Corrosion protective performance of amino trimethylene phosphonic acid-metal complex layers fabricated on the cold-rolled steel substrate via one-step assembly

NASA Astrophysics Data System (ADS)

Yan, Ru; He, Wei; Zhai, Tianhua; Ma, Houyi

2018-06-01

Seeing that amino trimethylene phosphonic acid (ATMP) possesses very strong complexation ability to metal ions and the phosphonic acid group has good affinity for the oxidized iron surface, herein a simple and rapid film-forming method (one-step assembly method) was developed to construct the ATMP-Zn complex conversion layers (ATMP-Zn layers for short) on the cold-rolled steel (CRS) substrate. Zinc ions were found to participate in the formation process of ATMP-based composite film, which made the Zn-containing ATMP film significantly different in appearance, thickness, microstructure and film-forming mechanisms from the Zn-free ATMP film. There was mainly iron (ш) phosphonate in the Zn-free ATMP film, whereas there were Zn2+-ATMP complex and a certain amount of ZnO in the ATMP-Zn composite film. In addition, electrochemical test results clearly indicate that corrosion resistance of ATMP-Zn composite film was greatly enhanced due to the presence of Zn component. Moreover, the corrosion resistance performance could be controlled by adjusting film-forming time, pH and ATMP concentration in the film-forming solutions. The present study provides a new method for the design and fabrication of high-quality environmentally-friendly conversion layers.

Crystal structure of the complex of carboxypeptidase A with a strongly bound phosphonate in a new crystalline form: comparison with structures of other complexes.

PubMed

Kim, H; Lipscomb, W N

1990-06-12

O-[[(1R)-[[N-(Phenylmethoxycarbonyl)-L-alanyl]amino]ethyl] hydroxyphosphinyl]-L-3-phenyllacetate [ZAAP(O)F], an analogue of (benzyloxycarbonyl)-Ala-Ala-Phe or (benzyloxycarbonyl)-Ala-Ala-phenyllactate, binds to carboxypeptidase A with great affinity (Ki = 3 pM). Similar phosphonates have been shown to be transition-state analogues of the CPA-catalyzed hydrolysis [Hanson, J. E., Kaplan, A. P., & Bartlett, P. A. (1989) Biochemistry 28, 6294-6305]. In the present study, the structure of the complex of this phosphonate with carboxypeptidase A has been determined by X-ray crystallography to a resolution of 2.0 A. The complex crystallizes in the space group P2(1)2(1)2(1) with cell dimensions a = 61.9 A, b = 67.2 A, and c = 76.2 A. The structure of the complex was solved by molecular replacement. Refinement of the structure against 20,776 unique reflections between 10.0 and 2.0 A yields a crystallographic residual of 0.193, including 140 water molecules. The two phosphinyl oxygens of the inhibitor bind to the active-site zinc at 2.2 A on the electrophilic (Arg-127) side and 3.1 A on the nucleophilic (Glu-270) side. Various features of the binding mode of this phosphonate inhibitor are consistent with the hypothesis that carboxypeptidase A catalyzed hydrolysis proceeds through a general-base mechanism in which the carbonyl carbon of the substrate is attacked by Zn-hydroxyl (or Zn-water). An unexpected feature of the bound inhibitor, the cis carbamoyl ester bond at the benzyloxycarbonyl linkage to alanine, allows the benzyloxycarbonyl phenyl ring of the inhibitor to interact favorably with Tyr-198. This complex structure is compared with previous structures of carboxypeptidase A, including the complexes with the potato inhibitor, a hydrated keto methylene substrate analogue, and a phosphonamidate inhibitor. Comparisons are also made with the complexes of thermolysin with some phosphonamidate inhibitors.

Acute effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate, on cardiovascular parameters in anaesthetized, artificially ventilated rats

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

Watanabe, Yoshimasa; Itoh, Takeo, E-mail: titoh@med.nagoya-cu.ac.jp; Shiraishi, Hiroaki

The organophosphorus compound sarin irreversibly inhibits acetylcholinesterase. We examined the acute cardiovascular effects of a sarin-like organophosphorus agent, bis(isopropyl methyl)phosphonate (BIMP), in anaesthetized, artificially ventilated rats. Intravenous administration of BIMP (0.8 mg/kg; the LD50 value) induced a long-lasting increase in blood pressure and tended to increase heart rate. In rats pretreated with the non-selective muscarinic-receptor antagonist atropine, BIMP significantly increased both heart rate and blood pressure. In atropine-treated rats, hexamethonium (antagonist of ganglionic nicotinic receptors) greatly attenuated the BIMP-induced increase in blood pressure without changing the BIMP-induced increase in heart rate. In rats treated with atropine plus hexamethonium, intravenous phentolaminemore » (non-selective α-adrenergic receptor antagonist) plus propranolol (non-selective β-adrenergic receptor antagonist) completely blocked the BIMP-induced increases in blood pressure and heart rate. In atropine-treated rats, the reversible acetylcholinesterase inhibitor neostigmine (1 mg/kg) induced a transient increase in blood pressure, but had no effect on heart rate. These results suggest that in anaesthetized rats, BIMP induces powerful stimulation of sympathetic as well as parasympathetic nerves and thereby modulates heart rate and blood pressure. They may also indicate that an action independent of acetylcholinesterase inhibition contributes to the acute cardiovascular responses induced by BIMP. - Highlights: • A sarin-like agent BIMP markedly increased blood pressure in anaesthetized rats. • Muscarinic receptor blockade enhanced the BIMP-induced increase in blood pressure. • Ganglionic nicotinic receptor blockade attenuated the BIMP-induced response. • Blockade of α- as well as β-receptors attenuated the BIMP-induced response.« less

Phosphonic acid: preparation and applications

PubMed Central

Sevrain, Charlotte M; Berchel, Mathieu; Couthon, Hélène

2017-01-01

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H3PO3) and that produce a phosphonic acid functional group simultaneously to the formation of the P–C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids. PMID:29114326

Phosphonic acid: preparation and applications.

PubMed

Sevrain, Charlotte M; Berchel, Mathieu; Couthon, Hélène; Jaffrès, Paul-Alain

2017-01-01

The phosphonic acid functional group, which is characterized by a phosphorus atom bonded to three oxygen atoms (two hydroxy groups and one P=O double bond) and one carbon atom, is employed for many applications due to its structural analogy with the phosphate moiety or to its coordination or supramolecular properties. Phosphonic acids were used for their bioactive properties (drug, pro-drug), for bone targeting, for the design of supramolecular or hybrid materials, for the functionalization of surfaces, for analytical purposes, for medical imaging or as phosphoantigen. These applications are covering a large panel of research fields including chemistry, biology and physics thus making the synthesis of phosphonic acids a determinant question for numerous research projects. This review gives, first, an overview of the different fields of application of phosphonic acids that are illustrated with studies mainly selected over the last 20 years. Further, this review reports the different methods that can be used for the synthesis of phosphonic acids from dialkyl or diaryl phosphonate, from dichlorophosphine or dichlorophosphine oxide, from phosphonodiamide, or by oxidation of phosphinic acid. Direct methods that make use of phosphorous acid (H 3 PO 3 ) and that produce a phosphonic acid functional group simultaneously to the formation of the P-C bond, are also surveyed. Among all these methods, the dealkylation of dialkyl phosphonates under either acidic conditions (HCl) or using the McKenna procedure (a two-step reaction that makes use of bromotrimethylsilane followed by methanolysis) constitute the best methods to prepare phosphonic acids.

Investigation into 64Cu-labeled Bis(selenosemicarbazone) and Bis(thiosemicarbazone) complexes as hypoxia imaging agents.

PubMed

McQuade, Paul; Martin, Katherine E; Castle, Thomas C; Went, Michael J; Blower, Philip J; Welch, Michael J; Lewis, Jason S

2005-02-01

Cu-diacetyl-bis(N4-methylthiosemicarbazone) [Cu-ATSM], although excellent for oncology applications, may not be suitable for delineating cardiovascular or neurological hypoxia. For this reason, new Cu hypoxia positron emission tomography (PET) imaging agents are being examined to search for a higher selectivity for hypoxic or ischemic tissue at higher oxygen concentrations found in these tissues. Two approaches are to increase alkylation or to replace the sulfur atoms with selenium, resulting in the formation of selenosemicarbazones. Three 64Cu-labeled selenosemicarbazone complexes were synthesized and one was screened for hypoxia selectivity in vitro using EMT-6 mouse mammary carcinoma cells. Rodent biodistribution and small animal PET images were obtained from BALB/c mice implanted with EMT-6 tumors. One alkylated thiosemicarbazone was synthesized and examined. Of the three bis(selenosemicarbazone) ligands synthesized and examined, only 64Cu-diacetyl-bis(selenosemicarbazone) [64Cu-ASSM] was isolated in high-enough radiochemical purity to undertake cell uptake experiments where uptake was shown to be independent of oxygen concentration. The bis(thiosemicarbazone) complex synthesized, 64Cu-diacetyl-bis(N4-ethylthiosemicarbazone) [64Cu-ATSE], showed hypoxia selectivity similar to 64Cu-ATSM although at a higher oxygen concentration. Biodistribution studies for 64Cu-ASSM and 64Cu-ATSE showed high tumor uptake at 20 min (64Cu-ASSM, 10.33+/-0.78% ID/g; 64Cu-ATSE, 7.71+/-0.46% ID/g). PET images of EMT-6 tumor-bearing mice visualized the tumor with 64Cu-ATSE and revealed hypoxia selectivity consistent with the in vitro data. Of the compounds synthesized, only 64Cu-ASSM and 64Cu-ATSE could be examined in vitro and in vivo. Although the stability of bis(selenosemicarbazone) complexes increased upon addition of methyl groups to the diimine backbone, the fully alkylated species, 64Cu-ASSM, demonstrated no hypoxia selectivity. However, the additional alkylation present in Cu

Electron paramagnetic resonance and density-functional theory studies of Cu(II)-bis(oxamato) complexes.

PubMed

Bräuer, Björn; Weigend, Florian; Fittipaldi, Maria; Gatteschi, Dante; Reijerse, Edward J; Guerri, Annalisa; Ciattini, Samuele; Salvan, Georgeta; Rüffer, Tobias

2008-08-04

In this work we present the investigation of the influence of electronic and structural variations induced by varying the N,N'-bridge on the magnetic properties of Cu(II)- bis(oxamato) complexes. For this study the complexes [Cu(opba)] (2-) ( 1, opba = o-phenylene- bis(oxamato)), [Cu(nabo)] (2-) ( 2, nabo = 2,3-naphthalene- bis(oxamato)), [Cu(acbo)] (2-) ( 3, acbo = 2,3-anthrachinone- bis(oxamato)), [Cu(pba)] (2-) ( 4, pba = propylene- bis(oxamato)), [Cu(obbo)] (2-) ( 5, obbo = o-benzyl- bis(oxamato)), and [Cu(npbo)] (2-) ( 6, npbo = 1,8-naphthalene- bis(oxamato)), and the respective structurally isomorphic Ni(II) complexes ( 8- 13) have been prepared as ( (n)Bu 4N) (+) salts. The new complex ( (n)Bu 4N) 2[Cu(R-bnbo)].2H 2O ( 7, R-bnbo = (R)-1,1'-binaphthalene-2,2'- bis(oxamato)) was synthesized and is the first chiral complex in the series of Cu(II)-bis(oxamato) complexes. The molecular structure of 7 has been determined by single crystal X-ray analysis. The Cu(II) ions of the complexes 1- 7 are eta (4)(kappa (2) N, kappa (2) O) coordinated with a more or less distorted square planar geometry for 1- 6 and a distorted tetrahedral geometry for 7. Using pulsed Electron Nuclear Double Resonance on complex 6, detailed information about the relative orientation of the hyperfine ( A) and nuclear quadrupole tensors ( Q) of the coordinating nitrogens with respect to the g tensor were obtained. Electron Paramagnetic Resonance studies in the X, Q, and W-band at variable temperatures were carried out to extract g and A values of N ligands and Cu ion for 1- 7. The hyperfine values were interpreted in terms of spin population on the corresponding atoms. The obtained trends of the spin population for the monomeric building blocks were shown to correlate to the trends obtained in the dependence of the exchange interaction of the corresponding trinuclear complexes on their geometry.

Octa- and hexametallic iron(III)-potassium phosphonate cages.

PubMed

Gopal, Kandasamy; Tuna, Floriana; Winpenny, Richard E P

2011-12-07

Two new iron(III)-potassium phosphonate cage complexes with {K(2)Fe(6)} and {K(2)Fe(4)} cores are reported. Magnetic studies reveal antiferromagnetic interactions between the Fe(III) centres occur in these cages.

Method for synthesizing metal bis(borano) hypophosphite complexes

DOEpatents

Cordaro, Joseph G.

2013-06-18

The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

From bis(imidazole-2-thion-4-yl)phosphane to a flexible P-bridged bis(NHC) ligand and its silver complex.

PubMed

Majhi, Paresh Kumar; Schnakenburg, Gregor; Streubel, Rainer

2014-11-28

Synthesis of the first P(V)-bridged bis(NHC) ligand 7 was achieved via deprotonation of P(V)-functionalized bis(imidazolium) salt 6, which was obtained via oxidative desulfurization of bis(imidazole-2-thion-4-yl)phosphane 2. Bis(imidazolium) salt 6 was also employed to synthesize the corresponding silver complex 8. All new products were firmly established by spectroscopic and spectrometric methods as well as elemental analysis and, in addition, X-ray crystal structure analysis in the case of 3.

Direct assembly synthesis of metal complex-semiconductor hybrid photocatalysts anchored by phosphonate for highly efficient CO2 reduction.

PubMed

Suzuki, Tomiko M; Tanaka, Hiromitsu; Morikawa, Takeshi; Iwaki, Masayo; Sato, Shunsuke; Saeki, Shu; Inoue, Masae; Kajino, Tsutomu; Motohiro, Tomoyoshi

2011-08-14

Hybrid photocatalysts consisting of a ruthenium complex and p-type photoactive N-doped Ta(2)O(5) anchored with an organic group were successfully synthesized by a direct assembly method. The photocatalyst anchored by phosphonate exhibited excellent photoconversion activity of CO(2) to formic acid under visible-light irradiation with respect to the reaction rate and stability. This journal is © The Royal Society of Chemistry 2011

Controlling the oxidation of bis-tridentate cobalt(ii) complexes having bis(2-pyridylalkyl)amines: ligand vs. metal oxidation.

PubMed

Anjana, S; Donring, S; Sanjib, P; Varghese, B; Murthy, Narasimha N

2017-08-22

Two bis-tridentate chelated cobalt(ii) complexes, which differ in the ligand structure by a methylene group, activate molecular oxygen (O 2 ), and give different oxidation products. The O 2 reaction of [Co II (pepma) 2 ] 2+ (1) with unsymmetrical 2-(2-pyridyl)-N-(2-pyridylmethyl)ethanamine (pepma) results in ligand oxidation, to the corresponding Co(ii) imine complex [Co II (pepmi) 2 ] 2+ (2). Contrastingly, the Co(ii) complex [Co II (bpma) 2 ] 2+ (3) of similar symmetrical bis(2-pyridylmethyl)amine (bpma), undergoes metal oxidation, yielding a cobalt(iii) complex, [Co III (bpma) 2 ] 2+ (4). The reversibility of the amine to imine conversion and the stability of the Co(ii) imine complex (2) are investigated. Furthermore, the solution dynamics of Co(ii) complexes are highlighted with the help of paramagnetic 1 H-NMR spectroscopy.

Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

DOE PAGES

McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan

2017-10-27

Here, we have developed a single step palladium-catalyzed Heck coupling of aryl halides with vinyl phosphonic acid to produce functionalized (E)-styryl phosphonic acids. This pathway utilizes a variety of commercially available aryl halides, vinyl phosphonic acid and Pd(P(tBu) 3) 2 as catalyst. These conditions produce a wide range of styryl phosphonic acids with high purities and good to excellent yields (31–80%).

Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

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

McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan

Here, we have developed a single step palladium-catalyzed Heck coupling of aryl halides with vinyl phosphonic acid to produce functionalized (E)-styryl phosphonic acids. This pathway utilizes a variety of commercially available aryl halides, vinyl phosphonic acid and Pd(P(tBu) 3) 2 as catalyst. These conditions produce a wide range of styryl phosphonic acids with high purities and good to excellent yields (31–80%).

Data Analysis And Polarization Measurements With GEMS

NASA Technical Reports Server (NTRS)

Stohmayer, Tod

2011-01-01

The Gravity and Extreme Magnetism SMEX (GEMS) mission was selected by NASA for flight in 2014. GEMS will make the first sensitive survey of X-ray polarization across a wide range of source classes including black hole and neutron star binaries, AGN of different types, rotation and accretion-powered pulsars, magnetars, shell supernova remnants and pulsar wind nebulae. GEMS employs grazing-incidence foil mirrors and novel time-projection chamber (TPC) polarimeters leveraging the photoelectric effect. The GEMS detectors image the charge tracks of photoelectrons produced by 2 - 10 keV X-rays. The initial direction of the photoelectron is determined by the linear polarization of the photon. We present an overview of the data analysis challenges and methods for GEMS, including procedures for producing optimally filtered images of the charge tracks and estimating their initial directions. We illustrate our methods using laboratory measurements of polarized and unpolarized X-rays with flight-like detectors as well as from simulated tracks. We also present detailed simulations exploring the statistics of polarization measurements appropriate for GEMS, and make comparisons with previous work.

Preparation and use of crystalline bis-monoorganic phosphonate and phosphate salts of tetravalent metals

DOEpatents

Maya, L.

1980-06-26

A method of preparing and using the crystalline organic derivatives of the tetravalent metal phosphates and phosphonates provides for the contacting of an aqueous solution of a metal nitrate, with a solution of an organophosphorus acid for a period of time at room temperature that is sufficient for the formation of a metal phosphate product, and thereafter recovering said product. According to the invention, the product of the disclosed process is used in effecting analytical separations, such as ion exchange and chromatography.

Copper(II)-bis(thiosemicarbazonato) complexes as anti-chlamydial agents.

