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Sample records for donor ligand formed

  1. Expansion of the Ligand Knowledge Base for Chelating P,P-Donor Ligands (LKB-PP).

    PubMed

    Jover, Jesús; Fey, Natalie; Harvey, Jeremy N; Lloyd-Jones, Guy C; Orpen, A Guy; Owen-Smith, Gareth J J; Murray, Paul; Hose, David R J; Osborne, Robert; Purdie, Mark

    2012-08-13

    We have expanded the ligand knowledge base for bidentate P,P- and P,N-donor ligands (LKB-PP, Organometallics2008, 31, 1372-1383) by 208 ligands and introduced an additional steric descriptor (nHe8). This expanded knowledge base now captures information on 334 bidentate ligands and has been processed with principal component analysis (PCA) of the descriptors to produce a detailed map of bidentate ligand space, which better captures ligand variation and has been used for the analysis of ligand properties. PMID:24882917

  2. Synthesis of ligands containing N-oxide donor atoms and their assembly into metallosupramolecular structures.

    PubMed

    Bullock, Samantha J; Harding, Lindsay P; Moore, Michelle P; Mills, Andrew; Piela, Sean A F; Rice, Craig R; Towns-Andrews, Liz; Whitehead, Martina

    2013-04-28

    A series of ligands that contain both N-donor and N-oxide donor atoms have been synthesised and ligands L5, L6, L7 and L8 contain, 4, 6, 5, and 6 donor atoms respectively. The smallest ligand L5 forms a mononuclear complex with Cu2+ ([Cu(L5)(ClO4)2(MeCN)]) whereas L6 and L7 form dinuclear double helicates with Ni2+ and Cu2+ respectively ([Ni2(L6)2]4+ and [Cu2(L7)2]4+). L8 forms a tetranuclear cyclic helicate upon reaction with Co2+ ([Co4(L8)4]8+) and in all cases the complexes are characterised by single-crystal X-ray diffraction and ESI-MS. The N-oxide units imparts flexibility in the ligand strand and where the unoxidised ligand strand forms a cyclic helicate, the incorporation of an N-oxide unit allows the formation of the dinuclear double helicate.

  3. Synthesis, spectroscopic characterization and crystal structure of novel NNNN-donor μ-bis(bidentate) tetraaza acyclic Schiff base ligands

    NASA Astrophysics Data System (ADS)

    Habibi, Mohammad Hossein; Shojaee, Elahe; Nichol, Gary S.

    2012-12-01

    Novel NNNN-donor μ-bis(bidentate) tetraaza acyclic Schiff base ligands with different substituents (CF3, N(CH3)2 or OH groups) were synthesized by the condensation reaction of triethylenetetramine with 4-substituted benzaldehydes. Triethylenetetramine tris(4-trifluoromethylbenzylidene) (TTFMB), triethylenetetramine tris(4-dimethylaminobenzylidene) (TTDMB) and triethylenetetramine tris(2,4-dihydroxybenzylidene) (TTDHB) were formed as N4 donor ligands. The formation of a five-membered imidazolidine ring from the ethylenediamine backbone as a spacer-cumbridging unit gives rise to a new type of imidazolidine ligand. The structure of the TTFMB and TTDMB were determined by single crystal X-ray crystallography. The synthesized ligands have been characterized on the basis of the results of cyclic voltammetry (CV) and spectroscopic studies viz. FT-IR spectroscopy (FT-IR), mass spectroscopy (MS) and UV-Vis spectroscopy (UV-Vis).

  4. Synthesis, spectroscopic characterization and crystal structure of novel NNNN-donor μ-bis(bidentate) tetraaza acyclic Schiff base ligands.

    PubMed

    Habibi, Mohammad Hossein; Shojaee, Elahe; Nichol, Gary S

    2012-12-01

    Novel NNNN-donor μ-bis(bidentate) tetraaza acyclic Schiff base ligands with different substituents (CF(3), N(CH(3))(2) or OH groups) were synthesized by the condensation reaction of triethylenetetramine with 4-substituted benzaldehydes. Triethylenetetramine tris(4-trifluoromethylbenzylidene) (TTFMB), triethylenetetramine tris(4-dimethylaminobenzylidene) (TTDMB) and triethylenetetramine tris(2,4-dihydroxybenzylidene) (TTDHB) were formed as N(4) donor ligands. The formation of a five-membered imidazolidine ring from the ethylenediamine backbone as a spacer-cumbridging unit gives rise to a new type of imidazolidine ligand. The structure of the TTFMB and TTDMB were determined by single crystal X-ray crystallography. The synthesized ligands have been characterized on the basis of the results of cyclic voltammetry (CV) and spectroscopic studies viz. FT-IR spectroscopy (FT-IR), mass spectroscopy (MS) and UV-Vis spectroscopy (UV-Vis).

  5. Comparison of the electronic properties of diarylamido-based PNZ pincer ligands: redox activity at the ligand and donor ability toward the metal.

    PubMed

    Davidson, Jillian J; DeMott, Jessica C; Douvris, Christos; Fafard, Claudia M; Bhuvanesh, Nattamai; Chen, Chun-Hsing; Herbert, David E; Lee, Chun-I; McCulloch, Billy J; Foxman, Bruce M; Ozerov, Oleg V

    2015-03-16

    This paper presents the synthesis and characterization of a series of pincer ligands and their Ni, Pd, Pt, and Rh complexes. The ligands under examination are based on a diarylamine which is modified either by two phosphino (-PR2) substituents in the ortho-positions (PNP ligands) or by a combination of a phosphino and an iminyl (-CH═NX) substituent (PNN ligands). The ligands can be broken down into three groups: (a) C2v-symmetric PNP ligands with identical side -PR2 donors, (b) Cs-symmetric PNP' ligands with different -PR2 side donors, and (c) PNN ligands containing a -P(i)Pr2 side donor. All of the ligands under study readily formed square-planar complexes of the types (PNZ)PdCl, (PNZ)Pd(OAc), and (PNZ)RhCO, where PNZ is the corresponding anionic tridentate pincer ligand. For select PNP ligands, (PNP)NiCl and (PNP)PtCl were also studied. The (PNZ)MCl complexes (M = Ni, Pd, Pt) underwent quasireversible oxidation in cyclic voltammetry experiments. Based on the close similarity of formal potentials for Ni, Pd, and Pt analogs, and based on the previous literature evidence, these oxidation events are ascribed primarily to the PNZ ligand, and the E1/2 values can be used to compare the ease of oxidation of different ligands. A (PNP)PdCl complex containing methoxy substituents para- to the central nitrogen underwent two quasireversible oxidations. Two mono-oxidized complexes were isolated and structurally characterized in comparison to their neutral analog, revealing minimal changes in the bond distances and angles. Several other neutral complexes were also structurally characterized. The carbonyl stretching frequency in (PNZ)RhCO complexes was used to gauge the donating ability of the various pincer ligands toward the metal. Comparison of E1/2 values for (PNZ)PdCl and νCO values for (PNZ)RhCO revealed that the two are not consistently correlated across all the studied ligands and can be tuned to different degrees through judicious ligand alteration. PMID:25714352

  6. Donor conceived offspring conceive of the donor: the relevance of age, awareness, and family form.

    PubMed

    Hertz, Rosanna; Nelson, Margaret K; Kramer, Wendy

    2013-06-01

    Rarely have donor conceived offspring been studied. Recently, it has become more common for parents to disclose the nature of conception to their offspring. This new development raises questions about the donor's place in the offspring's life and identity. Using surveys collected by the Donor Sibling Registry, the largest U.S. web-based registry, during a 15 week period from October 2009 to January 2010, we found that donor offspring view the donor as a whole person, rather than as simple genetic material (he can know you; he has looks; he can teach you about yourself); they also believe that the donor should act on his humanity (he should know about you and not remain an anonymous genetic contributor). Other new issues that emerge from this research include the findings that offspring may want to control the decision about contacting their sperm donor in order to facilitate a bond between themselves and the donor that is separate from their relationship with their parents. They also wish to assure their parents that their natal families are primary and will not be disrupted. We discuss how the age at which offspring learned about their donor conception and their current age each make a difference in their responses to what they want from contact with their donor. Family form (heterosexual two-parent families and lesbian two-parent families) also affects donor terminology. The role of the genetic father is reconsidered in both types of families. Donor conceived offspring raised in heterosexual families discover that their natal father no longer carries biological information and he is relegated to being "only" a social father. Offspring raised by lesbian couples experience a dissipation of the family narrative that they have no father. The donor, an imagined father, offers clues to the offspring's personal identity. The natal family is no longer the sole keeper of identity or ancestry.

  7. Prospects for three-electron donor boronyl (BO) ligands and dioxodiborene (B2O2) ligands as bridging groups in binuclear iron carbonyl derivatives.

    PubMed

    Chang, Yu; Li, Qian-Shu; Xie, Yaoming; King, R Bruce

    2012-08-20

    Recent experimental work (2010) on (Cy(3)P)(2)Pt(BO)Br indicates that the oxygen atom of the boronyl (BO) ligand is more basic than that in the ubiquitous CO ligand. This suggests that bridging BO ligands in unsaturated binuclear metal carbonyl derivatives should readily function as three-electron donor bridging ligands involving both the oxygen and the boron atoms. In this connection, density functional theory shows that three of the four lowest energy singlet Fe(2)(BO)(2)(CO)(7) structures have such a bridging η(2)-μ-BO group as well as a formal Fe-Fe single bond. In addition, all four of the lowest energy singlet Fe(2)(BO)(2)(CO)(6) structures have two bridging η(2)-μ-BO groups and formal Fe-Fe single bonds. Other Fe(2)(BO)(2)(CO)(n) (n = 7, 6) structures are found in which the two BO groups have coupled to form a bridging dioxodiborene (B(2)O(2)) ligand with B-B bonding distances of ~1.84 Å. All of these Fe(2)(μ-B(2)O(2))(CO)(n) structures have long Fe···Fe distances indicating a lack of direct iron-iron bonding. One of the singlet Fe(2)(BO)(2)(CO)(7) structures has such a bridging dioxodiborene ligand with cis stereochemistry functioning as a six-electron donor to the pair of iron atoms. In addition, the lowest energy triplet structures for both Fe(2)(BO)(2)(CO)(7) and Fe(2)(BO)(2)(CO)(6) have bridging dioxodiborene ligands with trans stereochemistry functioning as a four-electron donor to the pair of iron atoms. PMID:22862812

  8. Several novel N-donor tridentate ligands formed in chemical studies of new fac-Re(CO)3 complexes relevant to fac-99mTc(CO)3 radiopharmaceuticals: attack of a terminal amine on coordinated acetonitrile.

    PubMed

    Perera, Theshini; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

    2010-03-01

    To evaluate syntheses of fac-[Re(CO)(3)L](+) complexes in organic solvents, we treated fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6)/BF(4) in acetonitrile with triamine ligands (L). When L had two primary or two tertiary terminal amine groups, the expected fac-[Re(CO)(3)L](+) complexes formed. In contrast, N,N-dimethyldiethylenetriamine (N,N-Me(2)dien) formed an unusual compound, fac-[Re(CO)(3)(DAE)]BF(4) {DAE = (Z)-N'-(2-(2-(dimethylamino)ethylamino)ethyl)acetimidamide = (Me(2)NCH(2)CH(2))NH(CH(2)CH(2)N=C(NH(2))Me)}. DAE is formed by addition of acetonitrile to the N,N-Me(2)dien terminal primary amine, converting this sp(3) nitrogen to an sp(2) nitrogen with a double bond to the original acetonitrile sp carbon. The three Ns bound to Re derive from N,N-Me(2)dien. The pathway to fac-[Re(CO)(3)(DAE)]BF(4) is suggested by a second unusual compound, fac-[Re(CO)(3)(MAE)]PF(6) {MAE = N-methyl-N-(2-(methyl-(2-(methylamino)ethyl)amino)ethyl)acetimidamide = MeN(H)-CH(2)CH(2)-N(Me)-CH(2)CH(2)-N(Me)-C(Me)=NH}, isolated after treating fac-[Re(CO)(3)(CH(3)CN)(3)]PF(6) with N,N',N''-trimethyldiethylenetriamine (N,N',N''-Me(3)dien). MAE chelates via a terminal and a central sp(3) N from N,N',N''-Me(3)dien and via one sp(2) NH in a C(Me)=NH group. This group is derived from acetonitrile by addition of the other N,N',N''-Me(3)dien terminal amine to the nitrile carbon. This addition creates an endocyclic NMe group within a seven-membered chelate ring. The structure and other properties of fac-[Re(CO)(3)(MAE)]PF(6) allow us to propose a reaction scheme for the formation of the unprecedented DAE ligand. The new compounds advance our understanding of the spectral and structural properties of Re analogues of (99m)Tc radiopharmaceuticals. PMID:20104873

  9. Developments in asymmetric catalysis by metal complexes of chiral chelating nitrogen-donor ligands.

    PubMed

    Caputo, Christine A; Jones, Nathan D

    2007-11-01

    In part because of their straightforward and modular syntheses from readily available enantiopure starting materials, and their capacity to bind a wide variety of transition metals, chiral, chelating nitrogen-donor ligands have played a prominent role in asymmetric catalysis. A large number of highly enantioselective transformations rely upon these ligands whose reported classes are built around amine, imine, pyrrole, pyrrolidine, oxazoline and oxazolidine donor groups, among others. In this Perspective, we examine a selection of transformative developments in asymmetric catalysis by metal complexes of bi- and polydentate members of this ligand family. We describe approaches to ligand design and synthesis, structure and bonding in coordination complexes, and limitations and future challenges. PMID:17940641

  10. Donor-Flexible Nitrogen Ligands for Efficient Iridium-Catalyzed Water Oxidation Catalysis.

    PubMed

    Navarro, Miquel; Li, Mo; Müller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2016-05-10

    A pyridylideneamide ligand with variable donor properties owing to a pronounced zwitterionic and a neutral diene-type resonance structure was used as a dynamic ligand at a Cp* iridium center to facilitate water oxidation catalysis, a reaction that requires the stabilization of a variety of different iridium oxidation states and that is key for developing an efficient solar fuel device. The ligand imparts high activity (nearly three-fold increase of turnover frequency compared to benchmark systems), and exceptionally high turnover numbers, which indicate a robust catalytic cycle and little catalyst degradation.

  11. Complexation of trivalent americium and lanthanides with terdentate 'N' donor ligands: the role of rigidity in the ligand structure.

    PubMed

    Bhattacharyya, Arunasis; Gadly, Trilochan; Pathak, Priyanath; Ghosh, Sunil K; Mohapatra, Manoj; Ghanty, Tapan K; Mohapatra, Prasanta K

    2014-08-28

    A systematic study on the Ln(3+) complexation behaviour with two terdentate 'N' donor ligands of varying structural rigidity, viz. 5,6-dimethyl-(1,2,4)-triazinylbipyridine (Me2TBipy) and 5,6-dimethyl-(1,2,4)-triazinylphenanthroline (Me2TPhen), is performed in the present work by UV-Vis spectrophotometry, time resolved fluorescence spectroscopy (TRFS) and electrospray ionization mass spectrometric (ESI-MS) studies. These studies indicate the formation of a 1 : 1 complex of La(3+), 1 : 2 complexes of Eu(3+) and Er(3+) with both the ligands. Density functional theoretical (DFT) study is carried out to determine the solution phase structure of the Eu(3+) complex considering the species (from UV-Vis spectrophotometry) and C2v site symmetry around the Eu(3+) ion (from TRFS study). Me2TPhen is found to be a stronger complexing ligand as compared to Me2TBipy irrespective of the Ln(3+) ions. The solid state crystal structure of the La(3+) complex of Me2TPhen is determined using the single crystal X-ray diffraction (SCXRD) technique. The complexation of the trivalent Am(3+) ion is also studied with both these ligands using UV-Vis spectrophotometric titrations which show the formation of 1 : 2 complexes with higher complexation constant values as compared to all the Ln(3+) ions studied, indicating the selectivity of these ligands for the trivalent actinides over the lanthanides. PMID:25001925

  12. Zinc acetylacetonate hydrate adducted with nitrogen donor ligands: Synthesis, spectroscopic characterization, and thermal analysis

    NASA Astrophysics Data System (ADS)

    Brahma, Sanjaya; Shivashankar, S. A.

    2015-12-01

    We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106 °C), decomposition temperature (202 °C) as that with zinc acetylacetonate (136 °C, 220 °C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process.

  13. Influencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands.

    PubMed

    Pugh, Thomas; Tuna, Floriana; Ungur, Liviu; Collison, David; McInnes, Eric J L; Chibotaru, Liviu F; Layfield, Richard A

    2015-01-01

    Single-molecule magnets are a type of coordination compound that can retain magnetic information at low temperatures. Single-molecule magnets based on lanthanides have accounted for many important advances, including systems with very large energy barriers to reversal of the magnetization, and a di-terbium complex that displays magnetic hysteresis up to 14 K and shows strong coercivity. Ligand design is crucial for the development of new single-molecule magnets: organometallic chemistry presents possibilities for using unconventional ligands, particularly those with soft donor groups. Here we report dysprosium single-molecule magnets with neutral and anionic phosphorus donor ligands, and show that their properties change dramatically when varying the ligand from phosphine to phosphide to phosphinidene. A phosphide-ligated, trimetallic dysprosium single-molecule magnet relaxes via the second-excited Kramers' doublet, and, when doped into a diamagnetic matrix at the single-ion level, produces a large energy barrier of 256 cm(-1) and magnetic hysteresis up to 4.4 K. PMID:26130418

  14. Influencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands.

    PubMed

    Pugh, Thomas; Tuna, Floriana; Ungur, Liviu; Collison, David; McInnes, Eric J L; Chibotaru, Liviu F; Layfield, Richard A

    2015-07-01

    Single-molecule magnets are a type of coordination compound that can retain magnetic information at low temperatures. Single-molecule magnets based on lanthanides have accounted for many important advances, including systems with very large energy barriers to reversal of the magnetization, and a di-terbium complex that displays magnetic hysteresis up to 14 K and shows strong coercivity. Ligand design is crucial for the development of new single-molecule magnets: organometallic chemistry presents possibilities for using unconventional ligands, particularly those with soft donor groups. Here we report dysprosium single-molecule magnets with neutral and anionic phosphorus donor ligands, and show that their properties change dramatically when varying the ligand from phosphine to phosphide to phosphinidene. A phosphide-ligated, trimetallic dysprosium single-molecule magnet relaxes via the second-excited Kramers' doublet, and, when doped into a diamagnetic matrix at the single-ion level, produces a large energy barrier of 256 cm(-1) and magnetic hysteresis up to 4.4 K.

  15. Influencing the properties of dysprosium single-molecule magnets with phosphorus donor ligands

    PubMed Central

    Pugh, Thomas; Tuna, Floriana; Ungur, Liviu; Collison, David; McInnes, Eric J.L.; Chibotaru, Liviu F.; Layfield, Richard A.

    2015-01-01

    Single-molecule magnets are a type of coordination compound that can retain magnetic information at low temperatures. Single-molecule magnets based on lanthanides have accounted for many important advances, including systems with very large energy barriers to reversal of the magnetization, and a di-terbium complex that displays magnetic hysteresis up to 14 K and shows strong coercivity. Ligand design is crucial for the development of new single-molecule magnets: organometallic chemistry presents possibilities for using unconventional ligands, particularly those with soft donor groups. Here we report dysprosium single-molecule magnets with neutral and anionic phosphorus donor ligands, and show that their properties change dramatically when varying the ligand from phosphine to phosphide to phosphinidene. A phosphide-ligated, trimetallic dysprosium single-molecule magnet relaxes via the second-excited Kramers' doublet, and, when doped into a diamagnetic matrix at the single-ion level, produces a large energy barrier of 256 cm−1 and magnetic hysteresis up to 4.4 K. PMID:26130418

  16. Stereochemical Properties of Multidentate Nitrogen Donor Ligands and Their Copper Complexes by Electronic CD and DFT.

    PubMed

    Poopari, Mohammad Reza; Dezhahang, Zahra; Xu, Yunjie

    2016-07-01

    UV-Vis and electronic circular dichroism (ECD) spectroscopy, complemented with Density Functional Theory (DFT) calculations, were used to elucidate the structural diversities of three multidentate nitrogen donor ligands and two associated copper complexes in solution directly. The three chiral salen ligands all consist of trans-cyclohexane-1,2-diamine as a chiral scaffold and also of pyridine rings as chromophores, differing only in the linking groups between the two functional groups mentioned above. Very different ECD intensities and somewhat different ECD patterns were observed for these ligands and satisfactorily interpreted theoretically. For the geometry optimization and spectral simulation of the open-shell metal complexes, the LANL2DZ basis set with effective core potential for the Cu and Cl atoms and pure cc-pVTZ for the rest of the atoms was utilized. The performance of the same calculations with the polarization functions (f,g) from the cc-pVTZ basis added to the LANL2DZ basis was compared. While the three ligands exhibit different conformational flexibility, the associated copper complexes show great rigidity imposed by the metal-ligand coordination, taking on a single structure in each case. In addition, dispersion interactions were shown to change the conformational stability ordering of the ligands noticeably and to exert considerable influence on the simulated UV-Vis and ECD spectra. Chirality 28:545-555, 2016. © 2016 Wiley Periodicals, Inc. PMID:27349956

  17. Stereochemical Properties of Multidentate Nitrogen Donor Ligands and Their Copper Complexes by Electronic CD and DFT.

    PubMed

    Poopari, Mohammad Reza; Dezhahang, Zahra; Xu, Yunjie

    2016-07-01

    UV-Vis and electronic circular dichroism (ECD) spectroscopy, complemented with Density Functional Theory (DFT) calculations, were used to elucidate the structural diversities of three multidentate nitrogen donor ligands and two associated copper complexes in solution directly. The three chiral salen ligands all consist of trans-cyclohexane-1,2-diamine as a chiral scaffold and also of pyridine rings as chromophores, differing only in the linking groups between the two functional groups mentioned above. Very different ECD intensities and somewhat different ECD patterns were observed for these ligands and satisfactorily interpreted theoretically. For the geometry optimization and spectral simulation of the open-shell metal complexes, the LANL2DZ basis set with effective core potential for the Cu and Cl atoms and pure cc-pVTZ for the rest of the atoms was utilized. The performance of the same calculations with the polarization functions (f,g) from the cc-pVTZ basis added to the LANL2DZ basis was compared. While the three ligands exhibit different conformational flexibility, the associated copper complexes show great rigidity imposed by the metal-ligand coordination, taking on a single structure in each case. In addition, dispersion interactions were shown to change the conformational stability ordering of the ligands noticeably and to exert considerable influence on the simulated UV-Vis and ECD spectra. Chirality 28:545-555, 2016. © 2016 Wiley Periodicals, Inc.

  18. Modification of σ-Donor Properties of Terminal Carbide Ligands Investigated Through Carbide-Iodine Adduct Formation.

    PubMed

    Reinholdt, Anders; Vosch, Tom; Bendix, Jesper

    2016-09-26

    The terminal carbide ligands in [(Cy3 P)2 X2 Ru≡C] complexes (X=halide or pseudohalide) coordinate molecular iodine, affording charge-transfer complexes rather than oxidation products. Crystallographic and vibrational spectroscopic data show the perturbations of iodine to vary with the auxiliary ligand sphere on ruthenium, demonstrating the σ-donor properties of carbide complexes to be tunable.

  19. Gas-phase ligand loss and ligand substitution reactions of platinum(II) complexes of tridentate nitrogen donor ligands.

    PubMed

    Wee, Sheena; O'Hair, Richard A J; McFadyen, W David

    2004-01-01

    The source of protons associated with the ligand loss channel of HX((n - 1)+) from [Pt(II)(dien)X](n+) (X = Cl, Br and I for n = 1 and X = NC(5)H(5) for n = 2) in the gas phase was investigated by deuterium-labelling studies. The results of these studies indicate that these protons originate from both the amino groups and the carbon backbone of the dien ligand. In some instances (e.g. X = Br and I), the protons lost from the carbon backbone can be even more abundant than the protons lost from the amino groups. The gas-phase substitution reactions of coordinatively saturated [Pt(II)(L(3))L(a)](2+) complexes (L(3) = tpy or dien) were also examined using ion-molecule reactions. The outcome of the ion-molecule reactions depends on both the ancillary ligand (L(3)) as well as the leaving group (L(a)). [Pt(II)(tpy)L(a)](2+) complexes undergo substitution reactions, with a faster rate when L(a) is a good leaving group, while the [Pt(II)(dien)L(a)](2+) complex undergoes a proton transfer reaction. PMID:15164352

  20. N6-benzyladenosine derivatives as novel N-donor ligands of platinum(II) dichlorido complexes.

    PubMed

    Starha, Pavel; Popa, Igor; Trávníček, Zdeněk; Vančo, Ján

    2013-01-01

    The platinum(II) complexes trans-[PtCl₂(Ln)₂]∙xSolv 1-13 (Solv = H₂O or CH3OH), involving N6-benzyladenosine-based N-donor ligands, were synthesized; L(n) stands for N6-(2-methoxybenzyl)adenosine (L₁, involved in complex 1), N6-(4-methoxy-benzyl)adenosine (L₂, 2), N6-(2-chlorobenzyl)adenosine (L₃, 3), N6-(4-chlorobenzyl)-adenosine (L₄, 4), N6-(2-hydroxybenzyl)adenosine (L₅, 5), N6-(3-hydroxybenzyl)-adenosine (L₆, 6), N6-(2-hydroxy-3-methoxybenzyl)adenosine (L₇, 7), N6-(4-fluoro-benzyl)adenosine (L₈, 8), N6-(4-methylbenzyl)adenosine (L₉, 9), 2-chloro-N6-(3-hydroxy-benzyl)adenosine (L₁₀, 10), 2-chloro-N6-(4-hydroxybenzyl)adenosine (L₁₁, 11), 2-chloro-N6-(2-hydroxy-3-methoxybenzyl)adenosine (L₁₂, 12) and 2-chloro-N6-(2-hydroxy-5-methylbenzyl)adenosine (L₁₃, 13). The compounds were characterized by elemental analysis, mass spectrometry, IR and multinuclear (¹H-, ¹³C-, ¹⁹⁵Pt- and ¹⁵N-) and two-dimensional NMR spectroscopy, which proved the N7-coordination mode of the appropriate N6-benzyladenosine derivative and trans-geometry of the title complexes. The complexes 1-13 were found to be non-toxic in vitro against two selected human cancer cell lines (HOS and MCF7; with IC₅₀ > 50.0 µM). However, they were found (by ESI-MS study) to be able to interact with the physiological levels of the sulfur-containing biogenic biomolecule L-methionine by a relatively simple 1:1 exchange mechanism (one L(n) molecule was replaced by one L-methionine molecule), thus forming a mixed-nitrogen/sulfur-ligand dichlorido-platinum(II) coordination species. PMID:23771060

  1. Arene-ruthenium(II) complexes with hydrophilic P-donor ligands: versatile catalysts in aqueous media.

    PubMed

    Crochet, Pascale; Cadierno, Victorio

    2014-09-01

    In the last few years there has been increasing interest in the use of water as a reaction medium for catalysis, and therefore in designing water-soluble transition-metal catalysts. Half-sandwich (η(6)-arene)-ruthenium(ii) complexes are a versatile and well-known family of ruthenium compounds that exhibit a rich catalytic and coordination chemistry. This Perspective article focuses on the catalytic applications in aqueous media of (η(6)-arene)-ruthenium(ii) complexes containing water-soluble phosphines, and related hydrophilic P-donor ligands.

  2. Tridentate assembling ligands based on oxazoline and phosphorus donors in dinuclear Pd(I)-Pd(I) complexes.

    PubMed

    Zhang, Jing; Pattacini, Roberto; Braunstein, Pierre

    2009-12-21

    To examine the bonding preferences of potentially tridentate phosphorus, nitrogen donor ligands on a dinuclear metal core, we have studied the coordination of the oxazoline-based ligands bis(4,5-dihydro-2-oxazolylmethyl)phenylphosphine (NPN) and bis(4,4-dimethyl-2-oxazolyl dimethylmethoxy)phenylphosphine (NOPON(Me2)) toward the dinuclear d(9)-d(9) Pd(I) complex [Pd(2)(NCMe)(6)][BF(4)](2). In the dinuclear product [Pd(2)(NPN-N,P,N)(2)](BF(4))(2) (1), in which the Pd-Pd bond length of 2.5489(7) A is rather short, the two interacting metal centers are P,N bridged by two molecules of the NPN ligand, forming two six-membered rings. The other oxazoline ring of each ligand further chelates a Pd center through its nitrogen atom, forming five-membered chelates, as in the mononuclear complex [PdCl(2)(NPN-N,P)] (5). In contrast, the reaction between [Pd(2)(NCMe)(6)](BF(4))(2) and NOPON(Me2) in the presence of LiCl afforded the mononuclear cationic complex [Pd(NOPON(Me2)-N,P,N)Cl](BF(4)) (3), which is also obtained by halide abstraction from [Pd(NOPON(Me2)-N,P)Cl(2)] with NaBF(4). When this reaction was performed in the presence of 1 equiv of t-BuNC, the new dinuclear Pd(I)-Pd(I) complex [Pd(2)Cl(2)(CNt-Bu)(NOPON(Me2)-N,P,N)] (4) was isolated, which can also be obtained from a comproportionation reaction between Pd(II) and Pd(0) complexes. The oxazoline in the P,N bridge is involved in a seven-membered ring moiety, a situation rarely encountered in Pd(I)-Pd(I) chemistry. Its nitrogen atom is coordinated trans to the isonitrile ligand whereas that of the P,N chelate at Pd(1) is trans to Pd(2). The fluxional processes involving the oxazoline moieties of the NPN and NOPON(Me2) ligands in 1 and 4, respectively, were examined by variable-temperature NMR spectroscopy. The crystal structures of 1, 3.0.5CH(3)CN, and 4 have been determined by X-ray diffraction. Prior to this work, relatively few complexes have been reported in the literature in which a potentially tridentate functional

  3. A survey of 1700 women who formed their families using donor spermatozoa.

    PubMed

    Sawyer, Neroli; Blyth, Eric; Kramer, Wendy; Frith, Lucy

    2013-10-01

    This paper reports the results of an online survey of 1700 recipients of donor spermatozoa conducted by the Donor Sibling Registry, aiming to understand the perspectives of respondents who had used donor spermatozoa. The survey examined: choice of sperm bank and donor; reporting of births and genetic disorders; disclosure; contact with donor and half-siblings; regulation of sperm donor activity and genetic testing; and access to medical information. The respondents formed three groups: single women; women in a same-sex relationship; and women in a heterosexual relationship. Some differences between the three cohorts were observed: preinsemination counselling; acceptance of donors without medical records or with chronic or late-onset diseases; awareness of choice of bank and type of donor; and views on the right of offspring to know their genetic origins. However, important areas of common ground were identified: the wish by those who had used an anonymous donor that they had used an open-identity donor; support for, and willingness to pay for, comprehensive genetic testing of donors; and desire for access to their donor's family health information. The implications of these results for policies concerning the use and management of donor spermatozoa will be discussed. This paper reports the results of a survey of 1700 women who used donor spermatozoa to conceive a child. The survey considers their views on the following areas: choice of sperm bank and donor; reporting of births and genetic disorders; disclosure; contact with donor and half-siblings; regulation of sperm donor activity and genetic testing; and access to medical information. This was an online survey was designed and conducted by the Donor Sibling Registry (DSR), a US-based non-profit organization that supports donor sperm recipients, donors and donor-conceived people. The survey aimed to understand the experiences, perspectives and concerns of women who had used donor spermatozoa. The respondents

  4. DNA interaction and cytotoxic activities of square planar platinum(II) complexes with N, S-donor ligands

    NASA Astrophysics Data System (ADS)

    Patel, Mohan N.; Patel, Chintan R.; Joshi, Hardik N.; Thakor, Khyati P.

    2014-06-01

    The platinum(II) complexes with N, S-donor ligands have been synthesized and characterized by physicochemical methods viz. elemental, electronic, FT-IR, 1H NMR and LC-MS spectra. The binding mode and potency of the complexes with HS DNA (Herring Sperm) have been examined by absorption titration and viscosity measurement studies. The results revealed that complexes bind to HS DNA via covalent mode with the intrinsic binding constant (Kb) in the range 1.37-7.76 × 105 M-1. Decrease in the relative viscosity of HS DNA also supports the covalent mode of binding. The DNA cleavage activity of synthesized complexes has been carried out by gel electrophoresis experiment using supercoiled form of pUC19 DNA; showing the unwinding of the negatively charged supercoiled DNA. Brine shrimp (Artemia Cysts) lethality bioassay technique has been applied for the determination of toxic property of synthesized complexes in terms of μM.

  5. Programmed death ligand-1 expression on donor T cells drives graft-versus-host disease lethality.

    PubMed

    Saha, Asim; O'Connor, Roddy S; Thangavelu, Govindarajan; Lovitch, Scott B; Dandamudi, Durga Bhavani; Wilson, Caleph B; Vincent, Benjamin G; Tkachev, Victor; Pawlicki, Jan M; Furlan, Scott N; Kean, Leslie S; Aoyama, Kazutoshi; Taylor, Patricia A; Panoskaltsis-Mortari, Angela; Foncea, Rocio; Ranganathan, Parvathi; Devine, Steven M; Burrill, Joel S; Guo, Lili; Sacristan, Catarina; Snyder, Nathaniel W; Blair, Ian A; Milone, Michael C; Dustin, Michael L; Riley, James L; Bernlohr, David A; Murphy, William J; Fife, Brian T; Munn, David H; Miller, Jeffrey S; Serody, Jonathan S; Freeman, Gordon J; Sharpe, Arlene H; Turka, Laurence A; Blazar, Bruce R

    2016-07-01

    Programmed death ligand-1 (PD-L1) interaction with PD-1 induces T cell exhaustion and is a therapeutic target to enhance immune responses against cancer and chronic infections. In murine bone marrow transplant models, PD-L1 expression on host target tissues reduces the incidence of graft-versus-host disease (GVHD). PD-L1 is also expressed on T cells; however, it is unclear whether PD-L1 on this population influences immune function. Here, we examined the effects of PD-L1 modulation of T cell function in GVHD. In patients with severe GVHD, PD-L1 expression was increased on donor T cells. Compared with mice that received WT T cells, GVHD was reduced in animals that received T cells from Pdl1-/- donors. PD-L1-deficient T cells had reduced expression of gut homing receptors, diminished production of inflammatory cytokines, and enhanced rates of apoptosis. Moreover, multiple bioenergetic pathways, including aerobic glycolysis, oxidative phosphorylation, and fatty acid metabolism, were also reduced in T cells lacking PD-L1. Finally, the reduction of acute GVHD lethality in mice that received Pdl1-/- donor cells did not affect graft-versus-leukemia responses. These data demonstrate that PD-L1 selectively enhances T cell-mediated immune responses, suggesting a context-dependent function of the PD-1/PD-L1 axis, and suggest selective inhibition of PD-L1 on donor T cells as a potential strategy to prevent or ameliorate GVHD.

  6. Programmed death ligand-1 expression on donor T cells drives graft-versus-host disease lethality

    PubMed Central

    O’Connor, Roddy S.; Thangavelu, Govindarajan; Lovitch, Scott B.; Dandamudi, Durga Bhavani; Vincent, Benjamin G.; Tkachev, Victor; Pawlicki, Jan M.; Furlan, Scott N.; Kean, Leslie S.; Aoyama, Kazutoshi; Taylor, Patricia A.; Panoskaltsis-Mortari, Angela; Foncea, Rocio; Ranganathan, Parvathi; Devine, Steven M.; Burrill, Joel S.; Guo, Lili; Sacristan, Catarina; Snyder, Nathaniel W.; Blair, Ian A.; Milone, Michael C.; Dustin, Michael L.; Riley, James L.; Bernlohr, David A.; Murphy, William J.; Fife, Brian T.; Munn, David H.; Miller, Jeffrey S.; Serody, Jonathan S.; Freeman, Gordon J.; Sharpe, Arlene H.; Turka, Laurence A.

    2016-01-01

    Programmed death ligand-1 (PD-L1) interaction with PD-1 induces T cell exhaustion and is a therapeutic target to enhance immune responses against cancer and chronic infections. In murine bone marrow transplant models, PD-L1 expression on host target tissues reduces the incidence of graft-versus-host disease (GVHD). PD-L1 is also expressed on T cells; however, it is unclear whether PD-L1 on this population influences immune function. Here, we examined the effects of PD-L1 modulation of T cell function in GVHD. In patients with severe GVHD, PD-L1 expression was increased on donor T cells. Compared with mice that received WT T cells, GVHD was reduced in animals that received T cells from Pdl1–/– donors. PD-L1–deficient T cells had reduced expression of gut homing receptors, diminished production of inflammatory cytokines, and enhanced rates of apoptosis. Moreover, multiple bioenergetic pathways, including aerobic glycolysis, oxidative phosphorylation, and fatty acid metabolism, were also reduced in T cells lacking PD-L1. Finally, the reduction of acute GVHD lethality in mice that received Pdl1–/– donor cells did not affect graft-versus-leukemia responses. These data demonstrate that PD-L1 selectively enhances T cell–mediated immune responses, suggesting a context-dependent function of the PD-1/PD-L1 axis, and suggest selective inhibition of PD-L1 on donor T cells as a potential strategy to prevent or ameliorate GVHD. PMID:27294527

  7. Two Zn(II) coordination complexes assembled by trithiocyanuric acid and two different N-donor auxiliary ligands.

    PubMed

    He, Xiao Xiao; Guo, Ya Mei

    2014-08-01

    The dipyridyl-type building blocks 4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole (3-bpt) and 4,4'-bipyridine (bpy) have been used to assemble with Zn(II) in the presence of trithiocyanuric acid (ttcH3) to afford two coordination compounds, namely bis[4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole-κN(3)]bis(trithiocyanurato-κ(2)N,S)zinc(II), [Zn(C3H2N3S3)2(C12H10N6)2]·2H2O, (1), and catena-poly[[[bis(trithiocyanurato-κ(2)N,S)zinc(II)]-μ-4,4'-bipyridine-κ(2)N:N'] 4,4'-bipyridine monosolvate], {[Zn2(C3H2N3S3)4(C10H8N2)3]·C10H8N2}n, (2). Single-crystal X-ray analysis indicates that complex (1) is a mononuclear structure, while complex (2) presents a one-dimensional chain coordination motif. In both complexes, the central Zn(II) cation adopts an octahedral geometry, coordinated by four N- and two S-donor atoms. Notably, trithiocyanurate (ttcH2(-)) adopts the same bidentate chelating coordination mode in each complex and exists in the thione tautomeric form. The 3-bpt co-ligand in (1) adopts a monodentate coordination mode and serves as a terminal pendant ligand, whereas the 4,4'-bipyridine (bpy) ligand in (2) adopts a bidentate-bridging coordination mode. The different coordination characters of the different N-donor auxiliary ligands lead to structural diversity for complexes (1) and (2). Further analysis indicates that the resultant three-dimensional supramolecular networks for (1) and (2) arise through intermolecular N-H...S and N-H...N hydrogen bonds. Both complexes have been further characterized by FT-IR spectroscopy and elemental analyses.

  8. Modification of σ-Donor Properties of Terminal Carbide Ligands Investigated Through Carbide-Iodine Adduct Formation.

    PubMed

    Reinholdt, Anders; Vosch, Tom; Bendix, Jesper

    2016-09-26

    The terminal carbide ligands in [(Cy3 P)2 X2 Ru≡C] complexes (X=halide or pseudohalide) coordinate molecular iodine, affording charge-transfer complexes rather than oxidation products. Crystallographic and vibrational spectroscopic data show the perturbations of iodine to vary with the auxiliary ligand sphere on ruthenium, demonstrating the σ-donor properties of carbide complexes to be tunable. PMID:27612099

  9. Synthesis, biological and comparative DFT studies on Ni(II) complexes of NO and NOS donor ligands

    NASA Astrophysics Data System (ADS)

    Yousef, T. A.; El-Gammal, O. A.; Ahmed, Sara F.; Abu El-Reash, G. M.

    2015-01-01

    Three new NOS donor ligands have been prepared by addition ethanolic suspension of 2-hydrazino-2-oxo-N-phenyl-acetamide to phenyl isocyanate (H2PAPS), phenyl isothiocyanate (H2PAPT) and benzoyl isothiocyanate (H2PABT). The Ni(II) complexes prepared from the chloride salt and characterized by conventional techniques. The isolated complexes were assigned the formulaes, [Ni2(PAPS)(H2O)2](H2O)2, [Ni(H2PAPT)Cl2(H2O)](H2O)2 and [(Ni)2(HPABT)2Cl2(H2O)2], respectively. The IR spectra of complexes shows that H2PAPS behaves as a binegative pentadentate via both CO of hydrazide moiety in keto and enol form, enolized CO of cyanate moiety and the CN (azomethine) groups of enolization. H2PAPT behaves as neutral tridentate via both CO of hydrazide moiety and CN (azomethine) group due to SH formation and finally H2PABT behaves as mononegative tetradentate via CO and enolized CO of hydrazide moiety, CO of benzoyl moiety and Cdbnd S groups. The experimental IR spectra of ligands are compared with those obtained theoretically from DFT calculations. Also, the bond lengths, bond angles, HOMO (Highest Occupied Molecular Orbitals), LUMO (Lowest Unoccupied Molecular Orbital) and dipole moments have been calculated. The calculated HOMO-LUMO energy gap reveals that charge transfer occurs within the molecule. The theoretical values of binding energies indicate the higher stability of complexes than of ligands. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. The antibacterial activities were also tested against B. Subtilis and E. coli bacteria. The free ligands showed a higher antibacterial effect than their Ni(II) complexes. The antitumor activities of the Ligands and their Ni(II) complexes have been evaluated against liver (HePG2) and breast (MCF-7) cancer cells. All ligands were found to display cytotoxicity that are better than that of Fluorouracil (5-FU), while Ni

  10. Tris(carbene)borate ligands featuring imidazole-2-ylidene, benzimidazol-2-ylidene and 1,3,4-triazol-2-ylidene donors. Evaluation of donor properties in four-coordinate {NiNO}10 complexes

    PubMed Central

    Muñoz, Salvador B.; Foster, Wallace K.; Lin, Hsiu-Jung; Margarit, Charles G.; Dickie, Diane A.

    2012-01-01

    The synthesis and characterization of new tris(carbene)borate ligand precursors containing substituted benzimidazol-2-ylidene and 1,3,4-triazol-2-ylidene donor groups, as well as a new tris(imidazol-2-ylidene)borate ligand precursor are reported. The relative donor strength of the tris(carbene)borate ligands have been evaluated by the position of ν(NO) in four-coordinate {NiNO}10 complexes, and follows the order: imidazol-2-ylidene > benzimidazol-2-ylidene > 1,3,4-triazol-2-ylidene. There is a large variation in ν(NO), suggesting these ligands to have a wide range of donor strengths while maintaining a consistent ligand topology. All ligands are stronger donors than Tp* and Cp*. PMID:23140462

  11. Mixed tridentate π -donor and monodentate π -acceptor ligands as chelating systems for rhenium-188 and technetium-99m nitrido radiopharmaceuticals.

    PubMed

    Boschi, Alessandra; Uccelli, Licia; Pasquali, Micol; Pasqualini, Roberto; Guerrini, Remo; Duatti, Adriano

    2013-09-01

    A new molecular metallic fragment for labeling biologically active molecules with 99mTc and 188Re is described. This system is composed of a combination of tridentate π-donor and monodentate π-acceptor ligands bound to a [M Ξ N]2+ group (M = (99m)Tc, 188Re) in a pseudo square-pyramidal geometry. A simple structural model of the new metallic fragment was obtained by reacting the ligand 2, 2'-iminodiethanethiol [H2NS2 = NH(CH2CH2SH)2] and monodentate tertiary phosphines with the [M Ξ N]2+ group (M = (99m)Tc, (188)Re). In the resulting complexes (dubbed3+1complexes), the tridentate ligand binds the [M Ξ N]2+ core through the two deprotonated, negatively charged, thiol sulfur atoms and the neutral, protonated, amine nitrogen atom. The residual fourth position of the five-coordinated arrangement is occupied by a phosphine ligand. The chemical identity of these model (99m)Tc and (188)Re compounds was established by comparison with the chromatographic properties of the corresponding complexes obtained at the macroscopic level with the long-lived (99)Tc and natural Re isotopes. The investigation was further extended to comprise a series of ligands formed by simple combinations of two basic amino acids or pseudo-amino acids to yield potential tridentate chelating systems having [S, N, S] and [N, N, S] as sets of π-donor atoms. Labeling yields and in vitro stability were investigated using different ancillary ligands. Results showed that SNS-type ligands afforded the highest labeling yields and the most robust 3+1 nitrido complexes with both (99m)Tc and (188)Re. Thus, the new chelating system can be conveniently employed for labeling peptides and other biomolecules with the [M Ξ N]2+ group.

  12. Mixed tridentate π -donor and monodentate π -acceptor ligands as chelating systems for rhenium-188 and technetium-99m nitrido radiopharmaceuticals.

    PubMed

    Boschi, Alessandra; Uccelli, Licia; Pasquali, Micol; Pasqualini, Roberto; Guerrini, Remo; Duatti, Adriano

    2013-09-01

    A new molecular metallic fragment for labeling biologically active molecules with 99mTc and 188Re is described. This system is composed of a combination of tridentate π-donor and monodentate π-acceptor ligands bound to a [M Ξ N]2+ group (M = (99m)Tc, 188Re) in a pseudo square-pyramidal geometry. A simple structural model of the new metallic fragment was obtained by reacting the ligand 2, 2'-iminodiethanethiol [H2NS2 = NH(CH2CH2SH)2] and monodentate tertiary phosphines with the [M Ξ N]2+ group (M = (99m)Tc, (188)Re). In the resulting complexes (dubbed3+1complexes), the tridentate ligand binds the [M Ξ N]2+ core through the two deprotonated, negatively charged, thiol sulfur atoms and the neutral, protonated, amine nitrogen atom. The residual fourth position of the five-coordinated arrangement is occupied by a phosphine ligand. The chemical identity of these model (99m)Tc and (188)Re compounds was established by comparison with the chromatographic properties of the corresponding complexes obtained at the macroscopic level with the long-lived (99)Tc and natural Re isotopes. The investigation was further extended to comprise a series of ligands formed by simple combinations of two basic amino acids or pseudo-amino acids to yield potential tridentate chelating systems having [S, N, S] and [N, N, S] as sets of π-donor atoms. Labeling yields and in vitro stability were investigated using different ancillary ligands. Results showed that SNS-type ligands afforded the highest labeling yields and the most robust 3+1 nitrido complexes with both (99m)Tc and (188)Re. Thus, the new chelating system can be conveniently employed for labeling peptides and other biomolecules with the [M Ξ N]2+ group. PMID:24106999

  13. Monomer, dimer or cyclic helicate? Coordination diversity with hard-soft P,N-donor ligands.

    PubMed

    Constable, Edwin C; Hostettler, Nik; Housecroft, Catherine E; Murray, Niamh S; Schönle, Jonas; Soydaner, Umut; Walliser, Roché M; Zampese, Jennifer A

    2013-04-14

    We report the synthesis of copper(I) complexes of three ligands which contain a potential P,N,N,P-metal binding site. Elemental analysis confirms that the bulk products possess a composition of [CuL][PF6] where L = 1, 2 or 3. Electrospray mass spectrometry (ESI MS) provides evidence for speciation in MeCN or MeOH solutions and the formation of both [CuL]+ and [Cu2L2]2+; addition of NaCl to the ESI MS samples aids the observation of dinuclear species as [Cu2L2Cl]+ ions. NMR spectroscopic data for a CD3CN solution of [Cu(1)][PF6] were consistent with a mononuclear species, but more complex multinuclear spectra were observed for the same compound dissolved in CD2Cl2. In the solid state, dimeric species dominate. Crystals grown from CH2Cl2 solutions of [Cu(1)][PF6] are found to be [Cu2(1)2][PF6]2·6CH2Cl2; each Cu+ ion in the centrosymmetric cation is bound in an N,O,P,P-coordination sphere, the N-donor originating from the pyridine ring. In [Cu2(3)2][PF6]2, each bridging ligand in the centrosymmetric [Cu2(3)2]2+ ion acts as a P,N-chelate to each Cu+ ion. Competing with this dimeric assembly is that of a circular helicate in which each ligand 3 bridges adjacent pairs of copper(I) ions in a chiral, hexameric complex; both the Δ,Δ,Δ,Δ,Δ,Δ- and Λ,Λ,Λ,Λ,Λ,Λ-enantiomers are present in the crystal lattice; in [Cu6(3)6]6+, each ligand coordinates as a bis(P,N-chelate). The solution absorption spectra of [Cu(1)][PF6], [Cu(2)][PF6] and [Cu(3)][PF6] are dominated by ligand-based transitions and none of the copper(I) complexes exhibits emissive behaviour in solution.

  14. Utilization of mixed ligands to construct diverse Ni(II)-coordination polymers based on terphenyl-2,2‧,4,4‧-tetracarboxylic acid and varied N-donor co-ligands

    NASA Astrophysics Data System (ADS)

    Wang, Chao; Zhao, Jun; Xia, Liang; Wu, Xue-Qian; Wang, Jian-Fang; Dong, Wen-Wen; Wu, Ya-Pan

    2016-06-01

    Three new coordination polymers, namely, {[Ni(H2L)(bix)(H2O)2]·2h2O}n (1), {[Ni(HL)(Hdpa)(H2O)2]·H2O}n (2), {[Ni(L)0.5(bpp)(H2O)]·H2O}n (3) (H4L=terphenyl-2,2‧,4,4‧-tetracarboxylic acid; bix=1,4-bis(imidazol-1-ylmethyl)benzene; dpa =4,4‧-dipyridylamine; bpp=1,3-bis(4-pyridyl)propane), based on rigid H4L ligand and different N-donor co-ligands, have been synthesized under hydrothermal conditions. Compound 1 features a 3D 4-connected 66-dia-type framework with H4L ligand adopts a μ2-bridging mode with two symmetry-related carboxylate groups in μ1-η1:η0 monodentate mode. Compound 2 displays a 1D [Ni(HL)(Hdpa)]n ribbon chains motif, in which the H4L ligand adopts a μ2-bridging mode with two carboxylate groups in μ1-η1:η1 and μ1-η1:η0 monodentate modes, while 3 possesses a (4,4)-connected 3D frameworks with bbf topology, with H4L ligand displays a μ4-bridging coordination mode. The H4L ligand displays not only different deprotonated forms but also diverse coordination modes and conformations. The structural diversities among 1-3 have been carefully discussed, and the roles of N-donor co-ligands in the self-assembly of coordination polymers have been well documented.

  15. Synthesis and photoluminescence properties of silver(I) complexes based on N-benzoyl-L-glutamic acid and N-donor ligands with different flexibility

    NASA Astrophysics Data System (ADS)

    Yan, Ming-Jie; Feng, Qi; Song, Hui-Hua

    2016-05-01

    By changing the N-donor ancillary ligand, three novel silver (I) complexes {[Ag(HbzgluO) (4,4‧-bipy)]·H2O}n (1), {[Ag2(HbzgluO)2 (bpe)2]·2H2O}n (2) and {[Ag(HbzgluO)(bpp)]·2H2O}n (3) (H2bzgluO = N-benzoyl-L-glutamic acid, 4,4‧-bipy = 4,4ˊ-bipyridine, bpe = 1,2-di(4-pyridyl)ethane, bpp = 1,3-di(4-pyridyl)propane) were synthesized. Their structures have been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric analyses (TGA). In this study, the N-donor ligands are changed from rigidity (4,4‧-bipy), quasi-flexibility (bpe) to flexibility (bpp), the structures of complexes also change. Complex 1 features a 1D chain structure which is further linked together to construct a 2D supramolecular structure through hydrogen bonds. Complex 2 is a 1D double-chains configuration which eventually forms a 3D supramolecular network via hydrogen bonding interactions. Whereas, complex 3 exhibits a 2D pleated grid structure which is linked by hydrogen bonding interactions into a 3D supramolecular network. The present observations demonstrate that the modulation of coordination polymers with different structures can accomplish by changing the spacer length of N-donor ligands. In addition, the solid-state circular dichroism (CD) spectra indicated that compound 2 exhibited negative cotton effect which originated from the chiral ligands H2bzgluO and the solid-state fluorescence spectra of the three complexes demonstrated the auxiliary ligands have influence on the photoluminescence properties of the complexes.

  16. Probing the difference in covalence by enthalpy measurements: a new heterocyclic N-donor ligand for actinide/lanthanide separation.

    PubMed

    Yang, Yanqiu; Liu, Jun; Yang, Liang; Li, Kun; Zhang, Huabei; Luo, Shunzhong; Rao, Linfeng

    2015-05-21

    Complexation of Am(III), Nd(III), and Eu(III) with a new heterocyclic nitrogen-donor ligand, 2,9-di(quinazolin-2-yl)-1,10-phenanthroline (denoted as BQPhen in this paper), was studied by thermodynamic measurements and theoretical computations. The stability constants of two successive complexes in dimethylformamide, ML(3+) and ML2(3+) where M stands for Nd, Eu, or Am while L stands for the BQPhen ligand, were determined by absorption spectrophotometry. The enthalpy of complexation was determined by microcalorimetry. Results show that BQPhen forms ten times stronger complexes with Am(III) than Eu(III) or Nd(III) under identical conditions, suggesting that BQPhen could be used as an efficient extractant for the separations of trivalent actinides from lanthanides. The higher binding strength of BQPhen towards Am(III) than Nd(III) or Eu(III) is mainly due to the more favourable enthalpy of complexation for Am(III)/BQPhen complexes, implying a higher degree of covalence in the Am(III)/BQPhen complexes than the lanthanide(III)/BQPhen complexes. The thermodynamic trend was corroborated with computational results and validated by solvent extraction experiments that demonstrated BQPhen preferably extracted Am(III) more than Eu(III), with a separation factor of about 10. Discussions have been made to compare BQPhen with other phenanthroline derivatives such as CyMe4-BTPhen, a bis-triazine-phenanthroline derivative that was reported in the literature. Data suggest that, under identical conditions, BQPhen would form stronger complexes with Am(III), Eu(III), and Nd(III) than CyMe4-BTPhen.

  17. On the search for NNO-donor enantiopure scorpionate ligands and their coordination to group 4 metals.

    PubMed

    Otero, Antonio; Fernández-Baeza, Juan; Tejeda, Juan; Lara-Sánchez, Agustín; Sánchez-Molina, Margarita; Franco, Sonia; López-Solera, Isabel; Rodríguez, Ana M; Sánchez-Barba, Luis F; Morante-Zarcero, Sonia; Garcés, Andrés

    2009-06-15

    The preparation of new chiral bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the lithium derivatives [Li(bpzb)(THF)] [1; bpzb = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide] and [Li(bpzte)(THF)] [2; bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-p-tolylethoxide] or the alcohol ligands (bpzbH) (3) and (bpzteH) (4) has been carried out by 1,2-addition reactions with trimethylacetaldehyde or p-tolualdehyde. The separation of a racemic mixture of the alcohol ligand 3 has been achieved and gave an enantiopure NNO alcohol-scorpionate ligand in three synthetic steps: (i) 1,2-addition of the appropriate lithium derivative to trimethylacetaldehyde, (ii) esterification and separation of diastereoisomers 5, (iii) saponification. Subsequently, the enantiopure scorpionate ligand (R,R)-bpzmmH {6; R,R-bpzmmH = (1R)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol} was obtained with an excellent diastereomeric excess (>99% de) in a one-pot process utilizing the aldehyde (1R)-(-)-myrtenal as a chiral substrate to control the stereochemistry of the newly created asymmetric center. These new chiral heteroscorpionate ligands reacted with [MX(4)] (M = Ti, Zr; X = NMe(2), O(i)Pr, OEt, O(t)Bu) in a 1:1 molar ratio in toluene to give, after the appropriate workup, the complexes [MX(3)(kappa(3)-NNO)] (7-18). The reaction of Me(3)SiCl with [Ti(NMe(2))(3)(bpzb)] (7) or [Ti(NMe(2))(3)(R,R-bpzmm)] (11) in different molar ratios gave the halide-amide-containing complexes [TiCl(NMe(2))(2)(kappa(3)-NNO)] (19 and 20) and [TiCl(2)(NMe(2))(kappa(3)-NNO)] (21 and 22) and the halide complex [TiCl(3)(kappa(3)-NNO)] (23 and 24). The latter complexes can also be obtained by reaction of the lithium compound 1 with TiCl(4)(THF)(2) and deprotonation of the alcohol group of 6 with NaH, followed by reaction with TiCl(4)(THF)(2) in a 1:1 molar ratio, respectively. Isolation of only one of the three possible diastereoisomers of the

  18. Cationic mono and dicarbonyl pincer complexes of rhodium and iridium to assess the donor properties of PCcarbeneP ligands.

    PubMed

    Smith, Joel D; Logan, Jessamyn R; Doyle, Lauren E; Burford, Richard J; Sugawara, Shun; Ohnita, Chiho; Yamamoto, Yohsuke; Piers, Warren E; Spasyuk, Denis M; Borau-Garcia, Javier

    2016-08-01

    The donor properties of five different PCcarbeneP ligands are assessed by evaluation of the CO stretching frequencies in iridium(i) and rhodium(i) carbonyl cations. The ligands feature dialkyl phosphine units (R = (i)Pr or (t)Bu) linked to the central benzylic carbon by either an ortho-phenylene bridge, or a 2,3-benzo[b]thiophene linker; in the former, substituent patterns on the phenyl linker are varied. The carbonyl complexes are synthesized from the (PCcarbeneP)M-Cl starting materials via abstraction of the chlorides in the presence of CO gas. In addition to the expected mono carbonyl cations, products with two carbonyl ligands are produced, and for the rhodium example, a novel product in which the second carbonyl ligand adds reversibly across the Rh[double bond, length as m-dash]C bond to give an η(2) ketene moiety was characterized. The IR data for the complexes shows the 2,3-benzo[b]thiophene linked system to be the poorest overall donor, while the phenyl bridged ligands incorporating electron donating dialkyl amino groups para to the anchoring carbene are very strongly donating pincer arrays. PMID:27465584

  19. Norfloxacin and N-Donor Mixed-Ligand Copper(II) Complexes: Synthesis, Albumin Interaction, and Anti-Trypanosoma cruzi Activity

    PubMed Central

    Martins, Darliane A.; Gouvea, Ligiane R.; Muniz, Gabriel S. Vignoli; Louro, Sonia R. W.; Batista, Denise da Gama Jaen; Soeiro, Maria de Nazaré C.; Teixeira, Letícia R.

    2016-01-01

    Copper(II) complexes with the first-generation quinolone antibacterial agent norfloxacin containing a nitrogen donor heterocyclic ligand 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) were prepared and characterized by IR, EPR spectra, molar conductivity, and elemental analyses. The experimental data suggest that norfloxacin was coordinated to copper(II) through the carboxylato and ketone oxygen atoms. The interaction of the copper(II) complexes with bovine serum albumin (BSA) and human serum albumin (HSA) was investigated using fluorescence quenching of the tryptophan residues and copper(II) EPR spectroscopy. The results of fluorescence titration revealed that copper(II) complexes have a moderate ability to quench the intrinsic fluorescence of the albumins through a static quenching mechanism. EPR experiments showed that BSA and HSA Cu(II) sites compete with NOR for Cu(II)-bipy and Cu(II)-phen to form protein mixed-ligand complexes. Copper(II) complexes, together with the corresponding ligands, were evaluated for their trypanocidal activity in vitro against Trypanosoma cruzi, the causative agent of Chagas disease. The tests performed using bloodstream trypomastigotes showed that the Cu(II)-N-donor precursors and the metal complexes were more active than the free fluoroquinolone. PMID:26924953

  20. 77 FR 42000 - Notice of Request for Renewal of Information Collection for Donor Certification Form

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-17

    ... Office of the Secretary Notice of Request for Renewal of Information Collection for Donor Certification... at 202-208- 4867. Individuals providing comments should reference Donor Certification Form. FOR... submitted to OMB for approval for the Department and its bureaus to collect information from proposed...

  1. The influence of oxygen-17 enriched oxygen-donor ligands on the electronic spin relaxation behaviour of paramagnetic metal ions

    NASA Astrophysics Data System (ADS)

    Wells, Gregg B.; Yim, Moon B.; Makinen, Marvin W.

    Continuous wave microwave power saturation of high-spin paramagnetic metalloprotein complexes of Co2+ and Fe3+ showed that the value of the saturation parameter P1/2 is influenced by the coordination of oxygen-17 enriched water to the metal ion. No change was observed for H218O or 2H2O. Pulse saturation and recovery of paramagnetic high-spin Fe3+ heme proteins identified a fast relaxation component sensitive to isotopic oxygen-17 composition that was assigned to the process of spectral diffusion. It is shown that the change in relaxation time for spectral diffusion can alter the (apparent) spin-lattice relaxation to account for the observed changes in continuous wave microwave power saturation experiments. These changes are shown to correlate with alterations in the extent of covalency between the metal ion and oxygen-donor ligand. The experimental results provide a basis for use of continuous wave microwave saturation to identify the presence of oxygen-donor ligands within the inner coordination shell of high-spin Co2+ or Fe3+ in metalloprotein and small molecule complexes and to qualitatively assess the extent of covalency between the metal ion and the oxygen-donor ligand.

  2. Dichlorodioxomolybdenum(VI) complexes bearing oxygen-donor ligands as olefin epoxidation catalysts.

    PubMed

    Oliveira, Tânia S M; Gomes, Ana C; Lopes, André D; Lourenço, João P; Almeida Paz, Filipe A; Pillinger, Martyn; Gonçalves, Isabel S

    2015-08-21

    Treatment of the solvent adduct [MoO2Cl2(THF)2] with either 2 equivalents of N,N-dimethylbenzamide (DMB) or 1 equivalent of N,N'-diethyloxamide (DEO) gave the dioxomolybdenum(vi) complexes [MoO2Cl2(DMB)2] () and [MoO2Cl2(DEO)] (). The molecular structures of and were determined by single-crystal X-ray diffraction. Both complexes present a distorted octahedral geometry and adopt the cis-oxo, trans-Cl, cis-L configuration typical of complexes of the type [MoO2X2(L)n], with either the monodentate DMB or bidentate DEO oxygen-donor ligands occupying the equatorial positions trans to the oxo groups. The complexes were applied as homogeneous catalysts for the epoxidation of olefins, namely cis-cyclooctene (Cy), 1-octene, trans-2-octene, α-pinene and (R)-(+)-limonene, using tert-butylhydroperoxide (TBHP) as oxidant. In the epoxidation of Cy at 55 °C, the desired epoxide was the only product and turnover frequencies in the range of ca. 3150-3200 mol molMo(-1) h(-1) could be reached. The catalytic production of cyclooctene oxide was investigated in detail, varying either the reaction temperature or the cosolvent. Complexes and were also applied in liquid-liquid biphasic catalytic epoxidation reactions by using an ionic liquid of the type [C4mim][X] (C4mim = 1-n-butyl-3-methylimidazolium; X = NTf2, BF4 or PF6] as a solvent to immobilise the metal catalysts. Recycling for multiple catalytic runs was achieved without loss of activity. PMID:26174418

  3. Dichlorodioxomolybdenum(VI) complexes bearing oxygen-donor ligands as olefin epoxidation catalysts.

    PubMed

    Oliveira, Tânia S M; Gomes, Ana C; Lopes, André D; Lourenço, João P; Almeida Paz, Filipe A; Pillinger, Martyn; Gonçalves, Isabel S

    2015-08-21

    Treatment of the solvent adduct [MoO2Cl2(THF)2] with either 2 equivalents of N,N-dimethylbenzamide (DMB) or 1 equivalent of N,N'-diethyloxamide (DEO) gave the dioxomolybdenum(vi) complexes [MoO2Cl2(DMB)2] () and [MoO2Cl2(DEO)] (). The molecular structures of and were determined by single-crystal X-ray diffraction. Both complexes present a distorted octahedral geometry and adopt the cis-oxo, trans-Cl, cis-L configuration typical of complexes of the type [MoO2X2(L)n], with either the monodentate DMB or bidentate DEO oxygen-donor ligands occupying the equatorial positions trans to the oxo groups. The complexes were applied as homogeneous catalysts for the epoxidation of olefins, namely cis-cyclooctene (Cy), 1-octene, trans-2-octene, α-pinene and (R)-(+)-limonene, using tert-butylhydroperoxide (TBHP) as oxidant. In the epoxidation of Cy at 55 °C, the desired epoxide was the only product and turnover frequencies in the range of ca. 3150-3200 mol molMo(-1) h(-1) could be reached. The catalytic production of cyclooctene oxide was investigated in detail, varying either the reaction temperature or the cosolvent. Complexes and were also applied in liquid-liquid biphasic catalytic epoxidation reactions by using an ionic liquid of the type [C4mim][X] (C4mim = 1-n-butyl-3-methylimidazolium; X = NTf2, BF4 or PF6] as a solvent to immobilise the metal catalysts. Recycling for multiple catalytic runs was achieved without loss of activity.

  4. Phenylthiolate as a sigma- and pi- donor ligand: synthesis of a 3-D organometallic coordination polymer [K2Fe(SPh)4]n.

    PubMed

    Yu, Xiao-Yan; Jin, Guo-Xin; Weng, Lin-Hong

    2004-07-01

    The synthesis and crystal structure of the first mixed-metal organometallic polymer network containing phenylthiolato ligands, [K2Fe(SPh)4]n, are investigated. The simple phenylthiolate acts as a sigma- and pi-donor ligand to give a 3-D potassium iron coordination polymer with both metal-carbon and metal-sulfur coordination interactions.

  5. Syntheses, structures and photoluminescence of lanthanide-organic frameworks assembled from multifunctional N,O-donor ligand

    SciTech Connect

    Che, Guang-Bo; Liu, Shu-Yu; Zhang, Qing; Liu, Chun-Bo; Zhang, Xing-Jing

    2015-05-15

    Four new lanthanide complexes [Ln(O–NCP){sub 2}(NO{sub 3})]{sub n} based on multifunctional N,O-donor ligand 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline (O–HNCP) and Ln(NO{sub 3}){sub 3}·6H{sub 2}O (Ln=Nd(1), La(2), Sm(3), Eu(4)) have been achieved under hydrothermal conditions and characterized by elemental analyses, infrared spectra and single crystal X-ray diffraction. Structural analyses revealed that all of these four complexes possess similar two-dimensional layer structures. In addition, thermal stability and luminescent properties of these complexes were also investigated. - Graphical abstract: A series of lanthanide(III) coordination polymers with intriguing structures based on 2-(2-carboxyphenyl)imidazo(4,5-f)-(1,10)phenanthroline ligand have been hydrothermally synthesized. The thermal stabilities and photoluminescence properties of these complexes have been investigated. - Highlights: • Four lanthanide(III) complexes have been hydrothermally synthesized. • The N,O-donor O–HNCP was used as the ligand. • TGA and PL properties of complexes 1–4 have been investigated.

  6. Electrophilic addition to cyanide ligands in tungsten(II) four-electron-donor alkyne complexes

    SciTech Connect

    Frohnapfel, D.S.; Reinartz, S.; White, P.S.; Templeton, J.L.

    1998-08-17

    Extended reflux of Tp{prime}(CO)(I)W(RC{triple_bond}CR{prime}) (Tp{prime} = hydridotris(3,5-dimethylpyrazolyl)borate) complexes in ethyl acetate in the presence of silver cyanide produces Tp{prime}(CO)(CN)W(RC{triple_bond}CR{prime}) complexes in moderate to high yields. A single-crystal X-ray structure of Tp{prime}(CO)(CN)W(PhC{triple_bond}CMe) shows that the alkyne is aligned parallel to the M{single_bond}CO axis. Electrophilic attack at the nitrogen of the cyanide ligand with methyl triflate or triflic acid yields cationic isocyanide complexes, whereas attack with HBF{sub 4} results in neutral BF{sub 3} adduct complexes. Coordination of the Tp{prime}(CO)(PhC{triple_bond}CMe)W{sup +} fragment to the cyanide nitrogen of Tp{prime}(CO)(CN)W(HC{triple_bond}CBu{sup n}) to form a CN-bridged dinuclear complex has been achieved. Variable-temperature {sup 1}H NMR measurements reflect acetylene rotation barriers in the Tp{prime}(CO)(L)W(HC{triple_bond}CH){sup n+} series (L = CO, CNH, CNMe {l_brace}n = 1{r_brace}; CN{sup {minus}}, CNBF{sub 3}{sup {minus}} {l_brace}n = 0{r_brace}) and, thus, quantify {pi}-effects for the cyanide and isocyanide ligands with respect to steric considerations. Extended Hueckel molecular orbital calculations were carried out on a series of model complexes, [H{sub 3}(CO)(L)W(HC{triple_bond}CH)]{sup n{minus}} (L = CO, CNH {l_brace}n = 1{r_brace}; CN{sup {minus}}, H{sup {minus}} {l_brace}n = 2{r_brace}) to augment the experimental data.

  7. Synthesis, crystal structures, and properties of two novel cadmium(II)-organic frameworks based on asymmetric dicarboxylate and N-donor ligands

    NASA Astrophysics Data System (ADS)

    Chen, Xiaoli; Gao, Loujun; Zhang, Xiaoge; Han, Xuhua; Wang, Yao; Sun, Rong

    2014-08-01

    Two novel cadmium(II)-organic frameworks with asymmetric dicarboxylate and N-donor ligands, namely [Cd(cpa)(phen)]n (1) and {[Cd2(cpa)2(bpy)1.5]·0.5H2O}n (2) (H2cpa = 3-(4-benzoic)propionic acid, phen = 1,10-phenanthroline, bpy = 4,4";-bipyridine) have been hydrothermally synthesized and characterized by elemental analyses, FT-IR spectra, single-crystal X-ray diffraction analyses, TGA, powder XRD and fluorescent measurements. 1 displays a double zigzag chain structure containing 8-number and 22-number circles. 2 Shows a 6-connected 3D polymer network based on tetranuclear cadmium cluster units. The most striking feature of 2 is that a pair of identical 3D networks are interlocked with each other to the form a 2-fold interpenetrated 3D α-Po structural topology. The diverse structures of two complexes indicate that the skeleton of N-donor ligands plays a great role in the assembly of such different frameworks. In addition, the thermal stabilities, XRD and photoluminescence properties of 1-2 were also studied.

  8. Donor Properties of a New Class of Guanidinate Ligands Possessing Ketimine Backbones: A Comparative Study Using Iron.

    PubMed

    Maity, Arnab K; Metta-Magaña, Alejandro J; Fortier, Skye

    2015-10-19

    Addition of 1 equiv of LiN═C(t)Bu2 or LiN═Ad (Ad = 2-adamantyl) to the aryl carbodiimide C(NDipp)2 (Dipp = 2,6-diisopropylphenyl) readily generates the lithium ketimine-guanidinates Li(THF)2[(X)C(NDipp)2] (X = N═C(t)Bu2 (1-(t)Bu), N═Ad (1-Ad)) in excellent yields. These new ligands can be readily metalated with iron to give the N,N'-bidentate chelates [{(X)C(NDipp)2}FeBr]2 (X = N═C(t)Bu2 (5-(t)Bu), N═Ad (5-Ad)), in which the ketimines behave as noncoordinating backbone substituents. In an effort to understand the potential electronic contributions of the ketimine group to the ligand architecture, a thorough structural and electronic study was conducted comparing the features and properties of 5-(t)Bu and 5-Ad to their guanidinate and amidinate analogues [{(X)C(NDipp)2}FeBr]2 (X = (i)Pr2N (6), (t)Bu (7)). Solid-state structural analyses indicate little electronic contribution from the N-ketimine nitrogen atom, while solution-phase electronic absorption spectra of 5-(t)Bu and 5-Ad are qualitatively similar to the amidinate complex 7. Yet, electrochemical measurements do show the donor properties of the ketimine-guanidinate in 5-(t)Bu to be intermediate between its guanidinate and amidinate counterparts in 6 and 7. Preliminary reactivity studies also show that the reduction chemistry of 5-(t)Bu diverges significantly from that of 6 and 7. Treatment of 5-(t)Bu with excess magnesium or 1 equiv of KC8 leads to the formation of the Fe(I)-Fe(I) complex [{μ-((t)Bu2C═N)C(NDipp)2}2Fe2] (11), which possesses an exceedingly short Fe═Fe bond (2.1516(5) Å), while neither 6 nor 7 forms dinuclear complexes upon reduction. This result demonstrates that ketimine-guanidinates do not simply behave as amidinate variants but can contribute to distinctive metal chemistry of their own. PMID:26419613

  9. Cu{sup II} coordination polymers based on 5-methoxyisophthalate and flexible N-donor ligands: Structures and magnetic properties

    SciTech Connect

    Chang, Xin-Hong; Qin, Jian-Hua; Ma, Lu-Fang; Wang, Li-Ya

    2014-04-01

    Three Cu{sup II} coordination polymers, ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib)]){sub n} (1), ([Cu{sub 2}(CH{sub 3}O-ip){sub 2}(bmib){sub 2}]){sub n} (2) and ([Cu(CH{sub 3}O-ip)(bbip)]∙2H{sub 2}O){sub n} (3) (CH{sub 3}O-H{sub 2}ip is 5-methoxyisophthalic acid, bmib is 1,4-bis(2-methylimidazol-1-yl)butane and bbip is 1,3-bis(1H-benzimidazolyl)propane), have been synthesized by hydrothermal methods. Complexes 1–3 were structurally characterized by elemental analysis, infrared (IR) spectra and X-ray single-crystal diffraction. Complex 1 shows a 3D six-connected self-penetrating network based on paddlewheel secondary building units. Complex 2 has a 3-fold interpenetrating 3D diamond framework. Complex 3 possesses a 1D tube-like chain. Thermo-gravimetric and magnetic properties of 1–3 were also investigated. - Graphical abstract: Structures and magnetic properties of copper(II) coordination polymers constructed from 5-methoxyisophthalate linker and two flexible N-donor ancillary ligands. Three copper(II) coordination polymers with 5-methoxyisophthalate and two related flexible N-donor ancillary ligands have been synthesized and structurally characterized. Moreover, thermal behaviors and magnetic properties of these complexes have also been investigated. - Highlights: • Three Cu(II) coordination polymers were synthesized. • The conformations of N-donor ligands and pH value have an effect on the final structures. • The magnetic properties of 1–3 have been investigated.

  10. Syntheses, characterizations and structures of NO donor Schiff base ligands and nickel(II) and copper(II) complexes

    NASA Astrophysics Data System (ADS)

    Şenol, Cemal; Hayvali, Zeliha; Dal, Hakan; Hökelek, Tuncer

    2011-06-01

    New Schiff base derivatives ( L 1 and L 2) were prepared by the condensation of 2-hydroxy-3-methoxybenzaldehyde ( o-vanillin) and 3-hydroxy-4-methoxybenzaldehyde ( iso-vanillin) with 5-methylfurfurylamine. Two new complexes [Ni(L 1) 2] and [Cu(L 1) 2] have been synthesized with bidentate NO donor Schiff base ligand ( L 1). The Ni(II) and Cu(II) atoms in each complex are four coordinated in a square planar geometry. Schiff bases ( L 1 and L 2) and complexes [Ni(L 1) 2] and [Cu(L 1) 2] were characterized by elemental analyses, FT-IR, UV-vis, mass and 1H, 13C NMR spectroscopies. The crystal structures of the ligand ( L 2) and complexes [Ni(L 1) 2] and [Cu(L 1) 2] have also been determined by using X-ray crystallographic technique.

  11. Modular syntheses of multidentate ligands with variable N-donors: applications to tri- and tetracopper(I) complexes.

    PubMed

    Brown, Eric C; Johnson, Brandon; Palavicini, Sara; Kucera, Benjamin E; Casella, Luigi; Tolman, William B

    2007-07-28

    A general method for the preparation of multidentate ligands comprised of a multi-imine platform derived from 1,1,1-tris(aminomethyl)ethane or tris(aminoethyl)amine connected to bi- and tridentate N-donor chelates has been developed. The feasibility of the method has been demonstrated through the synthesis and characterization of a large set of these ligand types. Complexation to Cu(I) was accomplished for several cases, yielding tri- and tetracopper(I) complexes that have been characterized in solution by NMR spectroscopy and conductivity, and in the solid state by elemental analysis, mass spectrometry, and/or X-ray crystallography. These complexes are potentially useful for modeling multicopper protein active sites. PMID:17622421

  12. Redox interplay of oxo-thio-tungsten centers with sulfur-donor co-ligands.

    PubMed

    Thomas, Simon; Eagle, Aston A; Sproules, Stephen A; Hill, Jason P; White, Jonathan M; Tiekink, Edward R T; George, Graham N; Young, Charles G

    2003-09-22

    The oxo-thio-W(VI) complexes TpWOS(S(2)PR(2)-S) and TpWOS(pyS-S) (Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate, R = OEt, Ph; pyS = pyridine-2-thiolate) have been prepared and characterized by microanalytical, spectroscopic, and structural techniques. Crystals of the 1,2-dichloroethane hemisolvate of TpWOS(S(2)PPh(2)-S) belong to the triclinic space group Ponemacr; with a = 10.732(6) A, b = 16.91(1) A, c = 10.021(4) A, alpha = 104.40(4) degrees, beta = 107.52(3) degrees, gamma = 96.09(5) degrees, V = 1647(1) A(3) for Z = 2. The complex exhibits a distorted octahedral structure featuring a facial tridentate Tp ligand and mutually cis terminal oxo (W-O(1) = 1.712(7) A), terminal thio (W-S(1) = 2.162(3) A), and monodentate dithiophosphinate ligands. X-ray absorption and extended X-ray absorption fine structure results support a related oxo-thio formulation for TpWOS(pyS-S). The complexes are reduced to the corresponding oxo-thio-W(V) anions, [TpWOS(S(2)PR(2)-S)](-) and [TpWOS(pyS-S)](-), which exhibit highly anisotropic EPR spectra. They are oxidized to form the EPR-active (dithio)oxo-W(V) cations, [TpWO(S(3)PR(2)-S,S')](+) and [TpWO(pyS(2)-N,S)](+) (pyS(2) = pyridine-2-dithio). Green [TpWO(pyS(2)-N,S)]BF(4), formed in the reaction of TpWOS(pyS) and NOBF(4), has been isolated and spectroscopically and structurally characterized. Crystals of [TpWO(pyS(2)-N,S)]BF(4) belong to the monoclinic space group Cc with a = 16.007(5) A, b = 14.091(4) A, c = 13.608(4) A, beta = 124.525(4) degrees, V = 2528.8(13) A(3) for Z = 4. The cation exhibits a distorted octahedral structure featuring facial tridentate Tp, terminal oxo (W-O(1) = 1.632(12) A), and bidentate pyridine-2-dithio-N,S (W-S(1) = 2.317(7) A, S(1)-S(2) = 2.037(9) A) ligands. The structures and redox behavior of the complexes are compared and contrasted with those of the related molybdenum complexes, TpMo(VI)OS(S(2)PR(2)-S) and TpMo(IV)O(pyS(2)-N,S) (Hill, J. P.; Laughlin, L. J.; Gable, R. W.; Young, C. G. Inorg. Chem

  13. Auxiliary Ligand-Dependent Assembly of Several Ni/Ni-Cd Compounds with N 2 O 2 Donor Tetradentate Symmetrical Schiff Base Ligand

    SciTech Connect

    Ge, Ying-Ying; Li, Guo-Bi; Fang, Hua-Cai; Zhan, Xu-Lin; Gu, Zhi-Gang; Chen, Jin-Hao; Sun, Feng; Cai, Yue-Peng; Thallapally, Praveen K.

    2010-11-03

    Several low-dimensional Ni/Ni-Cd complexes containing N2O2 donor tetradentate symmetrical Schiff base ligand bis(acetylacetone)ethylene-diamine (sy-H2L2), namely, [Ni(sy-L2)]2∙HLa∙ClO4 (2), (HLa)2∙(ClO4)∙(NO3) (3), [Ni(sy-L2)X]2](4,4’-bipy) (where La = 5,7-dimethyl-3,6-dihydro-2H-1,4-diazepine, X = ClO4 (4), X=NO3 (5), [Ni(sy-L2)Cd(SCN)2]n (6) and [Ni(sy-L2)∙Cd(N3)2]n (7) have been synthesized from [Ni(sy-L2)]2∙H2O (1). Complex 2, is three component discrete assembly generated from (HLa)+ moiety bridged with [Ni(sy-L2)] unit and ClO4- anion. A solution containing complex 2 and Cd(NO3)2 results in a mixture of 1 and 3. Further re-crystallization of 1 and 3 with various auxiliary ligands, provides coordination complexes 4 – 7 stabilized by weak hydrogen bonds in which 6 and 7 represent the first 1D heteronuclear complexes based on symmetric acacen-base Schiff base ligand.

