligand coordinated to nickel for preparing tantalum-nickel heterobimetallic complexes.

PubMed

Laskar, Payel; Yamamoto, Keishi; Srinivas, Anga; Mifleur, Alexis; Nagae, Haruki; Tsurugi, Hayato; Mashima, Kazushi

2017-10-03

A mononuclear tantallacyclopentadiene complex, TaCl 3 (C 4 H 2 tBu 2 ) (3), serves as a unique ligand to nickel: the addition of Ni(COD) 2 to 3 selectively afforded heterobimetallic Ta-Ni complex 4. The cyclooctadiene ligand bound to the nickel center in complex 4 was readily substituted by monodentate and bidentate phosphine ligands, such as dimethylphenylphosphine, 1,2-bis(diphenylphosphino)ethane, and 1,2-bis(diethylphosphino)ethane, to give the corresponding phosphine complexes 5, 6a, and 6b. We also examined a ligand substitution reaction with 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) to produce the corresponding Ta-Ni complex 7. These newly prepared Ta-Ni heterobimetallic complexes were characterized spectroscopically together with the crystal structures of 4, 6a, and 7.

Composition, Characterization and Antibacterial activity of Mn(II), Co(II),Ni(II), Cu(II) Zn(II) and Cd(II) mixed ligand complexes Schiff base derived from Trimethoprim with 8-Hydroxy quinoline

NASA Astrophysics Data System (ADS)

Numan, Ahmed T.; Atiyah, Eman M.; Al-Shemary, Rehab K.; Ulrazzaq, Sahira S. Abd

2018-05-01

New Schiff base ligand 2-((4-amino-5-(3, 4, 5-trimethoxybenzyl) pyrimidin-2-ylimino) (phenyl)methyl)benzoic acid] = [HL] was synthesized using microwave irradiation trimethoprim and 2-benzoyl benzoic acid. Mixed ligand complexes of Mn((II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) are reacted in ethanol with Schiff base ligand [HL] and 8-hydroxyquinoline [HQ] then reacted with metal salts in ethanol as a solvent in (1:1:1) ratio. The ligand [HL] is characterized by FTIR, UV-Vis, melting point, elemental microanalysis (C.H.N), 1H-NMR, 13C-NMR, and mass spectra. The mixed ligand complexes are characterized by infrared spectra, electronic spectra, (C.H.N), melting point, atomic absorption, molar conductance and magnetic moment measurements. These measurements indicate that the ligand [HL] coordinates with metal (II) ion in a tridentate manner through the oxygen and nitrogen atoms of the ligand, octahedral structures are suggested for these complexes. Antibacterial activity of the ligands [HL], [HQ] and their complexes are studied against (gram positive) and (gram negative) bacteria.

Effect of the ortho-Hydroxyl Groups on a Bipyridine Ligand of Iridium Complexes for the High-Pressure Gas Generation from the Catalytic Decomposition of Formic Acid.

PubMed

Iguchi, Masayuki; Zhong, Heng; Himeda, Yuichiro; Kawanami, Hajime

2017-12-14

The hydroxyl groups of a 2,2'-bipyridine (bpy) ligand near the metal center activated the catalytic performance of the Ir complex for the dehydrogenation of formic acid at high pressure. The position of the hydroxyl groups on the ligand affected the catalytic durability for the high-pressure H 2 generation through the decomposition of formic acid. The Ir complex with a bipyridine ligand functionalized with para-hydroxyl groups shows a good durability with a constant catalytic activity during the reaction even under high-pressure conditions, whereas deactivation was observed for an Ir complex with a bipyridine ligand with ortho-hydroxyl groups (2). In the presence of high-pressure H 2 , complex 2 decomposed into the ligand and an Ir trihydride complex through the isomerization of the bpy ligand. This work provides the development of a durable catalyst for the high-pressure H 2 production from formic acid. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water-dispersible sugar-coated iron oxide nanoparticles. An evaluation of their relaxometric and magnetic hyperthermia properties.