PubMed

Marsh, James W; Djoko, Karrera Y; McEwan, Alastair G; Huston, Wilhelmina M

2017-09-29

Lipophilic copper (Cu)-containing complexes have shown promising antibacterial activity against a range of bacterial pathogens. To examine the susceptibility of the intracellular human pathogen Chlamydia trachomatis to copper complexes containing bis(thiosemicarbazone) ligands [Cu(btsc)], we tested the in vitro effect of CuII-diacetyl- and CuII-glyoxal-bis[N(4)-methylthiosemicarbazonato] (Cu(atsm) and Cu(gtsm), respectively) on C. trachomatis. Cu(atsm) and to a greater extent, Cu(gtsm), prevented the formation of infectious chlamydial progeny. Impacts on host cell viability and respiration were also observed in addition to the Chlamydia impacts. This work suggests that copper-based complexes may represent a new lead approach for future development of new therapeutics against chlamydial infections, although host cell impacts need to be fully explored. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Imidazoline phosphonic acids

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

Redmore, D.

1972-07-04

Nitrogen-heterocyclic phosphonic acids and derivatives are characterized by aminomethyl (or substituted methyl) phosphonic acids or derivatives thereof bonded directly or indirectly, i.e., through a N-side chain to the nitrogen atom in the heterocyclic ring, for example those containing in the molecule at least one of the following units: ..pi..Equation/sup -/ where represents a heterocyclic ring having a nitrogen atom on the ring; -R'N- represents an amino- terminated side chain attached directly to the ring nitrogen (which side chain may or may not be present); and ..pi..Equation/sup -/ represents a methyl (or substituted methyl) phosphonic acid group where M is hydrogen,more » an alcohol or a salt moiety, and X and Y are hydrogen or a substituted group such as alkyl, aryl, etc., of which one or 2 units may be present depending on the available nitrogen bonded by hydrogens, and to uses for these compounds, for example, as scale inhibitors, corrosion inhibitors, etc. (5 claims)« less

Study of the GEM detector performance in BM@N experiment

NASA Astrophysics Data System (ADS)

Bazylev, Sergei; Kapishin, Mikhail; Kapusniak, Kacper; Karjavine, Vladimir; Khabarov, Sergei; Kolesnikov, Alexander; Kulish, Elena; Lenivenko, Vasilisa; Makankin, Alexander; Maksymchuk, Anna; Mehl, Bertrand; De Oliveira, Rui; Palchik, Vladimir; Pokatashkin, Gleb; Rodriguez, A.; Rufanov, Igor; Shutov, Alexander; Slepnev, Ilya; Slepnev, Vyacheslav; Vasiliev, Sergei; Zinchenko, Alexander

2018-04-01

BM@N is the fixed target experiment at the accelerator complex NICA-Nuclotron aimed to study nuclear matter in the relativistic heavy ion collisions. Triple-GEM detectors were identified as appropriate for the BM@N tracking system located inside the analyzing magnet. Seven GEM chambers are integrated into the BM@N experimental setup and data acquisition system. GEM construction, main characteristics and first obtained results of the GEM tracking system performance in the technical run with the deuteron beam are shortly reviewed.

Octahedral d[sup 6] Bis(maleimide) and Bis(maleic anhydride) complexes of molybdenum

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

Lai, Chen-Hsing; Cheng, Chien-Hong; Liao, Fen-Ling

1993-12-08

Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] reacts with 2 equiv of alkene, where the alkene is maleimide (MI), N-phenylmaleimide (PhMI), or N-methylmaleimide, to give the corresponding Mo(CO)[sub 2](alkene)[sub 2](CH[sub 3]CN)[sub 2] complex (1a-c, respectively) in excellent yield. Dissolution of 1 in DMSO led to the substitution of acetonitrile ligands by DMSO to form the corresponding cis bis(DMSO) complexes 2a-c. Addition of 1 equiv of NN to 1 yields MO(CO)[sub 2](alkene)[sub 2](alkene)[sub 2](NN) (NN = en, alkene = PhMI (3b), MeMI (3c); NN = o-phenylenediamine, alkene = PhMI (4)). Treatment of Mo-(CO)[sub 4](NN) (NN = phen or bpy), with 2 equiv of alkenemore » in refluxed acetonitrile for 2 h gave Mo(CO)[sub 2]-(alkene)[sub 2](NN) (NN = phen, alkene = MI (5a), PhMI (5b); NN = bpy, alkene = MI (6a), PhMI (6b)). Treatment of Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] with 2 equiv of maleic anhydride (MA) gave Mo(CO)[sub 2](MA)[sub 2](CH[sub 3]CN)[sub 2] (7). The acetonitrile ligands in 7 were replaced by DMSO molecules to give complex 8 as 7 was dissolved in DMSO. Similarly, the reaction of 7 with a bidentate ligand NN (phen or bpy) gave the substituted product Mo(CO)[sub 2](MA)[sub 2](NN) (9 or 10). The structures and conformations of 1b and 7 were determined by X-ray diffraction. Both molecules adopt an octahedral geometry with mutually perpendicular trans alkene ligands and each alkene ligand eclipses a N-Mo-CO vector. Each PhMI or MA is oriented so that the central nitrogen or oxygen atom points to a carbonyl group. 1b crystallizes in triclinic space group P1. There are three possible conformations for a trans bis(maleimide) or bis(maleic anhydride) complex (I-III). The results of X-ray and NMR studies indicated that the main conformation of complexes 1-10 is I both in the solid state and in solution.« less

Chemoselective recognition with phosphonate cavitands: the ephedrine over pseudoephedrine case.

PubMed

Biavardi, Elisa; Ugozzoli, Franco; Massera, Chiara

2015-02-25

Complete discrimination of ephedrine and pseudoephedrine, both in solution and in the solid state, was achieved with a phosphonate cavitand receptor. The molecular origin of the epimer discrimination was revealed by the crystal structure of the respective complexes.

Hyperspectral imaging: gem identification and authentication

NASA Astrophysics Data System (ADS)

Gomez, Richard B.; Del Re, Nicholas

2005-01-01

Through the centuries gem materials have been highly prized and sought after. The varieties of gem materials run into the hundreds if not thousands, characterized by a gamut of material classes running from organic to inorganic and from crystalline to amorphous. All consisting of numerous chemical compositions and characterized by various physical and optical properties. In addition, most gem materials have been subject to numerous modifications to enhance and imitate the most pleasing of esthetic qualities, e.g., dyeing, impregnation, heating, reconstruction, high pressure and temperature, irradiation, and diffusion. Of concern is the ability not only to identify the gem material in question, but if applicable, the treatment. Up until recent, the main instruments utilized to detect these have been simple but quite effective such as a binocular microscope, refractometer, hand spectroscope, dichroscope, and measuring of specific gravity. New gem materials and techniques involved in treatments have become increasingly sophisticated such as ultraviolet-visible-infrared and Raman spectroscopy. In certain cases, some of the most recent techniques have become time consuming and expensive. Here is the opportunity to overview and utilize a powerful technology found in the field of remote sensing, i.e., Hyperspectral Imaging. This technology has been in effect for many years but only recently has it been used to focus on areas similar to the ones in this paper. In particular, hyperspectral imaging technology and its potential application to gem identification and authentication are covered in this paper.

Structure of complexes of nitrilo tris methylene phosphonic acid with copper, [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] and Na{sub 4}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O, as bactericides and inhibitors of scaling and corrosion

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

Somov, N. V., E-mail: somov@phys.unn.ru; Chausov, F. F., E-mail: chaus@uni.udm.ru

2015-03-15

Nitrilotris methylene phosphonate triaqua copper and octasodium bis(nitrilotris methylene phosphonate cuprate(II)) nonadecahydrate have been synthesized and investigated. [CuN(CH{sub 2}PO{sub 3}){sub 3}(H{sub 2}O){sub 3}] is crystallized in the sp. gr. P2{sub 1}/c, Z = 4, a = 9.2506(2) Å, b = 15.9815(2) Å, c = 9.5474(2) Å, β = 113.697(2)°. The copper atom is coordinated by oxygen atoms in the configuration of elongated octahedron; the ligand (of bridge type) links neighboring copper atoms. Na{sub 8}[CuN(CH{sub 2}PO{sub 3}){sub 3}]{sub 2} · 19H{sub 2}O is crystallized in the sp. gr. P2{sub 1}/c, Z = 2, a = 11.24550(10) Å, b = 17.38980(10) Å,more » c = 13.5852(2) Å, β = 127.8120(10)°. This complex is chelating; the copper atom closes three five-membered N-C-P-O-Cu cycles with a shared Cu-N bond. Copper is coordinated in a distorted trigonal-bipyramidal configuration.« less

Rhenium complexes of bidentate, bis-bidentate and tridentate N-heterocyclic carbene ligands.

PubMed

Chan, Chung Ying; Barnard, Peter J

2015-11-28

A series of eight Rhenium(I)-N-heterocyclic carbene (NHC) complexes of the general form [ReCl(CO)3(C^C)] (where C^C is a bis(NHC) bidentate ligand), [ReCl(CO)3(C^C)]2 (where C^C is a bis-bidentate tetra-NHC ligand) and [Re(CO)3(C^N^C)](+)[X](-) (where C^N^C is a bis(NHC)-amine ligand and the counter ion X is either the ReO4(-) or PF6(-)) have been synthesised using a Ag2O transmetallation protocol. The novel precursor imidazolium salts and Re(I) complexes were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy and the molecular structures for two imidazolium salt and six Re(I) complexes were determined by single crystal X-ray diffraction. These NHC ligand systems are of interest for possible applications in the development of Tc-99m or Re-186/188 radiopharmaceuticals and as such the stability of two complexes of the form [ReCl(CO)3(C^C)] and [Re(CO)3(C^N^C)][ReO4] were evaluated in ligand challenge experiments using the metal binding amino acids L-histidine or L-cysteine. These studies showed that the former was unstable, with the chloride ligand being replaced by either cysteine or histidine, while no evidence for transchelation was observed for the latter suggesting that bis(NHC)-amine ligands of this type may be suitable for biological applications.

X-Ray Polarimetry with GEMS

NASA Technical Reports Server (NTRS)

Strohmayer, Tod

2011-01-01

The polarization properties of cosmic X-ray sources are still largely unexplored. The Gravity and Extreme Magnetism SMEX (GEMS) will carry out the first sensitive X-ray polarization survey of a wide range of sources including; accreting compact objects (black holes and neutron stars), AGN, supernova remnants, magnetars and rotation-powered pulsars. GEMS employs grazing-incidence foil mirrors and novel time-projection chamber (TPC) polarimeters leveraging the photoelectric effect to achieve high polarization sensitivity in the 2 - 10 keV band. I will provide an update of the project status, illustrate the expected performance with several science examples, and provide a brief overview of the data analysis challenges

Origins of GEMS Grains

NASA Technical Reports Server (NTRS)

Messenger, S.; Walker, R. M.

2012-01-01

Interplanetary dust particles (IDPs) collected in the Earth s stratosphere contain high abundances of submicrometer amorphous silicates known as GEMS grains. From their birth as condensates in the outflows of oxygen-rich evolved stars, processing in interstellar space, and incorporation into disks around new stars, amorphous silicates predominate in most astrophysical environments. Amorphous silicates were a major building block of our Solar System and are prominent in infrared spectra of comets. Anhydrous interplanetary dust particles (IDPs) thought to derive from comets contain abundant amorphous silicates known as GEMS (glass with embedded metal and sulfides) grains. GEMS grains have been proposed to be isotopically and chemically homogenized interstellar amorphous silicate dust. We evaluated this hypothesis through coordinated chemical and isotopic analyses of GEMS grains in a suite of IDPs to constrain their origins. GEMS grains show order of magnitude variations in Mg, Fe, Ca, and S abundances. GEMS grains do not match the average element abundances inferred for ISM dust containing on average, too little Mg, Fe, and Ca, and too much S. GEMS grains have complementary compositions to the crystalline components in IDPs suggesting that they formed from the same reservoir. We did not observe any unequivocal microstructural or chemical evidence that GEMS grains experienced prolonged exposure to radiation. We identified four GEMS grains having O isotopic compositions that point to origins in red giant branch or asymptotic giant branch stars and supernovae. Based on their O isotopic compositions, we estimate that 1-6% of GEMS grains are surviving circumstellar grains. The remaining 94-99% of GEMS grains have O isotopic compositions that are indistinguishable from terrestrial materials and carbonaceous chondrites. These isotopically solar GEMS grains either formed in the Solar System or were completely homogenized in the interstellar medium (ISM). However, the

Recent advances in H-phosphonate chemistry. Part 1. H-phosphonate esters: synthesis and basic reactions.

PubMed

Sobkowski, Michal; Kraszewski, Adam; Stawinski, Jacek

2015-01-01

This review covers recent progress in the preparation of H-phosphonate mono- and diesters, basic studies on mechanistic and stereochemical aspects of this class of phosphorus compounds, and their fundamental chemistry in terms of transformation of P-H bonds into P-heteroatom bonds. Selected recent applications of H-phosphonate derivatives in basic organic phosphorus chemistry and in the synthesis of biologically important phosphorus compounds are also discussed.

Not Your Ordinary GEM

NASA Technical Reports Server (NTRS)

2001-01-01

Through Small Business Innovation Research (SBIR) funding from NASA's Stennis Space Center, Geophex devised a new design for broadband electromagnetic sensors. Geophex developed a patented sensing technology, capable not only of coastal monitoring, but also a variety of other functions, including environmental pollution characterization, groundwater contamination detection, archaeological study, and mineral detection. The new technology is offered in several of the company's products the GEM-2, GEM-2A, and the GEM-3. The Geophex products consist of two primary electromagnetic coils, which are stimulated by alternating currents that generate a magnetic field in the object targeted for investigation. GEM-2 is a handheld, lightweight, programmable, digital device. GEM-2A is an airborne version of the sensor. Suspended from a helicopter, the GEM-2A is used to search for mineral deposits and to survey large tracts of land. The GEM-3 is capable of detecting buried landmines and other active munitions. GEM-3 identifies landmines by their brand names. Because each landmine has its own unique electromagnetic response to the broad frequency band emitted by the GEM-3, bomb identification and disposal strategies are made easier.

Cobalt(II) complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine: Structures, photoluminescent and photocatalytic properties

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

Li, Jin-Ping; Fan, Jian-Zhong; Wang, Duo-Zhi, E-mail: wangdz@xju.edu.cn

2016-07-15

Six new Co{sup II} complexes [Co(L{sup 1}){sub 4}(OH){sub 2}] (1), {[Co(L"1)(H_2O)_4]·2ClO_4}{sub ∞} (2), {[Co(L"1)(H_2O)_4]·SiF_6}{sub ∞} (3), {[Co(L"1)_3]·2ClO_4}{sub ∞} (4), [Co(L{sup 2})Cl{sub 2}]{sub ∞} (5) and {[Co(L"2)_2]·SiF_6}{sub ∞} (6) [L{sup 1}=3,6-bis(N-imidazolyl) pyridazine, L{sup 2}=3,6-bis (N-benzimidazolyl) pyridazine] have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complex 1 has a mononuclear structure, while complexes 2 and 3 have 1-D chain structures. Considering the Co{sup II} centers were linked by the L{sup 1} ligands, the 3-D framework of complex 4 can be rationalized to be a {4^12.6^3} 6-c topological net with the stoichiometry uninodal net. 5 revealsmore » a coordination 1-D zigzag chain structure consisting of a neutral chain [Co(L{sup 2})Cl{sub 2}]{sub n} with the Co{sup II} centers. Complex 6 has a rhombohedral grid with a (4, 4) topology. The TGA property, fluorescent property and photocatalytic activity of complexes 1–6 have been investigated and discussed. - Graphical abstract: Six Co{sup II} complexes of bis(N-imidazolyl/benzimidazolyl)pyridazine were synthesized and structurally characterized. The fluorescence properties and photocatalytic activity for dye degradation under UV light of all complexes have been investigated and discussed. Display Omitted - Highlights: • Six new Co{sup II} complexes with bis(N-imidazolyl/benzimidazolyl) pyridazine. • Structural analysis of all complexes. • Fluorescent property of all complexes. • Photocatalytic activity for dye degradation under UV light of all complexes.« less

In Vitro and In Vivo Behaviour of 111In Complexes of TTHA, TTHA-Bis(Butylamide) and TTHA-Bis(Glucamide): Stability, Biodistribution and Excretion Studied by Gamma Imaging

PubMed Central

Prata, M. I. M.; Ribeiro, M. J.; Santos, A. C.; Peters, J. A.; Nepveu, F.; de Lima, J. J. P.

1998-01-01

Aiming at radiopharmaceutical application, 111In3+ complexes of the polyaminocarboxylates TTHA, TTHA-bis(butylamide) and TTHA-bis(glucamide) were investigated. The in vitro stability of 111In(TTHA)3− and 111In(TTHA-bis(butylamide)- was evaluated by measuring the exchange of 111In3+ from the complexes to transferrin and the results were compared with those for 111In(DTPA)2−. We also performed biodistribution studies of the three 111In3+ complexes by gamma-imaging in Wistar rats and by measuring the radioactivity in their organs. TTHA and its derivatives seem to have similar in vivo biodistribution with prevailing renal excretion. PMID:18475854

CTA1: Purified and display onto gram-positive enhancer matrix (GEM) particles as mucosal adjuvant.

PubMed

Zhang, Yuanpeng; Yu, Xiaoming; Hou, Liting; Chen, Jin; Li, Pengcheng; Qiao, Xuwen; Zheng, Qisheng; Hou, Jibo

2018-01-01

The A1 subunit of cholera toxin (CTA1) retains the adjuvant function of CT, without its toxic side effects, making the molecule a promising mucosal adjuvant. However, the methods required to obtain a pure product are both complicated and expensive, constricting its potential commercial applicability. Here, we fused the peptidoglycan binding domain (PA) to the C-terminus of CTA1, which enabled the fusion protein to be expressed by Bacillus subtilis, and secreted into the culture medium. CTA1 was then purified and displayed on GEM particles using a one step process, which resulted in the formation of CTA1-GEM complexes. Next, the CTA1-GEM complexes were used as an adjuvant to enhance the immune responses of mice to the influenza subunit vaccine. It was observed that the CTA1-GEM complexes enhanced specific systemic (IgG) and mucosal (IgA) immune responses against antigen, and induced cellular immune responses as well. The data presented here suggests that CTA1-GEM complexes can serve as a viable mucosal adjuvant. Copyright © 2017 Elsevier Inc. All rights reserved.

Rhodium-catalyzed enantioselective cyclizations of γ-alkynylaldehydes with acyl phosphonates: ligand- and substituent-controlled C-P or C-H bond cleavage.