  14. New [Mo(eta3-allyl)(CO)2L3]+ complexes with monodentate or tridentate nitrogen-donor ligands.

    PubMed

    Pérez, Julio; Morales, Dolores; Nieto, Sonia; Riera, Lucía; Riera, Víctor; Miguel, Daniel

    2005-03-01

    Cationic complexes [Mo(eta(3)-allyl)(CO)2L3]+ (L3 = either nitrogen-donor tridentate ligand or three monodentate ligands) were prepared in high yield and under mild conditions using as precursors either the triflato complex [Mo(eta(3)-allyl)(OTf)(CO)2(NCMe)2] or the combination of the chloro complex [Mo(eta(3)-allyl)Cl(CO)2(NCMe)2] and the salt NaBAr'(4)(Ar'= 3,5-bis(trifluoromethyl)phenyl). The tridentate ligands employed were 2,2':6',2'-terpyridine (terpy) and cis,cis-1,3,5-cyclohexanetriamine (CHTA), whereas the monodentate ligands imidazole (im) and 3,5-dimethylpyrazole (dmpz) were chosen. In order to stabilize the labile intermediates, an excess of acetonitrile was used in most of the syntheses. However, the pyrazole complex was prepared through a nitrile-free route to avoid reactions at the coordinated nitrile. The solid state structures of [Mo(eta(3)-methallyl)(CO)2(terpy)]OTf (2), [Mo(eta(3)-methallyl)(CO)2(CHTA)]BAr'4 (3), [Mo(eta(3)-methallyl)(CO)2(NCMe)3]BAr'4 (4), [Mo(eta(3)-allyl)(CO)2(im)3]OTf (5) and [Mo(eta(3)-allyl)(CO)2(dmpz)3]BAr'4 (6) were determined by means of single-crystal X-ray diffraction. PMID:15726140

  15. Rhenium(V) and technetium(V) nitrido complexes with mixed tridentate π-donor and monodentate π-acceptor ligands.

    PubMed

    Boschi, Alessandra; Cazzola, Emiliano; Uccelli, Licia; Pasquali, Micol; Ferretti, Valeria; Bertolasi, Valerio; Duatti, Adriano

    2012-03-01

    Mixed-ligand [M(N)(SNS)(PPh(3))] complexes (M = Tc, Re) (1, 2) were prepared by reaction of the precursor [M(N)Cl(2)(PPh(3))(2)] with ligand 2,2'-dimercaptodiethylamine [H(2)SNS = NH(CH(2)CH(2)SH)(2)] in refluxing dichloromethane/ethanol mixtures. In these compounds, 2,2'-dimercaptodiethylamine acts as a dianionic tridentate chelating ligand bound to the [M≡N](2+) group through the two π-donor deprotonated sulfur atoms and the protonated amine nitrogen atom. Triphenylphosphine completes the coordination sphere, acting as a monodentate ligand. [M(N)(NS(2))(PPh(3))] complexes can assume two different isomeric forms depending on the syn and anti orientations of the hydrogen atom bound to the central nitrogen atom of the SNS ligand with respect to the M≡N moiety. X-ray crystallography of the syn isomer of complex 2 demonstrated that it has a distorted trigonal bipyramidal geometry with the nitrido group and the two sulfur atoms defining the equatorial plane, the phosphorus atom of the monophosphine and the protonated amine nitrogen of the tridentate ligand spanning the two reciprocal trans positions along the axis perpendicular to the trigonal plane. Synthesis of the analogous Tc derivatives with tris(2-cyanoethyl)phosphine, [Tc(N)(SNS)(PCN)] [(PCN = P(CH(2)CH(2)CN)(3)], required the preliminary preparation of the new precursor [Tc(N)(PCN)(2)Cl(2)](2) (3), which was prepared by reacting [n-NBu(4)][Tc(N)Cl(4)] with a high excess of PCN. The crystal structure of compound 3 consists of a noncrystallographic centrosymmetric dimer of Tc(V) nitrido complexes having an octahedral geometry. In this arrangement, the apical positions are occupied by two tris(2-cyanoethyl)phosphine groups and the equatorial positions by the nitrido group whereas the two Cl(-) anions and one cyano ligand belong to the other octahedral component of the dimer. By reacting the new precursor [Tc(N)(PCN)(2)Cl(2)](2) with the ligand H(2)SNS the complex [Tc(N)(SNS)(PCN)] (5) was finally obtained in

  16. Rhenium(V) and technetium(V) nitrido complexes with mixed tridentate π-donor and monodentate π-acceptor ligands.

    PubMed

    Boschi, Alessandra; Cazzola, Emiliano; Uccelli, Licia; Pasquali, Micol; Ferretti, Valeria; Bertolasi, Valerio; Duatti, Adriano

    2012-03-01

    Mixed-ligand [M(N)(SNS)(PPh(3))] complexes (M = Tc, Re) (1, 2) were prepared by reaction of the precursor [M(N)Cl(2)(PPh(3))(2)] with ligand 2,2'-dimercaptodiethylamine [H(2)SNS = NH(CH(2)CH(2)SH)(2)] in refluxing dichloromethane/ethanol mixtures. In these compounds, 2,2'-dimercaptodiethylamine acts as a dianionic tridentate chelating ligand bound to the [M≡N](2+) group through the two π-donor deprotonated sulfur atoms and the protonated amine nitrogen atom. Triphenylphosphine completes the coordination sphere, acting as a monodentate ligand. [M(N)(NS(2))(PPh(3))] complexes can assume two different isomeric forms depending on the syn and anti orientations of the hydrogen atom bound to the central nitrogen atom of the SNS ligand with respect to the M≡N moiety. X-ray crystallography of the syn isomer of complex 2 demonstrated that it has a distorted trigonal bipyramidal geometry with the nitrido group and the two sulfur atoms defining the equatorial plane, the phosphorus atom of the monophosphine and the protonated amine nitrogen of the tridentate ligand spanning the two reciprocal trans positions along the axis perpendicular to the trigonal plane. Synthesis of the analogous Tc derivatives with tris(2-cyanoethyl)phosphine, [Tc(N)(SNS)(PCN)] [(PCN = P(CH(2)CH(2)CN)(3)], required the preliminary preparation of the new precursor [Tc(N)(PCN)(2)Cl(2)](2) (3), which was prepared by reacting [n-NBu(4)][Tc(N)Cl(4)] with a high excess of PCN. The crystal structure of compound 3 consists of a noncrystallographic centrosymmetric dimer of Tc(V) nitrido complexes having an octahedral geometry. In this arrangement, the apical positions are occupied by two tris(2-cyanoethyl)phosphine groups and the equatorial positions by the nitrido group whereas the two Cl(-) anions and one cyano ligand belong to the other octahedral component of the dimer. By reacting the new precursor [Tc(N)(PCN)(2)Cl(2)](2) with the ligand H(2)SNS the complex [Tc(N)(SNS)(PCN)] (5) was finally obtained in

  17. New NO donor ligands and complexes containing furfuryl or crown ether moiety: Syntheses, crystal structures and tautomerism in ortho-hydroxy substituted compounds as studied by UV-vis spectrophotometry

    NASA Astrophysics Data System (ADS)

    Şahin, Duygu; Koçoğlu, Serhat; Şener, Öznur; Şenol, Cemal; Dal, Hakan; Hökelek, Tuncer; Hayvalı, Zeliha

    2015-12-01

    NO donor ligands were prepared by the condensation of methoxy substituted salicylaldehyde with 5-methylfurfurylamine (1 and 2) and 4‧-aminobenzo-15-crown 5 (3-5). New crown ether ligands of Schiff base type (3-5) containing recognition sites for alkali metal and transition guest cations. Ni(II) complexes (1a-5a) have been synthesized with bidentate NO donor Schiff base ligands (1-5) with Ni(CH3COO)2.·4H2O. Monotopic crystalline 1:1 (Na+:ligand) sodium complexes (3b-5b) of the crown ether ligands were also prepared. Schiff bases (1-5) and complexes (1a-5a, 3b-5b) were characterized by elemental analyses, FT-IR, 1H-, 13C-NMR and mass spectroscopies. The crystal structures of 1, 1a and 2 were verified by X-ray diffraction analysis. The tautomeric equilibria (phenol-imine, O-H⋯N and keto-amine, O⋯H-N forms) have been systematically studied by using UV-vis spectrophotometry for the o-hydroxy substituted compounds (1-5). The UV-visible spectra of these ligands (1-5) were recorded and commented in polar, non-polar, acidic and basic media.

  18. Minimalistic Ditopic Ligands: An α-S,N-Donor-Substituted Alkyne as Effective Intermetallic Conjugation Linker.

    PubMed

    Rüger, Julia; Timmermann, Christopher; Villinger, Alexander; Hinz, Alexander; Hollmann, Dirk; Seidel, Wolfram W

    2016-08-01

    The capability of donor-substituted alkynes to link different metal ions in a side-on carbon donor-chelate coordination mode is extended from the donor centers S and P to the second period element N. The complex [Tp'W(CO)2 {η(2) -C2 (S)(NHBn)}] (Tp'=hydrido-tris(3,5-dimethylpyrazolyl)borate, Bn=benzyl) bearing a terminal sulfur atom and a secondary amine substituent is accessible by a metal-template synthesis. Subsequent deprotonation allowed the formation of remarkably stable heterobimetallic complexes with the [(η(5) -C5 H5 )Ru(PPh3 )] and the [Ir(ppy)2 ] moiety. Electrochemical and spectroscopic investigations (cyclic voltammetry, IR, UV/Vis, luminescence, EPR), as well as DFT calculations, and X-ray structure determinations of the W-Ru complex in two oxidation states reveal a strong metal-metal coupling but also a limited delocalization of excited states. PMID:27272102

  19. Minimalistic Ditopic Ligands: An α-S,N-Donor-Substituted Alkyne as Effective Intermetallic Conjugation Linker.

    PubMed

    Rüger, Julia; Timmermann, Christopher; Villinger, Alexander; Hinz, Alexander; Hollmann, Dirk; Seidel, Wolfram W

    2016-08-01

    The capability of donor-substituted alkynes to link different metal ions in a side-on carbon donor-chelate coordination mode is extended from the donor centers S and P to the second period element N. The complex [Tp'W(CO)2 {η(2) -C2 (S)(NHBn)}] (Tp'=hydrido-tris(3,5-dimethylpyrazolyl)borate, Bn=benzyl) bearing a terminal sulfur atom and a secondary amine substituent is accessible by a metal-template synthesis. Subsequent deprotonation allowed the formation of remarkably stable heterobimetallic complexes with the [(η(5) -C5 H5 )Ru(PPh3 )] and the [Ir(ppy)2 ] moiety. Electrochemical and spectroscopic investigations (cyclic voltammetry, IR, UV/Vis, luminescence, EPR), as well as DFT calculations, and X-ray structure determinations of the W-Ru complex in two oxidation states reveal a strong metal-metal coupling but also a limited delocalization of excited states.

  20. Linear free energy relationships for metal-ligand complexation: Bidentate binding to negatively-charged oxygen donor atoms

    NASA Astrophysics Data System (ADS)

    Carbonaro, Richard F.; Atalay, Yasemin B.; Di Toro, Dominic M.

    2011-05-01

    Stability constants for metal complexation to bidentate ligands containing negatively-charged oxygen donor atoms can be estimated from the following linear free energy relationship (LFER): log KML = χOO( αO log KHL,1 + αO log KHL,2) where KML is the metal-ligand stability constant for a 1:1 complex, KHL,1 and KHL,2 are the proton-ligand stability constants (the ligand p Ka values), and αO is the Irving-Rossotti slope. The parameter χOO is metal specific and has slightly different values for five and six membered chelate rings. LFERs are presented for 21 different metal ions and are accurate to within approximately 0.30 log units in predictions of log KML values. Ligands selected for use in LFER development include dicarboxylic acids, carboxyphenols, and ortho-diphenols. For ortho-hydroxybenzaldehydes, α-hydroxycarboxylic acids, and α-ketocarboxylic acids, a modification of the LFER where log KHL,2 is set equal to zero is required. The chemical interpretation of χOO is that it accounts for the extra stability afforded to metal complexes by the chelate effect. Cu-NOM binding constants calculated from the bidentate LFERs are similar in magnitude to those used in WHAM 6. This LFER can be used to make log KML predictions for small organic molecules. Since natural organic matter (NOM) contains many of the same functional groups (i.e. carboxylic acids, phenols, alcohols), the LFER log KML predictions shed light on the range of appropriate values for use in modeling metal partitioning in natural systems.

  1. Influence of killer immunoglobulin-like receptor/HLA ligand matching on achievement of T-cell complete donor chimerism in related donor nonmyeloablative allogeneic hematopoietic stem cell transplantation.

    PubMed

    Sobecks, R M; Ball, E J; Askar, M; Theil, K S; Rybicki, L A; Thomas, D; Brown, S; Kalaycio, M; Andresen, S; Pohlman, B; Dean, R; Sweetenham, J; Macklis, R; Bernhard, L; Cherni, K; Copelan, E; Maciejewski, J P; Bolwell, B J

    2008-04-01

    Achievement of complete donor chimerism (CDC) after allogeneic nonmyeloablative hematopoietic stem cell transplantation (NMHSCT) is important for preventing graft rejection and for generating a graft-vs-malignancy effect. The alloreactivity of NK cells and some T-cell subsets is mediated through the interaction of their killer immunoglobulin-like receptors (KIRs) with target cell HLA/KIR ligands. The influence of KIR matching on the achievement of T-cell CDC after NMHSCT has not been previously described. We analyzed 31 patients undergoing T-cell replete related donor NMHSCT following fludarabine and 200 cGy TBI. Recipient inhibitory KIR genotype and donor HLA/KIR ligand matches were used to generate an inhibitory KIR score from 1 to 4 based upon the potential number of recipient inhibitory KIRs that could be engaged with donor HLA/KIR ligands. Patients with a score of 1 were less likely to achieve T-cell CDC (P=0.016) and more likely to develop graft rejection (P=0.011) than those with scores greater than 1. Thus, patients with lower inhibitory KIR scores may have more active anti-donor immune effector cells that may reduce donor chimerism. Conversely, patients with greater inhibitory KIR scores may have less active NK cell and T-cell populations, which may make them more likely to achieve CDC.

  2. Assessment of a self-deferral form for screening blood donors, Chiang Mai University Hospital, Thailand.

    PubMed

    Thaikruea, Lakkana; Nantachit, Niwes; Leetrakool, Nipapan; Fongsatitkul, Ladda; Sompan, Prakai; Heaton, Andrew; Nelson, Kenrad E

    2008-09-01

    A self-deferral form has been used to screen Chiang Mai University Hospital blood donors and was improved in 2005. It has never been evaluated. The study aimed to assess the self-deferral form procedures in detecting infected donors. Sera from 5,083 donors, who passed the self-deferral screening form, were tested with the routine immuno-assays (serology) for HIV 1 and 2 antibodies, P24 antigen, HCV antibodies, HBV surface antigen, and syphilis. Antibody negative sera were also tested individually with the the Procleix Ultrio Assay for HIV-1 DNA, HCV RNA, and HBV DNA. The donors who had discrepant results between serology and NAT were evaluated with additional tests, including a more sensitive Alternative Nucleic Acid Test, AntiBcore IgM, AntiBcore IgG, HBsAg and Anti HBs. Among 5,083 donors, 331 (6.5%) had at least one positive marker. In multiple logistic regression analysis, the statistically significant factors (adjusted odds ratio and 95% CI) for infection were age 30 years or below [1.45 (1.03, 2.03)], male gender [2.73 (1.64, 4.56)], primary school or lower education [1.56 (1.09, 2.23)], first-time donation [1.82 (1.25, 2.67)], and frequent donation [0.80 (0.70, 0.92)]. The safest donors were females, older than 30 years, with an education more than primary school, and frequent donation. Because of missing responses to some sensitive questions, there remains a need for further improvement of the self-deferral form.

  3. Circularly Polarized Luminescence in Enantiopure Europium and Terbium Complexes with Modular, All-Oxygen Donor Ligands

    PubMed Central

    Seitz, Michael; Do, King; Ingram, Andrew J.; Moore, Evan G.; Muller, Gilles; Raymond, Kenneth N.

    2009-01-01

    Abstract: Circulaly polarized luminescence from terbium(III) complexed and excited by chiral antenna ligands gives strong emission The modular synthesis of three new octadentate, enantiopure ligands are reported - one with the bidentate chelating unit 2-hydroxyisophthalamide (IAM) and two with 1-hydroxy-2-pyridinone (1,2-HOPO) units. A new design principle is introduced for the chiral, non-racemic hexamines which constitute the central backbones for the presented class of ligands. The terbium(III) complex of the IAM ligand, as well as the europium(III) complexes of the 1,2-HOPO ligands are synthesized and characterized by various techniques (NMR, UV, CD, luminescence spectroscopy). All species exhibit excellent stability and moderate to high luminescence efficiency (quantum yields ΦEu = 0.05–0.08 and ΦTb = 0.30–0.57) in aqueous solution at physiological pH. Special focus is put onto the properties of the complexes in regard to circularly polarized luminescence (CPL). The maximum luminescence dissymmetry factors (glum) in aqueous solution are high with |glum|max = 0.08 – 0.40. Together with the very favorable general properties (good stability, high quantum yields, long lifetimes), the presented lanthanide complexes can be considered as good candidates for analytical probes based on CPL in biologically relevant environments. PMID:19639983

  4. Probing the role of secondary versus tertiary amine donor ligands for indium catalysts in lactide polymerization.

    PubMed

    Osten, Kimberly M; Aluthge, Dinesh C; Patrick, Brian O; Mehrkhodavandi, Parisa

    2014-09-15

    The role of the central amine donor in a previously reported dinuclear indium catalyst, [N(Me2)N(H)O)InCl]2(μ-Cl)(μ-OEt) (1), for the polymerization of lactide was investigated through experimental methods. The solid state structural data of a series of dimeric complexes related to 1, including the previously reported bromide derivative [(N(Me2)N(H)O)InBr](μ-Br)(μ-OEt) (2) and the newly synthesized methylated derivative [(N(Me2)N(Me)O)InCl]2(μ-Cl)(μ-OEt) (6), showed that weak hydrogen bonding may be present within some of these complexes in the solid state. The polymerization of rac-lactide with 2, 6, and a related achiral complex [(L(H))InCl]2(μ-Cl)(μ-OEt) (8) synthesized for this study indicates that hydrogen bonding may not influence the reactivity of these compounds. The nature of the central amine donor may play a role in tuning the reactivity of these types of catalysts. Catalysts with central secondary amine donors, such as complexes 1, 2, and 8, are 2 orders of magnitude more reactive than those with central tertiary amine donors, such as complex 6.

  5. Behavior of the potential antitumor V(IV)O complexes formed by flavonoid ligands. 1. Coordination modes and geometry in solution and at the physiological pH.

    PubMed

    Sanna, Daniele; Ugone, Valeria; Lubinu, Giuseppe; Micera, Giovanni; Garribba, Eugenio

    2014-11-01

    The coordination modes and geometry assumed in solution by the potent antitumor oxidovanadium(IV) complexes formed by different flavonoids were studied by spectroscopic (Electron Paramagnetic Resonance, EPR) and computational (Density Functional Theory, DFT) methods. A series of bidentate flavonoid ligands (L) with increasing structural complexity was examined, which can involve (CO, O(-)) donors and formation of five- and six-membered chelate rings, or (O(-), O(-)) donors and five-membered chelate rings. The geometry corresponding to these coordination modes can be penta-coordinated, [VOL2], or cis-octahedral, cis-[VOL2(H2O)]. The results show that, at physiological pH, ligands provided with (CO, O(-)) donor set yield cis-octahedral species with "maltol-like" coordination when five-membered chelate rings are formed (as with 3-hydroxyflavone), while penta-coordinated structures with "acetylacetone-like" coordination are preferred when the chelate rings are six-membered (as with chrysin). When both the binding modes are possible, as with morin, the "acetylacetone-like" coordination is observed. For the ligands containing a catecholic donor set, such as 7,8-dihydroxyflavone, baicalein, fisetin, quercetin and rutin, the formation of square pyramidal complexes with (O(-), O(-)) "catechol-like" coordination and five-membered chelate rings is preferred at physiological pH. The determination of the different coordination modes and geometry is important to define the biotransformation in the blood and the interaction of these complexes with the biological membranes.

  6. Supramolecular isomers of metal-organic frameworks: the role of a new mixed donor imidazolate-carboxylate tetradentate ligand.

    PubMed

    Richards, Victoria J; Argent, Stephen P; Kewley, Adam; Blake, Alexander J; Lewis, William; Champness, Neil R

    2012-04-14

    Five new metal-organic frameworks prepared from the ligand 5-bis(3-(1-imidazolyl)propylcarbamoyl)terephthalate (bipta(2-)) and transition metal salts, Zn(2+) (1), Co(2+) (2), Mn(2+) (3, 4) and Cu(2+) (5), are reported. Single crystal X-ray studies reveal that the bipta(2-) ligand acts as a tetradentate ligand and combines with four-coordinate cationic metal nodes to give four-connected framework structures. Whilst reaction of bipta(2-) with Zn(II) gives rise to a framework of diamondoid topology 1, the analogous frameworks with Co(II), Mn(II) and Cu(II) afford frameworks that incorporate square-planar nodes. Whereas 2 and 5 form frameworks of Cd(SO(4)) (cds) and square 4(4) nets (sql), respectively, reaction of Mn(II) with bipta(2-) forms two supramolecular isomers of topology cds for 3 and sql for 4.

  7. Circularly Polarized Luminescence in Enantiopure Europium and Terbium Complexes with Modular, All-Oxygen Donor Ligands

    SciTech Connect

    Seitz, Michael; Do, King; Ingram, Andrew; Moore, Evan; Muller, Gilles; Raymond, Kenneth

    2009-06-04

    The modular syntheses of three new octadentate, enantiopure ligands are reported, one with the bidentate chelating unit 2-hydroxyisophthalamide (IAM) and two with bidentate 1-hydroxy-2-pyridinone (1,2-HOPO) units. A new design principle is introduced for the chiral, non-racemic hexamines which constitute the central backbones for the presented class of ligands. The terbium(III) complex of the IAM ligand, as well as the europium(III) complexes of the 1,2-HOPO ligands, are synthesized and characterized by various techniques (NMR, UV, CD, luminescence spectroscopy). All species exhibit excellent stability and moderate to high luminescence efficiency (quantum yields {phi}{sub Eu} = 0.05-0.08 and {phi}{sub Tb} = 0.30-0.57) in aqueous solution at physiological pH. Special focus is put onto the properties of the complexes in regard to circularly polarized luminescence (CPL). The maximum luminescence dissymmetry factors (glum) in aqueous solution are high with |glum|max = 0.08-0.40. Together with the very favorable general properties (good stability, high quantum yields, long lifetimes), the presented lanthanide complexes can be considered as good candidates for analytical probes based on CPL in biologically relevant environments.

  8. Thermodynamic study of the complexation of trivalent actinide and lanthanide cations by ADPTZ, a tridentate N-donor ligand.

    PubMed

    Miguirditchian, Manuel; Guillaneux, Denis; Guillaumont, Dominique; Moisy, Philippe; Madic, Charles; Jensen, Mark P; Nash, Kenneth L

    2005-03-01

    To better understand the bonding in complexes of f-elements by polydentate N-donor ligands, the complexation of americium(III) and lanthanide(III) cations by 2-amino-4,6-di-(pyridin-2-yl)-1,3,5-triazine (ADPTZ) was studied using a thermodynamic approach. The stability constants of the 1:1 complexes in a methanol/water mixture (75/25 vol %) were determined by UV-visible spectrophotometry for every lanthanide(III) ion (except promethium), and yttrium(III) and americium(III) cations. The thermodynamic parameters (DeltaH degrees , DeltaS degrees) of complexation were determined from the temperature dependence of the stability constants and by microcalorimetry. The trends of the variations of DeltaG degrees , DeltaH degrees , and DeltaS degrees across the lanthanide series are compared with published results for other tridentate ligands and confirm strongly ionic bonding in the lanthanide-ADPTZ complexes. Comparison of the thermodynamic properties between the Am- and Ln-ADPTZ complexes highlights an increase in stability of the complexes by a factor of 20 in favor of the americium cation. This difference arises from a more exothermic reaction enthalpy in the case of Am, which is correlated with a greater degree of covalency in the americium-nitrogen bonds. Quantum chemistry calculations performed on a series of trivalent actinide and lanthanide-ADPTZ complexes support the experimental results, showing a slightly greater covalence in the actinide-ligand bonds that originates from a charge transfer from the ligand sigma orbitals to the 5f and 6d orbitals of the actinide ion. PMID:15732980

  9. Charge transfer adducts of metal complexes of π-donor ligands with I 2 and TCNQ

    NASA Astrophysics Data System (ADS)

    Bera, T. R.; Sen, D.; Ghosh, R.

    1989-01-01

    Copper(II) and nickel(II) biguanides and O-alkyl-1-amidinourea can act as donors for the formation of charge transfer (CT) adducts with I 2 and tetracyanoquinodimethane (TNCQ) as acceptors. Iodine adducts are characterized both in solid and solution states whereas TCNQ adducts obtain only in solution. Appearance of a broad band at 355 nm for iodine adducts and at 335 nm for TNCQ adducts and shifting of i.r. frequencies support the formation of donor acceptor associates. Elemental analysis establishes 1:1 stoichiometry of the solid adducts. The K and ɛ values determined by modified Benesi—Hildebrand, Scott and Rose—Drago equations are found to be of the order of 10 4 and 10 3 respectively at 298 K in methanol. The solvent effect on the K values is discussed in terms of coupled solute-solute and solute-solvent equilibria.

  10. Dramatic tuning of ligand donor properties in (Ttz)CuCO through remote binding of H+ (Ttz = hydrotris(triazolyl)borate).

    PubMed

    Dixon, Natalie A; McQuarters, Ashley B; Kraus, Jodi S; Soffer, Jonathan B; Lehnert, Nicolai; Schweitzer-Stenner, Reinhard; Papish, Elizabeth T

    2013-06-21

    Complexes with bulky hydrotris(triazolyl)borate (Ttz) ligands, TtzCuCO, were used to probe how acids change the donor properties of Ttz ligands. (Ttz(tBu,Me))CuCO shows four distinct protonation states and a gradual increase in the CO stretch. The increased electrophilic nature of the Cu center upon protonation leads to enhanced C-H activation catalysis. PMID:23675583

  11. Informing egg donors of the potential for embryonic research: A survey of consent forms from US IVF clinics

    PubMed Central

    Schaefer, G. Owen; Sinaii, Ninet; Grady, Christine

    2013-01-01

    Objective To understand whether and to what extent US in vitro fertilization (IVF) clinics inform egg donors that resultant embryos initially intended to be implanted for reproductive purposes may in fact be used for research instead. Design 470 US IVF were asked to respond to a questionnaire and provide a copy of the egg donor consent form(s) used at the clinic. Setting 470 US IVF clinics listed in a Centers for Disease Control and Prevention database; only forms from clinics that both accepted donor eggs and provided excess embryos for research were analyzed for content. Main Outcome Measures Responses to the questionnaire, demographic data from a Centers for Disease Control and Prevention database and the content of egg donor consent forms. Results Of 222 US IVF clinics who responded to our query, 100 clinics both accepted donor eggs and provided some excess embryos for research. We received 66 consent forms from these 100 clinics, which showed that although most egg donor consent forms inform donors that they will not have control over embryos resulting from their eggs, 30% inform them that some embryos may be used for research, and even fewer mention stem cell research. Conclusion Egg donors in the US, including some who may have a moral objection to research and stem cell research, are not being informed that embryos created with their donated eggs may in fact be used for these purposes. This can be corrected with the inclusion of succinct, non-technical language in egg donor consent forms. PMID:22196714

  12. Diverse Cd(II) compounds based on N-benzoyl-L-glutamic acid and N-donor ligands: Structures and photoluminescent properties

    NASA Astrophysics Data System (ADS)

    Ma, Ning; Guo, Wei-Ying; Song, Hui-Hua; Yu, Hai-Tao

    2016-01-01

    Five new Cd(II) coordination polymers with N-benzoyl-L-glutamic acid (H2bzgluO) and different N-donor ligands, [Cd(bzgluO)(2,2‧-bipy)(H2O)]n (1), [Cd(bzgluO)(2,4‧-bipy)2(H2O)·3H2O]n (2), [Cd(bzgluO)(phen)·H2O]n (3), [Cd(bzgluO)(4,4‧-bipy)(H2O)]n (4), [Cd(bzgluO)(bpp)(H2O)·2H2O]n (5) were synthesized (2,2‧-bipy=2,2‧-bipyridine, 2,4‧-bipy=2,4‧-bipyridine, phen=1,10-phenanthroline, 4,4‧-bipy=4,4‧-bipyridine, bpp=1,3-di(4-pyridyl)propane). Compounds 1-2 exhibit a 1D single-chain structure. Compound 1 generates a 2D supramolecular structure via π-π stacking and hydrogen bonding, 3D architecture of compound 2 is formed by hydrogen bonding. Compound 3 features a 1D double-chain structure, which are linked by π-π interactions into a 2D supramolecular layer. Compounds 4-5 display a 2D network structure. Neighboring layers of 4 are extended into a 3D supramolecular architecture through hydrogen bonding. The structural diversity of these compounds is attributed to the effect of ancillary N-donor ligands and coordination modes of H2bzgluO. Luminescent properties of 1-5 were studied at room temperature. Circular dichroism of compounds 1, 2 and 5 were investigated.

  13. The enhanced catalytic performance of cobalt catalysts towards butadiene polymerization by introducing a labile donor in a salen ligand.

    PubMed

    Gong, Dirong; Wang, Baolin; Jia, Xiaoyu; Zhang, Xuequan

    2014-03-14

    A family of cobalt complexes supported by a tridentate Schiff base ligand with a labile donor (O, S, N) as a pendant arm (Co1-Co12, formulated as CoL2) were synthesized by the treatment of the corresponding ligands with cobalt acetate tetrahydrate. The resultant complexes were well characterized by elemental analysis, FT-IR, magnetic moment as well as EI-MS. The solid-state structures of Co7 and Co12 were determined by X-ray diffraction and both established a distorted octahedron geometry around the cobalt center. The butadiene polymerization capabilities of the 12 complexes were evaluated and compared in representative cases. Diethylaluminum chloride (AlEt2Cl) was found to be the compatible activator resulting in highly active catalysts for producing polybutadiene of 93.8-98.2% cis-1,4 enchainment with negligible 1,2-structure and trans-1,4 units. It appears that a certain degree of lability of the donor is beneficial for high catalytic activity, generally following the order of O > S > N, and the high cis-1,4 selectivity. Moreover, the remarkable thermal stability of these systems has been achieved: the catalytic systems have the ability of conducting a high level of active and selective polymerization, reaching an upper limit of polymerization temperature of about 70 °C. The enhanced catalytic performances were further rationalized by the established diene polymerization mechanism, which could shed light on developing highly selective and reactive industrially applicable catalysts with an enhanced thermal stability. PMID:24468706

  14. The enhanced catalytic performance of cobalt catalysts towards butadiene polymerization by introducing a labile donor in a salen ligand.

    PubMed

    Gong, Dirong; Wang, Baolin; Jia, Xiaoyu; Zhang, Xuequan

    2014-03-14

    A family of cobalt complexes supported by a tridentate Schiff base ligand with a labile donor (O, S, N) as a pendant arm (Co1-Co12, formulated as CoL2) were synthesized by the treatment of the corresponding ligands with cobalt acetate tetrahydrate. The resultant complexes were well characterized by elemental analysis, FT-IR, magnetic moment as well as EI-MS. The solid-state structures of Co7 and Co12 were determined by X-ray diffraction and both established a distorted octahedron geometry around the cobalt center. The butadiene polymerization capabilities of the 12 complexes were evaluated and compared in representative cases. Diethylaluminum chloride (AlEt2Cl) was found to be the compatible activator resulting in highly active catalysts for producing polybutadiene of 93.8-98.2% cis-1,4 enchainment with negligible 1,2-structure and trans-1,4 units. It appears that a certain degree of lability of the donor is beneficial for high catalytic activity, generally following the order of O > S > N, and the high cis-1,4 selectivity. Moreover, the remarkable thermal stability of these systems has been achieved: the catalytic systems have the ability of conducting a high level of active and selective polymerization, reaching an upper limit of polymerization temperature of about 70 °C. The enhanced catalytic performances were further rationalized by the established diene polymerization mechanism, which could shed light on developing highly selective and reactive industrially applicable catalysts with an enhanced thermal stability.

  15. Complexation Studies of Bidentate Heterocyclic N-Donor Ligands with Nd(III) and Am(III)

    SciTech Connect

    Ogden, Mark; Hoch, Courtney L.; Sinkov, Sergey I.; Meier, Patrick; Lumetta, Gregg J.; Nash, Kenneth L.

    2011-11-28

    A new bidentate nitrogen donor complexing agent that combines pyridine and triazole functional groups, 2-((4-phenyl-1H-1,2,3-triazol-1-yl)methyl)pyridine (PTMP), has been synthesized. The strength of its complexes with trivalent americium (Am3+) and neodymium (Nd3+) in anhydrous methanol has been evaluated using spectrophotometric techniques. The purpose of this investigation is to assess this ligand (as representative of a class of similarly structured species) as a possible model compound for the challenging separation of trivalent actinides from lanthanides. This separation, important in the development of advanced nuclear fuel cycles, is best achieved through the agency of multidentate chelating agents containing some number of nitrogen or sulfur donor groups. To evaluate the relative strength of the bidentate complexes, the derived constants are compared to those of the same metal ions with 2,2*-bipyridyl (bipy), 1,10-phenanthroline (phen), and 2-pyridin-2-yl-1H-benzimidazole (PBIm). At issue is the relative affinity of the triazole moiety for trivalent f element ions. For all ligands, the derived stability constants are higher for Am3+ than Nd3+. In the case of Am3+ complexes with phen and PBIm, the presence of 1:2 (AmL2) species is indicated. Possible separations are suggested based on the relative stability and stoichiometry of the Am3+ and Nd3+ complexes. It can be noted that the 1,2,3-triazolyl group imparts a potentially useful selectivity for trivalent actinides (An(III)) over trivalent lanthanides (Ln(III)), though the attainment of higher complex stoichiometries in actinide compared with lanthanide complexes may be an important driver for developing successful separations.

  16. Experimental and computational studies of a multi-electron donor-acceptor ligand containing the thiazolo[5,4-d]thiazole core and its incorporation into a metal-organic framework.

    PubMed

    Rizzuto, Felix J; Faust, Thomas B; Chan, Bun; Hua, Carol; D'Alessandro, Deanna M; Kepert, Cameron J

    2014-12-22

    A ligand containing the thiazolo[5,4-d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N'-(thiazolo[5,4-d]thiazole-2,5-diylbis(4,1-phenylene))bis(N-(pyridine-4-yl)pyridin-4-amine (1), was designed as a donor-acceptor system for incorporation into electronically active metal-organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis-near-infrared spectroelectrochemistry (UV/Vis-NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge-transfer interactions between the terminal triarylamine moieties upon oxidation, whereas radical species localized on the TzTz core were formed upon reduction. Conversion of 1 to diamagnetic 2+ and 4+ species resulted in marked changes in the emission spectra. Incorporation of this highly delocalized multi-electron donor-acceptor ligand into a new two-dimensional MOF, [Zn(NO3 )2 (1)] (2), resulted in an inhibition of the oxidation processes, but retention of the reduction capability of 1. Changes in the electrochemistry of 1 upon integration into 2 are broadly consistent with the geometric and electronic constraints enforced by ligation. PMID:25346539

  17. Synthesis, electronic structure and catalytic activity of ruthenium-iodo-carbonyl complexes with thioether containing NNS donor ligand

    NASA Astrophysics Data System (ADS)

    Jana, Subrata; Jana, Mahendra Sekhar; Biswas, Sujan; Sinha, Chittaranjan; Mondal, Tapan Kumar

    2014-05-01

    The ruthenium carbonyl complexes 1 and 2 with redox noninnocent NNS donor ligand, 1-methyl-2-{(o-thiomethyl)phenylazo}imidazole (L) have been synthesized and characterized by various analytical and spectroscopic (IR, UV-Vis and 1H NMR) techniques. The complexes exhibit a quasi-reversible one electron Ru(II)/Ru(III) oxidation couple at 1.11 V for 1 and 0.76 V for 2 along with two successive one electron ligand reductions. Catalytic activity of the compounds has been investigated to the oxidation of PhCH2OH to PhCHO, 2-butanol (C4H9OH) to 2-butanone, 1-phenylethanol (PhC2H4OH) to acetophenone, cyclopentanol (C5H9OH) to cyclopentanone, cyclohexanol to cyclohexanone, cycloheptanol to cycloheptanone and cycloctanol to cycloctanone using N-methylmorpholine-N-oxide (NMO) as oxidant. The catalytic efficiency of 2 is greater than complex 1 and well correlate with the metal oxidation potential. DFT, NBO and TDDFT calculations in DFT/B3LYP/6-31G(d)/lanL2TZ(f) method are employed to interpret the structural and electronic features of the complexes.

  18. Lanthanide coordination polymers based on multi-donor ligand containing pyridine and phthalate moieties: Structures, luminescence and magnetic properties

    SciTech Connect

    Feng, Xun; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Qiang Shi, Zhi; Wu, Xu-Hong; Ng, Seik-Weng

    2013-10-15

    A new family of five lanthanide-organic coordination polymers incorporating multi-functional N-hetrocyclic dicarboxylate ligand, namely, [Ln{sub 2}(Hdpp){sub 2}(dpp){sub 2}]{sub n}Ln=Pr(1), Eu(2), Gd(3), Dy(4), Er(5) (H{sub 2}dpp=1-(3, 4-dicarboxyphenyl) pyridin-4-ol) have been fabricated successfully through solvothermal reaction of 1-(3,4-dicarboxyphenyl)-4-hydroxypyridin-1-ium chloride with trivalent lanthanide salts, and have been characterized systematically. The complexes 1–5 are isomorphous and isostructural. They all feature three dimensional (3D) frameworks based on the interconnection of 1D double chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 4+} basic carboxylate as secondary building unit (SBU). The results of magnetic analysis shows the same bridging fashion of carboxylic group in this case results in the different magnetic properties occurring within lanthanide polymers. Moreover, the Eu(III) and Dy(III) complexes display characteristic luminescence emission in the visible regions. - Graphical abstract: A new family of lanthanide-organic frameworks incorporating multi-donor twisted ligand has been fabricated successfully, and has been characterized systematically. The complexes 1–5 are isostructural, and all feather three dimensional (3D) frameworks based on the interconnection of 1D double stride chains composed of the binuclear moiety [Ln{sub 2}(Hdpp){sub 2}]{sup 2+} basic carboxylate as secondary building unit (SBU). Display Omitted - Highlights: • New family of lanthanide–organic coordination polymers incorporating multifunctional N-hetrocyclic dicarboxylate ligand has been fabricated. • They have been characterized systematically. • They all feather three dimensional frameworks based on the binuclear moiety of [Ln{sub 2}(Hdpp){sub 2}]{sup 2+}. • The Eu(III) and Dy(III) analogues exhibit intense photoluminescence.

  19. Palladium(II) Complexes Containing Mixed Nitrogen-Sulphur Donor Ligands: Interaction of [Pd(Methionine Methyl Ester)(H2O)2]2+ with Biorelevant Ligands

    PubMed Central

    Shoukry, Mohamed M.; Ezzat, Sameya M. T.

    2014-01-01

    Pd(MME)Cl2 complex (MME = methionine methyl ester) was synthesised and characterized by physicochemical measurements. The reaction of [Pd(MME)(H2O)2]2+ with amino acids, peptides, or dicarboxylic acids was investigated at 25°C and 0.1 M ionic strength. Amino acids and dicarboxylic acids form 1 : 1 complexes. Peptides form both 1 : 1 complexes and the corresponding deprotonated amide species. The stability of the complexes formed was determined and the binding centres of the ligands were assigned. Effect of solvent on the stability constant of Pd(MME)-CBDCA complex, taken as a representative example, shows that the complex is more favoured in a medium of low dielectric constant. The concentration distribution diagrams of the complexes were evaluated. PMID:25214826

  20. Diverse Zn(II) MOFs assembled from V-shaped asymmetric multicarboxylate and N-donor ligands

    NASA Astrophysics Data System (ADS)

    Ye, Run-Ping; Yang, Jin-Xia; Zhang, Xin; Zhang, Lei; Yao, Yuan-Gen

    2016-02-01

    By reacting an asymmetry semi-rigid V-shaped linker H3L (H3L = 3-(3-carboxyphenoxy) phthalic acid) and Zn(NO3)2·6H2O under different N-donor ligands in different solvents, four new Zn-based coordination polymers, [Zn(HL)(2,2‧-bpy)(H2O)]n(1), [Zn(HL)(4,4‧-bpy)]n·n(DMA) (2), [Zn3(L)2(phen)3(H2O)]n·n(H2O) (3) and [Zn(HL)(phen)(H2O)]2(4) (2,2‧-bpy = 2,2‧-bipyridine; 4,4‧-bpy = 4,4‧-bipyridine; phen = 1,10-phenanthroline; DMA = N,N-dimethylacetamide) have been obtained. All of these compounds have been clearly identified by single crystal X-ray diffraction analysis. Compound 1 exhibits one-dimensional (1D) chain structure constructed from uninuclear Zn(II) motif, which further extends into 2D supramolecular architecture via intermolecular π-π interactions and hydrogen bonds. Structural analysis reveals that the structure of 2 and 3 can be described as a 2D hcb topology network with the point symbol of {63}. Compound 4 shows a 0D binuclear motif while its 3D packing network has a large potential solvent voids. The results of this research demonstrate that the solvent and the secondary ligands could co-regulate different structural coordination polymers with interesting properties. In addition, the thermal stabilities and solid-state luminescence properties of compounds 1-4 have also been investigated.

  1. Diverse Zn(II) MOFs assembled from V-shaped asymmetric multicarboxylate and N-donor ligands

    NASA Astrophysics Data System (ADS)

    Ye, Run-Ping; Yang, Jin-Xia; Zhang, Xin; Zhang, Lei; Yao, Yuan-Gen

    2016-02-01

    By reacting an asymmetry semi-rigid V-shaped linker H3L (H3L = 3-(3-carboxyphenoxy) phthalic acid) and Zn(NO3)2·6H2O under different N-donor ligands in different solvents, four new Zn-based coordination polymers, [Zn(HL)(2,2‧-bpy)(H2O)]n(1), [Zn(HL)(4,4‧-bpy)]n·n(DMA) (2), [Zn3(L)2(phen)3(H2O)]n·n(H2O) (3) and [Zn(HL)(phen)(H2O)]2(4) (2,2‧-bpy = 2,2‧-bipyridine; 4,4‧-bpy = 4,4‧-bipyridine; phen = 1,10-phenanthroline; DMA = N,N-dimethylacetamide) have been obtained. All of these compounds have been clearly identified by single crystal X-ray diffraction analysis. Compound 1 exhibits one-dimensional (1D) chain structure constructed from uninuclear Zn(II) motif, which further extends into 2D supramolecular architecture via intermolecular π-π interactions and hydrogen bonds. Structural analysis reveals that the structure of 2 and 3 can be described as a 2D hcb topology network with the point symbol of {63}. Compound 4 shows a 0D binuclear motif while its 3D packing network has a large potential solvent voids. The results of this research demonstrate that the solvent and the secondary ligands could co-regulate different structural coordination polymers with interesting properties. In addition, the thermal stabilities and solid-state luminescence properties of compounds 1-4 have also been investigated.

  2. 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

  3. DNA binding, anti-inflammatory and analgesic evaluation of metal complexes of N/S/O donor ligands; Synthesis, spectral characterization

    NASA Astrophysics Data System (ADS)

    Kumar Naik, K. H.; Ashok, B.; Naik, Nagaraja; Mulla, Jameel Ahmed S.; Prakasha, Avinash

    2015-04-01

    Transition metal complexes containing tri-dentate NSN donor ligands i.e., 5-((1(aminomethyl)cyclohexyl)methyl)-1,3,4-thiadiazol-2-amine (AMTA) (2) and 5-(2-aminophenyl)-1,3,4-thiadiazol-2-amine (ATA) (4i-ii) have been synthesized. The newly synthesized ligands and their respective complexes were characterized by elemental analysis, molar conductance measurement and various spectral studies [infrared (IR), electronic, and NMR (for ligands only)]. Metal complexes are like [M(AMTA)2], [M(ATA)2] type, where M = Mn(II), Co(II) and Cu(II). The proposed geometries of the complexes are octahedral in nature. The synthesized ligands and their complexes were exhibits effective anti-inflammatory, analgesic and DNA binding activities. All the tested compounds exhibited significant analgesic activity, whereas the compound 4i, 4(ia) and 4(iib) is equipotent with Diclofenac sodium.

  4. Luminescent zinc terephthalate coordination polymers with pyridylnicotinamide ligands: Effect of added base and nitrogen donor disposition on topology

    NASA Astrophysics Data System (ADS)

    Goldsworthy, Jessica S.; Staples, Richard J.; LaDuca, Robert L.

    2014-03-01

    Hydrothermal reaction of zinc nitrate, potassium terephthalate (K2tere), and 3-pyridylnicotinamide (3-pna) or 4-pyridylnicotinamide (4-pna) afforded coordination polymers with different dimensionality depending on nitrogen donor disposition and the initial pH of the reaction mixture. {[Zn(tere)(3-pna)2(H2O)2]ṡ2H2O}n (1) was prepared in the presence of aqueous NaOH, and manifests 1-D coordination polymer chains with monodentate 3-pna ligands. A mixture of {[Zn(tere)(3-pna)]ṡ3H2O}n (2) and {[Zn4(tere)3(OH)2(3-pna)2]ṡ2H2O}n (3) was prepared by performing a similar reaction in the absence of extra base. Compound 2 shows a 2-D (6,3) hexagonal grid topology with very tight interdigitation, while 3 has a 2-fold interpenetrated 3-D pcu network built from {Zn4(OCO)2(OH)2} centrosymmetric tetrameric nodes. {[Zn(tere)(4-pna)]ṡH2O}n (4) has parallel 2-fold interpenetrated sawtooth layer motifs. Luminescent and thermal decomposition properties are also discussed.

  5. Platinum(II) oxalato complexes involving adenosine-based N-donor ligands: synthesis, characterization and cytotoxicity evaluation.

    PubMed

    Starha, Pavel; Popa, Igor; Trávníček, Zdeněk

    2014-01-01

    A one-step synthetic procedure using the reaction of potassium bis(oxalato)platinate(II) with the corresponding N6-benzyladenosine derivative (nL) provided the [Pt(ox)(nL)₂]∙1.5H₂O oxalato (ox) complexes 1-5, involving the nL molecules as monodentate coordinated N-donor ligands. The complexes were thoroughly characterized by elemental analysis, multinuclear (¹H, ¹³C, ¹⁵N, 1¹⁹⁵Pt) and two dimensional NMR, infrared and Raman spectroscopy, and mass spectrometry, proving their composition and purity as well as coordination of nL through the N7 atom of the purine moiety. Geometry of [Pt(ox)(4FL)₂] (5) was optimized at the B3LYP/LANLTZ/6-311G** level of theory. The complexes were screened for their in vitro cytotoxicity against two human cancer cell lines (HOS osteosarcoma and MCF7 breast adenocarcinoma), but they did not show any effect up to the concentration of 50.0 µM (compounds 1, 2) or 20.0 µM (compounds 3-5). PMID:24662093

  6. Chromium complexes of an isomeric N-donor ligand, 2-[(N-arylamino)phenylazo]pyridine: amination reactions, X-ray structure, and redox properties.

    PubMed

    Kamar, Kunal K; Saha, Amrita; Castiñeiras, Alfonso; Hung, Chen-Hsiung; Goswami, Sreebrata

    2002-08-26

    The chromium chemistry of two positional isomers of the ligand 2-[(N-arylamino)phenylazo]pyridine (HL(1)and HL(2)) are described. While the ligand HL(1) coordinates as a bischelating tridentate N,N,N-donor, [L(1)](-), with deprotonation of the amine nitrogen, its isomer HL(2) coordinates as a neutral bidentate N,N-donor. The amine nitrogen in this case remains protonated. Thus the reaction of CrCl(3).nH(2)O with HL(1) produced the brown cationic complex, [Cr(L(1))(2)](+), [1](+). The representative X-ray structure of [1a](ClO(4)) is reported. The two azo nitrogens of the anioinc tridentate ligand approach the metal center closest with Cr(1)-N(azo) av 1.862(6) A. There is a significant degree of ligand backbone conjugation in the coordinated ligands, which resulted in shortening of the C-N distances and also in lengthening of the diazo (N=N) distances. Two synthetic approaches for the synthesis of chromium complexes of HL(2) are investigated. The first approach is based on the substitution reaction, wherein all the coordinated CO ligands of Cr(CO)(6) were completely substituted by the three bidentate HL(2) ligands to produce a violet complex [Cr(HL(2))(3)]. The second approach is based on para-amination reaction of coordinated 2-(phenylazo)pyridine (pap). Thus the reaction of an inert complex, [CrCl(2)(pap)(2)], with ArNH(2) yields a mixed ligand complex, [CrCl(2)(pap)(HL(2))], 3. In this reaction one of the two coordinated pap ligands in [CrCl(2)(pap)(2)] undergoes amination at the para carbon (with respect to the diazo function) to yield HL(2) in situ. This metal-promoted transformation is authenticated by the X-ray structure determination of a representative complex, [CrCl(2)(pap)(HL(2a))], 3a. Notable differences in bond distances along the ligand backbones of the two coordinated ligands in 3a indicate different levels of metal-ligand overlap in this complex. All the chromium complexes of HL(2) are characterized by their intense blue-violet color. The

  7. Recipient myeloid-derived immunomodulatory cells induce PD-1 ligand-dependent donor CD4+Foxp3+ regulatory T cell proliferation and donor-recipient immune tolerance after murine nonmyeloablative bone marrow transplantation.

    PubMed

    van der Merwe, Marie; Abdelsamed, Hossam A; Seth, Aman; Ong, Taren; Vogel, Peter; Pillai, Asha B

    2013-12-01

    We showed previously that nonmyeloablative total lymphoid irradiation/rabbit anti-thymocyte serum (TLI/ATS) conditioning facilitates potent donor-recipient immune tolerance following bone marrow transplantation (BMT) across MHC barriers via recipient invariant NKT (iNKT) cell-derived IL-4-dependent expansion of donor Foxp3(+) naturally occurring regulatory T cells (nTregs). In this study, we report a more specific mechanism. Wild-type (WT) BALB/c (H-2(d)) hosts were administered TLI/ATS and BMT from WT or STAT6(-/-) C57BL/6 (H-2(b)) donors. Following STAT6(-/-) BMT, donor nTregs demonstrated no loss of proliferation in vivo, indicating that an IL-4-responsive population in the recipient, rather than the donor, drives donor nTreg proliferation. In graft-versus-host disease (GVHD) target organs, three recipient CD11b(+) cell subsets (Gr-1(high)CD11c(-), Gr-1(int)CD11c(-), and Gr-1(low)CD11c(+)) were enriched early after TLI/ATS + BMT versus total body irradiation/ATS + BMT. Gr-1(low)CD11c(+) cells induced potent H-2K(b+)CD4(+)Foxp3(+) nTreg proliferation in vitro in 72-h MLRs. Gr-1(low)CD11c(+) cells were reduced significantly in STAT6(-/-) and iNKT cell-deficient Jα18(-/-) BALB/c recipients after TLI/ATS + BMT. Depletion of CD11b(+) cells resulted in severe acute GVHD, and adoptive transfer of WT Gr-1(low)CD11c(+) cells to Jα18(-/-) BALB/c recipients of TLI/ATS + BMT restored day-6 donor Foxp3(+) nTreg proliferation and protection from CD8 effector T cell-mediated GVHD. Blockade of programmed death ligand 1 and 2, but not CD40, TGF-β signaling, arginase 1, or iNOS, inhibited nTreg proliferation in cocultures of recipient-derived Gr-1(low)CD11c(+) cells with donor nTregs. Through iNKT-dependent Th2 polarization, myeloid-derived immunomodulatory dendritic cells are expanded after nonmyeloablative TLI/ATS conditioning and allogeneic BMT, induce PD-1 ligand-dependent donor nTreg proliferation, and maintain potent graft-versus-host immune tolerance.

  8. Development of a dipodal Schiff base ligand with N-imine and O-naphtholate donors: A potential chelator towards Cu(II) metal ion established through potentiometric and spectrophotometric studies

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    A novel hydroxynaphthaldehyde derived Schiff base ligand N,N'-bis-[2-[(2-hydroxy-1-naphthyl)methyleneamino]ethyl]propanediamide (DOTA2HNAP) containing nitrogen and oxygen donor atoms has been developed. The lowest energy molecular structure of DOTA2HNAP and its complexes with Cu (II) metal ion were examined by molecular mechanics using MM+ force which later was re-optimized by semi-empirical method. The theoretical IR and UV spectra of the ligand were obtained using semi empirical/ZINDO/PM3 and were compared with the experimental ones. The coordinating ability of DOTA2HNAP with H+ and Cu(II) ions was investigated in 1:99 (DMSO: water) binary solvent mixture at 25±1°C by potentiometric and spectrophotometric method. The electronic spectra of the ligand show three distinct peaks (253nm, 320nm and 360nm) implicating existence of the Schiff base in quinone form that was well supported by theoretical spectral studies. Out of various complex species forming in solution, all the metal ions show higher stability of complexes when in 1:1 metal-ligand stoichiometry, binding through two N-imine and two O-naphtholate groups.

  9. Development of a dipodal Schiff base ligand with N-imine and O-naphtholate donors: A potential chelator towards Cu(II) metal ion established through potentiometric and spectrophotometric studies

    SciTech Connect

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

    2015-08-28

    A novel hydroxynaphthaldehyde derived Schiff base ligand N,N’-bis-[2-[(2-hydroxy-1-naphthyl)methyleneamino]ethyl]propanediamide (DOTA2HNAP) containing nitrogen and oxygen donor atoms has been developed. The lowest energy molecular structure of DOTA2HNAP and its complexes with Cu (II) metal ion were examined by molecular mechanics using MM+ force which later was re-optimized by semi-empirical method. The theoretical IR and UV spectra of the ligand were obtained using semi empirical/ZINDO/PM3 and were compared with the experimental ones. The coordinating ability of DOTA2HNAP with H{sup +} and Cu(II) ions was investigated in 1:99 (DMSO: water) binary solvent mixture at 25±1°C by potentiometric and spectrophotometric method. The electronic spectra of the ligand show three distinct peaks (253nm, 320nm and 360nm) implicating existence of the Schiff base in quinone form that was well supported by theoretical spectral studies. Out of various complex species forming in solution, all the metal ions show higher stability of complexes when in 1:1 metal-ligand stoichiometry, binding through two N-imine and two O-naphtholate groups.

  10. Tricarbonyltechnetium(I) and tricarbonylrhenium(I) complexes of amino acids: crystal and molecular structure of a novel cyclic dimeric Re(CO)3-amino acid complex comprised of the OON donor atom set of the tridentate ligand.

    PubMed

    Nayak, Dipak Kumar; Halder, Kamal Krishna; Baishya, Rinku; Sen, Tuhinadri; Mitra, Partha; Debnath, Mita Chatterjee

    2013-10-01

    Radiolabeled complexes of monoamino polycarboxylic, polyamino monocarboxylic and thiol containing amino acid ligands were prepared from a fac-[(99m)Tc(CO)3(H2O)3](+) precursor.The overall radiochemical yield was 94-98%. The complexes exhibited substantial in vitro and in vivo stability. The corresponding Re(I) complexes of the ligands DAPA, Asp and CysH were prepared and characterized by means of IR, NMR, and MS spectroscopic studies, as well as X-ray crystallography (for those containing D,L-DAPA and D,L-Asp). The rhenium complexes have been structurally correlated with the technetium complexes by means of HPLC studies. The reaction of Re(CO)5Cl with D,L-Asp in presence of triethylamine led to the formation of a new class of cyclic dimeric complexes formed by the OON donor atom set of the tridentate ligands. The amino carboxylate ligand system formed well defined complexes with a fac-[M(CO)3(H2O)3](+) core and shows good promise in (99m)Tc(CO)3 tracer development. PMID:23900487

  11. Synthesis and structural evaluation of five coordination complexes of benzenepentacarboxylic acid with aza-donor ligands

    NASA Astrophysics Data System (ADS)

    Shimpi, Manishkumar R.; Biswas, Sharmita Nandy; Sarkar, Sohini; Pedireddi, V. R.

    2016-06-01

    Synthesis and structural features of five new coordination assemblies, [Co(bpyH)(H2O)5](BPCH)·(bpyH2)0.5·(H2O) (1a), [{Cu(H2O)3}·{Cu0.5(bpy)0.5(H2O)0.5}2(μ-BPCH)] (1b), [{Cd0.5(BPCH)}2·{Cd0.5(bpy)(H2O)2}2]·6(H2O) (1c), [Cu(BPCH2)(bpyeaH)]·2(H2O) (1d) and [Cd2 (bpyea)0.5(oxalate)0.5(μ-BPC) (H2O)]·(bpyeaH2)·2(H2O) (1e), have been reported. All the assemblies were prepared by co-crystallization of benzenepentacarboxylic acid (BPCH5) either with 4,4‧-bipyridine (bpy) or 1,2-bis(4-pyridyl)ethane (bpyea) in the presence of a transition metal ion (either Co(II), Cu(II) or Cd(II)) as the case may be. All the five compounds were synthesized by hydrothermal method and structures were determined by single crystal X-ray diffraction. All the obtained compounds, 1a-1e, exhibit distinct 3-D polymeric architectures either in the form of stacked layers or host-guest networks in which water molecules play a pivotal role providing additional stabilization by coordinate bonds as well as hydrogen bonds. Other non-covalent interactions such as C-H … π and π … π stacking also participate in the formation of exotic 3-D structures of these complexes.

  12. Extraction of metals using supercritical fluid and chelate forming ligand

    DOEpatents

    Wai, C.M.; Laintz, K.E.

    1998-03-24

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent is described. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated {beta}-diketone. In especially preferred embodiments the extraction solvent is supercritical carbon dioxide, and the chelating agent comprises a fluorinated {beta}-diketone and a trialkyl phosphate, or a fluorinated {beta}-diketone and a trialkylphosphine oxide. Although a trialkyl phosphate can extract lanthanides and actinides from acidic solutions, a binary mixture comprising a fluorinated {beta}-diketone and a trialkyl phosphate or a trialkylphosphine oxide tends to enhance the extraction efficiencies for actinides and lanthanides. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The method is particularly useful for extracting actinides and lanthanides from acidic solutions. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs.

  13. Tetrahedral nickel nitrosyl complexes with tripodal [N3] and [Se3] donor ancillary ligands: structural and computational evidence that a linear nitrosyl is a trivalent ligand.

    PubMed

    Landry, Victoria K; Pang, Keliang; Quan, Stephanie M; Parkin, Gerard

    2007-02-28

    Linear nickel nitrosyl compounds supported by tridentate nitrogen and selenium ligands, namely the tris(3,5-dimethylpyrazolyl)hydroborato and tris(2-seleno-1-mesitylimidazolyl)hydroborato complexes, [TpMe2]NiNO and [TseMes]NiNO, have been synthesized and structurally characterized by X-ray diffraction. Computational studies demonstrate that the linear nitrosyl ligand behaves as a trivalent X3 ligand such that the Ni-N interaction has multiple bond character. PMID:17297507

  14. Affinity of An(VI) for N4-Tetradentate Donor Ligands: Complexation of the Actinyl(VI) Ions with N4-Tetradentate Ligands

    SciTech Connect

    Ogden, Mark; Sinkov, Sergey I.; Lumetta, Gregg J.; Nash, Kenneth L.

    2012-05-01

    In this report the affinity of four N4-tetradentate ligands that incorporate the 2- methylpyridyl functionality with hexavalent actinides (AnO2+2 ) has been investigated in methanol solution. The ligands studied include N,N*-bis(2-methylpyridyl)diaminoethane (BPMDAE), N,N-bis(2-methylpyridyl)-1,3-diaminopropane (BPMDAP), N,N*-bis(2-pyridylmethyl) piperazine (BPMPIP), and trans-N,N-bis(2-pyridylmethyl)-1,2-diaminocyclohexane (BPMDAC). Conditional stability constants describing the strength of the interaction were determined by UV-visible spectrophotometry. The log10K101 values for both U(VI) and Pu(VI) are comparable and show the same trend of stability with ligand structure. Dinuclear complexes are also indicated as being important. The log10K201 values for Pu(VI) complexation with the N4-ligands are identical for the four ligands (within experimental error), indicating that the structure of the ligand backbone has little effect on the stability of the (PuO2)2L2+ complex. The exception to this trend is the behavior of N,N*- bis(2-pyridylmethyl)piperazine (BPMPIP) with Pu(VI). This ligand displays a tendency to reduce Pu(VI) within the experimental time frame of 45 minutes. BPMPIP is the only ligand tested that contains tertiary amines in the ligand backbone. The decomposition of BPMPIP by Pu(VI) suggests a susceptibility of tertiary amines to oxidative degradation.

  15. Hydrogen abstraction in the neutral molecular cluster of benzophenone and hydrogen donors formed in a supersonic free jet expansion

    SciTech Connect

    Matsushita, Yoshihisa; Kajii, Yoshizumi; Obi, Kinichi

    1992-08-06

    This paper discusses how benzophenone undergoes photoreduction to form benzophenone ketyl radical by an intracellular reaction in the benzophenone 1,4-cyclohexadiene mixed expansion in a supersonic free jet expansion. No ketyl radical fluorescence is observed when triethylamine, 2-propanol, or ethanol is the hydrogen donor; thus the normal molecular cluster activity depends on the nature of the hydrogen donor. 36 refs., 5 figs.

  16. Synthesis and coordination chemistry of two N2-donor chelating di(indazolyl)methane ligands: structural characterization and comparison of their metal chelation aptitudes.

    PubMed

    Pettinari, Claudio; Marinelli, Alessandro; Marchetti, Fabio; Ngoune, Jean; Galindo, Agustín; Álvarez, Eleuterio; Gómez, Margarita

    2010-11-15

    The N(2)-donor bidentate ligands di(1H-indazol-1-yl)methane (L(1)) and di(2H-indazol-2-yl)methane (L(2)) (L in general) have been synthesized, and their coordination behavior toward Zn(II), Cd(II), and Hg(II) salts has been studied. Reaction of L(1) and L(2) with ZnX(2) (X = Cl, Br, or I) yields [ZnX(2)L] species (1-6), that, in the solid state, show a tetrahedral structure with dihapto ligand coordination via the pyrazolyl arms. The reaction of L(1) and L(2) with Zn(NO(3))(2)·6H(2)O is strongly dependent on the reaction conditions and on the ligand employed. Reaction of L(1) with equimolar quantities of Zn(NO(3))(2)·6H(2)O yields the neutral six-coordinate species [Zn(NO(3))(2)(L(1))], 7. On the other hand the use of L(1) excess gives the 2:1 adduct [Zn(NO(3))(2)(L(1))(2)], 8 where both nitrates act as a unidentate coordinating ligand. Analogous stoichiometry is found in the compound obtained from the reaction of L(2) with Zn(NO(3))(2)·6H(2)O which gives the ionic [Zn(NO(3))(L(2))(2)](NO(3)), 10. Complete displacement of both nitrates from the zinc coordination sphere is observed when the reaction between L(1) excess and the zinc salt was carried out in hydrothermal conditions. The metal ion type is also determining structure and stoichiometry: the reaction of L(2) with CdCl(2) gave the 2:1 adduct [CdCl(2)(L(2))(2)] 11 where both chlorides complete the coordination sphere of the six-coordinate cadmium center; on the other hand from the reaction of L(1) with CdBr(2) the polynuclear [CdBr(2)(L(1))](n) 12 is obtained, the Br(-) anion acting as bridging ligands in a six-coordinate cadmium coordination environment. The reaction of L(1) and L(2) with HgX(2) (X = Cl, I, SCN) is also dependent on the reaction conditions and the nature of X, two different types of adducts being formed [HgX(L)] (14: L = L(1), 16, 17: L = L(1) or L(2), X = I, 19: L = L(2), X = SCN) and [HgX(L)(2)] (15: L = L(2), X = Cl, 18: L = L(1), X = SCN). The X-ray diffraction analyses of compounds 1

  17. Potential Toxicity of Up-Converting Nanoparticles Encapsulated with a Bilayer Formed by Ligand Attraction

    PubMed Central

    2015-01-01

    The cellular toxicity of nanoparticles that were capped with a bilayered ligand was studied using an up-converting (UC) phosphor material as a representative nanoparticle (NP). The results indicate that although UC NPs are known to be nontoxic, the toxicity of the NPs depends strongly on ligand coordination conditions, in addition to the other commonly known parameters such as size, structure, surface charge etc. Oleate-capped hydrophobic NaYF4:Yb,Er NPs were surface modified to yield three extreme conditions: bare particles that were stripped of the oleate ligands; particles with covalently bound poly(ethylene glycol) (PEG) ligands; and particles with an bilayer of PEG-oleate ligands using the oleate surface group that was remained after synthesis. It was found that the bare particles and the covalent PEG NPs induced little toxicity. However, particles that were rendered biocompatible by forming a bilayer with an amphiphilic ligand (i.e., PEG-oleate) resulted in significant cell toxicity. These findings strongly suggest that the PEG-oleate group dissociated from the bilayered oleate-capped NPs, resulting in significant toxicity by exposing the hydrophobic oleate-capped NPs to the cell. Based on results with bare particles, the NaLnF4:Yb,Er (Ln = Y, Gd) up-converting phosphors are essentially less-toxic. Capping and functionalizing these particles with ligand intercalation may, however, not be a suitable method for rendering the NPs suitable for bioapplication as the ligand can potentially dissociate upon cellular interaction, leading to significant toxicity. PMID:24971524

  18. Donor-Recipient Matching for KIR Genotypes Reduces Chronic GVHD and Missing Inhibitory KIR Ligands Protect against Relapse after Myeloablative, HLA Matched Hematopoietic Cell Transplantation

    PubMed Central

    Faridi, Rehan Mujeeb; Kemp, Taylor J.; Dharmani-Khan, Poonam; Lewis, Victor; Rajalingam, Raja; Berka, Noureddine; Storek, Jan; Masood Khan, Faisal

    2016-01-01

    Background Allogeneic hematopoietic cell transplantation (HCT) can be curative for many hematologic diseases. However, complications such as graft-versus-host disease (GVHD) and relapse of primary malignancy remain significant and are the leading causes of morbidity and mortality. Effects of killer Ig-like receptors (KIR)-influenced NK cells on HCT outcomes have been extensively pursued over the last decade. However, the relevance of the reported algorithms on HLA matched myeloablative HCT with rabbit antithymocyte globulin (ATG) is used for GVHD prophylaxis remains elusive. Here we examined the role of KIR and KIR-ligands of donor-recipient pairs in modifying the outcomes of ATG conditioned HLA matched sibling and unrelated donor HCT Methods and Findings The study cohort consisted of 281 HLA matched sibling and unrelated donor-recipient pairs of first allogeneic marrow or blood stem cell transplantation allocated into ‘discovery’ (135 pairs) and ‘validation’ (146 pairs) cohorts. High resolution HLA typing was obtained from the medical charts and KIR gene repertoires were obtained by a Luminex® based SSO method. All surviving patients were followed-up for a minimum of two years. KIR and HLA class I distributions of HCT pairs were stratified as per applicable definitions and were tested for their association with cause specific outcomes [acute GVHD grade II-IV (aGVHD), chronic GVHD needing systemic therapy (cGVHD) and relapse] using a multivariate competing risks regression model as well as with survival outcomes [relapse-free survival (RFS), cGVHD & relapse free survival (cGRFS) and overall survival (OS)] by multivariate Cox proportional hazards regression model. A significant association between KIR genotype mismatching (KIR-B/x donor into KIR-AA recipient or vice versa) and cGVHD was found in both discovery (p = 0.001; SHR = 2.78; 95%CI: 1.50–5.17) and validation cohorts (p = 0.005; SHR = 2.61; 95%CI: 1.33–5.11). High incidence of cGVHD associated

  19. Hydrothermal syntheses, structures and characterizations of two luminescent cadmium(II) complexes with p-xylenediphosphonic acid and N-donor ligands

    SciTech Connect

    Sun Yanqiong; Hu Jin; Zhang Hanhui; Chen Yiping

    2012-02-15

    Two novel cadmium diphosphonates [Cd(cis-H{sub 4}BDPP)(2,2 Prime -bipy){sub 2}]{center_dot}(trans-H{sub 2}BDPP)]{sub n} (1) and [Cd(trans-H{sub 2}BDPP)(phen)]{sub n} (2) (H{sub 4}BDPP=p-xylenediphosphonic acid, phen=1,10-phenanthroline, 2,2 Prime -bipy=2,2 Prime -bipyridine) were hydrothermally synthesized from p-xylenediphosphonic acid and CdSO{sub 4}{center_dot}3H{sub 2}O with phen or 2,2 Prime -bipy as second ligand components and characterized by means of elemental analyses, IR, TG analysis, luminescence spectroscopy and single crystal X-ray diffraction. Compound 1 consists of a novel one-dimensional (1D) sinusoidal [Cd(cis-H{sub 4}BDPP)(2,2 Prime -bipy){sub 2}] chains and trans-H{sub 2}BDPP anions. Compound 2 possesses a three-dimensional architecture built from double zigzag -Cd-O-P-O-Cd- chains pillared by trans-p-xylylenediphosphonate ligands from four different directions. There are hexagonal channels running along the c-axis and the coordinated phen ligands suspend in the hexagonal channels. The results indicate that p-xylenediphosphonic acid can adopt varied coordination modes and conformations in the formation of the complexes and the influence of the N-donor ligands on the structure of the complexes is discussed. - Graphical abstract: Two new cadmium diphosphonates were obtained by using two different auxiliary ligands. The influence of the N-donor ligands on the structure of the complexes is discussed. Highlights: Black-Right-Pointing-Pointer The first example of cadmium(II)-p-xylenediphosphonates templated by second ligand. Black-Right-Pointing-Pointer The role of size of the auxiliary ligand on the structure of cadmium p-xylenediphosphonates. Black-Right-Pointing-Pointer The cis and trans configurations of p-xylenediphosphonates exist in the same crystal structure. Black-Right-Pointing-Pointer Three-dimensional 4-connected framework with PtS network topology.

  20. 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.

  1. Complete recovery of actinides from UREX-like raffinates using a combination of hard and soft donor ligands. II. soft donor structure variation

    DOE PAGESBeta

    Zalupski, Peter R.; Klaehn, John R.; Peterman, Dean R.

    2015-07-30

    The feasibility of simultaneous separation of uranium, neptunium, plutonium, americium, and curium from a simulated dissolved used fuel simulant adjusted to 1.0 M nitric acid is investigated using a mixture of the soft donor bis(bis-3,5-trifluoromethyl)phenyl) dithiophosphinic acid (“0”) and the hard donor synergist trioctylphosphine oxide (TOPO) dissolved in toluene. The results reported in this work are compared to our recent demonstration of a complete actinide recovery from a simulated dissolved fuel solution using a synergistic combination of bis(o-trifluoromethylphenyl)dithiophosphinic acid (“1”) and TOPO dissolved in either toluene or trifluoromethylphenyl sulfone. While the extraction efficiency of americium was enhanced for the liquid-liquidmore » system containing “0”, enabling to accomplish a trivalent An/Ln separation at 1.0 M HNO3, the extraction of neptunium was drastically diminished, relative to “1”. The partitioning behavior of curium was also negatively impacted, introducing an effective opportunity for americium/curium separation. Radiometric and spectrophotometric studies demonstrate that the complete actinide recovery using the solvent based upon “0” and TOPO is not feasible. Additionally, the importance of radiolytic degradation processes is discussed through the comparisons of extraction properties of liquid-liquid systems based on both soft donor reagents.« less

  2. Complete recovery of actinides from UREX-like raffinates using a combination of hard and soft donor ligands. II. soft donor structure variation

    SciTech Connect

    Zalupski, Peter R.; Klaehn, John R.; Peterman, Dean R.

    2015-07-30

    The feasibility of simultaneous separation of uranium, neptunium, plutonium, americium, and curium from a simulated dissolved used fuel simulant adjusted to 1.0 M nitric acid is investigated using a mixture of the soft donor bis(bis-3,5-trifluoromethyl)phenyl) dithiophosphinic acid (“0”) and the hard donor synergist trioctylphosphine oxide (TOPO) dissolved in toluene. The results reported in this work are compared to our recent demonstration of a complete actinide recovery from a simulated dissolved fuel solution using a synergistic combination of bis(o-trifluoromethylphenyl)dithiophosphinic acid (“1”) and TOPO dissolved in either toluene or trifluoromethylphenyl sulfone. While the extraction efficiency of americium was enhanced for the liquid-liquid system containing “0”, enabling to accomplish a trivalent An/Ln separation at 1.0 M HNO3, the extraction of neptunium was drastically diminished, relative to “1”. The partitioning behavior of curium was also negatively impacted, introducing an effective opportunity for americium/curium separation. Radiometric and spectrophotometric studies demonstrate that the complete actinide recovery using the solvent based upon “0” and TOPO is not feasible. Additionally, the importance of radiolytic degradation processes is discussed through the comparisons of extraction properties of liquid-liquid systems based on both soft donor reagents.

  3. Four homochiral coordination polymers contain N-acetyl-L-tyrosine and different N-donor ligand: Influence of metal cations, ancillary ligands and coordination modes

    SciTech Connect

    Li, Meng-Li; Song, Hui-Hua

    2013-10-15

    Using the chiral ligand N-acetyl-L-tyrosine (Hacty) and maintaining identical reaction conditions, Zn(II), Co(II), and Cd(II) salts provided four novel homochiral coordination polymers ([Zn(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}1, ([Co(acty)(bipy){sub 2}(H{sub 2}O){sub 2}]·NO{sub 3}·2H{sub 2}O){sub n}2, ([Cd(acty){sub 2}(bipy)H{sub 2}O]·H{sub 2}O){sub n}3, and ([Cd(acty)(bpe){sub 2}(Ac)]·6H{sub 2}O){sub n}4 (bipy=4,4′-bipyridine; bpe=1,2-di(4-pyridyl)ethane) in the presence of ancillary ligands. Compounds 1 and 2 are isostructural 1D chain structures. The neighboring chains are further linked into a 3D supramolecular structure via π⋯π stacking and hydrogen bond interactions. Compound 3 shows a 2D network and 4 generates 1D infinite chains along the c-axis. Compounds 3 and 4 are further connected into 3D supramolecular network by hydrogen bond interactions. More importantly, coordination in acyl oxygen atoms and ancillary ligands (bpe) as monodentate decorating ligands in 4 are rarely reported. Ancillary ligands and metal cations significantly influence the structure of the complexes. The photoluminescence properties of 1, 3, and 4 were studied at room temperature. Circular dichroism (CD) of the complexes have been investigated. - Graphical abstract: Four new homochiral coordination polymers were prepared and structurally characterized, which investigate the influence of the ancillary ligands and metal ions on the design and synthesis of coordination polymers. Display Omitted - Highlights: • It is rarely reported that the chiral coordination polymers prepared with N-acetyl-L-tyrosine ligands. • The alkalescent acetyl oxygen atom is difficult to participate in coordination but it is happened in the N-acetyl-L-tyrosine ligands. • The ancillary ligands (4,4′-bipy and bpe) are present in an unusual coordination modes, monodentate decorating ligands in 1, 2 and 4. • Structure comparative analyses results indicate that the

  4. Interaction of Co(II), Ni(II) and Cu(II) with dibenzo-substituted macrocyclic ligands incorporating both symmetrically and unsymmetrically arranged N, O and S donors.

    PubMed

    Vasilescu, I M; Baldwin, D S; Bourne, D J; Clegg, J K; Li, F; Lindoy, L F; Meehan, G V

    2011-09-14

    The synthesis and characterisation of four 17-membered, dibenzo-substituted macrocyclic ligands incorporating unsymmetrical arrangements of their N(3)S(2), N(3)O(2) and N(3)OS (two ligands) donor atoms are described; these rings complete the matrix of related macrocyclic systems incorporating both symmetric and unsymmetric donor sets reported previously. The X-ray structures of three of the new macrocycles are reported. In two of the Cu(II) structures only three of the possible five donor atoms present in the corresponding macrocyclic ligand bind to the Cu(II) site, whereas all five donors are coordinated in each of the remaining complexes. The interaction of Co(II), Ni(II) and Cu(II) with the unsymmetric macrocycle series has been investigated by potentiometric (pH) titration in 95% methanol; X-ray structures of two nickel and three copper complexes of these ligands, each exhibiting 1:1 (M:L) ratios, have been obtained. The results are discussed in the context of previous results for these metals with the analogous 17-membered ring systems incorporating symmetrical arrangements of their donor atoms, with emphasis being given to both the influence of the donor atom set, as well as the donor atom sequence, on the nature of the resulting complexes.

  5. Ni(II) and Pd(II) complexes with new N,O donor thiophene appended Schiff base ligand: Synthesis, electrochemistry, X-ray structure and DFT calculation

    NASA Astrophysics Data System (ADS)

    Kundu, Subhankar; Pramanik, Ajoy Kumar; Mondal, Apurba Sau; Mondal, Tapan Kumar

    2016-07-01

    The thiophene appended Schiff's base ligand, 1-(2-(thiophen-2-yl)ethylimino)methyl)naphthalene-2-ol (HL) with N,O donor sites has been synthesized by the condensation between 2-hydroxy-1-naphthaldehyde and thiophene-2-ethylamine. The square planar 1:2 complexes of HL having general formula [M(L)2] (M = Ni(1) and Pd(2)) with nickel(II) and palladium(II) have been synthesized and characterized by several spectroscopic techniques. The geometry has been confirmed by single crystal X-ray study for complex 1. The electronic structure and spectral properties of the complexes are interpreted by DFT and TDDFT studies.

  6. Metal complexes of ONO donor Schiff base ligand as a new class of bioactive compounds; Synthesis, characterization and biological evolution

    NASA Astrophysics Data System (ADS)

    Kumar Naik, K. H.; Selvaraj, S.; Naik, Nagaraja

    2014-10-01

    Present work reviews that, the synthesis of (E)-N";-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide [L] ligand and their metal complexes. The colored complexes were prepared of type [M2+L]X2, where M2+ = Mn, Co, Ni, Cu, Sr and Cd, L = (7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide, X = Cl-. Ligand derived from the condensation of 8-formyl-7-hydroxy-4-methylcoumarin and benzohydrazide in the molar ratio 1:1 and in the molar ratio 1:2 for metal complexes have been prepared. The chelation of the ligand to metal ions occurs through the both oxygen groups, as well as the nitrogen atoms of the azomethine group of the ligand. Reactions of the Schiff base ligand with Manganese(II), Cobalt(II), Nickel(II), Copper(II), Strontium(II), and Cadmium(II) afforded the corresponding metal complexes. The structures of the obtained ligand and their respective metal complexes were elucidated by infra-red, elemental analysis, Double beam UV-visible spectra, conductometric measurements, magnetic susceptibility measurements and also thermochemical studies. The metal complex exhibits octahedral coordination geometrical arrangement. Schiff base ligand and their metal complexes were tested against antioxidants, antidiabetic and antimicrobial activities have been studied. The Schiff base metal complexes emerges effective α-glucosidase inhibitory activity than free Schiff base ligand.

  7. Metal complexes of ONO donor Schiff base ligand as a new class of bioactive compounds: synthesis, characterization and biological evolution.

    PubMed

    Kumar Naik, K H; Selvaraj, S; Naik, Nagaraja

    2014-10-15

    Present work reviews that, the synthesis of (E)-N'-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide [L] ligand and their metal complexes. The colored complexes were prepared of type [M(2+)L]X2, where M(2+)=Mn, Co, Ni, Cu, Sr and Cd, L=(7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzohydrazide, X=Cl(-). Ligand derived from the condensation of 8-formyl-7-hydroxy-4-methylcoumarin and benzohydrazide in the molar ratio 1:1 and in the molar ratio 1:2 for metal complexes have been prepared. The chelation of the ligand to metal ions occurs through the both oxygen groups, as well as the nitrogen atoms of the azomethine group of the ligand. Reactions of the Schiff base ligand with Manganese(II), Cobalt(II), Nickel(II), Copper(II), Strontium(II), and Cadmium(II) afforded the corresponding metal complexes. The structures of the obtained ligand and their respective metal complexes were elucidated by infra-red, elemental analysis, Double beam UV-visible spectra, conductometric measurements, magnetic susceptibility measurements and also thermochemical studies. The metal complex exhibits octahedral coordination geometrical arrangement. Schiff base ligand and their metal complexes were tested against antioxidants, antidiabetic and antimicrobial activities have been studied. The Schiff base metal complexes emerges effective α-glucosidase inhibitory activity than free Schiff base ligand.

  8. Four homochiral coordination polymers contain N-acetyl-L-tyrosine and different N-donor ligand: Influence of metal cations, ancillary ligands and coordination modes

    NASA Astrophysics Data System (ADS)

    Li, Meng-Li; Song, Hui-Hua

    2013-10-01

    Using the chiral ligand N-acetyl-L-tyrosine (Hacty) and maintaining identical reaction conditions, Zn(II), Co(II), and Cd(II) salts provided four novel homochiral coordination polymers {[Zn(acty)(bipy)2(H2O)2]·NO3·2H2O}n1, {[Co(acty)(bipy)2(H2O)2]·NO3·2H2O}n2, {[Cd(acty)2(bipy)H2O]·H2O}n3, and {[Cd(acty)(bpe)2(Ac)]·6H2O}n4 (bipy=4,4‧-bipyridine; bpe=1,2-di(4-pyridyl)ethane) in the presence of ancillary ligands. Compounds 1 and 2 are isostructural 1D chain structures. The neighboring chains are further linked into a 3D supramolecular structure via π⋯π stacking and hydrogen bond interactions. Compound 3 shows a 2D network and 4 generates 1D infinite chains along the c-axis. Compounds 3 and 4 are further connected into 3D supramolecular network by hydrogen bond interactions. More importantly, coordination in acyl oxygen atoms and ancillary ligands (bpe) as monodentate decorating ligands in 4 are rarely reported. Ancillary ligands and metal cations significantly influence the structure of the complexes. The photoluminescence properties of 1, 3, and 4 were studied at room temperature. Circular dichroism (CD) of the complexes have been investigated.

  9. Reactions of the cationic zinc thiolate model complex [Zn(Tab)4](PF6)2 with N-donor ligands and cobalt dichloride.

    PubMed

    Zheng, Ai-Xia; Si, Jing; Tang, Xiao-Yan; Miao, Li-Li; Yu, Miao; Hou, Kai-Peng; Wang, Fan; Li, Hong-Xi; Lang, Jian-Ping

    2012-10-01

    Reactions of [Zn(Tab)(4)](PF(6))(2) (Tab = 4-(trimethylammonio)benzenethiolate) (1) with 2,2'-bipyridine (2,2'-bipy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (2,9-dmphen), N-methylimidazole (N-Meim), and 2,6-bis(pyrazol-3-yl)pyridine (bppy) or with CoCl(2)·6H(2)O at the presence of N-donor ligands (2,2'-bipy, phen, 4,4'-dimethyl-2,2'-bipyridine (4,4'-dmbpy), 2,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (bdmppy))gave rise to a family of zinc or cobalt thiolate complexes, [Zn(Tab)(2)(L)](PF(6))(2) (2: L = 2,2'-bipy, 3: L = phen, 4: L = 2,9-dmphen), [Zn(Tab)(2)(N-Meim)(2)](PF(6))(2) (5), [Zn(Tab)(2)(bppy)](PF(6))(2) (6), [Co(Tab)(2)(L)(2)](PF(6))(3) (7: L = 2,2'-bipy, 8: L = phen, 9: L = 4,4'-dmbpy), and [Co(Tab)(bdmppy)Cl](PF(6)) (10). These compounds were characterized by elemental analysis, IR spectra, UV-vis spectra,(1)H NMR, electrospray ionization (ESI) mass spectra, and single-crystal X-ray diffraction. The Zn(II) in [Zn(Tab)(2)L(n)](2+)dications of 2-5 is tetrahedrally coordinated by two Tab ligands and one L or two N-Meim ligands. In 6, the Zn(II) has a distorted trigonal-bipyramidal geometry, coordinated by two Tab ligands and one tridentate bppy ligand. The Co(III) in the [Co(Tab)(2)(L)(2)](3+) trications of 7-9 is octahedraly chelated by two bidentate L ligands and two Tab ligands. In 10, the Co(II) adopts a distorted trigonal-bipyramidal geometry, coordinated by one Cl(-), one Tab ligand, and one tridentate bdmppy. In the formation of 2-6, two Tab ligands are removed from the [Zn(Tab)(4)](2+) dication when it is attacked by L ligands, while in the cases of 7-9, the Zn(II) of the [Zn(Tab)(4)](2+) dication was replaced by Co(III) (derived from oxidation of Co(II) by O(2)) followed by the removal of two Tab ligands via L ligands. In the case of 10, the central Zn(II) of the [Zn(Tab)(4)](2+) dication was displaced by Co(II) followed by the removal of three Tab ligands via one Cl(-) and one tridentate bdmppy. These ligand and metal

  10. Synthesis and structural characterisation of Pd(II) and Pt(II) complexes with a flexible, ferrocene-based P,S-donor amidophosphine ligand.