PubMed

Lartigue, Lenaic; Innocenti, Claudia; Kalaivani, Thangavel; Awwad, Azzam; Sanchez Duque, Maria del Mar; Guari, Yannick; Larionova, Joulia; Guérin, Christian; Montero, Jean-Louis Georges; Barragan-Montero, Véronique; Arosio, Paolo; Lascialfari, Alessandro; Gatteschi, Dante; Sangregorio, Claudio

2011-07-13

Synthesis of functionalized magnetic nanoparticles (NPs) for biomedical applications represents a current challenge. In this paper we present the synthesis and characterization of water-dispersible sugar-coated iron oxide NPs specifically designed as magnetic fluid hyperthermia heat mediators and negative contrast agents for magnetic resonance imaging. In particular, the influence of the inorganic core size was investigated. To this end, iron oxide NPs with average size in the range of 4-35 nm were prepared by thermal decomposition of molecular precursors and then coated with organic ligands bearing a phosphonate group on one side and rhamnose, mannose, or ribose moieties on the other side. In this way a strong anchorage of the organic ligand on the inorganic surface was simply realized by ligand exchange, due to covalent bonding between the Fe(3+) atom and the phosphonate group. These synthesized nanoobjects can be fully dispersed in water forming colloids that are stable over very long periods. Mannose, ribose, and rhamnose were chosen to test the versatility of the method and also because these carbohydrates, in particular rhamnose, which is a substrate of skin lectin, confer targeting properties to the nanosystems. The magnetic, hyperthermal, and relaxometric properties of all the synthesized samples were investigated. Iron oxide NPs of ca. 16-18 nm were found to represent an efficient bifunctional targeting system for theranostic applications, as they have very good transverse relaxivity (three times larger than the best currently available commercial products) and large heat release upon application of radio frequency (RF) electromagnetic radiation with amplitude and frequency close to the human tolerance limit. The results have been rationalized on the basis of the magnetic properties of the investigated samples.

Formation mechanism and biological activity of novel thiolated human-like collagen iron complex.

PubMed

Zhu, Chenhui; Liu, Lingyun; Deng, Jianjun; Ma, Xiaoxuan; Hui, Junfeng; Fan, Daidi

2016-03-01

To develop an iron supplement that is effectively absorbed and utilized, thiolated human-like collagen was created to improve the iron binding capacity of human-like collagen. A thiolated human-like collagen-iron complex was prepared in a phosphate buffer, and one mole of thiolated human-like collagen-iron possessed approximately 28.83 moles of iron. The characteristics of thiolated human-like collagen-iron were investigated by ultraviolet-visible absorption spectroscopy, Fourier transform infrared spectroscopy, circular dichroism, and differential scanning calorimetry. The results showed that the thiolated human-like collagen-iron complex retained the secondary structure of human-like collagen and had greater thermodynamic stability than human-like collagen, although interactions between iron ions and human-like collagen occurred during the formation of the complex. In addition, to evaluate the bioavailability of thiolated human-like collagen-iron, an in vitro Caco-2 cell model and an in vivo iron deficiency anemia mouse model were employed. The data demonstrated that the thiolated human-like collagen-iron complex exhibited greater bioavailability and was more easily utilized than FeSO4, ferric ammonium citrate, or ferrous glycinate. These results indicated that the thiolated human-like collagen-iron complex is a potential iron supplement in the biomedical field. © The Author(s) 2016.

Chromium metal organic frameworks and synthesis of metal organic frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hong-Cai; Liu, Tian-Fu; Lian, Xizhen

The present invention relates to monocrystalline metal organic frameworks comprising chromium ions and carboxylate ligands and the use of the same, for example their use for storing a gas. The invention also relates to methods for preparing metal organic frameworks comprising chromium, titanium or iron ions and carboxylate ligands. The methods of the invention allow such metal organic frameworks to be prepared in monocrystalline or polycrystalline forms.

Targeting multiple types of tumors using NKG2D-coated iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Wu, Ming-Ru; Cook, W. James; Zhang, Tong; Sentman, Charles L.