PubMed

Masuda, Kengo; Sakiyama, Norifumi; Tanaka, Rie; Noguchi, Keiichi; Tanaka, Ken

2011-05-11

It has been established that a cationic rhodium(I)/(R)-H(8)-BINAP or (R)-Segphos complex catalyzes two modes of enantioselective cyclizations of γ-alkynylaldehydes with acyl phosphonates via C-P or C-H bond cleavage. The ligands of the Rh(I) complexes and the substitutents of both γ-alkynylaldehydes and acyl phosphonates control these two different pathways. © 2011 American Chemical Society

Structural diversity of benzil bis(benzoylhydrazone): Mononuclear, binuclear and trinuclear complexes.

PubMed

López-Torres, Elena; Mendiola, M Antonia

2009-10-07

The coordination behaviour of the Schiff-base, benzil bis(benzoylhydrazone), LH(2) towards divalent nickel, lead, cadmium, zinc and copper ions has been investigated. The complexes have been fully characterized by techniques including (113)Cd and (207)Pb NMR, as well as (13)C and (113)Cd CP/MAS NMR and by single crystal X-ray diffraction. All the complexes have the general formula [ML](n) (n = 1-3 depending on the metal ion), with the ligand doubly deprotonated. The nickel complex [NiL] is a monomeric compound, the lead complex [PbL](2) shows a binuclear structure, whereas zinc [ZnL](3) and copper [CuL](3) complexes are trinuclear helicates. The cadmium complex seems to be a dimer with a structure similar to that of . In the nickel and lead derivatives, the ligand behaves as a tetradentate N(2)O(2) chelate and in complex also as a bridge through one of the O atoms. In the crystal structures of Zn and Cu complexes [ML](3) each metal is in a pentadentate N(3)O(2) environment formed by two different ligands, one tridentate chelate and the other bidentate chelate, giving rise to trinuclear helicates. These results point out the versatility of benzil bis(benzoylhydrazone) on its coordination.

40 CFR 721.10677 - Alkyl phosphonate (generic).

Code of Federal Regulations, 2014 CFR

2014-07-01

... CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10677 Alkyl phosphonate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl phosphonate (PMN P-12-584...

Ru-bis(pyridine)pyrazolate (bpp)-Based Water-Oxidation Catalysts Anchored on TiO2: The Importance of the Nature and Position of the Anchoring Group.

PubMed

Francàs, Laia; Richmond, Craig; Garrido-Barros, Pablo; Planas, Nora; Roeser, Stephan; Benet-Buchholz, Jordi; Escriche, Lluís; Sala, Xavier; Llobet, Antoni

2016-04-04

Three distinct functionalisation strategies have been applied to the in,in-[{Ru(II)(trpy)}2(μ-bpp)(H2O)2](3+) (trpy=2,2':6',2''-terpyridine, bpp=bis(pyridine)pyrazolate) water-oxidation catalyst framework to form new derivatives that can adsorb onto titania substrates. Modifications included the addition of sulfonate, carboxylate, and phosphonate anchoring groups to the terpyridine and bis(pyridyl)pyrazolate ligands. The complexes were characterised in solution by using 1D NMR, 2D NMR, and UV/Vis spectroscopic analysis and electrochemical techniques. The complexes were then anchored on TiO2-coated fluorinated tin oxide (FTO) films, and the reactivity of these new materials as water-oxidation catalysts was tested electrochemically through controlled-potential electrolysis (CPE) with oxygen evolution detected by headspace analysis with a Clark electrode. The results obtained highlight the importance of the catalyst orientation with respect to the titania surface in regard to its capacity to catalytically oxidize water to dioxygen. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radical bonding: structure and stability of bis(phenalenyl) complexes of divalent metals from across the periodic table.

PubMed

Craciun, Smaranda; Donald, Kelling J

2009-07-06

We examine the bonding possibilities of the bis(phenalenyl) MP(2) sandwich complexes of the divalent metals M = Be, Mg, Ca, Sr, Ba, Zn, Cd, and Hg, at the B3LYP level of theory. The outcome is an extraordinarily diverse class of low symmetry bis(phenalenyl)metal complexes in which bonding preferences and binding enthalpies differ dramatically. The lowest energy group 2 metal MP(2) complexes include an intriguing eta(1),eta(3) BeP(2) structure, and bent eta(6),eta(6) systems for M = Ca, Sr, and Ba. The group 12 bis(phenalenyl) complexes are thermodynamically unstable eta(1),eta(1) slip-sandwich structures. To better understand changes in the structural preferences going from the (eta(6),eta(6)) group 2 to the (eta(1),eta(1)) group 12 complexes, we explored the bonding in the bis(phenalenyl) complexes of transition metals with stable +2 oxidations states between Ca and Zn in period 4. The computed binding enthalpies are large and negative for nearly all of the minimum energy bis(phenalenyl) complexes of the group 2 and the transition metals; they are tiny for MgP(2), and are quite positive for the group 12 systems. The structural preferences and stability of the complexes is a subtle negotiation of several influences: the (un)availability of (n - 1)d and np, orbitals for bonding, the cost of the rehybridization at carbon sites in the phenalenyl rings in preparation for bonding to the metals, and the (P---P) interaction between the phenalenyl radicals.

Cyclometalated ruthenium(II) complexes with a bis-carbene CCC-pincer ligand.

PubMed

Zhang, You-Ming; Shao, Jiang-Yang; Yao, Chang-Jiang; Zhong, Yu-Wu

2012-08-21

The first series of cyclometalated ruthenium complexes with a CCC-pincer bis-carbene ligand have been obtained as bench-stable compounds. Single-crystal X-ray analysis of one of these complexes with 4'-di-p-anisylamino-2,2':6',2''-terpyridine is presented. The Ru(II/III) redox potentials and MLCT absorptions of these complexes can be varied by attaching an electron-donating or -withdrawing group on the noncyclometalating ligand.

Divergent Mechanistic Routes for the Formation of gem-Dimethyl Groups in the Biosynthesis of Complex Polyketides

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

Poust, S; Phelan, RM; Deng, K

The gem-dimethyl groups in polyketide-derived natural products add steric bulk and, accordingly, lend increased stability to medicinal compounds, however, our ability to rationally incorporate this functional group in modified natural products is limited. In order to characterize the mechanism of gem-dimethyl group formation, with a goal toward engineering of novel compounds containing this moiety, the gem-dimethyl group producing polyketide synthase (PKS) modules of yersiniabactin and epothilone were characterized using mass spectrometry. The work demonstrated, contrary to the canonical understanding of reaction order in PKSs, that methylation can precede condensation in gem-dimethyl group producing PKS modules. Experiments showed that both PKSsmore » are able to use dimethylmalonyl acyl carrier protein (ACP) as an extender unit. Interestingly, for epothilone module8, use of dimethylmalonyl-ACP appeared to be the sole route to form a gem-dimethylated product, while the yersiniabactin PKS could methylate before or after ketosynthase condensation.« less

Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.

PubMed

Bellec, Nathalie; Vacher, Antoine; Barrière, Frédéric; Xu, Zijun; Roisnel, Thierry; Lorcy, Dominique

2015-05-18

Tetrathiafulvalenes (TTF) and bis(cyclopentadienyl) molybdenum dithiolene complexes, Cp2Mo(dithiolene) complexes, are known separately to act as good electron donor molecules. For an investigation of the interaction between both electrophores, two types of complexes were synthesized and characterized. The first type has one Cp2Mo fragment coordinated to one TTF dithiolate ligand, and the second type has one TTF bis(dithiolate) bridging two Cp2Mo fragments. Comparisons of the electrochemical properties of these complexes with those of models of each separate electrophore provide evidence for their mutual influence. All of these complexes act as very good electron donors with a first oxidation potential 430 mV lower than the tetrakis(methylthio)TTF. DFT calculations suggest that the HOMO of the neutral complex and the SOMO of the cation are delocalized across the whole TTF dithiolate ligand. The X-ray crystal structure analyses of the neutral and the mono-oxidized Cp2Mo(dithiolene)(bismethylthio)TTF complexes are consistent with the delocalized assignment of the highest occupied frontier molecular orbitals. UV-vis-NIR spectroelectrochemical investigations confirm this electronic delocalization within the TTF dithiolate ligand.

Synthesis and properties of ApA analogues with shortened phosphonate internucleotide linkage.

PubMed

Králíková, Sárka; Buděšínský, Miloš; Barvík, Ivan; Masojídková, Milena; Točík, Zdeněk; Rosenberg, Ivan

2011-01-01

A complete series of the 2 '-5 ' and 3 '-5 ' regioisomeric types of r(ApA) and 2 '-d(ApA) analogues with the α-hydroxy-phosphonate C3 '-O-P-CH(OH)-C4 ″ internucleotide linkage, isopolar but non-isosteric with the phosphodiester one, were synthesized and their hybridization properties with polyU studied. Due to the chirality on the 5 '-carbon atom of the modified internucleotide linkage bearing phosphorus and hydroxy moieties, each regioisomeric type of ApA dimer is split into epimeric pairs. To examine the role of the 5 '-hydroxyl of the α-hydroxy-phosphonate moiety during hybridization, the appropriate r(ApA) analogues with 3 '(2 ')-O-P-CH(2)-C4 ″ linkage lacking the 5 '-hydroxyl were synthesized. Nuclear magnetic resonance (NMR) spectroscopy study on the conformation of the modified sugar-phosphate backbone, along with the hybridization measurements, revealed remarkable differences in the stability of complexes with polyU, depending on the 5 '-carbon atom configuration. Potential usefulness of the α-hydroxy-phosphonate linkage in modified oligoribonucleotides is discussed.

Homo- and Heterometallic Bis(Pentafluorobenzoyl)Methanide Complexes of Copper(II) and Cobalt(II)

NASA Astrophysics Data System (ADS)

Crowder, Janell M.

beta-Diketones are well known to form metal complexes with practically every known metal and metalloid. Metal complexes of fluorinated beta-diketones generally exhibit increased volatility and thermal stability compared to the non-fluorinated analogues, and thus are used extensively in various chemical vapor deposition (CVD) processes for the deposition of metal, simple or mixed metal oxides, and fluorine-doped metal oxide thin films. Furthermore, the electron-withdrawing nature of the fluorinated ligand enhances the Lewis acidity of a coordinatively unsaturated metal center which facilitates additional coordination reactions. The physical and structural properties of fluorinated beta-diketonate complexes are discussed in Chapter 1 and a few key application examples are given. The focus of this work is the synthesis and single crystal X-ray structural characterization of unsolvated and coordinatively unsaturated metal complexes of bis(pentafluorobenzoyl)- methanide (L, C6F5COCHCOC 6F5-). In Chapter 2, we present the preparation and isolation of the unsolvated complex [Cu(L)2] in pure crystalline form for the first time. We subsequently investigated the reaction of unsolvated [Cu(L)2] with sodium hexafluoroacetylacetonate [Na(hfac)] in a solvent-free environment. This reaction allowed the isolation of the first heterometallic Na-Cu diketonate [Na2Cu2(L) 4(hfac)2] structurally characterized by single crystal X-ray crystallography. Thermal decomposition of [Na2Cu2(L) 4(hfac)2] was investigated for its potential application in MOCVD processes. In the final chapter, we present the first exploration of the anhydrous synthesis of Co(II) complexed with bis(pentafluorobenzoyl)methanide in order to produce a complex without ligated water. Single crystal X-ray crystallographic investigations revealed the isolation of the ethanol adduct, [Co2(L)4(C2H5OH)2], and following the removal of ethanol, a 1,4-dioxane adduct, [{Co 2(L)4}2(C4H8O2)]. In this work, we have provided the

Preparation and Biodistribution Studies of a Radiogallium-Acetylacetonate Bis (Thiosemicarbazone) Complex in Tumor-Bearing Rodents

PubMed Central

Jalilian, Amir Reza; Yousefnia, Hassan; Shafaii, Kamaleddin; Novinrouz, Aytak; Rajamand, Amir Abbas

2012-01-01

Various radiometal complexes have been developed for tumor imaging, especially Ga-68 tracer. In the present study, the development of a radiogallium bis-thiosemicarbazone complex has been reported. [67Ga] acetylacetonate bis(thiosemicarbazone) complex ([67Ga] AATS) was prepared starting [67Ga]Gallium acetate and freshly prepared acetylacetonate bis (thiosemicarbazone) (AATS) in 30 min at 90°C. The partition co-efficient and the stability of the tracer were determined in final solution (25°C) and the presence of human serum (37°C) up to 24 h. The biodistribution of the labeled compound in wild-type and fibrosarcoma-bearing rodents were determined up to 72 h. The radiolabled Ga complex was prepared in high radiochemical purity (> 97%, HPLC) followed by initial biodistribution data with the significant tumor accumulation of the tracer in 2 h which is far higher than free Ga-67 cation while the compound wash-out is significantly faster. Above-mentioned pharmacokinetic properties suggest an interesting radiogallium complex while prepared by the PET Ga radioisotope, 68Ga, in accordance with the physical half life, for use in fibrosarcoma tumors, and possibly other malignancies. PMID:24250475

Reactions of bis(2,2,3,3-tetrafluoropropyl) phosphorisocyanatidite and tris(2,2,3,3-tetrafluoropropyl) phosphite with carbonyl compounds

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

Konovalova, I.V.; Burnaeva, L.A.; Khusnutdinova, E.K.

1986-11-20

The authors studied the reactions of bis(2,2,3,3-tetrafluoropropyl) phosphorisocyanatidite with carbonyl and ..cap alpha..-halo carbonyl compounds, namely, benzil, ethyl phenylglyoxylate, methyl chloropyruvate, and diethyl (trichloroacetyl)phosphonate. The reaction of bis(2,2,3,3-tetrachloropropyl) phosphorisocyanatidite with benzil required severe conditions (3 h at 40/sup 0/C). The /sup 31/P NMR spectrum of the reaction mixture contains two signals at 12 and -55 ppm, which probably belong to the azaphospholine and its dimer. By vacuum fractionation they isolated a thick liquid, the /sup 31/P NMR spectrum of which contains a signal 12 ppm corresponding to 5-benzoyl-4-oxo-5-phenyl-2,2-bis(2,2,3,3-tetrafluoropropoxy)-..delta../sup 2/-1,3,2lambda/sup 5/-oxazaphospholine.

Defining the electronic and geometric structure of one-electron oxidized copper-bis-phenoxide complexes.

PubMed

Storr, Tim; Verma, Pratik; Pratt, Russell C; Wasinger, Erik C; Shimazaki, Yuichi; Stack, T Daniel P

2008-11-19

The geometric and electronic structure of an oxidized Cu complex ([CuSal](+); Sal = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV-vis-NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal](+) (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal](+), affording exclusively a Cu(III) species in the solid state (4-300 K). Variable-temperature solution studies suggest that [CuSal](+) exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal(*)](+) (S = 1) and the high-valent metal form [Cu(III)Sal](+) (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine-bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSal(red)](+) (Sal(red) = N,N'-bis(3,5-di- tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)-ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu-bis-phenoxide complexes.

Defining the Electronic and Geometric Structure of One-Electron Oxidized Copper–Bis-phenoxide Complexes

PubMed Central

Storr, Tim; Verma, Pratik; Pratt, Russell C.; Wasinger, Erik C.; Shimazaki, Yuichi; Stack, T. Daniel P.

2009-01-01

The geometric and electronic structure of an oxidized Cu complex ([CuSal]+; Sal = N, N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-(1R,2R)-diamine) with a non-innocent salen ligand has been investigated both in the solid state and in solution. Integration of information from UV–vis–NIR spectroscopy, magnetic susceptibility, electrochemistry, resonance Raman spectroscopy, X-ray crystallography, X-ray absorption spectroscopy, and density functional theory calculations provides critical insights into the nature of the localization/delocalization of the oxidation locus. In contrast to the analogous Ni derivative [NiSal]+ (Storr, T.; et al. Angew. Chem., Int. Ed. 2007, 46, 5198), which exists solely in the Ni(II) ligand-radical form, the locus of oxidation is metal-based for [CuSal]+, affording exclusively a Cu(III) species in the solid state (4–300 K). Variable-temperature solution studies suggest that [CuSal]+ exists in a reversible spin-equilibrium between a ligand-radical species [Cu(II)Sal•]+ (S = 1) and the high-valent metal form [Cu(III)Sal]+ (S = 0), indicative of nearly isoenergetic species. It is surprising that a bis-imine–bis-phenolate ligation stabilizes the Cu(III) oxidation state, and even more surprising that in solution a spin equilibrium occurs without a change in coordination number. The oxidized tetrahydrosalen analogue [CuSalred]+ (Salred = N, N′-bis(3,5-di-tert-butylhydroxybenzyl)-1,2-cyclohexane-(1R,2R)-diamine) exists as a temperature-invariant Cu(II)–ligand-radical complex in solution, demonstrating that ostensibly simple variations of the ligand structure affect the locus of oxidation in Cu–bis-phenoxide complexes. PMID:18939830

A Bispidol Chelator with a Phosphonate Pendant Arm: Synthesis, Cu(II) Complexation, and 64Cu Labeling.

PubMed

Gillet, Raphaël; Roux, Amandine; Brandel, Jérémy; Huclier-Markai, Sandrine; Camerel, Franck; Jeannin, Olivier; Nonat, Aline M; Charbonnière, Loïc J

2017-10-02

Here we present the synthesis and characterization of a new bispidine (3,7-diazabicyclo[3.3.1]nonane) ligand with N-methanephosphonate substituents (L 2 ). Its physicochemical properties in water, as well as those of the corresponding Cu(II) and Zn(II) complexes, have been evaluated by using UV-visible absorption spectroscopy, potentiometry, 1 H and 31 P NMR, and cyclic voltammetry. Radiolabeling experiments with 64 Cu II have been carried out, showing excellent radiolabeling properties. Quantitative complexation was achieved within 60 min under stoichiometric conditions, at room temperature and in the nanomolar concentration range. It was also demonstrated that the complexation occurred below pH 2. Properties have been compared to those of the analogue bispidol bearing a N-methanecarboxylate substituent (L 1 ). Although both systems meet the required criteria to be used as new chelator for 64/67 Cu in terms of the kinetics of formation, thermodynamic stability, selectivity for Cu(II), and kinetic inertness regarding redox- or acid-assisted decomplexation processes, substitution of the carboxylic acid function by the phosphonic moiety is responsible for a significant increase in the thermodynamic stability of the Cu(II) complex (+2 log units for pCu) and also leads to an increase in the radiochemical yields with 64 Cu II which is quantitative for L 2 .