    PubMed

    Tauchman, Jiří; Císařová, Ivana; Stěpnička, Petr

    2014-01-28

    1'-Diphenylphosphino-1-{[(2-(methylthio)ethyl)amino]carbonyl}ferrocene (1), accessible via amidation of 1'-(diphenylphosphino)ferrocene-1-carboxylic acid (Hdpf) with 2-(methylthio)ethylamine, reacts with [PdCl2(cod)] (cod = cycloocta-1,5-diene) at a 1 : 1 metal-to-ligand ratio to give trans-[PdCl2(1-κ(2)P,S)] (trans-2) as the sole product. A similar reaction with [PtCl2(cod)] affords a mixture of cis- and trans-[PtCl2(1-κ(2)P,S)] (cis- and trans-3), which can be separated by fractional crystallisation. Complexation reactions performed with 2 equiv. of the ligand are less selective, yielding mixtures of the expected bis-phosphine complexes (i.e., trans-[PdCl2(1-κP)2], or a mixture of cis- and trans-[PtCl2(-κP)2]) with the respective monophosphine complexes. The structures of 1, trans-2, cis-3 and trans-3 determined by X-ray diffraction demonstrate the ability of the title ligand to act as a flexible cis- or trans-P,S-chelate donor (the ligand bite angles are 174.03(2)/173.05(2)° for trans-2/3 and 92.86(2)° for cis-3).

  11. 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.

  12. Photoactivity of mono- and dicarbonyl complexes of ruthenium(II) bearing an N,N,S-donor ligand: role of ancillary ligands on the capacity of CO photorelease.

    PubMed

    Gonzalez, Margarita A; Carrington, Samantha J; Chakraborty, Indranil; Olmstead, Marilyn M; Mascharak, Pradip K

    2013-10-01

    One monocarbonyl and one dicarbonyl complex of ruthenium(II), namely, [Ru(Cl)(CO)(qmtpm)(PPh3)]BF4 (2) and [Ru(Cl)(CO)2(qmtpm)]ClO4 (3), derived from the tridentate ligand 2-quinoline-N-(2'-methylthiophenyl)methyleneimine (qmtpm) have been synthesized and structurally characterized. The qmtpm ligand binds in a meridional fashion in these carbonyl complexes, and in 3, the two carbon monoxide (CO) ligands are cis to each other. Solutions of 2 in ethanol, chloroform, or acetonitrile rapidly release CO upon illumination with low-power (3-15 mW) light in the 300-450 nm range. Loss of CO from 2 brings about a dramatic color change from yellow to magenta because of the formation of [Ru(Cl)(MeCN)(qmtpm)(PPh3)]BF4 (4). In acetonitrile, photorelease of CO from 3 under 360 nm light occurs in two steps, and the violet photoproduct [Ru(Cl)(MeCN)2(qmtpm)](+) upon reaction with Ag(+) and PPh3 affords red [Ru(MeCN)2(qmtpm)(PPh3)](ClO4)2 (5). The structure of 5 has also been determined by X-ray crystallography. Reduced myoglobin assay confirms that 2 and 3 act as photoactive CO-releasing molecules (photoCORMs) that deliver 1 and 2 equiv of CO, respectively. The results of density functional theory (DFT) and time-dependent DFT studies confirm that electronic transitions from molecular orbitals with predominantly Ru-CO character to ligand-based π* orbitals facilitate CO release from these two photoCORMs. Complexes 2-5 have provided an additional opportunity to analyze the roles of the ancillary ligands, namely, PPh3, Cl(-), and MeCN, in shifting the positions of the metal-to-ligand charge-transfer bands and the associated sensitivity of the two photoCORMs to different wavelengths of light. Collectively, the results provide helpful hints toward the future design of photoCORMs that release CO upon exposure to visible light.

  13. Using Ion Channel-Forming Peptides to Quantify Protein-Ligand Interactions

    PubMed Central

    Mayer, Michael; Semetey, Vincent; Gitlin, Irina; Yang, Jerry; Whitesides, George M.

    2008-01-01

    This paper proposes a method for sensing affinity interactions by triggering disruption of self-assembly of ion channel-forming peptides in planar lipid bilayers. It shows that the binding of a derivative of alamethicin carrying a covalently attached sulfonamide ligand to carbonic anhydrase II (CA II) resulted in the inhibition of ion channel conductance through the bilayer. We propose that the binding of the bulky CA II protein (MW ~30 kD) to the ion channel-forming peptides (MW ~2.5 kD) either reduced the tendency of these peptides to self-assemble into a pore, or extracted them from the bilayer altogether. In both outcomes, the interactions between the protein and the ligand lead to a disruption of self-assembled pores. Addition of a competitive inhibitor – 4-carboxybenzenesulfonamide – to the solution released CA II from the alamethicin-sulfonamide conjugate and restored the current flow across the bilayer by allowing reassembly of the ion channels in the bilayer. Time-averaged recordings of the current over discrete time intervals made it possible to quantify this monovalent ligand binding interaction. This method gave a dissociation constant of ~2 µM for the binding of CA II to alamethicin-sulfonamide in the bilayer recording chamber: this value is consistent with a value obtained independently with CA II and a related sulfonamide derivative by isothermal titration calorimetry. PMID:18179217

  14. Crystal structure of the urokinase receptor in a ligand-free form.

    PubMed

    Xu, Xiang; Gårdsvoll, Henrik; Yuan, Cai; Lin, Lin; Ploug, Michael; Huang, Mingdong

    2012-03-01

    The urokinase receptor urokinase-type plasminogen activator receptor (uPAR) is a surface receptor capable of not only focalizing urokinase-type plasminogen activator (uPA)-mediated fibrinolysis to the pericellular micro-environment but also promoting cell migration and chemotaxis. Consistent with this multifunctional role, uPAR binds several extracellular ligands, including uPA and vitronectin. Structural studies suggest that uPAR possesses structural flexibility. It is, however, not clear whether this flexibility is an inherent property of the uPAR structure per se or whether it is induced upon ligand binding. The crystal structure of human uPAR in its ligand-free state would clarify this issue, but such information remains unfortunately elusive. We now report the crystal structures of a stabilized, human uPAR (H47C/N259C) in its ligand-free form to 2.4 Å and in complex with amino-terminal fragment (ATF) to 3.2 Å. The structure of uPAR(H47C/N259C) in complex with ATF resembles the wild-type uPAR·ATF complex, demonstrating that these mutations do not perturb the uPA binding properties of uPAR. The present structure of uPAR(H47C/N259C) provides the first structural definition of uPAR in its ligand-free form, which represents one of the biologically active conformations of uPAR as defined by extensive biochemical studies. The domain boundary between uPAR DI-DII domains is more flexible than the DII-DIII domain boundary. Two important structural features are highlighted by the present uPAR structure. First, the DI-DIII domain boundary may face the cell membrane. Second, loop 130-140 of uPAR plays a dynamic role during ligand loading/unloading. Together, these studies provide new insights into uPAR structure-function relationships, emphasizing the importance of the inter-domain dynamics of this modular receptor. PMID:22285761

  15. First-row transition metal complexes of ENENES ligands: the ability of the thioether donor to impact the coordination chemistry.

    PubMed

    Dub, Pavel A; Scott, Brian L; Gordon, John C

    2016-01-28

    The reactions of two variants of ENENES ligands, E(CH2)2NH(CH)2SR, where E = 4-morpholinyl, R = Ph (), Bn () with MCl2 (M = Mn, Fe, Co, Ni and Cu) in coordinating solvents (MeCN, EtOH) affords isolable complexes, whose magnetic susceptibility measurements suggest paramagnetism and a high-spin formulation. X-Ray diffraction studies of available crystals show that the ligand coordinates to the metal in either a bidentate κ(2)[N,N'] or tridentate κ(3)[N,N',S] fashion, depending on the nature of ligand and/or identity of the metal atom. In the case of a less basic SPh moiety, a bidentate coordination mode was identified for harder metals (Mn, Fe), whereas a tridentate coordination mode was identified in the case of a more basic SBn moiety with softer metals (Ni, Cu). In the intermediate case of Co, ligands and coordinate via κ(2)[N,N'] and κ(3)[N,N',S] coordination modes, which can be conveniently predicted by DFT calculations. For the softest metal (Cu), ligand coordinates in a κ(3)[N,N',S] fashion.

  16. Synthesis and characterisation of a novel mixed donor P,O,P' nixantphos ligand and its metal complex

    NASA Astrophysics Data System (ADS)

    Marimuthu, Thashree; Bala, Muhammad D.; Friedrich, Holger B.

    2016-02-01

    The complex [(NixC8OH)Ir(cod)Cl] 4 has been synthesized and structurally characterized by NMR, IR and single crystal X-ray diffraction. The synthesis and characterisation of the novel ligand NixC8OH is also presented. The coordination around Ir is trigonal bipyramidal with both P groups of the NixC8OH ligand bound in a bis-equatorial mode. The bis-chelating cod (C8H12) ligand occupies the remaining equatorial position and an axial position. This mode of bonding has resulted in a large bite angle (P1-Ir-P2) of 102.92(12)° for the title complex 4. The IR and NMR data further support the elucidated structure. Thermal analyses of 4 indicate that it is thermally stable up to a decomposition temperature of >400 °C.

  17. Synthesis and characterisation of a novel mixed donor P,O,P' nixantphos ligand and its metal complex

    NASA Astrophysics Data System (ADS)

    Marimuthu, Thashree; Bala, Muhammad D.; Friedrich, Holger B.

    2016-02-01

    The complex [(NixC8OH)Ir(cod)Cl] 4 has been synthesized and structurally characterized by NMR, IR and single crystal X-ray diffraction. The synthesis and characterisation of the novel ligand NixC8OH is also presented. The coordination around Ir is trigonal bipyramidal with both P groups of the NixC8OH ligand bound in a bis-equatorial mode. The bis-chelating cod (C8H12) ligand occupies the remaining equatorial position and an axial position. This mode of bonding has resulted in a large bite angle (P1-Ir-P2) of 102.92(12)° for the title complex 4. The IR and NMR data further support the elucidated structure. Thermal analyses of 4 indicate that it is thermally stable up to a decomposition temperature of >400 °C.

  18. Synthesis, characterization and physiochemical information, along with antimicrobial studies of some metal complexes derived from an ON donor semicarbazone ligand

    NASA Astrophysics Data System (ADS)

    Siji, V. L.; Kumar, M. R. Sudarsana; Suma, S.; Kurup, M. R. Prathapachandra

    2010-06-01

    Eight new transition metal complexes of benzaldehyde- N(4)-phenylsemicarbazone have been synthesized and characterized by elemental analyses, molar conductance, electronic and infrared spectral studies. In all the complexes, the semicarbazone is coordinated as neutral bidentate ligand. 1H NMR spectrum of [Zn(HL) 2(OAc) 2] shows that there is no enolisation of the ligand in the complex. The magnetic susceptibility measurements indicate that Cr(III), Mn(II), Fe(III), Co(II) and Cu(II) complexes are paramagnetic and Ni(II) is diamagnetic. The EPR spectrum of [Mn(HL) 2(OAc) 2] in DMF solution at 77 K shows hyperfine sextet with low intensity forbidden lines lying between each of the two main hyperfine lines. The g values calculated for the [Cu(HL) 2SO 4] complex in frozen DMF, indicate the presence of unpaired electron in the d orbital. The metal ligand bonding parameters evaluated showed strong in-plane σ bonding and in-plane π bonding. The ligand and complexes were screened for their possible antimicrobial activities.

  19. Structure of the fimbrial protein Mfa4 from Porphyromonas gingivalis in its precursor form: implications for a donor-strand complementation mechanism.

    PubMed

    Kloppsteck, Patrik; Hall, Michael; Hasegawa, Yoshiaki; Persson, Karina

    2016-01-01

    Gingivitis and periodontitis are chronic inflammatory diseases that can lead to tooth loss. One of the causes of these diseases is the Gram-negative Porphyromonas gingivalis. This periodontal pathogen is dependent on two fimbriae, FimA and Mfa1, for binding to dental biofilm, salivary proteins, and host cells. These fimbriae are composed of five proteins each, but the fimbriae assembly mechanism and ligands are unknown. Here we reveal the crystal structure of the precursor form of Mfa4, one of the accessory proteins of the Mfa1 fimbria. Mfa4 consists of two β-sandwich domains and the first part of the structure forms two well-defined β-strands that run over both domains. This N-terminal region is cleaved by gingipains, a family of proteolytic enzymes that encompass arginine- and lysine-specific proteases. Cleavage of the N-terminal region generates the mature form of the protein. Our structural data allow us to propose that the new N-terminus of the mature protein may function as a donor strand in the polymerization of P. gingivalis fimbriae. PMID:26972441

  20. Structure of the fimbrial protein Mfa4 from Porphyromonas gingivalis in its precursor form: implications for a donor-strand complementation mechanism

    PubMed Central

    Kloppsteck, Patrik; Hall, Michael; Hasegawa, Yoshiaki; Persson, Karina

    2016-01-01

    Gingivitis and periodontitis are chronic inflammatory diseases that can lead to tooth loss. One of the causes of these diseases is the Gram-negative Porphyromonas gingivalis. This periodontal pathogen is dependent on two fimbriae, FimA and Mfa1, for binding to dental biofilm, salivary proteins, and host cells. These fimbriae are composed of five proteins each, but the fimbriae assembly mechanism and ligands are unknown. Here we reveal the crystal structure of the precursor form of Mfa4, one of the accessory proteins of the Mfa1 fimbria. Mfa4 consists of two β-sandwich domains and the first part of the structure forms two well-defined β-strands that run over both domains. This N-terminal region is cleaved by gingipains, a family of proteolytic enzymes that encompass arginine- and lysine-specific proteases. Cleavage of the N-terminal region generates the mature form of the protein. Our structural data allow us to propose that the new N-terminus of the mature protein may function as a donor strand in the polymerization of P. gingivalis fimbriae. PMID:26972441

  1. New mixed ligand zinc(II) complexes based on the antiepileptic drug sodium valproate and bioactive nitrogen-donor ligands. Synthesis, structure and biological properties.

    PubMed

    Darawsheh, Mohanad; Abu Ali, Hijazi; Abuhijleh, A Latif; Rappocciolo, Emilia; Akkawi, Mutaz; Jaber, Suhair; Maloul, Salam; Hussein, Yasmeen

    2014-07-23

    Starting from the precursor [Zinc Valproate complex] (1), new mixed ligand zinc(II) complexes of valproic acid and nitrogen-based ligands, formulating as, [Zn(valp)22,9-dmphen] (2), [Zn2(valp)4(quin)2] (3), [Zn(valp)2(2-ampy)2] (4), and [Zn(valp)2(2-ampic)2] (5) (valp = valproate, 2,9-dmphen = 2,9-dimethyl-1,10-phenanthroline, quin = quinoline, 2-ampy = 2-aminopyridine, 2-ampic = 2-amino-6-picoline) were synthesized and characterized using IR, (1)H NMR, (13)C{(1)H} NMR and UV-Vis spectrometry. The crystal structures of complexes 2, 3 and 4 were determined using single-crystal X-ray diffraction. The complexes were also evaluated for their anti-bacterial activity using in-vitro agar diffusion method against three Gram-positive (Micrococcus luteus, Staphylococcus aureus, and Bacillus subtilis) and three Gram-negative (Escherichia coli, Klebsiella pneumoniae, and Proteus mirabilis) species. Complex 2 showed considerable activity against all tested microorganisms and the effect of complexation on the anti-bacterial activity of the parent ligand of 2 was also investigated. The anti-bacterial activity of 2,9-dmphen against Gram-negative bacteria was enhanced upon complexation with zinc valproate. On the other hand, complexes 1 and 3 showed weak inhibition activity against the tested species and complexes 4 and 5 didn't show any activity at all. Two methods were used for testing the inhibition of ferriprotoporphyrinIX bio-mineralization: a semi-quantitative micro-assay and a previously self-developed quantitative in-vitro method. Both were used to study the efficiency of these complexes in inhibiting the formation of the Malaria pigment which considered being the target of many known anti-malarial drugs such as Chloroquine and Amodiaquine. Results showed that the efficiency of complex 2 in preventing the formation of β-Hematin was 80%. The efficiency of Amodiaquine as a standard drug was reported to give 91%.

  2. Tridentate ligands containing the SNS donor atom set as a novel backbone for the development of technetium brain-imaging agents.

    PubMed

    Mastrostamatis, S G; Papadopoulos, M S; Pirmettis, I C; Paschali, E; Varvarigou, A D; Stassinopoulou, C I; Raptopoulou, C P; Terzis, A; Chiotellis, E

    1994-09-30

    In developing 99mTc complexes as potential brain-imaging agents, we investigated the coordination chemistry of ligands containing sulfur and nitrogen donor atoms with the general formula R-CH2CH2N(CH2CH2SH)2 (R = C2H5S, (C2H5)2N). These ligands act as tridentate SNS chelates to the TcO3+ core, leaving open one coordination site cis to the oxo group. In reactions with the highly reactive [99TcOCl4]- precursor, this vacancy was occupied by a chlorine atom. When the ligands reacted in the presence of 4-methoxythiophenol, using 99Tc(V)-gluconate as precursor, the vacancy was filled with 4-methoxythiophenol, which acted as coligand. Thus neutral mixed ligand complexes of the general formula [TcO((SCH2CH2)2NCH2CH2R)X], where X = Cl or 4-methoxythiophenol, were synthesized. The complexes were characterized by UV-vis, IR, 1H NMR, crystallographic, and elemental analyses. The crystal structures of 3a (R = C2H5S, X = Cl) and 4b (R = (C2H5)2N, X = 4-methoxythiophenol) demonstrated that the coordination geometry is trigonal bipyramidal with the N1 and Cl or S3 occupying the apical positions and the basal plane defined by the S1 and S2 of the tridentate ligand and the oxo group. The complexes 4a(99mTc) (R = C2H5S, X = 4-methoxythiophenol) and 4b(99mTc) were prepared using 99mTc-glucoheptonate as precursor and were purified by HPLC. Biodistribution in mice showed high initial brain uptake (3.68% and 3.56% dose/organ for 4a(99mTc) and 4b(99m-Tc), respectively). Complex 4b(99mTc) displayed significantly higher brain/blood values and prolonged retention in brain as well. The results suggest that structural modifications based on configurations 4a,b may provide novel 99mTc brain-imaging agents with improved biological characteristics. PMID:7932548

  3. Two new helical compounds based on Keggin clusters and N-donor multidentate ligand: Syntheses, structures and properties

    SciTech Connect

    Zhou, Shi; Liu, Bo; Li, Xiao-Min; Shi, Tian; Chen, Ya-Guang

    2014-11-15

    Two isostructural polyoxometalate-based inorganic–organic hybrids with 1D helical chain, [CuH{sub 3}L{sub 2}(GeMo{sub 12}O{sub 40})]·2H{sub 2}O (1) and [CuH{sub 3}L{sub 2}(SiMo{sub 12}O{sub 40})]·2H{sub 2}O (2), where L=2,4,5-tri(4-pyridyl)-imidazole have been synthesized under hydrothermal conditions. It is the first time to use the L ligand to synthesis the Keggin-type polyoxometalate-based inorganic–organic hybrids. The two compounds possess the left- and right-handed helical chains and the POMs as pendants attach in the helical chains through Cu–O bonds. The two compounds have been characterized by elemental analyses, infrared (IR) spectroscopy, powder X-ray diffraction (PXRD), X-ray photoelectron spectra (XPS), thermogravimetric analysis (TGA) and photoluminescent spectroscopy. Moreover, nitrogen adsorption−desorption measurement, electrochemical and photocatalysis properties for degradation of methylene blue (MB) upon a UV irradiation of compound 1 have been examined. - Graphical abstract: Two new compounds, [CuH{sub 3}L{sub 2}(GeMo{sub 12}O{sub 40})]·2H{sub 2}O (1) and [CuH{sub 3}L{sub 2}(SiMo{sub 12}O{sub 40})]·2H{sub 2}O (2) have been synthesized under hydrothermal conditions. The two compounds possess the left- and right-handed helical chains. - Highlights: • The tridentate L ligand is first used to synthesis Keggin-type polyoxometalates. • The two compounds possess the left- and right-handed Cu–L helical chains. • Relationship between surface properties and photocatalytic activity was studied. • Two compounds exhibit photoluminescence of ligand-to-metal charge transfer.

  4. Ab initio and density functional theoretical design and screening of model crown ether based ligand (host) for extraction of lithium metal ion (guest): effect of donor and electronic induction.

    PubMed

    Boda, Anil; Ali, Sk Musharaf; Rao, Hanmanth; Ghosh, Sandip K

    2012-08-01

    The structures, energetic and thermodynamic parameters of model crown ethers with different donor, cavity and electron donating/ withdrawing functional group have been determined with ab initio MP2 and density functional theory in gas and solvent phase. The calculated values of binding energy/ enthalpy for lithium ion complexation are marginally higher for hard donor based aza and oxa crown compared to soft donor based thia and phospha crown. The calculated values of binding enthalpy for lithium metal ion with 12C4 at MP2 level of theory is in good agreement with the available experimental result. The binding energy is altered due to the inductive effect imparted by the electron donating/ withdrawing group in crown ether, which is well correlated with the values of electron transfer. The role of entropy for extraction of hydrated lithium metal ion by different donor and functional group based ligand has been demonstrated. The HOMO-LUMO gap is decreased and dipole moment of the ligand is increased from gas phase to organic phase because of the dielectric constant of the solvent. The gas phase binding energy is reduced in solvent phase as the solvent molecules weaken the metal-ligand binding. The theoretical values of extraction energy for LiCl salt from aqueous solution in different organic solvent is validated by the experimental trend. The study presented here should contribute to the design of model host ligand and screening of solvent for metal ion recognition and thus can contribute in planning the experiments.

  5. Synthesis, spectral characterization, computational calculations and biological activity of complexes designed from NNO donor Schiff-base ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, Ola A.; El-Reash, G. M. Abu; Yousef, T. A.; Mefreh, M.

    2015-07-01

    A new series of Co(II), Ni(II) and Cu(II) complexes of (Z)-2-oxo-2-(phenylamino)-N‧-(1-(pyridin-2-yl)ethylidene)acetohydrazide (H2OPPAH) have been prepared and characterized by conventional techniques. The spectral data indicated that the ligand acts as neutral or mononegative NNO tridentate. On the basis of magnetic and electronic spectral data an octahedral geometry for Ni(II) and Cu(II) complexes and a tetrahedral geometry for Co(II) complex have been proposed. The molecular modeling using DFT method are drawn showing the bond length, bond angle, chemical reactivity, energy components (kcal/mol) and binding energy (kcal/mol) for all title compounds. The Kinetic parameters were determined for each thermal degradation stages of the ligand and its complexes using Coats-Redfern and Horowitz-Metzger methods. Also, the compounds were screened for antioxidant activity using ABTS free radical, anti-hemolytic, and in vitro cytotoxic assay. H2OPPAH showed the potent antioxidant activity followed by Co(II) and Cu(II) complexes. On the other hand Ni(II) complex exhibited weak antioxidant activity using ABTS free radical and Erlich and strong erythrocyte hemolysis activity.

  6. Polymeric networks of copper(II) phenylmalonate with heteroaromatic n-donor ligands: synthesis, crystal structure, and magnetic properties.

    PubMed

    Pasán, Jorge; Sanchiz, Joaquín; Ruiz-Pérez, Catalina; Lloret, Francesc; Julve, Miguel

    2005-10-31

    Two new phenylmalonate-bridged copper(II) complexes with the formulas [Cu(4,4'-bpy)(Phmal)](n).2nH(2)O (1) and [Cu(2,4'-bpy)(Phmal)(H(2)O)](n)() (2) (Phmal = phenylmalonate dianion, 4,4'-bpy = 4,4'-bipyridine, 2,4'-bpy = 2,4'-bipyridine) have been synthesized and characterized by X-ray diffraction. Complex 1 crystallizes in monoclinic space group P2(1), Z = 4, with unit cell parameters of a = 9.0837(6) Angstroms, b = 9.3514(4) Angstroms, c = 11.0831(8) Angstroms, and beta = 107.807(6) degrees , whereas complex 2 crystallizes in orthorhombic space group C2cb, Z = 8, with unit cell parameters of a = 10.1579(7) Angstroms, b = 10.3640(8) Angstroms, and c = 33.313(4) Angstroms. The structures of 1 and 2 consist of layers of copper(II) ions with bridging bis-monodentate phenylmalonate (1 and 2) and 4,4'-bpy (1) ligands and terminal monodentate 2,4'-bpy (2) groups. Each layer in 1 contains rectangles with dimensions of 11.08 x 4.99 Angstroms(2), the edges being defined by the Phmal and 4,4'-bpy ligands. The intralayer copper-copper separations in 1 through the anti-syn equatorial-apical carboxylate-bridge and the 4,4'-bpy molecule are 4.9922(4) and 11.083(1) Angstroms, respectively. The anti-syn equatorial-equatorial carboxylate bridge links the copper(II) atoms in complex 2 within each layer with a mean copper-copper separation of 5.3709(8) Angstroms. The presence of 2,4'-bpy as a terminal ligand accounts for the large interlayer separation of 15.22 Angstroms. The copper(II) environment presents a static pseudo-Jahn-Teller disorder which has been studied by EPR and low-temperature X-ray diffraction. Magnetic susceptibility measurements of both compounds in the temperature range 2-290 K show the occurrence of weak antiferromagnetic [J = -0.59(1) cm(-1) (1)] and ferromagnetic [J = +0.77(1) cm(-1) (2)] interactions between the copper(II) ions. The conformation of the phenylmalonate-carboxylate bridge and other structural factors, such as the planarity of the exchange

  7. Synthesis, spectroscopic, antimicrobial, DNA binding and cleavage studies of some metal complexes involving symmetrical bidentate N, N donor Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Arish, D.; Nair, M. Sivasankaran

    2011-11-01

    The Schiff base ligand, N, N'-bis-(4-isopropylbenzaldimine)-1,2-diaminoethane (L), obtained by the condensation of 4-isopropylbenzaldehyde and 1,2-diaminoethane, has been used to synthesize the complexes of the type [ML 2X 2] [M = Co(II), Ni(II) and Zn(II); X = Cl and OAc]. The newly synthesized ligand (L) and its complexes have been characterized on the basis of elemental analyses, mass, 1H and 13C-NMR, molar conductance, IR, UV-vis, magnetic moment, CV and thermal analyses, powder XRD and SEM. IR spectral data show that the ligand is coordinated to the metal ions in a bidentate manner. The geometrical structures of these complexes are found to be octahedral. Interestingly, reaction with Cu(II) ion with this ligand undergoes hydrolytic cleavage to form ethylenediamine copper(II) complex and the corresponding aldehyde. The antimicrobial results indicate that the chloro complexes exhibit more activity than the acetato complexes. The complexes bind to CT-DNA by intercalation modes. Novel chloroform soluble ZnL 2Cl 2 complex exhibits tremendous antimicrobial, DNA binding and cleaving properties.

  8. The Effect of Hg(II) on the Optical Characteristics of Cycloiridated 2-Phenylbenzothiazole Complexes with Chelating Ligands Containing Sulfur Donor Atoms

    NASA Astrophysics Data System (ADS)

    Katlenok, E. A.; Balashev, K. P.

    2016-03-01

    The [Ir(bt)2(S^S)], [Ir(bt)2(S^N)], and [Ir(bt)2(CH3CN)2]PF6 complexes, where (bt)- is a deprotonated form of 2-phenylbenzothiazole and (S^S)- and (S^N)- are diethyldithiocarbamate, O-ethyldithiocarbonate, 2-mercaptobenzothiazolate, 2-mercaptobenzoxazolate, and 2-mercaptopyridinate ions, and the effect of Hg(II), Cu(II), Cd(II), and Zn(II) cations on the optical characteristics of these complexes are studied by electron absorption spectroscopy and emission spectroscopy. A hypsochromic shift of the absorption and phosphorescence bands of complexes in substituting the (S^S)- and (S^N)- chelating ligands with acetonitrile ligands is attributed to a lower energy of d Ir orbitals compared with the mixed d Ir/ p(S) orbitals. It is shown that the presence of Hg(II) cations results in a hypsochromic shift of the absorption and phosphorescence bands of complexes [Ir(bt)2(S^S)] and [Ir(bt)2(S^N)] because of an effective reaction of substitution of chelating ligands to acetonitrile ligands.

  9. High-contrast fluorescence sensing of aqueous Cu(I) with triaryl-pyrazoline probes: Dissecting the roles of ligand donor strength and excited state proton transfer

    PubMed Central

    Morgan, M. Thomas; Bagchi, Pritha; Fahrni, Christoph J.

    2012-01-01

    Cu(I)-responsive fluorescent probes based on a photoinduced electron transfer (PET) mechanism generally show incomplete fluorescence recovery relative to the intrinsic quantum yield of the fluorescence reporter. Previous studies on probes with an N-aryl thiazacrown Cu(I)-receptor revealed that the recovery is compromised by incomplete Cu(I)-N coordination and resultant ternary complex formation with solvent molecules. Building upon a strategy that successfully increased the fluorescence contrast and quantum yield of Cu(I) probes in methanol, we integrated the arylamine PET donor into the backbone of a hydrophilic thiazacrown ligand with a sulfonated triarylpyrazoline as a water-soluble fluorescence reporter. This approach was not only expected to disfavor ternary complex formation in aqueous solution but also to maximize PET switching through a synergistic Cu(I)-induced conformational change. The resulting water-soluble probe 1 gave a strong 57-fold fluorescence enhancement upon saturation with Cu(I) with high selectivity over other cations, including Cu(II), Hg(II), and Cd(II); however, the recovery quantum yield did not improve over probes with the original N-aryl thiazacrown design. Concluding from detailed photophysical data, including responses to acidification, solvent isotope effects, quantum yields, and time-resolved fluorescence decay profiles, the fluorescence contrast of 1 is compromised by inadequate coordination of Cu(I) to the weakly basic arylamine nitrogen of the PET donor and by fluorescence quenching via two distinct excited state proton transfer pathways operating under neutral and acidic conditions. PMID:23169532

  10. Synthesis, spectroscopic characterization and DNA nuclease activity of Cu(II) complexes derived from pyrazolone based NSO-donor Schiff base ligands

    NASA Astrophysics Data System (ADS)

    Vyas, Komal M.; Joshi, Rushikesh G.; Jadeja, R. N.; Ratna Prabha, C.; Gupta, Vivek K.

    2011-12-01

    Two neutral mononuclear Cu(II) complexes have been prepared in EtOH using Schiff bases derived from 4-toluoyl pyrazolone and thiosemicarbazide. Both the ligands have been characterized on the basis of elemental analysis, IR, 1H NMR, 13C NMR and mass spectral data. The molecular geometry of one of these ligands has been determined by single crystal X-ray study. It reveals that these ligands exist in amine-one tautomeric form in the solid state. Microanalytical data, Cu-estimation, molar conductivity, magnetic measurements, IR, UV-Visible, FAB-Mass, TG-DTA data and ESR spectral studies were used to confirm the structures of the complexes. Electronic absorption and IR spectra of the complexes suggest a square-planar geometry around the central metal ion. The interaction of complexes with pET30a plasmid DNA was investigated by spectroscopic measurements. Results suggest that the copper complexes bind to DNA via an intercalative mode and can quench the fluorescence intensity of EB bound to DNA. The interaction between the complexes and DNA has also been investigated by agarose gel electrophoresis, interestingly, we found that the copper(II) complexes can cleave circular plasmid DNA to nicked and linear forms.

  11. The Hyperaccumulator Alyssum murale uses Complexation with Nitrogen and Oxygen Donor Ligands for Ni Transport and Storage

    SciTech Connect

    McNear, Jr., D.; Chanay, R; Sparks, D

    2010-01-01

    The Kotodesh genotype of the nickel (Ni) hyperaccumulator Alyssum murale was examined to determine the compartmentalization and internal speciation of Ni, and other elements, in an effort to ascertain the mechanism used by this plant to tolerate extremely high shoot (stem and leaf) Ni concentrations. Plants were grown either hydroponically or in Ni enriched soils from an area surrounding an historic Ni refinery in Port Colborne, Ontario, Canada. Electron probe micro-analysis (EPMA) and synchrotron based micro X-ray fluorescence ({mu}-SXRF) spectroscopy were used to determine the metal distribution and co-localization and synchrotron X-ray and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopies were used to determine the Ni speciation in plant parts and extracted sap. Nickel is concentrated in the dermal leaf and stem tissues of A. murale bound primarily to malate along with other low molecular weight organic ligands and possibly counter anions (e.g., sulfate). Ni is present in the plant sap and vasculature bound to histidine, malate and other low molecular weight compounds. The data presented herein supports a model in which Ni is transported from the roots to the shoots complexed with histidine and stored within the plant leaf dermal tissues complexed with malate, and other low molecular weight organic acids or counter-ions.

  12. The hyperaccumulator Alyssum murale uses complexation with nitrogen and oxygen donor ligands for Ni transport and storage.

    PubMed

    McNear, David H; Chaney, Rufus L; Sparks, Donald L

    2010-02-01

    The Kotodesh genotype of the nickel (Ni) hyperaccumulator Alyssum murale was examined to determine the compartmentalization and internal speciation of Ni, and other elements, in an effort to ascertain the mechanism used by this plant to tolerate extremely high shoot (stem and leaf) Ni concentrations. Plants were grown either hydroponically or in Ni enriched soils from an area surrounding an historic Ni refinery in Port Colborne, Ontario, Canada. Electron probe micro-analysis (EPMA) and synchrotron based micro X-ray fluorescence (micro-SXRF) spectroscopy were used to determine the metal distribution and co-localization and synchrotron X-ray and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopies were used to determine the Ni speciation in plant parts and extracted sap. Nickel is concentrated in the dermal leaf and stem tissues of A. murale bound primarily to malate along with other low molecular weight organic ligands and possibly counter anions (e.g., sulfate). Ni is present in the plant sap and vasculature bound to histidine, malate and other low molecular weight compounds. The data presented herein supports a model in which Ni is transported from the roots to the shoots complexed with histidine and stored within the plant leaf dermal tissues complexed with malate, and other low molecular weight organic acids or counter-ions. PMID:19954803

  13. A series of Zn-4f heterometallic coordination polymers and a zinc complex containing a flexible mixed donor dicarboxylate ligand.

    PubMed

    Feng, Xun; Feng, Yu-Quan; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Ng, Seik-Weng

    2013-06-01

    A new zinc compound, together with a corresponding series of Zn-4f heterometallic coordination polymers, namely, [Zn(H2PBDA)(PBDA)]n (1), {[Ln2(PBDA)2·2H2O] [Zn2(PBDA)2Cl2]}n [H2PBDA = 3-(pyridin-3-yl-oxy) benzene-1,2-dicarboxylic acid, and Ln = Pr(2), Nd(3), Eu(4), Gd(5), Dy(6), Ho(7), Er(8)] have been hydrothermally synthesized and characterized systematically. Polymers 2-8 feature two-dimensional (2D) 4,4 networks, containing the original 1D heterometallic double stranded chains composed of [Ln2Zn2(PBDA)2] entities. The extensive hydrogen bonding and π-π stacking interactions were observed to stabilize the extended architectures. The luminescence emission spectra of the polymers vary depending on the lanthanide(III) ion present. Informative magnetic susceptibility measurements show that the same carboxylate bridging fashion of the PBDA ligand results in the different magnetic properties occurring within the heterometallic coordination polymers. In addition, polymer 6 exhibits an interesting slow magnetic relaxation behavior at lower temperatures.

  14. Selective recognition and stabilization of new ligands targeting the potassium form of the human telomeric G-quadruplex DNA

    PubMed Central

    Lin, Yi-Hwa; Chuang, Show-Mei; Wu, Pei-Ching; Chen, Chun-Liang; Jeyachandran, Sivakamavalli; Lo, Shou-Chen; Huang, Hsu-Shan; Hou, Ming-Hon

    2016-01-01

    The development of a ligand that is capable of distinguishing among the wide variety of G-quadruplex structures and targeting telomeres to treat cancer is particularly challenging. In this study, the ability of two anthraquinone telomerase inhibitors (NSC749235 and NSC764638) to target telomeric G-quadruplex DNA was probed. We found that these ligands specifically target the potassium form of telomeric G-quadruplex DNA over the DNA counterpart. The characteristic interaction with the telomeric G-quadruplex DNA and the anticancer activities of these ligands were also explored. The results of this present work emphasize our understanding of the binding selectivity of anthraquinone derivatives to G-quadruplex DNA and assists in future drug development for G-quadruplex-specific ligands. PMID:27511133

  15. Selective recognition and stabilization of new ligands targeting the potassium form of the human telomeric G-quadruplex DNA

    NASA Astrophysics Data System (ADS)

    Lin, Yi-Hwa; Chuang, Show-Mei; Wu, Pei-Ching; Chen, Chun-Liang; Jeyachandran, Sivakamavalli; Lo, Shou-Chen; Huang, Hsu-Shan; Hou, Ming-Hon

    2016-08-01

    The development of a ligand that is capable of distinguishing among the wide variety of G-quadruplex structures and targeting telomeres to treat cancer is particularly challenging. In this study, the ability of two anthraquinone telomerase inhibitors (NSC749235 and NSC764638) to target telomeric G-quadruplex DNA was probed. We found that these ligands specifically target the potassium form of telomeric G-quadruplex DNA over the DNA counterpart. The characteristic interaction with the telomeric G-quadruplex DNA and the anticancer activities of these ligands were also explored. The results of this present work emphasize our understanding of the binding selectivity of anthraquinone derivatives to G-quadruplex DNA and assists in future drug development for G-quadruplex-specific ligands.

  16. Synthesis, characterization, crystal structure and HSA binding of two new N,O,O-donor Schiff-base ligands derived from dihydroxybenzaldehyde and tert-butylamine

    NASA Astrophysics Data System (ADS)

    Khosravi, Iman; Hosseini, Farnaz; Khorshidifard, Mahsa; Sahihi, Mehdi; Rudbari, Hadi Amiri

    2016-09-01

    Two new o-hydroxy Schiff-bases compounds, L1 and L2, were derived from the 1:1 M condensation of 2,3-dihydroxybenzaldehyde and 2,4-dihydroxybenzaldehyde with tert-butylamine and were characterized by elemental analysis, FT-IR, 1H and 13C NMR spectroscopies. The crystal structure of L2 was also determined by single crystal X-ray analysis. The crystal structure of L2 showed that the compound exists as a zwitterionic form in the solid state, with the H atom of the phenol group being transferred to the imine N atom. It adopts an E configuration about the central Cdbnd N double bond. Furthermore, binding of these Schiff base ligands to Human Serum Albumin (HSA) was investigated by fluorescence quenching, absorption spectroscopy, molecular docking and molecular dynamics (MD) simulation methods. The fluorescence emission of HSA was quenched by ligands. Also, suitable models were used to analyze the UV-vis absorption spectroscopy data for titration of HSA solution by various amounts of Schiff bases. The spectroscopic studies revealed that these Schiff bases formed 1:1 complex with HSA. Energy transfer mechanism of quenching was discussed and the values of 3.35 and 1.57 nm as the mean distances between the bound ligands and the HSA were calculated for L1 and L2, respectively. Molecular docking results indicated that the main active binding site for these Schiff bases ligands is in subdomain IB. Moreover, MD simulation results suggested that this Schiff base complex can interact with HSA, with a slight modification of its tertiary structure.

  17. Quantifying the electron donor and acceptor ability of the ketimide ligands in M(N=CtBu2)4 (M = V, Nb, Ta)

    PubMed Central

    Damon, Peter L.; Liss, Cameron J.; Lewis, Richard A.; Morochnik, Simona; Szpunar, David E.; Telser, Joshua; Hayton, Trevor W.

    2015-01-01

    Addition of 4 equiv of Li(N=CtBu2) to VCl3 in THF, followed by addition of 0.5 equiv I2, generates the homoleptic V(IV) ketimide complex, V(N=CtBu2)4 (1), in 42% yield. Similarly, reaction of 4 equiv of Li(N=CtBu2) with NbCl4(THF)2 in THF affords the homoleptic Nb(IV) ketimide complex, Nb(N=CtBu2)4 (2), in 55% yield. Seeking to extend the series to the tantalum congener, a new Ta(IV) starting material, TaCl4(TMEDA) (3), was prepared via reduction of TaCl5 with Et3SiH, followed by addition of TMEDA. Reaction of 3 with 4 equiv of Li(N=CtBu2) in THF results in a isolation of a Ta(V) ketimide complex, Ta(Cl)(N=CtBu2)4 (5), which can be isolated in 32% yield. Reaction of 5 with Tl(OTf) yields Ta(OTf)(N=CtBu2)4 (6) in 44% yield. Subsequent reduction of 6 with Cp*2Co in toluene generates the homoleptic Ta(IV) congener Ta(N=CtBu2)4 (7), although the yields are poor. All three homoleptic Group 5 ketimide complexes exhibit squashed tetrahedral geometries in the solid state, as determined by X-ray crystallography. This geometry leads to a dx2−y21 (2B1 in D2d) ground state, as supported by DFT calculations. EPR spectroscopic analysis of 1 and 2, performed at X- and Q-band frequencies (~9 and 35 GHz, respectively), further supports the 2B1 ground state assignment, while comparison of 1, 2, and 7 with related Group 5 tetra(aryl), tetra(amido) and tetra(alkoxo) complexes shows a higher M-L covalency in the ketimide-metal interaction. In addition, a ligand field analysis of 1 and 2 demonstrates that the ketimide ligand is both a strong π-donor and strong π-acceptor, an unusual combination found in very few organometallic ligands. PMID:26419513

  18. Synthesis and characterization of toluene-3,4-dithiolatoantimony(III) derivatives with some oxygen and/or sulphur donor ligands

    NASA Astrophysics Data System (ADS)

    Chauhan, H. P. S.; Bhatiya, Sumit; Bakshi, Abhilasha

    2009-09-01

    Replacement reactions of toluene-3,4-dithiolatoantimony(III) chloride with oxygen and/or sulphur donor ligands like benzoic acid, thiobenzoic acid, thioacetic acid, phenol, thiophenol, sodium salicylate and thio glycolic acid in 1:1 molar ratio as well as disodium oxalate in 2:1 molar ratio in refluxing anhydrous benzene yielded toluene-3,4-dithiolatoantimony(III) mono oxo and/or thio carboxylic or phenolic derivatives of the general formula ? {R = OOCC 6H 5, SOCC 6H 5, SOCCH 3, OC 6H 5, SC 6H 5, OOCC 6H 4(OH) and SCH 2COOH} and ? These newly synthesized derivatives are yellow and brown solids/liquids and are soluble in common organic solvents like benzene, chloroform, dichloromethane, etc. These derivatives have been characterized by melting point determination, molecular weight determination, elemental analysis (C, H, S and Sb), spectral {UV, IR and NMR ( 1H and 13C)} and thermal (TGA, DTA and DSC) studies.

  19. Synthetic aspects, spectral, thermal studies and antimicrobial screening on bis(N,N-dimethyldithiocarbamato-S,S')antimony(III) complexes with oxo or thio donor ligands.

    PubMed

    Chauhan, H P S; Carpenter, Jaswant; Joshi, Sapana

    2014-09-15

    The bis(N,N-dimethyldithiocarbamato-S,S')antimony(III) complexes have been obtained by the reaction of chloro bis(N,N-dimethyldithiocarbamato-S,S')antimony(III) with corresponding oxo or thio donor ligands such as sodium benzoate 1, sodium thioglycolate 2, phenol 3, sodium 1-propanethiolate 4, potassium thioacetate 5, sodium salicylate 6, ethane-1,2-dithiolate 7 and disodium oxalate 8. These complexes have been characterized by the physicochemical [melting point, molecular weight determination and elemental analysis (C, H, N, S and Sb)], spectral [UV-Visible, FT-IR, far IR, NMR (1H and 13C)], thermogravimetric (TG & DTA) analysis, ESI-Mass and powder X-ray diffraction studies. Thermogravimetric analysis of the complexes confirmed the final decomposition product as highly pure antimony sulfide (Sb2S3) and powder X-ray diffraction studies show that the complexes are in lower symmetry with monoclinic crystal lattice and nano-ranged particle size (11.51-20.82 nm). The complexes have also been screened against some bacterial and fungal strains for their antibacterial and antifungal activities and compared with standard drugs. These show that the complexes have greater activities against some human pathogenic bacteria and fungi than the activities of standard drugs.

  20. Synthesis, spectroscopic, thermal and antimicrobial studies of toluene-3,4-dithiolatoarsenic(III) derivatives with some oxygen and sulphur donor ligands

    NASA Astrophysics Data System (ADS)

    Chauhan, H. P. S.; Bhatiya, Sumit

    2012-11-01

    Replacement reactions of toluene-3,4-dithiolatoarsenic(III) chloride with oxygen and sulphur donor ligands like benzoic acid, thiobenzoic acid, anhydrous sodium acetate, thioacetic acid, phenol, thiophenol, sodium salicylate and thio glycolic acid in 1:1 molar ratio as well as disodium oxalate in 2:1 molar ratio in refluxing anhydrous benzene yielded toluene-3,4-dithiolatoarsenic(III) mono oxo or thio carboxylic or phenolic derivatives of the general formula SC6H3(CH3)SAsR {where R = OOCC6H5, SOCC6H5, OOCCH3, SOCCH3, OC6H5, SC6H5, OOCC6H4(OH), SCH2COOH} and SC6H3(CH3)SAsOOC-COOAsS(CH3)C6H3S. These synthesized derivatives are yellow, yellow-brown solids/ liquids and are soluble in common organic solvents like benzene, chloroform, dichloromethane, dimethyl formamide, dimethyl sulphoxide etc. These derivatives have been characterized by melting point determination, molecular weight determination, elemental analysis (C, H, S and As), spectral {UV, IR, NMR (1H and 13C), ESI-Mass, SEM and powder X-ray diffraction} and thermal (TGA, DTA and DSC) studies. Some of these compounds have been screened for their antimicrobial activities using the disc diffusion method. These derivatives have shown good activity as antibacterial and antifungal agents on some selected bacterial and fungal strains, which increased on increasing the concentration. Chloroamphenicol and terbinafin were used as standards for the comparison.

  1. Synthetic aspects, spectral, thermal studies and antimicrobial screening on bis(N,N-dimethyldithiocarbamato-S,S‧)antimony(III) complexes with oxo or thio donor ligands

    NASA Astrophysics Data System (ADS)

    Chauhan, H. P. S.; Carpenter, Jaswant; Joshi, Sapana

    2014-09-01

    The bis(N,N-dimethyldithiocarbamato-S,S‧)antimony(III) complexes have been obtained by the reaction of chloro bis(N,N-dimethyldithiocarbamato-S,S‧)antimony(III) with corresponding oxo or thio donor ligands such as sodium benzoate 1, sodium thioglycolate 2, phenol 3, sodium 1-propanethiolate 4, potassium thioacetate 5, sodium salicylate 6, ethane-1,2-dithiolate 7 and disodium oxalate 8. These complexes have been characterized by the physicochemical [melting point, molecular weight determination and elemental analysis (C, H, N, S and Sb)], spectral [UV-Visible, FT-IR, far IR, NMR (1H and 13C)], thermogravimetric (TG & DTA) analysis, ESI-Mass and powder X-ray diffraction studies. Thermogravimetric analysis of the complexes confirmed the final decomposition product as highly pure antimony sulfide (Sb2S3) and powder X-ray diffraction studies show that the complexes are in lower symmetry with monoclinic crystal lattice and nano-ranged particle size (11.51-20.82 nm). The complexes have also been screened against some bacterial and fungal strains for their antibacterial and antifungal activities and compared with standard drugs. These show that the complexes have greater activities against some human pathogenic bacteria and fungi than the activities of standard drugs.

  2. Dimeric Ube2g2 simultaneously engages donor and acceptor ubiquitins to form Lys48-linked ubiquitin chains

    PubMed Central

    Liu, Weixiao; Shang, Yongliang; Zeng, Yan; Liu, Chao; Li, Yanchang; Zhai, Linhui; Wang, Pan; Lou, Jizhong; Xu, Ping; Ye, Yihong; Li, Wei

    2014-01-01

    Cellular adaptation to proteotoxic stress at the endoplasmic reticulum (ER) depends on Lys48-linked polyubiquitination by ER-associated ubiquitin ligases (E3s) and subsequent elimination of ubiquitinated retrotranslocation products by the proteasome. The ER-associated E3 gp78 ubiquitinates misfolded proteins by transferring preformed Lys48-linked ubiquitin chains from the cognate E2 Ube2g2 to substrates. Here we demonstrate that Ube2g2 synthesizes linkage specific ubiquitin chains by forming an unprecedented homodimer: The dimerization of Ube2g2, mediated primarily by electrostatic interactions between two Ube2g2s, is also facilitated by the charged ubiquitin molecules. Mutagenesis studies show that Ube2g2 dimerization is required for ER-associated degradation (ERAD). In addition to E2 dimerization, we show that a highly conserved arginine residue in the donor Ube2g2 senses the presence of an aspartate in the acceptor ubiquitin to position only Lys48 of ubiquitin in proximity to the donor E2 active site. These results reveal an unanticipated mode of E2 self-association that allows the E2 to effectively engage two ubiquitins to specifically synthesize Lys48-linked ubiquitin chains. PMID:24366945

  3. BluB cannibalizes flavin to form the lower ligand of vitamin B12

    PubMed Central

    Taga, Michiko E.; Larsen, Nicholas A.; Howard-Jones, Annaleise R.; Walsh, Christopher T.; Walker, Graham C.

    2009-01-01

    Vitamin B12 (cobalamin) is among the largest known non-polymeric natural products, and the only vitamin synthesized exclusively by microorganisms1. The biosynthesis of the lower ligand of vitamin B12, 5,6-dimethylbenzimidazole (DMB), is poorly understood1–3. Recently, we discovered that a Sinorhizobium meliloti gene, bluB, is necessary for DMB biosynthesis4. Here we show that BluB triggers the unprecedented fragmentation and contraction of the bound flavin mononucleotide cofactor and cleavage of the ribityl tail to form DMB and D-erythrose 4-phosphate. Our structural analysis shows that BluB resembles an NAD(P)H-flavin oxidoreductase, except that its unusually tight binding pocket accommodates flavin mononucleotide but not NAD(P)H. We characterize crystallographically an early intermediate along the reaction coordinate, revealing molecular oxygen poised over reduced flavin. Thus, BluB isolates and directs reduced flavin to activate molecular oxygen for its own cannibalization. This investigation of the biosynthesis of DMB provides clarification of an aspect of vitamin B12 that was otherwise incomplete, and may contribute to a better understanding of vitamin B12-related disease. PMID:17377583

  4. DNA interaction, SOD, peroxidase and nuclease activity studies of iron complex having ligand with carboxamido nitrogen donors

    NASA Astrophysics Data System (ADS)

    Ghosh, Kaushik; Tyagi, Nidhi; Kumar, Hemant; Rathi, Sweety

    2015-07-01

    Complex (Et3HN)[FeIII(bpb)Cl2], 1 {where H2bpb: N,N‧-(1,2-phenylene)bis(pyridine-2-carboxamide)} was synthesized and characterized by reported procedure (Yang et al., 1991). Complex 1 was found to be effective in superoxide scavenging activity and an IC50 value of 4.1 μM was obtained in xanthine-xanthine oxidase nitro blue tetrazolium assay. Peroxidase-like activity of this complex was determined by the oxidation of 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). DNA interaction studies of complex 1 showed binding of DNA through external or groove binding. Complex 1 exhibited chemical nuclease activity in the presence of hydrogen peroxide and cleaved supercoiled pBR322 DNA to its linear and nicked circular form at physiological pH. Mechanistic studies indicated possible role of hydroxyl radical (radOH) species in DNA cleavage activity via hydroperoxo intermediate: [FeIIIsbnd OOH-]2+ → [FeIVdbnd O]2+ + radOH.

  5. Exploring oxorhenium '3+1' mixed-ligand complexes carrying the S-benzyl-3-[(2-hydroxyphenyl)methylene]dithiocarbazate [ONS]/monothiol [S] donor set: synthesis and characterization.

    PubMed

    Chen, Xiaoyuan; Femia, Frank J; Babich, John W; Zubieta, Jon

    2000-09-11

    The reaction of ReOCl(3)(PPh(3))(2) with the potentially tridentate ligand S-benzyl-3-[(2-hydroxyphenyl)methylene]dithiocarbazate ([ONS] donor set) and para-substituted benzenethiols [C(6)H(4)X-4-SH] (where X=H, F, Cl, Br and OCH(3)) in the presence of Et(3)N afforded a series of integrated '3+1' oxorhenium(V) complexes with general formula [ReO{eta(3)-OC(6)H(4)-2-CH=N-N=C(SCH(2)Ph)-S}(eta(1)-C(6)H(4)X-4-S)]. The molecular structure of [ReO{eta(3)-OC(6)H(4)-2-CH=N-N=C(SCH(2)Ph)-S}(eta(1)-C(6)H(4)F-4-S)] (4) was determined by single-crystal X-ray analysis. Complex 4 consists of a central oxorhenium(V) core with phenolic oxygen, azomethine nitrogen and thiol sulfur donor from the thiosemicarbazone Schiff base ligand and one sulfur donor from monothiol ligand completing a distorted square pyramidal environment. Crystal data for 4, C(21)H(16)FN(2)O(2)S(3)Re: orthorhombic, P2(1)2(1)2(1), a=5.6682(3), b=11.6600(6), c=31.697(2) A, V=2094.9(2) A(3), Z=4. PMID:20592952

  6. Syntheses, structures, and properties of transition metal coordination polymers based on a long semirigid tetracarboxylic acid and multidentate N-donor ligands

    NASA Astrophysics Data System (ADS)

    Gao, Peng; Bai, Hui; Bing, Ying-Ying; Hu, Ming

    2016-02-01

    Six transition metal coordination polymers based on a semirigid tetracarboxylic acid and the multidentate N-donor ligands have been synthesized by the hydrothermal method, namely, {[Co(H2obda) (μ2-H2O) (H2O)2]·2H2O}n (1), {[Co(obda)0.5(bpe) (H2O)2]·3H2O}n (2), {[Zn(H2obda) (H2O)4]·H4obda·6H2O}n (3), {[Zn(bpy) (H2O)4]·H2obda}n (4), {[Ni(bpy) (H2O)4]·H2obda}n (5) and {[Cu(H2obda) (bpy)2]}n (6) (H4obda = 1,4-bis(4-oxy-1,2-benzene dicarboxylic acid)benzene, bpe = 1,2-Bis(4-pyridyl)ethylene), bpy = 4,4‧-bipyridine). Compounds 1-6 were structurally characterized by the elemental analyses, infrared spectra, and single crystal X-ray diffractions. Compounds 1-2 exhibit the 2D quadrilateral and polygonal layered grid structures, respectively; a 3D supramolecular structure of 2 has been build via π···π and hydrogen bonds interactions. Compounds 3-6 reveal the 1D zigzag and linear chains structures, respectively; furthermore, 3-5 display the diverse 3D supramolecular structures via hydrogen bonds, respectively. The 1-D infinite water chain in 3 has been found between the lattice water molecules. In addition, the thermogravimetric analyses of 1-6, magnetic property of 1, and photoluminescence of 3-4 have been investigated, respectively.

  7. Syntheses, crystal structures, and characterization of three 1D, 2D and 3D complexes based on mixed multidentate N- and O-donor ligands

    SciTech Connect

    Yang, Huai-Xia; Liang, Zhen; Hao, Bao-Lian; Meng, Xiang-Ru

    2014-10-15

    Three new 1D to 3D complexes, namely, ([Ni(btec)(Himb){sub 2}(H{sub 2}O){sub 2}]·6H{sub 2}O){sub n} (1), ([Cd(btec){sub 0.5}(imb)(H{sub 2}O)]·1.5H{sub 2}O){sub n} (2), and ([Zn(btec){sub 0.5}(imb)]·H{sub 2}O){sub n} (3) (H{sub 4}btec=1,2,4,5-benzenetetracarboxylic acid, imb=2-(1H-imidazol-1-methyl)-1H-benzimidazole) have been synthesized by adjusting the central metal ions. Single-crystal X-ray diffraction analyses reveal that complex 1 possesses a 1D chain structure which is further extended into the 3D supramolecular architecture via hydrogen bonds. Complex 2 features a 2D network with Schla¨fli symbol (5{sup 3}·6{sup 2}·7)(5{sup 2}·6{sup 4}). Complex 3 presents a 3D framework with a point symbol of (4·6{sup 4}·8)(4{sup 2}·6{sup 2}·8{sup 2}). Moreover, their IR spectra, PXRD patterns, thermogravimetric curves, and luminescent emissions were studied at room temperature. - Graphical abstract: Three new 1D to 3D complexes with different structural and topological motifs have been obtained by modifying the central metal ions. Additionally, their IR, TG analyses and fluorescent properties are also investigated. - Highlights: • Three complexes based on mixed multidentate N- and O-donor ligands. • The complexes are characterized by IR, luminescence and TGA techniques. • Benzenetetracarboxylates display different coordination modes in complexes 1–3. • Changing the metal ions can result in complexes with completely different structures.

  8. Structure-function relationships of peptides forming the calcin family of ryanodine receptor ligands.

    PubMed

    Xiao, Liang; Gurrola, Georgina B; Zhang, Jing; Valdivia, Carmen R; SanMartin, Mario; Zamudio, Fernando Z; Zhang, Liming; Possani, Lourival D; Valdivia, Héctor H

    2016-05-01

    Calcins are a novel family of scorpion peptides that bind with high affinity to ryanodine receptors (RyRs) and increase their activity by inducing subconductance states. Here, we provide a comprehensive analysis of the structure-function relationships of the eight calcins known to date, based on their primary sequence, three-dimensional modeling, and functional effects on skeletal RyRs (RyR1). Primary sequence alignment and evolutionary analysis show high similarity among all calcins (≥78.8% identity). Other common characteristics include an inhibitor cysteine knot (ICK) motif stabilized by three pairs of disulfide bridges and a dipole moment (DM) formed by positively charged residues clustering on one side of the molecule and neutral and negatively charged residues segregating on the opposite side. [(3)H]Ryanodine binding assays, used as an index of the open probability of RyRs, reveal that all eight calcins activate RyR1 dose-dependently with Kd values spanning approximately three orders of magnitude and in the following rank order: opicalcin1 > opicalcin2 > vejocalcin > hemicalcin > imperacalcin > hadrucalcin > maurocalcin > urocalcin. All calcins significantly augment the bell-shaped [Ca(2+)]-[(3)H]ryanodine binding curve with variable effects on the affinity constants for Ca(2+) activation and inactivation. In single channel recordings, calcins induce the appearance of a subconductance state in RyR1 that has a unique fractional value (∼20% to ∼60% of the full conductance state) but bears no relationship to binding affinity, DM, or capacity to stimulate Ca(2+) release. Except for urocalcin, all calcins at 100 nM concentration stimulate Ca(2+) release and deplete Ca(2+) load from skeletal sarcoplasmic reticulum. The natural variation within the calcin family of peptides offers a diversified set of high-affinity ligands with the capacity to modulate RyRs with high dynamic range and potency. PMID:27114612

  9. Structure–function relationships of peptides forming the calcin family of ryanodine receptor ligands

    PubMed Central

    Xiao, Liang; Gurrola, Georgina B.; Zhang, Jing; Valdivia, Carmen R.; SanMartin, Mario; Zamudio, Fernando Z.; Zhang, Liming; Possani, Lourival D.

    2016-01-01

    Calcins are a novel family of scorpion peptides that bind with high affinity to ryanodine receptors (RyRs) and increase their activity by inducing subconductance states. Here, we provide a comprehensive analysis of the structure–function relationships of the eight calcins known to date, based on their primary sequence, three-dimensional modeling, and functional effects on skeletal RyRs (RyR1). Primary sequence alignment and evolutionary analysis show high similarity among all calcins (≥78.8% identity). Other common characteristics include an inhibitor cysteine knot (ICK) motif stabilized by three pairs of disulfide bridges and a dipole moment (DM) formed by positively charged residues clustering on one side of the molecule and neutral and negatively charged residues segregating on the opposite side. [3H]Ryanodine binding assays, used as an index of the open probability of RyRs, reveal that all eight calcins activate RyR1 dose-dependently with Kd values spanning approximately three orders of magnitude and in the following rank order: opicalcin1 > opicalcin2 > vejocalcin > hemicalcin > imperacalcin > hadrucalcin > maurocalcin >> urocalcin. All calcins significantly augment the bell-shaped [Ca2+]-[3H]ryanodine binding curve with variable effects on the affinity constants for Ca2+ activation and inactivation. In single channel recordings, calcins induce the appearance of a subconductance state in RyR1 that has a unique fractional value (∼20% to ∼60% of the full conductance state) but bears no relationship to binding affinity, DM, or capacity to stimulate Ca2+ release. Except for urocalcin, all calcins at 100 nM concentration stimulate Ca2+ release and deplete Ca2+ load from skeletal sarcoplasmic reticulum. The natural variation within the calcin family of peptides offers a diversified set of high-affinity ligands with the capacity to modulate RyRs with high dynamic range and potency. PMID:27114612

  10. Synthesis of N4 donor macrocyclic Schiff base ligands and their Ru (II), Pd (II), Pt (II) metal complexes for biological studies and catalytic oxidation of didanosine in pharmaceuticals

    NASA Astrophysics Data System (ADS)

    Ravi krishna, E.; Muralidhar Reddy, P.; Sarangapani, M.; Hanmanthu, G.; Geeta, B.; Shoba Rani, K.; Ravinder, V.

    2012-11-01

    A series of tetraaza (N4 donor) macrocyclic ligands (L1-L4) were derived from the condensation of o-phthalaldehyde (OPA) with some substituted aromatic amines/azide, and subsequently used to synthesize the metal complexes of Ru(II), Pd(II) and Pt(II). The structures of macrocyclic ligands and their metal complexes were characterized by elemental analyses, IR, 1H &13C NMR, mass and electronic spectroscopy, thermal, magnetic and conductance measurements. Both the ligands and their complexes were screened for their antibacterial activities against Gram positive and Gram negative bacteria by MIC method. Besides, these macrocyclic complexes were investigated as catalysts in the oxidation of pharmaceutical drug didanosine. The oxidized products were further treated with sulphanilic acid to develop the colored products to determine by spectrophotometrically. The current oxidation method is an environmentally friendly, simple to set-up, requires short reaction time, produces high yields and does not require co-oxidant.

  11. Synthesis, crystal structure, DFT study and photocatalytic property of a new Ni(II) complex of a symmetric N2O4-donor bis-Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Wang, Hu; Meng, Xiangmin; Fan, Chuanbin; Fan, Yuhua; Bi, Caifeng

    2016-03-01

    A new complex, Ni(C22H26N2O10S2)·2CH3OH, with a sexidentate (N2O4) symmetric bis-Schiff base ligand (C22H26N2O10S2 = 1,2-bis(2-methoxy-6-formylphenoxy)ethane-2-aminoethane-sulfonic acid) has been synthesized and characterized by physico-chemical and spectroscopic methods. The X-ray crystal structure shows that the Ni(II) atom of the complex is six-coordinated by two nitrogens from Cdbnd N groups, two oxygens from ether groups and two hydroxyl oxygens from sulfonic acid groups in the mono-ligand, forming a distorted octahedral geometry. Theoretical study of the complex is carried out by density functional theory (DFT) method and the B3LYP method employing the 6-3l+G* basis set. Moreover, the complex proved to be good candidate for the photocatalytic degradation of methylene blue.

  12. Synthesis, crystal structure, DFT study and photocatalytic property of a new Ni(II) complex of a symmetric N2O4-donor bis-Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Wang, Hu; Meng, Xiangmin; Fan, Chuanbin; Fan, Yuhua; Bi, Caifeng

    2016-03-01

    A new complex, Ni(C22H26N2O10S2)·2CH3OH, with a sexidentate (N2O4) symmetric bis-Schiff base ligand (C22H26N2O10S2 = 1,2-bis(2-methoxy-6-formylphenoxy)ethane-2-aminoethane-sulfonic acid) has been synthesized and characterized by physico-chemical and spectroscopic methods. The X-ray crystal structure shows that the Ni(II) atom of the complex is six-coordinated by two nitrogens from Cdbnd N groups, two oxygens from ether groups and two hydroxyl oxygens from sulfonic acid groups in the mono-ligand, forming a distorted octahedral geometry. Theoretical study of the complex is carried out by density functional theory (DFT) method and the B3LYP method employing the 6-3l+G* basis set. Moreover, the complex proved to be good candidate for the photocatalytic degradation of methylene blue.

  13. CO and O2 Binding to Pseudo-Tetradentate Ligand-Copper(I)-Complexes with a Variable N-Donor Moiety: Kinetic/Thermodynamic Investigation Reveals Ligand Induced Changes in Reaction Mechanism

    PubMed Central

    Lucas, Heather R.; Meyer, Gerald J.; Karlin, Kenneth D.

    2010-01-01

    The kinetics, thermodynamics, and coordination dynamics for O2 and CO 1:1 binding to a series of pseudo-tetradentate ligand-copper(I)-complexes (DLCuI) to give CuI/O2 and CuI/CO product species are reported. The DLCuI series possess an identical tridentate core structure where the cuprous ion binds to the bispicolylamine (L) fragment. DL also contains a fourth variable N-donor moiety {D = benzyl (Bz); pyridyl (Py); imidazolyl (Im); dimethylamino (NMe2-); tert-butylphenyl pyridyl (TBP); quinolyl (Q)}. The structural characteristics of DLCuI-CO and DLCuI are detailed, with X-ray crystal structures reported for TBPLCuI-CO, BzLCuI-CO, and QLCuI. Infrared studies (solution and solid-state) confirm that DLCuI-CO possess the same four-coordinate core structure in solution with the variable D moiety ‘dangling’, i.e. not coordinated to the copper(I) ion. Other trends observed for the present series appear to derive from the degree to which the D-group interacts with the cuprous ion center. Electrochemical studies reveal close similarities of behavior for ImLCuI and NMe2LCuI (as well as for TBPLCuI and QLCuI), which relate to the O2-binding kinetics and thermodynamics. Equilibrium CO binding data (KCO, ΔH°, ΔS°) were obtained by conducting UV-visible spectrophotometric CO titrations, while CO binding kinetics and thermodynamics (kCO ; ΔH‡, ΔS‡) were measured through variable temperature (193 K – 293 K) transient absorbance laser flash photolysis experiments, λex = 355 nm. Carbon monoxide dissociation rate constants (k−CO) and corresponding activation parameters (ΔH‡, ΔS‡) have also been obtained. CO binding to DLCuI follows an associative mechanism with the increased donation from D leading to higher kCO values. Unlike that seen in previous work, the KCO values increased as the kCO and k−CO values declines; the latter decreased at a faster rate. By using the ‘flash-and-trap’ method (λex = 355 nm ; 188 K – 218 K), the kinetics and

  14. A novel transition pathway of ligand-induced topological conversion from hybrid forms to parallel forms of human telomeric G-quadruplexes.

    PubMed

    Wang, Zi-Fu; Li, Ming-Hao; Chen, Wei-Wen; Hsu, Shang-Te Danny; Chang, Ta-Chau

    2016-05-01

    The folding topology of DNA G-quadruplexes (G4s) depends not only on their nucleotide sequences but also on environmental factors and/or ligand binding. Here, a G4 ligand, 3,6-bis(1-methyl-4-vinylpyridium iodide)-9-(1-(1-methyl-piperidinium iodide)-3,6,9-trioxaundecane) carbazole (BMVC-8C3O), can induce topological conversion of non-parallel to parallel forms in human telomeric DNA G4s. Nuclear magnetic resonance (NMR) spectroscopy with hydrogen-deuterium exchange (HDX) reveals the presence of persistent imino proton signals corresponding to the central G-quartet during topological conversion of Tel23 and Tel25 G4s from hybrid to parallel forms, implying that the transition pathway mainly involves local rearrangements. In contrast, rapid HDX was observed during the transition of 22-CTA G4 from an anti-parallel form to a parallel form, resulting in complete disappearance of all the imino proton signals, suggesting the involvement of substantial unfolding events associated with the topological transition. Site-specific imino proton NMR assignments of Tel23 G4 enable determination of the interconversion rates of individual guanine bases and detection of the presence of intermediate states. Since the rate of ligand binding is much higher than the rate of ligand-induced topological conversion, a three-state kinetic model was evoked to establish the associated energy diagram for the topological conversion of Tel23 G4 induced by BMVC-8C3O. PMID:26975658

  15. Spectroscopic studies, cyclic voltammetry and synthesis of nickel(II) complexes with N 4, N 2O 2 and N 4S 2 donor macrocyclic ligands

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Kumar, Rajiv

    2005-11-01

    Nickel(II) complexes of the general composition Ni(L)X 2 (where X = SCN, NO 3 and 1/2SO 4 and ligands = L 1 L 2 and L 3) have been synthesized and characterized by elemental analyses, magnetic moments, IR, 1H NMR, 13C NMR and electronic spectral studies. Nickel(II) ions, such as nitrates, thiocyantes and sulphates were found to act as templates for the cyclic condensations [1 + 1] and [2 + 2] of NH 2sbnd C 6H 4sbnd O sbnd CH 2sbnd CH 2sbnd O sbnd C 6H 4sbnd NH 2, NH 2sbnd (CH 2) 2sbnd NH 2 and NH 2sbnd CH(CH 3) sbnd CH 2sbnd NH 2 with C 6H 5sbnd CO sbnd CO sbnd C 6H 5, C 6H 5sbnd CO sbnd CH 2sbnd CO sbnd C 6H 5 and (COOH sbnd CH 2sbnd CH 2) 2S. All the complexes show magnetic moments corresponding to two unpaired electrons except [Ni(L 1)](NO 3) 2 and [Ni(L 2)](NO 3) 2 complexes which are diamagnetic. Electronic spectroscopy was used to analyse the differences between the paramagnetic and diamagnetic forms. Electrochemical properties have been studied extensively for Ni(III/II) and Ni(II/I) couples. The equilibrium between the paramagnetic and diamagnetic forms and the nickel(III/II) couple are strongly dependent on the electrolyte. It has been observed that the sulphate group coordinated selectively on the apical position of the nickel(II) centers of the compounds. The structural and electrochemical studies suggest that cooperative effects, involving coordination of sulphate to one nickel center, is responsible for the recognition of this anion. Various ligand field parameters have been calculated and discussed.

  16. Connecting mononuclear dysprosium single-molecule magnets to form dinuclear complexes via in situ ligand oxidation.

    PubMed

    Yutronkie, Nathan J; Kühne, Irina A; Korobkov, Ilia; Brusso, Jaclyn L; Murugesu, Muralee

    2016-01-14

    A Dy2 complex, exhibiting SMM behaviour, and its Y analogue were prepared via in situ oxidation of Py2TTA, a pincer type ligand, followed by dimerisation. This unique metal complexation and subsequent dimerization were followed by solution NMR studies. PMID:26567706

  17. Systematic analysis of the ability of Nitric Oxide donors to dislodge biofilms formed by Salmonella enterica and Escherichia coli O157:H7.

    PubMed

    Marvasi, Massimiliano; Chen, Charles; Carrazana, Manuel; Durie, Ian A; Teplitski, Max

    2014-01-01

    Biofilms in the industrial environment could be problematic. Encased in extracellular polymeric substances, pathogens within biofilms are significantly more resistant to chlorine and other disinfectants. Recent studies suggest that compounds capable of manipulating nitric oxide-mediated signaling in bacteria could induce dispersal of sessile bacteria and provide a foundation for novel approaches to controlling biofilms formed by some microorganisms. In this work, we compared the ability of five nitric oxide donors (molsidomine, MAHMA NONOate, diethylamine NONOate, diethylamine NONOate diethylammonium salt, spermine NONOate) to dislodge biofilms formed by non-typhoidal Salmonella enterica and pathogenic E. coli on plastic and stainless steel surfaces at different temperatures. All five nitric oxide donors induced significant (35-80%) dispersal of biofilms, however, the degree of dispersal and the optimal dispersal conditions varied. MAHMA NONOate and molsidomine were strong dispersants of the Salmonella biofilms formed on polystyrene. Importantly, molsidomine induced dispersal of up to 50% of the pre-formed Salmonella biofilm at 4°C, suggesting that it could be effective even under refrigerated conditions. Biofilms formed by E. coli O157:H7 were also significantly dispersed. Nitric oxide donor molecules were highly active within 6 hours of application. To better understand mode of action of these compounds, we identified Salmonella genomic region recA-hydN, deletion of which led to an insensitivity to the nitric oxide donors. PMID:24995149

  18. Cobalt(III) Werner Complexes with 1,2-Diphenylethylenediamine Ligands: Readily Available, Inexpensive, and Modular Chiral Hydrogen Bond Donor Catalysts for Enantioselective Organic Synthesis.

    PubMed

    Lewis, Kyle G; Ghosh, Subrata K; Bhuvanesh, Nattamai; Gladysz, John A

    2015-03-25

    In the quest for new catalysts that can deliver single enantiomer pharmaceuticals and agricultural chemicals, chemists have extensively mined the "chiral pool", with little in the way of inexpensive, readily available building blocks now remaining. It is found that Werner complexes based upon the D3 symmetric chiral trication [Co(en)3](3+) (en = 1,2-ethylenediamine), which features an earth abundant metal and cheap ligand type, and was among the first inorganic compounds resolved into enantiomers 103 years ago, catalyze a valuable carbon-carbon bond forming reaction, the Michael addition of malonate esters to nitroalkenes, in high enantioselectivities and without requiring inert atmosphere conditions. The title catalysts, [Co((S,S)-dpen)3](3+) ((S,S)-3 (3+)) 3X(-), employ a commercially available chiral ligand, (S,S)-1,2-diphenylethylenediamine. The rates and ee values are functions of the configuration of the cobalt center (Λ/Δ) and the counteranions, which must be lipophilic to solubilize the trication in nonaqueous media. The highest enantioselectivities are obtained with Λ and 2Cl(-)BArf (-), 2BF4 (-)BArf (-), or 3BF4 (-) salts (BArf (-) = B(3,5-C6H3(CF3)2)4 (-)). The substrates are not activated by metal coordination, but rather by second coordination sphere hydrogen bonding involving the ligating NH2 groups. Crystal structures and NMR data indicate enthalpically stronger interactions with the NH moieties related by the C3 symmetry axis, as opposed to those related by the C2 symmetry axes; rate trends and other observations suggest this to be the catalytically active site. Both Λ- and Δ-(S,S)-3 (3+) 2Cl(-)BArf (-) are effective catalysts for additions of β-ketoesters to RO2CN=NCO2R species (99-86% yields, 81-76% ee), which provide carbon-nitrogen bonds and valuable precursors to α-amino acids. PMID:27162946

  19. Cobalt(III) Werner Complexes with 1,2-Diphenylethylenediamine Ligands: Readily Available, Inexpensive, and Modular Chiral Hydrogen Bond Donor Catalysts for Enantioselective Organic Synthesis

    PubMed Central

    2015-01-01

    In the quest for new catalysts that can deliver single enantiomer pharmaceuticals and agricultural chemicals, chemists have extensively mined the “chiral pool”, with little in the way of inexpensive, readily available building blocks now remaining. It is found that Werner complexes based upon the D3 symmetric chiral trication [Co(en)3]3+ (en = 1,2-ethylenediamine), which features an earth abundant metal and cheap ligand type, and was among the first inorganic compounds resolved into enantiomers 103 years ago, catalyze a valuable carbon–carbon bond forming reaction, the Michael addition of malonate esters to nitroalkenes, in high enantioselectivities and without requiring inert atmosphere conditions. The title catalysts, [Co((S,S)-dpen)3]3+ ((S,S)-33+) 3X–, employ a commercially available chiral ligand, (S,S)-1,2-diphenylethylenediamine. The rates and ee values are functions of the configuration of the cobalt center (Λ/Δ) and the counteranions, which must be lipophilic to solubilize the trication in nonaqueous media. The highest enantioselectivities are obtained with Λ and 2Cl–BArf–, 2BF4–BArf–, or 3BF4– salts (BArf– = B(3,5-C6H3(CF3)2)4–). The substrates are not activated by metal coordination, but rather by second coordination sphere hydrogen bonding involving the ligating NH2 groups. Crystal structures and NMR data indicate enthalpically stronger interactions with the NH moieties related by the C3 symmetry axis, as opposed to those related by the C2 symmetry axes; rate trends and other observations suggest this to be the catalytically active site. Both Λ- and Δ-(S,S)-33+ 2Cl–BArf– are effective catalysts for additions of β-ketoesters to RO2CN=NCO2R species (99–86% yields, 81–76% ee), which provide carbon–nitrogen bonds and valuable precursors to α-amino acids. PMID:27162946

  20. Communication: Free energy of ligand-receptor systems forming multimeric complexes

    NASA Astrophysics Data System (ADS)

    Di Michele, Lorenzo; Bachmann, Stephan J.; Parolini, Lucia; Mognetti, Bortolo M.

    2016-04-01

    Ligand-receptor interactions are ubiquitous in biology and have become popular in materials in view of their applications to programmable self-assembly. Although complex functionalities often emerge from the simultaneous interaction of more than just two linker molecules, state of the art theoretical frameworks enable the calculation of the free energy only in systems featuring one-to-one ligand/receptor binding. In this Communication, we derive a general formula to calculate the free energy of systems featuring simultaneous direct interaction between an arbitrary number of linkers. To exemplify the potential and generality of our approach, we apply it to the systems recently introduced by Parolini et al. [ACS Nano 10, 2392 (2016)] and Halverson and Tkachenko [J. Chem. Phys. 144, 094903 (2016)], both featuring functionalized Brownian particles interacting via three-linker complexes.

  1. Communication: Free energy of ligand-receptor systems forming multimeric complexes.

    PubMed

    Di Michele, Lorenzo; Bachmann, Stephan J; Parolini, Lucia; Mognetti, Bortolo M

    2016-04-28

    Ligand-receptor interactions are ubiquitous in biology and have become popular in materials in view of their applications to programmable self-assembly. Although complex functionalities often emerge from the simultaneous interaction of more than just two linker molecules, state of the art theoretical frameworks enable the calculation of the free energy only in systems featuring one-to-one ligand/receptor binding. In this Communication, we derive a general formula to calculate the free energy of systems featuring simultaneous direct interaction between an arbitrary number of linkers. To exemplify the potential and generality of our approach, we apply it to the systems recently introduced by Parolini et al. [ACS Nano 10, 2392 (2016)] and Halverson and Tkachenko [J. Chem. Phys. 144, 094903 (2016)], both featuring functionalized Brownian particles interacting via three-linker complexes.

  2. Communication: Free energy of ligand-receptor systems forming multimeric complexes.

    PubMed

    Di Michele, Lorenzo; Bachmann, Stephan J; Parolini, Lucia; Mognetti, Bortolo M

    2016-04-28

    Ligand-receptor interactions are ubiquitous in biology and have become popular in materials in view of their applications to programmable self-assembly. Although complex functionalities often emerge from the simultaneous interaction of more than just two linker molecules, state of the art theoretical frameworks enable the calculation of the free energy only in systems featuring one-to-one ligand/receptor binding. In this Communication, we derive a general formula to calculate the free energy of systems featuring simultaneous direct interaction between an arbitrary number of linkers. To exemplify the potential and generality of our approach, we apply it to the systems recently introduced by Parolini et al. [ACS Nano 10, 2392 (2016)] and Halverson and Tkachenko [J. Chem. Phys. 144, 094903 (2016)], both featuring functionalized Brownian particles interacting via three-linker complexes. PMID:27131522

  3. Observed bromodomain flexibility reveals histone peptide- and small molecule ligand-compatible forms of ATAD2.

    PubMed

    Poncet-Montange, Guillaume; Zhan, Yanai; Bardenhagen, Jennifer P; Petrocchi, Alessia; Leo, Elisabetta; Shi, Xi; Lee, Gilbert R; Leonard, Paul G; Geck Do, Mary K; Cardozo, Mario G; Andersen, Jannik N; Palmer, Wylie S; Jones, Philip; Ladbury, John E

    2015-03-01

    Preventing histone recognition by bromodomains emerges as an attractive therapeutic approach in cancer. Overexpression of ATAD2 (ATPase family AAA domain-containing 2 isoform A) in cancer cells is associated with poor prognosis making the bromodomain of ATAD2 a promising epigenetic therapeutic target. In the development of an in vitro assay and identification of small molecule ligands, we conducted structure-guided studies which revealed a conformationally flexible ATAD2 bromodomain. Structural studies on apo-, peptide-and small molecule-ATAD2 complexes (by co-crystallization) revealed that the bromodomain adopts a 'closed', histone-compatible conformation and a more 'open' ligand-compatible conformation of the binding site respectively. An unexpected conformational change of the conserved asparagine residue plays an important role in driving the peptide-binding conformation remodelling. We also identified dimethylisoxazole-containing ligands as ATAD2 binders which aided in the validation of the in vitro screen and in the analysis of these conformational studies.

  4. A novel thermally stable hydroperoxo-copper(II) complex in a Cu(N2O2) chromophore of a potential N4O2 donor Schiff base ligand: synthesis, structure and catalytic studies.

    PubMed

    Biswas, Surajit; Dutta, Arpan; Debnath, Mainak; Dolai, Malay; Das, Kalyan K; Ali, Mahammad

    2013-09-28

    The generation and study of metal-hydroperoxo/metal-peroxo (LCu(II)-OOH or LCu(II)-OO˙) complexes is a fascinating area of research of many chemical and biochemical researchers, because of their involvement as active intermediates in many biological and industrial catalytic oxidation processes. For this purpose we have designed a bulky hexa-coordinating ligand with potential N4O2 donor atoms which could provide an opportunity to synthesize a mononuclear Cu(II) complex with an aim to utilize it in the catalytic oxidation of aromatic hydrocarbons by an environmentally benign oxidant, H2O2. The Cu(II) complex (1) was structurally characterized and found to have square-planar geometry with the two pyrazolyl groups remaining in dangling mode. A novel mononuclear complex [Et3NH][LCu(II)-OOH] (2) was found to form in the reaction between 1 and H2O2 in the presence of Et3N. The presence of this dangling groups favours the stability of hydroperoxo species, [LCu-OOH](-) (2) through H-bonding with the coordinated phenoxo oxygen atom, which was confirmed by ESI-MS(+) and MS(-) (m/z) mass analysis and DFT calculations. This complex was found to be thermally stable at room temperature [k(d) = (5.67 ± 0.03) × 10(-5) s(-1) at 25 °C] and may be due to the formation of O-O-H···O(phenoxo) H-bonding as delineated by the DFT calculations. Complex 1 was found to be an efficient catalyst for the oxidation of aromatic hydrocarbons to the corresponding aldehyde and alcohol in 2:1 mole ratio with TON ~300. PMID:23884097

  5. The CD30 ligand and CD40 ligand regulate CD54 surface expression and release of its soluble form by cultured Hodgkin and Reed-Sternberg cells.