2014-11-01

Iron oxide nanoparticles (IONPs) hold great potential for cancer therapy. Actively targeting IONPs to tumor cells can further increase therapeutic efficacy and decrease off-target side effects. To target tumor cells, a natural killer (NK) cell activating receptor, NKG2D, was utilized to develop pan-tumor targeting IONPs. NKG2D ligands are expressed on many tumor types and its ligands are not found on most normal tissues under steady state conditions. The data showed that mouse and human fragment crystallizable (Fc)-fusion NKG2D (Fc-NKG2D) coated IONPs (NKG2D/NPs) can target multiple NKG2D ligand positive tumor types in vitro in a dose dependent manner by magnetic cell sorting. Tumor targeting effect was robust even under a very low tumor cell to normal cell ratio and targeting efficiency correlated with NKG2D ligand expression level on tumor cells. Furthermore, the magnetic separation platform utilized to test NKG2D/NP specificity has the potential to be developed into high throughput screening strategies to identify ideal fusion proteins or antibodies for targeting IONPs. In conclusion, NKG2D/NPs can be used to target multiple tumor types and magnetic separation platform can facilitate the proof-of-concept phase of tumor targeting IONP development.

Redox chemistry of nickel(II) complexes supported by a series of noninnocent β-diketiminate ligands.

PubMed

Takaichi, June; Morimoto, Yuma; Ohkubo, Kei; Shimokawa, Chizu; Hojo, Takayuki; Mori, Seiji; Asahara, Haruyasu; Sugimoto, Hideki; Fujieda, Nobutaka; Nishiwaki, Nagatoshi; Fukuzumi, Shunichi; Itoh, Shinobu

2014-06-16

Nickel complexes of a series of β-diketiminate ligands ((R)L(-), deprotonated form of 2-substituted N-[3-(phenylamino)allylidene]aniline derivatives (R)LH, R = Me, H, Br, CN, and NO2) have been synthesized and structurally characterized. One-electron oxidation of the neutral complexes [Ni(II)((R)L(-))2] by AgSbF6 or [Ru(III)(bpy)3](PF6)3 (bpy = 2,2'-bipyridine) gave the corresponding metastable cationic complexes, which exhibit an EPR spectrum due to a doublet species (S = 1/2) and a characteristic absorption band in near IR region ascribable to a ligand-to-ligand intervalence charge-transfer (LLIVCT) transition. DFT calculations have indicated that the divalent oxidation state of nickel ion (Ni(II)) is retained, whereas one of the β-diketiminate ligands is oxidized to give formally a mixed-valence complex, [Ni(II)((R)L(-))((R)L(•))](+). Thus, the doublet spin state of the oxidized cationic complex can be explained by taking account of the antiferromagnetic interaction between the high-spin nickel(II) ion (S = 1) and the organic radical (S = 1/2) of supporting ligand. A single-crystal structure of one of the cationic complexes (R = H) has been successfully determined to show that both ligands in the cationic complex are structurally equivalent. On the basis of theoretical analysis of the LLIVCT band and DFT calculations as well as the crystal structure, the mixed-valence complexes have been assigned to Robin-Day class III species, where the radical spin is equally delocalized between the two ligands to give the cationic complex, which is best described as [Ni(II)((R)L(0.5•-))2](+). One-electron reduction of the neutral complexes with decamethylcobaltocene gave the anionic complexes when the ligand has the electron-withdrawing substituent (R = CN, NO2, Br). The generated anionic complexes exhibited EPR spectra due to a doublet species (S = 1/2) but showed no LLIVCT band in the near-IR region. Thus, the reduced complexes are best described as the d(9) nickel(I) complexes supported by two anionic β-diketiminate ligands, [Ni(I)((R)L(-))2](-). This conclusion was also supported by DFT calculations. Substituent effects on the electronic structures of the three oxidation states (neutral, cationic, and anionic) of the complexes are systematically evaluated on the basis of DFT calculations.

Synthesis, spectroscopic, coordination and biological activities of some organometallic complexes derived from thio-Schiff base ligands

NASA Astrophysics Data System (ADS)