Design and synthesis of novel adenine fluorescence probe based on Eu(III) complexes with dtpa-bis(guanine) ligand

NASA Astrophysics Data System (ADS)

Tian, Fengyun; Jiang, Xiaoqing; Dou, Xuekai; Wu, Qiong; Wang, Jun; Song, Youtao

2017-05-01

A novel adenine (Ad) fluorescence probe (EuIII-dtpa-bis(guanine)) was designed and synthesized by improving experimental method based on the Eu(III) complex and dtpa-bis(guanine) ligand. The dtpa-bis(guanine) ligand was first synthesized by the acylation action between dtpaa and guanine (Gu), and the corresponding Eu(III) complex was successfully prepared through heat-refluxing method with dtpa-bis(guanine) ligand. As a novel fluorescence probe, the EuIII-dtpa-bis(guanine) complex can detect adenine (Ad) with characteristics of strong targeting, high specificity and high recognition ability. The detection mechanism of the adenine (Ad) using this probe in buffer solution was studied by ultraviolet-visible (UV-vis) and fluorescence spectroscopy. When the EuIII-dtpa-bis(guanine) was introduced to the adenine (Ad) solution, the fluorescence emission intensity was significantly enhanced. However, adding other bases such as guanine (Gu), xanthine (Xa), hypoxanthine (Hy) and uric acid (Ur) with similar composition and structure to that of adenine (Ad) to the EuIII-dtpa-bis(guanine) solution, the fluorescence emission intensities are nearly invariable. Meanwhile, the interference of guanine (Gu), xanthine (Xa), hypoxanthine (Hy) and uric acid (Ur) on the detection of the adenine using EuIII-dtpa-bis(guanine) probe was also studied. It was found that presence of these bases does not affect the detection of adenine (Ad). A linear response of fluorescence emission intensities of EuIII-dtpa-bis(guanine) at 570 nm as a function of adenine (Ad) concentration in the range of 0.00-5.00 × 10- 5 mol L- 1 was observed. The detection limit is about 4.70 × 10- 7 mol L- 1.

A photofunctional bottom-up bis(dipyrrinato)zinc(II) complex nanosheet

PubMed Central

Sakamoto, Ryota; Hoshiko, Ken; Liu, Qian; Yagi, Toshiki; Nagayama, Tatsuhiro; Kusaka, Shinpei; Tsuchiya, Mizuho; Kitagawa, Yasutaka; Wong, Wai-Yeung; Nishihara, Hiroshi

2015-01-01

Two-dimensional polymeric nanosheets have recently gained much attention, particularly top-down nanosheets such as graphene and metal chalcogenides originating from bulk-layered mother materials. Although molecule-based bottom-up nanosheets manufactured directly from molecular components can exhibit greater structural diversity than top-down nanosheets, the bottom-up nanosheets reported thus far lack useful functionalities. Here we show the design and synthesis of a bottom-up nanosheet featuring a photoactive bis(dipyrrinato)zinc(II) complex motif. A liquid/liquid interfacial synthesis between a three-way dipyrrin ligand and zinc(II) ions results in a multi-layer nanosheet, whereas an air/liquid interfacial reaction produces a single-layer or few-layer nanosheet with domain sizes of >10 μm on one side. The bis(dipyrrinato)zinc(II) metal complex nanosheet is easy to deposit on various substrates using the Langmuir–Schäfer process. The nanosheet deposited on a transparent SnO2 electrode functions as a photoanode in a photoelectric conversion system, and is thus the first photofunctional bottom-up nanosheet. PMID:25831973

The supramolecular architecture of tris(naphthalene-1,5-diaminium) bis(5-aminonaphthalen-1-aminium) octakis[hydrogen (5-carboxypyridin-3-yl)phosphonate].

PubMed

Wilk, Magdalena; Janczak, Jan; Videnova-Adrabinska, Veneta

2012-09-01

The asymmetric unit of the title compound, 3C(10)H(12)N(2)(2+)·2C(10)H(11)N(2)(+)·8C(6)H(5)NO(5)P(-), contains one and a half naphthalene-1,5-diaminium cations, in which the half-molecule has inversion symmetry, one 5-aminonaphthalen-1-aminium cation and four hydrogen (5-carboxypyridin-3-yl)phosphonate anions. The crystal structure is layered and consists of hydrogen-bonded anionic monolayers between which the cations are arranged. The acid monoanions are organized into one-dimensional chains along the [101] direction via hydrogen bonds established between the phosphonate sites. (C)O-H···N(py) hydrogen bonds (py is pyridine) crosslink the chains to form an undulating (010) monolayer. The cations serve both to balance the charge of the anionic network and to connect neighbouring layers via multiple hydrogen bonds to form a three-dimensional supramolecular architecture.

Oxidative condensation reactions of (diethylenetriamine)cobalt(III) complexes with substituted bis(pyridin-2-yl)methane ligands

NASA Astrophysics Data System (ADS)

Zhou, Xiangting; Hockless, David C. R.; Willis, Anthony C.; Jackson, W. Gregory

2005-04-01

The synthesis and characterisation of Co(III) complexes derived from a condensation reaction with a central or terminal nitrogen of a dien ligand and the α-carbon of a range of substituted bis(pyridin-2-yl)methane ligands are described. Aerial oxidation of bpm {bis(pyridin-2-yl)methane with Co(II)/dien or direct reaction with Co(dien)Cl 3 provided in low yield a single C-N condensation product 1 (at the primary terminal NH 2) after the pyridyl -CH 2- is formally oxidised to -CH +-. The methyl substituted ligand bpe {1,1-bis(pyridin-2-yl)ethane} behaves likewise, except both terminal (prim) and central (sec) amines condense to yield isomeric products 2 and 3. Two of these three materials have been characterised by single crystal X-ray crystallography. The corresponding reactions for the bis(pyridyl) ligand bpk {bis(pyridin-2-yl)ketone} provided C-N condensation products without the requirement for oxidation at the α-C center; two carbinolamine complexes in different geometrical configurations resulted, mer-anti-[Co(dienbpc)Cl]ZnCl 4, 5, and unsym- fac-[Co(dienbpc)Cl]ZnCl 4, 6, {dienbpc=[2-(2-aminoethylamino)-ethylamino]-di-pyridin-2-yl-methanol}. In addition, a novel complex, [Co(bpk)(bpd-OH)Cl]ZnCl 4, 4, in which one bidentate N, N-bonded bpk ligand and one tridentate N, O, N-bonded bpd (the diol from bpk+OH -) were coordinated, was obtained via the Co(II)/O 2 synthetic route. When the bpc ligand (bpc=bis(pyridin-2-yl)methanol) was employed directly as a reagent along with dien, no condensation reactions were observed, but rather a single isomeric complex [Co(dien)(bpc)]Cl.ZnCl 4, 7, in which the ligand bpc acted as a N,N,O-bonded tridentate ligand rather than as a N,N-bidentate ligand was isolated. 13C, 1D and 2D 1H NMR studies are reported for all the complexes; they establish the structures unambiguously.

Inhibition of dog and human gastric lipases by enantiomeric phosphonate inhibitors: a structure-activity study.

PubMed

Miled, Nabil; Roussel, Alain; Bussetta, Cécile; Berti-Dupuis, Liliane; Rivière, Mireille; Buono, Gérard; Verger, Robert; Cambillau, Christian; Canaan, Stéphane

2003-10-14

The crystal structures of gastric lipases in the apo form [Roussel, A., et al. (1999) J. Biol. Chem. 274, 16995-17002] or in complex with the (R(P))-undecyl butyl phosphonate [C(11)Y(4)(+)] [Roussel, A., et al. (2002) J. Biol. Chem. 277, 2266-2274] have improved our understanding of the structure-activity relationships of acid lipases. In this report, we have performed a kinetic study with dog and human gastric lipases (DGL and HGL, respectively) using several phosphonate inhibitors by varying the absolute configuration of the phosphorus atom and the chain length of the alkyl/alkoxy substituents. Using the two previously determined structures and that of a new crystal structure obtained with the other (S(P))-phosphonate enantiomer [C(11)Y(4)(-)], we constructed models of phosphonate inhibitors fitting into the active site crevices of DGL and HGL. All inhibitors with a chain length of fewer than 12 carbon atoms were found to be completely buried in the catalytic crevice, whereas longer alkyl/alkoxy chains were found to point out of the cavity. The main stereospecific determinant explaining the stronger inhibition of the S(P) enantiomers is the presence of a hydrogen bond involving the catalytic histidine as found in the DGL-C(11)Y(4)(-) complex. On the basis of these results, we have built a model of the first tetrahedral intermediate corresponding to the tristearoyl-lipase complex. The triglyceride molecule completely fills the active site crevice of DGL, in contrast with what is observed with other lipases such as pancreatic lipases which have a shallower and narrower active site. For substrate hydrolysis, the supply of water molecules to the active site might be achieved through a lateral channel identified in the protein core.

Characterization of ternary bivalent metal complexes with bis(2-hydroxyethyl)iminotris(hydroxymethy)methane (Bis?Tris) and the comparison of five crystal structures of Bis?Tris complexes*1

NASA Astrophysics Data System (ADS)

Inomata, Yoshie; Gochou, Yoshihiro; Nogami, Masanobu; Howell, F. Scott; Takeuchi, Toshio

2004-09-01

Eleven bivalent metal complexes with bis(2-hydroxyethyl)iminotris(hydroxymethy)methane (Bis-Tris:hihm): [M(hihm)(H 2O)]SO 4· nH 2O (M: Co, Ni, Cu, Zn), [MCl(hihm)]Cl· nH 2O (M: Co, Ni, Cu), and [M(HCOO)(hihm)](HCOO) (M: Co, Ni, Cu, Zn) have been prepared and characterized by using their infrared absorption and powder diffuse reflection spectra, magnetic susceptibility, thermal analysis and powder X-ray diffraction analysis. The crystal structures of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2), [Cu(hihm)(H 2O)]SO 4 ( 3), [NiCl(hihm)]Cl·H 2O ( 6), [CuCl(hihm)]Cl ( 7) and [Co(HCOO)(hihm)](HCOO) ( 8) have been determined by single crystal X-ray diffraction analysis. The crystals of [Ni(hihm)(H 2O)]SO 4·H 2O ( 2) and [Cu(hihm)(H 2O)]SO 4 ( 3) are each orthorhombic with the space group P2 12 12 1 and Pna2 1. For both complexes, the metal atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and a water molecule. [NiCl(hihm)]Cl·H 2O ( 6) is monoclinic with the space group P2 1/ n. For complex ( 6), the nickel atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and a chloride ion. [CuCl(hihm)]Cl ( 7) is orthorhombic with the space group P2 12 12 1. Although in this copper(II) complex the copper atom is ligated by six atoms, it is more reasonable to think that the copper atom is in a trigonal bipyramidal geometry coordinated with five atoms: three hydroxyl oxygen atoms, a nitrogen atom and a chloride ion if the bond distances and angles surrounding the copper atom are taken into consideration. [Co(HCOO)(hihm)](HCOO) ( 8) is monoclinic with the space group P2 1. In cobalt(II) complex ( 8), the cobalt atom is in a distorted octahedral geometry, ligated by four hydroxyl oxygen atoms, a nitrogen atom and an oxygen atom of a formate ion. The structure of complex ( 8) is the same as the structure of [NiCl(hihm)]Cl·H 2O ( 6) except for the formate ion coordinating instead of the chloride ion. [M

New metal-organic complexes based on bis(tetrazole) ligands: Synthesis, structures and properties

NASA Astrophysics Data System (ADS)

Du, Ceng-Ceng; Fan, Jian-Zhong; Wang, Xin-Fang; Zhou, Sheng-Bin; Wang, Duo-Zhi

2017-04-01

In this paper, a series of new complexes, [Zn2(HL1)2(H2O)4]·H2O (1), [Co2(HL1)2]·TEA (2), [Co3(HL1)2(H2L1)2(H2O)4]n (3), [Cu(HL1)(H2O)2]n (4), {[Cu5(HL2)2(OH)4(ClO4)2]·4H2O}n (5) and [Cu2(L3)]n (6) were successfully prepared by utilizing three bis(tetrazole) ligands [bis-(1H-tetrazol-5-ylmethyl)-amine (H3L1), bis-(1H-tetrazol-5-ylethyl)-amine (H3L2) and 1,5-bis(5-tetrazolo)-3-thiapentane (H2L3)], all of which have been characterized by elemental analyses, FT-IR spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analyses as well as single-crystal X-ray diffraction analyses showing different dimensionalities (0D, 1D and 3D). Complexes 1 and 2 are 0D structures, 1 shows a dinuclear structure, 2 displays two crystallographically different mononuclear structures, 1 and 2 are further assembled to form 3D supramolecular framework and 2D supramolecular network by hydrogen-bonding interactions, respectively. Complexes 3, 4 and 5 are 1D structures, 3 features a mononuclear unit and a 1D chain, which are arranged into 3D supramolecular architecture by hydrogen-bonding interactions, 4 presents a zigzag chain, 5 shows an infinite chain structure constructed from pentanuclear Cu(II) subunits and ClO4- anions. Complex 6 exhibits a 3D coordination framework based on cyclic [Cu4(L3)2] dimmer subunits as nodes possessing an 8-connected network topology with the point symbol {424·64}. Further, semiconductor behaviors, the solid-state luminescent properties of the complexes 1-3 and 6 were measured and studied seriously at room temperature.

PLC-controlled cryostats for the BlackGEM and MeerLICHT detectors

NASA Astrophysics Data System (ADS)

Raskin, Gert; Morren, Johan; Pessemier, Wim; Bloemen, Steven; Klein-Wolt, Marc; Roelfsema, Ronald; Groot, Paul; Aerts, Conny

2016-08-01

BlackGEM is an array of telescopes, currently under development at the Radboud University Nijmegen and at NOVA (Netherlands Research School for Astronomy). It targets the detection of the optical counterparts of gravitational waves. The first three BlackGEM telescopes are planned to be installed in 2018 at the La Silla observatory (Chile). A single prototype telescope, named MeerLICHT, will already be commissioned early 2017 in Sutherland (South Africa) to provide an optical complement for the MeerKAT radio array. The BlackGEM array consists of, initially, a set of three robotic 65-cm wide-field telescopes. Each telescope is equipped with a single STA1600 CCD detector with 10.5k x 10.5k 9-micron pixels that covers a 2.7 square degrees field of view. The cryostats for housing these detectors are developed and built at the KU Leuven University (Belgium). The operational model of BlackGEM requires long periods of reliable hands-off operation. Therefore, we designed the cryostats for long vacuum hold time and we make use of a closed-cycle cooling system, based on Polycold PCC Joule-Thomson coolers. A single programmable logic controller (PLC) controls the cryogenic systems of several BlackGEM telescopes simultaneously, resulting in a highly reliable, cost-efficient and maintenance-friendly system. PLC-based cryostat control offers some distinct advantages, especially for a robotic facility. Apart of temperature monitoring and control, the PLC also monitors the vacuum quality, the power supply and the status of the PCC coolers (compressor power consumption and temperature, pressure in the gas lines, etc.). Furthermore, it provides an alarming system and safe and reproducible procedures for automatic cool down and warm up. The communication between PLC and higher-level software takes place via the OPC-UA protocol, offering a simple to implement, yet very powerful interface. Finally, a touch-panel display on the PLC provides the operator with a user-friendly and robust

Simultaneous Power Deposition Detection of Two EC Beams with the BIS Analysis in Moving TCV Plasmas

NASA Astrophysics Data System (ADS)

Curchod, L.; Pochelon, A.; Decker, J.; Felici, F.; Goodman, T. P.; Moret, J.-M.; Paley, J. I.

2009-11-01

Modulation of power amplitude is a widespread to determine the radial absorption profile of externally launched power in fusion plasmas. There are many techniques to analyze the plasma response to such a modulation. The break-in-slope (BIS) analysis can draw an estimated power deposition profile for each power step up. In this paper, the BIS analysis is used to monitor the power deposition location of one or two EC power beams simultaneously in a non-stationary plasma being displaced vertically in the TCV tokamak vessel. Except from radial discrepancies, the results have high time resolution and compare well with simulations from the R2D2-C3PO-LUKE ray-tracing and Fokker-Planck code suite.

40 CFR 721.10412 - Phosphonic acid ester (generic) (P-07-706).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Phosphonic acid ester (generic) (P-07... Specific Chemical Substances § 721.10412 Phosphonic acid ester (generic) (P-07-706). (a) Chemical substance... phosphonic acid ester (PMN P-07-706) is subject to reporting under this section for the significant new uses...

40 CFR 721.10412 - Phosphonic acid ester (generic) (P-07-706).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Phosphonic acid ester (generic) (P-07... Specific Chemical Substances § 721.10412 Phosphonic acid ester (generic) (P-07-706). (a) Chemical substance... phosphonic acid ester (PMN P-07-706) is subject to reporting under this section for the significant new uses...

40 CFR 721.10412 - Phosphonic acid ester (generic) (P-07-706).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Phosphonic acid ester (generic) (P-07... Specific Chemical Substances § 721.10412 Phosphonic acid ester (generic) (P-07-706). (a) Chemical substance... phosphonic acid ester (PMN P-07-706) is subject to reporting under this section for the significant new uses...

A direct conversion of benzylic and allylic alcohols to phosphonates

PubMed Central

Barney, Rocky J.; Richardson, Rebekah M.; Wiemer, David F.

2011-01-01

Benzyl phosphonate esters often serve as reagents in Horner-Wadsworth-Emmons reactions. In most cases, they can be prepared from benzylic alcohols via formation of the corresponding halide followed by an Arbuzov reaction. To identify a more direct synthesis of phosphonate esters, we have developed a one-flask procedure for conversion of benzylic and allylic alcohols to the corresponding phosphonates through treatment with triethyl phosphite and ZnI2. PMID:21405073

Nanocomposites of phosphonic-acid-functionalized polyethylenes with inorganic quantum dots.