    PubMed

    Gruss, H J; Scheffrahn, I; Hubinger, G; Duyster, J; Hermann, F

    1996-05-01

    The membrane-bound proteins CD30 ligand (CD30L), CD40L and 4-1BBL are members of the tumor necrosis factor (TNF) superfamily. They are expressed mainly by activated T cells. Primary and cultured Hodgkin and Reed-Sternberg (H-RS) cells, regarded as the malignant components of Hodgkin's disease (HD), display high levels of the counter-receptors for these ligands, ie CD30, CD40 and 4-1BB. CD30L and CD40L are known to share some biological activities that can be linked to the unbalanced secretion of cytokines seen in HD. In addition, cell contact-dependent molecules such as adhesion or activation antigens are critically involved in T cell/H-RS cell interactions. Primary and cultured H-RS cells frequently overexpress intercellular adhesion molecule-1 (ICAM-1/CD54), BB-1 (B7-1/CD80) and B70/B7-2 (CD86). Here we show that CD30L and CD40L, but not 4-1BBL upregulate CD54 expression by cultured H-RS cells on the mRNA and protein level, as a result of transcriptional gene activation. Furthermore, enhanced CD54 surface expression by these cells is accompanied by increased shedding of surface-bound CD54, as evidenced by high levels of the 82 kDa soluble (s) CD54 form detectable in culture supernatants after specific stimulation. Addition of CD30L in combination with CD40L to cultured H-RS cells additively enhanced CD54 surface expression and its shedding. These results may give a plausible explanation why sCD54 serum levels are increased in patients with HD.

  6. Zinc site redesign in T4 gene 32 protein: structure and stability of cobalt(II) complexes formed by wild-type and metal ligand substitution mutants.

    PubMed

    Guo, J; Giedroc, D P

    1997-01-28

    Phage T4 gene 32 protein (gp32) is a zinc metalloprotein which binds cooperatively and preferentially to single-stranded nucleic acids and functions as a replication and recombination accessory protein. Zn(II) coordination by gp32 employs a His-Cys3 metal ligand donor set derived from the His64-X12-Cys77-X9-Cys87-X2-Cys90 sequence in the ssDNA-binding core domain of the molecule. Crystallographic studies reveal that His64 and Cys77 are derived from two independent beta-strands within a distorted three-stranded beta-sheet and are relatively more buried from solvent than are Cys87 and Cys90, which are positioned immediately before and within, respectively, an alpha-helix. In an effort to understand the origin of the stability of the metal complex, we have employed an anaerobic optical spectroscopic, competitive metal binding assay to determine the coordination geometry and association constants (Ka) for the binding of Co(II) to wild-type gp32 and a series of zinc ligand substitution mutants. At pH 7.5, 25 degrees C, wild-type gp32 binds Co(II) with a Ka approximately 1 x 10(9) M-1. Competition experiments reveal that Ka for Zn(II) is 3.0 (+/-1.0) x 10(11) M-1. We find that all non-native metal complexes retain tetrahedral or distorted tetrahedral coordination geometry but are greatly destabilized in a manner essentially of whether a new protein-derived coordination bond is formed (e.g., in H64C gp32) or not. Co(II) binding isotherms obtained for three His64 substitution mutants, H64C, H64D, and H64N gp32s, suggest that each mutant forms a dimeric Cys4 tetrathiolate intermediate complex at limiting [Co(II)]f, each then rearranges at high [Co(II)]f to form a monomolecular site of the expected geometry and Ka approximately 1 x 10(4) M-1. Like the His64 mutants, C77A gp32 appears to form at least two types of complexes over the course of a Co(II) titration: one with octahedral coordination geometry formed at low [Co(II)]f, with a second tetrahedral or five

  7. Iron(III) complexes of N2O and N3O donor ligands as functional models for catechol dioxygenase enzymes: ether oxygen coordination tunes the regioselectivity and reactivity.

    PubMed

    Sundaravel, Karuppasamy; Suresh, Eringathodi; Saminathan, Kolandaivel; Palaniandavar, Mallayan

    2011-08-28

    A series of mononuclear iron(III) complexes of the type [Fe(L)Cl(3)], where L is a systematically modified N(2)O or N(3)O ligand with a methoxyethyl/tetrahydrofuryl ether oxygen donor atom, have been isolated and studied as models for catechol dioxygenases. The X-ray crystal structures of [Fe(L2)Cl(3)] 2, [Fe(L6)Cl(3)] 6, [Fe(L5)(TCC)Cl] 5a, where H(2)TCC = tetrachlorocatechol, [Fe(L6)(TCC)Br] 6a, and the μ-oxo dimer [{Fe(L6)Cl}(2)O](ClO(4))(2) 6b have been successfully determined. In [Fe(L2)Cl(3)] 2 the N(2)O ligand is facially coordinated to iron(III) through the pyridine and secondary amine nitrogen atoms and the tetrahydrofuryl oxygen atom. In [Fe(L6)Cl(3)] 6, [Fe(L5)(TCC)Cl] 5a and [Fe(L6)(TCC)Br] 6a the N(3)O donor ligands L5 and L6 act as a tridentate N3 donor ligand coordinated through two pyridine and one secondary amine nitrogen atoms, whereas the ether oxygen is not coordinated. The spectral and electrochemical properties of the adducts [Fe(L)(DBC)Cl] of 1-8, where H(2)DBC = 3,5-di-tert-butylcatechol, in DMF and their solvated adduct species [Fe(L)(DBC)(Sol)](+), where Sol = DMF/H(2)O, generated in situ in dichloromethane, respectively, have been investigated. The product analysis demonstrates that the adducts [Fe(L)(DBC)Cl] effect cleavage of catechol in the presence of O(2) in DMF to give mainly the intradiol (I) product with a small amount of the extradiol (E) product (E/I, 0.2:1-0.7:1). Interestingly, the solvated species [Fe(L)(DBC)(Sol)](+) derived from 1-4 cleave H(2)DBC to provide mainly the extradiol cleavage products with lower amounts of intradiol products (E/I, 2.3:1-4.3:1) in dichloromethane. In contrast, the solvated species [Fe(L)(DBC)(Sol)](+) derived from 5-8 cleave H(2)DBC to provide both extradiol and intradiol products (E/I, 0.6:1-2.3:1) due to the involvement of the ether oxygen donor of the methoxyethyl/tetrahydrofuryl arm in the coordination to iron(III) upon removal of a chloride ion. PMID:21766098

  8. Complex-forming organic ligands in cloud-point extraction of metal ions: a review.

    PubMed

    Pytlakowska, K; Kozik, V; Dabioch, M

    2013-06-15

    Cloud-point extraction (CPE), an easy, safe, environmentally friendly, rapid and inexpensive methodology for preconcentration and separation of trace metals from aqueous solutions has recently become an attractive area of research and an alternative to liquid-liquid extraction. Moreover, it provides results comparable to those obtained with other separation techniques and has a greater potential to be explored in improving detection limits and other analytical characteristics over other methods. A few reviews have been published covering different aspects of the CPE procedure and its relevant applications, such as the phenomenon of clouding, the application in the extraction of trace inorganic and organic materials, as well as pesticides and protein substrates from different sources, or incorporation of CPE into an FIA system. This review focuses on general properties of the most frequently used organic ligands in cloud-point extraction and on literature data (from 2000 to 2012) concerning the use of modern techniques in determination of metal ions' content in various materials. The article is divided according to the class of organic ligands to be used in CPE.

  9. 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

    2015-07-01

    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.

  10. 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

    2015-07-01

    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. PMID:26090963

  11. Capture of molybdenum in pyrite-forming sediments: role of ligand-induced reduction by polysulfides 1

    NASA Astrophysics Data System (ADS)

    Vorlicek, Trent P.; Kahn, Mani D.; Kasuya, Yasuhiro; Helz, George R.

    2004-02-01

    Capture of Mo by FeS 2 is an important sink for marine Mo. X-ray spectroscopy has shown that Mo forms Mo-Fe-S cuboidal clusters on pyrite. Reduction of Mo VI must occur to stabilize these structures. Sulfide alone is a poor reductant for Mo, producing instead a series of Mo VI thioanions (MoO xS 4-x2-, x = 0-3). In solutions that contain both H 2S and S 0-donors (i.e. polysulfides; dissolved S 8), Mo is transformed to Mo IV or Mo V2 polysulfide/sulfide anions. This intramolecular reduction requires no external reducing agent. Remarkably, an oxidizing agent (S 0 donor), rather than a reducing agent, stabilizes the reducible Mo VI complex. Thiomolybdates and their reduction products do not precipitate spontaneously; solutions supersaturated by 10 9 with respect to molybdenite, MoS 2, produce no precipitate in 40 days. In 10-minute exposures, pyrite can scavenge MoOS 32- and MoS 42- weakly at mildly alkaline pH but can scavenge an unidentified product of the S 0-induced reduction of MoOS 32- very strongly. On the basis of these observations, a reaction pathway for Mo capture by pyrite is proposed. Conditions that favor Mo capture by this pathway also favor pyrite growth. Ascribing Mo capture simply to low redox potential is too simplistic and neglects the likely role of oxidizing S 0-donors. The aqueous speciation of Mo in anoxic environments will be a function of the activity of zero-valent sulfur as well as the activity of H 2S(aq).

  12. A two-dimensional layered Cd(II) coordination polymer with a three-dimensional supramolecular architecture incorporating mixed multidentate N- and O-donor ligands.

    PubMed

    Huang, Qiu-Ying; Su, Ming-Yang; Meng, Xiang-Ru

    2015-06-01

    The combination of N-heterocyclic and multicarboxylate ligands is a good choice for the construction of metal-organic frameworks. In the title coordination polymer, poly[bis{μ2-1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole-κ(2)N(3):N(4)}(μ4-butanedioato-κ(4)O(1):O(1'):O(4):O(4'))(μ2-butanedioato-κ(2)O(1):O(4))dicadmium], [Cd(C4H4O4)(C9H8N6)]n, each Cd(II) ion exhibits an irregular octahedral CdO4N2 coordination geometry and is coordinated by four O atoms from three carboxylate groups of three succinate (butanedioate) ligands and two N atoms from two 1-[(1H-benzimidazol-2-yl)methyl]-1H-tetrazole (bimt) ligands. Cd(II) ions are connected by two kinds of crystallographically independent succinate ligands to generate a two-dimensional layered structure with bimt ligands located on each side of the layer. Adjacent layers are further connected by hydrogen bonding, leading to a three-dimensional supramolecular architecture in the solid state. Thermogravimetric analysis of the title polymer shows that it is stable up to 529 K and then loses weight from 529 to 918 K, corresponding to the decomposition of the bimt ligands and succinate groups. The polymer exhibits a strong fluorescence emission in the solid state at room temperature.

  13. Voltammetric determination of ruthenium in the form of complexes with biologically active ligands

    SciTech Connect

    Medyantseva, E.P.; Budnikov, G.K.; Balakaeva, T.A.

    1992-02-10

    The interest in the analytical chemistry of ruthenium and its compounds has recently been increasing. Ruthenium compounds can be used an antitumor agents and in the treatment of tuberculosis and fungal infections. It has been suggested that there is a specific relationship between the reduction potentials of the compounds and their biological activity. Of greatest interest among the biologically active compounds are the compounds with nitrogen-containing heterocycles. In order to obtain information on the degree of oxidation of the central atom in the complexes and to select the optimum conditions for the determination of the mono- and bi-nuclear complexes of ruthenium compounds with biologically active ligands such as imidazole (Im), histidine (His), benzimidazole (BIm) and its methyl derivative [1,2(CH{sub 3}){sub 2} - BIm], benzohyroxamic acid (Bha), and 1-phenyl-2-methylamino-1-propanol or ephedrine (Eph) in the present work, the authors studied their electrochemical behavior at dropping mercury (dme) and a platinum electrodes. 6 refs., 1 fig., 2 tabs.

  14. Face-driven corner-linked octahedral nanocages: M6L8 cages formed by C3-symmetric triangular facial ligands linked via C4-symmetric square tetratopic Pd(II) ions at truncated octahedron corners.

    PubMed

    Moon, Dohyun; Kang, Sangmi; Park, Jaejoon; Lee, Kyungjae; John, Rohith P; Won, Hosik; Seong, Gi Hun; Kim, Yang Sun; Kim, Ghyung Hwa; Rhee, Hakjune; Lah, Myoung Soo

    2006-03-22

    The face-driven corner-linked truncated octahedral nanocages, [Pd6L8]12+ (1, L1 = N,N',N' '-tris(3-pyridinyl)-1,3,5-benzenetricarboxamide; 2, L2 = N,N',N' '-tris(4-pyridinylmethyl)-1,3,5-benzenetricarboxamide), were prepared with eight C3-symmetric tridentate ligands and six square planar tetratopic palladium(II) ions. The combination of the nitrogen donor atom at a approximately 120 degrees kink position of the carboxamido pyridinyl group and the tilted pyridyl versus the facial plane of the ligands can provide the needed curvature for the formation of octahedral cages. The nitrogen atoms can coordinate to the square planar palladium(II) ions to form kinks with approximately 120 degrees angles at the C4-symmetric square planar corners of the truncated octahedron. Depending on the conformation of the ligand, L1, two different truncated octahedral cages of around 2.4 nm in diameters were formed. The major form of 1 with syn-conformational ligands has a cavity volume of approximately 1600 A3. The cage has 12 ports (3.4 x 3.5 A2) at all edges of the octahedron. The minor form of cage 1 with anti-conformational ligands has a slightly increased cavity volume ( approximately 1900 A3) and port size (3.3 x 8.0 A2). The insertion of a methylene group in L2 has not only increased the cavity volume of 2 to approximately 2200 A3 but also enlarged the port size to 4.1 x 8.0 A2. However, an atomic force microscopy (AFM) study of cage 2 showed that the cages had a height of 1.8 +/- 0.1 nm. This value is about 30% smaller than the calculated size of 2.6 nm from the crystal structure. This tip-induced decrease in height in cage 2 suggests the nonrigidity of cage 2. PMID:16536521

  15. Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: Synthesis, characterization, fluorescence and corrosion inhibitors of ligands

    NASA Astrophysics Data System (ADS)

    Ali, Omyma A. M.

    2014-11-01

    Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans.

  16. Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: synthesis, characterization, fluorescence and corrosion inhibitors of ligands.

    PubMed

    Ali, Omyma A M

    2014-11-11

    Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans. PMID:24858346

  17. Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: synthesis, characterization, fluorescence and corrosion inhibitors of ligands.

    PubMed

    Ali, Omyma A M

    2014-11-11

    Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans.

  18. Synthesis, characterization and biological relevance of some metal (II) complexes with oxygen, nitrogen and oxygen (ONO) donor Schiff base ligand derived from thiazole and 2-hydroxy-1-naphthaldehyde

    NASA Astrophysics Data System (ADS)

    Nagesh, G. Y.; Mruthyunjayaswamy, B. H. M.

    2015-04-01

    The novel Schiff base ligand 2-((2-hydroxynaphthalen-1-yl)methylene)-N-(4-phenylthiazol-2-yl)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-hydroxy-1-naphthaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), Zn(II) and Cd(II) complexes have been characterized by microanalysis, molar conductance, IR, 1H NMR, ESI-mass, UV-Visible, TGA/DTA, ESR and powder X-ray diffraction data to explicate their structures. The IR results confirmed the tridentate binding of the ligand involving oxygen atom of amide carbonyl, azomethine nitrogen and naphthol oxygen. 1H NMR spectral data of the ligand (L) and its Zn(II) complex agreed well with the proposed structures. Thermogravimetric studies for Cu(II) and Ni(II) complexes indicated the presence of coordinated water molecules and the final product is the metal oxide. In order to appraise the effect of antimicrobial activity of metal ions upon chelation, the newly synthesized ligand and its metal complexes were screened for their antimicrobial activity by minimum inhibitory concentration (MIC) method. The DNA cleavage activities were studied using plasmid DNA pBR322 (Bangal re Genei, Bengaluru, Cat. No 105850) as a target molecule by agarose gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties against Artemia salina. Furthermore, the antioxidant activity were determined in vitro by reduction of 1,1-diphenyl-2-picryl hydrazyl (DPPH). The ligand exhibited better in vitro-antioxidant activity than its metal complexes.

  19. Synthesis, spectroscopic characterization, electrochemistry and biological evaluation of some metal (II) complexes with ONO donor ligand containing benzo[b]thiophene and coumarin moieties

    NASA Astrophysics Data System (ADS)

    Mahendra Raj, K.; Mruthyunjayaswamy, B. H. M.

    2014-09-01

    Schiff base ligand 3-chloro-N‧-((7-hydroxy-4-methyl-2-oxo-2H-chromen-8-yl)methylene)benzo[b]thiophene-2-carbohydrazide and its Cu(II), Co(II), Ni(II) and Zn(II) complexes were synthesized, characterized by elemental analysis and various physico-chemical techniques like, IR, 1H NMR, ESI-mass, UV-Visible, thermogravimetry - differential thermal analysis, magnetic measurements and molar conductance. Spectral analysis indicates octahedral geometry for all the complexes. Cu(II) complex have 1:1 stoichiometry of the type [M(L)(Cl)(H2O)2], whereas Co(II), Ni(II) and Zn(II) complexes have 1:2 stoichiometric ratio of the type [M(L)2]. The bonding sites are the oxygen atom of amide carbonyl, nitrogen of azomethine function and phenolic oxygen of the Schiff base ligand via deprotonation. The thermogravimetry - differential thermal analysis studies gave evidence for the presence of coordinated water molecules in the composition of Cu(II) complex which was further supported by IR measurements. All the complexes were investigated for their electrochemical activity, but only the Cu(II) complex showed the redox property. In order to evaluate the effect of antimicrobial potency of metal ions upon chelation, ligand and its metal complexes along with their respective metal chlorides 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 ligand. Ligand and its complexes were screened for free radical scavenging activity by DPPH method and DNA cleavage activity using Calf-thymus DNA (Cat. No-105850).

  20. Structural, spectral, pH-metric and biological studies on mercury (II), cadmium (II) and binuclear zinc (II) complexes of NS donor thiosemicarbazide ligand.

    PubMed

    El-Gammal, Ola A; Abu El-Reash, Gaber M; El-Gamil, Mohammed M

    2014-04-01

    Hg(II), Cd(II) and binuclear Zn(II) complexes derived from the tetradentate N(1)-ethyl-N(2)-(pyridine-2-yl) hydrazine-1, 2-bis (carbothioamide) ligand (H2PET) have been prepared and characterized by conventional techniques. The isolated complexes acquired the formulas, [Hg(HPET)(H2O)2Cl]⋅H2O, [Cd(HPET)Cl] and [Zn2(HPET)(PET)(OAc)]⋅H2O, respectively. IR data revealed that the ligand behaves as monobasic tridentate through (CN)py, (C-S) and new (NC)azomethine(∗) groups in both Hg(II) and Cd(II) complexes. In the binuclear Zn(II) complex, the behavior of ligand contains two types, where H2PET acts as dibasic tetradentate via (CN)py, both deprotonated (C-SH) and the new (NC)azomethine(∗) towards two Zn atoms and also it acts as monobasic tridentate via (CS), deprotonated (C-SH) and (CN)py towards the same Zn atoms. An octahedral geometry for Hg(II) complex and tetrahedral geometry for both Cd(II) and Zn(II) complexes were proposed. The bond lengths, bond angles, HOMO, LUMO and dipole moment have been calculated by DFT using materials studio program to confirm the geometry of ligand and its metal complexes. The association constant of the ligand and the stability constants of its complexes as well as the thermodynamic parameters were calculated by pH metric measurements at 298, 308 and 318K in 50% dioxane-water mixture, respectively. Also, the kinetic and thermodynamic parameters for the different thermal degradation steps of the complexes were determined by Coats-Redfern and Horowitz-Metzger methods. Moreover, the anti-oxidant (using ABTS and DPPH methods), anti-hemolytic, and cytotoxic activities of the compounds have been tested.

  1. Complexation of nitrogen and sulphur donor Schiff's base ligand to Cr(III) and Ni(II) metal ions: Synthesis, spectroscopic and antipathogenic studies

    NASA Astrophysics Data System (ADS)

    Sharma, Amit Kumar; Chandra, Sulekh

    2011-01-01

    2,6-Diacetyl pyridine based ligand was synthesized by the reaction of 2,6-diacetyl pyridine with thiocarbohydrazide in presence of acetic acid. The coordination compounds with Cr(III) and Ni(II) metal ions having [Cr(L)X]X 2 and [Ni(L)X]X compositions (where L = ligand and X = NO 3-, Cl - and CH 3COO -) were synthesized and characterized by physicochemical and spectral studies. The studies like elemental analyses, molar conductance measurements, magnetic susceptibility measurements, IR, UV-Vis, NMR, mass and EPR reveal that the complexes are octahedral. The compounds were examined against the pathogenic fungal and bacterial strains like Alternaria brassicae, Aspergillus niger, Fusarium oxysporum, Xanthomonas compestris and Pseudomonas aeruginosa. A. niger causes the diseases Apergillosis and Otomycosis in humans.

  2. Spectroscopic, cyclic voltammetric and biological studies of transition metal complexes with mixed nitrogen-sulphur (NS) donor macrocyclic ligand derived from thiosemicarbazide

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Gupta, Lokesh Kumar; Sangeetika

    2005-11-01

    The complexation of new mixed thia-aza-oxa macrocycle viz., 2,12-dithio-5,9,14,18-tetraoxo-7,16-dithia-1,3,4,10,11,13-hexaazacyclooctadecane containing thiosemicarba-zone unit with a series of transition metals Co(II), Ni(II) and Cu(II) has been investigated, by different spectroscopic techniques. The structural features of the ligand have been studied by EI-mass, 1H NMR and IR spectral techniques. Elemental analyses, magnetic moment susceptibility, molar conductance, IR, electronic, and EPR spectral studies characterized the complexes. Electronic absorption and IR spectra of the complexes indicate octahedral geometry for chloro, nitrato, thiocyanato or acetato complexes. The dimeric and neutral nature of the sulphato complexes are confirmed from magnetic susceptibility and low conductance values. Electronic spectra suggests square-planar geometry for all sulphato complexes. The redox behaviour was studied by cyclic voltammetry, show metal-centered reduction processes for all complexes. The complexes of copper show both oxidation and reduction process. The redox potentials depend on the conformation of central atom in the macrocyclic complexes. Newly synthesized macrocyclic ligand and its transition metal complexes show markedly growth inhibitory activity against pathogenic bacterias and plant pathogenic fungi under study. Most of the complexes have higher activity than that of the metal free ligand.

  3. Predicted structure of the extracellular region of ligand-gated ion-channel receptors shows SH2-like and SH3-like domains forming the ligand-binding site.

    PubMed Central

    Gready, J. E.; Ranganathan, S.; Schofield, P. R.; Matsuo, Y.; Nishikawa, K.

    1997-01-01

    Fast synaptic neurotransmission is mediated by ligand-gated ion-channel (LGIC) receptors, which include receptors for acetylcholine, serotonin, GABA, glycine, and glutamate. LGICs are pentamers with extracellular ligand-binding domains and form integral membrane ion channels that are selective for cations (acetylcholine and serotonin 5HT3 receptors) or anions (GABAA and glycine receptors and the invertebrate glutamate-binding chloride channel). They form a protein superfamily with no sequence similarity to any protein of known structure. Using a 1D-3D structure mapping approach, we have modeled the extracellular ligand-binding domain based on a significant match with the SH2 and SH3 domains of the biotin repressor structure. Refinement of the model based on knowledge of the large family of SH2 and SH3 structures, sequence alignments, and use of structure templates for loop building, allows the prediction of both monomer and pentamer models. These are consistent with medium-resolution electron microscopy structures and with experimental structure/function data from ligand-binding, antibody-binding, mutagenesis, protein-labeling and subunit-linking studies, and glycosylation sites. Also, the predicted polarity of the channel pore calculated from electrostatic potential maps of pentamer models of superfamily members is consistent with known ion selectivities. Using the glycine receptor alpha 1 subunit, which forms homopentamers, the monomeric and pentameric models define the agonist and antagonist (strychnine) binding sites to a deep crevice formed by an extended loop, which includes the invariant disulfide bridge, between the SH2 and SH3 domains. A detailed binding site for strychnine is reported that is in strong agreement with known structure/function data. A site for interaction of the extracellular ligand-binding domain with the activation of the M2 transmembrane helix is also suggested. PMID:9144769

  4. Synthesis, spectral characterization, molecular modeling and in vitro antibacterial activity of complexes designed from O2, NO and NO donor Schiff-base ligand

    NASA Astrophysics Data System (ADS)

    El-Gammal, Ola A.; Abu El-Reash, G.; Ahmed, S. F.

    2015-01-01

    A new chelating agent, N‧-(4-methoxybenzylidene)-2-oxo-2-(phenylamino)acetohydrazide (H2OMPH) and its complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Hg(II) and U(IV)O22+ ions have been prepared and characterized by conventional techniques. The spectral data indicated that the ligand coordinates as neutral bidentate with Cu(II), Mn(II), U(IV)O22+ and Hg(II), neutral tridentate with Ni(II), mononegative tridentate with Co(II) and binegative tetradentate with Zn(II) ions. On basis of magnetic and electronic spectral data an octahedral geometry for Mn(II), Co(II) and Ni(II) complexes and a square planar geometry for Cu(II) complex have been proposed and confirmed by applying geometry optimization and conformational analysis. The protonation constants of H2OMPH and the stepwise stability constants of its complexes are calculated at 298, 308 and 318 k as well as their thermodynamic parameters. Also, the Kinetic parameters (Ea, A, ΔH*, ΔS* and ΔG*) were determined for each thermal degradation stage of some complexes using Coats-Redfern and Horowitz-Metzger methods. Moreover, the ligand and some complexes were screened for in vitro antibacterial activity against Staphylococcus epidermalies (St. epid); Streptococcus pyagenies (Strp. py.) as Gram +ve bacteria and Escherichia coli (E. coli); Klebsiella spp. (kleb. spp.) as Gram -ve bacteria using inhibition zone diameter.

  5. Synthesis, spectral characterization, molecular modeling and in vitro antibacterial activity of complexes designed from OO, NO and NN donor Schiff-base ligand [corrected].

    PubMed

    El-Gammal, Ola A; Abu El-Reash, G; Ahmed, S F

    2015-01-25

    A new chelating agent, N'-(4-methoxybenzylidene)-2-oxo-2-(phenylamino)acetohydrazide (H2OMPH) and its complexes with Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Hg(II) and U(IV)O2(2+) ions have been prepared and characterized by conventional techniques. The spectral data indicated that the ligand coordinates as neutral bidentate with Cu(II), Mn(II), U(IV)O2(2+) and Hg(II), neutral tridentate with Ni(II), mononegative tridentate with Co(II) and binegative tetradentate with Zn(II) ions. On basis of magnetic and electronic spectral data an octahedral geometry for Mn(II), Co(II) and Ni(II) complexes and a square planar geometry for Cu(II) complex have been proposed and confirmed by applying geometry optimization and conformational analysis. The protonation constants of H2OMPH and the stepwise stability constants of its complexes are calculated at 298, 308 and 318 k as well as their thermodynamic parameters. Also, the Kinetic parameters (Ea, A, ΔH(*), ΔS(*) and ΔG(*)) were determined for each thermal degradation stage of some complexes using Coats-Redfern and Horowitz-Metzger methods. Moreover, the ligand and some complexes were screened for in vitro antibacterial activity against Staphylococcus epidermalies (St. epid); Streptococcus pyagenies (Strp. py.) as Gram +ve bacteria and Escherichia coli (E. coli); Klebsiella spp. (kleb. spp.) as Gram -ve bacteria using inhibition zone diameter.

  6. Complexes of cis-dioxomolybdenum(VI) and oxovanadium(IV) with a tridentate ONS donor ligand: synthesis, spectroscopic properties, X-ray crystal structure and catalytic activity.

    PubMed

    Fayed, Ahmed M; Elsayed, Shadia A; El-Hendawy, Ahmed M; Mostafa, Mohamed R

    2014-08-14

    New cis-dioxomolybdenum(VI) and oxovanadium(IV) complexes of the Schiff base, derived from S-methyl dithiocarbazate and 2,3-dihydroxybenzaldehyde (H2dhsm), have been synthesized. The complexes of the type cis-[MoO2(dhsm)] (1a), cis-[MoO2(dhsm)(D)] (1b-1d) [D=neutral monodentate ligand; EtOH, pyridine (py) or imidazole (imz)], [VO(dhsm)(NN)] (2a, 2b) [NN=2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen)] and [VO(dhsm)] (2c) have been isolated, characterized by (1)H NMR, IR, UV-Vis and EPR spectral studies and investigated by cyclic voltammetry. The X-ray crystal structure of cis-[MoO2(dhsm)(EtOH)] (1b) has been determined and shows that the complex has a distorted octahedral geometry in which the H2dhsm behaves as a dianionic ONS tridentate ligand coordinating via phenoxide oxygen, hydrazinic nitrogen and thiolate sulfur. The oxomolybdenum(IV) complex [MoO(dhsm)] (1e) has obtained from dioxomolybdenum(VI) complex (1b) by oxo abstraction with PPh3. The reactivity of the complexes toward catalytic oxidation of alcohols in the presence of H2O2 and t-BuOOH as co-oxidants under solvent free conditions is reported. PMID:24747851

  7. Complexes of cis-dioxomolybdenum(VI) and oxovanadium(IV) with a tridentate ONS donor ligand: Synthesis, spectroscopic properties, X-ray crystal structure and catalytic activity

    NASA Astrophysics Data System (ADS)

    Fayed, Ahmed M.; Elsayed, Shadia A.; El-Hendawy, Ahmed M.; Mostafa, Mohamed R.

    2014-08-01

    New cis-dioxomolybdenum(VI) and oxovanadium(IV) complexes of the Schiff base, derived from S-methyl dithiocarbazate and 2,3-dihydroxybenzaldehyde (H2dhsm), have been synthesized. The complexes of the type cis-[MoO2(dhsm)] (1a), cis-[MoO2(dhsm)(D)] (1b-1d) [D = neutral monodentate ligand; EtOH, pyridine (py) or imidazole (imz)], [VO(dhsm)(Nsbnd N)] (2a, 2b) [Nsbnd N = 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)] and [VO(dhsm)] (2c) have been isolated, characterized by 1H NMR, IR, UV-Vis and EPR spectral studies and investigated by cyclic voltammetry. The X-ray crystal structure of cis-[MoO2(dhsm)(EtOH)] (1b) has been determined and shows that the complex has a distorted octahedral geometry in which the H2dhsm behaves as a dianionic ONS tridentate ligand coordinating via phenoxide oxygen, hydrazinic nitrogen and thiolate sulfur. The oxomolybdenum(IV) complex [MoO(dhsm)] (1e) has obtained from dioxomolybdenum(VI) complex (1b) by oxo abstraction with PPh3. The reactivity of the complexes toward catalytic oxidation of alcohols in the presence of H2O2 and t-BuOOH as co-oxidants under solvent free conditions is reported.

  8. A new crystal form of human tear lipocalin reveals high flexibility in the loop region and induced fit in the ligand cavity

    PubMed Central

    Breustedt, Daniel A.; Chatwell, Lorenz; Skerra, Arne

    2009-01-01

    Tear lipocalin (TLC) with the bound artificial ligand 1,4-butanediol has been crystallized in space group P21 with four protein molecules in the asymmetric unit and its X-ray structure has been solved at 2.6 Å resolution. TLC is a member of the lipocalin family that binds ligands with diverse chemical structures, such as fatty acids, phospholipids and cholesterol as well as microbial siderophores and the antibiotic rifampin. Previous X-ray structural analysis of apo TLC crystallized in space group C2 revealed a rather large bifurcated ligand pocket and a partially disordered loop region at the entrace to the cavity. Analysis of the P21 crystal form uncovered major conformational changes (i) in β-strands B, C and D, (ii) in loops 1, 2 and 4 at the open end of the β-­barrel and (iii) in the extended C-terminal segment, which is attached to the β-­barrel via a disulfide bridge. The structural comparison indicates high conformational plasticity of the loop region as well as of deeper parts of the ligand pocket, thus allowing adaptation to ligands that differ vastly in size and shape. This illustrates a mechanism for promiscuity in ligand recognition which may also be relevant for some other physiologically important members of the lipocalin protein family. PMID:19770509

  9. Mixed ligand two dimensional Cd(ii)/Ni(ii) metal organic frameworks containing dicarboxylate and tripodal N-donor ligands: Cd(ii) MOF is an efficient luminescent sensor for detection of picric acid in aqueous media.

    PubMed

    Rachuri, Yadagiri; Parmar, Bhavesh; Bisht, Kamal Kumar; Suresh, Eringathodi

    2016-05-01

    Two dimensional metal organic frameworks (MOFs) [Cd(5-BrIP)(TIB)]n () and [Ni2(5-BrIP)2(TIB)2]n (), involving the aromatic polycarboxylate ligand 5-bromo isophthalic acid (H2BrIP), flexible tripodal ligand 1,3,5-tris(imidazol-1-ylmethyl)benzene (TIB) and Cd(ii)/Ni(ii) metal nodes have been synthesized by different methods. These compounds were characterized by various analytical methods, and variable temperature X-ray diffraction data showed thermal stability of both MOFs up to 350 °C. Phase purity as well as water stability of the MOFs were established by powder X-ray diffraction, and the structural diversity of the compounds were investigated by single-crystal X-ray diffraction. Both the MOFs are mixed ligand 2D nets, and the topology of the network can be described as a binodal 3,5-c connected net with 3,5L2 topology having the point symbol {4(2)·6(7)·8}{4(2)·6}. Sensing of picric acid [2,4,6-trinitrophenol, TNP] by luminescence quenching among a large range of nitroanalytes in aqueous phase by the Cd(ii) luminescent MOF (LMOF) were been investigated. Structural studies on 1 : 1 co-crystals () of TIB and TNP were carried out. The selective and sensitive fluorescence quenching response of towards electron-deficient TNP over other nitro analytes in aqueous phase was demonstrated by fluorescence quenching titration. Concomitant occurrence of electron transfer/energy transfer processes and electrostatic interaction favours the selective sensing of TNP. A Cd(ii) LMOF ()-coated paper strip that we developed demonstrated fast and selective response to TNP, by the complete quenching of the blue fluorescence upon excitation of the paper strip at 365 nm radiation in its presence. PMID:27067118

  10. Design and synthesis of 60° dendritic donor ligands and their coordination-driven self-assembly into supramolecular rhomboidal metallodendrimers.

    PubMed

    Han, Qing; Li, Quan-Jie; He, Jiuming; Hu, Bingjie; Tan, Hongwei; Abliz, Zeper; Wang, Cui-Hong; Yu, Yihua; Yang, Hai-Bo

    2011-12-01

    The design and self-assembly of novel rhomboidal metallodendrimers via coordination-driven self-assembly is described. By employing newly designed 60° ditopic donor linkers substituted with Fréchet-type dendrons and appropriate 120° rigid di-Pt(II) acceptor subunits, a variety of [G-1]-[G-3] rhomboidal metallodendrimers with well-defined shape and size were prepared under mild conditions in high yields. The supramolecular metallodendrimers were characterized with multinuclear NMR ((1)H and (31)P), mass spectrometry (CSI-TOF-MS), and elemental analysis. Isotopically resolved mass spectrometry data support the existence of the metallodendrimers with rhomboidal cavities, and NMR data were consistent with the formation of all ensembles. The shape and size of all rhomboidal metallodendrimers were investigated with the PM6 semiempirical molecular orbital method.

  11. Studies of iron(II) and iron(III) complexes with fac-N2O, cis-N2O2 and N2O3 donor ligands: models for the 2-His 1-carboxylate motif of non-heme iron monooxygenases.

    PubMed

    Cappillino, Patrick J; Miecznikowski, John R; Tyler, Laurie A; Tarves, Paul C; McNally, Joshua S; Lo, Wayne; Kasibhatla, Bala Sundari T; Krzyaniak, Matthew D; McCracken, John; Wang, Feng; Armstrong, William H; Caradonna, John P

    2012-05-14

    Enzymes in the oxygen-activating class of mononuclear non-heme iron oxygenases (MNOs) contain a highly conserved iron center facially ligated by two histidine nitrogen atoms and one carboxylate oxygen atom that leave one face of the metal center (three binding sites) open for coordination to cofactor, substrate, and/or dioxygen. A comparative family of [Fe(II/III)(N(2)O(n))(L)(4-n))](±x), n = 1-3, L = solvent or Cl(-), model complexes, based on a ligand series that supports a facially ligated N,N,O core that is then modified to contain either one or two additional carboxylate chelate arms, has been structurally and spectroscopically characterized. EPR studies demonstrate that the high-spin d(5) Fe(III)g = 4.3 signal becomes more symmetrical as the number of carboxylate ligands decreases across the series Fe(N(2)O(3)), Fe(N(2)O(2)), and Fe(N(2)O(1)), reflecting an increase in the E/D strain of these complexes as the number of exchangeable/solvent coordination sites increases, paralleling the enhanced distribution of electronic structures that contribute to the spectral line shape. The observed systematic variations in the Fe(II)-Fe(III) oxidation-reduction potentials illustrate the fundamental influence of differential carboxylate ligation. The trend towards lower reduction potential for the iron center across the [Fe(III)(N(2)O(1))Cl(3)](-), [Fe(III)(N(2)O(2))Cl(2)](-) and [Fe(III)(N(2)O(3))Cl](-) series is consistent with replacement of the chloride anions with the more strongly donating anionic O-donor carboxylate ligands that are expected to stabilize the oxidized ferric state. This electrochemical trend parallels the observed dioxygen sensitivity of the three ferrous complexes (Fe(II)(N(2)O(1)) < Fe(II)(N(2)O(2)) < Fe(II)(N(2)O(3))), which form μ-oxo bridged ferric species upon exposure to air or oxygen atom donor (OAD) molecules. The observed oxygen sensitivity is particularly interesting and discussed in the context of α-ketoglutarate-dependent MNO enzyme

  12. Studies of iron(II) and iron(III) complexes with fac-N2O, cis-N2O2 and N2O3 donor ligands: models for the 2-His 1-carboxylate motif of non-heme iron monooxygenases.

    PubMed

    Cappillino, Patrick J; Miecznikowski, John R; Tyler, Laurie A; Tarves, Paul C; McNally, Joshua S; Lo, Wayne; Kasibhatla, Bala Sundari T; Krzyaniak, Matthew D; McCracken, John; Wang, Feng; Armstrong, William H; Caradonna, John P

    2012-05-14

    Enzymes in the oxygen-activating class of mononuclear non-heme iron oxygenases (MNOs) contain a highly conserved iron center facially ligated by two histidine nitrogen atoms and one carboxylate oxygen atom that leave one face of the metal center (three binding sites) open for coordination to cofactor, substrate, and/or dioxygen. A comparative family of [Fe(II/III)(N(2)O(n))(L)(4-n))](±x), n = 1-3, L = solvent or Cl(-), model complexes, based on a ligand series that supports a facially ligated N,N,O core that is then modified to contain either one or two additional carboxylate chelate arms, has been structurally and spectroscopically characterized. EPR studies demonstrate that the high-spin d(5) Fe(III)g = 4.3 signal becomes more symmetrical as the number of carboxylate ligands decreases across the series Fe(N(2)O(3)), Fe(N(2)O(2)), and Fe(N(2)O(1)), reflecting an increase in the E/D strain of these complexes as the number of exchangeable/solvent coordination sites increases, paralleling the enhanced distribution of electronic structures that contribute to the spectral line shape. The observed systematic variations in the Fe(II)-Fe(III) oxidation-reduction potentials illustrate the fundamental influence of differential carboxylate ligation. The trend towards lower reduction potential for the iron center across the [Fe(III)(N(2)O(1))Cl(3)](-), [Fe(III)(N(2)O(2))Cl(2)](-) and [Fe(III)(N(2)O(3))Cl](-) series is consistent with replacement of the chloride anions with the more strongly donating anionic O-donor carboxylate ligands that are expected to stabilize the oxidized ferric state. This electrochemical trend parallels the observed dioxygen sensitivity of the three ferrous complexes (Fe(II)(N(2)O(1)) < Fe(II)(N(2)O(2)) < Fe(II)(N(2)O(3))), which form μ-oxo bridged ferric species upon exposure to air or oxygen atom donor (OAD) molecules. The observed oxygen sensitivity is particularly interesting and discussed in the context of α-ketoglutarate-dependent MNO enzyme

  13. Oligomeric adiponectin forms and their complexes in the blood of healthy donors and patients with type 2 diabetes mellitus.

    PubMed

    Kogan, Alexander E; Filatov, Vladimir L; Kolosova, Olga V; Katrukha, Ivan A; Mironova, Ekaterina V; Zhuravleva, Natalya S; Nagibin, Oleg A; Kara, Andrei N; Bereznikova, Anastasiya V; Katrukha, Alexey G

    2013-01-01

    Adiponectin (Adn) is a protein that circulates in the blood in several oligomeric forms, namely low-, medium-, and high-molecular-weight forms. Adn may serve as a risk factor for type 2 diabetes mellitus (T2DM). The aims of this work were (1) to produce monoclonal antibodies (MAbs) specific to different Adn oligomeric forms, (2) to design immunoassays suitable for measuring the Adn forms present in human blood, and (3) to investigate the changes in Adn forms that occur in patients with T2DM. Gel filtration, fluoroimmunoassays, and Western blotting were utilized as major techniques in this study. MAbs recognizing various oligomeric forms of Adn were obtained. Complexes between Adn and complement component C1q and between the low molecular weight form of Adn and albumin were described in human blood. A decrease in the total Adn and Adn-albumin complex levels in the blood of patients with T2DM and no difference in the levels of the Adn-C1q complex in comparison with healthy volunteers were demonstrated. An Adn94-Adn63 fluoroimmunoassay was selected as the technique that most accurately measured the mass ratio of Adn oligomers in blood samples, and an Adn214-Adn27 assay that measured the low-molecular-weight form of Adn only.

  14. Computational studies of the first order kinetic reactions for mononuclear copper(II) complexes having a hard-soft NS donor ligand

    NASA Astrophysics Data System (ADS)

    Zaky, R. R.; Yousef, T. A.; Abdelghany, A. M.

    2014-09-01

    The chelation behaviour of 4-((E)-2-(1-(thiophen-2-yl)ethylidene)hydrazinyl)-1-(4-methoxyphenyl)-1H-pyrrole-3-carbonitrile (HL) towards Cu(II) ions has been investigated. These Cu(II) complexes are characterized by elemental analyses, molar-solid conductance, ESR, FTIR and electronic spectral studies. Also, the kinetic and thermodynamic parameters (Ea, A, ΔH, ΔS, ΔG) for all thermal decomposition steps have been evaluated using Coats-Redfern and Horowitz-Metzger methods. Furthermore, antimicrobial activity of the ligand and its complexes were studied against Gram-negative bacteria: Escherichia coli, Gram-positive Bacillus cereus, Bacillus subtilis and pathogenic fungi Pseudomonas aeruginosa by using minimum inhibitory concentrations (MICs) method.

  15. Coordination behavior of ligand based on NNS and NNO donors with ruthenium(III) complexes and their catalytic and DNA interaction studies

    NASA Astrophysics Data System (ADS)

    Manikandan, R.; Viswnathamurthi, P.

    2012-11-01

    Reactions of 2-acetylpyridine-thiosemicarbazone HL1, 2-acetylpyridine-4-methyl-thiosemicarbazone HL2, 2-acetylpyridine-4-phenyl-thiosemicarbazone HL3 and 2-acetylpyridine-semicarbazone HL4 with ruthenium(III) precursor complexes were studied and the products were characterized by analytical and spectral (FT-IR, electronic, EPR and EI-MS) methods. The ligands coordinated with the ruthenium(III) ion via pyridine nitrogen, azomethine nitrogen and thiolate sulfur/enolate oxygen. An octahedral geometry has been proposed for all the complexes based on the studies. All the complexes are redox active and display an irreversible and quasireversible metal centered redox processes. Further, the catalytic activity of the new complexes has been investigated for the transfer hydrogenation of ketones in the presence of isopropanol/KOH and the Kumada-Corriu coupling of aryl halides with aryl Grignard reagents. The DNA cleavage efficiency of new complexes has also been tested.

  16. Iron coordination chemistry with new ligands containing triazole and pyridine moieties. Comparison of the coordination ability of the N-donors.

    PubMed

    Ségaud, Nathalie; Rebilly, Jean-Noël; Sénéchal-David, Katell; Guillot, Régis; Billon, Laurianne; Baltaze, Jean-Pierre; Farjon, Jonathan; Reinaud, Olivia; Banse, Frédéric

    2013-01-18

    We report the synthesis, characterization, and solution chemistry of a series of new Fe(II) complexes based on the tetradentate ligand N-methyl-N,N'-bis(2-pyridyl-methyl)-1,2-diaminoethane or the pentadentate ones N,N',N'-tris(2-pyridyl-methyl)-1,2-diaminoethane and N,N',N'-tris(2-pyridyl-methyl)-1,3-diaminopropane, modified by propynyl or methoxyphenyltriazolyl groups on the amino functions. Six of these complexes are characterized by X-ray crystallography. In particular, two of them exhibit an hexadentate coordination environment around Fe(II) with two amino, three pyridyl, and one triazolyl groups. UV-visible and cyclic voltammetry experiments of acetonitrile solutions of the complexes allow to deduce accurately the structure of all Fe(II) species in equilibrium. The stability of the complexes could be ranked as follows: [L(5)Fe(II)-py](2+) > [L(5)Fe(II)-Cl](+) > [L(5)Fe(II)-triazolyl](2+) > [L(5)Fe(II)-(NCMe)](2+), where L(5) designates a pentadentate coordination sphere composed of the two amines of ethanediamine and three pyridines. For complexes based on propanediamine, the hierarchy determined is [L(5)Fe(II)-Cl](+) > [L(5)Fe(II)(OTf)](+) > [L(5)Fe(II)-(NCMe)](2+), and no ligand exchange could be evidenced for [L(5)Fe(II)-triazolyl](2+). Reactivity of the [L(5)Fe(II)-triazolyl](2+) complexes with hydrogen peroxide and PhIO is similar to the one of the parent complexes that lack this peculiar group, that is, generation of Fe(III)(OOH) and Fe(IV)(O), respectively. Accordingly, the ability of these complexes at catalyzing the oxidation of small organic molecules by these oxidants follows the tendencies of their previously reported counterparts. Noteworthy is the remarkable cyclooctene epoxidation activity by these complexes in the presence of PhIO.

  17. Solid State Structures of Alkali Metal Ion Complexes Formed by Low-Molecular-Weight Ligands of Biological Relevance.

    PubMed

    Aoki, Katsuyuki; Murayama, Kazutaka; Hu, Ning-Hai

    2016-01-01

    This chapter provides structural data, mainly metal binding sites/modes, observed in crystal structures of alkali metal ion complexes containing low-molecular-weight ligands of biological relevance, mostly obtained from the Cambridge Structural Database (the CSD version 5.35 updated to February 2014). These ligands include (i) amino acids and small peptides, (ii) nucleic acid constituents (excluding quadruplexes and other oligonucleotides), (iii) simple carbohydrates, and (iv) naturally occurring antibiotic ionophores. For some representative complexes of these ligands, some details on the environment of the metal coordination and structural characteristics are described. PMID:26860299

  18. Synthesis and characterization of the copper(II) complexes of new N2S2-donor macrocyclic ligands: synthesis and in vivo evaluation of the 64Cu complexes†

    PubMed Central

    Papini, Grazia; Alidori, Simone; Reichert, David E.; Pellei, Maura; Lobbia, Giancarlo Gioia; Biddlecombe, Gráinne B.; Anderson, Carolyn J.

    2015-01-01

    The aim of this work was to prepare a novel class of 64Cu(II) labeled complexes with the new macrocyclic ligands 1,10-dithia-4,7-diazacyclododecane-3,8-dicarboxylic acid (NEC-SE, 1), 1,10-dithia-4,7-diazacyclotridecane-3,8-dicarboxylic acid (NEC-SP, 2) and 1,10-dithia-4,7-diazacyclotetradecane-3,8-dicarboxylic acid, (NEC-SB, 3) to evaluate the usefulness of these macrocycles for potential utility as 64Cu(II) chelators. The corresponding non-radioactive complexes [Cu(NEC-SE)]·3H2O (4), [Cu(NEC-SP)]·3H2O (5) and [Cu(NEC-SB)] (6) were prepared and their 64Cu-analogs, [64Cu(NEC-SE)] (7) and [64Cu(NEC-SP)] (8) and [64Cu(NEC-SB)] (9) were produced in >98% radiochemical purity. Rats were injected with complex 7, 8 or 9 and were euthanized at 1, 4 and 24 h. All three complexes are cleared from the blood over the first hour following injection but there is poor clearance of this activity over 24 h. A similar pattern of retention was noted in the liver where the levels of activity in this tissue at 1 h are not statistically different from those at 24 h. Molecular mechanics and DFT studies were performed on the complexes in order to gain insight into the lower stability. PMID:19081987

  19. Synthesis, spectroscopic, thermal and antimicrobial studies of neodymium(III) and samarium(III) complexes derived from tetradentate ligands containing N and S donor atoms

    NASA Astrophysics Data System (ADS)

    Ain, Qurratul; Pandey, S. K.; Pandey, O. P.; Sengupta, S. K.

    2015-04-01

    Trivalent lanthanide complexes of the type [Ln(L)Cl(H2O)2] (where Ln = Nd(III) or Sm(III) and LH2 = Schiff bases derived by the condensation of 3-(phenyl/substitutedphenyl)-4-amino-5-mercapto-1,2,4-triazole with diacetyl/benzil) have been synthesized by the reactions of anhydrous lanthanide(III) chloride with Schiff bases in methanol. The structures of the complexes have been proposed on the basis of elemental analysis, electrical conductance, magnetic moment, spectroscopic measurements (IR, 1H, 13C NMR and UV-vis spectra) and X-ray diffraction studies. The spectral data reveal that the Schiff base ligands behave as dibasic tetradentate chelating agents having coordination sites at two thiol sulfur atoms and two azomethine nitrogen atoms. The presence of coordinated water in metal complexes was confirmed by thermal and IR data of the complexes. All the Schiff bases and their metal complexes have also been screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus and antifungal activities against Aspergillus niger, Curvularia pallescens and Colletotrichum capsici.

  20. Synthesis, spectroscopic, thermal and antimicrobial studies of neodymium(III) and samarium(III) complexes derived from tetradentate ligands containing N and S donor atoms.

    PubMed

    Ain, Qurratul; Pandey, S K; Pandey, O P; Sengupta, S K

    2015-04-01

    Trivalent lanthanide complexes of the type [Ln(L)Cl(H2O)2] (where Ln=Nd(III) or Sm(III) and LH2=Schiff bases derived by the condensation of 3-(phenyl/substitutedphenyl)-4-amino-5-mercapto-1,2,4-triazole with diacetyl/benzil) have been synthesized by the reactions of anhydrous lanthanide(III) chloride with Schiff bases in methanol. The structures of the complexes have been proposed on the basis of elemental analysis, electrical conductance, magnetic moment, spectroscopic measurements (IR, 1H, 13C NMR and UV-vis spectra) and X-ray diffraction studies. The spectral data reveal that the Schiff base ligands behave as dibasic tetradentate chelating agents having coordination sites at two thiol sulfur atoms and two azomethine nitrogen atoms. The presence of coordinated water in metal complexes was confirmed by thermal and IR data of the complexes. All the Schiff bases and their metal complexes have also been screened for their antibacterial activity against Bacillus subtilis, Staphylococcus aureus and antifungal activities against Aspergillus niger, Curvularia pallescens and Colletotrichum capsici.

  1. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study.

    PubMed

    Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H; Cavallo, Luigi; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-09-01

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(≡CtBu)(CH2 tBu)3 with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(≡SiOH)(≡SiNH2 )], leads to [(≡SiNH2 -)(≡SiO-)W(≡CHtBu)(CH2 tBu)2 ] and [(≡SiNH2 -)(≡SiO-)W(=CHtBu)2 (CH2 tBu). Variable temperature, (1) H-(1) H 2D double-quantum, (1) H-(13) C HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(≡Si-OH)(≡Si-NH2 )] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 °C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts.

  2. Spin Crossover Properties of Iron(ii) Complexes with a N4O2 Donor Set by Extended Π-CONJUGATED Schiff-Base Ligands

    NASA Astrophysics Data System (ADS)

    Kuroda, Takayoshi

    2013-09-01

    The preparation and magnetic properties of three Fe(II) Schiff-base complexes, [Fe(qnal-21)2]•CH2Cl2 (1), [Fe(qnal-12)2]•2C6H6 (2) and [Fe(Hqsalc)2] (3), (Hqnal-21 = N-(8'-quinolyl)-2-hydroxy-1-naphthaldimine, Hqnal-12 = N-(8'-quinolyl)-1-hydroxy-2-naphthaldimine, H2qsalc = 4-hydroxy-3-[(8-quinolinylimino)methyl]benzoic acid) are reported. X-ray single crystal structure analyses of 1 and 2 reveal that an Fe(II) ion in each complex is coordinated by two Schiff-base ligands, qnal-21 or qnal-12, in a meridional fashion. Molecular packing of 2 shows that a qnal-12 interacts with neighboring two qnal-12's through π-π interactions, which results in the formation of one-dimensional chain. Although the magnetic property of 2 shows a high-spin state at all the temperature range measured, the χT-T plot of 3 shows abrupt spin crossover behavior with a wide hysteresis of 21 K, probably due to the hydrogen-bond network originated by carboxyl groups.

  3. Tungsten(VI) Carbyne/Bis(carbene) Tautomerization Enabled by N-Donor SBA15 Surface Ligands: A Solid-State NMR and DFT Study.

    PubMed

    Bendjeriou-Sedjerari, Anissa; Sofack-Kreutzer, Julien; Minenkov, Yury; Abou-Hamad, Edy; Hamzaoui, Bilel; Werghi, Baraa; Anjum, Dalaver H; Cavallo, Luigi; Huang, Kuo-Wei; Basset, Jean-Marie

    2016-09-01

    Designing supported well-defined bis(carbene) complexes remains a key challenge in heterogeneous catalysis. The reaction of W(≡CtBu)(CH2 tBu)3 with amine-modified mesoporous SBA15 silica, which has vicinal silanol/silylamine pairs [(≡SiOH)(≡SiNH2 )], leads to [(≡SiNH2 -)(≡SiO-)W(≡CHtBu)(CH2 tBu)2 ] and [(≡SiNH2 -)(≡SiO-)W(=CHtBu)2 (CH2 tBu). Variable temperature, (1) H-(1) H 2D double-quantum, (1) H-(13) C HETCOR, and HETCOR with spin diffusion solid-state NMR spectroscopy demonstrate tautomerization between the alkyl alkylidyne and the bis(alkylidene) on the SBA15 surface. Such equilibrium is possible through the coordination of W to the surface [(≡Si-OH)(≡Si-NH2 )] groups, which act as a [N,O] pincer ligand. DFT calculations provide a rationalization for the surface-complex tautomerization and support the experimental results. This direct observation of such a process shows the strong similarity between molecular mechanisms in homogeneous and heterogeneous catalysis. In propane metathesis (at 150 °C), the tungsten bis(carbene) tautomer is favorable, with a turnover number (TON) of 262. It is the highest TON among all the tungsten alkyl-supported catalysts. PMID:27514022

  4. Synthesis and Characterization of a Ditriflate-Bridged, Diiron(II) Complex with Syn-N-Donor Ligands: [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](BARF)(2).

    PubMed

    Kodanko, Jeremy J; Lippard, Stephen J

    2008-03-01

    The synthesis and characterization of the diiron(II) complex [Fe(2)(μ-OTf)(2)-(PIC(2)DET)(2)](BARF)(2) (2), where PIC(2)DET is a 2,3-diethynyltriptycene-linked dipicolinic methyl ester ligand, are described. The dication in 2, contains, [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) two symmetry-equivalent iron atoms with octahedral coordination geometries. Each metal ion has a N(2)O(4) atom donor set that includes four atoms from two picolinic ester N,O chelate rings, as well as two oxygen atoms from the bridging trifluoromethanesulfonate groups. The Fe(2)(μ-OTf)(2) core of 2 is stabilized by two PIC(2)DET ligands that bind the two metal ions in a head-to-head fashion, leading to an Fe···Fe distance of 5.173(1)Å. Molar conductivity data for 2 are consistent with Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) retaining its identity in acetone solutions, where it behaves as a 2:1 electrolyte. (1)H NMR spectroscopic, solution (d(6)-acetone) and solid-state magnetic susceptibility data all indicate that the iron atoms of 2 are high-spin (S = 2). A fit of the magnetic data (2 - 300K) to a spin-only isotropic exchange Hamiltonian H = -2JS(1)·S(2) are consistent with weak antiferromagnetic coupling between the two iron atoms with J ~ -0.99(2) cm(-1) and g = 2.10(1). PMID:18458751

  5. Four-Electron-Donor Hemilabile N3-PPh3 Ligand that Binds through a C=C Bond Rather than an Agostic C-H Interaction, and Displaceement of the C=C by Methyl Iodide or Water

    SciTech Connect

    Cheng,T.; Szalda, D.; Hanson, J.; Muckerman, J.; Bullock, R.

    2008-01-01

    Hydride transfer from Cp(CO)2(PPh3)MoH to Ph3C+BAr'4- [Ar' = 3,5-bis(trifluoromethyl)phenyl] produces [Cp(CO)2(3-PPh3)Mo]+[BAr'4]-. Spectroscopic and crystallographic data indicate that one C{double_bond}C of a Ph ring is weakly bound to the Mo, so that the PPh3 ligand is a four-electron-donor ligand. Computations (DFT/B3LYP and MP2 on [Cp(CO)2(3-PPh3)Mo]+ and [Cp(CO)2(3-PH2Ph)Mo]+, and DFT/B3LYP on [Cp(CO)2(3-PHtBuPh)Mo]+ and [Cp(CO)2(3-PH2Ph)Nb]) provide further information on the bonding and on the preference for bonding of the metal to the C{double_bond}C bond rather than an agostic C-H interaction found in many related complexes. The hemilabile C{double_bond}C bond is readily displaced by CH3I or H2O, and crystal structures are reported for [Cp(CO)2(PPh3)Mo(ICH3)]+ and [Cp(CO)2(PPh3)Mo(OH2)]+. The equilibrium constant for [Cp(CO)2(3-PPh3)Mo]+ + ICH3 to give [Cp(CO)2(PPh3)Mo(ICH3)]+ is Keq = 5.2 x 102 M-1 in CD2Cl2 at 22 C.

  6. Synthesis and Characterization of a Ditriflate-Bridged, Diiron(II) Complex with Syn-N-Donor Ligands: [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](BARF)(2).

    PubMed

    Kodanko, Jeremy J; Lippard, Stephen J

    2008-03-01

    The synthesis and characterization of the diiron(II) complex [Fe(2)(μ-OTf)(2)-(PIC(2)DET)(2)](BARF)(2) (2), where PIC(2)DET is a 2,3-diethynyltriptycene-linked dipicolinic methyl ester ligand, are described. The dication in 2, contains, [Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) two symmetry-equivalent iron atoms with octahedral coordination geometries. Each metal ion has a N(2)O(4) atom donor set that includes four atoms from two picolinic ester N,O chelate rings, as well as two oxygen atoms from the bridging trifluoromethanesulfonate groups. The Fe(2)(μ-OTf)(2) core of 2 is stabilized by two PIC(2)DET ligands that bind the two metal ions in a head-to-head fashion, leading to an Fe···Fe distance of 5.173(1)Å. Molar conductivity data for 2 are consistent with Fe(2)(μ-OTf)(2)(PIC(2)DET)(2)](2+) retaining its identity in acetone solutions, where it behaves as a 2:1 electrolyte. (1)H NMR spectroscopic, solution (d(6)-acetone) and solid-state magnetic susceptibility data all indicate that the iron atoms of 2 are high-spin (S = 2). A fit of the magnetic data (2 - 300K) to a spin-only isotropic exchange Hamiltonian H = -2JS(1)·S(2) are consistent with weak antiferromagnetic coupling between the two iron atoms with J ~ -0.99(2) cm(-1) and g = 2.10(1).

  7. NMR studies of differences in the conformations and dynamics of ligand complexes formed with mutant dihydrofolate reductases

    SciTech Connect

    Birdsall, B.; Andrews, J.; Ostler, G.; Tendler, S.J.B.; Feeney, J.; Roberts, G.C.K.; Davies, R.W.; Cheung, H.T.A. )

    1989-02-07

    Two mutants of Lactobacillus casei dihydrofolate reductase, Trp 21 {yields} Leu and Asp 26 {yields} Glu, have been prepared by using site-directed mutagenesis methods, and their ligand binding and structural properties have been compared with those of the wild-type enzyme. {sup 1}H, {sup 13}C, and {sup 31}P NMR studies have been carried out to characterize the structural changes in the complexes of the mutant and wild-type enzymes. Replacement of the conserved Trp 21 by a Leu residue causes a decrease in activity of the enzyme and reduces the NADPH binding constant by a factor of 400. The binding of substrates and substrate analogues is only slightly affected. {sup 1}H NMR studies of the Trp 21 {yields} Leu enzyme complexes have confirmed the original resonance assignments for Trp 21. In complexes formed with methotrexate and the mutant enzyme, the results indicate some small changes in conformation occurring as much as 14 {angstrom} away from the site of substitution. For the enzyme-NADPH complexes, the chemical shifts of nuclei in the bound coenzyme indicate that the nicotinamide ring binds differently in complexes with the mutant and the wild-type enzyme. There are complexes where the wild-type enzyme has been shown to exist in solution as a mixture of conformations, and studies on the corresponding complexes with the Trp 21 {yields} Leu mutant indicate that the delicately poised equilibria can be perturbed. Some conformational adjustments are required to allow the carboxylate of Glu 26 to bind effectively to the N1 proton of inhibitors such as methotrexate and trimethoprim.

  8. Theoretical and experimental studies of Cu(II) and Zn(II) coordination compounds with N,O donor bidentate Schiff base ligand containing amino phenol moiety

    NASA Astrophysics Data System (ADS)

    Kusmariya, Brajendra S.; Tiwari, Anjali; Mishra, A. P.; Naikoo, Gowhar Ahmad

    2016-09-01

    We report here two mononuclear Cu(II) and Zn(II) coordination compounds of general formula [CuII(L)2].2H2O (1) and [ZnII(L)2].3H2O (2) derived from bidentate 2-chloro-6-{[(4-hydroxy-3-methoxyphenyl)methylidene]amino}-4 nitrophenol ligand (HL). These compounds were synthesized and characterized by elemental analysis, FT-IR, uv-vis, 1H NMR, molar conductance, thermal, PXRD, SEM-EDX and electrochemical studies. The PXRD and SEM analysis shows the amorphous/nanocrystalline nature of 1 and crystalline nature of 2. The diffraction peak broadening was explained in terms of domain size and the crystallite lattice strain. Thermogravimetric analysis in the range of 300-1172 K has been performed to determine the thermal stability of synthesized compounds. The non-isothermal kinetic parameters of degradation process were calculated using Coats-Redfern (C-R), Piloyan-Novikova (P-N) and Horowitz-Metzger (H-M) methods assuming first order degradation and proposed a random nucleation mechanism of thermal decomposition for both compounds. The cyclic voltammetric studies reveal the irreversibility of the oxidation/reduction process of synthesized compounds. To support the experimental findings theoretical calculations by means of DFT and TD-DFT at B3LYP level were incorporated. In addition; frequency calculations, HOMO-LUMO, energy gap (ΔE), molecular electrostatic potential (MEP), spin density and crystal packing were also computed at the same level of theory.

  9. Half-sandwich RuCl2(η(6)-p-cymene) core complexes containing sulfur donor aroylthiourea ligands: DNA and protein binding, DNA cleavage and cytotoxic studies.

    PubMed

    Jeyalakshmi, Kumaramangalam; Haribabu, Jebiti; Bhuvanesh, Nattamai S P; Karvembu, Ramasamy

    2016-08-01

    A series of Ru(ii)(η(6)-p-cymene) complexes (1-4) bearing the general formula [RuCl2(η(6)-p-cymene)L] (L = monodentate aroylthiourea ligand) has been synthesized and characterized by analytical and various spectroscopic techniques. The neutral monodentate coordination of aroylthiourea with Ru via an S atom was confirmed by single crystal X-ray diffraction study. The complexes were tested for their ability to interact with DNA and protein. The complexes bound with calf thymus DNA (CT DNA) with the intrinsic binding constant value in the order of 10(4) M(-1). The intercalative mode of binding was confirmed by the ethidium bromide (EB) displacement study. The interaction of the complexes with CT DNA was further supported by viscosity measurements and circular dichroic (CD) spectra. The Ru(ii) complexes cleaved the supercoiled DNA without the need of any external agent. The spectroscopic evidence showed good binding efficacy of the complexes with BSA (Bovine Serum Albumin). The alterations in the secondary structure of BSA by the Ru(ii) complexes were confirmed by synchronous fluorescence spectra. Cytotoxicity examination by MTT assay was carried out in two cancer cell lines (MCF7 and A549) and one non-cancerous cell line (L929). Complex 4 showed significant activity [IC50 = 52.3 (MCF7) and 54.6 (A549) μM] which was comparable with that of similar known complexes. The morphological changes assessed by Hoechst staining revealed that the cell death occurred by apoptosis. PMID:27435011

  10. The equilibrium between the octahedral and square pyramidal form and the influence of an axial ligand on the molecular properties of V(IV)O complexes: a spectroscopic and DFT study.

    PubMed

    Gorelsky, Serge; Micera, Giovanni; Garribba, Eugenio

    2010-07-19

    The previously unreported equilibrium in aqueous solution between the V(IV)O square pyramidal and trans octahedral form with an axial water molecule for a number of bidentate ligands with (N,O) and (O,O) donor sets (6-methylpicolinic (6-mepicH) and 6-methyl-2,3-pyridinedicarboxylic (6-me-2,3-pdcH(2)) acids, dipyridin-2-ylmethanol (Hdpmo) and 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone (Hdhp)) has been demonstrated by the combined application of EPR spectroscopy and DFT methods. The EPR spectra suggest that, with increasing ionic strength, the equilibrium is shifted towards the formation of the pentacoordinated species and values of K approximately 4.0 and 7.0 for the systems containing 6-methyl-2,3-pyridinedicarboxylic acid and dipyridin-2-ylmethanol were measured. DFT calculations performed with Gaussian 03 and ORCA software predict the (51)V anisotropic hyperfine coupling constant along the z axis (A(z)), which can be used to demonstrate the presence of an axially bound ligand trans to the V=O bond. The results suggest that an axial donor (charged or not) can lower |A(z)|, in contrast to what was previously believed on the basis of the "additivity rule", and this explains the anomalous behaviour of the V(IV)O complexes formed by N-{2-[(2-pyridylmethylene)amino]phenyl}pyridine-2-carboxamide (Hcapca) and several amidrazone derivatives. The decrease in |A(z)| for the axial binding of a solvent molecule is mainly a result of the reduction of |A(iso)| and this was also observed when the solid [VO(6-methylpicolinato)(2)] was dissolved in DMSO or DMF. The variations in the structural (V=O, V-O and V-N distances, O-V-O and N-V-N angles, and the trigonality index tau) and spectroscopic (|A(z)|, |A(iso)| and nu(V=O)) properties as a function of the axial V-OH(2) distance (R) are also presented. Finally, the electronic structures of the penta- and hexacoordinated complexes are discussed.

  11. Pyridazine-based Schiff base ligands with N 4O xS 2 ( x = 2, 4) donor set atoms: Synthesis, characterization, spectral studies and 13C chemical shifts computed by the GIAO-DFT and CSGT-DFT methodologies

    NASA Astrophysics Data System (ADS)

    Khanmohammadi, Hamid; Erfantalab, Malihe

    2010-01-01

    Six pyridazine-based Schiff base ligands, H 2L n ( n = 1-5) and H 4L, with N 4O 2S 2 and N 4O 4S 2 donor set atoms, respectively, were prepared by condensation reaction of 3,6-bis-((2-aminoethyl)thio)pyridazine with various salicyladehyde derivatives in ethanol and under solvent-free polyphosphate ester catalyzed conditions. The acid-base properties of H 2L 2 and H 2L 3 in DMSO/water (1:1) solution have been studied by spectrophotometric method at 25 °C. Optimized geometries of all compounds were also obtained at the B3LYP level of theory. Additionally, the 13C chemical shielding of gas phase H 2L 1 and H 2L 2 were studied by the gauge independent atomic orbital (GIAO) and continuous set of gauge transformations (CSGT) methods at the level of density functional theory (DFT). The 6-311++G* basis set was utilized for all of the atoms.

  12. Electron-transfer and acid-base properties of a two-electron oxidized form of quaterpyrrole that acts as both an electron donor and an acceptor.

    PubMed

    Zhang, Min; E, Wenbo; Ohkubo, Kei; Sanchez-Garcia, David; Yoon, Dae-Wi; Sessler, Jonathan L; Fukuzumi, Shunichi; Kadish, Karl M

    2008-02-21

    Electron-transfer interconversion between the four-electron oxidized form of a quaterpyrrole (abbreviated as P4 for four pyrroles) and the two-electron oxidized form (P4H2) as well as between P4H2 and its fully reduced form (P4H4) bearing analogous substituents in the alpha- and beta-pyrrolic positions was studied by means of cyclic voltammetry and UV-visible spectroelectrochemistry combined with ESR and laser flash photolysis measurements. The two-electron oxidized form, P4H2, acts as both an electron donor and an electron acceptor. The radical cation (P4H2*+) and radical anion (P4H2*-) are both produced by photoinduced electron transfer from dimeric 1-benzyl-1,4-dihydronicotinamide to P4H2, whereas the cation radical form of the compound is also produced by electron-transfer oxidation of P4H2 with [Ru(bpy)3]3+. The ESR spectra of P4H2*+ and P4H2*- were recorded at low temperature and exhibit spin delocalization over all four pyrrole units. Thus, the two-electron oxidized form of the quaterpyrrole (P4H2) displays redox and electronic features analogous to those seen in the case of porphyrins and may be considered as a simple, open-chain model of this well-studied tetrapyrrolic macrocycle. The dynamics of deprotonation from P4H2*+ and disproportionation of P4H2 were examined by laser flash photolysis measurements of photoinduced electron-transfer oxidation and reduction of P4H2, respectively.

  13. An electronic spectroscopic study of micellisation of surfactants and solvation of homomicelles formed by cationic or anionic surfactants using a solvatochromic electron donor acceptor dye

    NASA Astrophysics Data System (ADS)

    Kedia, Niraja; Sarkar, Amrita; Purkayastha, Pradipta; Bagchi, Sanjib

    2014-10-01

    Solvatochromic absorption and fluorescence bands of a donor-acceptor dye have been utilised for following the micellisation and for probing the polarity of the aqueous homomicellar phase provided separately by cationic (cetyltrimethylammonimum bromide, CTAB and dodecyltrimethylammonimum bromide, DTAB) and anionic (sodium dodecyl sulphate, SDS) surfactant. Results indicate that for a low concentration of surfactant (below cmc) the dye forms a dimer in aqueous solution. In a micellar media, however, the dye exists as monomers. A strong dye-micelle interaction, as indicated by the shift of the solvatochromic intramolecular charge transfer band of the dye, has also been indicated. The absorption and fluorescence parameters of the dye have been utilised for studying the onset of aggregation of the surfactants. An iterative procedure has been developed for the estimation of cmc and the distribution coefficient (KD) of the dye between the aqueous and the micellar phase. All the parameters provide convergent values of cmc. A high value of KD indicates that the dye exists predominantly in the micellar phase. The solvatochromic parameters characterising the dipolarity-polarisability (π*) and H-bond donation ability (α) of modes of solvation interaction in different micellar media have been estimated. The dye is found to distribute itself between two regions in a catanionic vesicle formed by surfactants SDS and DTAB, one being relatively polar than other. The distribution coefficients have been found out using the fluorescence data.

  14. An electronic spectroscopic study of micellisation of surfactants and solvation of homomicelles formed by cationic or anionic surfactants using a solvatochromic electron donor acceptor dye.

    PubMed

    Kedia, Niraja; Sarkar, Amrita; Purkayastha, Pradipta; Bagchi, Sanjib

    2014-10-15

    Solvatochromic absorption and fluorescence bands of a donor-acceptor dye have been utilised for following the micellisation and for probing the polarity of the aqueous homomicellar phase provided separately by cationic (cetyltrimethylammonimum bromide, CTAB and dodecyltrimethylammonimum bromide, DTAB) and anionic (sodium dodecyl sulphate, SDS) surfactant. Results indicate that for a low concentration of surfactant (below cmc) the dye forms a dimer in aqueous solution. In a micellar media, however, the dye exists as monomers. A strong dye-micelle interaction, as indicated by the shift of the solvatochromic intramolecular charge transfer band of the dye, has also been indicated. The absorption and fluorescence parameters of the dye have been utilised for studying the onset of aggregation of the surfactants. An iterative procedure has been developed for the estimation of cmc and the distribution coefficient (KD) of the dye between the aqueous and the micellar phase. All the parameters provide convergent values of cmc. A high value of KD indicates that the dye exists predominantly in the micellar phase. The solvatochromic parameters characterising the dipolarity-polarisability (π(*)) and H-bond donation ability (α) of modes of solvation interaction in different micellar media have been estimated. The dye is found to distribute itself between two regions in a catanionic vesicle formed by surfactants SDS and DTAB, one being relatively polar than other. The distribution coefficients have been found out using the fluorescence data.

  15. Carbodiphosphoranes and Related Ligands

    NASA Astrophysics Data System (ADS)

    Petz, Wolfgang; Frenking, Gernot

    The theoretical and experimental research on carbodiphosphoranes C(PR3)2 and related compounds CL2, both as free molecules and as ligands in transition metal complexes, is reviewed. Carbodiphosphoranes are examples of divalent carbon(0) compounds CL2 which have peculiar donor properties that are due to the fact that the central carbon atom has two lone electron pairs. The bonding situation is best described in terms of L→C←L donor acceptor interactions which distinguishes CL2 compounds (carbones) from divalent carbon(II) compounds (carbenes) through the number of lone electron pairs. The structures and stabilities of transition metal complexes with ligands CL2 can be understood and predictions can be made considering the double donor ability of the carbone compounds.

  16. Mixed donor-acceptor charge-transfer stacks formed via hierarchical self-assembly of a non-covalent amphiphilic foldamer.

    PubMed

    Jalani, Krishnendu; Kumar, Mohit; George, Subi J

    2013-06-01

    A non-covalent, amphiphilic foldamer design leads to an efficient charge-transfer complex between dipyrene (donor) and naphthalene diimide (acceptor) derivatives, which further self-assembles into one-dimensional nanofibers with an alternate (mixed) donor-acceptor arrangement. PMID:23628867

  17. Synthesis and transition metal coordination chemistry of a novel hexadentate bispidine ligand.

    PubMed

    Comba, Peter; Rudolf, Henning; Wadepohl, Hubert

    2015-02-14

    Reported is the new bispidine-derived hexadentate ligand (L = 3-(2-methylpyridyl)-7-(bis-2-methylpyridyl)-3,7-diazabicyclo[3.3.1]nonane) with two tertiary amine and four pyridine donor groups. This ligand can form heterodinuclear and mononuclear complexes and, in the mononuclear compounds discussed here, the ligand may coordinate as a pentadentate ligand, with one of the bispyridinemethane-based pyridine groups un- or semi-coordinated, or as a hexadentate ligand, leading to a pentagonal pyramidal coordination geometry or, with an additional monodentate ligand, to a heptacoordinate pentagonal bipyramidal structure. The solution and solid state data presented here indicate that, with the relatively small Cu(II) and high-spin Fe(II) ions the fourth pyridine group is only semi-coordinated for steric reasons and, with the larger high-spin Mn(II) ion genuine heptacoordination is observed but with a relatively large distortion in the pentagonal equatorial plane.

  18. Behavior of the potential antitumor V(IV)O complexes formed by flavonoid ligands. 3. Antioxidant properties and radical production capability.

    PubMed

    Sanna, Daniele; Ugone, Valeria; Fadda, Angela; Micera, Giovanni; Garribba, Eugenio

    2016-08-01

    The radical production capability and the antioxidant properties of some V(IV)O complexes formed by flavonoid ligands were examined. In particular, the bis-chelated species of quercetin (que), [VO(que)2](2-), and morin (mor), [VO(mor)2], were evaluated for their capability to reduce the stable radical 1,1-diphenyl-2-picrylhydrazyl (DPPH) and produce the hydroxyl radical (•)OH by Fenton-like reactions, where the reducing agent is V(IV)O(2+). The results were compared with those displayed by other V(IV)O complexes, such as [VO(H2O)5](2+), [VO(acac)2] (acac=acetylacetonate) and [VO(cat)2](2-) (cat=catecholate). The capability of the V(IV)O flavonoids complexes to reduce DPPH is much larger than that of the V(IV)O species formed by non-antioxidant ligands and it is due mainly to the flavonoid molecule. Through the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin trapping assay of the hydroxyl radical it was possible to demonstrate that in acidic solution V(IV)O(2+) has an effectiveness in producing (•)OH radicals comparable to that of Fe(2+). When V(IV)O complexes of flavonoids were taken into account, the amount of hydroxyl radicals produced in Fenton-like reactions depends on the specific structure of the ligand and on their capability to reduce H2O2 to give (•)OH. Both the formation of reactive oxygen species (ROS) under physiological conditions by V(IV)O complexes of flavonoid ligands and their radical scavenging capability can be put in relationship with their antitumor effectiveness and it could be possible to modulate these actions by changing the features of the flavonoid coordinated to the V(IV)O(2+) ion, such as the entity, nature and position of the substituents and the number of phenolic groups.

  19. Synthesis of the donor acceptor ligand 2-(4-dimethylaminobenzylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (dbpcd) and X-ray diffraction structure of the platinum(II) compound PtCl2(dbpcd) 1.5CH2Cl2

    SciTech Connect

    Atim, Silvia; Wang, Xiaoping; Richmond, Michael G.

    2010-01-01

    The synthesis of the donor acceptor ligand 2-(4-dimethylaminobenzylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (dbpcd) from the Knoevenagel condensation of 4-(dimethylamino)benzaldehyde with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) is reported. This new ligand reacts with PtCl2(cod) to afford the platinum(II) complex PtCl2(dbpcd) in high yield. The dbpcd ligand and PtCl2(dbpcd) have been isolated and characterized by IR and NMR spectroscopies, cyclic voltammetry, MO calculations at the extended H ckel level, and X-ray diffraction analysis in the case of PtCl2(dbpcd).

  20. Biphenyl-2,4,6,3',5'-pentacarboxylic acid as a tecton for six new Co(II) coordination polymers: pH and N-donor ligand-dependent assemblies, structure diversities and magnetic properties.

    PubMed

    Han, Min-Le; Bai, Liang; Tang, Ping; Wu, Xue-Qian; Wu, Ya-Pan; Zhao, Jun; Li, Dong-Sheng; Wang, Yao-Yu

    2015-09-01

    Six new Co(ii)-based mixed-ligand coordination polymers, namely, [Co2(H3bppc)2(2,2'-bpy)4]·H2O (), [Co2(Hbppc)(2,2'-bpy)2(H2O)]·H2O (), [Co(H2bppc)(H-bpp)]·2H2O (), [Co3(μ3-OH)(bppc)(dps)(CH3CH2OH)]·4H2O (), [Co2(bppc)(bib)(H2O)4]·(H2-bib)0.5·(H2O)3 (), and [Co2(Hbppc)(bix)2]·2H2O (), (H5bppc = biphenyl-2,4,6,3',5'-pentacarboxylic acid, 2,2'-bpy = 2,2'-bipyridine, bpp = 1,3-bis(4-pyridyl)propane, dps = 4,4'-sulfanediyldipyridine, bib = 1,4-bis(imidazol-1-yl)benzene, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), have been obtained under solvothermal conditions. exhibits a 3D supramolecular framework based on a [Co2(H3bppc)2(2,2'-bpy)4] unit. has a (3,4)-connected dmc net with a (4·8(2))(4·8(5)) topology containing alternate binuclear metal clusters and single metal centres. shows a 3D supramolecular architecture constructed from ladder-like arrays decorated with H-bpp. exhibits a binodal (5,7)-connected 3D network based on trinuclear [Co3(μ3-OH)](5+) units with an unusual (3·4(6)·5(2)·6)(3(2)·4(6)·5(7)·6(5)·7) topology. features a (4,6)-connected 3D fsc open framework with binuclear [Co2(H2O)(COO)](3+) units as nodes, and H2-bib and water molecules located in the voids of its framework by hydrogen bonds. possesses a 3D net containing unusual 2D polyrotaxane sheets. Topological analysis reveals that has a (3,4,4)-connected 3D network with a (4·6·7(4))(4·6·7)(6·7(2)·10(2)·11) topology. The structural difference of and is due to the different pH values of the reaction system. Though complexes were synthesised under similar reaction conditions, the carboxylic groups of H5bppc were partially deprotonated in , and and fully deprotonated in and . Complexes display diverse structures depending on different N-donor ligands and the coordination modes of the multicarboxylate ligand. Variable-temperature magnetic susceptibility measurements reveal that complexes show antiferromagnetic interactions.

  1. Molecular And Electronic Structures of Mononuclear Iron Complexes Using Strongly Electron-Donating Ligands And Their Oxidized Forms

    SciTech Connect

    Strautmann, J.B.H.; George, S.DeBeer; Bothe, E.; Bill, E.; Weyhermuller, T.; Stammler, A.; Bogge, H.; Glaser, T.