Abou-Hussein, Azza A.; Linert, Wolfgang

2014-01-01

Two series of mono- and binuclear complexes cyclic or acyclic thio-ferocine Schiff base ligands, derived from the condensation of 2-aminobenzenthiol (L) with monoacetyl ferrocene in the molar ratio 1:1 or in the molar ratio 1:2 for diacetyl ferocine have been prepared. The condensation reactions yield the corresponding Schiff Base ligands, HLa-Maf and H2Lb-Daf. The chelation of the ligands to metal ions occurs through the sulfur of the thiol group as well as the nitrogen atoms of the azomethine group of the ligands. HLa-Maf acts as monobasic bidentate or dibasic tetradentate, while H2Lb-Daf behaves as twice negatively cargend tetradentate ligand. The structures of these ligands were elucidated by elemental analysis, infrared, ultraviolet-visible spectra, as well as 1H NMR spectra. Reactions of the Schiff bases ligands with ruthenium(III), oxovanadium(IV) and dioxouranium(VI) afforded the corresponding transition metal complexes. The properties of the newly prepared complexes were analyse by elemental analyses, infrared, electronic spectra, 1H NMR as well as the magnetic susceptibility and conductivity measurement. The metal complexes exhibits different geometrical arrangements such as octahedral and square pyramidal coordination. Schiff base ligands and their metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi to study their biological activity. All the complexes exhibit antibacterial and antifungal activities against these organisms.

Studies on Cu(II) ternary complexes involving an aminopenicillin drug and imidazole containing ligands

NASA Astrophysics Data System (ADS)

Regupathy, Sthanumoorthy; Nair, Madhavan Sivasankaran

2010-02-01

Equilibrium studies on the ternary complex systems involving ampicillin (amp) as ligand (A) and imidazole containing ligands viz., imidazole (Him), benzimidazole (Hbim), histamine (Hist) and histidine (His) as ligands (B) at 37 °C and I = 0.15 mol dm -3 (NaClO 4) show the presence of CuABH, CuAB and CuAB 2. The proton in the CuABH species is attached to ligand A. In the ternary complexes the ligand, amp(A) binds the metal ion via amino nitrogen and carbonyl oxygen atom. The CuAB (B = Hist/His)/CuAB 2 (B = Him/Hbim) species have also been isolated and the analytical data confirmed its formation. Non-electrolytic behavior and monomeric type of chelates have been assessed from their low conductance and magnetic susceptibility values. The electronic and vibrational spectral results were interpreted to find the mode of binding of ligands to metal and geometry of the complexes. This is also supported by the g tensor values calculated from ESR spectra. The thermal behaviour of complexes were studied by TGA/DTA. The redox behavior of the complexes has been studied by cyclic voltammetry. The antimicrobial activity and CT DNA cleavage study of the complexes show higher activity for ternary complexes.

Significance of the concentration of chelating ligands on Fe3+-solubility, bioavailability, and uptake in rice plant.

PubMed

Hasegawa, Hiroshi; Rahman, M Mamunur; Kadohashi, Kouta; Takasugi, Yui; Tate, Yousuke; Maki, Teruya; Rahman, M Azizur

2012-09-01

Present study investigated the significance of the concentration of chelating ligand on Fe(3+)-solubility in growth medium and its influence on Fe bioavailability and uptake in rice plant. Rice seedlings were grown in modified Murashige and Skoog (MS) hydroponic growth medium with moderate (250 μM) and high (500 μM) concentrations of ethylenediaminetetraacetate (EDTA) and hydroxyiminodisuccinate (HIDS) under sterile and non-sterile conditions. Concentrations of soluble Fe in the growth medium increased with increasing ligand concentrations, and the growth of rice seedlings was higher at moderate ligand concentration than at control (without chelant) and high ligand concentration. This explains the relationship between Fe solubility and bioavailability in the growth medium, and its effect on Fe uptake in rice plant. Fe exists in the growth medium predominantly as particulate (insoluble) forms at low ligand concentration, and as soluble [Fe(OH)(2+), Fe(OH)(2)(+), Fe-L complex] and apparently soluble (colloidal) forms at moderate ligand concentration. At high ligand concentration, most of the Fe(3+) in the growth medium forms soluble Fe-L complex, however, the bioavailability of Fe from Fe-L complex decreased due to lopsided complex formation equilibrium reaction (CFER) between Fe and the ligands. Also, Fe is solubilized forming stable and soluble Fe-L complex, which is then detached as less stable, but soluble and bioavailable substance(s) after (time-dependent) biodegradation. Therefore- i) ligand concentration and stability constant of Fe-L complex (K(Fe-L)) influence Fe bioavailability and uptake in rice plant, and ii) the biodegradable ligands (e.g., HIDS) would be more effective Fe fertilizer than the environmentally persistent and less biodegradable ligands (e.g., EDTA). Copyright © 2012 Elsevier Masson SAS. All rights reserved.