PubMed

Rünzi, Thomas; Baier, Moritz C; Negele, Carla; Krumova, Marina; Mecking, Stefan

2015-01-01

Insertion of diethyl vinyl phosphonates and free vinyl phosphonic acid, respectively, into [(P^O)Pd(Me)(dmso)] ((P^O) = κ(2)-P,O-Ar2PC6H4SO2O with Ar = 2-MeOC6H4) (1-dmso) occurs in a 2,1- as well as 1,2-fashion, to form a four-and a five-membered chelate [(P^O)Pd{κ(2)-C,O-CH(P(O)(OR)2)CH2CH3}] and [(P^O)Pd{κ(2)-C,O-CH2CH(P(O)(OR)2)CH3}] (R = H, Et). No decomposition or other reactions of 1 by free phosphonic acid moieties occur. Copolymerization in a pressure reactor by 1-dmso yields linear random poly(ethylene-co-diethyl vinyl phosphonate) and poly(ethylene-co-vinyl phosphonic acid). In these copolymerizations, reversible coordination of the phosphonate moieties of free monomer as well as chelate formation by incorporated monomer retards chain growth as also evidenced by relative binding studies of diethyl phosphonate towards 1. Post-polymerization emulsification of poly(ethylene-co-vinyl phosphonic acid) together with CdSe/CdS quantum dots (QDs) yields submicron (ca. 50 nm from dynamic light scattering (DLS) and transmission electron microscopy (TEM)) polymer particles with the QDs embedded in the functionalized polyethylene in a nonaggregated fashion. This embedding benefits the fluorescence behavior in terms of continuous emission and life-time as revealed by wide-field fluorescence measurements. These composite particle dispersions are employed as a ″masterbatch" together with an aqueous high density polyethylene (HDPE) dispersion to generate thin films (by spin-coating) and bulk materials (from the melt), respectively, in which the inorganic nanoparticles remain highly disperse. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

GEnomes Management Application (GEM.app): a new software tool for large-scale collaborative genome analysis.

PubMed

Gonzalez, Michael A; Lebrigio, Rafael F Acosta; Van Booven, Derek; Ulloa, Rick H; Powell, Eric; Speziani, Fiorella; Tekin, Mustafa; Schüle, Rebecca; Züchner, Stephan

2013-06-01

Novel genes are now identified at a rapid pace for many Mendelian disorders, and increasingly, for genetically complex phenotypes. However, new challenges have also become evident: (1) effectively managing larger exome and/or genome datasets, especially for smaller labs; (2) direct hands-on analysis and contextual interpretation of variant data in large genomic datasets; and (3) many small and medium-sized clinical and research-based investigative teams around the world are generating data that, if combined and shared, will significantly increase the opportunities for the entire community to identify new genes. To address these challenges, we have developed GEnomes Management Application (GEM.app), a software tool to annotate, manage, visualize, and analyze large genomic datasets (https://genomics.med.miami.edu/). GEM.app currently contains ∼1,600 whole exomes from 50 different phenotypes studied by 40 principal investigators from 15 different countries. The focus of GEM.app is on user-friendly analysis for nonbioinformaticians to make next-generation sequencing data directly accessible. Yet, GEM.app provides powerful and flexible filter options, including single family filtering, across family/phenotype queries, nested filtering, and evaluation of segregation in families. In addition, the system is fast, obtaining results within 4 sec across ∼1,200 exomes. We believe that this system will further enhance identification of genetic causes of human disease. © 2013 Wiley Periodicals, Inc.

2,6-diacetylpyridine bis(thiosemicarbazones) zinc complexes: synthesis, structure, and biological activity.

PubMed

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

1995-05-15

The reaction of zinc chloride, acetate, or perchlorate with two bis(thiosemicarbazones) of 2,6-diacetylpyridine [H2daptsc = 2,6-diacetylpyridine bis(thiosemicarbazone) and H2dapipt = 2,6-diacetylpyridine bis(hydrazinopyruvoylthiosemicarbazone)] leads to the formation of four novel complexes that have been characterized by spectroscopic studies (NMR, IR) and biological properties. The crystal structures of the two compounds--[Zn(daptsc)]2.2DMF (1) and [Zn(H2dapipt)(OH2)2](CIO4)2.3H2O (2)--also have been determined by x-ray methods from diffractometer data. Compound (1) is dimeric and the two zinc atoms have a distorted octahedral coordination. The ligand is deprotonated. In compound (2), the coordination geometry about zinc is pentagonal--bipyramidal and the ligand is in the neutral form. The molecular structure of (2) consists of cations [Zn(H2dapipt)(OH2)]2+, CIO4- disordered anions, and three water molecules of solvation. Biological studies have shown that the ligands and the complexes Zn(daptsc).1/2EtOH and Zn(H2daptsc)Cl2 have an effect in vitro on cell proliferation and differentiation (inhibition); both are concentration dependent. [Zn(daptsc)]2.2DMF (1) shows the effects at lower concentration values with respect to other compounds.

Diversity and abundance of phosphonate biosynthetic genes in nature

USDA-ARS?s Scientific Manuscript database

Phosphonates, molecules containing direct C-P bonds, comprise a structurally diverse class of natural products with interesting and useful biological properties. Although their synthesis in protozoa was discovered more than fifty years ago, the extent and diversity of phosphonate production in natur...

On the Origin of GEMS

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.

2004-01-01

GEMS (glass with embedded metal and sulfides) are a major component of anhydrous interplanetary dust particles (IDPs) their physical and chemical characteristics show marked similarities to contemporary interstellar dust. Recent oxygen isotopic measurements confirm that at least a small fraction (less than 5%) of GEMS are demonstrably presolar, while the remainder have ratios that are indistinguishable from solar values. GEMS with solar oxygen isotopic compositions either (1) had their isotopic compositions homogenized through processing in the interstellar medium (ISM), or (2) formed in the early solar system. Isotopic homogenization necessarily implies chemical homogenization, so (interstellar) GEMS compositions should reflect the average composition of dust in the local ISM. We performed a systematic examination of the bulk chemistry of GEMS in primitive IDPs in order to test this hypothesis.

Isomorphous rare-earth bis[bis(2,6-diisopropylphenyl)phosphate] complexes and their self-assembly into two-dimensional frameworks by intramolecular hydrogen bonds.

PubMed

Minyaev, Mikhail E; Nifant'ev, Ilya E; Tavtorkin, Alexander N; Korchagina, Sof'ya A; Zeynalova, Shadana Sh; Ananyev, Ivan V; Churakov, Andrei V

2017-10-01

The crystal structures of rare-earth diaryl- or dialkylphosphate derivatives are poorly explored. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]chloridotetrakis(methanol-κO)neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (1), and of the lutetium, [Lu(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (2), and yttrium, [Y(C 24 H 34 O 4 P)Cl(CH 4 O) 4 ]·2CH 3 OH, (3), analogues have been obtained by reactions between lithium bis(2,6-diisopropylphenyl)phosphate and LnCl 3 (H 2 O) 6 (in a 2:1 ratio) in methanol. Compounds (1)-(3) crystallize in the C2/c space group. Their crystal structures are isomorphous. The molecule possesses C 2 symmetry with a twofold crystallographic axis passing through the Ln and Cl atoms. The bis(2,6-diisopropylphenyl)phosphate ligands all display a κ 1 O-monodentate coordination mode. The coordination polyhedron for the metal atom [coordination number (CN) = 7] is a distorted pentagonal bipyramid. Each [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 2 Cl(CH 3 OH) 4 ] molecular unit exhibits two intramolecular O-H...O hydrogen bonds, forming six-membered rings, and two intramolecular O-H...Cl interactions, forming four-membered rings. Intermolecular O-H...O hydrogen bonds connect each unit via four noncoordinating methanol molecules with four other units, forming a two-dimensional hydrogen-bond network. Crystals of bis[bis(2,6-diisopropylphenyl)phosphato-κO]tetrakis(methanol-κO)(nitrato-κ 2 O,O')neodymium methanol disolvate, [Nd(C 24 H 34 O 4 P)(NO 3 )(CH 4 O) 4 ]·2CH 3 OH, (4), have been obtained in an analogous manner from NdCl 3 (H 2 O) 6 . Compound (4) also crystalizes in the C2/c space group. Its crystal structure is similar to those of (1)-(3). The κ 2 O,O'-bidentate nitrate anion is disordered over a twofold axis, being located nearly on it. Half of the molecule is crystallographically unique (CN Nd = 8). Unlike (1)-(3), complex (4) exhibits disorder of all three methanol molecules, one isopropyl group of the

The GEM-T2 gravitational model

NASA Technical Reports Server (NTRS)

Marsh, J. G.; Lerch, F. J.; Putney, B. H.; Felsentreger, T. L.; Sanchez, B. V.; Klosko, S. M.; Patel, G. B.; Robbins, J. W.; Williamson, R. G.; Engelis, T. E.

1989-01-01

The GEM-T2 is the latest in a series of Goddard Earth Models of the terrestrial field. It was designed to bring modeling capabilities one step closer towards ultimately determining the TOPEX/Poseidon satellite's radial position to an accuracy of 10-cm RMS (root mean square). It also improves models of the long wavelength geoid to support many oceanographic and geophysical applications. The GEM-T2 extends the spherical harmonic field to include more than 600 coefficients above degree 36 (which was the limit for its predecessor, GEM-T1). Like GEM-T1, it was produced entirely from satellite tracking data, but it now uses nearly twice as many satellites (31 vs. 17), contains four times the number of observations (2.4 million), has twice the number of data arcs (1132), and utilizes precise laser tracking from 11 satellites. The estimation technique for the solution has been augmented to include an optimum data weighting procedure with automatic error calibration for the gravitational parameters. Results for the GEM-T2 error calibration indicate significant improvement over previous satellite-only models. The error of commission in determining the geoid has been reduced from 155 cm in GEM-T1 to 105 cm for GEM-T2 for the 36 x 36 portion of the field, and 141 cm for the entire model. The orbital accuracies achieved using GEM-T2 are likewise improved. Also, the projected radial error on the TOPEX satellite orbit indicates 9.4 cm RMS for GEM-T2, compared to 24.1 cm for GEM-T1.

Identification of number and type of cations in water-soluble Cs+ and Na+ calix[4]arene-bis-crown-6 complexes by using ESI-TOF-MS.

PubMed

Kumagai, Shogo; Hayashi, Kotaro; Kameda, Tomohito; Morohashi, Naoya; Hattori, Tetsutaro; Yoshioka, Toshiaki

2018-04-01

The treatment of cesium-contaminated wastewater has become one of the biggest issues. The selective Cs + removal from wastewater containing competitive alkali metal ions such as Na + is desired to reduce the volume of sludge. Therefore, the present work focused on water-soluble calix[4]arene-bis-crown-6 (W-BisC6) to selectively capture Cs + . For characterization of the complex, UV-vis spectroscopy is commonly used, however, due to the limited availability of information it can be hard to quickly identify the specific structures of some complexes. In this work, the electrospray ionization time of flight spectrometry (ESI-TOF-MS) is successfully utilized to identify the number and type of cations in W-BisC6-cation complexes. ESI-TOF-MS accurately recognized 4 types of complex (W-BisC6-Na + , W-BisC6-Cs + , W-BisC6-2Na + , W-BisC6-Na + -Cs + ), and the experimental and simulated results were almost perfectly matched. It also revealed the difficulty of W-BisC6-2Cs + complex formation under the present conditions. Thus, this technique is significantly helpful for rapid identification of the specific structures of complexes during Cs + -contaminated wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

The GTP binding proteins Gem and Rad are negative regulators of the Rho–Rho kinase pathway

PubMed Central

Ward, Yvona; Yap, Seow-Fong; Ravichandran, V.; Matsumura, Fumio; Ito, Masaaki; Spinelli, Beth; Kelly, Kathleen

2002-01-01

The cytoskeletal changes that alter cellular morphogenesis and motility depend upon a complex interplay among molecules that regulate actin, myosin, and other cytoskeletal components. The Rho family of GTP binding proteins are important upstream mediators of cytoskeletal organization. Gem and Rad are members of another family of small GTP binding proteins (the Rad, Gem, and Kir family) for which biochemical functions have been mostly unknown. Here we show that Gem and Rad interface with the Rho pathway through association with the Rho effectors, Rho kinase (ROK) α and β. Gem binds ROKβ independently of RhoA in the ROKβ coiled-coil region adjacent to the Rho binding domain. Expression of Gem inhibited ROKβ-mediated phosphorylation of myosin light chain and myosin phosphatase, but not LIM kinase, suggesting that Gem acts by modifying the substrate specificity of ROKβ. Gem or Rad expression led to cell flattening and neurite extension in N1E-115 neuroblastoma cells. In interference assays, Gem opposed ROKβ- and Rad opposed ROKα-mediated cell rounding and neurite retraction. Gem did not oppose cell rounding initiated by ROKβ containing a deletion of the Gem binding region, demonstrating that Gem binding to ROKβ is required for the effects observed. In epithelial or fibroblastic cells, Gem or Rad expression resulted in stress fiber and focal adhesion disassembly. In addition, Gem reverted the anchorage-independent growth and invasiveness of Dbl-transformed fibroblasts. These results identify physiological roles for Gem and Rad in cytoskeletal regulation mediated by ROK. PMID:11956230

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

DOE PAGES

Zheng, Tao; Yang, Zaixing; Gui, Daxiang; ...

2017-05-30

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest voidmore » volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.« less

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

PubMed Central

Zheng, Tao; Yang, Zaixing; Gui, Daxiang; Liu, Zhiyong; Wang, Xiangxiang; Dai, Xing; Liu, Shengtang; Zhang, Linjuan; Gao, Yang; Chen, Lanhua; Sheng, Daopeng; Wang, Yanlong; Diwu, Juan; Wang, Jianqiang; Zhou, Ruhong; Chai, Zhifang; Albrecht-Schmitt, Thomas E.; Wang, Shuao

2017-01-01

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. Herein, we overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. These compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest void volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism. PMID:28555656

Overcoming the crystallization and designability issues in the ultrastable zirconium phosphonate framework system

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

Zheng, Tao; Yang, Zaixing; Gui, Daxiang

Metal-organic frameworks (MOFs) based on zirconium phosphonates exhibit superior chemical stability suitable for applications under harsh conditions. These compounds mostly exist as poorly crystallized precipitates, and precise structural information has therefore remained elusive. Furthermore, a zero-dimensional zirconium phosphonate cluster acting as secondary building unit has been lacking, leading to poor designability in this system. We overcome these challenges and obtain single crystals of three zirconium phosphonates that are suitable for structural analysis. Furthermore, these compounds are built by previously unknown isolated zirconium phosphonate clusters and exhibit combined high porosity and ultrastability even in fuming acids. SZ-2 possesses the largest voidmore » volume recorded in zirconium phosphonates and SZ-3 represents the most porous crystalline zirconium phosphonate and the only porous MOF material reported to survive in aqua regia. SZ-2 and SZ-3 can effectively remove uranyl ions from aqueous solutions over a wide pH range, and we have elucidated the removal mechanism.« less

Geophysical Monitoring Station (GEMS)

NASA Astrophysics Data System (ADS)

Banerdt, B.; Dehant, V. M.; Lognonne, P.; Smrekar, S. E.; Spohn, T.; GEMS Mission Team

2011-12-01

studies. The two instruments are moved from the lander deck to the martian surface by an Instrument Deployment Arm, with an appropriate location identified using an Instrument Deployment Camera. In order to ensure low risk within the tight Discovery cost limits, GEMS reuses the successful Lockheed Martin Phoenix spacecraft design, with a cruise and EDL system that has demonstrated capability for safe landing on Mars with well-understood costs. To take full advantage of this approach, all science requirements (such as instrument mass and power, landing site, and downlinked data volume) strictly conform to existing, demonstrated capabilities of the spacecraft and mission system. It is widely believed that multiple landers making simultaneous measurements (a network) are required to address the objectives for understanding terrestrial planet interiors. Nonetheless, comprehensive measurements from a single geophysical station are extremely valuable, because observations constraining the structure and processes of the deep interior of Mars are virtually nonexistent. GEMS would utilize sophisticated analysis techniques specific to single-station measurements to determine crustal thickness, mantle structure, core state and size, and heat flow, providing our first real look deep beneath the surface of Mars.

Little gem

NASA Image and Video Library

2015-08-03

This colourful bubble is a planetary nebula called NGC 6818, also known as the Little Gem Nebula. It is located in the constellation of Sagittarius (The Archer), roughly 6000 light-years away from us. The rich glow of the cloud is just over half a light-year across — humongous compared to its tiny central star — but still a little gem on a cosmic scale. When stars like the Sun enter retirement, they shed their outer layers into space to create glowing clouds of gas called planetary nebulae. This ejection of mass is uneven, and planetary nebulae can have very complex shapes. NGC 6818 shows knotty filament-like structures and distinct layers of material, with a bright and enclosed central bubble surrounded by a larger, more diffuse cloud. Scientists believe that the stellar wind from the central star propels the outflowing material, sculpting the elongated shape of NGC 6818. As this fast wind smashes through the slower-moving cloud it creates particularly bright blowouts at the bubble’s outer layers. Hubble previously imaged this nebula back in 1997 with its Wide Field Planetary Camera 2, using a mix of filters that highlighted emission from ionised oxygen and hydrogen (opo9811h). This image, while from the same camera, uses different filters to reveal a different view of the nebula. A version of the image was submitted to the Hubble’s Hidden Treasures image processing competition by contestant Judy Schmidt.

Epoxy Phosphonate Crosslinkers for Providing Flame Resistance to Cotton Textiles

USDA-ARS?s Scientific Manuscript database

Two new monomers (2-methyl-oxiranylmethyl)-phosphonic acid dimethyl ester (3) and [2-(dimethoxy-phosphorylmethyl)-oxyranylmethyl]-phosphonic acid dimethyl ester (6) were prepared and used with dicyandiamide (7) and citric acid (8) to impart flame resistance to cotton plain weave, twill, and 80:20-co...

Phosphonate Pendant Armed Propylene Cross-Bridged Cyclam: Synthesis and Evaluation as a Chelator for Cu-64

PubMed Central

2015-01-01

A propylene cross-bridged macrocyclic chelator with two phosphonate pendant arms (PCB-TE2P) was synthesized from cyclam. Various properties of the synthesized chelator, including Cu-complexation, Cu-complex stability, 64Cu-radiolabeling, and in vivo behavior, were studied and compared with those of a previously reported propylene cross-bridged chelator (PCB-TE2A). PMID:26617972

Biochemical properties and crystal structure of ethylmethylglyoxal bis(guanylhydrazone) sulfate--an extremely powerful novel inhibitor of adenosylmethionine decarboxylase.