    2009-05-26

    The ligand L{sup 2-} (H{sub 2}L = 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{sup III} complexes, namely, [LFe({eta}{sup 2}-NO{sub 3})] and [LFeCl]. L{sup 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}{sup 2}-NO{sub 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{sup +}/Fc and one

  2. Binding Affinity Prediction for Ligands and Receptors Forming Tautomers and Ionization Species: Inhibition of Mitogen-Activated Protein Kinase-Activated Protein Kinase 2 (MK2)

    PubMed Central

    2012-01-01

    Treatment of ionization and tautomerism of ligands and receptors is one of the unresolved issues in structure-based prediction of binding affinities. Our solution utilizes the thermodynamic master equation, expressing the experimentally observed association constant as the sum of products, each valid for a specific ligand–receptor species pair, consisting of the association microconstant and the fractions of the involved ligand and receptor species. The microconstants are characterized by structure-based simulations, which are run for individual species pairs. Here we incorporated the multispecies approach into the QM/MM linear response method and used it for structural correlation of published inhibition data on mitogen-activated protein kinase (MAPK)-activated protein kinase (MK2) by 66 benzothiophene and pyrrolopyridine analogues, forming up to five tautomers and seven ionization species under experimental conditions. Extensive cross-validation showed that the resulting models were stable and predictive. Inclusion of all tautomers and ionization ligand species was essential: the explained variance increased to 90% from 66% for the single-species model. PMID:22280316

  3. Thiopyridazine-Based Copper Boratrane Complexes Demonstrating the Z-type Nature of the Ligand.

    PubMed

    Holler, Stefan; Tüchler, Michael; Belaj, Ferdinand; Veiros, Luis F; Kirchner, Karl; Mösch-Zanetti, Nadia C

    2016-05-16

    In Z-type ligands the electrons for the coordination bond are formally provided by the metal. They represent an important addition to the much more extensively used L- and X-type σ-donor ligands for the development of transition metal complexes with new reactivities. We report here a new boron Z-type ligand with three tethering thiopyridazinyl donors forming exclusively complexes that feature a metal boron bond. Rational substitution pattern in the backbone of the pyridazinyl heterocycle led to a well-behaved ligand system that allowed preparation of a series of copper boratrane complexes in high yields. They are found to be more soluble in common organic solvents allowing reactivity studies in contrast to previous complexes with this type of ligand. Thus, copper complexes [Cu{B(Pn(Me,tBu))3}X] with X = Cl, OTf, N3, and κN-NCS are reported. Solution behavior was explored, and the molecular structures were determined by single-crystal X-ray diffraction analyses. The thiocyanate ligand is found to coordinate via its nitrogen atom pointing to a high oxidation state of the copper. Density functional theory calculations indicate a high positive charge on copper and a strong copper-boron interaction. Thus, here reported complexes deliver synthetic evidence for the Z-type nature of the ligand. These findings are important for further dissemination of these types of ligands in coordination chemistry.

  4. Crystal-contact engineering to obtain a crystal form of the Kelch domain of human Keap1 suitable for ligand-soaking experiments.

    PubMed

    Hörer, Stefan; Reinert, Dirk; Ostmann, Katja; Hoevels, Yvette; Nar, Herbert

    2013-06-01

    Keap1 is a substrate adaptor protein for a Cul3-dependent ubiquitin ligase complex and plays an important role in the cellular response to oxidative stress. It binds Nrf2 with its Kelch domain and thus triggers the ubiquitinylation and degradation of Nrf2. Oxidative stress prevents the degradation of Nrf2 and leads to the activation of cytoprotective genes. Therefore, Keap1 is an attractive drug target in inflammatory diseases. The support of a medicinal chemistry effort by structural research requires a robust crystallization system in which the crystals are preferably suited for performing soaking experiments. This facilitates the generation of protein-ligand complexes in a routine and high-throughput manner. The structure of human Keap1 has been described previously. In this crystal form, however, the binding site for Nrf2 was blocked by a crystal contact. This interaction was analysed and mutations were introduced to disrupt this crystal contact. One double mutation (E540A/E542A) crystallized in a new crystal form in which the binding site for Nrf2 was not blocked and was accessible to small-molecule ligands. The crystal structures of the apo form of the mutated Keap1 Kelch domain (1.98 Å resolution) and of the complex with an Nrf2-derived peptide obtained by soaking (2.20 Å resolution) are reported.

  5. A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment.

    PubMed

    Sinha, Shashi B; Shopov, Dimitar Y; Sharninghausen, Liam S; Vinyard, David J; Mercado, Brandon Q; Brudvig, Gary W; Crabtree, Robert H

    2015-12-23

    We describe facial and meridional isomers of [Rh(III)(pyalk)3], as well as meridional [Rh(IV)(pyalk)3](+) {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible Rh(III/IV) redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV-visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.

  6. Coordination complexes of NbX5 (X = F, Cl) with (N,O)- and (O,O)-donor ligands and the first X-ray characterization of a neutral NbF5 adduct.

    PubMed

    Bortoluzzi, Marco; Marchetti, Fabio; Pampaloni, Guido; Pucino, Margherita; Zacchini, Stefano

    2013-09-28

    A variety of fairly air-stable complexes were prepared by straightforward reactions of NbX5 (X = F, Cl) with a series of potential bidentate (N,O)- and (O,O)-donor ligands in CH2Cl2. NbF5 reacted with equimolar amounts of 2-[(2,6-diisopropylphenyl)iminomethyl]phenol (dpimpH) and 2-benzoyl-6-hydroxy-6-phenylpentafulvene (bhpfH) to afford the mononuclear complexes NbF5[κ(1)(O)-OC6H4CH=NHC6H3(CHMe2)2], 2, and NbF5[κ(1)(O)-bhpfH], 7, respectively. The 1:1 reactions of NbF5 with salicylaldehyde oxime (saoH2) and 2-phenylaminoethanol gave the hexafluoroniobato salts [NbF4{κ(1)(O)-ON(H)=CHC6H4OH}2][NbF6], 3, and [NbF4{κ(1)(O)-OCH2CH2NH2Ph}2][NbF6], 6, respectively. The syntheses of 2, 3 and 6 are accompanied by oxygen to nitrogen intramolecular H migration, leading to the formation of metal-alkoxide moieties. The parallel chemistry of NbCl5 is characterised by HCl release. The 1:1 reactions with dpimpH, saoH2 and bhpfH yielded, respectively, the ionic complex [NbCl2{κ(1)(N):κ(1)(O)-dpimp}2][NbCl6], 4a, the neutral-dinuclear Nb2Cl7[κ(1)(O)-saoH][κ(2)(O)-sao], 5, and the mononuclear NbCl4[κ(2)(O)-bhpf], 8. The tantalum species [TaCl2{κ(1)(N):κ(1)(O)-dpimp}2][TaCl6], 4b, was prepared from TaCl5/dpimpH. The new products 2-8 were fully characterized by analytical and spectroscopic techniques. Moreover the solid state structures of 2 and 8 were ascertained by X-ray diffraction studies; the structure of 2 exhibits an intramolecular bifurcated N-H···(O,F) hydrogen bond. DFT calculations were carried out in order to predict the lowest energy structures in the distinct cases, showing generally good agreement with the experimental data. PMID:23873411

  7. Antagonism of ligand-gated ion channel receptors: two domains of the glycine receptor alpha subunit form the strychnine-binding site.

    PubMed Central

    Vandenberg, R J; French, C R; Barry, P H; Shine, J; Schofield, P R

    1992-01-01

    The inhibitory glycine receptor (GlyR) is a member of the ligand-gated ion channel receptor superfamily. Glycine activation of the receptor is antagonized by the convulsant alkaloid strychnine. Using in vitro mutagenesis and functional analysis of the cDNA encoding the alpha 1 subunit of the human GlyR, we have identified several amino acid residues that form the strychnine-binding site. These residues were identified by transient expression of mutated cDNAs in mammalian (293) cells and examination of resultant [3H]strychnine binding, glycine displacement of [3H]strychnine, and electrophysiological responses to the application of glycine and strychnine. This mutational analysis revealed that residues from two separate domains within the alpha 1 subunit form the binding site for the antagonist strychnine. The first domain includes the amino acid residues Gly-160 and Tyr-161, and the second domain includes the residues Lys-200 and Tyr-202. These results, combined with analyses of other ligand-gated ion channel receptors, suggest a conserved tertiary structure and a common mechanism for antagonism in this receptor superfamily. PMID:1311851

  8. Ligand-functionalized degradable polyplexes formed by cationic poly(aspartic acid)-grafted chitosan-cyclodextrin conjugates.

    PubMed

    Song, Hai-Qing; Li, Rui-Quan; Duan, Shun; Yu, Bingran; Zhao, Hong; Chen, Da-Fu; Xu, Fu-Jian

    2015-03-19

    Polypeptide-based degradable polyplexes attracted considerable attention in drug delivery systems. Polysaccharides including cyclodextrin (CD), dextran, and chitosan (CS) were readily grafted with cationic poly(aspartic acid)s (PAsps). To further enhance the transfection performances of PAsp-based polyplexes, herein, different types of ligand (folic acid, FA)-functionalized degradable polyplexes were proposed based on the PAsp-grafted chitosan-cyclodextrin conjugate (CCPE), where multiple β-CDs were tied on a CS chain. The FA-functionalized CCPE (i.e., CCPE-FA) was obtained via a host-guest interaction between the CD units of CCPE and the adamantane (Ad) species of Ad-modified FA (Ad-FA). The resulting CCPE/pDNA, CCPE-FA/pDNA, and ternary CCPE-FA/CCPE/pDNA (prepared by layer-by-layer assembly) polyplexes were investigated in detail using different cell lines. The CCPE-based polyplexes displayed much higher transfection efficiencies than the CS-based polyplexes reported earlier by us. The ternary polyplexes of CCPE-FA/CCPE/pDNA produced excellent gene transfection abilities in the folate receptor (FR)-positive tumor cells. This work would provide a promising means to produce highly efficient polyplexes for future gene therapy applications. PMID:25758351

  9. Behavior of the potential antitumor V(IV)O complexes formed by flavonoid ligands. 3. Antioxidant properties and radical production capability.

    PubMed

    Sanna, Daniele; Ugone, Valeria; Fadda, Angela; Micera, Giovanni; Garribba, Eugenio

    2016-08-01

    The radical production capability and the antioxidant properties of some V(IV)O complexes formed by flavonoid ligands were examined. In particular, the bis-chelated species of quercetin (que), [VO(que)2](2-), and morin (mor), [VO(mor)2], were evaluated for their capability to reduce the stable radical 1,1-diphenyl-2-picrylhydrazyl (DPPH) and produce the hydroxyl radical (•)OH by Fenton-like reactions, where the reducing agent is V(IV)O(2+). The results were compared with those displayed by other V(IV)O complexes, such as [VO(H2O)5](2+), [VO(acac)2] (acac=acetylacetonate) and [VO(cat)2](2-) (cat=catecholate). The capability of the V(IV)O flavonoids complexes to reduce DPPH is much larger than that of the V(IV)O species formed by non-antioxidant ligands and it is due mainly to the flavonoid molecule. Through the 5,5-dimethyl-1-pyrroline N-oxide (DMPO) spin trapping assay of the hydroxyl radical it was possible to demonstrate that in acidic solution V(IV)O(2+) has an effectiveness in producing (•)OH radicals comparable to that of Fe(2+). When V(IV)O complexes of flavonoids were taken into account, the amount of hydroxyl radicals produced in Fenton-like reactions depends on the specific structure of the ligand and on their capability to reduce H2O2 to give (•)OH. Both the formation of reactive oxygen species (ROS) under physiological conditions by V(IV)O complexes of flavonoid ligands and their radical scavenging capability can be put in relationship with their antitumor effectiveness and it could be possible to modulate these actions by changing the features of the flavonoid coordinated to the V(IV)O(2+) ion, such as the entity, nature and position of the substituents and the number of phenolic groups. PMID:27184413

  10. Catalytic and mechanistic studies into the epoxidation of styrenes using manganese complexes of structurally similar polyamine ligands.

    PubMed

    Ilyashenko, Gennadiy; De Faveri, Giorgio; Follier, Thomas; Al-Safadi, Rawan; Motevalli, Majid; Watkinson, Michael

    2014-02-21

    Two structurally similar polyamine ligands (7 and 8) have been prepared, which differ only by the presence of either a secondary or tertiary nitrogen donor within their N5 donor set. The ligands, in combination with iron and manganese salts, have been screened for their efficacy as catalysts for the epoxidation of styrene, using both hydrogen peroxide and peracetic acid as oxidants. Clear differences in activity between the two systems were observed, with 7 proving most effective in the presence of MnSO4 with H2O2, whereas ligand 8 proved to be effective with Mn(OTf)2, MnCl2 and Mn(ClO4)2 using peracetic acid as the oxidant. A Hammett analysis of the initial rate kinetics of the optimal systems, combined with analysis by UV-vis spectroscopy, indicates that the small structural differences in the ligands elicit profound changes in the nature of the active species formed. PMID:24395191

  11. Soluble Forms and Ligands of the Receptor for Advanced Glycation End-Products in Patients with Acute Respiratory Distress Syndrome: An Observational Prospective Study

    PubMed Central

    Jabaudon, Matthieu; Blondonnet, Raiko; Roszyk, Laurence; Pereira, Bruno; Guérin, Renaud; Perbet, Sébastien; Cayot, Sophie; Bouvier, Damien; Blanchon, Loic; Sapin, Vincent; Constantin, Jean-Michel

    2015-01-01

    Background The main soluble form of the receptor for advanced glycation end-products (sRAGE) is elevated during acute respiratory distress syndrome (ARDS). However other RAGE isoforms and multiple ligands have been poorly reported in the clinical setting, and their respective contribution to RAGE activation during ARDS remains unclear. Our goal was therefore to describe main RAGE isoforms and ligands levels during ARDS. Methods 30 ARDS patients and 30 mechanically ventilated controls were prospectively included in this monocenter observational study. Arterial, superior vena cava and alveolar fluid levels of sRAGE, endogenous-secretory RAGE (esRAGE), high mobility group box-1 protein (HMGB1), S100A12 and advanced glycation end-products (AGEs) were measured in duplicate ELISA on day 0, day 3 and day 6. In patients with ARDS, baseline lung morphology was assessed with computed tomography. Results ARDS patients had higher arterial, central venous and alveolar levels of sRAGE, HMGB1 and S100A12, but lower levels of esRAGE and AGEs, than controls. Baseline arterial sRAGE, HMGB1 and S100A12 were correlated with nonfocal ARDS (AUC 0.79, 0.65 and 0.63, respectively). Baseline arterial sRAGE, esRAGE, S100A12 and AGEs were associated with severity as assessed by PaO2/FiO2. Conclusions This is the first kinetics study of levels of RAGE main isoforms and ligands during ARDS. Elevated sRAGE, HMGB1 and S100A12, with decreased esRAGE and AGEs, were found to distinguish patients with ARDS from those without. Our findings should prompt future studies aimed at elucidating RAGE/HMGB1/S100A12 axis involvement in ARDS. Trial Registration clinicaltrials.gov Identifier: NCT01270295. PMID:26274928

  12. Ligand-functionalized degradable polyplexes formed by cationic poly(aspartic acid)-grafted chitosan-cyclodextrin conjugates

    NASA Astrophysics Data System (ADS)

    Song, Hai-Qing; Li, Rui-Quan; Duan, Shun; Yu, Bingran; Zhao, Hong; Chen, Da-Fu; Xu, Fu-Jian

    2015-03-01

    Polypeptide-based degradable polyplexes attracted considerable attention in drug delivery systems. Polysaccharides including cyclodextrin (CD), dextran, and chitosan (CS) were readily grafted with cationic poly(aspartic acid)s (PAsps). To further enhance the transfection performances of PAsp-based polyplexes, herein, different types of ligand (folic acid, FA)-functionalized degradable polyplexes were proposed based on the PAsp-grafted chitosan-cyclodextrin conjugate (CCPE), where multiple β-CDs were tied on a CS chain. The FA-functionalized CCPE (i.e., CCPE-FA) was obtained via a host-guest interaction between the CD units of CCPE and the adamantane (Ad) species of Ad-modified FA (Ad-FA). The resulting CCPE/pDNA, CCPE-FA/pDNA, and ternary CCPE-FA/CCPE/pDNA (prepared by layer-by-layer assembly) polyplexes were investigated in detail using different cell lines. The CCPE-based polyplexes displayed much higher transfection efficiencies than the CS-based polyplexes reported earlier by us. The ternary polyplexes of CCPE-FA/CCPE/pDNA produced excellent gene transfection abilities in the folate receptor (FR)-positive tumor cells. This work would provide a promising means to produce highly efficient polyplexes for future gene therapy applications.Polypeptide-based degradable polyplexes attracted considerable attention in drug delivery systems. Polysaccharides including cyclodextrin (CD), dextran, and chitosan (CS) were readily grafted with cationic poly(aspartic acid)s (PAsps). To further enhance the transfection performances of PAsp-based polyplexes, herein, different types of ligand (folic acid, FA)-functionalized degradable polyplexes were proposed based on the PAsp-grafted chitosan-cyclodextrin conjugate (CCPE), where multiple β-CDs were tied on a CS chain. The FA-functionalized CCPE (i.e., CCPE-FA) was obtained via a host-guest interaction between the CD units of CCPE and the adamantane (Ad) species of Ad-modified FA (Ad-FA). The resulting CCPE/pDNA, CCPE

  13. 1,1'-Bis(pyrazol-3-yl)ferrocene: A Clip Ligand That Forms Supramolecular Aggregates and Prismatic Hexanuclear Coinage Metal Complexes.

    PubMed

    Veronelli, Mattia; Dechert, Sebastian; Demeshko, Serhiy; Meyer, Franc

    2015-07-20

    Two ferrocene derivatives with appended pyrazole substituents, namely, 1,1'-bis(5-methyl-1H-pyrazol-3-yl)ferrocene (H2LH) and 1,1'-bis(5-trifluoromethyl-1H-pyrazol-3-yl)ferrocene (H2LF), were synthesized. In solid state they form distinct H-bonded dimers with orthogonal (H2LH, C2 symmetry) or antiparallel (H2LF, C2h symmetry) arrangement of the two ferrocene/pyrazole hybrid molecules. Supramolecular dimerization was also detected in solution at low temperatures, though diffusion-ordered spectroscopy and variable-temperature NMR spectroscopy revealed several dynamic processes. Redox potentials of the ferrocene derivatives are affected by the nature of the pyrazole substituent (Me, CF3). In their deprotonated form [LR]2-, both ferrocene/pyrazole hybrids serve as ligands and form oligonuclear CuI, AgI, and AuI complexes that were identified by matrix-assisted laser desorption ionization mass spectrometry. X-ray crystallography revealed the structures of Cu6L3H and Ag6L3F, which both contain two parallel and eclipsed [M(μ-pz)]3 metallamacrocycles (M = Cu, Ag) linked by three ferrocene units. MI···MI distances between the two triangular M3N6 decks are shorter in Ag6L3F (3.28-3.30 vs 3.44-3.51 Å in the case of Cu6L3H), indicating substantial intramolecular closed-shell Ag(d10)-Ag(d10) interactions. However, Cu6L3H features close intermolecular Cu···Cu contacts as short as 3.37 Å. Mössbauer data for both the ligands and complexes were collected, and electrochemical properties were measured; preliminary luminescence data are reported.

  14. Crystallization and preliminary X-ray crystallographic analysis of peptide deformylase (PDF) from Bacillus cereus in ligand-free and actinonin-bound forms

    SciTech Connect

    Park, Joon Kyu; Moon, Jin Ho; Kim, Jae-Hong; Kim, Eunice EunKyeong

    2005-01-01

    Peptide deformylase (PDF) from B. cereus has been overexpressed, purified and crystallized in ligand-free and actinonin-bound forms. Diffraction data have been collected from these crystals to 1.7 and 2.0 Å resolution, respectively. In bacteria, protein expression initiates with an N-formyl group and this needs to be removed in order to ensure proper bacterial growth. These formylation and deformylation processes are unique to eubacteria; therefore, inhibition of these would provide a novel antibacterial therapy. Deformylation is carried out by peptide deformylase (PDF). PDF from Bacillus cereus, one of the major pathogenic bacteria, was cloned into expression plasmid pET-28a (Novagen), overexpressed in Escherichia coli BL21 (DE3) and purified to high quality. Crystals have been obtained of both ligand-free PDF and PDF to which actinonin, a highly potent naturally occurring inhibitor, is bound. Both crystals belong to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 42.72, b = 44.04, c = 85.19 Å and a = 41.31, b = 44.56, c = 84.47 Å, respectively. Diffraction data were collected to 1.7 Å resolution for the inhibitor-free crystals and to 2.0 Å resolution for the actinonin-bound crystals.

  15. I. Enabling Single-Chain Surfactants to Form Vesicles by Nonamphiphilic Liquid Crystals in Water II. Controlling Attachment and Ligand-Mediated Adherence of Candida albicans on Monolayers

    NASA Astrophysics Data System (ADS)

    Varghese, Nisha

    . Adhesion of C. albicans to a surface is a complex process and is governed by nonspecific attachment or multiple ligand-receptor interactions. The work demonstrates that the multiple ligand-receptor interactions used by C. albicans for adherence to a surface can be individually studied using self-assembled monolayers (SAMs) decorated with minimal motif of the ligands. The SAMs were also used to differentiate between the interactions of the two different morphological forms of C. albicans.. Chapter 5 presents a study on small molecules that were used to inhibit biofilm formed by C. albicans. The acyclic triazoles used in the study were not toxic to the C. albicans and were capable of inhibiting biofilm formed by C. albicans. The acyclic triazole can be used as promising candidates to design new antifungal agents. The chapter also reports the synthesis of squarylated homoserine lactones (SHLs) structural mimics of bacterial acyl homoserine lactones (AHLs) to study the inhibitory effects of SHLs on fungal biofilm. The bacterial AHLs are known to repress the growth of C. albicans and control fungal biofilm in native host environment. The synthesized SHLs were non-toxic to C. albicans and failed to inhibit biofilm formed by C. albicans. . Chapter 6 uses gradient nanotopography combined with controlled surface chemistry to confine bacterial biofilm formed by Escherichia coli. The E. coli biofilm were confined within micrometer sized regions of hydrophobic SAMs surrounded by polyol-terminated SAMs. The study reveals that surface with higher topography enhances the ability of the bioinert SAMs to resist bacterial adherence to surface.

  16. Redox activities of mono- and binuclear forms of low-molecular and protein-bound dinitrosyl iron complexes with thiol-containing ligands.

    PubMed

    Borodulin, Rostislav R; Dereven'kov, Ilia А; Burbaev, Dosymzhan Sh; Makarov, Sergei V; Mikoyan, Vasak D; Serezhenkov, Vladimir А; Kubrina, Lyudmila N; Ivanovic-Burmazovic, Ivana; Vanin, Anatoly F

    2014-08-31

    EPR, optical, electrochemical and stopped-flow methods were used to demonstrate that Fe(NO)2 fragments in paramagnetic mononuclear and diamagnetic binuclear forms of dinitrosyl iron complexes with glutathione are reversibly reduced by a two-electron mechanism to be further transformed from the initial state with d(7) configuration into states with the d(8) and d(9) electronic configurations of the iron atom. Under these conditions, both forms of DNIC display identical optical and EPR characteristics in state d(9) suggesting that reduction of the binuclear form of DNIC initiates their reversible decomposition into two mononuclear dinitrosyl iron fragments, one of which is EPR-silent (d(8)) and the other one is EPR-active (d(9)). Both forms of DNIC produce EPR signals with the following values of the g-factor: g⊥=2.01, g||=1.97, gaver.=2.0. M-DNIC with glutathione manifest an ability to pass into state d(9), however, only in solutions with a low content of free glutathione. Similar transitions were established for protein-bound М- and B-DNIC with thiol-containing ligands. PMID:24997418

  17. Cross-Linking the Fibers of Supramolecular Gels Formed from a Tripodal Terpyridine Derived Ligand with d-Block Metal Ions.

    PubMed

    Kotova, Oxana; Daly, Ronan; dos Santos, Cidália M G; Kruger, Paul E; Boland, John J; Gunnlaugsson, Thorfinnur

    2015-08-17

    The tripodal terpyridine ligand, L, forms 1D helical supramolecular polymers/gels in H2O-CH3OH solution mediated through hydrogen bonding and π-π interactions. These gels further cross-link into 3D supramolecular metallogels with a range of metal ions (M) such as Fe(II), Ni(II), Cu(II), Zn(II), and Ru(III); the cross-linking resulting in the formation of colored or colorless gels. The fibrous morphology of these gels was confirmed using scanning electron microscopy (SEM); while the self-assembly processes between L and M were investigated by absorbance and emission spectroscopy from which their binding constants were determined by using a nonlinear regression analysis. PMID:26222397

  18. 1D coordination polymers formed by tetranuclear lead(II) building blocks with carboxylate ligands: In situ isomerization of itaconic acid

    SciTech Connect

    Rana, Abhinandan; Jana, Swapan Kumar; Datta, Sayanti; Butcher, Raymond J.; Zangrando, Ennio; Dalai, Sudipta

    2013-11-15

    The synthesis of two new lead(II) coordination polymers, [Pb{sub 2}(mpic){sub 4}(H{sub 2}O)]·0.5H{sub 2}O (1) and [Pb{sub 2}(phen){sub 2}(cit)(mes)]·2H{sub 2}O (2) has been reported, where mpic=3-methyl picolinate, phen=o-phenanthroline, H{sub 2}cit=citraconic acid, H{sub 2}mes mesaconic acid. X-ray single crystal diffraction analyses showed that the complexes comprise topologically different 1D polymeric chains stabilized by weak interactions and both containing tetranuclear Pb{sub 4} units connected by carboxylate groups. In compound 1 3-methylpicolinic acid is formed in situ from 3-methyl piconitrile, and mesaconate and citraconate anions were surprisingly formed from itaconic acid during the synthesis of 2. The photoluminescence and thermal properties of the complexes have been studied. - Graphical abstract: Two new topologically different 1D coordination polymers formed by Pb{sub 4} clusters have been synthesized and characterized by X-ray analysis. The luminescence and thermal properties have been studied. Display Omitted - Highlights: • Both the complexes, made up of different ligands, forms topologycally different 1D polymeric chains containing Pb{sub 4} clusters. • The final structures are stabilized by weak interactions (H-bond, π∙∙∙π stacking). • In complex 1, the 3-methylpicolinic acid is generated in situ from 3-methyl piconitrile. • Mesaconate and citraconate anions are surprisingly formed in situ from itaconic acid during the synthesis of complex 2, indicating an exceptional transformation.

  19. Near infrared (NIR) lanthanide emissive Langmuir-Blodgett monolayers formed using Nd(III) directed self-assembly synthesis of chiral amphiphilic ligands.

    PubMed

    Barry, Dawn E; Kitchen, Jonathan A; Albrecht, Martin; Faulkner, Stephen; Gunnlaugsson, Thorfinnur

    2013-09-10

    The incorporation of chiral amphiphilic lanthanide-directed self-assembled Nd(III) complexes (Nd.13 and Nd.23) into stable Langmuir monolayers, and the subsequent Langmuir-Blodgett film formation of these, is described. The photophysical properties of the enantiomeric pair of ligands 1 and 2 in the presence of Nd(CF3SO3)3 were also investigated in CH3CN solutions using UV-vis, fluorescence, and lanthanide luminescence spectroscopies. Analysis of the resulting self-assembly processes revealed that two main species were formed in solution,1:1 and 1:3 Nd:L self-assembly complexes, with the latter being the dominant species upon the addition of 0.33 equivalents of Nd(III). Excited state lifetime measurements of Nd.13 and Nd.23 in CH3OH and CD3OD and CH3CN were also evaluated. The formation of the self-assembly in solution was also monitored by observing the changes in the circular dichroism (CD) spectra; and large differences were observed between the 1:3 and other stoichiometries in the spectra, allowing for correlation to be made with that seen in the emission studies of these systems. Surface pressure-area and surface pressure-time isotherms evidenced the formation of stable Langmuir monolayers of Nd.13 and Nd.23 at an air-water interface, and the deposition of these monolayers onto a quartz solid substrate (Langmuir-Blodgett films) gave rise to immobilized chiral monomolecular films which exhibited Nd(III) NIR luminescence upon excitation of the ligand chromophore, demonstrating efficient energy transfer to the Nd(III) excided state (sensitized) with concomitant emission centered at 800 and 1334 nm.

  20. Race, Ethnicity and Ancestry in Unrelated Transplant Matching for the National Marrow Donor Program: A Comparison of Multiple Forms of Self-Identification with Genetics

    PubMed Central

    Hollenbach, Jill A.; Saperstein, Aliya; Albrecht, Mark; Vierra-Green, Cynthia; Parham, Peter; Norman, Paul J.; Maiers, Martin

    2015-01-01

    We conducted a nationwide study comparing self-identification to genetic ancestry classifications in a large cohort (n = 1752) from the National Marrow Donor Program. We sought to determine how various measures of self-identification intersect with genetic ancestry, with the aim of improving matching algorithms for unrelated bone marrow transplant. Multiple dimensions of self-identification, including race/ethnicity and geographic ancestry were compared to classifications based on ancestry informative markers (AIMs), and the human leukocyte antigen (HLA) genes, which are required for transplant matching. Nearly 20% of responses were inconsistent between reporting race/ethnicity versus geographic ancestry. Despite strong concordance between AIMs and HLA, no measure of self-identification shows complete correspondence with genetic ancestry. In certain cases geographic ancestry reporting matches genetic ancestry not reflected in race/ethnicity identification, but in other cases geographic ancestries show little correspondence to genetic measures, with important differences by gender. However, when respondents assign ancestry to grandparents, we observe sub-groups of individuals with well- defined genetic ancestries, including important differences in HLA frequencies, with implications for transplant matching. While we advocate for tailored questioning to improve accuracy of ancestry ascertainment, collection of donor grandparents’ information will improve the chances of finding matches for many patients, particularly for mixed-ancestry individuals. PMID:26287376

  1. Race, Ethnicity and Ancestry in Unrelated Transplant Matching for the National Marrow Donor Program: A Comparison of Multiple Forms of Self-Identification with Genetics.

    PubMed

    Hollenbach, Jill A; Saperstein, Aliya; Albrecht, Mark; Vierra-Green, Cynthia; Parham, Peter; Norman, Paul J; Maiers, Martin

    2015-01-01

    We conducted a nationwide study comparing self-identification to genetic ancestry classifications in a large cohort (n = 1752) from the National Marrow Donor Program. We sought to determine how various measures of self-identification intersect with genetic ancestry, with the aim of improving matching algorithms for unrelated bone marrow transplant. Multiple dimensions of self-identification, including race/ethnicity and geographic ancestry were compared to classifications based on ancestry informative markers (AIMs), and the human leukocyte antigen (HLA) genes, which are required for transplant matching. Nearly 20% of responses were inconsistent between reporting race/ethnicity versus geographic ancestry. Despite strong concordance between AIMs and HLA, no measure of self-identification shows complete correspondence with genetic ancestry. In certain cases geographic ancestry reporting matches genetic ancestry not reflected in race/ethnicity identification, but in other cases geographic ancestries show little correspondence to genetic measures, with important differences by gender. However, when respondents assign ancestry to grandparents, we observe sub-groups of individuals with well- defined genetic ancestries, including important differences in HLA frequencies, with implications for transplant matching. While we advocate for tailored questioning to improve accuracy of ancestry ascertainment, collection of donor grandparents' information will improve the chances of finding matches for many patients, particularly for mixed-ancestry individuals.

  2. Triosmium clusters formed by oxidative addition and decarbonylation of 2-formylpyrrole: Crystal structures of three triosmium clusters containing aromatic or nonaromatic heterocyclic ligands derived from pyrrole

    SciTech Connect

    Day, M.W.; Hardcastle, K.I. ); Deeming, A.J. ); Arce, A.J.; De Sanctis, Y. )

    1990-01-01

    The {mu}-acyl cluster (Os{sub 3}H({mu}{sub 2}-NHCH=CHCH=CCO)(CO){sub 10}) (1) is formed by oxidative addition of 2-formylpyrrole to (Os{sub 3}(CO){sub 10}(MeCN){sub 2}) in refluxing cyclohexane in the same manner as with other aldehydes. The crystals of 1 are triclinic, space group P{bar 1}, with cell dimensions a = 14.882 (2) {angstrom}, b = 15.626 (4) {angstrom}, c = 9.447 (3) {angstrom}, {alpha} = 107.39 (2){degree}, {beta} = 97.29 (2){degree}, {gamma} = 97.84 (2){degree}, and Z = 4. The structure was refined to R{sub w} = 0.034. The pyrrolylacyl ligand bridges two osmium atoms through the C and O atoms of the original formyl group. Thermal loss of two COs from 1 gives two isomers of the cluster (Os{sub 3}H{sub 2}({mu}{sub 3}-C{sub 4}H{sub 3}N)(CO){sub 9}) (2 and 3), isomer 2 converting to 3 thermally. Isomer 2, (Os{sub 3}H{sub 2}({mu}{sub 3}-NHCH=CHC=C)(CO){sub 9}), retains the NH bond and is directly related to the N-methyl analogue of 2, (Os{sub 3}H{sub 2}({mu}{sub 3}-MeNCH=CHC=C)(CO){sub 9}) (5), and closely related to the benzyne cluster (Os{sub 3}H{sub 2}(C{sub 6}H{sub 4})(CO){sub 9}), both of known X-ray structure. Cluster 2 converts to 3 by cleavage of N-H and Os-C bonds and with formation of C-H and Os-N bonds. Crystals of 3 are monoclinic, space group P2{sub 1}/c, with cell dimensions a = 11.308 (2) {angstrom}, b = 12.457 (2) {angstrom}, c = 15.384 (3) {angstrom}, {beta} = 123.59 (2){degree}, and Z = 8. The structure was refined to R{sub w} = 0.052. The structure is best defined by a model in which the {mu}{sub 3}-N=CHCH=CHC ligand is coordinated to one Os atom through a N atom and to the other two through a single C atom forming a {mu}{sub 2}-alkylidene bridge. The C{sub 4}N ring is formally nonaromatic and is oriented vertically to the metal plane.

  3. Thermodynamic, kinetic and structural studies on the ternary palladium(II) complexes of thioether ligands.

    PubMed

    Nagy, Z; Fábián, I; Sóvágó, I

    2000-04-01

    Potentiometric, calorimetric, NMR and stopped-flow kinetic studies were performed on the palladium(II) complexes of thioether and/or nitrogen donor ligands. The ternary systems always contained a tridentate ligand (dien, terpy and dianions of dipeptides, GlyGly, GlyAla and GlyMet) and a monodentate thioether (AcMet). The stability constants of thioether complexes were obtained by indirect potentiometric measurements using uridine as a competitive ligand. The thermodynamic parameters revealed that selectivity of palladium(II) for thioether binding can be significantly influenced by the other donor atoms around the metal ion. [Pd(terpy)]2+ and [Pd(GlyMet)] had the lowest affinity for thioether binding and it was explained by steric and electronic effects. Ternary complexes of nitrogen donors have higher thermodynamic stability constants than the thioether complexes, but rate constants of the substitution reactions revealed that formation of thioether complexes is the faster reaction. As a consequence, the thermodynamic equilibrium state of a multicomponent system is characterized by the coordination of N-donors, which are formed via the existence of thioether-bonded intermediates. PMID:10830857

  4. Fas Ligand Is Present in Tumors of the Ewing’s Sarcoma Family and Is Cleaved into a Soluble Form by a Metalloproteinase

    PubMed Central

    Mitsiades, Nicholas; Poulaki, Vassiliki; Kotoula, Vassiliki; Leone, Alvaro; Tsokos, Maria

    1998-01-01

    Fas ligand (FasL) exists in transmembrane and soluble forms and induces apoptosis on cross-linking with the Fas receptor. We evaluated the biological significance of FasL and Fas in 61 tumor tissues and 9 cell lines of the Ewing’s sarcoma family of tumors (ESFT). FasL was present in 62.5% and Fas in 79.4% of primary ESFT. Metastatic tumors had higher expression of FasL (95%), suggesting association with a metastatic phenotype. FasL was detected in the cytoplasm and membrane of ESFT cells by immunofluorescence. Western blotting revealed transmembrane and soluble FasL in cytosolic extracts and soluble FasL in conditioned media. Both transmembrane and soluble FasL induced apoptosis of Fas-sensitive Jurkat cells in co-culture experiments with ESFT cells or their media. Treatment with phenanthroline and the synthetic metalloproteinase inhibitor BB-3103 reduced the levels of soluble FasL in the media, suggesting that in ESFT, FasL is processed by a metalloproteinase and released in the extracellular milieu. The released soluble FasL may serve to attack cells of the immune system and/or interfere with the binding of transmembrane FasL with Fas, and results in down-regulation of transmembrane FasL. Synthetic metalloproteinase inhibitors may modify the ratio of transmembrane to soluble FasL. PMID:9846984

  5. Synthesis, molecular and crystal structure of bis(triethanolamine)manganese(II) saccharinate: a seven-coordinate manganese complex with tri- and tetradentate triethanolamine ligands

    NASA Astrophysics Data System (ADS)

    Topcu, Yildiray; Andac, Omer; Yilmaz, Veysel T.; Harrison, William T. A.

    2002-06-01

    The synthesis, molecular and crystal structure of bis(triethanolamine)Mn(II) saccharinate, [Mn(tea) 2](sac) 2 are reported. The configuration of the tea ligands results in an unusual example of coordination number seven for the Mn(II) ion. The two triethanolamine (tea) ligands coordinate to the Mn(II) ion forming a monocapped trigonal prism geometry, in which one of the tea ligands behaves as a tridentate ligand, while the other one acts as a tetradentate donor. The free and coordinated hydroxyl hydrogens of the tea ligands are involved in hydrogen bonding with the amine nitrogen, carbonyl and sulfonyl oxygens of the neighbouring sac ions to form a three-dimensional infinite network. A weak π-π interaction between the phenyl rings of the sac ions also occurs.

  6. Both soluble and membrane-bound forms of Flt3 ligand enhance tumor immunity following "suicide" gene therapy in a murine colon carcinoma model.

    PubMed

    Alsheikhly, Abdul-Razzak; Zweiri, Jehad; Walmesley, Alice J; Watson, Alastair J M; Christmas, Stephen E

    2004-11-01

    In prodrug-activated ("suicide") gene therapy, tumor cells are transfected with the gene for an enzyme that converts an inactive prodrug, such as ganciclovir (GCV), to a toxic compound. Transfected cells are killed on administration of GCV, as also are untransfected "bystander" cells. The ability of the dendritic cell stimulatory cytokine Flt3 ligand (Flt3-L) to modulate prodrug-activated gene therapy has been investigated. Transfectants of the murine colon carcinoma MC26 were generated expressing soluble (FLS) and membrane-bound forms of Flt3-L. They were inoculated together with wild-type MC26 cells and cells expressing herpes simplex virus-1 (HSV1) thymidine kinase into BALB/c mice, which were then administered GCV. Expression of Flt3-L or FLS prevented regrowth of tumor in most mice, which was comparable to the effect of granulocyte-macrophage colony-stimulating factor (GM-CSF), while tumors recurred in all mice receiving "suicide" gene therapy alone. Recurring tumor cells were resistant to direct killing by GCV but sensitive to "bystander" killing in vitro. Mice without tumor recurrence were rechallenged with unmodified MC26 cells. Of those mice given transfectants expressing GM-CSF, Flt3-L, or FLS, approximately 50% were immune to rechallenge. These mice also showed cytotoxic and proliferative responses to MC26 cells. These experiments show that both soluble and membrane-bound forms of Flt3-L were able to induce a protective immune response to colon carcinoma cells in a fashion similar to GM-CSF.

  7. The solution structure of the soluble form of the lipid-modified azurin from Neisseria gonorrhoeae, the electron donor of cytochrome c peroxidase.

    PubMed

    Nóbrega, Cláudia S; Saraiva, Ivo H; Carreira, Cíntia; Devreese, Bart; Matzapetakis, Manolis; Pauleta, Sofia R

    2016-02-01

    Neisseria gonorrhoeae colonizes the genitourinary track, and in these environments, especially in the female host, the bacteria are subjected to low levels of oxygen, and reactive oxygen and nitrosyl species. Here, the biochemical characterization of N. gonorrhoeae Laz is presented, as well as, the solution structure of its soluble domain determined by NMR. N. gonorrhoeae Laz is a type 1 copper protein of the azurin-family based on its spectroscopic properties and structure, with a redox potential of 277±5 mV, at pH7.0, that behaves as a monomer in solution. The globular Laz soluble domain adopts the Greek-key motif, with the copper center located at one end of the β-barrel coordinated by Gly48, His49, Cys113, His118 and Met122, in a distorted trigonal geometry. The edge of the His118 imidazole ring is water exposed, in a surface that is proposed to be involved in the interaction with its redox partners. The heterologously expressed Laz was shown to be a competent electron donor to N. gonorrhoeae cytochrome c peroxidase. This is an evidence for its involvement in the mechanism of protection against hydrogen peroxide generated by neighboring lactobacilli in the host environment. PMID:26589091

  8. Synthesis and spectroscopic studies of mixed-ligand and polymeric dinuclear transition metal complexes with bis-acylhydrazone tetradentate ligands and 1,10-phenanthroline

    NASA Astrophysics Data System (ADS)

    Gup, Ramazan; Kırkan, Bülent

    2006-06-01

    Two types of dinuclear copper(II) and nickel(II) complexes with two tetradentate N 2O 2 donor ligands 1,4-bis(1-anthranoylhydrazonoethyl)benzene (L 1), 1,4-bis(1-salicyloylhydrazonoethyl)benzene (L 2) and N, N'-bidentate heterocyclic base [1,10-phenonthroline (phen)] have been synthesized and characterized by elemental analysis, infrared spectra, UV-vis electronic absorption spectra and magnetic susceptibility measurements. The reaction of metal(II) acetates with the solution containing ligand and 1,10-phenonthroline in methanol gives mixed-ligand dinuclear metal(II) complexes with general formula [M 2L(phen) 2]Cl 2 (L = L 1 or L 2), whereas, the ligands react with metal(II) acetates to form polymeric dinuclear complexes with general formula [(M 2L 2) n] (L = L 1 or L 2). In the complexes, the ligands act as dianionic tetradentate and coordination takes place in the enol tautomeric form with the enolic oxygen and azomethine nitrogen atoms while the phenolic hydroxyl and amino groups of aroylhydrazone moiety do not participate in coordination. The effect of varying pH and solvent on the absorption behavior of both ligands and complexes has been investigated.

  9. Ligand Control of Manganese Telluride Molecular Cluster Core Nuclearity.

    PubMed

    Choi, Bonnie; Paley, Daniel W; Siegrist, Theo; Steigerwald, Michael L; Roy, Xavier

    2015-09-01

    We report the synthesis, structural diversity, and chemical behavior of a family of manganese telluride molecular clusters whose charge-neutral cores are passivated by two-electron donor ligands. We describe three different core structures: a cubane-type Mn4Te4, a prismane Mn6Te6, and a dicubane Mn8Te8. We use various trialkylphosphines and N-heterocyclic carbenes (NHCs) as surface ligands and demonstrate that the formation of the different cluster core structures is controlled by the choice of ligand: bulky ligands such as P(i)Pr3, PCy3, or (i)Pr2NHC ((i)Pr2NHC = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) form the cubane-type core, while the smaller PMe3 produces the prismane core. The intermediate-sized PEt3 produces both cubane and prismane species. These manganese telluride molecular clusters are labile, and the capping phosphines can be replaced by stronger ligands, while the internal core structure of the cluster remains intact. The interplay of structural diversity and ligand versatility and lability makes these clusters potentially useful building blocks for the assembly of larger aggregates and extended structures. We demonstrate the simplest prototype of these solid-forming reactions: the direct coupling of two Mn4Te4((i)Pr2NHC)4 units to form the dicubane Mn8Te8((i)Pr2NHC)6. We also postulate the prismatic Mn6Te6 as the common ancestor of both Chevrel-type M6E8 and octanuclear rhombododecahedral M8E6 molecular clusters (M = transition metal and E = chalcogen), and we discuss the core structure of our molecular clusters as recognizable building units for the zinc blende and the hypothetical wurtzite lattices of MnTe.

  10. Structure-property relationship of extended π-conjugation of ancillary ligands with and without an electron donor of heteroleptic Ru(II) bipyridyl complexes for high efficiency dye-sensitized solar cells.

    PubMed

    Hussain, Maqbool; El-Shafei, Ahmed; Islam, Ashraful; Han, Liyuan

    2013-06-01

    Two new heteroleptic Ru(II) bipyridyl complexes MH06 and MH11 were designed, synthesized and characterized for DSSCs. While the ancillary ligand of MH06 was molecularly engineered with a strong electron donating group coupled with an extended π-conjugated system, the ancillary ligand of MH11 contained a longer π-conjugated system only. Molecular modeling, photophysical, and photovoltaic properties were compared under the same experimental conditions against the benchmark N719. In an effort to understand the structure-property relationship, their photovoltaic and photoelectrochemical properties including Jsc, Voc, ground and excited state oxidation potentials, UV-Vis absorption, and molar extinction coefficients were studied. The UV-Vis results showed intense MLCT absorption peaks of MH06 and MH11 in the visible region with a red shift of 12 and 18 nm, respectively, with significantly higher molar extinction coefficients compared to N719. Tetrabutylammonium (TBA) substituted MH11-TBA demonstrated the most efficient IPCE of over 90% in the plateau region covering the entire visible spectrum and extending into the near IR region (ca. 890 nm), which showed a solar-to-power conversion efficiency (η) of 10.06%, significantly higher than that of the benchmark N719 dye (9.32%). The superior performance in terms of the IPCE and Jsc of MH11 can be attributed to the bulky and highly hydrophobic nature of the pyrene-based ancillary ligand, which behaves as a shielding barrier for hole-transport recombination between TiO2 and the electrolyte. In addition, the IMPS results showed that the contribution of dyes to the conduction band shift of the TiO2 level is almost similar, regardless of different substitutions on the bipy-moiety. This implies that the open-circuit photovoltage (Voc) increases with reduced charge recombination in the presence of a thick layer of tetrabutyl ammonium ions (TBA) of the dye anchored on the surface of TiO2.

  11. ELF-2, a new member of the Eph ligand family, is segmentally expressed in mouse embryos in the region of the hindbrain and newly forming somites.

    PubMed Central

    Bergemann, A D; Cheng, H J; Brambilla, R; Klein, R; Flanagan, J G

    1995-01-01

    The Eph receptors are the largest known family of receptor tyrosine kinases and are notable for distinctive expression patterns in the nervous system and in early vertebrate development. However, all were identified as orphan receptors, and only recently have there been descriptions of a corresponding family of ligands. We describe here a new member of the Eph ligand family, designated ELF-2 (Eph ligand family 2). The cDNA sequence for mouse ELF-2 indicates that it is a transmembrane ligand. It shows closest homology to the other known transmembrane ligand in the family, ELK-L/LERK-2/Cek5-L, with 57% identity in the extracellular domain. There is also striking homology in the cytoplasmic domain, including complete identity of the last 33 amino acids, suggesting intracellular interactions. On cell surfaces, and in a cell-free system, ELF-2 binds to three closely related Eph family receptors, Elk, Cek10 (apparent ortholog of Sek-4 and HEK2), and Cek5 (apparent ortholog of Nuk/Sek-3), all with dissociation constants of approximately 1 nM. In situ hybridization of mouse embryos shows ELF-2 RNA expression in a segmental pattern in the hindbrain region and the segmenting mesoderm. Comparable patterns have been described for Eph family receptors, including Sek-4 and Nuk/Sek-3, suggesting roles for ELF-2 in patterning these regions of the embryo. PMID:7651410

  12. Phosphorus donors in highly strained silicon.

    PubMed

    Huebl, Hans; Stegner, Andre R; Stutzmann, Martin; Brandt, Martin S; Vogg, Guenther; Bensch, Frank; Rauls, Eva; Gerstmann, Uwe

    2006-10-20

    The hyperfine interaction of phosphorus donors in fully strained Si thin films grown on virtual Si(1-x)Ge(x) substrates with x< or =0.3 is determined via electrically detected magnetic resonance. For highly strained epilayers, hyperfine interactions as low as 0.8 mT are observed, significantly below the limit predicted by valley repopulation. Within a Green's function approach, density functional theory shows that the additional reduction is caused by the volume increase of the unit cell and a relaxation of the Si ligands of the donor.

  13. Synthesis, structure, photophysical and catalytic properties of CuI-Iodide complexes of di-imine ligands

    NASA Astrophysics Data System (ADS)

    Mondal, Jahangir; Ghorai, Anupam; Singh, Sunil K.; Saha, Rajat; Patra, Goutam K.

    2016-03-01

    Two new multifunctional CuII based complexes [CuI(L1)] (1) and [Cu2(μ-I)2(L2)] (2) with bidentate N-N donor ligands L1 and imino-pyridyl ligand L2 have been synthesized and characterized by elemental analysis, IR, UV-Vis, NMR and single crystal X-ray crystallography. The bidentate di-imine ligand (L1) forms monomeric CuI complex (1) whereas the bis-bidentate di-imine ligand (L2) favours the formation of dimeric CuI complex (2) in association with two bridging iodides. Structural analysis reveals that in complex 1 each monomeric units are connected by π⋯π and C-H⋯π interactions to form 3D supramolecular structure whereas in complex 2 each molecules are connected by only π⋯π interactions to form 3D supramolecular structure. The photoluminescence properties of the complexes have been studied at room temperature. Theoretical analysis shows that HOMO is focused on the Cu and iodides while LUMO is focused on di-imine ligands and the luminescence behaviour arises due to metal to ligand charge transfer (MLCT) and halide to ligand charge transfer (XLCT). The complexes 1 and 2 are effective catalysts for the synthesis of 2-substituted benzoxazoles.

  14. Chiroptical Probing of Lanthanide-Directed Self-Assembly Formation Using btp Ligands Formed in One-Pot Diazo-Transfer/Deprotection Click Reaction from Chiral Amines.

    PubMed

    Byrne, Joseph P; Martínez-Calvo, Miguel; Peacock, Robert D; Gunnlaugsson, Thorfinnur

    2016-01-11

    A series of enantiomeric 2,6-bis(1,2,3-triazol-4-yl)pyridines (btp)-containing ligands was synthesized by a one-pot two-step copper-catalyzed amine/alkyne click reaction. The Eu(III) - and Tb(III) -directed self-assembly formation of these ligands was studied in CH3 CN by monitoring their various photophysical properties, including their emerging circular dichroism and circularly polarized luminescence. The global analysis of the former enabled the determination of both the stoichiometry and the stability constants of the various chiral supramolecular species in solution. PMID:26555573

  15. Ligand-ligand charge-transfer excited states of Os(II) complexes

    SciTech Connect

    Perkins, T.A.; Schanze, K.S. ); Pourreau, D.B.; Netzel, T.L. )

    1989-06-01

    This paper examines the photophysics of metal-to-ligand charge-transfer (MLCT) and ligand-to-ligand charge-transfer (LLCT) excited states in a series of ((bpy){sub 2}Os{sup II}(CO)L){sup 2+} (Os-L) complexes. For each of the complexes studied, the d{pi}(Os) {yields} {pi}*(bpy) absorption band is the lowest energy transition that is apparent. For L = pyridine and benzonitrile, only long-lived, highly luminescent MLCT states are observed. However, when L = an electron-donor aminobenzonitrile (ABN) species (DMABN, TMABN, or CMI; see text), MLCT emission is quenched and in < 30 ps LLCT excited states are formed, *((bpy{sup {sm bullet}{minus}})-(bpy)OS{sup II}(CO)ABN{sup {sm bullet}+}){sup 2+}. The observed, weight-average radiationless decays of the LLCT excited states in acetonitrile and dichloromethane follow the squence Os-DMABN < Os-TMABN < Os-CMI in each solvent, and the calculated energies of the LLCT states for these complexes are in inverse order to the decay rates as expected if an energy gap law is followed. Finally, multiexponential relaxations of the LLCT states are pronounced in the nonpolar solvent dichloromethane. The dependence of these relaxations on the concentration of added electrolyte suggests that they may be due to ion-pair structure and dynamics.

  16. Some metal complexes of three new potentially heptadentate (N4O3) tripodal Schiff base ligands; synthesis, characterizatin and X-ray crystal structure of a novel eight coordinate Gd(III) complex

    NASA Astrophysics Data System (ADS)

    Golbedaghi, Reza; Moradi, Somaeyh; Salehzadeh, Sadegh; Blackman, Allan G.

    2016-03-01

    The symmetrical and asymmetrical potentially heptadentate (N4O3) tripodal Schiff base ligands (H3L1-H3L3) were synthesized from the condensation reaction of three tripodal tetraamine ligands tpt (trpn), tris (3-aminopropyl) amine; ppe (abap), (2-aminoethyl)bis(3-aminopropyl)amine, and tren, tris(2-aminoethyl)amine, with 5-methoxysalicylaldehyde. Then, the reaction of Ln(III) (Ln = Gd, La and Sm), Al(III), and Fe(III) metal ions with the above ligands was investigated. The resulting compounds were characterized by IR, mass spectrometry and elemental analysis in all cases and NMR spectroscopy in the case of the Schiff base ligands. The X-ray crystal structure of the Gd complex of H3L3 ligand showed that in addition to all donor atoms of the ligand one molecule of H2O is also coordinated to the metal ion and a neutral eight-coordinate complex is formed.

  17. Becoming a Donor

    MedlinePlus

    ... by Organ and Gender. > U.S. Waiting List Candidate Data HOW TO BECOME A DONOR The most important thing to do is to sign up as an organ and tissue donor in your state's donor registry. To cover all bases, it's also helpful to: Designate your decision on ...

  18. Co(II), Cu(II), Cd(II), Fe(III) and U(VI) complexes containing a NSNO donor ligand: Synthesis, characterization, optical band gap, in vitro antimicrobial and DNA cleavage studies

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    A new series of [Co(HPTP)Cl(H2O)2], [Cu(HPTP)Cl], [Cd(HPTP)Cl](H2O)4, [Fe(PTP)Cl(H2O)2](H2O), [UO2(HPTP)(OAc)(H2O)2] complexes of Schiff-bases derived from 4-(2-pyridyl)-3-thiosemicarbazide and pyruvic acid (H2PTP) have been synthesized and characterized by spectroscopic studies. Schiff-base exhibit thiol-thione tautomerism wherein sulfur plays an important role in the coordination. The coordination possibility of the Schiff-bases towards metal ions have been proposed in the light of elemental analyses, spectral (IR, UV-vis, 1H NMR, 13C NMR and ESR), magnetic and thermal studies. IR spectra show that H2PTP is coordinated to the metal ions in a mono or binegative tridentate manner. The electronic spectra of the complexes and their magnetic moments provide information about geometries. The room temperature solid state ESR spectra of the Cu(II) complexes show dx2-y2 as a ground state, suggesting square-planar geometry around Cu(II) center. The molecular parameters: total energy, binding energy, isolated atomic energy, electronic energy, heat of formation, dipole moment, HOMO and LUMO were calculated for the ligand and its 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) of the metal complexes has been calculated. The optical transition energy (Eg) is direct and equals 3.25, 3.26, 3.34 and 3.27 eV for Co, Cu, Fe and U complexes, respectively. The synthesized ligand, in comparison to its metal complexes is screened for its antibacterial activity against bacterial species, Bacillus thuringiensis, Staphylococcus aureus, Pseudomonas aeruginosa and Escherichia coli. The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species. Finally, the biochemical studies showed that, Cu, Cd and Fe complexes have powerful and complete

  19. Synthesis, molecular modeling and spectroscopic characterization of nickel(II), copper(II), complexes of new 16-membered mixed-donor macrocyclic schiff base ligand incorporating a pendant alcohol function

    NASA Astrophysics Data System (ADS)

    Chandra, Sulekh; Ruchi; Qanungo, Kushal; Sharma, Saroj K.

    2011-09-01

    Complexes of Cu(II) and Ni(II) of the composition [M(L)X] [where M = Ni(II), Cu(II) and X = Cl -, NO 3-, CH 3COO -] were synthesized with 1,5-dioxo-9,10-diaza-3,ol-tribenzo-(7,6,10,11,14,15) peptadecane, a N 2O 2 macrocyclic ligand. The complexes were characterized by elemental analysis, molar conductance measurements, UV-vis, IR, 1H NMR, 13C NMR, EPR and molecular modeling studies. All the complexes are non-electrolyte in nature. On the basis of spectral studies, an octahedral geometry has been assigned for Ni(II) complexes and a tetragonal geometry for Cu(II) complexes.

  20. Theoretical and experimental studies of two Co(II) and Ni(II) coordination complex with N,O donor 2-chloro-6-{[(4-hydroxy-3-methoxyphenyl)methylidene]amino}-4 nitrophenol ligand

    NASA Astrophysics Data System (ADS)

    Kusmariya, Brajendra S.; Tiwari, Sandeep; Tiwari, Anjali; Mishra, A. P.; Naikoo, Gowhar Ahmad; Pandit, Umar J.

    2016-07-01

    Here we report two mononuclear Co(II) and Ni(II) complexes of general formula [M(L)2(H2O)].2H2O; {M = CoII & NiII} derived from bidentate 2-chloro-6-{[(4-hydroxy-3-methoxyphenyl)methylidene]amino}-4 nitrophenol ligand (HL). These compounds were characterized by elemental analysis, spectral (FT-IR, electronic and 1H-NMR), molar conductance, thermal, PXRD, SEM and electrochemical studies. Distorted octahedral geometry was proposed around the metal center with ligand (HL). The PXRD and SEM analysis shows the crystalline nature of complexes. The broadening of diffraction peaks were explained in terms of domain size and the lattice strain according to Scherrer and Williamson-Hall method. TG of the synthesized complexes illustrates their general decomposition pattern and thermal stability. The kinetic and thermodynamic parameters viz. activation energy (E∗), pre-exponential factor (Z), entropy of activation (ΔS∗), enthalpy of activation (ΔH∗) and free energy of activation (ΔG∗) of degradation process were also evaluated using Coats-Redfern (C-R), Piloyan-Novikova (P-N) and Horowitz-Metzger (H-M) methods for both complexes assuming first order degradation. The optical band gap values of complexes were found to be in good agreement with calculated HOMO-LUMO energy gap (ΔE) and lie in semiconducting range. The cyclic voltammetric studies of synthesized compounds were carried out in order to examine their electrochemical behavior. In addition theoretical calculations by means of DFT at B3LYP level were incorporated to support the experimental findings.

  1. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions.

    PubMed

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J; Schanz, Hans-Jörg

    2015-01-01

    Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2',6'-dimethyl-4'-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes.

  2. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

    PubMed Central

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J

    2015-01-01

    Summary Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  3. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions.

    PubMed

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J; Schanz, Hans-Jörg

    2015-01-01

    Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2',6'-dimethyl-4'-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  4. Living donor nephrectomy.

    PubMed

    Jacobs, S C; Flowers, J L; Dunkin, B; Sklar, G N; Cho, E

    1999-03-01

    The need for more organs for kidney transplantation is increasing. Cadaver sources for these organs are stable, therefore living donation must increase if the need is to be met. Less perfect kidneys are now being transplanted. The pool of potential donors is being expanded. The process of kidney donation is being made easier in an effort to increase the number of donors. The donor work-up is being streamlined. Laparoscopic donor nephrectomy has been introduced, and appears to be promising as a technique of lessening donor pain and suffering, while maintaining excellent graft results.

  5. Binding of tetramethylammonium to polyether side-chained aromatic hosts. Evaluation of the binding contribution from ether oxygen donors.

    PubMed

    Bartoli, Sandra; De Nicola, Gina; Roelens, Stefano

    2003-10-17

    A set of macrocyclic and open-chain aromatic ligands endowed with polyether side chains has been prepared to assess the contribution of ether oxygen donors to the binding of tetramethylammonium (TMA), a cation believed incapable of interacting with oxygen donors. The open-chain hosts consisted of an aromatic binding site and side chains possessing a variable number of ether oxygen donors; the macrocyclic ligands were based on the structure of a previously investigated host, the dimeric cyclophane 1,4-xylylene-1,4-phenylene diacetate (DXPDA), implemented with polyether-type side chains in the backbone. Association to tetramethylammonium picrate (TMAP) was measured in CDCl(3) at T = 296 K by (1)H NMR titrations. Results confirm that the main contribution to the binding of TMA comes from the cation-pi interaction established with the aromatic binding sites, but they unequivocally show that polyether chains participate with cooperative contributions, although of markedly smaller entity. Water is also bound, but the two guests interact with aromatic rings and oxygen donors in an essentially noncompetitive way. An improved procedure for the preparation of cyclophanic tetraester derivatives has been developed that conveniently recycles the oligomeric ester byproducts formed in the one-pot cyclization reaction. An alternative entry to benzylic diketones has also been provided that makes use of a low-order cyanocuprate reagent to prepare in fair yields a class of compounds otherwise uneasily accessible.

  6. Inclusion of multiple fragment types in the Site Identification by Ligand Competitive Saturation (SILCS) approach

    PubMed Central

    Raman, E. Prabhu; Yu, Wenbo; Lakkaraju, Sirish K.; MacKerell, Alexander D.

    2014-01-01

    The Site Identification by Ligand Competitive Saturation (SILCS) method identifies the location and approximate affinities of small molecular fragments on a target macromolecular surface by performing Molecular Dynamics (MD) simulations of the target in an aqueous solution of small molecules representative of different chemical functional groups. In this study, we introduce a set of small molecules to map potential interactions made by neutral hydrogen bond donors and acceptors, and charged donor and acceptor fragments in addition to nonpolar fragments. The affinity pattern is obtained in the form of discretized probability or, equivalently, free energy maps, called FragMaps, which can be visualized with the target surface. We performed SILCS simulations for four proteins for which structural and thermodynamic data is available for multiple, diverse ligands. Good overlap is shown between high affinity regions identified by the FragMaps and the crystallographic positions of ligand functional groups with similar chemical functionality, thus demonstrating the validity of the qualitative information obtained from the simulations. To test the ability of FragMaps in providing quantitative predictions, we calculate the previously introduced Ligand Grid Free Energy (LGFE) metric and observe its correspondence with experimentally measured binding affinity. LGFE is computed for different conformational ensembles and improvement in prediction is shown with increasing ligand conformational sampling. Ensemble generation includes a Monte Carlo sampling approach that uses the GFE FragMaps directly as the energy function. The results show some, but not all experimental trends are predicted, and warrant improvements in the scoring methodology. In addition, the potential utility of atom-based free energy contributions to the LGFE scores and the use of multiple ligands in SILCS to identify displaceable water molecules during ligand design are discussed. PMID:24245913

  7. Conversion of membrane-bound Fas(CD95) ligand to its soluble form is associated with downregulation of its proapoptotic activity and loss of liver toxicity.

    PubMed

    Schneider, P; Holler, N; Bodmer, J L; Hahne, M; Frei, K; Fontana, A; Tschopp, J

    1998-04-20

    Human Fas ligand (L) (CD95L) and tumor necrosis factor (TNF)-alpha undergo metalloproteinase-mediated proteolytic processing in their extracellular domains resulting in the release of soluble trimeric ligands (soluble [s]FasL, sTNF-alpha) which, in the case of sFasL, is thought to be implicated in diseases such as hepatitis and AIDS. Here we show that the processing of sFasL occurs between Ser126 and Leu127. The apoptotic-inducing capacity of naturally processed sFasL was reduced by >1,000-fold compared with membrane-bound FasL, and injection of high doses of recombinant sFasL in mice did not induce liver failure. However, soluble FasL retained its capacity to interact with Fas, and restoration of its cytotoxic activity was achieved both in vitro and in vivo with the addition of cross-linking antibodies. Similarly, the marginal apoptotic activity of recombinant soluble TNF-related apoptosis-inducing ligand (sTRAIL), another member of the TNF ligand family, was greatly increased upon cross-linking. These results indicate that the mere trimerization of the Fas and TRAIL receptors may not be sufficient to trigger death signals. Thus, the observation that sFasL is less cytotoxic than membrane-bound FasL may explain why in certain types of cancer, systemic tissue damage is not detected, even though the levels of circulating sFasL are high. PMID:9547332

  8. A new chiral N,N',O-donor heteroscorpionate ligand. Structures of Ni2+, Cu2+, Zn2+ complexes and study of solution equilibria by means of 1H NMR/UV-vis titrations and EXSY NMR spectroscopy.

    PubMed

    Gennari, Marcello; Tegoni, Matteo; Lanfranchi, Maurizio; Pellinghelli, Maria Angela; Marchio, Luciano

    2007-04-16

    The N,N',O-heteroscorpionate ligand 1-(4-methoxy-3,5-dimethyl-pyridin-2-yl)-2-methyl-1-pyrazol-1-yl-propan-2-ol (LOH) was prepared in two high-yield steps. Complexes [M(LOH)2][MCl4] (M2+ = Cu2+ and Zn2+) and [M(LOH)2]Cl2 (M2+ = Ni2+ and Cu2+) were prepared and characterized by X-ray crystallography. The speciation in solution (methanol:water 95:5) of the M2+/LOH systems was investigated by means of spectrophotometric (Ni2+ and Cu2+) and 1H NMR (Zn2+) titrations. The beta1 and beta2 global formation constants for the [M(LOH)]2+ and [M(LOH)2]2+ species were obtained and are in agreement with the Irving-Williams series: Ni2+< Cu2+> Zn2+. The Zn2+/LOH system was studied by means of quantitative 1H-1H EXSY spectroscopy (300 K, mixing time = 0.2-0.8 s), which allows the description of the equilibria occurring between five octahedral [Zn(LOH)2]2+ structural isomers and tetrahedral [Zn(LOH)Cl]Cl species. Exchange constants kijex and associated rate constants kij suggest that two types of interconversion occur: octahedral-octahedral (faster) and octahedral-tetrahedral (slower). DFT calculations (B3LYP/6-311+G(d)) were employed to evaluate the relative stability of the [Zn(LOH)2]2+ isomers, which are comparable for the five complexes with a maximum energy difference of 6.3 kJ/mol.

  9. Synthesis, structure and electrochemistry behavior of a cobalt(III) compound with azide and methyl 2-pyridyl ketone semicarbazone ligands

    NASA Astrophysics Data System (ADS)

    Shaabani, Behrouz; Khandar, Ali Akbar; Mahmoudi, Farzaneh; Balula, Salete S.; Cunha-Silva, Luís

    2013-08-01

    An unprecedented cobalt(III) compound with methyl 2-pyridyl ketone semicarbazone (HL) and the auxiliary azide ligand, [Co(L)2] [Co(L)(N3)3] (1) was synthesized and further characterized crystallographically and spectroscopically. Compound 1 crystallizes in the triclinic system and space group of P-1 and its structure consists of two mononuclear crystallographic units with metal chromophore comprising two cobalt(III) centers revealing distorted octahedral geometries and formed by distinct ligands in the inner coordination spheres. Interestingly, compound 1 represents the first complex formed by two distinct mononuclear units involving this ligand. As consequence of various donor and acceptor groups in both crystallographic units, there are several strong Nsbnd H⋯N and Nsbnd H⋯O hydrogen bonding interactions interconnecting adjacent moieties, ultimately leading to a three-dimensional supramolecular network. Furthermore, the electrochemical behavior of the HL and compound 1 were investigated.

  10. Expanded criteria donors.

    PubMed

    Feng, Sandy; Lai, Jennifer C

    2014-08-01

    The greatest challenge facing liver transplantation today is the shortage of donor livers. Demand far exceeds supply, and this deficit has driven expansion of what is considered an acceptable organ. The evolving standard has not come without costs, however, as each new frontier of expanded donor quality (i.e., advancing donor age, donation after cardiac death, and split liver) may have traded wait-list for post-transplant morbidity and mortality. This article delineates the nature and severity of risk associated with specific deceased donor liver characteristics and recommends strategies to maximally mitigate these risks. PMID:25017080

  11. Potentiometric, spectroscopic, electrochemical and DFT characterization of oxovanadium(IV) complexes formed by citrate and tartrates in aqueous solution at high ligand to metal molar ratios: the effects of the trigonal bipyramidal distortion in bis-chelated species and biological implications.

    PubMed

    Lodyga-Chruscinska, Elzbieta; Sanna, Daniele; Garribba, Eugenio; Micera, Giovanni

    2008-09-28

    The complexation of VO(IV) ion with citrate (L3-), D-, L- and DL-tartrate (L2-) at high ligand to metal molar ratios was studied in aqueous solution through the combined application of potentiometric, spectroscopic (UV-vis and EPR) and electrochemical (cyclic voltammetry) techniques. Unlike in equimolar solution, mononuclear and not dinuclear species are formed with the binding of carboxylate-COO- and alcoholate-O- donors yielding mono- and bis-chelated species with VOLH, VOL, VOLH(-1) and VOL2H(-2) composition; for tartrates also the "sugar-like" (O-, O-) coordination is involved in the vanadium binding at basic pH values giving rise to the formation of VOL2H(-3) and VOL2H(-4) complexes. Among the species formed, VOL2H(-2) is characterised by a strong distortion towards the trigonal bipyramid with the two V-O(alcoholate) bonds in the equatorial and the two V-O(carboxylate) bonds in the axial positions. The geometry and electronic absorption spectra of such complexes were simulated by DFT methods and it was found that in aqueous solution the distortion follows the steric hindrance of the substituents on the alpha-carbon atom and the hydrophobicity of the ligands. The results were compared with those displayed by simple alpha-hydroxycarboxylates (glycolate, 2-hydroxyisobutyrate, 2-ethyl-2-hydroxybutyrate and benzilate). The trigonal bipyramidal distortion was correlated with the values of: i) Deltalambda = lambda2-lambda3, where lambda2 and lambda3 are the central bands in the electronic absorption spectrum; ii) |A(x)-A(y)|, where A(x) and A(y) are the 51V hyperfine coupling constants along the x and y axes in the anisotropic EPR spectrum; iii) the half-wave potential E(1/2) of oxidation of VO(IV) to the corresponding VO2(V) species in the cyclic voltammogram. Finally, a discussion on the possible form of VO(IV)-citrate complexes in blood serum is presented, where it is found that the most relevant species under physiological conditions should be [VO(citrH(-1))]2-.

  12. Aluminum complexes of the redox-active [ONO] pincer ligand.

    PubMed

    Szigethy, Géza; Heyduk, Alan F

    2012-07-14

    A series of aluminum complexes containing the tridentate, redox-active ligand bis(3,5-di-tert-butyl-2-phenol)amine ([ONO]H(3)) in three different oxidation states were synthesized. The aluminum halide salts AlCl(3) and AlBr(3) were reacted with the doubly deprotonated form of the ligand to afford five-coordinate [ONHO(cat)]AlX(solv) complexes (1a, X = Cl, solv = OEt(2); 1b, X = Br, solv = THF), each having a trigonal bipyramidal coordination geometry at the aluminum and containing the [ONHO(cat)](2-) ligand with a protonated, sp(3)-hybridized nitrogen donor. The [ONO] ligand platform may also be added to aluminum through the use of the oxidized ligand salt [ONO(q)]K, which was reacted with AlCl(3) in the presence of either diphenylacetylacetonate (acacPh(2)(-)) or 8-oxyquinoline (quinO(-)) to afford [ONO(q)]Al(acacPh(2))Cl (2) or [ONO(q)]Al(quinO)Cl (3), respectively, with well-defined [ONO(q)](-) ligands. Quinonate complexes 2 and 3 were reduced by one electron to afford the corresponding complexes K{[ONO(sq)]Al(acacPh(2))(py)} (4) and K{[ONO(sq)]Al(quinO)(py)} (5), respectively, containing well-defined [ONO(sq)](2-) ligands. The addition of tetrachloro-1,2-quinone to 1a in the presence of pyridine resulted in the expulsion of HCl and the formation of an aluminum complex with two different redox active ligands, [ONO]Al(o-O(2)C(6)Cl(4))(py) (6). Similar results were obtained when 1a was reacted with 9,10-phenanthrenequinone to afford [ONO]Al(o-O(2)C(14)H(8))(py) (7) or with pyrene-4,5-dione to afford [ONO]Al(o-O(2)C(16)H(8))(py) (8). Structural, spectroscopic and preliminary magnetic measurements on 6-8 suggest ligand non-innocent redox behavior in these complexes. PMID:22669327

  13. Ammine(2,2′-bipyridine-κ2 N,N′)silver(I) nitrate: a dimer formed by π–π stacking and ligand-unsupported Ag⋯Ag inter­actions

    PubMed Central

    Sun, Di; Zhang, Na; Luo, Geng-Geng; Huang, Rong-Bin; Zheng, Lan-Sun

    2010-01-01

    Reaction of AgNO3 and 2,2′-bipyridine (bipy) under ultrasonic treatment gave the title compound, [Ag(C10H8N2)(NH3)]NO3. The crystal structure consists of dimers formed by two symmetry-related AgI–bipy monomers connected through intra-dimer π–π stacking and ligand-unsupported Ag⋯Ag inter­actions. A crystallographic C2 axis passes through the mid-point of and is perpendicular to the Ag⋯Agi(−x + 1, y, −z + ) axis. In addition, each AgI cation is coordinated by one chelating bipy ligand and one ammine ligand, giving a trigonal coordination environment capped by the symmetry-equivalent Ag atom. Mol­ecules are assembled by Ag⋯Ag, π–π, hydrogen-bond (N—H⋯O and C—H⋯O) and weak Ag⋯π inter­actions into a three-dimensional framework. Comparing the products synthesized under different mechanical treatments, we found that reaction conditions have a significant influence on the resulting structures. The luminescence properties of the title compound are also discussed. PMID:20203399

  14. Donor Telomere Length SAA

    Cancer.gov

    A new NCI study has found that, among patients with severe aplastic anemia who received a hematopoietic cell transplant from an unrelated donor, those whose donor white blood cells had longer telomeres had higher survival rates five-years after transplant

  15. Rich Donors, Poor Countries

    ERIC Educational Resources Information Center

    Thomas, M. A.

    2012-01-01

    The shifting ideological winds of foreign aid donors have driven their policy towards governments in poor countries. Donors supported state-led development policies in poor countries from the 1940s to the 1970s; market and private-sector driven reforms during the 1980s and 1990s; and returned their attention to the state with an emphasis on…

  16. Dealing with Donor Anger.

    ERIC Educational Resources Information Center

    McNamee, Mike

    1995-01-01

    Techniques that reduce donors' resistance to college fund-raising requests, either direct mail or telephone solicitations, are offered. These include: respecting the prospects' concerns about privacy; offering nonintrusive giving options; honesty and clarity of communication; reinforcing donor sense of control; connecting with prospects'…

  17. Synthesis and structural characterization of zinc(II) and cobalt(II) complexes based on multidentate hydrazone ligands

    NASA Astrophysics Data System (ADS)

    Li, Li; Zhang, Yuan Zhuo; Liu, E.; Yang, Chengxiong; Golen, James A.; Rheingold, Arnold L.; Zhang, Guoqi

    2016-04-01

    Two multidentate Schiff base ligands containing a hydrazone unit have been synthesized and investigated for zinc(II) and cobalt(II) coordination chemistry. The reactions of the 4-pyridyl derived hydrazone ligand HL1 with zinc(II) or cobalt(II) salts gave three mononuclear complexes that were structurally characterized by X-ray diffraction analysis. The results revealed that the ligand could adopt different coordination modes when various counter anions were employed. While in the case that zinc dichloride was used as a metal salt a neutral mononuclear mono-ligand complex was formed, the deprotonation of hydrazone occurred when zinc(II) or cobalt(II) nitrate were present and two new isostructural mononuclear bis-ligand complexes were isolated. Modification of the hydrazone ligand with oxygen donors was found to have a significant impact on the ligand reactivity, and a similar reaction of H2L2 with cobalt(II) nitrate gave a protonated product of H2L2 without the incorporation of cobalt(II), which features a one-dimensional hydrogen-bonded network in the solid state.

  18. Mixed ligand ruthenium(III) complexes of benzaldehyde 4-methyl-3-thiosemicarbazones with triphenylphosphine/triphenylarsine co-ligands: Synthesis, DNA binding, DNA cleavage, antioxidative and cytotoxic activity

    NASA Astrophysics Data System (ADS)

    Sampath, K.; Sathiyaraj, S.; Raja, G.; Jayabalakrishnan, C.

    2013-08-01

    The new ruthenium(III) complexes with 4-methyl-3-thiosemicarbazone ligands, (E)-2-(2-chlorobenzylidene)-N-methylhydrazinecarbothioamide (HL1) and (E)-2-(2-nitrobenzylidene)-N-methylhydrazinecarbothioamide (HL2), were prepared and characterized by various physico-chemical and spectroscopic methods. The title compounds act as bidentate, monobasic chelating ligands with S and N as the donor sites and are preferably found in the thiol form in all the complexes studied. The molecular structure of HL1 and HL2 were determined by single crystal X-ray diffraction method. DNA binding of the ligands and complexes were investigated by absorption spectroscopy and IR spectroscopy. It reveals that the compounds bind to nitrogenous bases of DNA via intercalation. The oxidative cleavage of the complexes with CT-DNA inferred that the effects of cleavage are dose dependent. Antioxidant study of the ligands and complexes showed the significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of the ligands and complexes against MCF-7 cell line was assayed which showed higher cytotoxic activity with the lower IC50 values indicating their efficiency in killing the cancer cells even at low concentrations.

  19. An elusive vinyl radical isolated as an appended unit in a five-coordinate Co(iii)-bis(iminobenzosemiquinone) complex formed via ligand-centered C-S bond cleavage.

    PubMed

    Sarkar, Prasenjit; Tiwari, Archana; Sarmah, Amrit; Bhandary, Subhrajyoti; Roy, Ram Kinkar; Mukherjee, Chandan

    2016-08-23

    Redox-active ligand H4Pra(edt(AP/AP)) experienced C-S bond cleavage during complexation reaction with Co(OAc)2·2H2O in the presence of Et3N in CH3OH in air. Thus, formed complex 1 was composed of two iminobenzosemiquinone radicals in its coordination sphere and an unprecedented stable tethered-vinyl radical. The complex has been characterized by mass, X-ray single crystal, X-band EPR, variable-temperature magnetic moment measurements and DFT based computational study.

  20. Sperm donors describe the experience of contact with their donor-conceived offspring.

    PubMed

    Hertz, R; Nelson, M K; Kramer, W

    2015-01-01

    This study explores the attitudes and experiences of 57 sperm donors who responded to a survey posted online in the United States and indicated that they had had contact with their donor-conceived offspring or the parents of their donor-conceived offspring. On average, 18 years had elapsed since the respondents donated sperm. In the interim between donating and having contact with offspring, most had become curious about their offspring. Most made contact through a bank or online registry. Most respondents had communicated with at least one offspring at least once and most had exchanged photos with offspring. Approximately two-thirds had met in person once; the same proportion had communicated over email or text. Other forms of communication were less common. Almost half of the respondents now considered their donor-conceived offspring to be like a family member. At the same time, donors are respectful of the integrity of the family in which their offspring were raised. Donors with contact are open to having their partners and children know their donor-conceived offspring. Although contact is generally positive, donors report that establishing boundaries and defining the relationship can be very difficult. Some donors also urge those who are thinking of donating to consider the consequences and some suggest avoiding anonymity. There were no significant differences in attitudes and experiences between those who donated anonymously and those who had been identity-release for their offspring when they turned 18. PMID:26175887

  1. Sperm donors describe the experience of contact with their donor-conceived offspring

    PubMed Central

    Hertz, R.; Nelson, M.K.; Kramer, W.

    2015-01-01

    This study explores the attitudes and experiences of 57 sperm donors who responded to a survey posted online in the United States and indicated that they had had contact with their donor-conceived offspring or the parents of their donor-conceived offspring. On average, 18 years had elapsed since the respondents donated sperm. In the interim between donating and having contact with offspring, most had become curious about their offspring. Most made contact through a bank or online registry. Most respondents had communicated with at least one offspring at least once and most had exchanged photos with offspring. Approximately two-thirds had met in person once; the same proportion had communicated over email or text. Other forms of communication were less common. Almost half of the respondents now considered their donor-conceived offspring to be like a family member. At the same time, donors are respectful of the integrity of the family in which their offspring were raised. Donors with contact are open to having their partners and children know their donor-conceived offspring. Although contact is generally positive, donors report that establishing boundaries and defining the relationship can be very difficult. Some donors also urge those who are thinking of donating to consider the consequences and some suggest avoiding anonymity. There were no significant differences in attitudes and experiences between those who donated anonymously and those who had been identity-release for their offspring when they turned 18. PMID:26175887

  2. Expanding the live kidney donor pool: ethical considerations regarding altruistic donors, paired and pooled programs.

    PubMed

    Patel, Shaneel Rajendra; Chadha, Priyanka; Papalois, Vassilios

    2011-06-01

    In renal transplant, there is a well-known deficiency in organ supply relative to demand. Live donation provides superior results when compared with deceased donation including a better rate of graft success and fewer immunologic complications. This deficiency in organs leads to significant morbidity and mortality rates. Alternative avenues have been extensively explored that may expand the live donor pool. They include altruistic donation as well as paired and pooled exchange programs. Altruistic donation is a truly selfless act from a donor unknown to the recipient. Kidney paired donation involves 2 incompatible donor-recipient pairs swapping donors to produce compatibility. Pooled donation involves at least 2 pairs, and can take the form of domino chains in which altruistic input sets up a chain of transplants, in which each recipient's incompatible donor makes a donation for the next recipient. Despite application of these various methods, there lie extensive ethical issues surrounding them. Misconceptions frequently occur; for instance, the perceived benefit that donating an organ to a loved one is greater for a related donor than for an altruistic one. Additionally, it is frequently believed that immunologic incompatibility offers coerced donors liberation from surgery, and that overcoming these barriers by introducing exchange programs provides vulnerable donors less protection. This article explores these and other complex ethical issues surrounding the various methods of expanding the donor pool. The authors offer opinions that challenge the ethical issues and attempt to overcome those views that hinder progress in the field. PMID:21649566

  3. Surveying sterically demanding N-heterocyclic carbene ligands with restricted flexibility for palladium-catalyzed cross-coupling reactions.

    PubMed

    Würtz, Sebastian; Glorius, Frank

    2008-11-18

    Heterocyclic carbenes (NHCs), especially monodentate ones, have become the ligand of choice for many transition-metal-catalyzed transformations. They generally form highly stable complexes, have strong sigma-donor character, and have a unique shape that can be used to generate sterically demanding ligands.In this Account, we survey recent developments in the design and synthesis of some sterically demanding NHCs with a particularly strong influence on the metal's coordination sphere. We show the successful and insightful application of these ligands in transition-metal catalysis. First, we discuss methods for determining and classifying the electronic and steric properties of NHCs. In addition, we present data on the most important NHC ligands.The selective variation of either electronic or steric parameters of NHCs, and therefore of the catalyst, allows for the optimization of the reaction. Thus, we prepared several series of differentially substituted NHC derivatives. However, because the substituents varied were not directly connected to the carbene carbon, it was difficult to induce a large electronic variation. In contrast, an independent variation of the ligands' steric properties was more straightforward. We highlight three different classes of very sterically demanding NHCs that allow this kind of a steric variation: imidazo[1,5-a]pyridine-3-ylidenes, bioxazoline-derived carbenes (IBiox), and cyclic (alkyl)(amino)carbenes (CAAC).These latter NHC ligands can facilitate a number of challenging cross-coupling reactions. Successful transformations often require a monoligated palladium complex as the catalytically active species, and the sterically demanding NHC ligand favors this monoligated complex. In addition, the electron-rich NHC facilitates difficult oxidative addition steps. Moreover, the conformational flexibility of the ligands can facilitate the formation of catalytically active species and hemilabile interactions, such as agostic or anagostic bonds

  4. Donor-acceptor-donor tetrazines containing a ferrocene unit: synthesis, electrochemical and spectroscopic properties.

    PubMed

    Janowska, Izabela; Miomandre, Fabien; Clavier, Gilles; Audebert, Pierre; Zakrzewski, Janusz; Thi, Khuyen Hoang; Ledoux-Rak, Isabelle

    2006-11-30

    Donor-acceptor-donor tetrazines containing ferrocene moieties and phenyl unit as a pi-bridge have been synthesized and characterized. UV-vis spectroscopic and cyclic voltamperometric results indicate sizable intramolecular charge transfer interactions in the ground state when the ferrocene is directly bound to the tetrazine. On the other hand, the results show reduction of the electron-donor strength of ferrocene moieties when there is a phenyl linkage. Both tetrazines display a high reduction potential. The role of ferrocenyl groups appear to be detrimental to maximize the cubic hyperpolarizability gamma of tetrazines, as compared to purely organic groups such as thiophene. A possible explanation for this behavior may originate from metal-to-ligand charge transfer processes.