Determining the magnitude and direction of photoinduced ligand field switching in photochromic metal-organic complexes: molybdenum-tetracarbonyl spirooxazine complexes.

PubMed

Paquette, Michelle M; Patrick, Brian O; Frank, Natia L

2011-07-06

The ability to optically switch or tune the intrinsic properties of transition metals (e.g., redox potentials, emission/absorption energies, and spin states) with photochromic metal-ligand complexes is an important strategy for developing "smart" materials. We have described a methodology for using metal-carbonyl complexes as spectroscopic probes of ligand field changes associated with light-induced isomerization of photochromic ligands. Changes in ligand field between the ring-closed spirooxazine (SO) and ring-opened photomerocyanine (PMC) forms of photochromic azahomoadamantyl and indolyl phenanthroline-spirooxazine ligands are demonstrated through FT-IR, (13)C NMR, and computational studies of their molybdenum-tetracarbonyl complexes. The frontier molecular orbitals (MOs) of the SO and PMC forms differ considerably in both electron density distributions and energies. Of the multiple π* MOs in the SO and PMC forms of the ligands, the LUMO+1, a pseudo-b(1)-symmetry phenanthroline-based MO, mixes primarily with the Mo(CO)(4) fragment and provides the major pathway for Mo(d)→phen(π*) backbonding. The LUMO+1 is found to be 0.2-0.3 eV lower in energy in the SO form relative to the PMC form, suggesting that the SO form is a better π-acceptor. Light-induced isomerization of the photochromic ligands was therefore found to lead to changes in the energies of their frontier MOs, which in turn leads to changes in π-acceptor ability and ligand field strength. Ligand field changes associated with photoisomerizable ligands allow tuning of excited-state and ground-state energies that dictate energy/electron transfer, optical/electrical properties, and spin states of a metal center upon photoisomerization, positioning photochromic ligand-metal complexes as promising targets for smart materials.

Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands.

PubMed

Kaeser, Adrien; Mohankumar, Meera; Mohanraj, John; Monti, Filippo; Holler, Michel; Cid, Juan-José; Moudam, Omar; Nierengarten, Iwona; Karmazin-Brelot, Lydia; Duhayon, Carine; Delavaux-Nicot, Béatrice; Armaroli, Nicola; Nierengarten, Jean-François

2013-10-21

Preparation of [Cu(NN)(PP)](+) derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2-diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)](+) complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)](+) complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2](+) and [Cu(PP)2](+) complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)](+) complexes, marking the way for future developments in this field.

Rapid Hydrogen and Oxygen Atom Transfer by a High-Valent Nickel-Oxygen Species.

PubMed

Corona, Teresa; Draksharapu, Apparao; Padamati, Sandeep K; Gamba, Ilaria; Martin-Diaconescu, Vlad; Acuña-Parés, Ferran; Browne, Wesley R; Company, Anna

2016-10-05

Terminal high-valent metal-oxygen species are key reaction intermediates in the catalytic cycle of both enzymes (e.g., oxygenases) and synthetic oxidation catalysts. While tremendous efforts have been directed toward the characterization of the biologically relevant terminal manganese-oxygen and iron-oxygen species, the corresponding analogues based on late-transition metals such as cobalt, nickel or copper are relatively scarce. This scarcity is in part related to the "Oxo Wall" concept, which predicts that late transition metals cannot support a terminal oxido ligand in a tetragonal environment. Here, the nickel(II) complex (1) of the tetradentate macrocyclic ligand bearing a 2,6-pyridinedicarboxamidate unit is shown to be an effective catalyst in the chlorination and oxidation of C-H bonds with sodium hypochlorite as terminal oxidant in the presence of acetic acid (AcOH). Insight into the active species responsible for the observed reactivity was gained through the study of the reaction of 1 with ClO - at low temperature by UV-vis absorption, resonance Raman, EPR, ESI-MS, and XAS analyses. DFT calculations aided the assignment of the trapped chromophoric species (3) as a nickel-hypochlorite species. Despite the fact that the formal oxidation state of the nickel in 3 is +4, experimental and computational analysis indicate that 3 is best formulated as a Ni III complex with one unpaired electron delocalized in the ligands surrounding the metal center. Most remarkably, 3 reacts rapidly with a range of substrates including those with strong aliphatic C-H bonds, indicating the direct involvement of 3 in the oxidation/chlorination reactions observed in the 1/ClO - /AcOH catalytic system.