PubMed

Elo, H; Mutikainen, I; Alhonen-Hongisto, L; Laine, R; Jänne, J; Lumme, P

1986-01-01

Ethylmethylglyoxal bis(guanylhydrazone) (EMGBG) sulfate, an analog of the well-known anti-leukemic drug methylglyoxal bis(guanylhydrazone), was synthesized. It was shown to be an extremely powerful competitive inhibitor of eukaryotic S-adenosylmethionine decarboxylase, with an apparent Ki value 12 nM. Thus, it appears to be the most powerful known inhibitor of the enzyme, being almost an order of magnitude more powerful than the corresponding ethylglyoxal derivative. It neither inhibited the proliferation of mouse L1210 leukemia cells in vitro, nor did it potentiate the growth inhibition produced by alpha-difluoromethyl ornithine. In this respect, its properties are closely related to those of dimethylglyoxal, ethylglyoxal and propylglyoxal bis(guanylhydrazones), while in striking contrast to those of the antiproliferative glyoxal and methylglyoxal analogs. EMGBG also inhibited intestinal diamine oxidase activity (Ki 0.7 microM). EMGBG sulfate was crystallized from water, giving orthorhombic crystals (space group Pbcn). Their crystal and molecular structure was determined by X-ray diffraction methods. The carbon-nitrogen double bonds between the ethylmethylglyoxal part and the aminoguanidine moieties were found to have the same configuration as they are known to have in the salts of glyoxal, methylglyoxal and propylglyoxal bis(guanylhydrazones). The glyoxal bis(guanylhydrazone) chain of the EMGBG cation deviated strongly from planarity, thus differing dramatically from the corresponding chains of the glyoxal, methylglyoxal and propylglyoxal analogs.

Gem1 and ERMES Do Not Directly Affect Phosphatidylserine Transport from ER to Mitochondria or Mitochondrial Inheritance

PubMed Central

Nguyen, Tammy T; Lewandowska, Agnieszka; Choi, Jae-Yeon; Markgraf, Daniel F; Junker, Mirco; Bilgin, Mesut; Ejsing, Christer S; Voelker, Dennis R; Rapoport, Tom A; Shaw, Janet M

2012-01-01

In yeast, a protein complex termed the ER-Mitochondria Encounter Structure (ERMES) tethers mitochondria to the endoplasmic reticulum. ERMES proteins are implicated in a variety of cellular functions including phospholipid synthesis, mitochondrial protein import, mitochondrial attachment to actin, polarized mitochondrial movement into daughter cells during division, and maintenance of mitochondrial DNA (mtDNA). The mitochondrial-anchored Gem1 GTPase has been proposed to regulate ERMES functions. Here, we show that ERMES and Gem1 have no direct role in the transport of phosphatidylserine (PS) from the ER to mitochondria during the synthesis of phosphatidylethanolamine (PE), as PS to PE conversion is not affected in ERMES or gem1 mutants. In addition, we report that mitochondrial inheritance defects in ERMES mutants are a secondary consequence of mitochondrial morphology defects, arguing against a primary role for ERMES in mitochondrial association with actin and mitochondrial movement. Finally, we show that ERMES complexes are long-lived, and do not depend on the presence of Gem1. Our findings suggest that the ERMES complex may have primarily a structural role in maintaining mitochondrial morphology. PMID:22409400

Synthesis and structures of bis-ligated zinc complexes supported by tridentate ketoimines that initiate L-lactide polymerization.

PubMed

Gerling, Kimberly A; Rezayee, Nomaan M; Rheingold, Arnold L; Green, David B; Fritsch, Joseph M

2014-11-21

Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62-95% yield. The complexes were characterized with (1)H, (13)C, and (19)F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The (1)H and (19)F NMR spectra of complexes 1-7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14-98% with polymerization times varying from 15-1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with (1)H and (19)F NMR and appeared to yield an in situ generated zinc alkoxide complex.

Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

NASA Technical Reports Server (NTRS)

Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

1992-01-01

Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

Synthesis and kinetic evaluation of cyclophostin and cyclipostins phosphonate analogs as selective and potent inhibitors of microbial lipases.

PubMed

Point, Vanessa; Malla, Raj K; Diomande, Sadia; Martin, Benjamin P; Delorme, Vincent; Carriere, Frederic; Canaan, Stephane; Rath, Nigam P; Spilling, Christopher D; Cavalier, Jean-François

2012-11-26

A new series of customizable diastereomeric cis- and trans-monocyclic enol-phosphonate analogs to Cyclophostin and Cyclipostins were synthesized. Their potencies and mechanisms of inhibition toward six representative lipolytic enzymes belonging to distinct lipase families were examined. With mammalian gastric and pancreatic lipases no inhibition occurred with any of the compounds tested. Conversely, Fusarium solani Cutinase and lipases from Mycobacterium tuberculosis (Rv0183 and LipY) were all fully inactivated. The best inhibitors displayed a cis conformation (H and OMe) and exhibited higher inhibitory activities than the lipase inhibitor Orlistat toward the same enzymes. Our results have revealed that chemical group at the γ-carbon of the phosphonate ring strongly impacts the inhibitory efficiency, leading to a significant improvement in selectivity toward a target lipase over another. The powerful and selective inhibition of microbial (fungal and mycobacterial) lipases suggests that these seven-membered monocyclic enol-phosphonates should provide useful leads for the development of novel and highly selective antimicrobial agents.

Synthesis and kinetic evaluation of Cyclophostin and Cyclipostins phosphonate analogs as selective and potent inhibitors of microbial lipases

PubMed Central

Point, Vanessa; Malla, Raj K.; Diomande, Sadia; Martin, Benjamin P.; Delorme, Vincent; Carriere, Frederic; Canaan, Stephane; Rath, Nigam P.; Spilling, Christopher D.; Cavalier, Jean-François

2012-01-01

New series of customizable diastereomeric cis- and trans-monocyclic enol-phosphonate analogs to Cyclophostin and Cyclipostins were synthesized. Their potencies and mechanisms of inhibition toward six representative lipolytic enzymes belonging to distinct lipase families were examined. With mammalian gastric and pancreatic lipases no inhibition occurred with any of the compounds tested. Conversely, Fusarium solani Cutinase and lipases from Mycobacterium tuberculosis (Rv0183 and LipY) were all fully inactivated. Best inhibitors displayed a cis conformation (H and OMe) and exhibited higher inhibitory activities than the lipase inhibitor Orlistat towards same enzymes. Our results have revealed that chemical group at the γ-carbon of the phosphonate ring strongly impacts the inhibitory efficiency, leading to a significant improvement in selectivity toward a target lipase over another. The powerful and selective inhibition of microbial (fungal and mycobacterial) lipases suggests that these 7-membered monocyclic enol-phosphonates should provide useful leads for the development of novel and highly selective antimicrobial agents. PMID:23095026

Structural and electrochemical studies of TiO2 complexes with (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivative bases towards organic devices.

PubMed

Rozycka, Anna; Iwan, Agnieszka; Bogdanowicz, Krzysztof Artur; Filapek, Michal; Górska, Natalia; Hreniak, Agnieszka; Marzec, Monika

2018-06-12

Three (4,4'-((1E,1'E)-(2,5-bis(octyloxy)-1,4-phenylene)bis(ethene-2,1-diyl))bis-(E)-N-(2,5-bis(octyloxy)benzylidene)) imine derivatives were synthesized via a condensation reaction with p-toluenesulfonic acid as a catalyst. The effects of the end groups and vinylene (-HC[double bond, length as m-dash]CH-) moieties on the structural, thermal, optical, electrochemical and photovoltaic properties of imines were investigated to check the influence of TiO2 on the imine properties. The thermal behavior of imines and their complexes with TiO2 was widely investigated using FT-IR, XRD, DSC and POM methods in order to determine the order type in the imine structure. All imines present the highest occupied molecular orbital (HOMO) levels of about -5.39 eV (SAI1 and SAI2) and -5.27 eV (SAI3) and the lowest unoccupied molecular orbital (LUMO) levels at about -3.17 eV. The difference of the end groups in the imines in each case did not affect redox properties. Generally, both oxidation and reduction are easier after TiO2 addition and it also changes the HOMO-LUMO levels of imines. Moreover, changes in the characteristic bands for imines in the region 1500-1700 cm-1 observed as a drastic decrease of intensity or even disappearance of bands in the imine : TiO2 mixture suggest the formation of a complex (C[double bond, length as m-dash]N)-TiO2. Organic devices with the configuration of ITO/TiO2/SAIx (or SAIx : TiO2)/Au were fabricated and investigated in the presence and absence of visible light irradiation with an intensity of 93 mW cm-2. In all imines and complexes with TiO2, the generation of the photocurrent indicates their use as photodiodes and the best result was observed for SAI3 : TiO2 complexes.

Nanolayer formation on titanium by phosphonated gelatin for cell adhesion and growth enhancement

PubMed Central

Zhou, Xiaoyue; Park, Shin-Hye; Mao, Hongli; Isoshima, Takashi; Wang, Yi; Ito, Yoshihiro

2015-01-01

Phosphonated gelatin was prepared for surface modification of titanium to stimulate cell functions. The modified gelatin was synthesized by coupling with 3-aminopropylphosphonic acid using water-soluble carbodiimide and characterized by 31P nuclear magnetic resonance and gel permeation chromatography. Circular dichroism revealed no differences in the conformations of unmodified and phosphonated gelatin. However, the gelation temperature was changed by the modification. Even a high concentration of modified gelatin did not form a gel at room temperature. Time-of-flight secondary ion mass spectrometry showed direct bonding between the phosphonated gelatin and the titanium surface after binding. The binding behavior of phosphonated gelatin on the titanium surface was quantitatively analyzed by a quartz crystal microbalance. Ellipsometry showed the formation of a several nanometer layer of gelatin on the surface. Contact angle measurement indicated that the modified titanium surface was hydrophobic. Enhancement of the attachment and spreading of MC-3T3L1 osteoblastic cells was observed on the phosphonated gelatin-modified titanium. These effects on cell adhesion also led to growth enhancement. Phosphonation of gelatin was effective for preparation of a cell-stimulating titanium surface. PMID:26366080

Fluoride-Mediated Dephosphonylation of α-Diazo-β-carbonyl Phosphonates.

PubMed

Phatake, Ravindra S; Mullapudi, Venkannababu; Wakchaure, Vivek C; Ramana, Chepuri V

2017-01-20

The possibility of fluoride-mediated selective dephosphonylation of α-diazo-β-carbonyl phosphonates such as the Ohira-Bestmann reagent has been proposed and executed. The resulting α-diazocarbonyl intermediates undergo a (3 + 2)-cycloaddition at room temperature with conjugated olefins and benzynes. Interestingly, under the current conditions, the resulting cycloaddition products underwent either N-acylation (with excess α-diazo-β-carbonyl phosphonates) or Michael addition (with conjugated olefins).

Versatile chelating behavior of benzil bis(thiosemicarbazone) in zinc, cadmium, and nickel complexes.

PubMed

López-Torres, Elena; Mendiola, Ma Antonia; Pastor, César J; Pérez, Beatriz Souto

2004-08-23

Reactions of benzil bis(thiosemicarbazone), LH(6), with M(NO(3))(2).nH(2)O (M = Zn, Cd, and Ni), in the presence of LiOH.H(2)O, show the versatile behavior of this molecule. The structure of the ligand, with the thiosemicarbazone moieties on opposite sides of the carbon backbone, changes to form complexes by acting as a chelating molecule. Complexes of these metal ions with empirical formula [MLH(4)] were obtained, although they show different molecular structures depending on their coordinating preferences. The zinc complex is the first example of a crystalline coordination polymer in which a bis(thiosemicarbazone) acts as bridging ligand, through a nitrogen atom, giving a 1D polymeric structure. The coordination sphere is formed by the imine nitrogen and sulfur atoms, and the remaining position, in a square-based pyramid, is occupied by an amine group of another ligand. The cadmium derivative shows the same geometry around the metal ion but consists of a dinuclear structure with sulfur atoms acting as a bridge between the metal ions. However, in the nickel complex LH(6) acts as a N(2)S(2) ligand yielding a planar structure for the nickel atom. The ligand and its complexes have been characterized by X-ray crystallography, microanalysis, mass spectrometry, IR, (1)H, and (13)C NMR spectroscopies and for the cadmium complex by (113)Cd NMR in solution and in the solid state.

A COMSOL-GEMS interface for modeling coupled reactive-transport geochemical processes

NASA Astrophysics Data System (ADS)

Azad, Vahid Jafari; Li, Chang; Verba, Circe; Ideker, Jason H.; Isgor, O. Burkan

2016-07-01

An interface was developed between COMSOL MultiphysicsTM finite element analysis software and (geo)chemical modeling platform, GEMS, for the reactive-transport modeling of (geo)chemical processes in variably saturated porous media. The two standalone software packages are managed from the interface that uses a non-iterative operator splitting technique to couple the transport (COMSOL) and reaction (GEMS) processes. The interface allows modeling media with complex chemistry (e.g. cement) using GEMS thermodynamic database formats. Benchmark comparisons show that the developed interface can be used to predict a variety of reactive-transport processes accurately. The full functionality of the interface was demonstrated to model transport processes, governed by extended Nernst-Plank equation, in Class H Portland cement samples in high pressure and temperature autoclaves simulating systems that are used to store captured carbon dioxide (CO2) in geological reservoirs.

Isopropyl methyl phosphonic acid (IMPA)

Integrated Risk Information System (IRIS)

Isopropyl methyl phosphonic acid ( IMPA ) ; CASRN 1832 - 54 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assess

Gold(III) bis-thiosemicarbazonato complexes: synthesis, characterization, radiochemistry and X-ray crystal structure analysis.

PubMed

Bottenus, Brienne N; Kan, Para; Jenkins, Tyler; Ballard, Beau; Rold, Tammy L; Barnes, Charles; Cutler, Cathy; Hoffman, Timothy J; Green, Mark A; Jurisson, Silvia S

2010-01-01

A variety of (bis)thiosemicarbazone-based ligand systems have been investigated as chelating agents for Au(III) complexes with potential radiotherapeutic applications. Ligand systems containing an ethyl, propyl or butyl backbone between the two imine N donors have been synthesized to evaluate chelate ring size effects on the resultant Au(III) complex stability at the macroscopic and radiotracer levels. The Au(III) complexes were synthesized and characterized by NMR, electrospray ionization mass spectra, elemental analysis and X-ray crystallography. The (198)Au complexes were evaluated in vitro at the tracer level for stability in phosphate-buffered saline at pH 7.4 and 37 degrees C. One of these complexes [(198)Au(3,4-HxTSE)] showed high in vitro stability and was further evaluated in vivo in normal mice. [Au(ATSM)]AuCl(4).2CH(3)OH, (ATSM=diacetyl-bis(N(4)-methylthiosemicarbazone)) H(14)C(8)N(6)O(2)S(2)Cl(4)Au(2).2CH(3)OH, crystallized from methanol in the monoclinic space group P21/n with a=14.7293(13) A, b=7.7432(7) A, c=20.4363(18) A, beta=100.140(2) degrees, V=2294.4 (4) A(3), Z=4; [Au(3,4-HxTSE)]Cl.CH(3)CH(2)OH/AuCl(2), (3,4-HxTSE=3,4-hexanedione-bis(N(4)-ethylthiosemicarbazone)) H(26)C(13.6)N(6)O(0.8)S(2)Cl(1.2)Au(1.2), crystallized from ethanol in the monoclinic space group P21/c with a=10.1990(10) A, b=13.8833(14) A, c=15.1752(15) A, beta=99.353(2) degrees , V=2120.2 (4) A(3), Z=4. These studies revealed poor stability of the [(198)Au][Au(3,4-HxTSE)](+) complex; however, crystal structure data suggest potential alterations to the ligand backbone may increase stability. Copyright 2010 Elsevier Inc. All rights reserved.

FPGA-based GEM detector signal acquisition for SXR spectroscopy system

NASA Astrophysics Data System (ADS)

Wojenski, A.; Pozniak, K. T.; Kasprowicz, G.; Kolasinski, P.; Krawczyk, R.; Zabolotny, W.; Chernyshova, M.; Czarski, T.; Malinowski, K.

2016-11-01

The presented work is related to the Gas Electron Multiplier (GEM) detector soft X-ray spectroscopy system for tokamak applications. The used GEM detector has one-dimensional, 128 channel readout structure. The channels are connected to the radiation-hard electronics with configurable analog stage and fast ADCs, supporting speeds of 125 MSPS for each channel. The digitalized data is sent directly to the FPGAs using fast serial links. The preprocessing algorithms are implemented in the FPGAs, with the data buffering made in the on-board 2Gb DDR3 memory chips. After the algorithmic stage, the data is sent to the Intel Xeon-based PC for further postprocessing using PCI-Express link Gen 2. For connection of multiple FPGAs, PCI-Express switch 8-to-1 was designed. The whole system can support up to 2048 analog channels. The scope of the work is an FPGA-based implementation of the recorder of the raw signal from GEM detector. Since the system will work in a very challenging environment (neutron radiation, intense electro-magnetic fields), the registered signals from the GEM detector can be corrupted. In the case of the very intense hot plasma radiation (e.g. laser generated plasma), the registered signals can overlap. Therefore, it is valuable to register the raw signals from the GEM detector with high number of events during soft X-ray radiation. The signal analysis will have the direct impact on the implementation of photon energy computation algorithms. As the result, the system will produce energy spectra and topological distribution of soft X-ray radiation. The advanced software was developed in order to perform complex system startup and monitoring of hardware units. Using the array of two one-dimensional GEM detectors it will be possible to perform tomographic reconstruction of plasma impurities radiation in the SXR region.

A Binuclear 1,1'-Bis(boratabenzene) Complex: Unprecedented Intramolecular Metal-Metal Communication through a B-B Bond.

PubMed

Braunschweig, Holger; Demeshko, Serhiy; Ewing, William C; Krummenacher, Ivo; Macha, Bret B; Mattock, James D; Meyer, Franc; Mies, Jan; Schäfer, Marius; Vargas, Alfredo

2016-06-27

We report the synthesis of the first 1,1'-bis(boratabenzene) species by tetrabromodiborane(4)-induced ring-expansion reactions of cobaltocene. Six equivalents of cobaltocene are required as the species plays the dual role of reagent and reductant to yield [{(η(5) -C5 H5 )Co}2 {μ:η(6) ,η(6) -(BC5 H5 )2 }]. The formally dianionic bis(boratabenzene) moiety with a boron-boron single bond can be viewed as a symmetric dimer of the parent boratabenzene anion as well as the first example of a diboron analogue of biphenyl. The solution electrochemistry of the bimetallic complex shows four stepwise redox events, indicating significant intramolecular interaction between the cobalt ions across the 1,1'-bis(boratabenzene) unit. The magnetic properties, as investigated by variable-temperature SQUID magnetometry, reveal weak intramolecular antiferromagnetic interactions. Density functional theory calculations support the experimental results and add insight into the various electronic states of the complex. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biochemical characterization of propylglyoxal bis(guanylhydrazone). Facile synthesis of monoalkylglyoxal bis(guanylhydrazones).