  5. Crystal structure of a tetranuclear Cu(II) complex with an O,N,N'-donor Schiff base ligand: hexa-μ2-acetato-bis-(2-{[(2,2,6,6-tetra-methyl-piperidin-4-yl)imino]-meth-yl}phenolato-κ(3) O,N,N')tetra-copper(II).

    PubMed

    Huang, Guohui; Liu, Xiaoxuan

    2016-04-01

    The title compound, [Cu4(CH3COO)6(C16H23N2O)2], lies across a twofold rotation axis. The asymmetric unit contains two independent Cu(II) ions. The symmetry-unique terminal Cu(II) ion is O,N,N'-coordinated by a 2-{[(2,2,6,6-tetra-methyl-piperidin-4-yl)imino]-meth-yl}phenolate ligand and an O atom from an acetate group in a slightly distorted square-planar coordination environment. The symmetry-unique central Cu(II) ion is coordinated by a different O atom from the same acetate group and by four bridging acetate ligands, which connect the asymmetric unit into a dimeric complex and form a distorted square-pyramidal coordination environment. Within the complex there are two symmetry-equivalent intra-molecular N-H⋯O hydrogen bonds. In the crystal, weak C-H⋯O hydrogen bonds link the complex mol-ecules, forming a three-dimensional network. PMID:27375896

  6. A series of Zn/Cd coordination polymers constructed from 1,4-naphthalenedicarboxylate and N-donor ligands: Syntheses, structures and luminescence sensing of Cr3+ in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Hu, Dong-Cheng; Fan, Yan; Si, Chang-Dai; Wu, Ya-Jun; Dong, Xiu-Yan; Yang, Yun-Xia; Yao, Xiao-Qiang; Liu, Jia-Cheng

    2016-09-01

    A novel series of Zn/Cd coordination polymers based on H3L, namely, [Zn2(HL)2(bipy)2(H2O)6]n (1), [Zn(HL)(phen)]n (2), [Cd3L2(bbi)3]n (3), [Zn3L2(bbi)3]n (4) [(H3L =4-[(1-carboxynaphthalen-2-yl)oxy]phthalic acid, bipy =4,4‧-bipyridine, phen =1,10-phenanthroline, bbi =1,1‧-(1,4-butanediyl)bis(imidazole] have been successfully synthesized by solvothermal reaction. Compound 1 possesses two diverse 1D chains constructed by different bipy coligands, which were further connected to form a 3D supramolecular architecture by hydrogen bonding interactions. Compound 2 possesses a complicated 1D chain based on secondary building unit (SBU) with binuclear Zn cluster. Compounds 3 and 4 exhibit similar 2D→3D framework, which can be rationalized as (3,4,4)-connected 3D net with a Schläfli symbol of (63.8.102)2(63)2(64.8.10). In particular, compound 3 exhibited a high sensitivity for Cr3+ in aqueous solutions, which suggest that compound 3 is a promising luminescent probe for selectively sensing Cr3+.

  7. Synthesis, and characterization of low- and high-spin manganese(II) complexes of polyfunctional adipoyldihydrazone: Effect of coordination of N-donor ligands on stereo-redox chemistry

    NASA Astrophysics Data System (ADS)

    Basumatary, Debajani; Lal, Ram Ashray; Kumar, Arvind

    2015-07-01

    Manganese(II) complexes [MnII(npahH2)] (1), [MnII(npahH2)(A)2] and [MnII(npahH2)(NN)] (where A = pyridine, (2); 2-picoline, (3); 3-picoline, (4); 4-picoline, (5) and NN = 2,2‧ bipyridine, (6); 1,10-phenanthroline, (7)) have been synthesized from bis(2-hydroxy-1-naphthaldehyde)adipoyldihydrazone (npahH4) in methanol. The composition of metal complexes has been established by elemental analyses. Complexes (1) and (3) have been characterized by mass spectral data also. Structural assessments of the complexes have been based on data obtained from molar conductance, magnetic moment, electronic, electron paramagnetic resonance and infrared spectral studies. Conductivity measurements in DMSO suggest that they are non-electrolyte. Electronic spectral studies suggest a six-coordinate octahedral geometry around the manganese center in complexes (2) to (7) and square-planar geometry in complex (1). IR spectral studies reveal that the dihydrazone coordinates to the metal in keto form with an anti-cis configuration. Magnetic moment, and EPR studies suggest manganese in +2 oxidation state in all complexes with high-spin distorted octahedral stereochemistry in complexes (2-7) while low-spin square-planar stereochemistry is involved with significant metal-metal interactions in the solid state in complex (1). Cyclic voltammetric studies reveal that the metal center cycles among the MnII → MnI → Mn0 in complexes (2) to (7) and among MnII → MnI oxidation states in complex (1).

  8. Four-Electron Donor Hemilabile n3-PPh3 Ligand that Binds Through a C = C Bond Rather than an Agostic C-H Interaction, and Displacement of the C = C by Methyl Iodide or Water

    SciTech Connect

    Cheng, Tan-Yun; Szalda, David J.; Hanson, Jonathan C.; Muckerman, J. T.; Bullock, R. Morris

    2008-07-12

    Hydride transfer from Cp(CO)2(PPh3)MoH to Ph3C+ BAr'4 [Ar' = 3,5-bis(trifluoromethyl)phenyl] produces [Cp(CO)23 PPh3)Mo]+[BAr'4] . Spectroscopic and crystallographic data indicate that one C=C of a Ph ring is weakly bound to the Mo, so that the PPh3 ligand is four-electron donor ligand. Computations (DFT/B3LYP and MP2 on [Cp(CO)23 PPh3)Mo]+ and [Cp(CO)23 PH2Ph)Mo]+, and DFT/B3LYP on [Cp(CO)23 PHtBuPh)Mo]+ and [Cp(CO)23 PH2Ph)Nb]) provide further information on the bonding, and on the preference for bonding of the metal to the C=C bond rather than an agostic C H interaction found in many related complexes. The hemilabile C=C bond is readily displaced by CH3I or H2O, and crystal structures are reported for [Cp(CO)2(PPh3)Mo(ICH3)]+ and [Cp(CO)2(PPh3)Mo(OH2)]+. The equilibrium constant for [Cp(CO)23 PPh3)Mo]+ + ICH3 to give [Cp(CO)2(PPh3)Mo(ICH3)]+ is Keq = 5.2 x 102 M -1 in CD2Cl2 at 22 °C.

  9. Switching on oxygen activation by cobalt complexes of pentadentate ligands.

    PubMed

    Vad, Mads S; Nielsen, Anne; Lennartson, Anders; Bond, Andrew D; McGrady, John E; McKenzie, Christine J

    2011-10-28

    The monoanionic N(4)O ligand N-methyl-N,N'-bis(2-pyridylmethyl)ethylenediamine-N'-acetate (mebpena(-)) undergoes oxidative C-N bond cleavage in the presence of Co(II) and O(2). The two resultant fragments are coordinated to the metal ion in the product [Co(III)(2-pyridylformate)(mepena)]ClO(4) (mepena(-) = N-methyl-N'-(2-pyridylmethyl)ethylenediamine-N'-acetato). Bond cleavage does not occur in the presence of chloride ions and [Co(III)(mebpena)Cl](+), containing intact mebpena(-), can be isolated. The oxidative instability of the mebpena(-) in the presence of Co(II) and air stands in contrast to the oxidative stability of the family of very closely related penta- and hexa-dentate ligands in their cobalt complexes. Cyclic voltammetry on the matched pair [Co(III)Cl(mebpena)](+) and [Co(II)Cl(bztpen)](+), bztpen = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine, shows that substitution of a pyridine donor for a carboxylato donor results in a relatively small cathodic shift of 150 mV in the E°(Co(II)/Co(III)) oxidation potential, presumably this is enough to determine the contrasting metal oxidation state in the complexes isolated under ambient conditions. DFT calculations support a proposal that [Co(II)(mebpena)](+) reacts with O(2) to form a Co(III)-superoxide complex which can abstract an H atom from a ligand methylene C atom as the initial step towards the observed oxidative C-N bond cleavage.

  10. Mixed ligand complexes of bis(phenylimine) Schiff base ligands incorporating pyridinium moiety. Synthesis, characterization and antibacterial activity

    NASA Astrophysics Data System (ADS)

    Mohamed, Gehad G.; El-Wahab, Zeinab H. Abd

    2005-04-01

    The synthesis and structural characterization of mixed ligand complexes derived from 2,6-pyridinedicarboxaldehydebis( o-hydroxyphenylimine), 2,6-pyridinedicarboxaldehydebis( p-hydroxyphenylimine) (1 ry ligands) and 2-aminopyridne (2 ry ligand) are reported. The ligands and their transition metal complexes were characterized on the bases of their elemental analyses, IR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The mixed ligand complexes are formed in the 1:1:1 (M:L 1 or L 2:L') ratio as found from the elemental analyses and found to have the formulae [MX 2(L 1 or L 2)(L')]· nH 2O where M = Co(II), Ni(II), Cu(II) and Zn(II), L 1 = 2,6-pyridinedicarboxaldehydebis( p-hydroxyphenylimine), L 2 = 2,6-pyridine dicarboxaldehydebis( o-hydroxyphenylimine), L' = 2-aminopyridine, X = Cl - in case of Cu(II) complex and Br - in case of Co(II), Ni(II) and Zn(II) complexes and y = 0-3. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the Schiff bases are coordinated to the metal ions in a terdentate manner with NNN donor sites of the pyridine- N and two azomethine- N. While 2-aminopyridine coordinated to the metal ions via its pyridine- N. Magnetic and solid reflectance spectra are used to infer the coordinating capacity of the ligand and the geometrical structure of these complexes are found to be octahedral. The thermal behaviour of these chelates shows that the hydrated water molecules and the anions are removed in a successive two steps followed immediately by decomposition of the ligands (L 1, L 2 and L') in the subsequent steps. The activation thermodynamic parameters, such as, E*, Δ H*, Δ S* and Δ G* are calculated from the TG curves and discussed. The ligands and their metal chelates have been screened for their antimicrobial activities and the findings have been reported, explained and compared with some known antibiotics.

  11. A novel homozygous Fas ligand mutation leads to early protein truncation, abrogation of death receptor and reverse signaling and a severe form of the autoimmune lymphoproliferative syndrome.

    PubMed

    Nabhani, Schafiq; Hönscheid, Andrea; Oommen, Prasad T; Fleckenstein, Bernhard; Schaper, Jörg; Kuhlen, Michaela; Laws, Hans-Jürgen; Borkhardt, Arndt; Fischer, Ute

    2014-12-01

    We report a novel type of mutation in the death ligand FasL that was associated with a severe phenotype of the autoimmune lymphoproliferative syndrome in two patients. A frameshift mutation in the intracellular domain led to complete loss of FasL expression. Cell death signaling via its receptor and reverse signaling via its intracellular domain were completely abrogated. In vitro lymphocyte proliferation induced by weak T cell receptor stimulation could be blocked and cell death was induced by engagement of FasL in T cells derived from healthy individuals and a heterozygous carrier, but not in FasL-deficient patient derived cells. Expression of genes implicated in lymphocyte proliferation and activation (CCND1, NFATc1, NF-κB1) was increased in FasL-deficient T cells and could not be downregulated by FasL engagement as in healthy cells. Our data thus suggest, that deficiency in FasL reverse signaling may contribute to the clinical lymphoproliferative phenotype of ALPS. PMID:25451160

  12. Triple helices formed at oligopyrimidine*oligopurine sequences with base pair inversions: effect of a triplex-specific ligand on stability and selectivity.

    PubMed Central

    Kukreti, S; Sun, J S; Loakes, D; Brown, D M; Nguyen, C H; Bisagni, E; Garestier, T; Helene, C

    1998-01-01

    Oligonucleotide-directed triple helix formation is mostly restricted to oligopyrimidine*oligopurine sequences of double helical DNA. An interruption of one or two pyrimidines in the oligopurine target strand leads to a strong triplex destabilisation. We have investigated the effect of nucleotide analogues introduced in the third strand at the site opposite the base pair inversion(s). We show that a 3-nitropyrrole derivative (M) discriminates G*C from C*G, A*T and T*A in the presence of a triplex-specific ligand (a benzo[e]pyridoindole derivative, BePI). N6-methoxy-2,6-diaminopurine (K) binds to an A*T base pair better than a T*A, G*C or C*G base pair. Some discrimination is still observed in the presence of BePI and triplex stability is markedly increased. These findings should help in designing BePI-oligonucleotide conjugates to extend the range of DNA sequences available for triplex formation. PMID:9547278

  13. Cadaveric donor selection and management.

    PubMed

    Studer, Sean M; Orens, Jonathan B

    2006-10-01

    While there is little doubt that proper donor selection is extremely important to achieve good outcomes from transplantation, there are only limited data regarding the current criteria utilized to select the "ideal donor". Importantly, there are not enough donor lungs available for all of those in need. Until an adequate supply of donor organs exists, lives will be lost on the transplant waiting list. While efforts have been made to increase donor awareness, additional transplants can be realized by improving donor utilization. This can be achieved by active participation of transplant teams in donor management and by utilizing "extended criteria" organs. Further studies are needed to assess the impact of using "extended criteria" donors, as this practice could result in increased posttransplant morbidity and mortality. This article summarizes the approach to identification of potential lung donors, optimal donor management, and the clinical importance of various donor factors upon recipient outcomes.

  14. Laparoscopic donor nephrectomy.

    PubMed

    Deger, S; Giessing, M; Roigas, J; Wille, A H; Lein, M; Schönberger, B; Loening, S A

    2005-01-01

    Laparoscopic live donor nephrectomy (LDN) has removed disincentives of potential donors and may bear the potential to increase kidney donation. Multiple modifications have been made to abbreviate the learning curve while at the same time guarantee the highest possible level of medical quality for donor and recipient. We reviewed the literature for the evolution of the different LDN techniques and their impact on donor, graft and operating surgeon, including the subtleties of different surgical accesses, vessel handling and organ extraction. We performed a literature search (PubMed, DIMDI, medline) to evaluate the development of the LDN techniques from 1995 to 2003. Today more than 200 centres worldwide perform LDN. Hand-assistance has led to a spread of LDN. Studies comparing open and hand-assisted LDN show a reduction of operating and warm ischaemia times for the hand-assisted LDN. Different surgical access sites (trans- or retroperitoneal), different vessel dissection approaches, donor organ delivery techniques, delivery sites and variations of hand-assistance techniques reflect the evolution of LDN. Proper techniques and their combination for the consecutive surgical steps minimize both warm ischaemia time and operating time while offering the donor a safe minimally invasive laparoscopic procedure. LDN has breathed new life into the moribund field of living kidney donation. Within a few years LDN could become the standard approach in living kidney donation. Surgeons working in this field must be trained thoroughly and well acquainted with the subtleties of the different LDN techniques and their respective advantages and disadvantages. PMID:16754618

  15. Silyl phosphorus and nitrogen donor chelates for homogeneous ortho borylation catalysis.

    PubMed

    Ghaffari, Behnaz; Preshlock, Sean M; Plattner, Donald L; Staples, Richard J; Maligres, Peter E; Krska, Shane W; Maleczka, Robert E; Smith, Milton R

    2014-10-15

    Ir catalysts supported by bidentate silyl ligands that contain P- or N-donors are shown to effect ortho borylations for a range of substituted aromatics. The substrate scope is broad, and the modular ligand synthesis allows for flexible catalyst design.

  16. Silyl Phosphorus and Nitrogen Donor Chelates for Homogeneous Ortho Borylation Catalysis

    PubMed Central

    2015-01-01

    Ir catalysts supported by bidentate silyl ligands that contain P- or N-donors are shown to effect ortho borylations for a range of substituted aromatics. The substrate scope is broad, and the modular ligand synthesis allows for flexible catalyst design. PMID:25141136

  17. Distinctive Characteristics of Educational Donors

    ERIC Educational Resources Information Center

    James, Russell N., III.

    2008-01-01

    Examining the charitable behavior of 56,663 US households, this paper evaluates the distinctive characteristics of educational donors as compared with donors to noneducational charitable organizations and with nondonors. In general, educational donors had significantly greater income, wealth, and education than other donors. Educational donors…

  18. Independent donor ethical assessment: aiming to standardize donor advocacy.

    PubMed

    Choudhury, Devasmita; Jotterand, Fabrice; Casenave, Gerald; Smith-Morris, Carolyn

    2014-06-01

    Living organ donation has become more common across the world. To ensure an informed consent process, given the complex issues involved with organ donation, independent donor advocacy is required. The choice of how donor advocacy is administered is left up to each transplant center. This article presents the experience and process of donor advocacy at University of Texas Southwestern Medical Center administered by a multidisciplinary team consisting of physicians, surgeons, psychologists, medical ethicists and anthropologists, lawyers, a chaplain, a living kidney donor, and a kidney transplant recipient. To ensure that advocacy remains fair and consistent for all donors being considered, the donor advocacy team at University of Texas Southwestern Medical Center developed the Independent Donor Ethical Assessment, a tool that may be useful to others in rendering donor advocacy. In addition, the tool may be modified as circumstances arise to improve donor advocacy and maintain uniformity in decision making.

  19. Independent donor ethical assessment: aiming to standardize donor advocacy.

    PubMed

    Choudhury, Devasmita; Jotterand, Fabrice; Casenave, Gerald; Smith-Morris, Carolyn

    2014-06-01

    Living organ donation has become more common across the world. To ensure an informed consent process, given the complex issues involved with organ donation, independent donor advocacy is required. The choice of how donor advocacy is administered is left up to each transplant center. This article presents the experience and process of donor advocacy at University of Texas Southwestern Medical Center administered by a multidisciplinary team consisting of physicians, surgeons, psychologists, medical ethicists and anthropologists, lawyers, a chaplain, a living kidney donor, and a kidney transplant recipient. To ensure that advocacy remains fair and consistent for all donors being considered, the donor advocacy team at University of Texas Southwestern Medical Center developed the Independent Donor Ethical Assessment, a tool that may be useful to others in rendering donor advocacy. In addition, the tool may be modified as circumstances arise to improve donor advocacy and maintain uniformity in decision making. PMID:24919733

  20. Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance

    SciTech Connect

    Shao, Yuyan; Liu, Tianbiao L.; Li, Guosheng; Gu, Meng; Nie, Zimin; Engelhard, Mark H.; Xiao, Jie; Lu, Dongping; Wang, Chong M.; Zhang, Jiguang; Liu, Jun

    2013-11-04

    Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a coordination chemistry study of Mg(BH4)2 in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new and safer electrolyte is developed based on Mg(BH4)2, diglyme and optimized LiBH4 additive. The new electrolyte demonstrates 100% coulombic efficiency, no dendrite formation, and stable cycling performance with the cathode capacity retention of ~90% for 300 cycles in a prototype magnesium battery.

  1. Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance

    PubMed Central

    Shao, Yuyan; Liu, Tianbiao; Li, Guosheng; Gu, Meng; Nie, Zimin; Engelhard, Mark; Xiao, Jie; Lv, Dongping; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun

    2013-01-01

    Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a study in understanding coordination chemistry of Mg(BH4)2 in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new electrolyte is developed based on Mg(BH4)2, diglyme and LiBH4. The preliminary electrochemical test results show that the new electrolyte demonstrates a close to 100% coulombic efficiency, no dendrite formation, and stable cycling performance for Mg plating/stripping and Mg insertion/de-insertion in a model cathode material Mo6S8 Chevrel phase. PMID:24185310

  2. Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance

    DOE PAGESBeta

    Shao, Yuyan; Liu, Tianbiao L.; Li, Guosheng; Gu, Meng; Nie, Zimin; Engelhard, Mark H.; Xiao, Jie; Lu, Dongping; Wang, Chong M.; Zhang, Jiguang; et al

    2013-11-04

    Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a coordination chemistry study of Mg(BH4)2 in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new and safer electrolyte is developed based on Mg(BH4)2, diglyme and optimized LiBH4 additive.more » The new electrolyte demonstrates 100% coulombic efficiency, no dendrite formation, and stable cycling performance with the cathode capacity retention of ~90% for 300 cycles in a prototype magnesium battery.« less

  3. Hydroperoxides as Hydrogen Bond Donors

    NASA Astrophysics Data System (ADS)

    Møller, Kristian H.; Tram, Camilla M.; Hansen, Anne S.; Kjaergaard, Henrik G.

    2016-06-01

    Hydroperoxides are formed in the atmosphere following autooxidation of a wide variety of volatile organics emitted from both natural and anthropogenic sources. This raises the question of whether they can form hydrogen bonds that facilitate aerosol formation and growth. Using a combination of Fourier transform infrared spectroscopy, FT-IR, and ab initio calculations, we have compared the gas phase hydrogen bonding ability of tert-butylhydroperoxide (tBuOOH) to that of tert-butanol (tBuOH) for a series of bimolecular complexes with different acceptors. The hydrogen bond acceptor atoms studied are nitrogen, oxygen, phosphorus and sulphur. Both in terms of calculated redshifts and binding energies (BE), our results suggest that hydroperoxides are better hydrogen bond donors than the corresponding alcohols. In terms of hydrogen bond acceptor ability, we find that nitrogen is a significantly better acceptor than the other three atoms, which are of similar strength. We observe a similar trend in hydrogen bond acceptor ability with other hydrogen bond donors including methanol and dimethylamine.

  4. Activation of the manganese(I) tricarbonyl core by selective variation of bidentate ligands (L,L'-Bid = N,N' and N,O donor atom sets) in fac-[Mn(CO)3(L,L'-Bid)(CH3OH)](n) complexes.

    PubMed

    Twala, T N; Schutte-Smith, M; Roodt, A; Visser, H G

    2015-02-21

    A range of fac-[Mn(CO)3(L,L'-Bid)(H2O)](n) (L,L'-Bid = neutral or monoanionic bidentate ligands with varied L,L' donor atoms, N,N' and N,O, 1,10-phenanthroline, 2,2'-bipyridine, 2-picolinate, 2,4-quinolinate; n = 0, +1) has been synthesized and the methanol substitution has been investigated for the first time. The complexes were characterized by UV/vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Mn(CO)3(Bipy)(H2O)][CF3SO3] () and fac-[Mn(CO)3(Phen)(H2O)][CF3SO3] () are reported. A two order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N'-Bid) < (N,O-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k1, M(-1) s(-1); k-1, s(-1); K1, M(-1)) for pyridine as entering nucleophile are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (2.39 ± 5) × 10(-3), (1.5 ± 0.3) × 10(-5), 159 ± 32; fac-[Mn(CO)3(2,4-QuinH)(CH3OH)] (4.5 ± 0.2), (4 ± 1) × 10(-2), 113 ± 29. Activation parameters (ΔH, kJ mol(-1); ΔS, J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (bromide ions) 66.7 ± 0.6, -27 ± 2; (pyridine) 80 ± 3, -25 ± 11; fac-[Mn(CO)3(Pico)(CH3OH)] (bromide ions) 68 ± 2, -24 ± 5. A dissociative interchange mechanism is proposed.

  5. Activation of the manganese(I) tricarbonyl core by selective variation of bidentate ligands (L,L'-Bid = N,N' and N,O donor atom sets) in fac-[Mn(CO)3(L,L'-Bid)(CH3OH)](n) complexes.

    PubMed

    Twala, T N; Schutte-Smith, M; Roodt, A; Visser, H G

    2015-02-21

    A range of fac-[Mn(CO)3(L,L'-Bid)(H2O)](n) (L,L'-Bid = neutral or monoanionic bidentate ligands with varied L,L' donor atoms, N,N' and N,O, 1,10-phenanthroline, 2,2'-bipyridine, 2-picolinate, 2,4-quinolinate; n = 0, +1) has been synthesized and the methanol substitution has been investigated for the first time. The complexes were characterized by UV/vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Mn(CO)3(Bipy)(H2O)][CF3SO3] () and fac-[Mn(CO)3(Phen)(H2O)][CF3SO3] () are reported. A two order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N'-Bid) < (N,O-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k1, M(-1) s(-1); k-1, s(-1); K1, M(-1)) for pyridine as entering nucleophile are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (2.39 ± 5) × 10(-3), (1.5 ± 0.3) × 10(-5), 159 ± 32; fac-[Mn(CO)3(2,4-QuinH)(CH3OH)] (4.5 ± 0.2), (4 ± 1) × 10(-2), 113 ± 29. Activation parameters (ΔH, kJ mol(-1); ΔS, J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (bromide ions) 66.7 ± 0.6, -27 ± 2; (pyridine) 80 ± 3, -25 ± 11; fac-[Mn(CO)3(Pico)(CH3OH)] (bromide ions) 68 ± 2, -24 ± 5. A dissociative interchange mechanism is proposed. PMID:25598494

  6. Understanding Philanthropic Motivations of Northeast State Community College Donors

    ERIC Educational Resources Information Center

    Cook, Heather J.

    2012-01-01

    At Northeast State Community College (NeSCC) nearly 70% of students need some form of financial aid to attend. State support is flattening or decreasing and the gap is filled by private donors' support (Northeast State Community College, 2011). Hundreds of donors have made significant contributions to aid in the education of those in the…

  7. Drawing Mononuclear Octahedral Coordination Compounds Containing Tridentate Chelating Ligands

    ERIC Educational Resources Information Center

    Mohamadou, Aminou; Ple, Karen; Haudrechy, Arnaud

    2011-01-01

    Complexes with tridentate ligands of the type [M(A-B-C)2], where A [not equal to] B [not equal to] C and with an imposed bonding sequence A-B-C, require special attention to draw all possible stereoisomers. Depending on the nature of the central donor atom B of the tridentate ligand, an easy drawing method is presented that shows seven chiral…

  8. New carbon- and sulfur-based ligands in catalysis.

    PubMed

    Dorta, Reto

    2011-01-01

    Homogeneous catalysis is a field of research that has gained central importance in both organic and inorganic chemistry and the use of well-defined ligand systems in the synthesis of transition metal complexes has had an enormous impact on the development of such catalysts. Neutral, two-electron donor ligands based on phosphorous and nitrogen have been tremendously successful as ancillary entities for late-transition metal (LTM) catalysts, whereas ligands based on anionic nitrogen, oxygen and the cyclopentadienyl motif (Cp(-)) have propelled early-transition metal (ETM) catalysis forward. We believe that expanding the ligand families capable of acting as successful entities in metal-mediated reactivity and catalysis is crucial for future discoveries in this field. Research in our group therefore tries to identify new non-chiral and chiral ligands for late-transition metal chemistry that are based on neutral, two-electron carbon and sulfur donor atoms. In particular, we have until now focused on the development of modular, monodentate N-heterocyclic carbene ligands (NHCs) that can serve as a basis for the development of chiral ligand frameworks for the application to asymmetric catalytic transformations. In the second major research project developed over the last six years, we have started an investigation on the use of chelating sulfoxide-based ligands in asymmetric late transition-metal based catalysis.

  9. Synthesis, Characterization and Biological Evaluation of Transition Metal Complexes Derived from N, S Bidentate Ligands

    PubMed Central

    Md Yusof, Enis Nadia; Ravoof, Thahira Begum S. A.; Tiekink, Edward R. T.; Veerakumarasivam, Abhimanyu; Crouse, Karen Anne; Mohamed Tahir, Mohamed Ibrahim; Ahmad, Haslina

    2015-01-01

    Two bidentate NS ligands were synthesized by the condensation reaction of S-2-methylbenzyldithiocarbazate (S2MBDTC) with 2-methoxybenzaldehyde (2MB) and 3-methoxybenzaldehyde (3MB). The ligands were reacted separately with acetates of Cu(II), Ni(II) and Zn(II) yielding 1:2 (metal:ligand) complexes. The metal complexes formed were expected to have a general formula of [M(NS)2] where M = Cu2+, Ni2+, and Zn2+. These compounds were characterized by elemental analysis, molar conductivity, magnetic susceptibility and various spectroscopic techniques. The magnetic susceptibility measurements and spectral results supported the predicted coordination geometry in which the Schiff bases behaved as bidentate NS donor ligands coordinating via the azomethine nitrogen and thiolate sulfur. The molecular structures of the isomeric S2M2MBH (1) and S2M3MBH (2) were established by X-ray crystallography to have very similar l-shaped structures. The Schiff bases and their metal complexes were evaluated for their biological activities against estrogen receptor-positive (MCF-7) and estrogen receptor-negative (MDA-MB-231) breast cancer cell lines. Only the Cu(II) complexes showed marked cytotoxicity against the cancer cell lines. Both Schiff bases and other metal complexes were found to be inactive. In concordance with the cytotoxicity studies, the DNA binding studies indicated that Cu(II) complexes have a strong DNA binding affinity. PMID:25988384

  10. Why Minority Donors Are Needed

    MedlinePlus

    ... Español Search Register with your state as an Organ Donor Home Why Donate Becoming a Donor About Donation & ... Why Donate RELATED INFORMATION Minority Focused Grantee Publications Organ Donation Process Enrolling as a Donor Trying to Save a Life Testing for Brain ...

  11. [Pd4(μ3-SbMe3)4(SbMe3)4]: A Pd(0) Tetrahedron with μ3-Bridging Trimethylantimony Ligands.

    PubMed

    Benjamin, Sophie L; Krämer, Tobias; Levason, William; Light, Mark E; Macgregor, Stuart A; Reid, Gillian

    2016-06-01

    The palladium(II) chlorostibine complex [PdCl2(SbMe2Cl)2]2 has a dimeric structure in the solid state, stabilized by hyper-coordination at the Lewis amphoteric Sb centers. Reaction with 8 equiv of MeLi forms [Pd4(μ3-SbMe3)4(SbMe3)4], whose structure comprises a tetrahedral Pd(0) core with four terminal SbMe3 ligands and four μ3-SbMe3 ligands, one capping each triangular Pd3 face. Density functional theory calculations, supported by energy decomposition analysis and the natural orbitals for chemical valence scheme, highlight significant donor and acceptor orbital contributions to the bonding between both the terminal and the bridging SbMe3 ligands and the Pd4 core.

  12. Syntheses and structural characterization of mercury (II) coordination polymers with neutral bidentate flexible pyrazole-based ligands

    NASA Astrophysics Data System (ADS)

    Lalegani, Arash; Khaledi Sardashti, Mohammad; Salavati, Hossein; Asadi, Amin; Gajda, Roman; Woźniak, Krzysztof

    2016-03-01

    Mercury(II) coordination compounds [Hg(μ-bbd)(μ-SCN)4]n(1) and [Hg(bpp)(SCN)2] (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(3,5-dimethypyrazol-1-yl)butane (bbd) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp), NCS- ligand and appropriate mercury(II) salts. Compound 1 forms a polymeric network with moieties which are connected by SCN groups and the mercury ions present as HgN3S2 trigonal bipyramides. The crystal structure of 2 is build of monomers and the mercury(II) ion adopts an HgN2S2 tetrahedral geometry. In the complex 1, each bbd acts as bridging ligand connecting Hg(μ-SCN)4 ions, while in the complex 2, the bpp ligand is coordinated to an mercury(II) ion in a cyclic-bidentate fashion forming an eight-membered metallocyclic ring. Moreover, in the tetrahedral structure of 2, the neutral molecules form a 1D chain structure through the C-H···N hydrogen bonds, whereas in 1 no hydrogen bonds are observed. Coordination compounds 1 and 2 have been characterized by infrared spectroscopy, elemental analyses and single-crystal X-ray diffraction.

  13. Conformational readout of RNA by small ligands

    PubMed Central

    Kligun, Efrat; Mandel-Gutfreund, Yael

    2013-01-01

    RNA molecules have highly versatile structures that can fold into myriad conformations, providing many potential pockets for binding small molecules. The increasing number of available RNA structures, in complex with proteins, small ligands and in free form, enables the design of new therapeutically useful RNA-binding ligands. Here we studied RNA ligand complexes from 10 RNA groups extracted from the protein data bank (PDB), including adaptive and non-adaptive complexes. We analyzed the chemical, physical, structural and conformational properties of binding pockets around the ligand. Comparing the properties of ligand-binding pockets to the properties of computed pockets extracted from all available RNA structures and RNA-protein interfaces, revealed that ligand-binding pockets, mainly the adaptive pockets, are characterized by unique properties, specifically enriched in rare conformations of the nucleobase and the sugar pucker. Further, we demonstrate that nucleotides possessing the rare conformations are preferentially involved in direct interactions with the ligand. Overall, based on our comprehensive analysis of RNA-ligand complexes, we suggest that the unique conformations adopted by RNA nucleotides play an important role in RNA recognition by small ligands. We term the recognition of a binding site by a ligand via the unique RNA conformations “RNA conformational readout.” We propose that “conformational readout” is a general way by which RNA binding pockets are recognized and selected from an ensemble of different RNA states. PMID:23618839

  14. Canonical and non-canonical Notch ligands

    PubMed Central

    D’SOUZA, BRENDAN; MELOTY-KAPELLA, LAURENCE; WEINMASTER, GERRY

    2015-01-01

    Notch signaling induced by canonical Notch ligands is critical for normal embryonic development and tissue homeostasis through the regulation of a variety of cell fate decisions and cellular processes. Activation of Notch signaling is normally tightly controlled by direct interactions with ligand-expressing cells and dysregulated Notch signaling is associated with developmental abnormalities and cancer. While canonical Notch ligands are responsible for the majority of Notch signaling, a diverse group of structurally unrelated non-canonical ligands has also been identified that activate Notch and likely contribute to the pleiotropic effects of Notch signaling. Soluble forms of both canonical and non-canonical ligands have been isolated, some of which block Notch signaling and could serve as natural inhibitors of this pathway. Ligand activity can also be indirectly regulated by other signaling pathways at the level of ligand expression, serving to spatio-temporally compartmentalize Notch signaling activity and integrate Notch signaling into a molecular network that orchestrates developmental events. Here, we review the molecular mechanisms underlying the dual role of Notch ligands as activators and inhibitors of Notch signaling. Additionally, evidence that Notch ligands function independent of Notch are presented. We also discuss how ligand post-translational modification, endocytosis, proteolysis and spatio-temporal expression regulate their signaling activity. PMID:20816393

  15. Blood Donor Management in China

    PubMed Central

    Shi, Ling; Wang, Jingxing; Liu, Zhong; Stevens, Lori; Sadler, Andrew; Ness, Paul; Shan, Hua

    2014-01-01

    Summary Despite a steady increase in total blood collections and voluntary non-remunerated blood donors, China continues to have many challenges with its blood donation system. The country's donation rate remains low at 9%o, with over 60% of donors being first-time donors. Generally there is a lack of adequate public awareness about blood donation. The conservative donor selection criteria, the relatively long donation interval, and the small donation volume have further limited blood supply. To ensure a sufficient and safe blood supply that meets the increasing clinical need for blood products, there is an urgent need to strengthen the country's blood donor management. This comprehensive effort should include educating and motivating more individuals especially from the rural areas to be involved in blood donation, developing rational and evidence-based selection criteria for donor eligibility, designing a donor follow-up mechanism to encourage more future donations, assessing the current donor testing strategy, improving donor service and care, building regional and national shared donor deferral database, and enhancing the transparency of the blood donation system to gain more trust from the general public. The purpose of the review is to provide an overview of the key process of and challenges with the blood donor management system in China. PMID:25254023

  16. Thermodynamic, kinetic and structural studies on the mixed ligand complexes of palladium(II) with tridentate and monodentate ligands.

    PubMed

    Nagy, Zoltán; Fábián, István; Bényei, Attila; Sóvágó, Imre

    2003-03-01

    Stability constants of the complexes formed in the reaction of [Pd(bpma)](2+) [bpma=bis(pyridin-2-ylmethyl)amine] with monodentate nitrogen and thioether ligands including uridine, MeUH, cytidine, MeC, EtGH, AcHis, AcHm, AcLys and AcMet were determined by potentiometric method. The coordination chemistry of [Pd(bpma)](2+) shows a significant similarity to that of [Pd(terpy)](2+), but it is different from [Pd(dien)](2+). The formation of hydroxo and dinuclear complexes is especially enhanced in the case of [Pd(bpma)](2+) and [Pd(terpy)](2+), but the affinity of palladium(II) ions for the coordination of thioether residues is reduced in the presence of pyridine nitrogen atoms. Stopped-flow kinetic measurements reveal that the substitution reactions of the thioether ligand AcMet are much faster than those of the N-donor cytidine. The presence of the two pyridyl residues significantly enhances the kinetic reactivity of [Pd(bpma)](2+) as compared to that of [Pd(dien)](2+). The Pd-S(thioether) bonded species can be important intermediates in multicomponent systems, but the equilibrium state is characterised by the formation of Pd-N bonded species. The complex [Pd(bpma)NO(3)]NO(3) has been prepared in solid state and its structure was elucidated by single crystal X-ray diffraction method. PMID:12628710

  17. Bis[2,6-bis­(1H-pyrazol-1-yl)pyridine]­deca­kis­(μ2-3-nitro­benzoato)bis­(3-nitro­benzoato)tetra­dysprosium(III): a linear tetra­nuclear dysprosium compound based on mixed N- and O-donor ligands

    PubMed Central

    Hua, Rong; Wu, Xiao-Liu; Li, Jin-Ying

    2014-01-01

    The title compound, [Dy4(C7H4NO4)12(C11H9N5)2] or Dy4(L1)12(L2)2, where HL1 = 3-nitro­benzoic acid and HL2 = 2,6-bis­(1H-pyrazol-1-y1)pyridine, is a linear tetra­nuclear complex possessing inversion symmetry. The two central inversion-related DyIII atoms are seven-coordinate, DyO7, with a monocapped triangular-prismatic geometry. The outer two DyIII atoms are eight-coordinate, DyO5N3, with a bicapped triangular-prismatic geometry. The outer adjacent DyIII atoms are bridged by three L1− carboxyl­ate groups, while the inner inversion-related DyIII atoms are bridged by four L1− carboxyl­ate groups. The L2 ligands are terminally coordinated to the outer DyIII atoms in a tridentate manner. In the crystal, mol­ecules are linked via C—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (001). Two carboxyl­ate O atoms, and N and O atoms of three nitro groups, are disordered over two positions, with a refined occupancy ratio of 0.552 (6):0.448 (6). PMID:24860300

  18. [Nursing management of a refractory cardiac death donor].

    PubMed

    Kaufmann, Marion

    2016-09-01

    The nursing management of a refractory circulatory death donor is a new procedure which forms an integral part of patient care. It comprises technical and organisational aspects, and requires a conceptual, ethical and deontological effort. PMID:27596504

  19. Synthesis, Characterization, Antimicrobial, DNA Cleavage, and In Vitro Cytotoxic Studies of Some Metal Complexes of Schiff Base Ligand Derived from Thiazole and Quinoline Moiety

    PubMed Central

    Yernale, Nagesh Gunvanthrao; Bennikallu Hire Mathada, Mruthyunjayaswamy

    2014-01-01

    A novel Schiff base ligand N-(4-phenylthiazol-2yl)-2-((2-thiaxo-1,2-dihydroquinolin-3-yl)methylene)hydrazinecarboxamide (L) obtained by the condensation of N-(4-phenylthiazol-2-yl)hydrazinecarboxamide with 2-thioxo-1,2-dihydroquinoline-3-carbaldehyde and its newly synthesized Cu(II), Co(II), Ni(II), and Zn(II) complexes have been characterized by elemental analysis and various spectral studies like FT-IR, 1H NMR, ESI mass, UV-Visible, ESR, TGA/DTA, and powder X-ray diffraction studies. The Schiff base ligand (L) behaves as tridentate ONS donor and forms the complexes of type [ML(Cl)2] with square pyramidal geometry. The Schiff base ligand (L) and its metal complexes have been screened in vitro for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC) method. The DNA cleavage activity of ligand and its metal complexes were studied using plasmid DNA pBR322 as a target molecule by gel electrophoresis method. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties for the ligand and its metal complexes against Artemia salina. The results showed that the biological activities of the ligand were found to be increased on complexation. PMID:24729778

  20. Preparation and characterization of half-apo dopamine-[beta]-hydroxylase by selective removal of Cu[sub A]. Identification of a sulfur ligand at the dioxygen binding site by EXAFS and FTIR spectroscopy

    SciTech Connect

    Reedy, B.J.; Blackburn, N.J. )

    1994-03-09

    Progress has been made in determining the individual coordination of each of the copper sites (Cu[sub A] and Cu[sub B]) which comprise the active center in dopamine-[beta]-hydroxylase. Previous studies have determined the average ligand environment per copper in the fully metalated enzyme as two to three histidines and one to two O/N donors in the Cu(II) form changing to 2-3 histidines and 0.5 sulfur donors upon reduction to the Cu(I) form. Derivatives of the Cu(I) form of DBH have been made in which Cu[sub A] has been selectively removed, allowing Cu[sub B], the O[sub 2] binding center to be studied by EXAFS and FTIR. Cu[sub B] has been found to be coordinated to two histidines (Cu-N = 1.99 [+-] 0.03 [angstrom]), a S-donor ligand (Cu-S = 2.25 [+-] 0.03 [angstrom]), and a fourth, as yet unidentified ligand X (Cu-X = 2.53 [+-] 0.03 [angstrom]). The FTIR spectrum of the carbonyl derivative of Cu[sub B] indicates that V[sub CO] (2089 cm[sup [minus]1]) is identical to that found for the fully metalated enzyme, providing strong evidence that the Cu[sub B] site is not perturbed by Cu[sub A] removal. EXAFS results on Cu[sub B]-CO indicate that CO binding does not displace the S ligand but appears to displace the weakly bound ligand X. 44 refs., 4 figs., 3 tabs.

  1. Design and Application of Latent Olefin Metathesis Catalysts Featuring S-Chelating Alkylidene Ligands

    NASA Astrophysics Data System (ADS)

    Szadkowska, Anna; Grela, Karol

    This review article is devoted to recent advances in the design and application of so-called “dormant” or “latent” ruthenium olefin metathesis catalysts bearing S-chelating alkylidene ligands. Selected ruthenium complexes containing S-donor ligands, which possess controllable initiation behaviour are presented. Applications of these complexes in olefin metathesis are described.

  2. Oligo-nuclear silver thiocyanate complexes with monodentate tertiary phosphine ligands, including novel 'cubane' and 'step' tetramer forms of AgSCN : PR3 (1:1)4.

    PubMed

    Bowmaker, Graham A; Di Nicola, Corrado; Effendy; Hanna, John V; Healy, Peter C; King, Scott P; Marchetti, Fabio; Pettinari, Claudio; Robinson, Ward T; Skelton, Brian W; Sobolev, Alexandre N; Tăbăcaru, Aurel; White, Allan H

    2013-01-01

    Adducts of a number of tertiary pnicogen ligands ER(3) (triphenyl-phosphine and -arsine (PPh(3),AsPh(3)), diphenyl,2-pyridylphosphine (PPh(2)py), tris(4-fluorophenyl)phosphine (P(C(6)H(4)-4F)(3)), tris(2-tolyl)phosphine (P(o-tol)(3)), tris(cyclohexyl)phosphine (PCy(3))), with silver(I) thiocyanate, AgSCN are structurally and spectroscopically characterized. The 1:3 AgSCN : ER(3) complexes structurally defined (for PPh(3),AsPh(3) (diversely solvated)) take the form [(R(3)E)(3)AgX], the thiocyanate X = NCS being N-bound, thus [(Ph(3)E)Ag(NCS)]. A 1:2 complex with PPh(2)py, takes the binuclear form [(pyPh(2)P)(2)Ag()Ag(PPh(2)py)(2)] with an eight-membered cyclic core. 1:1 complexes are defined with PPh(2)py, P(o-tol)(3) and PCy(3); binuclear forms [(R(3)P)Ag()Ag(PR(3))] are obtained with P(o-tol)(3) (two polymorphs), while novel isomeric tetranuclear forms, which may be envisaged as dimers of dimers, are obtained with PPh(2)py, and, as further polymorphs, with PCy(3); these latter may be considered as extensions of the 'cubane' and 'step' forms previously described for [(R(3)E)AgX](4) (X = halide) complexes. Solvent-assisted mechanochemical or solvent-assisted solid-state synthesis methods were employed in some cases, where complexes could not be obtained by conventional solution methods, or where such methods yielded a mixture of polymorphs unsuitable for solid-state spectroscopy. The wavenumbers of the ν(CN) bands in the IR spectra are in broad agreement with the empirical rule that distinguishes bridging from terminal bonding, but exceptions occur for compounds that have a double SCN bridged dimeric structure, and replacement of PPh(3) with PPh(2)py apparently causes a significant decrease in ν(CN) to well below the range expected for bridging SCN in these structures. (31)P CP MAS NMR spectra yield additional parameters that allow a correlation between the structures and spectra.

  3. Conformation-selective coordination-driven self-assembly of a ditopic donor with Pd(II) acceptors.

    PubMed

    Howlader, Prodip; Mukherjee, Sandip; Saha, Rajat; Mukherjee, Partha Sarathi

    2015-12-21

    Coordination-driven self-assembly of 3-(5-(pyridin-3-yl)-1H-1,2,4-triazol-3-yl)pyridine (L) was investigated with 90°cis-blocked Pd(II) acceptors and tetratopic Pd(NO3)2. Although the ligand is capable of binding in several different conformations (acting as a ditopic donor through the pyridyl nitrogens), the experimental results (including X-ray structures) showed that it adopts a particular conformation when it binds with 90°cis-blocked Pd(II) acceptors (two available sites) to yield [2 + 2] self-assembled macrocycles. On the other hand, with Pd(NO3)2 (where four available sites are present) a different conformer of the same donor was selectively bound to form a molecular cubic cage. The experimental findings were corroborated well with the density functional theory (B3LYP) calculations. The tetratopic Pd(NO3)2 yielded a [6 + 12] self-assembled Pd6L12 molecular cube, which contains a potential void occupied by nitrate and perchlorate ions. Being a triazole based ligand, the free space inside the cage is enriched with several sp(2) hybridised nitrogen atoms with lone pairs of electrons to act as Lewis basic sites. Knoevenagel condensation reactions of several aromatic aldehydes with active methylene compounds were successfully performed in reasonably high yields in the presence of the cage. PMID:26544720

  4. Solution thermodynamic stability of complexes formed with the octadentate hydroxypyridinonate ligand 3,4,3-LI(1,2-HOPO): a critical feature for efficient chelation of lanthanide(IV) and actinide(IV) ions.

    PubMed

    Deblonde, Gauthier J-P; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J

    2013-08-01

    The solution thermodynamics of water-soluble complexes formed between Ce(III), Ce(IV), Th(IV) and the octadentate chelating agent 3,4,3-LI(1,2-HOPO) were investigated. Several techniques including spectrofluorimetric and automated spectrophotometric titrations were used to overcome the slow spontaneous oxidation of Ce(III) complexes yielding to stability constants of log β110 = 17.4 ± 0.5, log β11-1 = 8.3 ± 0.4 and log β111 = 21.2 ± 0.4 for [Ce(III)(3,4,3-LI(1,2-HOPO))](-), [Ce(III)(3,4,3-LI(1,2-HOPO)(OH)](2-), and [Ce(III)(3,4,3-LI(1,2-HOPO)H], respectively. Using the spectral properties of the hydroxypyridinonate chelator in ligand competition titrations against nitrilotriacetic acid, the stability constant log β110 = 41.5 ± 0.5 was determined for [Ce(IV)(3,4,3-LI(1,2-HOPO))]. Finally, the extraordinarily stable complex [Ce(IV)(3,4,3-LI(1,2-HOPO))] was used in Th(IV) competition titrations, resulting in a stability constant of log β110 = 40.1 ± 0.5 for [Th(IV)3,4,3-LI(1,2-HOPO))]. These experimental values are in excellent agreement with previous estimates, they are discussed with respect to the ionic radius and oxidation state of each cationic metal, and allow predictions on the stability of other actinide complexes including [U(IV)(3,4,3-LI(1,2-HOPO))], [Np(IV)(3,4,3-LI(1,2-HOPO))], and [Pu(IV)(3,4,3-LI(1,2-HOPO))]. Comparisons with the standard ligand diethylenetriamine pentaacetic acid (DTPA) provide a thermodynamic basis for the observed significantly higher efficacy of 3,4,3-LI(1,2-HOPO) as an in vivo actinide decorporation agent. PMID:23855806

  5. Solution thermodynamic stability of complexes formed with the octadentate hydroxypyridinonate ligand 3,4,3-LI(1,2-HOPO): A critical feature for efficient chelation of lanthanide(IV) and actinide(IV) ions

    PubMed Central

    Deblonde, Gauthier J-P.; Sturzbecher-Hoehne, Manuel; Abergel, Rebecca J.

    2013-01-01

    The solution thermodynamics of water soluble complexes formed between Ce(III), Ce(IV), Th(IV) and the octadentate chelating agent 3,4,3-LI(1,2-HOPO) were investigated. Several techniques including spectrofluorimetric and automated spectrophotometric titrations were used to overcome the slow spontaneous oxidation of Ce(III) complexes yielding to stability constants of log β110 = 17.4 ± 0.5, log β11-1 = 8.3 ± 0.4 and log β111 = 21.2 ± 0.4 for [Ce(III)(3,4,3-LI(1,2-HOPO))]−, [Ce(III)(3,4,3-LI(1,2-HOPO)(OH)]2− and [Ce(III)(3,4,3-LI(1,2-HOPO)H], respectively. Using the spectral properties of the hydroxypyridinonate chelator in ligand competition titrations against nitrilotriacetic acid, the stability constant log β110 = 41.5 ± 0.5 was determined for [Ce(IV)(3,4,3-LI(1,2-HOPO))]. Finally, the extraordinarily stable complex [Ce(IV)(3,4,3-LI(1,2-HOPO))] was used in Th(IV) competition titrations, resulting in a stability constant of log β110 = 40.1 ± 0.5 for [Th(IV)3,4,3-LI(1,2-HOPO))]. These experimental values are in excellent agreement with previous estimates, they are discussed with respect to the ionic radius and oxidation state of each cationic metal and allow predictions on the stability of other actinide complexes including [U(IV)(3,4,3-LI(1,2-HOPO))], [Np(IV)(3,4,3-LI(1,2-HOPO))] and [Pu(IV)(3,4,3-LI(1,2-HOPO))]. Comparisons with the standard ligand diethylenetriamine pentaacetic acid (DTPA) provide a thermodynamic basis for the observed significantly higher efficacy of 3,4,3-LI(1,2-HOPO) as an in vivo actinide decorporation agent. PMID:23855806

  6. NHC-based pincer ligands: carbenes with a bite.

    PubMed

    Andrew, Rhiann E; González-Sebastián, Lucero; Chaplin, Adrian B

    2016-01-28

    In this frontier article we overview the emergence and scope of NHC-based CCC and CNC pincer systems, i.e. complexes containing mer-tridentate ligands bearing two NHC donor groups, comment on their effectiveness in applications, and highlight areas for future development and exploitation.

  7. A modular approach to neutral P,N-ligands: synthesis and coordination chemistry

    PubMed Central

    Blasius, Clemens K; Intorp, Sebastian N; Wadepohl, Hubert

    2016-01-01

    Summary We report the modular synthesis of three different types of neutral κ2-P,N-ligands comprising an imine and a phosphine binding site. These ligands were reacted with rhodium, iridium and palladium metal precursors and the structures of the resulting complexes were elucidated by means of X-ray crystallography. We observed that subtle changes of the ligand backbone have a significant influence on the binding geometry und coordination properties of these bidentate P,N-donors. PMID:27340475

  8. IR and ESR studies on novel Cu(II) theophyllinato complexes containing mono- or bidentate ligands

    NASA Astrophysics Data System (ADS)

    Forizs, Edit; David, L.; Cozar, O.; Chiş, V.; Damian, G.; Csibi, Jolán

    1999-05-01

    Three mixed-ligand copper(II) complexes containing theophylline and mono- or bidentate N-donor ligands (2,2'-bipyridine, 4-fluoraniline and 1,10-phenanthroline) were synthesized and characterized by elemental analysis, IR and ESR spectra. According to IR and ESR data the Cu(II) complexes exhibit a distorted tetrahedral coordination of copper by two nitrogen atoms of the monodentate or bidentate ligands and the two monodentate theophyllinate anion bonded through N(7) atom.

  9. Synthesis, characterization, spectroscopic and theoretical studies of new zinc(II), copper(II) and nickel(II) complexes based on imine ligand containing 2-aminothiophenol moiety

    NASA Astrophysics Data System (ADS)

    Shafaatian, Bita; Mousavi, S. Sedighe; Afshari, Sadegh

    2016-11-01

    New dimer complexes of zinc(II), copper(II) and nickel(II) were synthesized using the Schiff base ligand which was formed by the condensation of 2-aminothiophenol and 2-hydroxy-5-methyl benzaldehyde. This tridentate Schiff base ligand was coordinated to the metal ions through the NSO donor atoms. In order to prevent the oxidation of the thiole group during the formation of Schiff base and its complexes, all of the reactions were carried out under an inert atmosphere of argon. The X-ray structure of the Schiff base ligand showed that in the crystalline form the SH groups were oxidized to produce a disulfide Schiff base as a new double Schiff base ligand. The molar conductivity values of the complexes in dichloromethane implied the presence of non-electrolyte species. The fluorescence properties of the Schiff base ligand and its complexes were also studied in dichloromethane. The products were characterized by FT-IR, 1H NMR, UV/Vis spectroscopies, elemental analysis, and conductometry. The crystal structure of the double Schiff base was determined by single crystal X-ray diffraction. Furthermore, the density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d,p) level of theory for the determination of the optimized structures of Schiff base complexes.

  10. Evaluating the extent of intramolecular charge transfer in the excited states of rhenium(I) donor-acceptor complexes with time-resolved vibrational spectroscopy.

    PubMed

    Yue, Yuankai; Grusenmeyer, Tod; Ma, Zheng; Zhang, Peng; Pham, Tri Tat; Mague, Joel T; Donahue, James P; Schmehl, Russell H; Beratan, David N; Rubtsov, Igor V

    2013-12-12

    Excited states in transition-metal complexes, even in those featuring ligands with strong electron donating and accepting properties, often involve only partial charge transfer between the donor and acceptor ligands. The excited-state properties of [Re(bpy)(CO)3L](+) compounds were studied, where L is 4-dimethylaminobenzonitrile (Re4DMABN), 3-dimethylaminobenzonitrile (Re3DMABN), and benzonitrile (ReBN) using time-resolved infrared (TRIR) and electronic spectroscopy methods as well as electronic structure computations. The DMABN complexes exhibit strongly solvent-dependent luminescence; the excited state lifetime decreases from microseconds in dichloromethane to several nanoseconds in mixed MeOH:DCM (1:1) solvent. Despite the similarities in the solvent dependence of the excited state dynamics and redox properties for Re3DMABN and Re4DMABN, the nature of the lowest energy excited states formed in these two compounds is drastically different. For example, the lowest energy excited state for Re4DMABN in the mixed solvent is assigned to the (4DMABN → bpy) ligand-to-ligand charge transfer (LLCT) state featuring partial charge transfer character. An equilibrium between a 3DMABN intraligand triplet ((3)IL) and a metal-ligand-to-ligand charge transfer (MLLCT) state is found for Re3DMABN in the mixed solvent with the latter at ca. 400 cm(-1) lower energy. The origin of such a drastic difference between the states involved in Re4DMABN and Re3DMABN is attributed to a difference in the energies of polarized quinoidal resonance structures in 4DMABN and 3DMABN ligands.

  11. Donor Motivations and Decision Making: Understanding the Major Gift Development Process from a Donor's Perspective

    ERIC Educational Resources Information Center

    Morrison, Anna Lee

    2015-01-01

    Higher education is faced with a challenge to its traditional funding structure. As a result, academic programs must seek alternative sources of support. Chief among these sources is philanthropy in the form of major gifts. Insight into donor motivations and decision making when approached to consider a major gift may help to maximize the success…

  12. Donor-Appended N,C-Chelate Organoboron Compounds: Influence of Donor Strength on Photochromic Behaviour.

    PubMed

    Mellerup, Soren K; Yuan, Kang; Nguyen, Carmen; Lu, Zheng-Hong; Wang, Suning

    2016-08-22

    Recently, four-coordinated N,C-chelate organoboron compounds have been found to show many interesting photochemical transformations depending on the nature of their chelating framework. As such, the effect of substitution on the chelate ligand has been well-established and understood, but the impact of the aryl groups attached to the boron atom remains less clear. To investigate the effect of enhanced charge-transfer character, a series of new N,C-chelate organoboron compounds with donor-functionalized aryl groups have been synthesized and characterized using NMR, UV/Vis, and electrochemical methods. These compounds were found to possess bright and tunable charge-transfer luminescence which is dependent on the donor strength of the amino substituent. In addition, some of these compounds undergo photochromic switching, producing dark isomers of various colors. This work establishes that donor-functionalization of the aryl groups in N,C-chelate boron compounds is an effective strategy for tuning both the photophysical and photochemical properties of such systems. The new findings also help elucidate the influence of electronic structure on the photoreactivity of N,C-chelate organoboron compounds which appears to be as important as steric crowding around the boron atom.

  13. Platelet donation drives: a novel initiative to recruit platelet donors.

    PubMed

    Tendulkar, Anita; Shah, Sneha; Patil, Dipali; Tambe, Manisha

    2014-06-01

    The most important strategy to ensure a safe and an adequate supply of blood and blood products is motivation, recruitment, selection and retention of voluntary non remunerated blood donors. With a view of the increased platelet necessity in our oncology setup, the first platelet donation drive in the city and to the best of our knowledge, in India was conducted by our hospital in November 2009. The aim was to identify target groups and expand our donor database. It was also essential that the donor's contribution is acknowledged and appropriately felicitated. A campaign called "Save a Life" was initiated and publicized locally. A core team consisting of Transfusion Medicine specialists, clinicians and an NGO (nongovernment organization) was formed. The best suitable date and venue were finalized for the platelet camp. The audience was addressed and willing donors were registered as volunteer platelet donors with our institute. In a span of 40 months, 15 platelet camps were organized in colleges, social organizations, and corporate offices. A total of 1035 donors were registered out of which, 382 (37%) donated platelets in our hospital. 125/382 (33.2%) donated Single Donor Platelets (SDP) more than once. The largest number of platelet donations by a single camp donor was 24 times. Due to multiple donations from donors, the SDP number was enhanced considerably and lead to addition of 699 SDP units to our inventory. The annual indoor and camp voluntary platelet donor numbers increased from 142 in 2006 to 631 in 2012 due to platelet drives. All platelet donations were altruistic as no incentives were offered to the donors. Ready availability of platelets and planning SDP inventory as per patient blood group requirements had a positive impact on clinical services.

  14. Characterization of human milk donors.

    PubMed

    Osbaldiston, Richard; Mingle, Leigh A

    2007-11-01

    The primary objective of this research was to create a detailed characterization of human milk donors, including descriptive information about demographics and lifestyle, involvement with the milk bank, reasons for donating, problems encountered while breastfeeding and pumping milk, barriers to donating milk, affective experiences, and personal values. Data were collected via telephone interview of 87 donors and 19 nondonor controls. Few relationships were found between the descriptive information and amount of milk donated. Donors reported fewer problems pumping milk than nondonors. Strategies for recruiting new donors and strategies for increasing donation amounts are presented.

  15. Ligand-induced Epitope Masking

    PubMed Central

    Mould, A. Paul; Askari, Janet A.; Byron, Adam; Takada, Yoshikazu; Jowitt, Thomas A.; Humphries, Martin J.

    2016-01-01

    We previously demonstrated that Arg-Gly-Asp (RGD)-containing ligand-mimetic inhibitors of integrins are unable to dissociate pre-formed integrin-fibronectin complexes (IFCs). These observations suggested that amino acid residues involved in integrin-fibronectin binding become obscured in the ligand-occupied state. Because the epitopes of some function-blocking anti-integrin monoclonal antibodies (mAbs) lie near the ligand-binding pocket, it follows that the epitopes of these mAbs may become shielded in the ligand-occupied state. Here, we tested whether function-blocking mAbs directed against α5β1 can interact with the integrin after it forms a complex with an RGD-containing fragment of fibronectin. We showed that the anti-α5 subunit mAbs JBS5, SNAKA52, 16, and P1D6 failed to disrupt IFCs and hence appeared unable to bind to the ligand-occupied state. In contrast, the allosteric anti-β1 subunit mAbs 13, 4B4, and AIIB2 could dissociate IFCs and therefore were able to interact with the ligand-bound state. However, another class of function-blocking anti-β1 mAbs, exemplified by Lia1/2, could not disrupt IFCs. This second class of mAbs was also distinguished from 13, 4B4, and AIIB2 by their ability to induce homotypic cell aggregation. Although the epitope of Lia1/2 was closely overlapping with those of 13, 4B4, and AIIB2, it appeared to lie closer to the ligand-binding pocket. A new model of the α5β1-fibronectin complex supports our hypothesis that the epitopes of mAbs that fail to bind to the ligand-occupied state lie within, or very close to, the integrin-fibronectin interface. Importantly, our findings imply that the efficacy of some therapeutic anti-integrin mAbs could be limited by epitope masking. PMID:27484800

  16. Donor exclusion in the National Blood Service Tissue Services living bone donor programme.

    PubMed

    Pink, F; Warwick, R M; Purkis, J; Pearson, J

    2006-01-01

    National Blood Service (NBS) Tissue Services (TS) operates living donor and deceased donor tissue banking programmes. The living bone donor programme operates in collaboration with 91 orthopaedic departments across the country and collects bone donations, in the form of surgically removed femoral heads (FHs), from over 5,000 patients per annum undergoing total hip replacement. Bone donated via the living programme constitutes approximately 55% of the total bone donated to NBS. Non-NBS tissue banks, primarily in hospital orthopaedic departments, also bank donated bone for the UK. A survey of information received from 16 collaborating orthopaedic centres, between April 2003 and August 2004, identified 709 excluded donors. The total number of donations banked from these sites was 1,538. Donations can be excluded before collection if there are contraindications noted in a potential donor's medical history before their operation. Donors may also be excluded after collection of the FH, for instance because of reactive microbiology tests for blood borne viruses, or if the donation storage conditions or related documentation have not met stringent quality requirements. In this survey, bone or joint conditions were the major reasons for excluding potential donors before donation (154 of 709 exclusions, 22%), followed by a current or a past history of malignancy (139 of 709 exclusions, 20%). Local staffing and operational difficulties sometimes resulted in potential donors being missed, or specific reasons for exclusion not being reported (117 exclusions). These out numbered exclusions due to patient refusal (80 exclusions). A small number (< 5) appear to have been excluded erroneously. There was considerable local variation in the reasons given for exclusion and certainly under-reporting. A survey of donations discarded after collection in the same period highlighted that 43% were donor related; 110 of 370 did not provide a follow-up blood sample. More than 30% were due to

  17. Donor exclusion in the National Blood Service Tissue Services living bone donor programme.

    PubMed

    Pink, F; Warwick, R M; Purkis, J; Pearson, J

    2006-01-01

    National Blood Service (NBS) Tissue Services (TS) operates living donor and deceased donor tissue banking programmes. The living bone donor programme operates in collaboration with 91 orthopaedic departments across the country and collects bone donations, in the form of surgically removed femoral heads (FHs), from over 5,000 patients per annum undergoing total hip replacement. Bone donated via the living programme constitutes approximately 55% of the total bone donated to NBS. Non-NBS tissue banks, primarily in hospital orthopaedic departments, also bank donated bone for the UK. A survey of information received from 16 collaborating orthopaedic centres, between April 2003 and August 2004, identified 709 excluded donors. The total number of donations banked from these sites was 1,538. Donations can be excluded before collection if there are contraindications noted in a potential donor's medical history before their operation. Donors may also be excluded after collection of the FH, for instance because of reactive microbiology tests for blood borne viruses, or if the donation storage conditions or related documentation have not met stringent quality requirements. In this survey, bone or joint conditions were the major reasons for excluding potential donors before donation (154 of 709 exclusions, 22%), followed by a current or a past history of malignancy (139 of 709 exclusions, 20%). Local staffing and operational difficulties sometimes resulted in potential donors being missed, or specific reasons for exclusion not being reported (117 exclusions). These out numbered exclusions due to patient refusal (80 exclusions). A small number (< 5) appear to have been excluded erroneously. There was considerable local variation in the reasons given for exclusion and certainly under-reporting. A survey of donations discarded after collection in the same period highlighted that 43% were donor related; 110 of 370 did not provide a follow-up blood sample. More than 30% were due to

  18. Organ Donor FAQ's: Who Can Be a Donor

    MedlinePlus

    ... citizens have been organ donors. Can non-resident aliens donate and receive organs? Non-resident aliens can both donate and receive organs in the ... the 12,375 organ donors were non-resident aliens. In this same year, 259 (1%) of the ...

  19. Similarity metrics for ligands reflecting the similarity of the target proteins.

    PubMed

    Schuffenhauer, Ansgar; Floersheim, Philipp; Acklin, Pierre; Jacoby, Edgar

    2003-01-01

    In this study we evaluate how far the scope of similarity searching can be extended to identify not only ligands binding to the same target as the reference ligand(s) but also ligands of other homologous targets without initially known ligands. This "homology-based similarity searching" requires molecular representations reflecting the ability of a molecule to interact with target proteins. The Similog keys, which are introduced here as a new molecular representation, were designed to fulfill such requirements. They are based only on the molecular constitution and are counts of atom triplets. Each triplet is characterized by the graph distances and the types of its atoms. The atom-typing scheme classifies each atom by its function as H-bond donor or acceptor and by its electronegativity and bulkiness. In this study the Similog keys are investigated in retrospective in silico screening experiments and compared with other conformation independent molecular representations. Studied were molecules of the MDDR database for which the activity data was augmented by standardized target classification information from public protein classification databases. The MDDR molecule set was split randomly into two halves. The first half formed the candidate set. Ligands of four targets (dopamine D2 receptor, opioid delta-receptor, factor Xa serine protease, and progesterone receptor) were taken from the second half to form the respective reference sets. Different similarity calculation methods are used to rank the molecules of the candidate set by their similarity to each of the four reference sets. The accumulated counts of molecules binding to the reference target and groups of targets with decreasing homology to it were examined as a function of the similarity rank for each reference set and similarity method. In summary, similarity searching based on Unity 2D-fingerprints or Similog keys are found to be equally effective in the identification of molecules binding to the same

  20. Intramolecular Charge-Transfer Interaction of Donor-Acceptor-Donor Arrays Based on Anthracene Bisimide.

    PubMed

    Iwanaga, Tetsuo; Ogawa, Marina; Yamauchi, Tomokazu; Toyota, Shinji

    2016-05-20

    We designed anthracene bisimide (ABI) derivatives having two triphenylamine (TPA) groups as donor units at the 9,10-positions to form a novel π-conjugated donor-acceptor system. These compounds and their analogues with ethynylene linkers were synthesized by Suzuki-Miyaura and Sonogashira coupling reactions, respectively. In UV-vis spectra, the linker-free derivatives showed broad absorption bands arising from intramolecular charge-transfer interactions. Introducing ethynylene linkers resulted in a considerable red shift of the absorption bands. In fluorescence spectra, the ethynylene derivatives showed intense emission bands at 600-650 nm. Their photophysical and electrochemical properties were compared with those of the corresponding mono TPA derivatives on the basis of theoretical calculations and cyclic voltammetry to evaluate the intramolecular electronic interactions between the donor and acceptor units.

  1. Scalable quantum computer architecture with coupled donor-quantum dot qubits

    DOEpatents

    Schenkel, Thomas; Lo, Cheuk Chi; Weis, Christoph; Lyon, Stephen; Tyryshkin, Alexei; Bokor, Jeffrey

    2014-08-26

    A quantum bit computing architecture includes a plurality of single spin memory donor atoms embedded in a semiconductor layer, a plurality of quantum dots arranged with the semiconductor layer and aligned with the donor atoms, wherein a first voltage applied across at least one pair of the aligned quantum dot and donor atom controls a donor-quantum dot coupling. A method of performing quantum computing in a scalable architecture quantum computing apparatus includes arranging a pattern of single spin memory donor atoms in a semiconductor layer, forming a plurality of quantum dots arranged with the semiconductor layer and aligned with the donor atoms, applying a first voltage across at least one aligned pair of a quantum dot and donor atom to control a donor-quantum dot coupling, and applying a second voltage between one or more quantum dots to control a Heisenberg exchange J coupling between quantum dots and to cause transport of a single spin polarized electron between quantum dots.

  2. A nickel tripeptide as a metallodithiolate ligand anchor for resin-bound organometallics.

    PubMed

    Green, Kayla N; Jeffery, Stephen P; Reibenspies, Joseph H; Darensbourg, Marcetta Y

    2006-05-17

    The molecular structure of the acetyl CoA synthase enzyme has clarified the role of individual nickel atoms in the dinickel active site which mediates C-C and C-S coupling reactions. The NiN2S2 portion of the biocatalyst (N2S2 = a cysteine-glycine-cysteine or CGC4- tripeptide ligand) serves as an S-donor ligand comparable to classical bidentate ligands operative in organometallic chemistry, ligating the second nickel which is redox and catalytically active. Inspired by this biological catalyst, the synthesis of NiN2S2 metalloligands, including the solid-phase synthesis of resin-bound Ni(CGC)2-, and sulfur-based derivatization with W(CO)5 and Rh(CO)2+ have been carried out. Through comparison to analogous well-characterized, solution-phase complexes, Attenuated Total Reflectance FTIR spectroscopy establishes the presence of unique heterobimetallic complexes, of the form [Ni(CGC)]M(CO)x, both in solution and immobilized on resin beads. This work provides the initial step toward exploitation of such an evolutionarily optimized nickel peptide as a solid support anchor for hybrid bioinorganic-organometallic catalysts.

  3. Effect of Ligand Field Tuning on the SMM Behavior for Three Related Alkoxide-Bridged Dysprosium Dimers.

    PubMed

    Peng, Yan; Mereacre, Valeriu; Baniodeh, Amer; Lan, Yanhua; Schlageter, Martin; Kostakis, George E; Powell, Annie K

    2016-01-01

    The synthesis and characterization of three Dy2 compounds, [Dy2(HL1)2(NO3)4] (1), [Dy2(L2)2(NO3)4] (2), and [Dy2(HL3)2(NO3)4] (3), formed using related tripodal ligands with a central tertiary amine bearing picolyl and alkoxy arms, 2-[(2-hydroxy-ethyl)-pyridin-2-ylmethylamino]-ethanol (H2L1), 2-(bis-pyridin-2-ylmethylamino)-ethanol (HL2), and 2-(bis-pyridin-2-ylmethylamino)-propane-1,3-diol (H2L3), are reported. The compounds are rare examples of alkoxide-bridged {Dy2} complexes and display capped square antiprism coordination geometry around each Dy(III) ion. Changes in the ligand field environment around the Dy(III) ions brought about through variations in the ligand donors can be gauged from the magnetic properties, with compounds 1 and 2 showing antiparallel coupling between the Dy(III) ions and 3 showing parallel coupling. Furthermore, slow relaxation of the magnetization typical of SMM behavior could be observed for compounds 2 and 3, suggesting that small variations in the ligand field can have a significant influence on the slow relaxation processes responsible for SMM behavior of Dy(III)-based systems. PMID:26652937

  4. Investigating the effect of flexible ligands on the crystal engineering of the iron(II) coordination compounds

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

    Iron(II) coordination compounds [Fe(bib)2(NCS)2]n(1) and [Fe(bpp)(NCS)2] (2) were synthesized by using the neutral flexible bidentate N-donor ligands 1,4-bis(imidazolyl)butane (bib) and 1,3-bis(3,5-dimethylpyrazolyl)propane (bpp), mono-anionic NCS- ligand and appropriate iron(II) salts. In the CdSO4 network structure of 1, the iron(II) ion lies on an inversion center and exhibits an FeN6 octahedral arrangement while, in the monomeric structure of 2, the iron(II) ion adopts an FeN4 tetrahedral 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 an iron(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. An attempt to synthesize [Fe(bbd)(NCS)2] (3) (bbd = 1,4-bis(3,5-dimethylpyrazolyl)butane) with the reaction of bbd, Fe(NH4)2(SO4)2·6H2O and KNCS was failed.

  5. Metal-ligand synergistic effects in the complex Ni(η(2)-TEMPO)2: synthesis, structures, and reactivity.

    PubMed

    Isrow, Derek; DeYonker, Nathan J; Koppaka, Anjaneyulu; Pellechia, Perry J; Webster, Charles Edwin; Captain, Burjor

    2013-12-16

    In the current investigation, reactions of the "bow-tie" Ni(η(2)-TEMPO)2 complex with an assortment of donor ligands have been characterized experimentally and computationally. While the Ni(η(2)-TEMPO)2 complex has trans-disposed TEMPO ligands, proton transfer from the C-H bond of alkyne substrates (phenylacetylene, acetylene, trimethylsilyl acetylene, and 1,4-diethynylbenzene) produce cis-disposed ligands of the form Ni(η(2)-TEMPO)(κ(1)-TEMPOH)(κ(1)-R). In the case of 1,4-diethynylbenzene, a two-stage reaction occurs. The initial product Ni(η(2)-TEMPO)(κ(1)-TEMPOH)[κ(1)-CC(C6H4)CCH] is formed first but can react further with another equivalent of Ni(η(2)-TEMPO)2 to form the bridged complex Ni(η(2)-TEMPO)(κ(1)-TEMPOH)[κ(1)-κ(1)-CC(C6H4)CC]Ni(η(2)-TEMPO)(κ(1)-TEMPOH). The corresponding reaction with acetylene, which could conceivably also yield a bridging complex, does not occur. Via density functional theory (DFT), addition mechanisms are proposed in order to rationalize thermodynamic and kinetic selectivity. Computations have also been used to probe the relative thermodynamic stabilities of the cis and trans addition products and are in accord with experimental results. Based upon the computational results and the geometry of the experimentally observed product, a trans-cis isomerization must occur.

  6. Architecture of the Yeast Mitochondrial Iron-Sulfur Cluster Assembly Machinery: THE SUB-COMPLEX FORMED BY THE IRON DONOR, Yfh1 PROTEIN, AND THE SCAFFOLD, Isu1 PROTEIN.

    PubMed

    Ranatunga, Wasantha; Gakh, Oleksandr; Galeano, Belinda K; Smith, Douglas Y; Söderberg, Christopher A G; Al-Karadaghi, Salam; Thompson, James R; Isaya, Grazia

    2016-05-01

    The biosynthesis of Fe-S clusters is a vital process involving the delivery of elemental iron and sulfur to scaffold proteins via molecular interactions that are still poorly defined. We reconstituted a stable, functional complex consisting of the iron donor, Yfh1 (yeast frataxin homologue 1), and the Fe-S cluster scaffold, Isu1, with 1:1 stoichiometry, [Yfh1]24·[Isu1]24 Using negative staining transmission EM and single particle analysis, we obtained a three-dimensional reconstruction of this complex at a resolution of ∼17 Å. In addition, via chemical cross-linking, limited proteolysis, and mass spectrometry, we identified protein-protein interaction surfaces within the complex. The data together reveal that [Yfh1]24·[Isu1]24 is a roughly cubic macromolecule consisting of one symmetric Isu1 trimer binding on top of one symmetric Yfh1 trimer at each of its eight vertices. Furthermore, molecular modeling suggests that two subunits of the cysteine desulfurase, Nfs1, may bind symmetrically on top of two adjacent Isu1 trimers in a manner that creates two putative [2Fe-2S] cluster assembly centers. In each center, conserved amino acids known to be involved in sulfur and iron donation by Nfs1 and Yfh1, respectively, are in close proximity to the Fe-S cluster-coordinating residues of Isu1. We suggest that this architecture is suitable to ensure concerted and protected transfer of potentially toxic iron and sulfur atoms to Isu1 during Fe-S cluster assembly.

  7. The Lombardy Rare Donor Programme

    PubMed Central

    Revelli, Nicoletta; Villa, Maria Antonietta; Paccapelo, Cinzia; Manera, Maria Cristina; Rebulla, Paolo; Migliaccio, Anna Rita; Marconi, Maurizio

    2014-01-01

    Background In 2005, the government of Lombardy, an Italian region with an ethnically varied population of approximately 9.8 million inhabitants including 250,000 blood donors, founded the Lombardy Rare Donor Programme, a regional network of 15 blood transfusion departments coordinated by the Immunohaematology Reference Laboratory of the Ca’ Granda Ospedale Maggiore Policlinico in Milan. During 2005 to 2012, Lombardy funded LORD-P with 14.1 million euros. Materials and methods During 2005–2012 the Lombardy Rare Donor Programme members developed a registry of blood donors and a bank of red blood cell units with either rare blood group phenotypes or IgA deficiency. To do this, the Immunohaematology Reference Laboratory performed extensive serological and molecular red blood cell typing in 59,738 group O or A, Rh CCDee, ccdee, ccDEE, ccDee, K− or k− donors aged 18–55 with a record of two or more blood donations, including both Caucasians and ethnic minorities. In parallel, the Immunohaematology Reference Laboratory implemented a 24/7 service of consultation, testing and distribution of rare units for anticipated or emergent transfusion needs in patients developing complex red blood cell alloimmunisation and lacking local compatible red blood cell or showing IgA deficiency. Results Red blood cell typing identified 8,747, 538 and 33 donors rare for a combination of common antigens, negative for high-frequency antigens and with a rare Rh phenotype, respectively. In June 2012, the Lombardy Rare Donor Programme frozen inventory included 1,157 red blood cell units. From March 2010 to June 2012 one IgA-deficient donor was detected among 1,941 screened donors and IgA deficiency was confirmed in four previously identified donors. From 2005 to June 2012, the Immunohaematology Reference Laboratory provided 281 complex red blood cell alloimmunisation consultations and distributed 8,008 Lombardy Rare Donor Programme red blood cell units within and outside the region

  8. [Altruism and the donor].

    PubMed

    Langlois, A

    1991-08-01

    On December 20, 1988, the government of France passed a law to protect people who voluntarily participate in biomedical research. This article makes extensive reference to a major study, titled From Biology to Ethics, by Jean Bernard, a well-respected authority in the field of bioethics. The author looks at models proposed by Bernard, as examples for health volunteers, in particular, the blood donor and the self-experimenter. To set the tone of the article, she recalls the concept of altruism, as first proposed by Auguste Comte, then makes a linkage between his philosophy and Bernard's point of view. By trial and error, in their discussions, various ethics committees and the French State Council have agreed upon what constitutes fair compensation under the law. Unlike their Canadian counterparts, medical researchers in France have free access to volunteers who are not in perfect health--e.g., the elderly, people suffering from kidney deficiency, cirrhosis of the liver, etc.--but these "experimental subjects" receive no monetary compensation. Thus, healthy and less-than-healthy volunteers do not receive equal treatment under the law. This inequity, added to the fear of what amounts to a tax on the human body and the difficulty of ensuring just compensation, is giving rise to a great deal of uncertainty.

  9. [Altruism and the donor].

    PubMed

    Langlois, A

    1991-08-01

    On December 20, 1988, the government of France passed a law to protect people who voluntarily participate in biomedical research. This article makes extensive reference to a major study, titled From Biology to Ethics, by Jean Bernard, a well-respected authority in the field of bioethics. The author looks at models proposed by Bernard, as examples for health volunteers, in particular, the blood donor and the self-experimenter. To set the tone of the article, she recalls the concept of altruism, as first proposed by Auguste Comte, then makes a linkage between his philosophy and Bernard's point of view. By trial and error, in their discussions, various ethics committees and the French State Council have agreed upon what constitutes fair compensation under the law. Unlike their Canadian counterparts, medical researchers in France have free access to volunteers who are not in perfect health--e.g., the elderly, people suffering from kidney deficiency, cirrhosis of the liver, etc.--but these "experimental subjects" receive no monetary compensation. Thus, healthy and less-than-healthy volunteers do not receive equal treatment under the law. This inequity, added to the fear of what amounts to a tax on the human body and the difficulty of ensuring just compensation, is giving rise to a great deal of uncertainty. PMID:1878857

  10. Handling ligands with Coot

    PubMed Central

    Debreczeni, Judit É.; Emsley, Paul

    2012-01-01

    Coot is a molecular-graphics application primarily aimed to assist in model building and validation of biological macromolecules. Recently, tools have been added to work with small molecules. The newly incorporated tools for the manipulation and validation of ligands include interaction with PRODRG, subgraph isomorphism-based tools, representation of ligand chemistry, ligand fitting and analysis, and are described here. PMID:22505262

  11. Probing Ternary Complex Equilibria of Crown Ether Ligands by Time-Resolved Fluorescence Spectroscopy

    PubMed Central

    2015-01-01

    Ternary complex formation with solvent molecules and other adventitious ligands may compromise the performance of metal-ion-selective fluorescent probes. As Ca(II) can accommodate more than 6 donors in the first coordination sphere, commonly used crown ether ligands are prone to ternary complex formation with this cation. The steric strain imposed by auxiliary ligands, however, may result in an ensemble of rapidly equilibrating coordination species with varying degrees of interaction between the cation and the specific donor atoms mediating the fluorescence response, thus diminishing the change in fluorescence properties upon Ca(II) binding. To explore the influence of ligand architecture on these equilibria, we tethered two structurally distinct aza-15-crown-5 ligands to pyrazoline fluorophores as reporters. Due to ultrafast photoinduced electron-transfer (PET) quenching of the fluorophore by the ligand moiety, the fluorescence decay profile directly reflects the species composition in the ground state. By adjusting the PET driving force through electronic tuning of the pyrazoline fluorophores, we were able to differentiate between species with only subtle variations in PET donor abilities. Concluding from a global analysis of the corresponding fluorescence decay profiles, the coordination species composition was indeed strongly dependent on the ligand architecture. Altogether, the combination of time-resolved fluorescence spectroscopy with selective tuning of the PET driving force represents an effective analytical tool to study dynamic coordination equilibria and thus to optimize ligand architectures for the design of high-contrast cation-responsive fluorescence switches. PMID:25313708

  12. Chemistry of stannylene-based Lewis pairs: dynamic tin coordination switching between donor and acceptor character.

    PubMed

    Krebs, Kilian M; Freitag, Sarah; Schubert, Hartmut; Gerke, Birgit; Pöttgen, Rainer; Wesemann, Lars

    2015-03-16

    The coordination chemistry of cyclic stannylene-based intramolecular Lewis pairs is presented. The P→Sn adducts were treated with [Ni(COD)2] and [Pd(PCy3)2] (COD = 1,5-cyclooctadiene, PCy3 = tricyclohexylphosphine). In the isolated coordination compounds the stannylene moiety acts either as an acceptor or a donor ligand. Examples of a dynamic switch between these two coordination modes of the P-Sn ligand are illustrated and the structures in the solid state together with heteronuclear NMR spectroscopic findings are discussed. In the case of a Ni(0) complex, (119)Sn Mössbauer spectroscopy of the uncoordinated and coordinated phosphastannirane ligand is presented.