Mixed-ligand approach to design of heterometallic single-source precursors with discrete molecular structure.

PubMed

Lieberman, Craig M; Navulla, Anantharamulu; Zhang, Haitao; Filatov, Alexander S; Dikarev, Evgeny V

2014-05-05

Heterometallic single-source precursors for the Pb/Fe = 1:1 oxide materials, PbFe(β-dik)4 (β-dik = hexafluoroacetylacetonate (hfac, 1), acetylacetonate (acac, 2), and trifluoroacetylacetonate (tfac, 4)), have been isolated by three different solid-state synthetic methods. The crystal structures of heterometallic diketonates 1, 2, and 4 were found to contain polymeric chains built on alternating [Fe(β-dik)2] and [Pb(β-dik)2] units that are held together by bridging M-O interactions. Heterometallic precursors are highly volatile, but soluble only in coordinating solvents, in which they dissociate into solvated homometallic fragments. In order to design the heterometallic precursor with a proper metal/metal ratio and with a discrete molecular structure, we used a combination of two different diketonate ligands. Heteroleptic complex Pb2Fe2(hfac)6(acac)2 (5) has been obtained by optimized stoichiometric reaction of an addition of homo-Fe(acac)2 to heterometallic Pb2Fe(hfac)6 (3) diketonate that can be run in solution on a high scale. The combination of two ligands with electron-withdrawing and electron-donating groups allows changing the connectivity pattern within the heterometallic assembly and yields the precursor with a discrete tetranuclear structure. In accord with its molecular structure, heteroleptic complex 5 is soluble even in noncoordinating solvents and was found to retain its heterometallic structure in solution. Thermal decomposition of heterometallic precursors in air at 750 °C resulted in the target Pb2Fe2O5 oxide, a prospective multiferroic material. Prolonging the annealing time or increasing the decomposition temperature leads to another phase-pure lead-iron oxide PbFe12O19 that is a representative of the important family of magnetic hexaferrites.

An unexpected semi-hydrogenation of a ligand in the complexation of 2,7-bispyridinyl-1,8-naphthyridine with Ru3(CO)12.

PubMed

Liao, Bei-Sih; Liu, Yi-Hung; Peng, Shie-Ming; Reddy, K Rajender; Liu, Shin-Hung; Chou, Pi-Tai; Liu, Shiuh-Tzung

2014-03-07

Thermal reaction of 2,7-bis(2-pyridinyl)-l,8-naphthyridine () with Ru3(CO)12 in the presence of moisture resulted in the formation of a formate-bridged diruthenium complex [(-H3)Ru2(μ-HCOO)(CO)4] (), in which the ligand was partially hydrogenated. Complex was fully characterized by spectroscopic analyses and X-ray single crystal determination. Regarding the partially reduced ligand in , it occurs through a water-gas shift type reduction. The bridging formate ligand can be substituted by other carboxylate ligands. Physical and chemical properties of the newly prepared complexes were investigated.

Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

PubMed

Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

2014-02-15

The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

A general access to organogold(iii) complexes by oxidative addition of diazonium salts.

PubMed

Huang, Long; Rominger, Frank; Rudolph, Matthias; Hashmi, A Stephen K

2016-05-11

At room temperature under mild photochemical conditions, namely irradiation with a simple blue light LED, gold(i) chloro complexes of both phosphane and carbene ligands in combination with aryldiazonium salts afford arylgold(iii) complexes. With chelating P,N-ligands cationic six- or five-membered chelate complexes were isolated in the form of salts with weakly coordinating counter anions that were brought in from the diazonium salt. With monodentate P ligands or N-heterocyclic carbene ligands and diazonium chlorides neutral arylgold(iii) dichloro complexes were obtained. The coordination geometry was determined by X-ray crystal structure analyses of representative compounds, a cis arrangement of the aryl and the phosphane ligand at the square planar gold(iii) center is observed.