PubMed

Elo, H; Laine, R; Alhonen-Hongisto, L; Jänne, J; Mutikainen, I; Lumme, P

1985-01-01

Propylglyoxal bis(guanylhydrazone) sulfate, a novel analog of the well-known antileukemic drug methylglyoxal bis(guanylhydrazone), has been prepared from 2,2-dibromopentanal, and the compound has been characterized biochemically. Although it is a powerful inhibitor of S-adenosylmethionine decarboxylase, its Ki value (0.2 microM) is considerably higher than that of ethylglyoxal bis(guanylhydrazone) (0.06 microM). The compound is only poorly taken up by tumor cells, and its accumulation is not stimulated by a prior exposure of the tumor cells to difluoromethylornithine, a compound that causes polyamine depletion. Thus, the uptake characteristics of the compound are similar to those of ethylglyoxal bis(guanylhydrazone), but in striking contrast to those of methylglyoxal and glyoxal bis(guanylhydrazones). Since the configuration of the double bonds in glyoxal, methylglyoxal and propylglyoxal bis(guanylhydrazones) has been shown to be identical, the different uptake characteristics are probably only due to differences in side chain size and/or hydrophobicity.

Inorganic resist materials based on zirconium phosphonate for atomic force microscope lithography

NASA Astrophysics Data System (ADS)

Kang, Mankyu; Kim, Seonae; Jung, JinHyuck; Kim, Heebom; Shin, Inkyun; Jeon, Chanuk; Lee, Haiwon

2014-03-01

New inorganic resist materials based on metal complexes were investigated for atomic force microscope (AFM) lithography. Phosphoric acids are good for self-assembly because of their strong binding energy. In this work, zirconium phosphonate system are newly synthesized for spin-coatable materials in aqueous solutions and leads to negative tone pattern for improving line edge roughness. Low electron exposure by AFM lithography could generate a pattern by electrochemical reaction and cross-linking of metal-oxo complexes. It has been reported that the minimum pattern results are affected by lithographic speed, and the applied voltage between a tip and a substrate.

GEMS and New Pre-Accretionally Irradiated RELICT Grains in Interplanetary Dust - The Plot Thickens

NASA Astrophysics Data System (ADS)

Bradley, J.

1995-09-01

microscopic studies of the local petrographic environment of GEMS in IDPs are continuing. There is evidence of a population of relict grains associated with GEMS. Some of these relict grains have distinctive compositions and they appear to have functioned as (pre-existing) depositional substrates while GEMS were being formed. Thus, it may be possible to begin to assign a chronology to the seemingly complex admixture of grains that make up the ultrafine-grained matrices of anhydrous chondritic IDPs. References: [1] Bradley J. P. (1994) Science, 265, 925-929. [2] Flynn G. J. (1994) Nature, 371, 287-288. [3] Martin P. G. (1995) Astrophys. J., 445, L63-L66. [4] Mathis J. S. (1986) Astrophys. J., 308, 281-287. [5] Mathis J. S. (1993) Rept. Prog. Phys., 56, 605-652. [6] Walker R. M. (1994) in Analysis of Interplanetary Dust (M. E. Zolensky et al., eds.), pp. 203-209, AIP Conf. Proc. 310.

Synthesis of palladium(0) and -(II) complexes with chelating bis(N-heterocyclic carbene) ligands and their application in semihydrogenation.

PubMed

Sluijter, Soraya N; Warsink, Stefan; Lutz, Martin; Elsevier, Cornelis J

2013-05-28

A transmetallation route, using silver(I) precursors, to several zero- and di-valent palladium complexes with chelating bis(N-heterocyclic carbene) ligands bearing various N-substituents has been established. The resulting complexes have been characterized by NMR and mass spectroscopy. In addition, the structure of a representative compound, [Pd(0)(bis-(Mes)NHC)(η(2)-ma)] (3a), was confirmed by X-ray crystal structure determination. In contrast to the transfer semihydrogenation, in which only low activity was observed, complex 3a showed activity (TOF = 49 mol(sub) mol(cat)(-1) h(-1)) and selectivity comparable to its monodentate counterparts in the semihydrogenation of 1-phenyl-1-propyne with molecular hydrogen.

The cytotoxicity and mechanism of action of new multinuclear Scaffold AuIII, PdII pincer complexes containing a bis(diphenylphosphino) ferrocene/non-ferrocene ligand.

PubMed

Tabrizi, Leila; Chiniforoshan, Hossein

2017-10-24

New multinuclear gold(iii), palladium(ii) pincer complexes containing bis(diphenylphosphino) ferrocene/non-ferrocene ligands of formula [(L)Au(μ 2 -η 2 -CS 3 )Pd(dppf)](PF 6 ) 2 , 1, and [(L)Au(μ 2 -η 2 -CS 3 )Pd(dppe)](PF 6 ) 2 , 2 (HL = 5-methoxy-1,3-bis (1-methyl-1H-benzo[d]imidazol-2-yl)benzene, dppf = 1,1'-bis(diphenylphosphino)ferrocene, and dppe = bis(diphenylphosphino)ethane) have been synthesized and fully characterized. Both complexes are more cytotoxic to a number of human cancer cell lines than cisplatin. Moreover, complex 1 is more active than auranofin as the reference gold compound against a panel of several human tumor cell lines. Chemosensitivity tests completed on cisplatin sensitive and resistant cell lines have confirmed that both complexes were able to overcome cisplatin resistance. The complexes successfully inhibited the enzymes thioredoxin reductase (TrxR) and glutathione reductase (GR). The cellular uptake of both gold and palladium of the complexes was studied, which indicated a high biological stability of the complexes. The complexes 1 and 2 increase the production of ROS in HCT-15 cells. In addition, these complexes induce major levels of cancer cell death by apoptosis.

Six complexes based on bis(imidazole/benzimidazole-1-yl)pyridazine ligands: Syntheses, structures and properties

NASA Astrophysics Data System (ADS)

Wang, Xin-Fang; Du, Ceng-Ceng; Zhou, Sheng-Bin; Wang, Duo-Zhi

2017-01-01

Herein we reported six new Ni(II)/Cu(II)/Zn(II) complexes, namely, [Ni(L1)4(OH)2] (1), [Cu(L1)4(OH)2] (2), [Cu(L1)2(SiF6)]n (3), {[Cu(L2)(HCOO)2]·H2O·CH3OH}n (4), [Ni(L2)2(NO3)2]n (5) and {[Zn(L2)Cl2]·DMF}n (6) (L1 = 3,6-bis(imidazole-1-yl)pyridazine, L2 = 3,6-bis(benzimidazole-1-yl)pyridazine), which were characterized by single-crystal X-ray diffraction, elemental analysis, IR, PXRD. These complexes have been successfully constructed under interface diffusion process, heating reflux or hydrothermal conditions. The structures of 1 and 2 are mononuclear complexes. Complex 3 exhibits a 6-connected 3D topology network with the Schläfli symbol of (412·63). In complex 4, two Cu(II) were connected through two HCOO- anions to form dinuclear structure unit, which is arranged into a 1D ladder-like structure by μ2-L2 ligands. Complexes 5 and 6 are 1D zigzag chains connected by L2 ligands, but the Ni(II) ion is six-coordinated in 5 and the Zn(II) ion is four-coordinated in 6. Moreover, the solid-state luminescence property and UV-vis diffuse reflection spectrum of complex 6 have been investigated and discussed.

Bis(1,3-di-tert-butylimidazolin-2-iminato) titanium complexes as effective catalysts for the monodisperse polymerization of propylene.

PubMed

Sharma, Manab; Yameen, Haneen Simaan; Tumanskii, Boris; Filimon, Sabina-Alexandra; Tamm, Matthias; Eisen, Moris S

2012-10-17

The use of bis(1,3-di-tert-butylimidazolin-2-iminato) titanium dichloride (1) and dimethyl (2) complexes in the polymerization of propylene is presented. The complexes were activated using different amounts of methylalumoxane (MAO), giving in each case a very active catalytic mixture and producing polymers with a narrow molecular weight distribution (polydispersity = 1.10). The use of the cocatalyst triphenylcarbenium (trityl) tetra(pentafluorophenyl)borate totally inhibits the reaction, producing the corresponding bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(III) methyl complex, the trityl radical ((•)CPh(3)), the anionic MeB(C(6)F(5))(4)(-), B(C(6)F(5))(3), and the bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(IV) dimethyl·B(C(6)F(5))(3) complex. The use of a combination of physical methods such as NMR, ESR-C(60), and MALDI-TOF analyses enabled us to propose a plausible mechanism for the polymerization of propylene, presenting that the polymerization is mainly carried out in a living fashion. In addition, we present a slow equilibrium toward a small amount of a dormant species responsible for 2,1-misinsertions and chain transfer processes.

Implementation of the P barANDA Planar-GEM tracking detector in Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Divani Veis, Nazila; Ehret, Andre; Firoozabadi, Mohammad M.; Karabowicz, Radoslaw; Maas, Frank; Saito, Nami; Saito, Takehiko R.; Voss, Bernd; PANDA Gem-Tracker Subgroup

2018-02-01

The P barANDA experiment at FAIR will be performed to investigate different aspects of hadron physics using anti-proton beams interacting with a fixed nuclear target. The experimental setup consists of a complex series of detector components covering a large solid angle. A detector with a gaseous active media equipped with gas electron multiplier (GEM) technique will be employed to measure tracks of charged particles at forward direction in order to achieve a high momentum resolution. In this work, a full setup of the GEM tracking detector has been implemented in the P barANDA Monte Carlo simulation package (PandaRoot) based on the current technical and conceptual design, and the expected performance of the P barANDA GEM-tracking detector has been investigated. Furthermore, material-budget studies in terms of the radiation length of the P barANDA GEM-tracking detector have been made in order to investigate the effect of the detector materials and its associated structures to particle measurements.

Remote Sensing of Air Pollution from Geo with GEMS and TEMPO

NASA Astrophysics Data System (ADS)

Lasnik, J.; Nicks, D. K., Jr.; Baker, B.; Canova, B.; Chance, K.; Liu, X.; Suleiman, R. M.; Pennington, W. F.; Flittner, D. E.; Al-Saadi, J. A.; Rosenbaum, D. M.

2017-12-01

The Geostationary Environmental Monitoring System (GEMS) and Tropospheric Emissions: Monitoring of Pollution (TEMPO) instruments will provide a new capability for the understanding of air quality and pollution. Ball Aerospace is the instrument developer. The GEMS and TEMPO instruments use well-proven remote sensing techniques and take advantage of a geostationary orbit to take hourly measurements of the same geographical area. The high spatial and temporal resolution of these instruments will allow for measurements of the complex diurnal cycle of pollution driven by the combination of photochemistry, chemical composition and the dynamic nature of the atmosphere. Status of the manufacturing, test and calibration efforts will be presented.The GEMS instrument is being built for the Korea Aerospace Research Institute and their customer the National Institute of Environmental Research (NIER). The TEMPO instrument is being built for NASA under the Earth Venture Instrument EVI Program. NASA Langley Research Center (LaRC) is the managing center and the Principle Investigator (PI) is Kelly Chance of the Smithsonian Astrophysical Observatory (SAO).

Numerical Investigation on Electron and Ion Transmission of GEM-based Detectors

NASA Astrophysics Data System (ADS)

Bhattacharya, Purba; Sahoo, Sumanya Sekhar; Biswas, Saikat; Mohanty, Bedangadas; Majumdar, Nayana; Mukhopadhyay, Supratik

2018-02-01

ALICE at the LHC is planning a major upgrade of its detector systems, including the TPC, to cope with an increase of the LHC luminosity after 2018. Different R&D activities are currently concentrated on the adoption of the Gas Electron Multiplier (GEM) as the gas amplification stage of the ALICE-TPC upgrade version. The major challenge is to have low ion feedback in the drift volume as well as to ensure a collection of good percentage of primary electrons in the signal generation process. In the present work, Garfield simulation framework has been adopted to numerically estimate the electron transparency and ion backflow fraction of GEM-based detectors. In this process, extensive simulations have been carried out to enrich our understanding of the complex physical processes occurring within single, triple and quadruple GEM detectors. A detailed study has been performed to observe the effect of detector geometry, field configuration and magnetic field on the above mentioned characteristics.

GEM - The Global Earthquake Model

NASA Astrophysics Data System (ADS)

Smolka, A.

2009-04-01

Over 500,000 people died in the last decade due to earthquakes and tsunamis, mostly in the developing world, where the risk is increasing due to rapid population growth. In many seismic regions, no hazard and risk models exist, and even where models do exist, they are intelligible only by experts, or available only for commercial purposes. The Global Earthquake Model (GEM) answers the need for an openly accessible risk management tool. GEM is an internationally sanctioned public private partnership initiated by the Organisation for Economic Cooperation and Development (OECD) which will establish an authoritative standard for calculating and communicating earthquake hazard and risk, and will be designed to serve as the critical instrument to support decisions and actions that reduce earthquake losses worldwide. GEM will integrate developments on the forefront of scientific and engineering knowledge of earthquakes, at global, regional and local scale. The work is organized in three modules: hazard, risk, and socio-economic impact. The hazard module calculates probabilities of earthquake occurrence and resulting shaking at any given location. The risk module calculates fatalities, injuries, and damage based on expected shaking, building vulnerability, and the distribution of population and of exposed values and facilities. The socio-economic impact module delivers tools for making educated decisions to mitigate and manage risk. GEM will be a versatile online tool, with open source code and a map-based graphical interface. The underlying data will be open wherever possible, and its modular input and output will be adapted to multiple user groups: scientists and engineers, risk managers and decision makers in the public and private sectors, and the public-at- large. GEM will be the first global model for seismic risk assessment at a national and regional scale, and aims to achieve broad scientific participation and independence. Its development will occur in a

Structure of the Escherichia coli phosphonate binding protein PhnD and rationally optimized phosphonate biosensors.

PubMed

Alicea, Ismael; Marvin, Jonathan S; Miklos, Aleksandr E; Ellington, Andrew D; Looger, Loren L; Schreiter, Eric R

2011-12-02

The phnD gene of Escherichia coli encodes the periplasmic binding protein of the phosphonate (Pn) uptake and utilization pathway. We have crystallized and determined structures of E. coli PhnD (EcPhnD) in the absence of ligand and in complex with the environmentally abundant 2-aminoethylphosphonate (2AEP). Similar to other bacterial periplasmic binding proteins, 2AEP binds near the center of mass of EcPhnD in a cleft formed between two lobes. Comparison of the open, unliganded structure with the closed 2AEP-bound structure shows that the two lobes pivot around a hinge by ~70° between the two states. Extensive hydrogen bonding and electrostatic interactions stabilize 2AEP, which binds to EcPhnD with low nanomolar affinity. These structures provide insight into Pn uptake by bacteria and facilitated the rational design of high signal-to-noise Pn biosensors based on both coupled small-molecule dyes and autocatalytic fluorescent proteins. Copyright © 2011 Elsevier Ltd. All rights reserved.

Structure of the Escherichia coli Phosphonate Binding Protein PhnD and Rationally Optimized Phosphonate Biosensors

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

Alicea, Ismael; Marvin, Jonathan S.; Miklos, Aleksandr E.

2012-09-17

The phnD gene of Escherichia coli encodes the periplasmic binding protein of the phosphonate (Pn) uptake and utilization pathway. We have crystallized and determined structures of E. coli PhnD (EcPhnD) in the absence of ligand and in complex with the environmentally abundant 2-aminoethylphosphonate (2AEP). Similar to other bacterial periplasmic binding proteins, 2AEP binds near the center of mass of EcPhnD in a cleft formed between two lobes. Comparison of the open, unliganded structure with the closed 2AEP-bound structure shows that the two lobes pivot around a hinge by {approx}70{sup o} between the two states. Extensive hydrogen bonding and electrostatic interactionsmore » stabilize 2AEP, which binds to EcPhnD with low nanomolar affinity. These structures provide insight into Pn uptake by bacteria and facilitated the rational design of high signal-to-noise Pn biosensors based on both coupled small-molecule dyes and autocatalytic fluorescent proteins.« less

Gaseous Electron Multiplier (GEM) Detectors

NASA Astrophysics Data System (ADS)

Gnanvo, Kondo

2017-09-01

Gaseous detectors have played a pivotal role as tracking devices in the field of particle physics experiments for the last fifty years. Recent advances in photolithography and micro processing techniques have enabled the transition from Multi Wire Proportional Chambers (MWPCs) and Drift Chambers to a new family of gaseous detectors refer to as Micro Pattern Gaseous Detectors (MPGDs). MPGDs combine the basic gas amplification principle with micro-structure printed circuits to provide detectors with excellent spatial and time resolution, high rate capability, low material budget and high radiation tolerance. Gas Electron Multiplier (GEMs) is a well-established MPGD technology invented by F. Sauli at CERN in 1997 and deployed various high energy physics (HEP) and nuclear NP experiment for tracking systems of current and future NP experiments. GEM detector combines an exceptional high rate capability (1 MHz / mm2) and robustness against harsh radiation environment with excellent position and timing resolution performances. Recent breakthroughs over the past decade have allowed the possibility for large area GEMs, making them cost effective and high-performance detector candidates to play pivotal role in current and future particle physics experiments. After a brief introduction of the basic principle of GEM technology, I will give a brief overview of the GEM detectors used in particle physics experiments over the past decades and especially in the NP community at Thomas Jefferson National Laboratory (JLab) and Brookhaven National Laboratory (BNL). I will follow by a review of state of the art of the new GEM development for the next generation of colliders such as Electron Ion Collider (EIC) or High Luminosity LHC and future Nuclear Physics experiments. I will conclude with a presentation of the CERN-based RD51 collaboration established in 2008 and its major achievements regarding technological developments and applications of MPGDs.