  13. Fluorescent ligands to investigate GPCR binding properties and oligomerization.

    PubMed

    Cottet, Martin; Faklaris, Orestis; Falco, Amadine; Trinquet, Eric; Pin, Jean-Philippe; Mouillac, Bernard; Durroux, Thierry

    2013-02-01

    Fluorescent ligands for GPCRs (G-protein-coupled receptors) have been synthesized for a long time but their use was usually restricted to receptor localization in the cell by fluorescent imaging microscopy. During the last two decades, the emergence of new fluorescence-based strategies and the concomitant development of fluorescent measurement apparatus have dramatically widened the use of fluorescent ligands. Among the various strategies, TR (time-resolved)-FRET (fluorescence resonance energy transfer) approaches exhibit an interesting potential to study GPCR interactions with various partners. We have derived various sets of ligands that target different GPCRs with fluorophores, which are compatible with TR-FRET strategies. Fluorescent ligands labelled either with a fluorescent donor (such as europium or terbium cryptate) or with a fluorescent acceptor (such as fluorescein, dy647 or Alexa Fluor® 647), for example, kept high affinities for their cognate receptors. These ligands turn out to be interesting tools to develop FRET-based binding assays. We also used these fluorescent ligands to analyse GPCR oligomerization by measuring FRET between ligands bound to receptor dimers. In contrast with FRET strategies, on the basis of receptor labelling, the ligand-based approach we developed is fully compatible with the study of wild-type receptors and therefore with receptors expressed in native tissues. Therefore, by using fluorescent analogues of oxytocin, we demonstrated the existence of oxytocin receptor dimers in the mammary gland of lactating rats.

  14. Metal-assisted in situ formation of a tridentate acetylacetone ligand for complexation of fac-Re(CO)3+ for radiopharmaceutical applications.

    PubMed

    Benny, Paul D; Fugate, Glenn A; Barden, Adam O; Morley, Jennifer E; Silva-Lopez, Elsa; Twamley, Brendan

    2008-04-01

    Reaction of [NEt4]2[ReBr3(CO)3] with 2,4-pentanedione (acac) yields a complex of the type fac-Re(acac)(OH2)(CO)3 (1) under aqueous conditions. 1 was further reacted with a monodentate ligand (pyridine) to yield a fac-Re(acac)(pyridine)(CO)3 complex (2). Complex 1 was found to react with primary amines to generate a Schiff base (imine) in aqueous solutions. When a mixed-nitrogen donor bidentate ligand, 2-(2-aminoethyl)pyridine, that has different coordination affinities for fac-Re(acac)(OH2)(CO)3 was utilized, a unique tridentate ligand was formed in situ utilizing a metal-assisted Schiff base formation to yield a complex fac-Re(CO)3(3[(2-phenylethyl)imino]-2-pentanone) (3). Tridentate ligand formation was found to occur only with the Re-coordinated acac ligand. Reactions of acac with fac-Re(CO)3Br(2-(2-aminoethyl)pyridine) (4) or a mixture of [NEt4]2[ReBr3(CO)3], acac, and 2-(2-aminoethyl)pyridine did not yield the formation of complex 3 in water. PMID:18298058

  15. Living kidney donors and ESRD.

    PubMed

    Ross, Lainie Friedman

    2015-07-01

    There are more than 325 living kidney donors who have developed end-stage renal disease and have been listed on the Organ Procurement and Transplantation Network (OPTN)/United Network for Organ Sharing (UNOS) deceased donor kidney wait list. The OPTN/UNOS database records where these kidney donors are listed and, if they donated after April 1994, where that donation occurred. These 2 locations are often not the same. In this commentary, I examine whether a national living donor registry should be created and whether transplantation centers should be notified when one of their living kidney donors develops end-stage renal disease. I consider and refute 5 potential objections to center notification. I explain that transplantation centers should look back at these cases and input data into a registry to attempt to identify patterns that could improve donor evaluation protocols. Creating a registry and mining the information it contains is, in my view, our moral and professional responsibility to future patients and the transplantation endeavor. As individuals and as a community, we need to acknowledge the many unknown risks of living kidney donation and take responsibility for identifying these risks. We then must share information about these risks, educate prospective donors about them, and attempt to minimize them.

  16. Cancer of the colon in an egg donor: policy repercussions for donor recruitment.

    PubMed

    Ahuja, K K; Simons, E G

    1998-01-01

    This paper describes the tragic case of a young woman who died of cancer of the colon after successfully donating eggs to her younger sister. Although there is no direct link between her operation and the subsequent development of bowel carcinoma, this case imparts a feeling of unease when seen in conjunction with other cases reported during the last few years. It is a reminder that little is known of the long-term consequences of some aspects of assisted conception. Women undergoing ovarian stimulation for themselves or a matched recipient have the right to be advised, in an agreed format, that there is some concern about unproven potential risks from the stimulatory drugs. The safety of egg donors must assume priority over all other considerations, including lack of donors or any moral position. The recent decision by the Human Fertilisation and Embryology Authority (HFEA) to withdraw any form of payment or recompense to egg donors does not seem to us to be based on a balance of scientific advances, patient needs and the ethics of gamete supply. They state that the intention to withdraw payments was implicit in the 1990 Human Fertilisation and Embryology (HFE) Act. However the Act was based on the Warnock report made 6 years earlier. Even in 1990 ovum donation was uncommon and fertility drugs had not yet caused any unease. The Act provided the HFEA with discretionary powers to issue directions so that the future policies would be consistent with any emerging new medical evidence. It is imperative that the HFEA provide convincing evidence on how the current policy of payment to donors harms society, donors or recipients, and how in the UK the new policy will improve medical practice in assisted conception. Successful pilot studies must precede the implementation of any new policy. Failure to do this could cause irreversible harm to the practice of assisted conception using donor gametes, which will ultimately be against the basic aims of the 1990 HFE Act.

  17. Prostate-Specific Antigen: Nonspecific in Deceased Organ Donors.

    PubMed

    Pabisiak, K; Ostrowski, M; Kram, A; Safranow, K; Myślak, M; Sieńko, J; Sulikowski, T; Ciechanowski, K

    2016-06-01

    Currently, there is no clear position regarding the donation of organs from donors with prostate carcinoma (CaP) in European countries, except Italy. The lengthening of life expectancy increases the probability of prostate cancer among potential organ donors. The concentration of prostate-specific antigen (PSA) >2 ng/mL at 60 years of age is related to the increasing possibility of identifying an advanced form of CaP. In recent years in Poland, the recommendation has been to determine tumor markers in potential donors. In the first year of the recommendation, 10% of potential male cadaveric donors were disqualified in West Pomerania, Poland, on the basis of elevated PSA levels (>10 ng/mL). To avoid reduction of the actual donor pool, each potential male donor reported to the center since January 2010 undergoes a routine histologic evaluation of the whole prostate, regardless of the PSA level, before organ implantation. In the study group (N = 52), histopathologic evaluation revealed 6 cases of CaP (12%). In CaP positive group Gleason score range from 2+2 to 3+4. In CaP donors PSA level have been noticed in range 1.79 ng/mL - 7.66 ng/mL. There was no correlation between histologically confirmed CaP and the PSA level. PMID:27496408

  18. Ruthenium Bis-diimine Complexes with a Chelating Thioether Ligand: Delineating 1,10-Phenanthrolinyl and 2,2'-Bipyridyl Ligand Substituent Effects

    SciTech Connect

    Al-Rawashdeh, Nathir A. F.; Chatterjee, Sayandev; Krause, Jeanette A.; Connick, William B.

    2014-01-06

    A new series of ruthenium(II) bis-diimine complexes with a chelating thioether donor ligand has been prepared: Ru(diimine)2(dpte)2+ (diimine=1,10-phenanthroline (phen) (1); 5-CH3-phen (2), 5-Cl-phen (3); 5-Br-phen (4); 5-NO2-phen (5); 3,4,7,8-tetramethyl-phen (6); 4,7-diphenyl-phen (7); 5,5'-dimethyl-2,2'-bipyridine (8); 4,4'-di-tert-butyl-2,2'-bipyridine (9)). Crystal structures of 2, 5, 7 and 9 show that the complexes form 2 of the 12 possible conformational/configurational isomers, adopting compact C2-symmetric structures with short intramolecular transannular interactions between the diimine ligands and dpte phenyl groups; crystals of 2 and 5 contain non-statistical distributions of geometric isomers. In keeping with the π-acidity of the dpte, the Ru(III/II) couple, E°'(Ru3+/2+), occurs at relatively high potentials (1.4-1.7 V vs Ag/AgCl), and the lowest spin-allowed MLCT absorption band occurs near 400 nm. Surprisingly, the complexes also exhibit fluid-solution luminescence originating from a lowest MLCT excited state with lifetimes in the 140-750 ns time range; in acetonitrile, compound 8 undergoes photo-induced solvolysis. Variations in the MLCT energies and redox potentials are quantitatively described using a summative Hammett parameter (σT), as well as using Lever's electrochemical parameters (EL). Recommended parameterizations for 2,2'-bipyridyl and 1,10-phenanthrolinyl ligands were derived from analysis of correlations based on 199 measurements of E°'(Ru3+/2+) for 99 homo- and heteroleptic ruthenium(II) tris-diimine complexes. Variations in E°'(Ru3+/2+) due to substituents at the 4- and 4'-positions of bipyridyl ligands and 4- and 7-positions of phenanthrolinyl ligands are significantly more strongly correlated with σp+ than either σm or σp. Substituents at the 5- and 6-positions of phenanthrolinyl ligands are best described by σm and have effects comparable to those of substituents at the 3- and 8-positions. Correlations of EL with σT for 20

  19. Construction of Polynuclear Lanthanide (Ln = Dy(III), Tb(III), and Nd(III)) Cage Complexes Using Pyridine-Pyrazole-Based Ligands: Versatile Molecular Topologies and SMM Behavior.

    PubMed

    Bala, Sukhen; Sen Bishwas, Mousumi; Pramanik, Bhaskar; Khanra, Sumit; Fromm, Katharina M; Poddar, Pankaj; Mondal, Raju

    2015-09-01

    Employment of two different pyridyl-pyrazolyl-based ligands afforded three octanuclear lanthanide(III) (Ln = Dy, Tb) cage compounds and one hexanuclear neodymium(III) coordination cage, exhibiting versatile molecular architectures including a butterfly core. Relatively less common semirigid pyridyl-pyrazolyl-based asymmetric ligand systems show an interesting trend of forming polynuclear lanthanide cage complexes with different coordination environments around the metal centers. It is noteworthy here that construction of lanthanide complex itself is a challenging task in a ligand system as soft N-donor rich as pyridyl-pyrazol. We report herein some lanthanide complexes using ligand containing only one or two O-donors compare to five N-coordinating sites. The resultant multinuclear lanthanide complexes show interesting magnetic and spectroscopic features originating from different spatial arrangements of the metal ions. Alternating current (ac) susceptibility measurements of the two dysprosium complexes display frequency- and temperature-dependent out-of-phase signals in zero and 0.5 T direct current field, a typical characteristic feature of single-molecule magnet (SMM) behavior, indicating different energy reversal barriers due to different molecular topologies. Another aspect of this work is the occurrence of the not-so-common SMM behavior of the terbium complex, further confirmed by ac susceptibility measurement. PMID:26347289

  20. Syntheses and structures of closely related copper(I) complexes of tridentate (2-pyridylmethyl)imine and (2-pyridylmethyl)amine ligands and their use in mediating atom transfer radical polymerizations.

    PubMed

    Turner, Sara A; Remillard, Zachary D; Gijima, Desire T; Gao, Emily; Pike, Robert D; Goh, Christopher

    2012-10-15

    A series of five copper(I) bromide complexes of tridentate (N,N,L) pyridine-imine and pyridine-amine ligands with a third amine, ether, or thioether neutral donor was synthesized and utilized in the atom transfer radical polymerization of styrene. The ligand design illustrated a systematic approach to the development of copper complexes for use in ATRP. Variations in the nature of the ligand impacted the solid state structures of the complexes. A mononuclear [CuBr(L)] complex was observed for L = pyridine-amine-amine, whereas complexes of L = pyridine-imine-amine and -thioether formed dinuclear [CuBr(L)](2) structures with a central 10-membered ring. A doubly-bromide-bridged dimer was revealed for the [CuBr(L)] complex of L = pyridine-imine-ether and a polymeric species for [CuBr(L)], where L = pyridine-imine-amine and the imine-amine spacer was extended from two to three carbon atoms. In the application of these complexes to the ATRP of styrene, the redox potentials of the complexes were found to be one indicator of ATRP efficiency. Of the series presented, two complexes in particular provided fast polymerization rates and good to excellent molecular weight control. In both of these complexes, the ligand contained all nitrogen-based donor moieties. PMID:23020186

  1. Construction of Polynuclear Lanthanide (Ln = Dy(III), Tb(III), and Nd(III)) Cage Complexes Using Pyridine-Pyrazole-Based Ligands: Versatile Molecular Topologies and SMM Behavior.

    PubMed

    Bala, Sukhen; Sen Bishwas, Mousumi; Pramanik, Bhaskar; Khanra, Sumit; Fromm, Katharina M; Poddar, Pankaj; Mondal, Raju

    2015-09-01

    Employment of two different pyridyl-pyrazolyl-based ligands afforded three octanuclear lanthanide(III) (Ln = Dy, Tb) cage compounds and one hexanuclear neodymium(III) coordination cage, exhibiting versatile molecular architectures including a butterfly core. Relatively less common semirigid pyridyl-pyrazolyl-based asymmetric ligand systems show an interesting trend of forming polynuclear lanthanide cage complexes with different coordination environments around the metal centers. It is noteworthy here that construction of lanthanide complex itself is a challenging task in a ligand system as soft N-donor rich as pyridyl-pyrazol. We report herein some lanthanide complexes using ligand containing only one or two O-donors compare to five N-coordinating sites. The resultant multinuclear lanthanide complexes show interesting magnetic and spectroscopic features originating from different spatial arrangements of the metal ions. Alternating current (ac) susceptibility measurements of the two dysprosium complexes display frequency- and temperature-dependent out-of-phase signals in zero and 0.5 T direct current field, a typical characteristic feature of single-molecule magnet (SMM) behavior, indicating different energy reversal barriers due to different molecular topologies. Another aspect of this work is the occurrence of the not-so-common SMM behavior of the terbium complex, further confirmed by ac susceptibility measurement.

  2. Donor states in inverse opals

    SciTech Connect

    Mahan, G. D.

    2014-09-21

    We calculate the binding energy of an electron bound to a donor in a semiconductor inverse opal. Inverse opals have two kinds of cavities, which we call octahedral and tetrahedral, according to their group symmetry. We put the donor in the center of each of these two cavities and obtain the binding energy. The binding energies become very large when the inverse opal is made from templates with small spheres. For spheres less than 50 nm in diameter, the donor binding can increase to several times its unconfined value. Then electrons become tightly bound to the donor and are unlikely to be thermally activated to the semiconductor conduction band. This conclusion suggests that inverse opals will be poor conductors.

  3. Being a Living Donor: Risks

    MedlinePlus

    ... for blood transfusions side effects associated with allergic reactions to the anesthesia death The best source of information about risks and expected donor outcomes is your transplant team. In addition, it’s important to take an active role in ...

  4. Donor states in inverse opals

    NASA Astrophysics Data System (ADS)

    Mahan, G. D.

    2014-09-01

    We calculate the binding energy of an electron bound to a donor in a semiconductor inverse opal. Inverse opals have two kinds of cavities, which we call octahedral and tetrahedral, according to their group symmetry. We put the donor in the center of each of these two cavities and obtain the binding energy. The binding energies become very large when the inverse opal is made from templates with small spheres. For spheres less than 50 nm in diameter, the donor binding can increase to several times its unconfined value. Then electrons become tightly bound to the donor and are unlikely to be thermally activated to the semiconductor conduction band. This conclusion suggests that inverse opals will be poor conductors.

  5. Interactions between alkaline earth cations and oxo ligands. DFT study of the affinity of the Mg²+ cation for phosphoryl ligands.

    PubMed

    da Costa, Leonardo Moreira; de Mesquita Carneiro, José Walkimar; Paes, Lilian Weitzel Coelho

    2011-08-01

    DFT (B3LYP/6-31+G(d)) calculations of Mg(2+) affinities for a set of phosphoryl ligands were performed. Two types of ligands were studied: a set of trivalent [O = P(R)] and a set of pentavalent phosphoryl ligands [O = P(R)(3)] (R = H, F, Cl, Br, OH, OCH(3), CH(3), CN, NH(2) and NO(2)), with R either bound directly to the phosphorus atom or to the para position of a phenyl ring. The affinity of the Mg(2+) cation for the ligands was quantified by means of the enthalpy for the substitution of one water molecule in the [Mg(H(2)O)(6)](2+) complex for a ligand. The enthalpy of substitution was correlated with electronic and geometric parameters. Electron-donor groups increase the interaction between the cation and the ligand, while electron-acceptor groups decrease the interaction enthalpy. PMID:21161556

  6. Donor selection in heart transplantation

    PubMed Central

    Emani, Sitaramesh; Sai-Sudhakar, Chittoor B.; Higgins, Robert S. D.; Whitson, Bryan A.

    2014-01-01

    There is increased scrutiny on the quality in health care with particular emphasis on institutional heart transplant survival outcomes. An important aspect of successful transplantation is appropriate donor selection. We review the current guidelines as well as areas of controversy in the selection of appropriate hearts as donor organs to ensure optimal outcomes. This decision is paramount to the success of a transplant program as well as recipient survival and graft function post-transplant. PMID:25132976

  7. "Planned Giving" Gains Favor Among Donors and Colleges.

    ERIC Educational Resources Information Center

    Bailey, Anne Lowrey

    1986-01-01

    Planned or deferred giving (through which a donor to a college or university contributes capital in the form of an annuity, life-income trust, insurance policy, pooled income fund, real estate, or other asset, to the institution but retains its financial benefit during his lifetime) is an increasingly popular form of donation to endowments. (MSE)

  8. Subcostal Skin Graft Donor Site for Autologous Ear Construction.

    PubMed

    Hassanein, Aladdin H; Greene, Arin K

    2015-06-01

    Autologous ear construction for microtia creates an auricle using a costal cartilage framework. To separate the construct from the mastoid, a skin graft is required to form a retroauricular sulcus. Skin graft donor sites that have been described include the inguinal area (split or full-thickness) or scalp (split-thickness). The purpose of this study is to report a novel skin graft donor site for ear construction. We harvest a full-thickness graft from the subcostal area based on the previous scar from the cartilage harvest. Unlike the inguinal donor site, this method does not place an additional scar on the child. In contrast to the scalp donor site, the technique is simpler and a full-thickness graft minimizes contraction of the retroauricular sulcus. PMID:26080199

  9. Predictive binding geometry of ligands to DNA minor groove: isohelicity and hydrogen-bonding pattern.

    PubMed

    Stockert, Juan C

    2014-01-01

    The interaction of drugs and dyes with nucleic acids, particularly when binding to DNA minor groove occurs, has increasing importance in biomedical sciences. This is due to the resulting biological activity and to the possibility of recognizing AT and GC base pairs. In such cases, DNA binding can be predicted if appropriate helical and hydrogen-bonding parameters are deduced from DNA models, and a simplified geometrical rule in the form of a stencil is then applied on computer-drawn molecules of interest. Relevant structure parameter values for minor groove binders are the length (4.6 < L < 5.4 Å) and angle (152 < σ < 156.5°) between three consecutive units, measured at the level of hydrogen donor or acceptor groups. Application of the stencil shows that predictive methods can aid in the design of new compounds, by checking the possible binding of isohelical sequence-specific ligands along the DNA minor groove. PMID:24162975

  10. Motivations for Giving of Alumni Donors, Lapsed Donors and Non-Donors: Implications for Christian Higher Education

    ERIC Educational Resources Information Center

    Rugano, Emilio Kariuki

    2011-01-01

    This descriptive and causal comparative study sought to identify motivations for alumni donor acquisition and retention in Christian institutions of higher learning. To meet this objective, motivations for alumni donors, lapsed donors, and non-donors were analyzed and compared. Data was collected through an electronic survey of a stratified sample…

  11. Acetonitrile hydration and ethyl acetate hydrolysis by pyrazolate-bridged cobalt(II) dimers containing hydrogen-bond donors.

    PubMed

    Zinn, Paul J; Sorrell, Thomas N; Powell, Douglas R; Day, Victor W; Borovik, A S

    2007-11-26

    The preparation of new CoII-mu-OH-CoII dimers with the binucleating ligands 3,5-bis{bis[(N'-R-ureaylato)-N-ethyl]aminomethyl}-1H-pyrazolate ([H4PRbuam]5-, R=tBu, iPr) is described. The molecular structure of the isopropyl derivative reveals that each CoII center has a trigonal-bipyramidial coordination geometry, with a Co...Co separation of 3.5857(5) A. Structural and spectroscopic studies show that there are four hydrogen-bond (H-bond) donors near the CoII-micro-OH-CoII moiety; however, they are too far away to be form intramolecular H-bonds with the bridging hydroxo ligand. Treating [CoII2H4PRbuam(micro-OH)]2- with acetonitrile led to the formation of bridging acetamidato complexes, [CoII2H4PRbuam(micro-1,3-OC(NH)CH3)]2-; in addition, these CoII-micro-OH-CoII dimers hydrolyze ethyl acetate to form CoII complexes with bridging acetato ligands. The CoII-1,3-micro-X'-CoII complexes (X'=OAc-, [OC(NH)CH3]-) were prepared independently by reacting [CoII2H3PRbuam]2- with acetamide or [CoII2H4PRbuam]- with acetate. X-ray diffraction studies show that the orientation of the acetate ligand within the H-bonding cavity depends on the size of the R substituent appended from the urea groups. The tetradentate ligand 3-{bis[(N'-tert-butylureaylato)-N-ethyl]aminomethyl}-5-tert-butyl-1H-pyrazolato ([H2PtBuuam]3-) was also developed and its CoII-OH complex prepared. In the crystalline state, [CoIIH2PtBuuam(OH)]2- contains two intramolecular H-bonds between the urea groups of [H2PtBuuam]3- and the terminal hydroxo ligand. [nPr4N]2[CoIIH2PtBuuam(OH)] does not hydrate acetonitrile or hydrolyze ethyl acetate. In contrast, K2[CoIIH2PtBuuam(OH)] does react with ethyl acetate to produce KOAc; this enhanced reactivity is attributed to the presence of the K+ ions, which can possibly interact with the CoII-OH unit and ester substrate to assist in hydrolysis. However, K2[CoIIH2PtBuuam(OH)] was still unable to hydrate acetonitrile.

  12. Bonding in titanocenyl complexes containing O,O‧-cyclic ligands

    NASA Astrophysics Data System (ADS)

    Conradie, Jeanet

    Density functional theory calculations show that the formal 16-electron count of d0 [Cp2TiIV(O,O‧-BID)]0/1 complexes containing a O,O‧-chelated bidentate ligand O,O‧-BID of different ring size, is increased via Ti←O π bonding when both the O donor atoms carry a formal negative charge. The Ti←O π bonding occurs by symmetry lowering of the complex by either symmetrical (Cs) or unsymmetrical (C2) folding of the O,O‧-BID ligand round the O···O axis. An NBO analysis confirms the Ti←O π charge transfer via back-bonding.

  13. 3'-Phosphoadenosine-5'-phosphosulfate: Photoaffinity ligand for sulfotransferase enzymes

    SciTech Connect

    Otterness, D.M.; Powers, S.P.; Miller, L.J.; Weinshilboum, R.M. )

    1991-01-01

    Sulfation is an important pathway in the biotransformation of many drugs, xenobiotic compounds, neurotransmitters, and hormones. The sulfate donor for these reactions is 3'-phosphoadenosine-5'-phosphosulfate (PAPS). We set out to determine whether PAPS might serve as a photoaffinity ligand for sulfotransferase enzymes. UV irradiation of (35S)PAPS with partially purified human liver thermostable (TS) phenol sulfotransferase (PST) radioactively labeled a protein with a molecular mass of 35 kDa, as estimated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Photoaffinity labeling of TS PST with (35S) PAPS did not require the presence of a phenolic substrate but rather was inhibited by p-nitrophenol, a sulfate acceptor substrate for TS PST. Inhibitors of TS PST enzymatic activity, including 3'-phosphoadenosine-5'-phosphate, ATP, ADP, and 2,6-dichloro-4-nitrophenol, also inhibited photoaffinity labeling of the 35-kDa protein with (35S)PAPS, in a concentration-dependent fashion, with IC50 values of 14 microM, 2.1 mM, 7.7 mM, and 91 microM, respectively. The 35-kDa protein that was radioactively labeled by (35S)PAPS in the presence of UV light coeluted with TS PST enzymatic activity during gel filtration high performance liquid chromatography. (35S)PAPS was then used to photoaffinity label another sulfotransferase enzyme, the thermolabile (TL) form of PST partially purified from human liver. Therefore, (35S)PAPS appears to be a photoaffinity ligand that could be used to study a variety of PAPS-dependent sulfotransferases. Photoaffinity labeling of TS and TL PST, as well as other PAPS-dependent sulfotransferases, should enhance our ability to purify this important group of enzymes and to determine amino acid sequences at or near their active sites.

  14. Mono- and binuclear copper(II) complexes of new hydrazone ligands derived from 4,6-diacetylresorcinol: Synthesis, spectral studies and antimicrobial activity

    NASA Astrophysics Data System (ADS)

    Shebl, Magdy; El-ghamry, Mosad A.; Khalil, Saied M. E.; Kishk, Mona A. A.

    Two new hydrazone ligands, H2L1 and H2L2, were synthesized by the condensation of 4,6-diacetylresorcinol with 3-hydrazino-5,6-diphenyl-1,2,4-triazine and isatin monohydrazone, respectively. The structures of the ligands were elucidated by elemental analyses, IR, 1H NMR, electronic and mass spectra. Reactions of the ligands with several copper(II) salts, including AcO-, NO3-, SO42-, Cl- and Br- afforded mono- and binuclear metal complexes. Also, the ligands were allowed to react with Cu(II) ion in the presence of a secondary ligand (L‧) [N,O-donor; 8-hydroxyquinoline, N,N-donor; 1,10-phenanthroline or O,O-donor; benzoylacetone]. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, electronic, mass and ESR spectra as well as conductivity and magnetic susceptibility measurements. The ESR spin Hamiltonian parameters of some complexes were calculated. The spectroscopic data showed that the H2L1 ligand acts as a neutral or monobasic tridentate ligand while the H2L2 ligand acts as a bis(monobasic tridentate) ligand. The coordination sites with the copper(II) ion are phenolic oxygen, azomethine nitrogen and triazinic nitrogen (H2L1 ligand) or isatinic oxygen (H2L2 ligand). The metal complexes exhibited octahedral and square planar geometrical arrangements depending on the nature of the anion. The ligands and some metal complexes showed antimicrobial activity.

  15. Blood Donation by Elderly Repeat Blood Donors

    PubMed Central

    Zeiler, Thomas; Lander-Kox, Jutta; Alt, Timo

    2014-01-01

    Summary Background Upper age limits for blood donors are intended to protect elderly blood donors from donor reactions. However, due to a lack of data about adverse reactions in elderly blood donors, upper age limits are arbitrary and vary considerably between different countries. Methods Here we present data from 171,231 voluntary repeat whole blood donors beyond the age of 68 years. Results Blood donations from repeat blood donors beyond the age of 68 years increased from 2,114 in 2005 to 38,432 in 2012 (from 0,2% to 4.2% of all whole blood donations). Adverse donor reactions in repeat donors decreased with age and were lower than in the whole group (0.26%), even in donors older than 71 years (0.16%). However, from the age of 68 years, the time to complete recovery after donor reactions increased. Donor deferrals were highest in young blood donors (21.4%), but increased again in elderly blood donors beyond 71 years (12.6%). Conclusion Blood donation by regular repeat blood donors older than 71 years may be safely continued. However, due to a lack of data for donors older than 75 years, blood donation in these donors should be handled with great caution. PMID:25254019

  16. Ligand modeling and design

    SciTech Connect

    Hay, B.P.

    1997-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used in the cost-effective removal of specific radionuclides from nuclear waste streams. Organic ligands with metal ion specificity are critical components in the development of solvent extraction and ion exchange processes that are highly selective for targeted radionuclides. The traditional approach to the development of such ligands involves lengthy programs of organic synthesis and testing, which in the absence of reliable methods for screening compounds before synthesis, results in wasted research effort. The author`s approach breaks down and simplifies this costly process with the aid of computer-based molecular modeling techniques. Commercial software for organic molecular modeling is being configured to examine the interactions between organic ligands and metal ions, yielding an inexpensive, commercially or readily available computational tool that can be used to predict the structures and energies of ligand-metal complexes. Users will be able to correlate the large body of existing experimental data on structure, solution binding affinity, and metal ion selectivity to develop structural design criteria. These criteria will provide a basis for selecting ligands that can be implemented in separations technologies through collaboration with other DOE national laboratories and private industry. The initial focus will be to select ether-based ligands that can be applied to the recovery and concentration of the alkali and alkaline earth metal ions including cesium, strontium, and radium.

  17. Multiple complexation of CO and related ligands to a main-group element.

    PubMed

    Braunschweig, Holger; Dewhurst, Rian D; Hupp, Florian; Nutz, Marco; Radacki, Krzysztof; Tate, Christopher W; Vargas, Alfredo; Ye, Qing

    2015-06-18

    The ability of an atom or molecular fragment to bind multiple carbon monoxide (CO) molecules to form multicarbonyl adducts is a fundamental trait of transition metals. Transition-metal carbonyl complexes are vital to industry, appear naturally in the active sites of a number of enzymes (such as hydrogenases), are promising therapeutic agents, and have even been observed in interstellar dust clouds. Despite the wealth of established transition-metal multicarbonyl complexes, no elements outside groups 4 to 12 of the periodic table have yet been shown to react directly with two or more CO units to form stable multicarbonyl adducts. Here we present the synthesis of a borylene dicarbonyl complex, the first multicarbonyl complex of a main-group element prepared using CO. The compound is additionally stable towards ambient air and moisture. The synthetic strategy used--liberation of a borylene ligand from a transition metal using donor ligands--is broadly applicable, leading to a number of unprecedented monovalent boron species with different Lewis basic groups. The similarity of these compounds to conventional transition-metal carbonyl complexes is demonstrated by photolytic liberation of CO and subsequent intramolecular carbon-carbon bond activation. PMID:26085273

  18. Multiple complexation of CO and related ligands to a main-group element.

    PubMed

    Braunschweig, Holger; Dewhurst, Rian D; Hupp, Florian; Nutz, Marco; Radacki, Krzysztof; Tate, Christopher W; Vargas, Alfredo; Ye, Qing

    2015-06-18

    The ability of an atom or molecular fragment to bind multiple carbon monoxide (CO) molecules to form multicarbonyl adducts is a fundamental trait of transition metals. Transition-metal carbonyl complexes are vital to industry, appear naturally in the active sites of a number of enzymes (such as hydrogenases), are promising therapeutic agents, and have even been observed in interstellar dust clouds. Despite the wealth of established transition-metal multicarbonyl complexes, no elements outside groups 4 to 12 of the periodic table have yet been shown to react directly with two or more CO units to form stable multicarbonyl adducts. Here we present the synthesis of a borylene dicarbonyl complex, the first multicarbonyl complex of a main-group element prepared using CO. The compound is additionally stable towards ambient air and moisture. The synthetic strategy used--liberation of a borylene ligand from a transition metal using donor ligands--is broadly applicable, leading to a number of unprecedented monovalent boron species with different Lewis basic groups. The similarity of these compounds to conventional transition-metal carbonyl complexes is demonstrated by photolytic liberation of CO and subsequent intramolecular carbon-carbon bond activation.

  19. A Selenium-Containing Diarylamido Pincer Ligand: Synthesis and Coordination Chemistry with Group 10 Metals.

    PubMed

    Charette, Bronte J; Ritch, Jamie S

    2016-06-20

    The synthesis of new bifunctional organoselenium diarylamine compounds RN(4-Me-2-SeMe-C6H3)2 (R = Me: 1; R = tert-butoxycarbonyl (Boc): 2; R = H: 3-H) via aryllithium chemistry is disclosed. Compound 1 serves as a Se,Se-bidentate neutral ligand toward Pd(II), forming the coordination complex {PdCl2[MeN(4-Me-2-SeMe-C6H3)2-κ(2)Se)]} (1-Pd) in reaction with [PdCl2(COD)] (COD = 1,5-cyclooctadiene), while the protio ligand 3-H forms tridentate pincer complexes [MCl(N(4-Me-2-SeMe-C6H3)2)] (M = Pd: 3-Pd; M = Pt: 3-Pt) with [MCl2(COD)] (M = Pd, Pt) in the presence of triethylamine. Complex 1-Pd does not undergo N-C cleavage at high temperature, unlike related alkylphosphine-bearing complexes. All compounds have been characterized by multinuclear ((1)H, (13)C, (77)Se) NMR spectroscopy, and crystal structures of 1, 1-Pd, 3-Pd, and 3-Pt are reported. Additionally, density functional theory calculations have been performed on the pincer complexes to contrast them with well-known analogues containing phosphine donor groups. PMID:27281450

  20. Multiple complexation of CO and related ligands to a main-group element

    NASA Astrophysics Data System (ADS)

    Braunschweig, Holger; Dewhurst, Rian D.; Hupp, Florian; Nutz, Marco; Radacki, Krzysztof; Tate, Christopher W.; Vargas, Alfredo; Ye, Qing

    2015-06-01

    The ability of an atom or molecular fragment to bind multiple carbon monoxide (CO) molecules to form multicarbonyl adducts is a fundamental trait of transition metals. Transition-metal carbonyl complexes are vital to industry, appear naturally in the active sites of a number of enzymes (such as hydrogenases), are promising therapeutic agents, and have even been observed in interstellar dust clouds. Despite the wealth of established transition-metal multicarbonyl complexes, no elements outside groups 4 to 12 of the periodic table have yet been shown to react directly with two or more CO units to form stable multicarbonyl adducts. Here we present the synthesis of a borylene dicarbonyl complex, the first multicarbonyl complex of a main-group element prepared using CO. The compound is additionally stable towards ambient air and moisture. The synthetic strategy used--liberation of a borylene ligand from a transition metal using donor ligands--is broadly applicable, leading to a number of unprecedented monovalent boron species with different Lewis basic groups. The similarity of these compounds to conventional transition-metal carbonyl complexes is demonstrated by photolytic liberation of CO and subsequent intramolecular carbon-carbon bond activation.

  1. Who is the best alternative allotransplant donor?

    PubMed Central

    Gale, RP; Eapen, M

    2015-01-01

    Assuming that most physicians will chose an HLA-identical sibling as the best allotransplant donor, the question arises who is the best alternative donor when an HLA-identical sibling is unavailable? The most commonly used alternative donors are HLA-identical or -mismatched unrelated donors, HLA-matched or -mismatched umbilical cord blood donor or a related, HLA-haplotype-matched related donors. Each alternative donor option has advantages and disadvantages. We discuss selected aspects of these issues based on data from randomized clinical trials and observational databases. However, because there are limited data to address specific clinical settings, quantification of expert opinion is sometimes needed. PMID:26039206

  2. Donor substrate regulation of transketolase.

    PubMed

    Esakova, Olga A; Meshalkina, Ludmilla E; Golbik, Ralph; Hübner, Gerhard; Kochetov, German A

    2004-11-01

    The influence of substrates on the interaction of apotransketolase with thiamin diphosphate was investigated in the presence of magnesium ions. It was shown that the donor substrates, but not the acceptor substrates, enhance the affinity of the coenzyme either to only one active center of transketolase or to both active centers, but to different degrees in each, resulting in a negative cooperativity for coenzyme binding. In the absence of donor substrate, negative cooperativity is not observed. The donor substrate did not affect the interaction of the apoenzyme with the inactive coenzyme analogue, N3'-pyridyl-thiamin diphosphate. The influence of the donor substrate on the coenzyme-apotransketolase interaction was predicted as a result of formation of the transketolase reaction intermediate 2-(alpha,beta-dihydroxyethyl)-thiamin diphosphate, which exhibited a higher affinity to the enzyme than thiamin diphosphate. The enhancement of thiamin diphosphate's affinity to apotransketolase in the presence of donor substrate is probably one of the mechanisms underlying the substrate-affected transketolase regulation at low coenzyme concentrations.

  3. Being Sherlock Holmes: the Internet as a tool for assessing live organ donors.

    PubMed

    Bramstedt, Katrina A; Katznelson, Steven

    2009-01-01

    Donor advocacy is a critical feature of live donor transplantation. Donor Advocates and Donor Advocate Teams (DAT) are now routine to the practice of live donor evaluation in the USA. Multidisciplinary in nature, DATs gather both medical and psychosocial information about potential live organ donors and then render a decision as to whether or not these individuals are suitable to participate. Because of the critical ethical and psychosocial concerns about live donation, thorough donor evaluations are essential. Additionally, the information gathered must be accurate, and this requires honest disclosure by the donor candidate. In this paper, we describe how DATs can use various forms of free, public content available on the Internet to aid live donor assessments. In this way, the DAT assumes somewhat of an investigative role; however, this is ethically justified in light of the DAT duty to protect the donor. The protective effect can also spread to the transplant program, in general, when inappropriate donors are excluded from the donation process.

  4. Synthesis and spectroscopic characterization of some transition metal complexes of a new hexadentate N(2)S(2)O(2) Schiff base ligand.

    PubMed

    Sarkar, Saikat; Dey, Kamalendu

    2005-11-01

    A novel interesting hexadentate dibasic N(2)S(2)O(2) donor Schiff base ligand, H(4)dcsalpte, was synthesized by the condensation of 3-formylsalicylic acid and 1,2-di(o-aminophenylthio)ethane and characterized. The reactions of the ligand with different metal(II/III)salts under varied reaction conditions afforded a series of metal complexes. The ligand, H(4)dcsalpte, behaves either as a dibasic or neutral hexadentate one, depending on the reaction conditions. Structural investigations on the ligand and their complexes have been made based on elemental analyses, molar conductance values, magnetic moment values, cryomagnetic and spectral (UV-vis, IR, (1)H NMR, and Mössbauer) data. Based on magnetic susceptibility, Mössbauer and electronic spectral data the iron(III) complex [Fe(III)(H(2)dcsalpte)]ClO(4) (8), isolated in the present investigation, it is inferred that the spin states 5/2 and 1/2 are in equilibrium. Similarly a tri-iron(III) complex [Fe(III)(3)(H(2)dcsalpte)(H(3)dcsalpte)Cl(3)]Cl(3) (7), isolated in this study, has been inferred to contain two iron(III) sites in tetrahedral environment and one in the octahedral environment. The aerial oxidation of an equimolar mixture of H(4)dcsalpte and Co(CH(3)COO)(2).4H(2)O in ethanol under reflux gave two products, [Co(H(2)dcsalpte)]CH(3)COO (10) and [(Hbtcsaldm)Co(Hbvcsaldm)] (11), a cobalt(III) complex bound to two dissimilar tridentate NSO donor ligands formed as a result of the oxidative cleavage of the CS bond. In the complex 11, Hbtcsaldm stands for the dianion of the tridentate Schiff base ligand N-(2'-benzenethiol)-3-carboxysalicylaldimine and Hbvcsaldm stands for the mono anion of the tridentate Schiff base ligand N-(benzene-2'-S-vinyl)-3-carboxysalicylaldimine, both being formed as a result of the oxidative cleavage of H(4)dcsalpte. PMID:16257739

  5. Synthesis and spectroscopic characterization of some transition metal complexes of a new hexadentate N 2S 2O 2 Schiff base ligand

    NASA Astrophysics Data System (ADS)

    Sarkar, Saikat; Dey, Kamalendu

    2005-11-01

    A novel interesting hexadentate dibasic N 2S 2O 2 donor Schiff base ligand, H4dcsalpte, was synthesized by the condensation of 3-formylsalicylic acid and 1,2-di( o-aminophenylthio)ethane and characterized. The reactions of the ligand with different metal(II/III)salts under varied reaction conditions afforded a series of metal complexes. The ligand, H4dcsalpte, behaves either as a dibasic or neutral hexadentate one, depending on the reaction conditions. Structural investigations on the ligand and their complexes have been made based on elemental analyses, molar conductance values, magnetic moment values, cryomagnetic and spectral (UV-vis, IR, 1H NMR, and Mössbauer) data. Based on magnetic susceptibility, Mössbauer and electronic spectral data the iron(III) complex [Fe III( H2dcsalpte)]ClO 4 ( 8), isolated in the present investigation, it is inferred that the spin states 5/2 and 1/2 are in equilibrium. Similarly a tri-iron(III) complex [Fe III3( H2dcsalpte)( H3dcsalpte)Cl 3]Cl 3 ( 7), isolated in this study, has been inferred to contain two iron(III) sites in tetrahedral environment and one in the octahedral environment. The aerial oxidation of an equimolar mixture of H4dcsalpte and Co(CH 3COO) 2·4H 2O in ethanol under reflux gave two products, [Co( H2dcsalpte)]CH 3COO ( 10) and [( Hbtcsaldm)Co( Hbvcsaldm)] ( 11), a cobalt(III) complex bound to two dissimilar tridentate NSO donor ligands formed as a result of the oxidative cleavage of the C sbnd S bond. In the complex 11, Hbtcsaldm stands for the dianion of the tridentate Schiff base ligand N-(2'-benzenethiol)-3-carboxysalicylaldimine and Hbvcsaldm stands for the mono anion of the tridentate Schiff base ligand N-(benzene-2'-S-vinyl)-3-carboxysalicylaldimine, both being formed as a result of the oxidative cleavage of H4dcsalpte.

  6. Gadolinium speciation with Tetradentate, N-donor extractants for minor actinide/lanthanide separation: an XRD, mass spectrometry and EPR study

    SciTech Connect

    Whittaker, D.M.; Sharrad, C.A.; Sproules, S.

    2013-07-01

    The hydrophobic organic molecules CyMe{sub 4}-BTPhen (1) and CyMe{sub 4}-BTBP (2) have been developed and tuned over many years to be able to separate the trivalent actinides from the trivalent lanthanides (Ln) selectively in bi-phasic solvent extraction processes for the separation of the long-lived radio-toxic minor actinides from spent nuclear fuel. The ability of these N-donor ligands to perform this separation is poorly understood, as is their speciation with the metal ions when extracted into the organic phase. Our previous work has shown Ln{sup 3+} speciation to be largely 1:2 Ln:L in nature with another small molecule, either water or nitrate, occupying a cavity between the tetradentate bound N-donor ligands. The identity of the small molecule changes across the lanthanide series, and here we continue investigations into this speciation. Complexes of these N-donor ligands with Gd{sup 3+} have been synthesised and characterised by X-ray crystallography, mass spectrometry and EPR spectroscopy. We show that the N-donor ligands have no effect on the electronic configuration of Gd{sup 3+} and that the lanthanide contraction with the steric rigidity of the N-donor ligand appears to determine the size of the cavity between the coordinated ligands. This in turn appears to control the identity of the small molecule on the ninth site in the 1:2 Gd:L species. (authors)

  7. Ligand modeling and design

    SciTech Connect

    Hay, B.

    1996-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used tin applications for the cost-effective removal of specific radionuclides from nuclear waste streams.

  8. Minimally invasive surgery for live kidney donors: techniques and challenges.

    PubMed

    Brook, Nicholas R; Nicholson, Michael L

    2005-09-01

    Live kidney donation is assuming an increasingly prominent role in kidney transplantation programs. The traditional operative approach has been through an incision in the upper quadrant of the abdomen or in the loin, with the attendant potential postoperative complications associated with a large surgical wound. These problems may act as disincentives to prospective donors. The introduction of laparoscopic donor surgery in 1995 heralded a new era offering reduced post-operative pain and improved cosmetic result. It is hoped that these benefits may counter some disincentives and thereby increase donation rates. Three minimal-access approaches and their advantages and disadvantages are described: classical laparoscopic, hand-assisted laparoscopic, and retroperitoneoscopic surgery. Published reports indicate extensive experience with the first 2 of these approaches and less experience with the latter. All 3 approaches present technical, physiological, and anatomical challenges in the context of retrieving an organ that is fit for transplantation. For minimal-access surgery to be accepted as the procedure of choice for live kidney donors, it must be demonstrated that morbidity is not transferred from donor to recipient when these techniques are used. Some concerns about these procedures are addressed. High-level evidence in the form of randomized controlled trials is generally lacking, but experiences of surgeons and patients suggest that, with appropriate modifications, these techniques are safe for both donors and allografts and also benefit donors' recovery. PMID:16252632

  9. Shuttling electrons on and off As donor atoms in silicon

    NASA Astrophysics Data System (ADS)

    Tyryshkin, A. M.; Lyon, S. A.; Lo, C. C.; Lo Nardo, R.; Morton, J. J. L.; Simmons, S.; Weis, C. D.; Schenkel, T.; Bokor, J.; Meijer, J.; Rogalla, D.

    2013-03-01

    Hybrid quantum devices where electron spins are used for state initialization, fast manipulation, long range entanglement and detection, while nuclear spins are used for long term storage promise revolutionary advantages. Here we report our first experiments using a silicon-based device that utilizes electron and nuclear spins of arsenic donors. The device is a large-area, parallel-plate capacitor fabricated on a silicon-on-insulator (SOI) wafer where the SOI layer is implanted with arsenic donors, and a back gate is formed in the silicon below the buried oxide by a high-energy boron implantation. The electrons can be controllably stripped from the donors and then reintroduced to the ionized donors by applying appropriate gate voltages. We use ensemble ESR experiments (X-band, magnetic field of 0.35 T) to track the occupancy of the donors during these operations. Pulsed ESR is used to characterize the spin state of the donor electrons and the effect of applied electric fields below the ionization threshold. The spin state of the arsenic nuclei, and the effect of electron removal and reintroduction on the nuclear state is expected to be observable in pulsed ENDOR experiments. The work is funded by LPS and NSF-MWN.

  10. [Living donor transplantation. Surgical complications].

    PubMed

    Karam, Georges

    2008-02-01

    Although nephrectomy by open surgery is the most used technique for the extraction of kidney transplants in the living donor, nephrectomy under laparaoscopy is increasingly practiced. Laparoscopic nephrectomy is less invasive and performed under videoscopy control, after insufflation of the peritoneal cavity. Three to four incisions are done in order to enter the surgical instruments. The kidney is extracted through a horizontal sus-pubic incision. The exposition is either exclusively transperitoneal, retroperitoneal or hand assisted. The advantages of laparoscopy are esthetical, financial due to a shorter hospitalisation and a quicker recovery, as well a confort for the donor. The disadvantages are a longer warm ischemia time and possibly a higher risk of delayed graft function. Randomised studies having compared laparoscopy and open surgery in the living donor have not find any significant difference regarding the per- and perioperative in the complications.

  11. [Living donor transplantation. Surgical complications].

    PubMed

    Karam, Georges

    2008-02-01

    Although nephrectomy by open surgery is the most used technique for the extraction of kidney transplants in the living donor, nephrectomy under laparaoscopy is increasingly practiced. Laparoscopic nephrectomy is less invasive and performed under videoscopy control, after insufflation of the peritoneal cavity. Three to four incisions are done in order to enter the surgical instruments. The kidney is extracted through a horizontal sus-pubic incision. The exposition is either exclusively transperitoneal, retroperitoneal or hand assisted. The advantages of laparoscopy are esthetical, financial due to a shorter hospitalisation and a quicker recovery, as well a confort for the donor. The disadvantages are a longer warm ischemia time and possibly a higher risk of delayed graft function. Randomised studies having compared laparoscopy and open surgery in the living donor have not find any significant difference regarding the per- and perioperative in the complications. PMID:18160357

  12. Selective high affinity polydentate ligands and methods of making such

    DOEpatents

    DeNardo, Sally; DeNardo, Gerald; Balhorn, Rodney

    2010-02-16

    This invention provides novel polydentate selective high affinity ligands (SHALs) that can be used in a variety of applications in a manner analogous to the use of antibodies. SHALs typically comprise a multiplicity of ligands that each bind different region son the target molecule. The ligands are joined directly or through a linker thereby forming a polydentate moiety that typically binds the target molecule with high selectivity and avidity.

  13. Supramolecular donor-acceptor hybrids of porphyrins/phthalocyanines with fullerenes/carbon nanotubes: electron transfer, sensing, switching, and catalytic applications.

    PubMed

    D'Souza, Francis; Ito, Osamu

    2009-09-01

    Since the three-dimensional electron-accepting fullerene has been found to be an excellent building block for self-assembled supramolecular systems, we have investigated photoinduced electron transfer processes in supramolecular fullerene systems with porphyrins and phthalocyanines as electron donors to mimic natural photosynthesis. We have successfully formed self-assembled supramolecular dyads and triads via metal-ligand coordination, crown-ether inclusion, ion pairing, hydrogen-bonding, or pi-pi stacking interactions. Although the single mode of binding gives usually flexible supramolecular structures, the newly developed strategy of multiple modes of binding results in conjugates of defined distance and orientation between the donor and acceptor entities, which influences the overall electron transfer reactions. In these conjugates, we observe the anticipated acceleration of the charge separation process and deceleration of the charge recombination process. Applications of these supramolecular systems for reversible photoswitching of inter- and intramolecular electron transfer events open up new opportunities in the area of photosensors. Extension of the self-assembly approaches to single wall carbon nanotubes (SWNT) results in SWNT-porphyrin/phthalocyanine nanohybrids capable of undergoing photoinduced electron transfer. These photochemical processes lead to photocatalytic reactions accumulating redox active substances of electron acceptor/mediator entities with the help of a sacrificial electron donor. Studies on these self-assembled supramolecular dyads, triads, tetrads, etc., are only in the beginning stages and future studies anticipate involvement of more complex systems targeted for better performances in light-driven devices. PMID:19668806

  14. Donor criteria in hepatic transplantation.

    PubMed

    Jonas, S; Bechstein, W O; Keck, H; Lemmens, H P; Blumhardt, G; Neuhaus, P

    1994-01-01

    The early outcome of 201 liver grafts transplanted consecutively between September 1988 and November 1991 was investigated retrospectively. Donors were categorized according to their hospitalization periods in an intensive care unit (ICU) prior to harvesting, their causes of death, and the variables generally believed to be critical in liver donation, such as arterial hypotension (n = 69; 34.3%), cardiopulmonary resuscitation (n = 20; 9.9%), elevated serum-aminotransferases (s-AT) (n = 11; 5.5%), or an age over 50 years (n = 16; 8.0%). Ninety-one donors (45.3%) spent less than 24 h in an ICU; 29 donors (14.4%) and 14 donors (7.0%) had hospitalization periods generally considered critical of 4-6 days and more than 6 days, respectively. The most common causes of death were subarachnoidal bleeding (n = 70; 34.8%), isolated head injuries (n = 68; 33.8%), and polytraumata (n = 33; 16.4%). The postischemic hepatocellular damage was evaluated comparing peak post-transplant s-AT, which did not differ significantly between groups; nor did donor and recipient ages or cold ischemia times. Fourteen grafts (7.0%) showed a reversible preservation injury presenting with post-transplant s-AT elevated above 2000 IU/l. Five cases (2.5%) of a primary non-functioning graft (PNF) underwent early retransplantation successfully. Serum-aminotransferases (AST: 4944 +/- 2280 IU/l; ATL: 3186 +/- 1918 IU/l) were significantly (P < 0.01) elevated as compared to primary functioning grafts (AST: 699 +/- 935 IU/l; ALT: 620 +/- 701 IU/l). The donor structure of both groups reflected the distribution of variables in the entire collective. No significant overrepresentations were observed.(ABSTRACT TRUNCATED AT 250 WORDS)

  15. [The safety of blood donors].

    PubMed

    Courchelle, J; Baudry, C; Bourboul, M-C; Coudurier, N

    2011-04-01

    For a long time, safety has been patient-centred and taken for granted. Indeed, it needed a dramatic accident and the study of post-donation information for the question to be looked into again. However, under various statutory, organizational aspects and the professionalization of the staffs, safety has always accompanied the donor throughout its course of donation. Self-sufficiency is, certainly, the first mission of the Établissement Français du Sang: while we have to supply patients with sufficient blood products complying with quality criteria, we must not however forget the essential respect for the safety of the donor.

  16. First principles NEXAFS simulations of N-donor Uranyl complexes

    NASA Astrophysics Data System (ADS)

    Pemmaraju, C. D.; Duan, R.; Copping, R.; Jeon, B.; Teat, S. J.; Janousch, M.; Tyliszczak, T.; Canning, A.; Grønbech-Jensen, N.; Shuh, D. K.; Prendergast, D.

    2013-03-01

    The synthesis and study of soft-donor uranyl complexes can provide new insights into the coordination chemistry of non-aqueous [UO]2+ Recently, the tunable N-donor ligand 2,6-Bis(2-benzimidazyl)pyridine (BBP) was employed to produce novel uranyl complexes in which the [UO]2+ cation is ligated by anionic and covalent groups with discrete chemical differences. In this work we investigate the electronic structure of the three such uranyl-BBP complexes via near-edge X-ray absorption fine structure (NEXAFS) experiments and simulations using the eXcited electron and Core-Hole (XCH) approach. The evolution of the structural as well as electronic properties across the three complexes is studied systematically. Computed N K-edge and O K-edge NEXAFS spectra are compared with experiment and spectral features assigned to specific electronic transitions in these complexes. Studying the variations in spectral features arising from N K-edge absorption provides a clear picture of ligand-uranyl bonding in these systems.

  17. Singlet-triplet donor-quantum-dot qubit in silicon

    NASA Astrophysics Data System (ADS)

    Harvey-Collard, Patrick; Ten Eyck, Gregory A.; Wendt, Joel R.; Pluym, Tammy; Lilly, Michael P.; Carroll, Malcolm S.; Pioro-Ladrière, Michel

    2015-03-01

    Electron spins bound to phosphorus (P) donors in silicon (Si) are promising qubits due to their high fidelities, but donor-donor coupling is challenging. We propose an alternative two-electron singlet-triplet quantum-dot (QD) and donor (D) hybrid qubit. A QD is formed at a MOS 28-Si interface and is tunnel-coupled to implanted P. The proposed two-axis system is defined by the exchange and contact hyperfine interactions. We demonstrate that a few electron QD can be formed and tuned to interact with a donor. We investigate the spin filling of the QD-D system through charge-sensed (CS) magnetospectroscopy and identify spin-up loading consistent with a singlet-triplet splitting of ~100 μeV near a QD-D anti-crossing. We also demonstrate an enhanced CS readout contrast and time window due to the restricted relaxation path of the D through the QD. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  18. Single-Donor Leukophoretic Technique

    NASA Technical Reports Server (NTRS)

    Eberhardt, R. N.

    1977-01-01

    Leukocyte separation-and-retrieval device utilizes granulocyte and monocyte property of leukoadhesion to glass surfaces as basis of their separation from whole blood. Device is used with single donor technique and has application in biological and chemical processing, veterinary research and clinical care.

  19. Beta-Phosphinoethylboranes as Ambiphilic Ligands in Nickel-Methyl Complexes

    SciTech Connect

    Fischbach, Andreas; Bazinet, Patrick R.; Waterman, Rory; Tilley, T. Don

    2007-10-28

    The ambiphilic {beta}-phosphinoethylboranes Ph{sub 2}PCH{sub 2}CH{sub 2}BR{sub 2} (BR{sub 2} = BCy{sub 2} (1a), BBN (1b)), which feature a ethano spacer CH{sub 2}CH{sub 2} between the Lewis acidic boryl and Lewis basic phosphino groups, were synthesized in nearly quantitative yields via the hydroboration of vinyldiphenylphosphine. Compounds 1a and 1b were fully characterized by elemental analysis, and by NMR and IR spectroscopy. X-ray crystallographic studies of compound 1b revealed infinite helical chains of the molecules connected through P{hor_ellipsis}B donor-acceptor interactions. The ability of these ambiphilic ligands to concurrently act as donors and acceptors was highlighted by their reactions with (dmpe)NiMe{sub 2}. Zwitterionic complexes (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}BCy{sub 2}Me) (2a) and (dmpe)NiMe(Ph{sub 2}PCH{sub 2}CH{sub 2}[BBN]Me) (2b) were generated via the abstraction of one of the methyl groups, forming a borate, and intramolecular coordination of the phosphine moiety to the resulting cationic metal center. Compound 2b was characterized by X-ray crystallography. Furthermore, B(C{sub 6}F{sub 5}){sub 3} abstracts the methyl group of a coordinated borate ligand to generate a free, 3-coordinate borane center in [(dmpe)NiMe(1a)]{sup +}[MeB(C{sub 6}F{sub 5}){sub 3}]{sup -} (3).

  20. Open-Identity Sperm Donation: How Does Offering Donor-Identifying Information Relate to Donor-Conceived Offspring's Wishes and Needs?

    PubMed

    Ravelingien, An; Provoost, Veerle; Pennings, Guido

    2015-09-01

    Over the past years, a growing number of countries have legislated open-identity donation, in which donor-conceived offspring are given access to the donor's identity once the child has reached maturity. It is held that donor anonymity creates identity problems for such children similar to the "genealogical bewilderment" described within the adoption context. The study of the social and psychological effects of open-identity donation is still very much in its infancy, but what has been left unquestioned is whether (and to what extent) offering access to the donor's name and address is an adequate response to such effects. This study has two goals: First, we aim to provide a systematic review of the reasons why donor-conceived (DC) offspring want to know the identity of their sperm donor. Second, we examine to what extent the provision of donor-identifying information can satisfy the reasons mentioned. The most important motivations appear to be: (1) to avoid medical risks and consanguineous relationships; (2) to satisfy curiosity; (3) to learn more about the self or to complete one's identity; (4) to learn more about what kind of person the donor is (biographical information, why he donated, etc.); (5) to form a relationship with the donor and/or his family; and (6) to learn about one's ancestry/genealogy. Our analysis shows that for nearly all of these reasons access to the donor's identity is not necessary. In those cases where it is, moreover, donor identification is not sufficient. What is really needed is (extended) contact with the donor, rather than the mere provision of his name.

  1. Open-Identity Sperm Donation: How Does Offering Donor-Identifying Information Relate to Donor-Conceived Offspring's Wishes and Needs?

    PubMed

    Ravelingien, An; Provoost, Veerle; Pennings, Guido

    2015-09-01

    Over the past years, a growing number of countries have legislated open-identity donation, in which donor-conceived offspring are given access to the donor's identity once the child has reached maturity. It is held that donor anonymity creates identity problems for such children similar to the "genealogical bewilderment" described within the adoption context. The study of the social and psychological effects of open-identity donation is still very much in its infancy, but what has been left unquestioned is whether (and to what extent) offering access to the donor's name and address is an adequate response to such effects. This study has two goals: First, we aim to provide a systematic review of the reasons why donor-conceived (DC) offspring want to know the identity of their sperm donor. Second, we examine to what extent the provision of donor-identifying information can satisfy the reasons mentioned. The most important motivations appear to be: (1) to avoid medical risks and consanguineous relationships; (2) to satisfy curiosity; (3) to learn more about the self or to complete one's identity; (4) to learn more about what kind of person the donor is (biographical information, why he donated, etc.); (5) to form a relationship with the donor and/or his family; and (6) to learn about one's ancestry/genealogy. Our analysis shows that for nearly all of these reasons access to the donor's identity is not necessary. In those cases where it is, moreover, donor identification is not sufficient. What is really needed is (extended) contact with the donor, rather than the mere provision of his name. PMID:24996630

  2. Mononuclear and Oligonuclear Manganese Complexes with Organic Multidentate Ligands

    NASA Astrophysics Data System (ADS)

    Mikuriya, Masahiro

    The crystal structures of manganese complexes with tridentate, tetradentate, pentadentate, hexadentate, and dodecadentate ligands with oxygen and nitrogen donors are described. Reactions of these ligands with manganese salts afforded mononuclear (MnII, MnIII, and MnIV), dinuclear (MnII2, MnIII2, and MnIIMnIII), trinuclear (MnIII3), and tetranuclear (MnII2MnIII2 and MnIII4) complexes. As for MnII complexes, octahedral, trigonal prismatic, capped trigonal prismatic, and square antiprismatic geometries were found depending on the combination of the organic and anionic ligands. In the case of MnIII complexes, the Jahn-Teller distortions due to the high-spin d4 electronic configuration were observed as elongated or compressed octahedral geometries. An octahedral geometry was confirmed for the Mn (IV) complexes.

  3. Multifunctional ligand for use as a diagnostic or therapeutic pharmaceutical

    DOEpatents

    Katti, K.V.; Volkert, W.A.; Ketring, A.R.; Singh, P.R.

    1996-05-14

    A compound and method of making a compound for use as a diagnostic or therapeutic pharmaceutical are revealed. The ligand comprises either a phosphorous or germanium core and at least two hydrazine groups forming a ligand for bonding to a metal extending from the phosphorous or germanium core.

  4. Technetium radiodiagnostic fatty acids derived from bisamide bisthiol ligands

    DOEpatents

    Jones, Alun G.; Lister-James, John; Davison, Alan

    1988-05-24

    A bisamide-bisthiol ligand containing fatty acid substituted thiol useful for producing Tc-labelled radiodiagnostic imaging agents is described. The ligand forms a complex with the radionuclide .sup.99m Tc suitable for administration as a radiopharmaceutical to obtain images of the heart for diagnosis of myocardial disfunction.

  5. Triethylenetetramine penta- and hexa-acetamide ligands and their ytterbium complexes as paraCEST contrast agents for MRI.

    PubMed

    Burdinski, Dirk; Lub, Johan; Pikkemaat, Jeroen A; Moreno Jalón, Diana; Martial, Sophie; Del Pozo Ochoa, Carolina

    2008-08-21

    The ligand triethylenetetramine-N,N,N',N'',N''',N'''-hexaacetamide (ttham) was synthesized with the aim of forming lanthanide complexes suitable as contrast agents for magnetic resonance imaging applications utilizing the chemical exchange-dependent saturation transfer (CEST) effect. It was designed to exclude water molecules from the first coordination sphere and provide a high number of CEST active amide protons per lanthanide ion. The ligand was characterized by its protonation behavior and its complexation properties with ytterbium ions in aqueous solution. The basicity of the ttham backbone amine protons decreases in the order N(central(1)) > N(terminal(1)) > N(terminal(2)) > N(central(2)), as deduced from NMR titration experiments and from a comparison of its protonation constants with those of two ttham derivatives, in which either a terminal (N-benzyl-triethylenetetramine-N,N',N'',N''',N'''-pentaacetamide, 1bttpam) or a central acetamide group (N'-benzyl-triethylenetetramine-N,N,N'',N''',N'''-pentaacetamide, 4bttpam) is substituted with a benzyl group. This protonation sequence results from the combined influence of inductive effects, the intramolecular hydrogen bonding network, and the Coulomb repulsion between protonated ammonium groups. The ytterbium complex of ttham, [Yb(ttham)]Cl(3), is coordinatively frustrated. Due to steric constraints, in addition to the four backbone nitrogen atoms, only three of the four symmetry-equivalent terminal acetamide donors can coordinate simultaneously to the ytterbium ion, and the dangling fourth one exchanges quickly with the other three. The ytterbium complexes of a total of five ligands (ttham, 1bttpam, 4bttpam, 2,2',2''-triaminotriethylaminehexaacetamide (ttaham), and diethylenetriamine-N,N,N',N'',N''-pentaacetamide (dtpam)) were studied with respect to their CEST properties. In solution, all of these complexes have a low symmetry. The presence of multiple magnetically different amide groups in each complex

  6. Are the MDGs Enough? Donor Perspectives and Recipient Visions of Education and Poverty Reduction in Rwanda

    ERIC Educational Resources Information Center

    Hayman, Rachel

    2007-01-01

    Achieving the millennium development goals (MDGs) forms the central focus of many donor agencies' policies, resulting in a renewed focus on basic education. This paper explores the different perspectives of donors and the Government of Rwanda (GoR) with regard to education and training. GoR discourse mirrors the international poverty reduction…

  7. Architectural repertoire of ligand-binding pockets on protein surfaces.

    PubMed

    Weisel, Martin; Kriegl, Jan M; Schneider, Gisbert

    2010-03-01

    Knowledge of the three-dimensional structure of ligand binding sites in proteins provides valuable information for computer-assisted drug design. We present a method for the automated extraction and classification of ligand binding site topologies, in which protein surface cavities are represented as branched frameworks. The procedure employs a growing neural gas approach for pocket topology assignment and pocket framework generation. We assessed the structural diversity of 623 known ligand binding site topologies based on framework cluster analysis. At a resolution of 5 A only 23 structurally distinct topology groups were formed; this suggests an overall limited structural diversity of ligand-accommodating protein cavities. Higher resolution allowed for identification of protein-family specific pocket features. Pocket frameworks highlight potentially preferred modes of ligand-receptor interactions and will help facilitate the identification of druggable subpockets suitable for ligand affinity and selectivity optimization. PMID:20069621

  8. Copper(I) Complexes of Pyridine-Bridged Phosphaalkene-Oxazoline Pincer Ligands.

    PubMed

    Serin, Spencer C; Pick, Fraser S; Dake, Gregory R; Gates, Derek P

    2016-07-01

    The synthesis of enantiomerically pure pyridine-bridged phosphaalkene-oxazolines ArP═C(Ph)(2,6-C5H3NOx) (1, Ar = Mes/Mes*, Ox = CNOCH(i-Pr)CH2/CNOCH(CH2Ph)CH2) is reported. This new ligand forms a κ(P), κ(2)(NN) dimeric complex with copper(I) (7) that dissociates into a cationic κ(3)(PNN) monomeric complex upon addition of a neutral ligand {[1a·CuL]OTf (8a-e): L = PPh3 (a), P(OPh)3 (b), 2,6-lutidine (c), 4-DMAP (d), 1-methylimidazole (e)}. The P-Cu bond lengths in 8 are influenced by the π-accepting/σ-donating properties of L, and this can be observed by changes in the δ(31)PP═C NMR shift. The donor-acceptor properties in complexes of type 8 have also been investigated by UV/vis spectroscopy and density functional theory calculations.

  9. Copper(I) Complexes of Pyridine-Bridged Phosphaalkene-Oxazoline Pincer Ligands.

    PubMed

    Serin, Spencer C; Pick, Fraser S; Dake, Gregory R; Gates, Derek P

    2016-07-01

    The synthesis of enantiomerically pure pyridine-bridged phosphaalkene-oxazolines ArP═C(Ph)(2,6-C5H3NOx) (1, Ar = Mes/Mes*, Ox = CNOCH(i-Pr)CH2/CNOCH(CH2Ph)CH2) is reported. This new ligand forms a κ(P), κ(2)(NN) dimeric complex with copper(I) (7) that dissociates into a cationic κ(3)(PNN) monomeric complex upon addition of a neutral ligand {[1a·CuL]OTf (8a-e): L = PPh3 (a), P(OPh)3 (b), 2,6-lutidine (c), 4-DMAP (d), 1-methylimidazole (e)}. The P-Cu bond lengths in 8 are influenced by the π-accepting/σ-donating properties of L, and this can be observed by changes in the δ(31)PP═C NMR shift. The donor-acceptor properties in complexes of type 8 have also been investigated by UV/vis spectroscopy and density functional theory calculations. PMID:27315353

  10. Becoming a Blood Stem Cell Donor

    MedlinePlus

    ... total__ Find out why Close Becoming a Blood Stem Cell Donor NCIcancertopics Subscribe Subscribed Unsubscribe 359 359 Loading... ... Ever considered becoming a bone marrow or blood stem cell donor? Follow this true story of a former ...

  11. Role of ligand-ligand vs. core-core interactions in gold nanoclusters.

    PubMed

    Milowska, Karolina Z; Stolarczyk, Jacek K

    2016-05-14

    The controlled assembly of ligand-coated gold nanoclusters (NCs) into larger structures paves the way for new applications ranging from electronics to nanomedicine. Here, we demonstrate through rigorous density functional theory (DFT) calculations employing novel functionals accounting for van der Waals forces that the ligand-ligand interactions determine whether stable assemblies can be formed. The study of NCs with different core sizes, symmetry forms, ligand lengths, mutual crystal orientations, and in the presence of a solvent suggests that core-to-core van der Waals interactions play a lesser role in the assembly. The dominant interactions originate from combination of steric effects, augmented by ligand bundling on NC facets, and related to them changes in electronic properties induced by neighbouring NCs. We also show that, in contrast to standard colloidal theory approach, DFT correctly reproduces the surprising experimental trends in the strength of the inter-particle interaction observed when varying the length of the ligands. The results underpin the importance of understanding NC interactions in designing gold NCs for a specific function. PMID:27097887

  12. The heterobifunctional ligand 5-[4-(1,2,4-triazol-4-yl)phenyl]-1H-tetrazole and its role in the construction of a CdII metal-organic chain structure.

    PubMed

    Lysenko, Andrey B

    2012-10-01

    5-[4-(1,2,4-Triazol-4-yl)phenyl]-1H-tetrazole, C(9)H(7)N(7), (I), an asymmetric heterobifunctional organic ligand containing triazole (tr) and tetrazole (tz) termini linked directly through a 1,4-phenylene spacer, crystallizes in the polar space group Pc. The heterocyclic functions, serving as single hydrogen-bond donor (tz) or acceptor (tr) units, afford hydrogen-bonded zigzag chains with no crystallographic centre of inversion. In the structure of catena-poly[[diaquacadmium(II)]bis{μ(2)-5-[4-(1,2,4-triazol-4-yl)phenyl]tetrazol-1-ido-κ(2)N(1):N(1')}], [Cd(C(9)H(6)N(7))(2)(H(2)O)(2)](n), (II), the Cd(II) dication resides on a centre of inversion in an octahedral {N(4)O(2)} environment. In the equatorial plane, the Cd(II) polyhedron is built up from four N atoms of two kinds, namely of trans-coordinating tr and tz fragments [Cd-N = 2.2926 (17) and 2.3603 (18) Å], and the coordinating aqua ligands occupy the two apical sites. The metal centres are separated at a distance of 11.1006 (7) Å by means of the double-bridging tetrazolate anion, L(-), forming a chain structure. The water ligands and tz fragments interact with one another, like a double hydrogen-bond donor-acceptor synthon, leading to a hydrogen-bonded three-dimensional array.

  13. Transport spectroscopy of coupled donors in silicon nano-transistors

    PubMed Central

    Moraru, Daniel; Samanta, Arup; Anh, Le The; Mizuno, Takeshi; Mizuta, Hiroshi; Tabe, Michiharu

    2014-01-01

    The impact of dopant atoms in transistor functionality has significantly changed over the past few decades. In downscaled transistors, discrete dopants with uncontrolled positions and number induce fluctuations in device operation. On the other hand, by gaining access to tunneling through individual dopants, a new type of devices is developed: dopant-atom-based transistors. So far, most studies report transport through dopants randomly located in the channel. However, for practical applications, it is critical to control the location of the donors with simple techniques. Here, we fabricate silicon transistors with selectively nanoscale-doped channels using nano-lithography and thermal-diffusion doping processes. Coupled phosphorus donors form a quantum dot with the ground state split into a number of levels practically equal to the number of coupled donors, when the number of donors is small. Tunneling-transport spectroscopy reveals fine features which can be correlated with the different numbers of donors inside the quantum dot, as also suggested by first-principles simulation results. PMID:25164032

  14. Designing shallow donors in diamond

    NASA Astrophysics Data System (ADS)

    Moussa, Jonathan

    2015-03-01

    The production of n-type semiconducting diamond has been a long-standing experimental challenge. The first-principles simulation of shallow dopants in semiconductors has been a long-standing theoretical challenge. A desirable theoretical goal is to identify impurities that will act as shallow donors in diamond and assess their experimental viability. I will discuss this identification process for the LiN4 donor complex. It builds a scientific argument from several models and computational results in the absence of computational tools that are both trustworthy and computationally tractable for this task. I will compare the theoretical assessment of viability with recent experimental efforts to co-dope diamond with lithium and nitrogen. Finally, I discuss the computational tools needed to facilitate future work on this problem and some preliminary simulations of donors near diamond surfaces. Sandia National Laboratories is a multi-program lab managed and operated by Sandia Corp., a wholly owned subsidiary of Lockheed Martin Corp., for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  15. Electron Transfer within Self-Assembling Cyclic Tetramers Using Chlorophyll-Based Donor-Acceptor Building Blocks

    SciTech Connect

    Gunderson, Victoria L; Smeigh, Amanda L; Kim, Chul Hoon; Co, Dick T; Wasielewski, Michael R

    2012-05-09

    The synthesis and photoinduced charge transfer properties of a series of Chl-based donor-acceptor triad building blocks that self-assemble into cyclic tetramers are reported. Chlorophyll a was converted into zinc methyl 3-ethylpyrochlorophyllide a (Chl) and then further modified at its 20-position to covalently attach a pyromellitimide (PI) acceptor bearing a pyridine ligand and one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) secondary electron acceptors to give Chl-PI-NDI and Chl-PI-NDI2. The pyridine ligand within each ambident triad enables intermolecular Chl metal-ligand coordination in dry toluene, which results in the formation of cyclic tetramers in solution, as determined using small- and wide-angle X-ray scattering at a synchrotron source. Femtosecond and nanosecond transient absorption spectroscopy of the monomers in toluene-1% pyridine and the cyclic tetramers in toluene shows that the selective photoexcitation of Chl results in intramolecular electron transfer from 1*Chl to PI to form Chl+.-PI-.-NDI and Chl+.-PI-.-NDI2. This initial charge separation is followed by a rapid charge shift from PI-. to NDI and subsequent charge recombination of Chl+.-PI-NDI-. and Chl+.-PI-(NDI)NDI-. on a 5-30 ns time scale. Charge recombination in the Chl-PI-NDI2 cyclic tetramer (τCR = 30 ± 1 ns in toluene) is slower by a factor of 3 relative to the monomeric building blocks (τCR = 10 ± 1 ns in toluene-1% pyridine). This indicates that the self-assembly of these building blocks into the cyclic tetramers alters their structures in a way that lengthens their charge separation lifetimes, which is an advantageous strategy for artificial photosynthetic systems.

  16. Impact of killer immunoglobulin-like receptor-human leukocyte antigens ligand incompatibility among renal transplantation

    PubMed Central

    Alam, S.; Rangaswamy, D.; Prakash, S.; Sharma, R. K.; Khan, M. I.; Sonawane, A.; Agrawal, S.

    2015-01-01

    Killer immunoglobulin-like receptor (KIR) gene shows a high degree of polymorphism. Natural killer cell receptor gets activated once they bind to self-human leukocyte antigens (HLAs) with specific ligand. KIR gene and HLA ligand incompatibility due to the presence/absence of KIR in the recipient and the corresponding HLA ligand in the allograft may impact graft survival in solid organ transplantation. This study evaluates the effect of matches between KIR genes and known HLA ligands. KIR genotypes were determined using sequence specific primer polymerase chain reaction. Presence of certain KIR in a recipient, where the donor lacked the corresponding HLA ligand was considered a mismatch. The allograft was considered matched when both KIR receptor and HLA alloantigen reveald compatibility among recipient and donor. The data revealed better survival among individuals with matched inhibitory KIR receptors and their corresponding HLA ligands (KIR2DL2/DL3-HLAC2, KIR3DL1-HLABw4). On the contrary, no adverse effect was seen for matched activating KIR receptors and their corresponding HLA ligands. One of the activating gene KIR2DS4 showed risk (P = 0.0413, odds ratio = 1.91, 95% confidence interval = 1.02-3.57) association with renal allograft rejection. We conclude that the presence of inhibitory KIR gene leads to better survival; whereas activating motifs show no significant role in renal allograft survival. PMID:25684869

  17. Impact of killer immunoglobulin-like receptor-human leukocyte antigens ligand incompatibility among renal transplantation.

    PubMed

    Alam, S; Rangaswamy, D; Prakash, S; Sharma, R K; Khan, M I; Sonawane, A; Agrawal, S

    2015-01-01

    Killer immunoglobulin-like receptor (KIR) gene shows a high degree of polymorphism. Natural killer cell receptor gets activated once they bind to self-human leukocyte antigens (HLAs) with specific ligand. KIR gene and HLA ligand incompatibility due to the presence/absence of KIR in the recipient and the corresponding HLA ligand in the allograft may impact graft survival in solid organ transplantation. This study evaluates the effect of matches between KIR genes and known HLA ligands. KIR genotypes were determined using sequence specific primer polymerase chain reaction. Presence of certain KIR in a recipient, where the donor lacked the corresponding HLA ligand was considered a mismatch. The allograft was considered matched when both KIR receptor and HLA alloantigen reveald compatibility among recipient and donor. The data revealed better survival among individuals with matched inhibitory KIR receptors and their corresponding HLA ligands (KIR2DL2/DL3-HLAC2, KIR3DL1-HLABw4). On the contrary, no adverse effect was seen for matched activating KIR receptors and their corresponding HLA ligands. One of the activating gene KIR2DS4 showed risk (P = 0.0413, odds ratio = 1.91, 95% confidence interval = 1.02-3.57) association with renal allograft rejection. We conclude that the presence of inhibitory KIR gene leads to better survival; whereas activating motifs show no significant role in renal allograft survival.

  18. Changing Pattern of Donor Selection Criteria in Deceased Donor Liver Transplant: A Review of Literature

    PubMed Central

    Routh, Dronacharya; Naidu, Sudeep; Sharma, Sanjay; Ranjan, Priya; Godara, Rajesh

    2013-01-01

    During the last couple of decades, with standardization and progress in surgical techniques, immunosuppression and post liver transplantation patient care, the outcome of liver transplantation has been optimized. However, the principal limitation of transplantation remains access to an allograft. The number of patients who could derive benefit from liver transplantation markedly exceeds the number of available deceased donors. The large gap between the growing list of patients waiting for liver transplantation and the scarcity of donor organs has fueled efforts to maximize existing donor pool and identify new avenues. This article reviews the changing pattern of donor for liver transplantation using grafts from extended criteria donors (elderly donors, steatotic donors, donors with malignancies, donors with viral hepatitis), donation after cardiac death, use of partial grafts (split liver grafts) and other suboptimal donors (hypernatremia, infections, hypotension and inotropic support). PMID:25755521

  19. Light-induced copper(II) coordination by a bicyclic tetraaza chelator through a ligand-to-metal charge-transfer reaction.

    PubMed

    Holm-Jørgensen, Jacob R; Jensen, Mikael; Bjerrum, Morten J

    2011-12-19

    To enable utilization of the broad potential of copper isotopes in nuclear medicine, rapid and robust chelation of the copper is required. Bowl adamanzanes (bicyclic tetraaza ligands) can form kinetically stable copper complexes, but they are usually formed at low rates unless high pH values and high temperatures are applied. We have investigated the effects of the variation in the pH, different anions, and UV irradiation on the chelation rate. UV spectra of mixtures of Cu(2+) and [2(4).3(1)]adz in water show the existence of a long-lived two-coordinated copper(II) intermediate (only counting coordinated amine groups) at pH above 6. These findings are supported by pH titrations of mixtures of Cu(2+) and [2(4).3(1)]adz in water. Irradiation of this complex in the ligand-to-metal charge-transfer (LMCT) band by a diode-array spectrophotometer leads to photodeprotonation and subsequently to formation of the four-coordinated copper(II) complex at a rate up to 7800-fold higher at 25 °C than in the dark. Anions in the solution were found to have three major effects: competitive inhibition due to Cu(II) binding anions, inhibition of the photoinduced transchelation from UV-absorbing anions, and photoredox inhibition from acido ligands capable of acting as electron donors in LMCT reactions. Dissolved O(2) was also found to result in photoredox inhibition.

  20. Charge transport and exciton dissociation in organic solar cells consisting of dipolar donors mixed with C70

    NASA Astrophysics Data System (ADS)

    Griffith, Olga L.; Liu, Xiao; Amonoo, Jojo A.; Djurovich, Peter I.; Thompson, Mark E.; Green, Peter F.; Forrest, Stephen R.

    2015-08-01

    We investigate dipolar donor materials mixed with a C70 acceptor in an organic photovoltaic (OPV) cell. Dipolar donors that have donor-acceptor-acceptor (d-a-a') structure result in high conductivity pathways due to close coupling between neighboring molecules in the mixed films. We analyze the charge transfer properties of the dipolar donor:C70 mixtures and corresponding neat donors using a combination of time-resolved electroluminescence from intermolecular polaron pair states and conductive tip atomic force microscopy, from which we infer that dimers of the d-a-a' donors tend to form a continuous network of nanocrystalline clusters within the blends. Additional insights are provided by quantum-mechanical calculations of hole transfer coupling and hopping rates between donor molecules using nearest-neighbor donor packing motifs taken from crystal structural data. The approximation using only nearest-neighbor interactions leads to good agreement between donor hole hopping rates and the conductive properties of the donor:C70 blends. This represents a significant simplification from requiring details of the nano- and mesoscale morphologies of thin films to estimate their electronic characteristics. Using these dipolar donors, we obtain a maximum power conversion efficiency of 9.6 ±0.5 % under 1 sun, AM1.5G simulated illumination for an OPV comprised of an active layer containing a dipolar donor mixed with C70.

  1. Management of the feline blood donor.

    PubMed

    Kaufman, P M

    1992-12-01

    The feline blood donor should be considered a valuable asset to the veterinary clinic. As public awareness increases, so will the demand for high-quality blood products. Meeting this demand will require planning and a blood donor management program tailored to the clinic's needs. Consideration should be given to the areas of blood value, donor selection, blood collection, and maintaining donor health when developing a donor management program. Suggestions for reducing the stress and aggravation often associated with feline blood collection are provided.

  2. Spin Isomers and Ligand Isomerization in a Three-Coordinate Cobalt(I) Carbonyl Complex.

    PubMed

    Al-Afyouni, Malik H; Suturina, Elizaveta; Pathak, Shubhrodeep; Atanasov, Mihail; Bill, Eckhard; DeRosha, Daniel E; Brennessel, William W; Neese, Frank; Holland, Patrick L

    2015-08-26

    Hemilabile ligands, which have one donor that can reversibly bind to a metal, are widely used in transition-metal catalysts to create open coordination sites. This change in coordination at the metal can also cause spin-state changes. Here, we explore a cobalt(I) system that is poised on the brink of hemilability and of a spin-state change and can rapidly interconvert between different spin states with different structures ("spin isomers"). The new cobalt(I) monocarbonyl complex L(tBu)Co(CO) (2) is a singlet ((1)2) in the solid state, with an unprecedented diketiminate binding mode where one of the C═C double bonds of an aromatic ring completes a pseudo-square-planar coordination. Dissolving the compound gives a substantial population of the triplet ((3)2), which has exceptionally large uniaxial zero-field splitting due to strong spin-orbit coupling with a low-lying excited state. The interconversion of the two spin isomers is rapid, even at low temperature, and temperature-dependent NMR and electronic absorption spectroscopy studies show the energy differences quantitatively. Spectroscopically validated computations corroborate the presence of a low minimum-energy crossing point (MECP) between the two potential energy surfaces and elucidate the detailed pathway through which the β-diketiminate ligand "slips" between bidentate and arene-bound forms: rather than dissociation, the cobalt slides along the aromatic system in a pathway that balances strain energy and cobalt-ligand bonding. These results show that multiple spin states are easily accessible in this hemilabile system and map the thermodynamics and mechanism of the transition. PMID:26267848

  3. Functional osteoclastogenesis: the baseline variability in blood donor precursors is not associated with age and gender.

    PubMed

    Pivetta, Eliana; Wassermann, Bruna; Bulian, Pietro; Steffan, Agostino; Colombatti, Alfonso; Polesel, Jerry; Spessotto, Paola

    2015-10-13

    Mononuclear osteoclast precursors circulate in the monocyte fraction of peripheral blood and form multinuclear cells with all osteoclastic phenotypic characteristics when cultured in the presence of macrophage colony stimulating factor (M-CSF) and receptor activator of nuclear factor kB ligand (RANKL). The method to obtain osteoclast precursors from peripheral blood is simple but the number of recovered osteoclasts is often largely insufficient for functional analyses. The original aim of this study was to develop a rapid and efficient method that could overcome the donor variability and enrich the osteoclast precursors from a small volume of peripheral blood as a basis for future clinical studies to correlate the differentiation potential of circulating osteoclast precursors with bone lesions in cancer patients. We improved the efficiency of osteoclastogenesis by reducing isolation and purification times and overcame the use of flow cytometry and immunomagnetic purification procedures. In our culture system the osteoclast number was increased several-fold and the precursors were able to reach a full differentiation within seven days of culture. Both age as well as gender differences in osteoclastogenesis efficiency were no longer evident by processing limited volume blood samples with this simple and rapid method.

  4. Synthesis and Fluorescence Properties of Pyrimidine-Based Diboron Complexes with Donor-π-Acceptor Structures.

    PubMed

    Kubota, Yasuhiro; Kasatani, Kouhei; Niwa, Takahiro; Sato, Hiroyasu; Funabiki, Kazumasa; Matsui, Masaki

    2016-01-26

    Pyrimidine-based diboron complexes bearing β-iminoenolate ligands and phenyl groups as bulky substituents on the boron atoms were synthesized as novel fluorescent dyes, and their fluorescence properties were investigated in solution and in the solid state. The diboron complexes with donor-π-acceptor structures showed positive solvatochromism in the fluorescence spectra. The cyano derivative exhibited the most dramatic redshift of the fluorescence maximum Fmax with increasing solvent polarity (from 551 nm in n-hexane to 710 nm in acetonitrile). The diboron complexes showed solid-state fluorescence in the range of 578-706 nm with fluorescence quantum yields of 0.06-0.28. Additionally, the trifluoromethyl derivative exhibited solvent-inclusion solid-state fluorescence. The trifluoromethyl derivative formed toluene-inclusion and ethyl acetate-inclusion crystals. The toluene-inclusion crystal (Fmax = 668 nm, Φf = 0.16) showed a blueshifted Fmax and higher Φf value compared to the original trifluoromethyl derivative (Fmax = 694 nm, Φf = 0.08) in the solid state. On the other hand, the Fmax (709 nm) and Φf (0.04) values of the ethyl acetate-inclusion crystal were redshifted and lower, respectively. PMID:26670268

  5. The probability of finding suitable directed donors.

    PubMed

    Kanter, M; Selvin, S; Myhre, B A

    1989-02-01

    A series of tables based on mathematical calculations is given as guidelines for the number of directed donors needed by members of various ethnic/racial groups to provide a desired number of units of blood with a selected probability of achieving this result. From these tables, certain conclusions can be drawn. Unrelated donors who do not know their blood type are an inefficient source of directed donors. Rh-negative patients are unlikely to obtain enough directed-donor units from either related or unrelated donors with confidence unless these donors known their blood type. In general, siblings, parents, and offspring are the most efficient directed donors from the standpoint of compatibility. Cousins, uncles, aunts, nieces, and nephews are not much more likely to be compatible than unrelated donors are. It is easier to obtain suitable directed-donor units among Hispanics than among whites, blacks, or Asians, due to their skewed blood group frequencies. In general, using O-negative directed donors for Rh-positive recipients does not significantly increase the likelihood of finding suitable donors.

  6. The identification of potential cadaveric organ donors.

    PubMed

    Thompson, J F; McCosker, C J; Hibberd, A D; Chapman, J R; Compton, J S; Mahony, J F; Mohacsi, P J; MacDonald, G J; Spratt, P M

    1995-02-01

    Most Australian transplantation programs are severely restricted in their activities by a limited availability of cadaveric donor organs. To investigate possible reasons for this problem, an audit was undertaken over three 12-month periods of all deaths in 13 hospitals in New South Wales and the Australian Capital Territory. From 7406 deaths, 271 patients were classified as having been realistic, medically suitable potential donors. Of these, only 60 (22%) became actual donors. In the other 211 patients, donation did not occur because of unsuccessful resuscitation (30%), permission refusal by relatives (34%), and failure to identify or support the potential donors (36%). If the impediments to organ donation which were identified in this study could be overcome, allowing a greater number of potential donors to become actual donors, the chronic shortage of cadaveric donor organs for transplantation could be at least partly relieved.

  7. Riboswitch structure: an internal residue mimicking the purine ligand

    PubMed Central

    Delfosse, Vanessa; Bouchard, Patricia; Bonneau, Eric; Dagenais, Pierre; Lemay, Jean-François; Lafontaine, Daniel A.; Legault, Pascale

    2010-01-01

    The adenine and guanine riboswitches regulate gene expression in response to their purine ligand. X-ray structures of the aptamer moiety of these riboswitches are characterized by a compact fold in which the ligand forms a Watson–Crick base pair with residue 65. Phylogenetic analyses revealed a strict restriction at position 39 of the aptamer that prevents the G39–C65 and A39–U65 combinations, and mutational studies indicate that aptamers with these sequence combinations are impaired for ligand binding. In order to investigate the rationale for sequence conservation at residue 39, structural characterization of the U65C mutant from Bacillus subtilis pbuE adenine riboswitch aptamer was undertaken. NMR spectroscopy and X-ray crystallography studies demonstrate that the U65C mutant adopts a compact ligand-free structure, in which G39 occupies the ligand-binding site of purine riboswitch aptamers. These studies present a remarkable example of a mutant RNA aptamer that adopts a native-like fold by means of ligand mimicking and explain why this mutant is impaired for ligand binding. Furthermore, this work provides a specific insight into how the natural sequence has evolved through selection of nucleotide identities that contribute to formation of the ligand-bound state, but ensures that the ligand-free state remains in an active conformation. PMID:20022916

  8. Simulation shows that HLA-matched stem cell donors can remain unidentified in donor searches.

    PubMed

    Sauter, Jürgen; Solloch, Ute V; Giani, Anette S; Hofmann, Jan A; Schmidt, Alexander H

    2016-01-01

    The heterogeneous nature of HLA information in real-life stem cell donor registries may hamper unrelated donor searches. It is even possible that fully HLA-matched donors with incomplete HLA information are not identified. In our simulation study, we estimated the probability of these unnecessarily failed donor searches. For that purpose, we carried out donor searches in several virtual donor registries. The registries differed by size, composition with respect to HLA typing levels, and genetic diversity. When up to three virtual HLA typing requests were allowed within donor searches, the share of unnecessarily failed donor searches ranged from 1.19% to 4.13%, thus indicating that non-identification of completely HLA-matched stem cell donors is a problem of practical relevance. The following donor registry characteristics were positively correlated with the share of unnecessarily failed donor searches: large registry size, high genetic diversity, and, most strongly correlated, large fraction of registered donors with incomplete HLA typing. Increasing the number of virtual HLA typing requests within donor searches up to ten had a smaller effect. It follows that the problem of donor non-identification can be substantially reduced by complete high-resolution HLA typing of potential donors.

  9. Simulation shows that HLA-matched stem cell donors can remain unidentified in donor searches

    PubMed Central

    Sauter, Jürgen; Solloch, Ute V.; Giani, Anette S.; Hofmann, Jan A.; Schmidt, Alexander H.

    2016-01-01

    The heterogeneous nature of HLA information in real-life stem cell donor registries may hamper unrelated donor searches. It is even possible that fully HLA-matched donors with incomplete HLA information are not identified. In our simulation study, we estimated the probability of these unnecessarily failed donor searches. For that purpose, we carried out donor searches in several virtual donor registries. The registries differed by size, composition with respect to HLA typing levels, and genetic diversity. When up to three virtual HLA typing requests were allowed within donor searches, the share of unnecessarily failed donor searches ranged from 1.19% to 4.13%, thus indicating that non-identification of completely HLA-matched stem cell donors is a problem of practical relevance. The following donor registry characteristics were positively correlated with the share of unnecessarily failed donor searches: large registry size, high genetic diversity, and, most strongly correlated, large fraction of registered donors with incomplete HLA typing. Increasing the number of virtual HLA typing requests within donor searches up to ten had a smaller effect. It follows that the problem of donor non-identification can be substantially reduced by complete high-resolution HLA typing of potential donors. PMID:26876789

  10. Dinitrogen extrusion from enoldiazo compounds under thermal conditions: synthesis of donor-acceptor cyclopropenes.

    PubMed

    Deng, Yongming; Jing, Changcheng; Doyle, Michael P

    2015-08-21

    Donor-acceptor cyclopropenes are formed quantitatively or in high yield from enoldiazoacetates and enoldiazoacetamides under moderate thermal conditions. They are more versatile than their corresponding enoldiazocarbonyl compounds as carbene precursors.

  11. LigandRNA: computational predictor of RNA-ligand interactions.

    PubMed

    Philips, Anna; Milanowska, Kaja; Lach, Grzegorz; Bujnicki, Janusz M

    2013-12-01

    RNA molecules have recently become attractive as potential drug targets due to the increased awareness of their importance in key biological processes. The increase of the number of experimentally determined RNA 3D structures enabled structure-based searches for small molecules that can specifically bind to defined sites in RNA molecules, thereby blocking or otherwise modulating their function. However, as of yet, computational methods for structure-based docking of small molecule ligands to RNA molecules are not as well established as analogous methods for protein-ligand docking. This motivated us to create LigandRNA, a scoring function for the prediction of RNA-small molecule interactions. Our method employs a grid-based algorithm and a knowledge-based potential derived from ligand-binding sites in the experimentally solved RNA-ligand complexes. As an input, LigandRNA takes an RNA receptor file and a file with ligand poses. As an output, it returns a ranking of the poses according to their score. The predictive power of LigandRNA favorably compares to five other publicly available methods. We found that the combination of LigandRNA and Dock6 into a "meta-predictor" leads to further improvement in the identification of near-native ligand poses. The LigandRNA program is available free of charge as a web server at http://ligandrna.genesilico.pl.

  12. Analysis of macromolecules, ligands and macromolecule-ligand complexes

    DOEpatents

    Von Dreele, Robert B.

    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.

  13. Ligand structure and mechanical properties of single-nanoparticle thick membranes

    SciTech Connect

    Salerno, Kenneth Michael; Bolintineanu, Dan S.; Lane, J. Matthew D.; Grest, Gary S.

    2015-06-16

    We believe that the high mechanical stiffness of single-nanoparticle-thick membranes is the result of the local structure of ligand coatings that mediate interactions between nanoparticles. These ligand structures are not directly observable experimentally. We use molecular dynamics simulations to observe variations in ligand structure and simultaneously measure variations in membrane mechanical properties. We have shown previously that ligand end group has a large impact on ligand structure and membrane mechanical properties. Here we introduce and apply quantitative molecular structure measures to these membranes and extend analysis to multiple nanoparticle core sizes and ligand lengths. Simulations of nanoparticle membranes with a nanoparticle core diameter of 4 or 6 nm, a ligand length of 11 or 17 methylenes, and either carboxyl (COOH) or methyl (CH3) ligand end groups are presented. In carboxyl-terminated ligand systems, structure and interactions are dominated by an end-to-end orientation of ligands. In methyl-terminated ligand systems large ordered ligand structures form, but nanoparticle interactions are dominated by disordered, partially interdigitated ligands. Core size and ligand length also affect both ligand arrangement within the membrane and the membrane's macroscopic mechanical response, but are secondary to the role of the ligand end group. Additionally, the particular end group (COOH or CH3) alters the nature of how ligand length, in turn, affects the membrane properties. The effect of core size does not depend on the ligand end group, with larger cores always leading to stiffer membranes. Asymmetry in the stress and ligand density is observed in membranes during preparation at a water-vapor interface, with the stress asymmetry persisting in all membranes after drying.

  14. Ligand structure and mechanical properties of single-nanoparticle thick membranes

    DOE PAGESBeta

    Salerno, Kenneth Michael; Bolintineanu, Dan S.; Lane, J. Matthew D.; Grest, Gary S.

    2015-06-16

    We believe that the high mechanical stiffness of single-nanoparticle-thick membranes is the result of the local structure of ligand coatings that mediate interactions between nanoparticles. These ligand structures are not directly observable experimentally. We use molecular dynamics simulations to observe variations in ligand structure and simultaneously measure variations in membrane mechanical properties. We have shown previously that ligand end group has a large impact on ligand structure and membrane mechanical properties. Here we introduce and apply quantitative molecular structure measures to these membranes and extend analysis to multiple nanoparticle core sizes and ligand lengths. Simulations of nanoparticle membranes with amore » nanoparticle core diameter of 4 or 6 nm, a ligand length of 11 or 17 methylenes, and either carboxyl (COOH) or methyl (CH3) ligand end groups are presented. In carboxyl-terminated ligand systems, structure and interactions are dominated by an end-to-end orientation of ligands. In methyl-terminated ligand systems large ordered ligand structures form, but nanoparticle interactions are dominated by disordered, partially interdigitated ligands. Core size and ligand length also affect both ligand arrangement within the membrane and the membrane's macroscopic mechanical response, but are secondary to the role of the ligand end group. Additionally, the particular end group (COOH or CH3) alters the nature of how ligand length, in turn, affects the membrane properties. The effect of core size does not depend on the ligand end group, with larger cores always leading to stiffer membranes. Asymmetry in the stress and ligand density is observed in membranes during preparation at a water-vapor interface, with the stress asymmetry persisting in all membranes after drying.« less

  15. Ligand structure and mechanical properties of single-nanoparticle-thick membranes.

    PubMed

    Salerno, K Michael; Bolintineanu, Dan S; Lane, J Matthew D; Grest, Gary S

    2015-06-01

    The high mechanical stiffness of single-nanoparticle-thick membranes is believed to result from the local structure of ligand coatings that mediate interactions between nanoparticles. These ligand structures are not directly observable experimentally. We use molecular dynamics simulations to observe variations in ligand structure and simultaneously measure variations in membrane mechanical properties. We have shown previously that ligand end group has a large impact on ligand structure and membrane mechanical properties. Here we introduce and apply quantitative molecular structure measures to these membranes and extend analysis to multiple nanoparticle core sizes and ligand lengths. Simulations of nanoparticle membranes with a nanoparticle core diameter of 4 or 6 nm, a ligand length of 11 or 17 methylenes, and either carboxyl (COOH) or methyl (CH(3)) ligand end groups are presented. In carboxyl-terminated ligand systems, structure and interactions are dominated by an end-to-end orientation of ligands. In methyl-terminated ligand systems large ordered ligand structures form, but nanoparticle interactions are dominated by disordered, partially interdigitated ligands. Core size and ligand length also affect both ligand arrangement within the membrane and the membrane's macroscopic mechanical response, but are secondary to the role of the ligand end group. Moreover, the particular end group (COOH or CH(3)) alters the nature of how ligand length, in turn, affects the membrane properties. The effect of core size does not depend on the ligand end group, with larger cores always leading to stiffer membranes. Asymmetry in the stress and ligand density is observed in membranes during preparation at a water-vapor interface, with the stress asymmetry persisting in all membranes after drying.

  16. Ligand structure and mechanical properties of single-nanoparticle-thick membranes

    NASA Astrophysics Data System (ADS)

    Salerno, K. Michael; Bolintineanu, Dan S.; Lane, J. Matthew D.; Grest, Gary S.

    2015-06-01

    The high mechanical stiffness of single-nanoparticle-thick membranes is believed to result from the local structure of ligand coatings that mediate interactions between nanoparticles. These ligand structures are not directly observable experimentally. We use molecular dynamics simulations to observe variations in ligand structure and simultaneously measure variations in membrane mechanical properties. We have shown previously that ligand end group has a large impact on ligand structure and membrane mechanical properties. Here we introduce and apply quantitative molecular structure measures to these membranes and extend analysis to multiple nanoparticle core sizes and ligand lengths. Simulations of nanoparticle membranes with a nanoparticle core diameter of 4 or 6 nm, a ligand length of 11 or 17 methylenes, and either carboxyl (COOH) or methyl (CH3) ligand end groups are presented. In carboxyl-terminated ligand systems, structure and interactions are dominated by an end-to-end orientation of ligands. In methyl-terminated ligand systems large ordered ligand structures form, but nanoparticle interactions are dominated by disordered, partially interdigitated ligands. Core size and ligand length also affect both ligand arrangement within the membrane and the membrane's macroscopic mechanical response, but are secondary to the role of the ligand end group. Moreover, the particular end group (COOH or CH3) alters the nature of how ligand length, in turn, affects the membrane properties. The effect of core size does not depend on the ligand end group, with larger cores always leading to stiffer membranes. Asymmetry in the stress and ligand density is observed in membranes during preparation at a water-vapor interface, with the stress asymmetry persisting in all membranes after drying.

  17. New formamidine ligands and their mixed ligand palladium(II) oxalate complexes: Synthesis, characterization, DFT calculations and in vitro cytotoxicity

    NASA Astrophysics Data System (ADS)

    Soliman, Ahmed A.; Alajrawy, Othman I.; Attabi, Fawzy A.; Shaaban, Mohamed R.; Linert, W.

    2016-01-01

    A series of new ternary palladium(II) complexes of the type [Pd(L1-4)ox]·xH2O where L = formamidine ligands and ox = oxalate, were synthesized and characterized by elemental analyses, magnetic susceptibility, UV-Vis, infrared (IR) and mass spectroscopy and thermal analysis. The spectroscopic data indicated that the formamidine ligands act as bidentate N2 donors and the oxalate as O2 ligand. The complexes (1-4) are diamagnetic and the optimization of their structures indicated that the geometry is distorted square planer with O-Pd-O and N-Pd-N bond angles ranged 82.70-83.87° and 88.21-95.02°; respectively which is acceptable for the heteroleptic complexes. The dipole moment of the complexes (13.97-18.77 Debye) indicating that the complexes are more polarized than the ligands (1.93-4.96 Debye). The complexes are thermally stable as shown from their relatively higher overall activation energies (441-688 kJ mol-1). The ligands and the complexes are proved to have good cytotoxicity with IC50 (μM) in the range of (0.011-0.168) against MCF-7, (0.012-0.150) against HCT-116, (0.042-0.094) against PC-3 and (0.006-0.222) against HepG-2 cell lines, which open the field for further application as antitumor compounds.

  18. Impact of donor-acceptor geometry and metal chelation on photophysical properties and applications of triarylboranes.

    PubMed

    Hudson, Zachary M; Wang, Suning

    2009-10-20

    Three-coordinate organoboron compounds have recently found a wide range of applications in materials chemistry as nonlinear optical materials, chemical sensors, and emitters for organic light-emitting diodes (OLEDs). These compounds are excellent electron acceptors due to the empty p(pi) orbital on the boron center. When accompanied by electron donors such as amines, these molecules possess large electronic dipoles, which promote donor-acceptor charge-transfer upon excitation with light. Because of this, donor-acceptor triarylboranes are often highly luminescent both in the solid state and in solution. In this Account, we describe our research to develop donor-acceptor triarylboranes as efficient blue emitters for OLEDs. Through the use of hole-transporting donor groups such as 1-napthylphenylamines, we have prepared multifunctional triarylboranes that can act as the emissive, electron transport, or hole transport layers in OLEDs. We have also examined donor-acceptor compounds based on 2,2'-dipyridylamine or 7-azaindolyl donors, several of which have fluorescent quantum efficiencies approaching 100%. We are also investigating the chemistry of metal-containing triarylboranes. Our studies show that the electron-deficient boryl group can greatly facilitate metal-to-ligand charge-transfer transitions and phosphorescence. In addition, electronegative linker groups such as 2,2'-bipyridine can act in synergy with metal chelation to greatly improve the electron-accepting ability and Lewis acidity of triarylboranes. Donor-acceptor triarylboranes developed in our laboratory can also serve as a series of "switch-on" sensors for fluoride ions. When the donor and acceptor are linked by rigid naphthyl or nonrigid silane linkers, donor-acceptor conjugation is disrupted and charge transfer occurs primarily through space. The binding of fluoride ions to the boron center disrupts this charge transfer, activating alternative pi --> pi* transitions in the molecule and changing the

  19. Ligand exclusion on acetylcholinesterase.

    PubMed

    Berman, H A; Leonard, K

    1990-11-27

    This paper examines covalent reactivity of AchE with respect to cationic and uncharged methylphosphonates and substrates in the absence and presence of cationic ligands selective for the active center and the peripheral anionic site. The organophosphorus inhibitors are enantiomeric alkyl methylphosphonothioates (1-5) containing cycloheptyl and isopropyl phosphono ester groups and S-methyl, S-n-pentyl, and S-[beta-(trimethylammonio)ethyl] leaving groups; these agents differ in their configuration about phosphorus and their steric, hydrophobic, and electrostatic characteristics. The synthetic substrates examined are acetylthiocholine, p-nitrophenyl acetate, and 7-acetoxy-4-methylcoumarin (7AMC). Antagonism of the methylphosphonothioate reaction by cationic ligands is strongly dependent on the nature of both the cation and the methylphosphonate but independent of the configuration about phosphorus. While all cations cause linear mixed inhibition of acetylthiocholine hydrolysis, there are observed a variety of inhibition patterns of 7AMC and p-nitrophenyl acetate hydrolysis that are distinctly nonlinear, as well as patterns in which the reciprocal plots intersect in the upper right quadrant. Strong antagonism of cationic (methylphosphonyl)thiocholines correlates very well with linear inhibition of acetylthiocholine. Ligands that cause only negligible antagonism of the uncharged methylphosphonates display nonlinear inhibition of uncharged substrates. These relationships, since they are most pronounced for peripheral site ligands and are strongly dependent on the charge carried by the reactant, suggest that the peripheral anionic site alters enzyme reactivity through an electrostatic interaction with the net negative active center. Such behavior indicates a potential role for the peripheral anionic site in conserving AchE catalytic efficiency within a narrow range of values. PMID:2271673

  20. Donor free radical explosive composition

    DOEpatents

    Walker, Franklin E. [15 Way Points Rd., Danville, CA 94526; Wasley, Richard J. [4290 Colgate Way, Livermore, CA 94550

    1980-04-01

    An improved explosive composition is disclosed and comprises a major portion of an explosive having a detonation velocity between about 1500 and 10,000 meters per second and a minor amount of a donor additive comprising an organic compound or mixture of organic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and which is not an explosive, or an inorganic compound or mixture of inorganic compounds capable of releasing low molecular weight free radicals or ions under mechanical or electrical shock conditions and selected from ammonium or alkali metal persulfates.

  1. Weak Intermolecular Hydrogen Bonds with Fluorine: Detection and Implications for Enzymatic/Chemical Reactions, Chemical Properties, and Ligand/Protein Fluorine NMR Screening.

    PubMed

    Dalvit, Claudio; Vulpetti, Anna

    2016-05-23

    It is known that strong hydrogen-bonding interactions play an important role in many chemical and biological systems. However, weak or very weak hydrogen bonds, which are often difficult to detect and characterize, may also be relevant in many recognition and reaction processes. Fluorine serving as a hydrogen-bond acceptor has been the subject of many controversial discussions and there are different opinions about it. It now appears that there is compelling experimental evidence for the involvement of fluorine in weak intramolecular or intermolecular hydrogen bonds. Using established NMR methods, we have previously characterized and measured the strengths of intermolecular hydrogen-bond complexes involving the fluorine moieties CH2 F, CHF2 , and CF3 , and have compared them with the well-known hydrogen-bond complex formed between acetophenone and the strong hydrogen-bond donor p-fluorophenol. We now report evidence for the formation of hydrogen bonds involving fluorine with significantly weaker donors, namely 5-fluoroindole and water. A simple NMR method is proposed for the simultaneous measurement of the strengths of hydrogen bonds between an acceptor and a donor or water. Important implications of these results for enzymatic/chemical reactions involving fluorine, for chemical and physical properties, and for ligand/protein (19) F NMR screening are analyzed through experiments and theoretical simulations.

  2. EGF receptor ligands: recent advances

    PubMed Central

    Singh, Bhuminder; Carpenter, Graham; Coffey, Robert J.

    2016-01-01

    Seven ligands bind to and activate the mammalian epidermal growth factor (EGF) receptor (EGFR/ERBB1/HER1): EGF, transforming growth factor-alpha (TGFA), heparin-binding EGF-like growth factor (HBEGF), betacellulin (BTC), amphiregulin (AREG), epiregulin (EREG), and epigen (EPGN). Of these, EGF, TGFA, HBEGF, and BTC are thought to be high-affinity ligands, whereas AREG, EREG, and EPGN constitute low-affinity ligands. This focused review is meant to highlight recent studies related to actions of the individual EGFR ligands, the interesting biology that has been uncovered, and relevant advances related to ligand interactions with the EGFR.

  3. EGF receptor ligands: recent advances.

    PubMed

    Singh, Bhuminder; Carpenter, Graham; Coffey, Robert J

    2016-01-01

    Seven ligands bind to and activate the mammalian epidermal growth factor (EGF) receptor (EGFR/ERBB1/HER1): EGF, transforming growth factor-alpha (TGFA), heparin-binding EGF-like growth factor (HBEGF), betacellulin (BTC), amphiregulin (AREG), epiregulin (EREG), and epigen (EPGN). Of these, EGF, TGFA, HBEGF, and BTC are thought to be high-affinity ligands, whereas AREG, EREG, and EPGN constitute low-affinity ligands. This focused review is meant to highlight recent studies related to actions of the individual EGFR ligands, the interesting biology that has been uncovered, and relevant advances related to ligand interactions with the EGFR. PMID:27635238

  4. EGF receptor ligands: recent advances

    PubMed Central

    Singh, Bhuminder; Carpenter, Graham; Coffey, Robert J.

    2016-01-01

    Seven ligands bind to and activate the mammalian epidermal growth factor (EGF) receptor (EGFR/ERBB1/HER1): EGF, transforming growth factor-alpha (TGFA), heparin-binding EGF-like growth factor (HBEGF), betacellulin (BTC), amphiregulin (AREG), epiregulin (EREG), and epigen (EPGN). Of these, EGF, TGFA, HBEGF, and BTC are thought to be high-affinity ligands, whereas AREG, EREG, and EPGN constitute low-affinity ligands. This focused review is meant to highlight recent studies related to actions of the individual EGFR ligands, the interesting biology that has been uncovered, and relevant advances related to ligand interactions with the EGFR. PMID:27635238

  5. Deceased donor skin allograft banking: Response and utilization

    PubMed Central

    Gore, Madhuri A.; De, Anuradha S.

    2010-01-01

    Background: In the absence of xenograft and biosynthetic skin substitutes, deceased donor skin allografts is a feasible option for saving life of patient with extensive burn injury in our country. Aims: The first deceased donor skin allograft bank in India became functional at Lokmanya Tilak Municipal (LTM) medical college and hospital on 24th April 2000. The response of Indian society to this new concept of skin donation after death and the pattern of utilization of banked allografts from 2000 to 2010 has been presented in this study. Settings and Design: This allograft skin bank was established by the department of surgery. The departments of surgery and microbiology share the responsibility of smooth functioning of the bank. Materials and Methods: The response in terms of number of donations and the profile of donors was analyzed from records. Pattern and outcome of allograft utilization was studied from specially designed forms. Results: During these ten years, 262 deceased donor skin allograft donations were received. The response showed significant improvement after counselling was extended to the community. Majority of the donors were above 70 years of age and procurement was done at home for most. Skin allografts from 249 donors were used for 165 patients in ten years. The outcome was encouraging with seven deaths in 151 recipients with burn injuries. Conclusions: Our experience shows that the Indian society is ready to accept the concept of skin donation after death. Use of skin allografts is life saving for large burns. We need to prepare guidelines for the establishment of more skin banks in the country. PMID:21321645

  6. Rescoring ligand docking poses.

    PubMed

    Zhong, Shijun; Zhang, Youping; Xiu, Zhilong

    2010-05-01

    The ranking of ligand docking poses according to certain scoring systems to identify the best fit is the most important step in virtual database screening for drug discovery. By focusing on method development strategy, this review provides possibilities for constructing rescoring approaches based on an overview of recent developments in the field. These developments can be classified into three categories. The first category involves a scaling approach that employs a factor to scale the primary scoring function. These scaling factors are defined with respect to the geometrical match between the location of a ligand and the target binding site, or defined according to a molecular weight distribution consistent with the empirical range of molecular weights of drug-like compounds. The second category involves consensus scoring approaches that use multiple scoring functions to rank the ligand poses retained in a docking procedure, based on the preliminary ranking according to a primary scoring function. The final category involves the addition of selected accuracy-oriented energy terms, such as the solvent effect and quantum mechanics/molecular mechanics treatments. PMID:20443166

  7. Gamete donors' expectations and experiences of contact with their donor offspring

    PubMed Central

    Kirkman, Maggie; Bourne, Kate; Fisher, Jane; Johnson, Louise; Hammarberg, Karin

    2014-01-01

    STUDY QUESTION What are the expectations and experiences of anonymous gamete donors about contact with their donor offspring? SUMMARY ANSWER Rather than consistently wanting to remain distant from their donor offspring, donors' expectations and experiences of contact with donor offspring ranged from none to a close personal relationship. WHAT IS KNOWN ALREADY Donor conception is part of assisted reproduction in many countries, but little is known about its continuing influence on gamete donors' lives. STUDY DESIGN, SIZE, DURATION A qualitative research model appropriate for understanding participants' views was employed; semi-structured interviews were conducted during January–March 2013. PARTICIPANTS/MATERIALS, SETTING, METHODS Before 1998, gamete donors in Victoria, Australia, were subject to evolving legislation that allowed them to remain anonymous or (from 1988) to consent to the release of identifying information. An opportunity to increase knowledge of donors' expectations and experiences of contact with their donor offspring recently arose in Victoria when a recommendation was made to introduce mandatory identification of donors on request from their donor offspring, with retrospective effect. Pre-1998 donors were invited through an advertising campaign to be interviewed about their views, experiences and expectations; 36 sperm donors and 6 egg donors participated. MAIN RESULTS AND THE ROLE OF CHANCE This research is unusual in achieving participation by donors who would not normally identify themselves to researchers or government inquiries. Qualitative thematic analysis revealed that most donors did not characterize themselves as parents of their donor offspring. Donors' expectations and experiences of contact with donor offspring ranged from none to a close personal relationship. LIMITATIONS, REASONS FOR CAUTION It is not possible to establish whether participants were representative of all pre-1998 donors. WIDER IMPLICATIONS OF THE FINDINGS Anonymous

  8. De Novo Design of Ligands for Metal Separation - Final Report - 09/15/1996 - 09/14/2000

    SciTech Connect

    Marshall, Garland, R.

    2001-09-14

    This application focuses on the development of appropriate computation tools and parameters for the de novo design of selective metal ligands. We have developed a successful suite of tools for computer-aided design of ligands for receptors of known three-dimensional structure (structure-based design), including the prediction of affinity. Adaptation of the algorithms to place donor atoms at appropriate geometrical locations surrounding the metal of interest, rather than filling up a cavity with donor/acceptor atoms placed optimally to interact with a protein active site, is straightforward. Appropriate geometrical parameters for metals can be derived from crystal structures and force constants adapted from recent advances in theories of metal-ligand interactions. The practical goal is computer-aided design of ligands which would be selective for one metal over another with a predicted selectivity ratio and affinity.

  9. Affinity screening using competitive binding with fluorine-19 hyperpolarized ligands.

    PubMed

    Kim, Yaewon; Hilty, Christian

    2015-04-13

    Fluorine-19 NMR and hyperpolarization form a powerful combination for drug screening. Under a competitive equilibrium with a selected fluorinated reporter ligand, the dissociation constant (K(D)) of other ligands of interest is measurable using a single-scan Carr-Purcell-Meiboom-Gill (CPMG) experiment, without the need for a titration. This method is demonstrated by characterizing the binding of three ligands with different affinities for the serine protease trypsin. Monte Carlo simulations show that the highest accuracy is obtained when about one-half of the bound reporter ligand is displaced in the binding competition. Such conditions can be achieved over a wide range of affinities, allowing for rapid screening of non-fluorinated compounds when a single fluorinated ligand for the binding pocket of interest is known.

  10. Detection and Identification of Ligands for Mammalian RPTP Extracellular Domains.

    PubMed

    Stoker, Andrew William

    2016-01-01

    Receptor protein tyrosine phosphatases (RPTPs) form a group of over 20 enzymes in vertebrates, each with unique ectodomains subject to potential extracellular interactions with ligands. It has recently become clear that a remarkably diverse range of ligands exist, including homophilic binders, adhesion molecules, neurotrophin receptors, and proteoglycans. Individual RPTPs can bind several ligands, and vice versa, suggesting that complex cell signaling networks exist. The identification of RPTP ligands and where they are located in tissues remains a challenge for a large number of these enzymes. Here we describe some powerful methods that have proved successful for several research groups, leading to our improved understanding of RPTP-ligand interactions and functional regulation. PMID:27514811

  11. PL-PatchSurfer2: Improved Local Surface Matching-Based Virtual Screening Method That Is Tolerant to Target and Ligand Structure Variation.

    PubMed

    Shin, Woong-Hee; Christoffer, Charles W; Wang, Jibo; Kihara, Daisuke

    2016-09-26

    Virtual screening has become an indispensable procedure in drug discovery. Virtual screening methods can be classified into two categories: ligand-based and structure-based. While the former have advantages, including being quick to compute, in general they are relatively weak at discovering novel active compounds because they use known actives as references. On the other hand, structure-based methods have higher potential to find novel compounds because they directly predict the binding affinity of a ligand in a target binding pocket, albeit with substantially lower speed than ligand-based methods. Here we report a novel structure-based virtual screening method, PL-PatchSurfer2. In PL-PatchSurfer2, protein and ligand surfaces are represented by a set of overlapping local patches, each of which is represented by three-dimensional Zernike descriptors (3DZDs). By means of 3DZDs, the shapes and physicochemical complementarities of local surface regions of a pocket surface and a ligand molecule can be concisely and effectively computed. Compared with the previous version of the program, the performance of PL-PatchSurfer2 is substantially improved by the addition of two more features, atom-based hydrophobicity and hydrogen-bond acceptors and donors. Benchmark studies showed that PL-PatchSurfer2 performed better than or comparable to popular existing methods. Particularly, PL-PatchSurfer2 significantly outperformed existing methods when apo-form or template-based protein models were used for queries. The computational time of PL-PatchSurfer2 is about 20 times shorter than those of conventional structure-based methods. The PL-PatchSurfer2 program is available at http://www.kiharalab.org/plps2/ . PMID:27500657

  12. PL-PatchSurfer2: Improved Local Surface Matching-Based Virtual Screening Method That Is Tolerant to Target and Ligand Structure Variation.

    PubMed

    Shin, Woong-Hee; Christoffer, Charles W; Wang, Jibo; Kihara, Daisuke

    2016-09-26

    Virtual screening has become an indispensable procedure in drug discovery. Virtual screening methods can be classified into two categories: ligand-based and structure-based. While the former have advantages, including being quick to compute, in general they are relatively weak at discovering novel active compounds because they use known actives as references. On the other hand, structure-based methods have higher potential to find novel compounds because they directly predict the binding affinity of a ligand in a target binding pocket, albeit with substantially lower speed than ligand-based methods. Here we report a novel structure-based virtual screening method, PL-PatchSurfer2. In PL-PatchSurfer2, protein and ligand surfaces are represented by a set of overlapping local patches, each of which is represented by three-dimensional Zernike descriptors (3DZDs). By means of 3DZDs, the shapes and physicochemical complementarities of local surface regions of a pocket surface and a ligand molecule can be concisely and effectively computed. Compared with the previous version of the program, the performance of PL-PatchSurfer2 is substantially improved by the addition of two more features, atom-based hydrophobicity and hydrogen-bond acceptors and donors. Benchmark studies showed that PL-PatchSurfer2 performed better than or comparable to popular existing methods. Particularly, PL-PatchSurfer2 significantly outperformed existing methods when apo-form or template-based protein models were used for queries. The computational time of PL-PatchSurfer2 is about 20 times shorter than those of conventional structure-based methods. The PL-PatchSurfer2 program is available at http://www.kiharalab.org/plps2/ .

  13. Electron Donor Potential of Eastern North Dakota Shale Formations

    NASA Astrophysics Data System (ADS)

    Salinas Klapperich, R. J.; Korom, S. F.

    2007-12-01

    We have a network of 16 in situ mesocosms (ISMs) used to study aquifer denitrification at 9 sites in North Dakota and Minnesota. The site in the Elk Valley aquifer in northeastern North Dakota has the highest denitrification rates and the greatest concentration of electron donors (organic carbon ~0.4%, pyrite as S ~0.4%, and ferrous iron ~0.3%) in the sediments. In contrast, denitrification rates at our other ISM sites are lower (or even below detection), as are the electron donor concentrations in the sediments. Knowing that the sediments at all of our ISM sites were placed as outwash during the last Wisconsinan glaciation (~12ka), we wonder what caused the variation in electron donor supplies in our aquifers. It has been suggested that variations is the electron donor concentrations in the various Late Cretaceous shale strata exposed during glaciation may help explain the variation in electron donor concentrations in overlying aquifers formed nearby. The purpose of this study is to evaluate the amount of electron donors available in these bedrock units. Bedrock samples (n = 39) from 20 sites in eastern North Dakota were obtained by drilling during the summer of 2006 in conjunction with the North Dakota State Water Commission. Samples were frozen before analysis for bulk mineralogical content by X-ray diffraction, organic carbon, pyrite as inorganic S, and ferrous iron contents. It was hypothesized that the Pierre Shale would have the highest donor concentration, but it appears that other formations, such as the Carlile and Greenhorn contain higher concentrations of electron donors. Organic carbon concentrations in the Pierre (< 0.01% to 1.0%) are relatively low while concentrations in the Carlile (3.5% - 6.5%) and Greenhorn (~8.5%) are significantly higher. Pyrite as inorganic S concentrations in the Pierre (< 0.01% to 0.2%), Carlile (0.3% - 0.5%), and Greenhorn (~0.5%) are similarly distributed. In the future, it may be possible to create a qualitative index

  14. Living-donor liver transplantation: current perspective.

    PubMed

    Lobritto, Steven; Kato, Tomoaki; Emond, Jean

    2012-11-01

    The disparity between the number of available deceased liver donors and the number of patients awaiting transplantation continues to be an ongoing issue predisposing to death on the liver transplant waiting list. Deceased donor shortage strategies including the use of extended donor-criteria deceased donor grafts, split liver transplants, and organs harvested after cardiac death have fallen short of organ demand. Efforts to raise donor awareness are ongoing, but the course has been arduous to date. Living donor transplantation is a means to access an unlimited donor organ supply and offers potential advantages to deceased donation. Donor safety remains paramount demanding improvements and innovations in both the donor and recipient operations to ensure superior outcomes. The specialty operation is best preformed at centers with specific expertise and shuttling of select patients to these centers supported by third party payers is critical. Training future surgeons at centers with this specific experience can help disseminate this technology to improve local availability. Ongoing research in immunosuppression minimization, withdrawal and tolerance induction may make living donation a desired first-line operation rather than a necessary albeit less-desirable option. This chapter summarizes the progress of living liver donation and its potential applications. PMID:23397534

  15. [Living donor liver transplantation in adults].

    PubMed

    Neumann, U P; Neuhaus, P; Schmeding, M

    2010-09-01

    The worldwide shortage of adequate donor organs implies that living donor liver transplantation represents a valuable alternative to cadaveric transplantation. In addition to the complex surgical procedure the correct identification of eligible donors and recipients plays a decisive role in living donor liver transplantation. Donor safety must be of ultimate priority and overrules all other aspects involved. In contrast to the slightly receding numbers in Europe and North America, in recent years Asian programs have enjoyed constantly increasing living donor activity. The experience of the past 15 years has clearly demonstrated that technical challenges of both bile duct anastomosis and venous outflow of the graft significantly influence postoperative outcome. While short-term in-hospital morbidity remains increased compared to cadaveric transplantation, long-term survival of both graft and patient are comparable or even better than in deceased donor transplantation. Especially for patients expecting long waiting times under the MELD allocation system, living donor liver transplantation offers an excellent therapeutic alternative. Expanding the so-called "Milan criteria" for HCC patients with the option for living donor liver transplantation is currently being controversially debated.

  16. Gamete donation: ethical implications for donors.

    PubMed

    Shenfield, Francoise

    1999-01-01

    The interests of gamete donors have only recently been recognized in assisted reproduction; traditionally, the interests of the patients (typically a couple) and the prospective child are paramount. However, assisted reproduction would not be possible without donors, and the simple utilitarian view would be to place their interests first to maximize the availability of the practice. There are several ethical issues on both sides of the donor--recipient equation, some of which are mutual and others are in conflict. For example, the word 'donation' implies there is no payment. Informed consent for donation is essential if the autonomy of the donor is to be respected, and includes information about the results of screening. This is a sensitive issue, especially when pathology is found in a donor who is not being screened for his or her own immediate benefit. Counselling may result in donors refusing to take part, but may also lead to selection by the person recruiting the donors, sometimes as a consequence of examining the motivation of the donor. In this case, the main problem is the ethical basis of the selection process. Other aspects of gamete donation may lead to a conflict of interests between the donor, the recipients and even the prospective child, particularly in terms of anonymity and the information that is made available about the specific circumstances of donation. Implications and support counselling are essential tools in achieving an acceptable balance for all parties involved.

  17. Bonding and charge transfer in nitrogen-donor uranyl complexes: insights from NEXAFS spectra.

    PubMed

    Pemmaraju, C D; Copping, Roy; Wang, Shuao; Janousch, Markus; Teat, Simon J; Tyliszcak, Tolek; Canning, Andrew; Shuh, David K; Prendergast, David

    2014-11-01

    We investigate the electronic structure of three newly synthesized nitrogen-donor uranyl complexes [(UO2)(H2bbp)Cl2], [(UO)2(Hbbp)(Py)Cl], and [(UO2)(bbp)(Py)2] using a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments and simulations. The complexes studied feature derivatives of the tunable tridentate N-donor ligand 2,6-bis(2-benzimidazyl)pyridine (bbp) and exhibit discrete chemical differences in uranyl coordination. The sensitivity of the N K-edge X-ray absorption spectrum to local bonding and charge transfer is exploited to systematically investigate the evolution of structural as well as electronic properties across the three complexes. A thorough interpretation of the measured experimental spectra is achieved via ab initio NEXAFS simulations based on the eXcited electron and Core-Hole (XCH) approach and enables the assignment of spectral features to electronic transitions on specific absorbing sites. We find that ligand-uranyl bonding leads to a signature blue shift in the N K-edge absorption onset, resulting from charge displacement toward the uranyl, while changes in the equatorial coordination shell of the uranyl lead to more subtle modulations in the spectral features. Theoretical simulations show that the flexible local chemistry at the nonbinding imidazole-N sites of the bbp ligand is also reflected in the NEXAFS spectra and highlights potential synthesis strategies to improve selectivity. In particular, we find that interactions of the bbp ligand with solvent molecules can lead to changes in ligand-uranyl binding geometry while also modulating the K-edge absorption. Our results suggest that NEXAFS spectroscopy combined with first-principles interpretation can offer insights into the coordination chemistry of analogous functionalized conjugated ligands. PMID:25330350

  18. Bexarotene ligand pharmaceuticals.

    PubMed

    Hurst, R E

    2000-12-01

    Bexarotene (LGD-1069), from Ligand, was the first retinoid X receptor (RXR)-selective, antitumor retinoid to enter clinical trials. The company launched the drug for the treatment of cutaneous T-cell lymphoma (CTCL), as Targretin capsules, in the US in January 2000 [359023]. The company filed an NDA for Targretin capsules in June 1999, and for topical gel in December 1999 [329011], [349982] specifically for once-daily oral administration for the treatment of patients with early-stage CTCL who have not tolerated other therapies, patients with refractory or persistent early stage CTCL and patients with refractory advanced stage CTCL. The FDA approved Targretin capsules at the end of December 1999 for once-daily oral treatment of all stages of CTCL in patients refractory to at least one prior systemic therapy, at an initial dose of 300 mg/m2/day. After an NDA was submitted in December 1999 for Targretin gel, the drug received Priority Review status for use as a treatment of cutaneous lesions in patients with stage IA, IB or IIA CTCL [354836]. The FDA issued an approvable letter in June 2000, and granted marketing clearance for CTCL in the same month [370687], [372768], [372769], [373279]. Ligand had received Orphan Drug designation for this indication [329011]. At the request of the FDA, Ligand agreed to carry out certain post-approval phase IV and pharmacokinetic studies [351604]. The company filed an MAA with the EMEA for Targretin Capsules to treat lymphoma in November 1999 [348944]. The NDA for Targretin gel is based on a multicenter phase III trial that was conducted in the US, Canada, Europe and Australia involving 50 patients and a multicenter phase I/II clinical program involving 67 patients. Targretin gel was evaluated for the treatment of patients with early stage CTCL (IA-IIA) who were refractory to, intolerant to, or reached a response plateau for at least 6 months on at least two prior therapies. Efficacy results exceeded the protocol-defined response

  19. Blood Donors on Medication - an Approach to Minimize Drug Burden for Recipients of Blood Products and to Limit Deferral of Donors.

    PubMed

    Becker, Christian D K; Stichtenoth, Dirk O; Wichmann, Michael G; Schaefer, Christof; Szinicz, Ladislaus

    2009-01-01

    BACKGROUND: Blood products derived from donors on medication can contain drugs which might pose a risk for the recipients or influence the quality of the product itself. MATERIAL AND METHODS: To judge the eligibility of blood donors on medication, 4 drug classes have been formed with respect to their pharmacological properties, and blood products have been divided in accordance with their single-donor plasma contents. RESULTS: For drugs with dose-dependent pharmacodynamics, no deferral periods are necessary for donation of blood products containing less than 50 ml single-donor plasma for application to adults. Waiting periods of t(max) + 5 t(1/2) were calculated for the other blood products. Teratogenic drugs do not require special considerations (exception: retinoids, thalidomide and lenalidomide, dutasteride or finasteride with waiting periods for all blood products). A deferral period of t(max) + 24 t(1/2) is proposed for every blood product from blood donors on genotoxic drugs. Drugs without systemic effects can be neglected. Irreversible inhibitors of platelet function cause a 10-day waiting period if production of platelet concentrates is intended. CONCLUSION: Donors on medication are allowed to donate blood for blood products containing less than 50 ml plasma of a single donor, like red blood cell concentrates, for the use in adults without deferral periods, except those taking retinoids, thalidomide, lenalidomide, dutasteride, finasteride, or genotoxic drugs. PMID:20823991

  20. Coordination chemistry of amine bis(phenolate) titanium complexes: tuning complex type and structure by ligand modification.

    PubMed

    Tshuva, E Y; Goldberg, I; Kol, M; Goldschmidt, Z

    2001-08-13

    The coordination chemistry of titanium(IV) complexes of amine bis(phenolate) ligands was investigated by synthesizing various types of complexes and analyzing them specroscopically and structurally. Steric effects of tridentate [ONO]- and tetradentate [ONNO]-type ligands were studied by reacting the ligand precursors with titanium tetra(isopropoxide). [ONNO]-type ligands featuring an amine donor located on a pendant arm led to octahedral bis(isopropoxide) complexes, regardless of the steric bulk around the metal. Several such complexes having varying steric crowding were thus synthesized. On the other hand, steric effects were found to play a major role in determining the complex constitution when [ONO]-type ligands, featuring no side donor, were involved. Relatively sterically undemanding ligands led to octahedral bis(homoleptic) complexes, whereas increased steric bulk resulted in the formation of pentacoordinate bis(isopropoxide) complexes. These pentacoordinate complexes readily lead to bis(heteroleptic) complexes by reaction with nonsterically demanding [ONO]- and [ONNO]-type ligand precursors. In the latter case the sidearm nitrogen remains uncoordinated to the metal. The bis(isopropoxide) complexes of the [ONNO]-type ligands may also lead to bis(heteroleptic) complexes, however, these reactions are much slower. PMID:11487331

  1. Synthesis, spectral and structural characterization of a novel phenoxo-bridged dinuclear Co II complex with a tridentate phenol-functionalized diazamesocyclic ligand

    NASA Astrophysics Data System (ADS)

    Du, Miao; An, Dao-Li; Guo, Ya-Mei; Bu, Xian-He

    2002-11-01

    A novel phenoxo-bridged dinuclear Co II complex with a diazamesocyclic ligand bearing one additional phenol functional donor group, [CoLCl] 2·2C 3H 6O ( 1) (where HL=1-(2-hydroxybenzyl)-1,5-diazacyclooctane), has been synthesized and characterized by elemental analyses, conductance, thermal analyses, IR and UV-vis spectra. The crystal structure of complex 1 has been determined by X-ray diffraction technique, which reveals that it is a neutral complex and resides on a crystallographic inversion center. The two Co II centers bridged by the phenoxo groups are penta-coordinated, taking a coordination sphere in the midst of the ideal square-pyramid and trigonal bipyramid. 1,5-Diazacyclooctane of the ligand takes a boat/ chair conformation and an H atom from it effectively blocks the axial coordination site opposite the Cl - ligand to form CoN 2O 2Cl geometry. The crystal structure is stabilized by the N-H⋯O hydrogen bond between the amino group and the acetone molecule.

  2. DGTI Register of Rare Donors

    PubMed Central

    Hustinx, Hein

    2014-01-01

    Summary For patients with antibodies against the most common blood groups a rapid and efficient supply of compatible erythrocyte concentrates is self-evident. But typically we have to make the greatest effort providing blood for these patients, which have made antibodies against common blood groups. There are however patients with antibodies against rare blood group antigens that need special blood. The supply of such blood can be very difficult and mostly time-consuming. For this reason we set up a database of blood donors with rare blood groups. Since 2005 the BTS SRC Berne Ltd. has run this database on behalf of the Swiss BTS SRC. After a reorganization and extension of the database, conducted during 2011/2012, the data file was renamed ‘DGTI Register of Rare Donors’ and is now run under the patronage of the German Society for Transfusion Medicine and Immunohematology (DGTI). PMID:25538534

  3. [Liver transplants from living donors].

    PubMed

    Rogiers, X; Danninger, F; Malagó, M; Knoefel, W T; Gundlach, M; Bassas, A; Burdelski, M; Broelsch, C E

    1996-03-01

    In this article the authors discuss the advantages of Living Related Liver Transplantation (LRLT), criteria for the selection of donors and the standard operation technique. Among a total of 241 liver transplantation (LTx), 42 LRLT were performed at the University of Hamburg between October 1, 1991 and December 19, 1994. The body weight of recipients for LRLT ranged from 4,6 to 39 kg, with 64,2% having less than 10 kg. The volume of the donor left lateral liver lobe ranged from 100 cc to 350 cc. The average one year survival rate among electively operated patients-status 3-4 (UNOS 1995 classification) was 86.7%, two year survival rate 83.3%. The main advantages of LRLT are consired the following: 1. Absence of mortality on the waiting list, 2. Optimal timing of the transplantation (elective procedure, patient in a good condition), 3. Excellent organ (no primary non function), 4. A possible immunologic advantage, 5. Relief of the waiting list for cadaveric organs, 6. Psychological benefit for the family, 7. Cost effectiveness. Potential candidates for living donation with more than one cardiovascular risk factors were excluded. Social and psychological reasons leading to rejection of candidates were as follows: unstable family structure, expected professional or financial difficulties after living donation or withdrawal from consent. LRLT gives parents of a child with TLD a chance to avoid the risk of death on the waiting list or primary non function of the graft. LRLT has therefore established an important place in pediatric liver transplantation. PMID:8768973

  4. Distribution patterns of small-molecule ligands in the protein universe and implications for origin of life and drug discovery

    PubMed Central

    Ji, Hong-Fang; Kong, De-Xin; Shen, Liang; Chen, Ling-Ling; Ma, Bin-Guang; Zhang, Hong-Yu

    2007-01-01

    Background Extant life depends greatly on the binding of small molecules (such as ligands) with macromolecules (such as proteins), and one ligand can bind multiple proteins. However, little is known about the global patterns of ligand-protein mapping. Results By examining 2,186 well-defined small-molecule ligands and thousands of protein domains derived from a database of druggable binding sites, we show that a few ligands bind tens of protein domains or folds, whereas most ligands bind only one, which indicates that ligand-protein mapping follows a power law. Through assigning the protein-binding orders (early or late) for bio-ligands, we demonstrate that the preferential attachment principle still holds for the power-law relation between ligands and proteins. We also found that polar molecular surface area, H-bond acceptor counts, H-bond donor counts and partition coefficient are potential factors to discriminate ligands from ordinary molecules and to differentiate super ligands (shared by three or more folds) from others. Conclusion These findings have significant implications for evolution and drug discovery. First, the chronology of ligand-protein binding can be inferred by the power-law feature of ligand-protein mapping. Some nucleotide-containing ligands, such as ATP, ADP, GDP, NAD, FAD, dihydro-nicotinamide-adenine-dinucleotide phosphate (NDP), nicotinamide-adenine-dinucleotide phosphate (NAP), flavin mononucleotide (FMN) and AMP, are found to be the earliest cofactors bound to proteins, agreeing with the current understanding of evolutionary history. Second, the finding that about 30% of ligands are shared by two or more domains will help with drug discovery, such as in finding new functions from old drugs, developing promiscuous drugs and depending more on natural products. PMID:17727706

  5. Developing Ligands for Palladium(II)-Catalyzed C–H Functionalization: Intimate Dialogue between Ligand and Substrate

    PubMed Central

    Engle, Keary M.; Yu, Jin-Quan

    2013-01-01

    Homogeneous transition metal–catalyzed reactions are indispensable to all facets of modern chemical synthesis. It is thus difficult to imagine that for much of the early 20th century, the reactivity and selectivity of all known homogeneous metal catalysts paled in comparison to their heterogeneous and biological counterparts. In the intervening decades, advances in ligand design bridged this divide, such that today some of the most demanding bond-forming events are mediated by ligand-supported homogeneous metal species. While ligand design has propelled many areas of homogeneous catalysis, in the field of Pd(II)-catalyzed C–H functionalization, suitable ligand scaffolds are lacking, which has hampered the development of broadly practical transformations based on C–H functionalization logic. In this review, we offer an account of our research employing three ligand scaffolds, mono-N-protected amino acids, 2,6-disubstituted pyridines, and 2,2′-bipyridines, to address challenges posed by several synthetically versatile substrate classes. Drawing on this work, we discuss principles of ligand design, such as the need to match a ligand to a particular substrate class, and how ligand traits such as tunability and modularity can be advantageous in reaction discovery. PMID:23565982

  6. Application of donor-donor energy migration (DDEM) for examining protein structure and function

    NASA Astrophysics Data System (ADS)

    Bergstrom, Fredrik; Hagglof, Peter; Karolin, Jan; Ny, Tor; Johansson, Lennart B.

    1999-05-01

    Donor-Donor Energy Migration (DDEM) and fluorescence anisotropy experiments can be utilized as a versatile tool for examining protein structure and function. For this, pairs of identical fluorescent probes (D) are attached to unique residues created by means of site specific mutagenesis. Present work illustrates the applicability of the method on the latent form of Plasminogen Activator Inhibitor-1 (PAI-1). Different DD-pairs of mutated PAI-1 were prepared and studied, namely; V106C-H185C, H185C-M266C and M266C-V106C. The Cys residues were labelled with a sulfhydryl specific derivative of BODIPYR [N-(4,4-difluoro-5,7-dimethyl-4-bora-3a,4a- diaza-s-indacene-3-yl)methyl iodo-acetamide]. To determine the rate of DDEM within such a pair, intramolecular order and dynamics must be considered (Biophys. J., 74, 11-21, 1997). For analysis of data, additonal information was obtained from experiments with the corresponding D-labelled single Cys mutants, that is, V106C, H185C and M266C. The stability of values determined was tested by generating and re-analyzing synthetic data. The intramolecular distances obtained agree, reasonably well, with those determined from the X-ray structure of latent PAI-1.

  7. Synthesis and Structure of a New Lithium Amide Ligand Precursor: A Tridentate Nitrogen-Based Donor Set of the Formula N(SiMe(2)CH(2)NMe(2))(2). Synthesis and Structure of the Group 4 Amides MCl(3)[N(SiMe(2)CH(2)NMe(2))(2)] (M = Ti, Zr, Hf).

    PubMed

    Fryzuk, Michael D.; Hoffman, Vera; Kickham, James E.; Rettig, Steven J.; Gambarotta, Sandro

    1997-07-30

    The new lithium amide LiN(SiMe(2)CH(2)NMe(2))(2) was prepared by reaction of NH(3) with the corresponding silylamine Me(2)NSiMe(2)CH(2)NMe(2) followed by addition of butyllithium. This lithium derivative exists as a dimer in the solid state wherein the two lithium ions are bridged by the two amido units with the amine arms of each unit bonded to opposite lithium centers in an overall pseudo D(2) structure; however, in solution, a fluxional process serves to interconvert the enantiomeric forms of the dimer unit. The coordination chemistry of the lithium amide dimer has been investigated; reaction with a series of group 4 starting halides, MCl(4), leads to the corresponding complexes MCl(3)[N(SiMe(2)CH(2)NMe(2))(2)], where M = Ti, Zr, and Hf. The structures of these starting trihalides in solution and in the solid state are presented. PMID:11670025

  8. A new three-dimensional zinc(II) coordination polymer involving 2-[(1H-1,2,4-triazol-1-yl)methyl]-1H-benzimidazole and benzene-1,4-dicarboxylate ligands.

    PubMed

    Jian, Shou Jun; Han, Qian Qian; Yang, Huai Xia; Meng, Xiang Ru

    2016-07-01

    Metal-organic frameworks (MOFs) based on multidentate N-heterocyclic ligands involving imidazole, triazole, tetrazole, benzimidazole, benzotriazole or pyridine present intriguing molecular topologies and have potential applications in ion exchange, magnetism, gas sorption and storage, catalysis, optics and biomedicine. The 2-[(1H-1,2,4-triazol-1-yl)methyl]-1H-benzimidazole (tmb) ligand has four potential N-atom donors and can act in monodentate, chelating, bridging and tridentate coordination modes in the construction of complexes, and can also act as both a hydrogen-bond donor and acceptor. In addition, the tmb ligand can adopt different coordination conformations, resulting in complexes with helical structures due to the presence of the flexible methylene spacer. A new three-dimensional coordination polymer, poly[[bis(μ2-benzene-1,4-dicarboxylato)-κ(4)O(1),O(1'):O(4),O(4');κ(2)O(1):O(4)-bis{μ2-2-[(1H-1,2,4-triazol-1-yl)methyl-κN(4)]-1H-benzimidazole-κN(3)}dizinc(II)] trihydrate], {[Zn(C8H4O4)(C10H9N5)]·1.5H2O}n, has been synthesized by the reaction of ZnCl2 with tmb and benzene-1,4-dicarboxylic acid (H2bdic) under solvothermal conditions. There are two crystallographically distinct bdic(2-) ligands [bdic(2-)(A) and bdic(2-)(B)] in the structure which adopt different coordination modes. The Zn(II) ions are bridged by tmb ligands, leading to one-dimensional helical chains with different handedness, and adjacent helices are linked by bdic(2-)(A) ligands, forming a two-dimensional network structure. The two-dimensional layers are further connected by bdic(2-)(B) ligands, resulting in a three-dimensional framework with the topological notation 6(6). The IR spectra and thermogravimetric curves are consistent with the results of the X-ray crystal structure analysis and the title polymer exhibits good fluorescence in the solid state at room temperature. PMID:27377273

  9. Formation of new non-oxido vanadium(IV) species in aqueous solution and in the solid state by tridentate (O, N, O) ligands and rationalization of their EPR behavior.

    PubMed

    Sanna, Daniele; Várnagy, Katalin; Lihi, Norbert; Micera, Giovanni; Garribba, Eugenio

    2013-07-15

    The systems formed by the V(IV)O(2+) ion with tridentate ligands provided with the (O, N(imine), O) donor set were described. The ligands studied were 2,2'-dihydroxyazobenzene (Hdhab), α-(2-hydroxy-5-methylphenylimino)-o-cresol (Hhmpic), calmagite (H2calm), anthracene chrome red A (H3anth), calcon (H2calc), and calconcarboxylic acid (H3calc(C)). They can bind vanadium with the two deprotonated phenol groups and the imine nitrogen to give (5,6)-membered chelate rings. The systems were studied with EPR, UV-vis and IR spectroscopy, pH-potentiometry, and DFT methods. The ligands form unusual non-oxido V(IV) compounds both in aqueous solution and in the solid state. [V(anthH(-1))2](4-) and [V(calmH(-1))2](2-) (formed in water at the physiological pH) and [V(dhabH(-1))2] and [V(hmpicH(-1))2] (formed in the solid state in MeOH) are hexa-coordinated with geometry intermediate between the octahedron and the trigonal prism and an unsymmetric facial arrangement of the two ligand molecules. DFT calculations were used to predict the structure and (51)V hyperfine coupling tensor A of the non-oxido species. The EPR behavior of 13 non-oxido V(IV) species was put into relationship with the relevant geometrical parameters and was rationalized in terms of the spin density on the d(xy) orbital. Depending on the geometric isomer formed (meridional or facial), d(z)(2) mixes with the d(xy) orbital, and this effect causes the lowering of the highest (51)V A value. PMID:23819442

  10. Supramolecular coordination and antimicrobial activities of constructed mixed ligand complexes

    NASA Astrophysics Data System (ADS)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Abou-Dobara, M. I.; Seyam, H. A.

    2013-03-01

    A novel series of copper(II) and palladium(II) with 4-derivatives benzaldehyde pyrazolone (Ln) were synthesized. The mixed ligand complexes were prepared by using 1,10-phenanthroline (Phen) as second ligand. The structure of these complexes was identified and confirm by elemental analysis, molar conductivity, UV-Vis, IR and 1H NMR spectroscopy and magnetic moment measurements as well as thermal analysis. The ligand behaves as a neutral bidentate ligand through ON donor sites. ESR spectra show the simultaneous presence of a planar trans and a nearly planar cis isomers in the 1:2 ratio for all N,O complexes [Cu(Ln)2]Cl2ṡ2H2O. Schiff bases (Ln) were tested against bacterial species; namely two Gram positive bacteria (Staphylococcus aureus and Bacillus cereus) and two Gram negative bacteria (Escherichia coli and Klebsiella pneumoniae) and fungal species (Aspergillus niger, Fusarium oxysporium, Penicillium italicum and Alternaria alternata). The tested compounds have antibacterial activity against S. aureus, B. cereus and K. pneumoniae.

  11. Two 2D silver(I) coordination polymers derived from mixed ligands: Syntheses, structures, photoluminescent and thermal properties

    NASA Astrophysics Data System (ADS)

    Liu, Fu-Jing; Sun, Di; Li, Yun-Hua; Hao, Hong-Jun; Huang, Rong-Bin; Zheng, Lan-Sun

    2011-07-01

    Two isomers of the aminobenzonitrile were reacted with Ag 2O and phthalic acid under ultrasonic condition, yielding two coordination polymers (CPs) of the formula [Ag 2( o-abn)(pa)] n ( 1) and [Ag 4( m-abn)(pa) 2] n ( 2). They have been characterized by elemental analysis, IR spectrum and single crystal X-ray diffraction. Both complexes 1 and 2 are 2D sheet structures which contain two different Ag(I) aggregates, 1D silver helical chain and 2D silver sheet for 1 and 2, respectively. The o-abn in 1 adopts a rare tridentate μ 3- N, N' N' mode to bridge the neighboring 1D silver chains to form a 2D coordination network, while the m-abn ligand just acts as a monodentate N-donor in 2 and does not contribute to the extension of the 2D silver sheet to the higher dimensionality. As the change of the relative position of amino and cyano groups of the aminobenzonitrile ligand, the dimensionality of the Ag(I) aggregates in 1 and 2 increases from 1D to 2D, which indicates that the relative positions of amino and cyano groups of aminobenzonitrile play an important role in the formation of the diverse Ag(I) aggregates, as a consequence, different 2D coordination networks are produced. Additionally, results about emissive behaviors and thermal stabilities of them are discussed.

  12. Carbon monoxide as an intrinsic ligand to iron in the active site of the iron-sulfur-cluster-free hydrogenase H2-forming methylenetetrahydromethanopterin dehydrogenase as revealed by infrared spectroscopy.

    PubMed

    Lyon, Erica J; Shima, Seigo; Boecher, Reinhard; Thauer, Rudolf K; Grevels, Friedrich-Wilhelm; Bill, Eckhard; Roseboom, Winfried; Albracht, Simon P J

    2004-11-01

    The iron-sulfur-cluster-free hydrogenase Hmd (H(2)-forming methylenetetrahydromethanopterin dehydrogenase) from methanogenic archaea has recently been found to contain one iron associated tightly with an extractable cofactor of yet unknown structure. We report here that Hmd contains intrinsic CO bound to the Fe. Chemical analysis of Hmd revealed the presence of 2.4 +/- 0.2 mol of CO/mol of iron. Fourier transform infrared spectra of the native enzyme showed two bands of almost equal intensity at 2011 and 1944 cm(-)(1), interpreted as the stretching frequencies of two CO molecules bound to the same iron in an angle of 90 degrees . We also report on the effect of extrinsic (12)CO, (13)CO, (12)CN(-), and (13)CN(-) on the IR spectrum of Hmd.

  13. Delivering carbide ligands to sulfide-rich clusters.

    PubMed

    Reinholdt, Anders; Herbst, Konrad; Bendix, Jesper

    2016-02-01

    The propensity of the terminal ruthenium carbide Ru(C)Cl2(PCy3)2 (RuC) to form carbide bridges to electron-rich transition metals enables synthetic routes to metal clusters with coexisting carbide and sulfide ligands. Electrochemical experiments show the Ru≡C ligand to exert a relatively large electron-withdrawing effect compared with PPh3, effectively shifting redox potentials.

  14. Metallogel formation in aqueous DMSO by perfluoroalkyl decorated terpyridine ligands.

    PubMed

    Tatikonda, Rajendhraprasad; Bhowmik, Sandip; Rissanen, Kari; Haukka, Matti; Cametti, Massimo

    2016-08-01

    Terpyridine based ligands 1 and 2, decorated with a C8F17 perfluorinated tag, are able to form stable thermoreversible gels in the presence of several d-block metal chloride salts. The gel systems obtained have been characterized by NMR, X-ray diffraction, electron microscopies and Tgel experiments in order to gain insights into the observed different behaviour of the two similar ligands, also in terms of the effect of additional common anionic species. PMID:27460754

  15. The value of living donor liver transplantation.

    PubMed

    Yang, Xiaoli; Gong, Junhua; Gong, JianPing

    2012-12-31

    Living donor liver transplantation (LDLT) is a very successful procedure that develops liver resources in case of worldwide shortages. As the technology has developed so much in the past 2 decades, LDLT has the same good prognosis as DDLT. However, LDLT still has lots of ethical & technical problems. It causes great psychiatric, physical and psychosocial harm to donors. Also, it has some negative effects on society by providing a platform for organ trade. Therefore, there is much controversy about the social value of LDLT. After review of recent papers, we find much progress can be made in inspiring the public to become organ donors and creating donation model new to improve the consent rate for solid organ donation from deceased donors. That is the key strategy for increasing the liver supply. With this serious shortage of organs, liver donor transplantation still has its advantages, but we should not place all our hopes on LDLT to increase the liver supply. We all need to try our best to increase donor awareness and promote organ donor registration--when cadaver organs could meet the needs for liver transplantation, living donor liver transplants would not be necessary. PMID:23274332

  16. 42 CFR 35.64 - Donors.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 42 Public Health 1 2010-10-01 2010-10-01 false Donors. 35.64 Section 35.64 Public Health PUBLIC HEALTH SERVICE, DEPARTMENT OF HEALTH AND HUMAN SERVICES MEDICAL CARE AND EXAMINATIONS HOSPITAL AND STATION MANAGEMENT Contributions for the Benefit of Patients § 35.64 Donors. Authorized contributions...

  17. The Experience of Living Kidney Donors

    ERIC Educational Resources Information Center

    Brown, Judith Belle; Karley, Mary Lou; Boudville, Neil; Bullas, Ruth; Garg, Amit X.; Muirhead, Norman

    2008-01-01

    This article describes the experiences, feelings, and ideas of living kidney donors. Using a phenomenological, qualitative research approach, the authors interviewed 12 purposefully selected living kidney donors (eight men and four women), who were between four and 29 years since donation. Interviews were audiotaped, and transcribed verbatim, and…

  18. 21 CFR 610.41 - Donor deferral.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... GENERAL BIOLOGICAL PRODUCTS STANDARDS Testing Requirements for Communicable Disease Agents § 610.41 Donor... testing reactive by a screening test for evidence of infection due to a communicable disease agent(s... infection due to a communicable disease agent(s) listed in § 610.40(a) may serve as a donor for blood...

  19. 21 CFR 610.41 - Donor deferral.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... GENERAL BIOLOGICAL PRODUCTS STANDARDS Testing Requirements for Communicable Disease Agents § 610.41 Donor... testing reactive by a screening test for evidence of infection due to a communicable disease agent(s... infection due to a communicable disease agent(s) listed in § 610.40(a) may serve as a donor for blood...

  20. 21 CFR 610.41 - Donor deferral.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... GENERAL BIOLOGICAL PRODUCTS STANDARDS Testing Requirements for Communicable Disease Agents § 610.41 Donor... testing reactive by a screening test for evidence of infection due to a communicable disease agent(s... infection due to a communicable disease agent(s) listed in § 610.40(a) may serve as a donor for blood...

  1. 21 CFR 610.41 - Donor deferral.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... GENERAL BIOLOGICAL PRODUCTS STANDARDS Testing Requirements for Communicable Disease Agents § 610.41 Donor... testing reactive by a screening test for evidence of infection due to a communicable disease agent(s... infection due to a communicable disease agent(s) listed in § 610.40(a) may serve as a donor for blood...

  2. 21 CFR 610.41 - Donor deferral.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... GENERAL BIOLOGICAL PRODUCTS STANDARDS Testing Requirements for Communicable Disease Agents § 610.41 Donor... testing reactive by a screening test for evidence of infection due to a communicable disease agent(s... infection due to a communicable disease agent(s) listed in § 610.40(a) may serve as a donor for blood...

  3. Recipients' views on payment of sperm donors.

    PubMed

    Ravelingien, An; Provoost, Veerle; Wyverkens, Elia; Buysse, Ann; De Sutter, Petra; Pennings, Guido

    2015-08-01

    The aim of this qualitative study was to explore how recipients viewed payment of sperm donors. The study was conducted in Belgium, where, as in many countries, sperm donors receive recompense for their time and expenses. Face-to-face semi-structured interviews were conducted with 34 heterosexual and lesbian couples who, at the time of data collection, had at least one donor-conceived child aged 7-10 years or who were undergoing donor conception treatment. Although participants commonly described the issue of financial compensation as something that did not really concern them, all supported the idea that some level of payment was acceptable or even necessary. The participants also identified several ways in which donor payment offered advantages to their own position as (future) parents. Although the idea is commonly rehearsed that sperm donation is a gift and that monetary transaction for conception is demeaning, the participants of this study did not generally share this view. To them, a small financial return served as a symbolic acknowledgement of the donor's contribution and helped secure the type of relationship they expected from their donor. There was clearly concern, however, over high payments and the risk of attracting the wrong kind of donor. PMID:26099446

  4. Payment for donor kidneys: pros and cons.

    PubMed

    Friedman, E A; Friedman, A L

    2006-03-01

    Continuous growth of the end stage renal disease population treated by dialysis, outpaces deceased donor kidneys available, lengthens the waiting time for a deceased donor transplant. As estimated by the United States Department of Health & Human Services: '17 people die each day waiting for transplants that can't take place because of the shortage of donated organs.' Strategies to expand the donor pool--public relations campaigns and Drivers' license designation--have been mainly unsuccessful. Although illegal in most nations, and viewed as unethical by professional medical organizations, the voluntary sale of purchased donor kidneys now accounts for thousands of black market transplants. The case for legalizing kidney purchase hinges on the key premise that individuals are entitled to control of their body parts even to the point of inducing risk of life. One approach to expanding the pool of kidney donors is to legalize payment of a fair market price of about 40,000 dollars to donors. Establishing a federal agency to manage marketing and purchase of donor kidneys in collaboration with the United Network for Organ Sharing might be financially self-sustaining as reduction in costs of dialysis balances the expense of payment to donors. PMID:16482095

  5. The value of living donor liver transplantation.

    PubMed

    Yang, Xiaoli; Gong, Junhua; Gong, JianPing

    2012-12-31

    Living donor liver transplantation (LDLT) is a very successful procedure that develops liver resources in case of worldwide shortages. As the technology has developed so much in the past 2 decades, LDLT has the same good prognosis as DDLT. However, LDLT still has lots of ethical & technical problems. It causes great psychiatric, physical and psychosocial harm to donors. Also, it has some negative effects on society by providing a platform for organ trade. Therefore, there is much controversy about the social value of LDLT. After review of recent papers, we find much progress can be made in inspiring the public to become organ donors and creating donation model new to improve the consent rate for solid organ donation from deceased donors. That is the key strategy for increasing the liver supply. With this serious shortage of organs, liver donor transplantation still has its advantages, but we should not place all our hopes on LDLT to increase the liver supply. We all need to try our best to increase donor awareness and promote organ donor registration--when cadaver organs could meet the needs for liver transplantation, living donor liver transplants would not be necessary.

  6. 21 CFR 630.6 - Donor notification.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... the reason for that decision; (ii) Where appropriate, the types of donation of blood or blood... GENERAL REQUIREMENTS FOR BLOOD, BLOOD COMPONENTS, AND BLOOD DERIVATIVES § 630.6 Donor notification. (a) Notification of donors. You, an establishment that collects blood or blood components, must make...

  7. Mono- and binuclear copper(II) complexes of new hydrazone ligands derived from 4,6-diacetylresorcinol: Synthesis, spectral studies and antimicrobial activity.

    PubMed

    Shebl, Magdy; El-ghamry, Mosad A; Khalil, Saied M E; Kishk, Mona A A

    2014-05-21

    Two new hydrazone ligands, H2L(1) and H2L(2), were synthesized by the condensation of 4,6-diacetylresorcinol with 3-hydrazino-5,6-diphenyl-1,2,4-triazine and isatin monohydrazone, respectively. The structures of the ligands were elucidated by elemental analyses, IR, (1)H NMR, electronic and mass spectra. Reactions of the ligands with several copper(II) salts, including AcO(-), NO3(-), SO4(2-), Cl(-) and Br(-) afforded mono- and binuclear metal complexes. Also, the ligands were allowed to react with Cu(II) ion in the presence of a secondary ligand (L') [N,O-donor; 8-hydroxyquinoline, N,N-donor; 1,10-phenanthroline or O,O-donor; benzoylacetone]. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, electronic, mass and ESR spectra as well as conductivity and magnetic susceptibility measurements. The ESR spin Hamiltonian parameters of some complexes were calculated. The spectroscopic data showed that the H2L(1) ligand acts as a neutral or monobasic tridentate ligand while the H2L(2) ligand acts as a bis(monobasic tridentate) ligand. The coordination sites with the copper(II) ion are phenolic oxygen, azomethine nitrogen and triazinic nitrogen (H2L(1) ligand) or isatinic oxygen (H2L(2) ligand). The metal complexes exhibited octahedral and square planar geometrical arrangements depending on the nature of the anion. The ligands and some metal complexes showed antimicrobial activity. PMID:24607473

  8. The use of nitric oxide donors in pharmacological studies.

    PubMed

    Feelisch, M

    1998-07-01

    A growing appreciation of the involvement of nitric oxide (NO) in numerous bioregulatory pathways has not only opened up new therapeutic avenues for organic nitrates and other NO donors but also led to an increased use of such compounds in pharmacological studies. By definition, all NO donors produce NO-related activity when applied to biological systems and are thus principally suited to either mimic an endogenous NO-related response or substitute for an endogenous NO deficiency. However, the pathways leading to enzymatic and/or non-enzymatic formation of NO differ greatly among individual compound classes, as do their chemical reactivities and kinetics of NO release. Moreover, since the reaction of NO with oxygen is a function of its concentration, the same absolute amounts of NO generated over different periods of time may lead to substantially different rates of NOx formation and, consequently, to varying extents of side reactions, such as nitration and/or nitrosation of biomolecules. Matters are further complicated by compound-specific formation of by-products, which may arise during decomposition or metabolism, sometimes in amounts far exceeding those of NO. The term "NO donor" implies that the compound releases the active mediator, NO. Ultimately, this may be true for many different chemical classes of compound, since the principal NO-related species generated may be converted to NO, if not directly released as such. However, in a biological system, the redox form of nitrogen monoxide (NO+, NO. or NO-) that is actually released makes a substantial difference to the NO donor's reactivity towards other biomolecules, the profile of by-products, and the bioresponse. Such considerations are likely to account for much of the discrepancy in experimental results obtained using the same cell or tissue preparation but different NO mimetics. Thus, compound selection is not a trivial issue and the investigator should be aware of the key properties and differences

  9. Chylous ascites secondary to laparoscopic donor nephrectomy.

    PubMed

    Shafizadeh, Stephen F; Daily, Patrick P; Baliga, Prabhakar; Rogers, Jeffrey; Baillie, G Mark; Rajagopolan, P R; Chavin, Kenneth D

    2002-08-01

    Live donor renal transplantation offers many significant advantages over cadaveric donor transplantation. Yet living donation continues to be underused, accounting for less than 30% of all donor renal transplants. In an attempt to remove the disincentives to live donation, Ratner et al. developed laparoscopic donor nephrectomy (LDN). LDN is gaining acceptance in the transplant community. The overriding concern must always be the safety and welfare of the donor. To this end, potential complications of LDN must be identified and discussed. We present a patient who developed the complication of chylous ascites from LDN. To improve the laparoscopic technique further, a discussion of its successes and complications needs to be encouraged. To this end, we present chylous ascites as a potential complication after LDN. We also offer suggestions to minimize the likelihood of this complication. PMID:12137847

  10. Kinetics of thermal donor generation in silicon

    NASA Technical Reports Server (NTRS)

    Mao, B.-Y.; Lagowski, J.; Gatos, H. C.

    1984-01-01

    The generation kinetics of thermal donors at 450 C in Czochralski-grown silicon was found to be altered by high-temperature preannealing (e.g., 1100 C for 30 min). Thus, when compared with as-grown Si, high-temperature preannealed material exhibits a smaller concentration of generated thermal donors and a faster thermal donor saturation. A unified mechanism of nucleation and oxygen diffusion-controlled growth (based on solid-state plate transformation theory) is proposed to account for generation kinetics of thermal donors at 450 C, in as-grown and high-temperature preannealed Czochralski silicon crystals. This mechanism is consistent with the main features of the models which have been proposed to explain the formation of oxygen thermal donors in silicon.

  11. Density functional theory approach to gold-ligand interactions: Separating true effects from artifacts

    NASA Astrophysics Data System (ADS)

    Koppen, Jessica V.; Hapka, Michał; Modrzejewski, Marcin; Szcześniak, Małgorzata M.; Chałasiński, Grzegorz

    2014-06-01

    Donor-acceptor interactions are notoriously difficult and unpredictable for conventional density functional theory (DFT) methodologies. This work presents a reliable computational treatment of gold-ligand interactions of the donor-acceptor type within DFT. These interactions require a proper account of the ionization potential of the electron donor and electron affinity of the electron acceptor. This is accomplished in the Generalized Kohn Sham framework that allows one to relate these properties to the frontier orbitals in DFT via the tuning of range-separated functionals. A donor and an acceptor typically require different tuning schemes. This poses a problem when the binding energies are calculated using the supermolecular method. A two-parameter tuning for the monomer properties ensures that a common functional, optimal for both the donor and the acceptor, is found. A reliable DFT approach for these interactions also takes into account the dispersion contribution. The approach is validated using the water dimer and the (HAuPH3)2 aurophilic complex. Binding energies are computed for Au4 interacting with the following ligands: SCN-, benzenethiol, benzenethiolate anion, pyridine, and trimethylphosphine. The results agree for the right reasons with coupled-cluster reference values.

  12. Bidentate coordinating behaviour of chalcone based ligands towards oxocations: VO(IV) and Mo(V)

    NASA Astrophysics Data System (ADS)

    Thaker, B. T.; Barvalia, R. S.

    2013-08-01

    We synthesized and studied the coordinating behaviour of chalcone based ligands derived from DHA and n-alkoxy benzaldehyde and their complexes of VO(IV) and MoO(V). The chalcone ligands are characterized by elemental analyses, UV-visible, IR, 1H NMR, and mass spectra. The resulting oxocation complexes are also characterized by elemental analyses, IR, 1H NMR, electronic, electron spin resonance spectra, magnetic susceptibility measurement and molar conductance studies. The IR and 1H NMR spectral data suggest that the chalcone ligands behave as a monobasic bidentate with O:O donor sequence towards metal ion. The molar conductivity data show them to be non-electrolytes. From the electronic, magnetic and ESR spectral data suggest that all the chalcone ligand complexes of VO(IV) and MoO(V) have distorted octahedral geometry.

  13. Donor-acceptor bonding in novel low-coordinated compounds of boron and group-14 atoms C-Sn.

    PubMed

    Frenking, Gernot; Hermann, Markus; Andrada, Diego M; Holzmann, Nicole

    2016-02-21

    A summary of theoretical and experimental work in the area of low-coordinated compounds of boron and group-14 atoms C-Sn in the last decade is presented. The focus of the account lies on molecules EL2, E2L2 and E3L3, which possess dative bonds between one, two or three atoms E and σ-donor ligands L that stabilize the atoms E through L→E donor-acceptor interactions. The interplay between theory and experiment provides detailed insight into the bonding situation of the molecules, which serves as guideline for the synthesis of molecules that possess unusual bonding motifs.

  14. Antimicrobial Activity of Metal & Metal Oxide Nanoparticles Interfaced With Ligand Complexes Of 8-Hydroxyquinoline And α-Amino Acids

    NASA Astrophysics Data System (ADS)

    Bhanjana, Gaurav; Kumar, Neeraj; Thakur, Rajesh; Dilbaghi, Neeraj; Kumar, Sandeep

    2011-12-01

    Antimicrobial nanotechnology is a recent addition to the fight against disease causing organisms, replacing heavy meta