Extending the ISC-GEM Global Earthquake Instrumental Catalogue

NASA Astrophysics Data System (ADS)

Di Giacomo, Domenico; Engdhal, Bob; Storchak, Dmitry; Villaseñor, Antonio; Harris, James

2015-04-01

After a 27-month project funded by the GEM Foundation (www.globalquakemodel.org), in January 2013 we released the ISC-GEM Global Instrumental Earthquake Catalogue (1900 2009) (www.isc.ac.uk/iscgem/index.php) as a special product to use for seismic hazard studies. The new catalogue was necessary as improved seismic hazard studies necessitate that earthquake catalogues are homogeneous (to the largest extent possible) over time in their fundamental parameters, such as location and magnitude. Due to time and resource limitation, the ISC-GEM catalogue (1900-2009) included earthquakes selected according to the following time-variable cut-off magnitudes: Ms=7.5 for earthquakes occurring before 1918; Ms=6.25 between 1918 and 1963; and Ms=5.5 from 1964 onwards. Because of the importance of having a reliable seismic input for seismic hazard studies, funding from GEM and two commercial companies in the US and UK allowed us to start working on the extension of the ISC-GEM catalogue both for earthquakes that occurred beyond 2009 and for earthquakes listed in the International Seismological Summary (ISS) which fell below the cut-off magnitude of 6.25. This extension is part of a four-year program that aims at including in the ISC-GEM catalogue large global earthquakes that occurred before the beginning of the ISC Bulletin in 1964. In this contribution we present the updated ISC GEM catalogue, which will include over 1000 more earthquakes that occurred in 2010 2011 and several hundreds more between 1950 and 1959. The catalogue extension between 1935 and 1949 is currently underway. The extension of the ISC-GEM catalogue will also be helpful for regional cross border seismic hazard studies as the ISC-GEM catalogue should be used as basis for cross-checking the consistency in location and magnitude of those earthquakes listed both in the ISC GEM global catalogue and regional catalogues.

A Novel Multi-Phosphonate Surface Treatment of Titanium Dental Implants: A Study in Sheep

PubMed Central

von Salis-Soglio, Marcella; Stübinger, Stefan; Sidler, Michéle; Klein, Karina; Ferguson, Stephen J.; Kämpf, Käthi; Zlinszky, Katalin; Buchini, Sabrina; Curno, Richard; Péchy, Péter; Aronsson, Bjorn-Owe; von Rechenberg, Brigitte

2014-01-01

The aim of the present study was to evaluate a new multi-phosphonate surface treatment (SurfLink®) in an unloaded sheep model. Treated implants were compared to control implants in terms of bone to implant contact (BIC), bone formation, and biomechanical stability. The study used two types of implants (rough or machined surface finish) each with either the multi-phosphonate Wet or Dry treatment or no treatment (control) for a total of six groups. Animals were sacrificed after 2, 8, and 52 weeks. No adverse events were observed at any time point. At two weeks, removal torque showed significantly higher values for the multi-phosphonate treated rough surface (+32% and +29%, Dry and Wet, respectively) compared to rough control. At 52 weeks, a significantly higher removal torque was observed for the multi-phosphonate treated machined surfaces (+37% and 23%, Dry and Wet, respectively). The multi-phosphonate treated groups showed a positive tendency for higher BIC with time and increased new-old bone ratio at eight weeks. SEM images revealed greater amounts of organic materials on the multi-phosphonate treated compared to control implants, with the bone fracture (from the torque test) appearing within the bone rather than at the bone to implant interface as it occurred for control implants. PMID:25215424

Does Comet WILD-2 contain Gems?

NASA Technical Reports Server (NTRS)

Chi, M.; Ishii, H.; Dai, Z. R.; Toppani, A.; Joswiak, D. J.; Leroux, H.; Zolensky, M.; Keller, L. P.; Browning, N. D.

2007-01-01

It is expected that Comet Wild-2 dust should resemble anhydrous carbon-rich, chondritic porous (CP) interplanetary dust particles (IDPs) collected in the stratosphere because some CP IDPs are suspected to be from comets. The rarity of carbonaceous grains and presolar silicates, as well as the presence of high-temperature inner solar nebula minerals in the Wild-2 sample (e.g. osbornite and melilite), appear incompatible with most CP IDPs. However, it is premature to draw firm conclusions about the mineralogy of comet Wild-2 because only approx. 1% of the sample has been examined. The most abundant silicates in CP IDPs are GEMS (glass with embedded metal and sulfides). Nonsolar O isotopic compositions confirm that at least some GEMS in IDPs are presolar amorphous silicates. The presence or absence of GEMS in the Wild-2 sample is important because it addresses, (a) the relationship between CP IDPs and comets, and (b) the hypothesis that other GEMS in IDPs formed in the solar nebula. Here we show that most of the GEMSlike materials so far identified in Stardust aerogel were likely impact generated during collection. At the nanometer scale, they are compositionally and crystallographically distinct from GEMS in IDPs.

Synthesis and Structural Studies of Calcium and Magnesium Phosphinate and Phosphonate Compounds

NASA Astrophysics Data System (ADS)

Bampoh, Victoria Naa Kwale

The work presented herein describes synthetic methodologies leading to the design of a wide array of magnesium and calcium based phosphinate and phosphonates with possible applications as bone scaffolding materials or additives to bone cements. The challenge to the chemistry of the alkaline earth phosphonate target compounds includes poor solubility of compounds, and poorly understood details on the control of the metal's coordination environment. Hence, less is known on phosphonate based alkaline earth metal organic frameworks as compared to transition metal phosphonates. Factors governing the challenges in obtaining crystalline, well-defined magnesium and calcium solids lie in the large metal diameters, the absence of energetically available d-orbitals to direct metal geometry, as well as the overall weakness of the metal-ligand bonds. A significant part of this project was concerned with the development of suitable reaction conditions to obtain X-ray quality crystals of the reaction products to allow for structural elucidation of the novel compounds. Various methodologies to aid in crystal growth including hydrothermal methods and gel crystallization were employed. We have used phosphinate and phosphonate ligands with different number of phosphorus oxygen atoms as well as diphosphonates with different linker lengths to determine their effects on the overall structural features. An interesting correlation is observed between the dimensionality of products and the increasing number of donor oxygen atoms in the ligands as we progress from phosphinic acid to the phosphorous acids. As an example, monophosphinate ligand only yielded one-dimensional compounds, whereas the phosphonates crystallize as one and two-dimensional compounds, and the di- and triphosphonate based compounds display two or three-dimensional geometries. This thesis provides a selection of calcium and magnesium compounds with one-dimensional geometry, as represented in a calcium phosphinate to novel

Ruthenium(II) carbonyl complexes bearing CCC-pincer bis-(carbene) ligands: synthesis, structures and activities toward recycle transfer hydrogenation reactions.

PubMed

Naziruddin, Abbas Raja; Huang, Zhao-Jiunn; Lai, Wei-Chih; Lin, Wan-Jung; Hwang, Wen-Shu

2013-09-28

A new series of ruthenium(II) carbonyl complexes with benzene-based CCC-pincer bis-(carbene) ligands, [((R)CCC(R))Ru(CO)2(X)](0/+) and [((R)CCC(R))Ru(CO)(NN)](+) ((R)CCC(R) = 2,6-bis-(1-alkylimidazolylidene)benzene, R = Me or (n)Bu; X = I, Br, CH3CN, or 6-(aminomethyl)pyridine (ampy); NN = 2·CH3CN, or chelating ampy or bipyridine), was synthesized and fully characterized. X-Ray structure determinations revealed that these eight complexes have pseudo-octahedral configurations around the ruthenium center with the pincer ligand occupying three meridional sites. These complexes prove to be efficient precatalysts demonstrating very good activity and reusability for the transfer hydrogenation of ketones.

Synthesis of a new family of acyclic nucleoside phosphonates, analogues of TPases transition states.

PubMed

Dayde, Bénédicte; Benzaria, Samira; Pierra, Claire; Gosselin, Gilles; Surleraux, Dominique; Volle, Jean-Noël; Pirat, Jean-Luc; Virieux, David

2012-05-07

A 6-step procedure was developed for the synthesis of a new family of acyclic nucleoside phosphonates (ANPs), "PHEEPA" [(2-pyrimidinyl-2-(2-hydroxyethoxy)ethyl)phosphonic acids] in overall yields ranging from 4.5% to 32%. These compounds, which possess on one side a hydroxy function and on the other side a phosphonate group, can be considered either as potential antiviral agents or as transition state analogues of nucleoside phosphorylases such as thymidine phosphorylase.

The role of evaporites in the formation of gems during metamorphism of carbonate platforms: a review

NASA Astrophysics Data System (ADS)

Giuliani, Gaston; Dubessy, Jean; Ohnenstetter, Daniel; Banks, David; Branquet, Yannick; Feneyrol, Julien; Fallick, Anthony E.; Martelat, Jean-Emmanuel

2018-01-01

The mineral and fluid inclusions trapped by gemstones during the metamorphism of carbonate platform successions are precious markers for the understanding of gem genesis. The nature and chemical composition of inclusions highlight the major contribution of evaporites through dissolution or fusion, depending on the temperature of formation from greenschist to granulite facies. The fluids are highly saline NaCl-brines circulating either in an open system in the greenschist facies (Colombian and Afghan emeralds) and with huge fluid-rock metasomatic interactions, or sulphurous fluids (ruby, garnet tsavorite, zoisite tanzanite and lapis-lazuli) or molten salts formed in a closed system with a low fluid mobility (ruby in marble) in the conditions of the amphibolite to granulite facies. These chloride-fluoride-sulphate ± carbonate-rich fluids scavenged the metals essential for gem formation. At high temperature, the anions SO4 2-, NO3 -, BO3 - and F- are powerful fluxes which lower the temperature of chloride- and fluoride-rich ionic liquids. They provided transport over a very short distance of aluminium and/or silica and transition metals which are necessary for gem growth. In summary, the genetic models proposed for these high-value and ornamental gems underline the importance of the metamorphism of evaporites formed on continental carbonate shelves and emphasise the chemical power accompanying metamorphism at moderate to high temperatures of evaporite-rich and organic matter-rich protoliths to form gem minerals.

Bacterial Degradation of Phosphonates Bound to High-Molecular-Weight Dissolved Organic Matter Produces Methane and Other Hydrocarbons

NASA Astrophysics Data System (ADS)

Sosa, O.; Ferron Smith, S.; Karl, D. M.; DeLong, E.; Repeta, D.

2016-02-01

The biological degradation of dissolved organic matter (DOM) plays important roles in the carbon cycle and energy balance of the ocean. Yet, the biochemical pathways that drive DOM turnover remain to be fully characterized. In this study, we tested the ability of two open ocean bacterial isolates (a Pseudomonas stutzeri strain (Gammaproteobacteria) and a Sulfitobacter isolate (Alphaproteobacteria)) to degrade DOM phosphonates. Each isolate encoded a complete phosphonate degradation pathway in its genome, and each was able to degrade simple alkyl-phosphonates like methyl phosphonate, releasing methane (or other short chain hydrocarbon gases) as a result. We found that cultures incubated in the presence of HMW DOM polysaccharides also produced methane and other trace gases under aerobic conditions. To demonstrate that phosphonates were the source of these gases, we constructed a P. stutzeri mutant disabled in the phosphonate degradation pathway. Unlike the wild type, the mutant strain was deficient in the production of methane and other gases from HMW DOM-associated phosphonates. These observations support the hypothesis that DOM-bound methyl phosphonates may be a significant source of methane in the water column, and that bacterial degradation of these compounds likely contribute to the subsurface methane maxima observed throughout the world's oceans.

Synthesis of triple-stranded complexes using bis(dipyrromethene) ligands.

PubMed

Zhang, Zhan; Dolphin, David

2010-12-20

The reaction of an α-free, β,β'-linked bis(dipyrromethene) ligand with Fe(3+) or Co(3+) led to noninterconvertible triple-stranded helicates and mesocates. In the present context, a stable α-free ligand 2 has been developed and complexation of ligands 1 and 2 with diamagnetic Co(3+), Ga(3+), and In(3+) has been studied. The triple-stranded M(2)1(3) (M = Ga, In) and M(2)2(3) (M = Co, Ga, In) complexes were characterized using matrix-assisted laser desorption ionization time-of-flight spectrometry, (1)H NMR and UV-vis spectroscopy, and X-ray crystallography. Again, the (1)H NMR analysis showed that both the triple-stranded helicates and mesocates were generated in this metal-directed assembly. Consistent with our previous finding on coordinatively inert Co(3+) complexes, variable-temperature NMR spectroscopy indicated that the triple-stranded helicate and mesocate of labile In(3+) did not interconvert in solution, either. However, the diastereoselectivity of the M(2)2(3) complexes was found to improve with an increase in the reaction temperature. Taken together, this study complements the coordination chemistry of poly(dipyrromethene) ligands and provides further insight into the formation of helicates versus mesocates.

Copper(I)- and copper(0)-promoted homocoupling and homocoupling-hydrodehalogenation reactions of dihalogenoclathrochelate precursors for C-C conjugated iron(II) bis-cage complexes.

PubMed

Varzatskii, Oleg A; Shul'ga, Sergey V; Belov, Alexander S; Novikov, Valentin V; Dolganov, Alexander V; Vologzhanina, Anna V; Voloshin, Yan Z

2014-12-28

Iron(II) dibromo- and diiodoclathrochelates undergo copper(I)-promoted reductive homocoupling in HMPA at 70-80 °C leading to C-C conjugated dibromo- and diiodo-bis-clathrochelates in high yields. Under the same conditions, their dichloroclathrochelate analog does not undergo the same homocoupling reaction, so the target dichloro-bis-cage product was obtained in high yield via dimerization of its heterodihalogenide iodochloromonomacrobicyclic precursor. The use of NMP as a solvent at 120-140 °C gave the mixture of bis-clathrochelates resulting from a tandem homocoupling-hydrodehalogenation reaction: the initial acetonitrile copper(I) solvato-complex at a high temperature underwent re-solvatation and disproportionation leading to Cu(II) ions and nano-copper, which promoted the hydrodehalogenation process even at room temperature. The most probable pathway of this reaction in situ includes hydrodehalogenation of the already formed dihalogeno-bis-clathrochelate via the formation of reduced anion radical intermediates. As a result, chemical transformations of the iron(II) dihalogenoclathrochelates in the presence of an acetonitrile copper(I) solvato-complex were found to depend both on the nature of halogen atoms in their ribbed chelate fragments and on reaction conditions (i.e. solvent and temperature). The C-C conjugated iron(II) dihalogeno-bis-clathrochelates easily undergo nucleophilic substitution with various N,S-nucleophiles giving ribbed-functionalized bis-cage species. These iron(II) complexes were characterized by elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (1)H and (13)C NMR spectroscopy, and by X-ray diffraction; their electrochemical properties were studied by cyclic voltammetry. The isomeric shift values in (57)Fe Mössbauer spectra of such cage compounds allowed identifying them as low-spin iron(II) complexes, while those of the quadrupole splitting are the evidence for a significant TP distortion of their FeN6-coordination polyhedra

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase.

PubMed

Kim, In-Hae; Park, Yong-Kyu; Nishiwaki, Hisashi; Hammock, Bruce D; Nishi, Kosuke

2015-11-15

Structure-activity relationships of amide-phosphonate derivatives as inhibitors of the human soluble epoxide hydrolase (sEH) were investigated. First, a series of alkyl or aryl groups were substituted on the carbon alpha to the phosphonate function in amide compounds to see whether substituted phosphonates can act as a secondary pharmacophore. A tert-butyl group (16) on the alpha carbon was found to yield most potent inhibition on the target enzyme. A 4-50-fold drop in inhibition was induced by other substituents such as aryls, substituted aryls, cycloalkyls, and alkyls. Then, the modification of the O-substituents on the phosphonate function revealed that diethyl groups (16 and 23) were preferable for inhibition to other longer alkyls or substituted alkyls. In amide compounds with the optimized diethylphosphonate moiety and an alkyl substitution such as adamantane (16), tetrahydronaphthalene (31), or adamantanemethane (36), highly potent inhibitions were gained. In addition, the resulting potent amide-phosphonate compounds had reasonable water solubility, suggesting that substituted phosphonates in amide inhibitors are effective for both inhibition potency on the human sEH and water solubility as a secondary pharmacophore. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of three bis-pyridyl-bis-amide ligands with various spacers on the structural diversity of new multifunctional cobalt(II) coordination polymers

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

Lin, Hong-Yan; Lu, Huizhe; Le, Mao

2015-03-15

Three new cobalt(II) coordination polymers [Co{sub 2}(1,4-NDC){sub 2}(3-bpye)(H{sub 2}O)] (1), [Co(1,4-NDC)(3-bpfp)(H{sub 2}O)] (2) and [Co(1,4-NDC)(3-bpcb)] (3) [3-bpye=N,N′-bis(3-pyridinecarboxamide)-1,2-ethane, 3-bpfp=bis(3-pyridylformyl)piperazine, 3-bpcb=N,N′-bis(3-pyridinecarboxamide)-1,4-benzene, and 1,4-H{sub 2}NDC=1,4-naphthalenedicarboxylic acid] have been hydrothermally synthesized. The structures of complexes 1–3 have been determined by X-ray single crystal diffraction analyses and further characterized by infrared spectroscopy (IR), powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA). Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup 8}) topology constructed from 3D [Co{sub 2}(1,4-NDC){sub 2}(H{sub 2}O)]{sub n} framework and bidentate 3-bpye ligands. Complex 2 shows 1D “cage+cage”-like chain formed by 1D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} ribbon chains and [Co{sub 2}(3-bpfp){submore » 2}] loops, which are further linked by hydrogen bonding interactions to form a 3D supramolecular network. Complex 3 displays a 3D coordination network with a 6-connected (4{sup 12}.6{sup 3}) topology based on 2D [Co{sub 2}(1,4-NDC){sub 2}]{sub n} layers and bidentate 3-bpcb bridging ligands. The influences of different bis-pyridyl-bis-amide ligands with various spacers on the structures of title complexes are studied. Moreover, the fluorescent properties, electrochemical behaviors and magnetic properties of complexes 1–3 have been investigated. - Graphical abstract: Three multifunctional cobalt(II) complexes constructed from three bis-pyridyl-bis-amide and 1,4-naphthalenedicarboxylic acid have been hydrothermally synthesized and characterized. The fluorescent, electrochemical and magnetic properties of 1–3 have been investigated. - Highlights: • Three multifunctional cobalt(II) complexes based on various bis-pyridyl-bis-amide ligands. • Complex 1 is a 3D coordination structure with 8-connected (4{sup 20}.6{sup

X-ray GEM Detectors for Burning Plasma Experiments

NASA Astrophysics Data System (ADS)

Puddu, S.; Bombarda, F.; Pizzicaroli, G.; Murtas, F.

2009-11-01

The harsh environment and higher values of plasma parameters to be expected in future burning plasma experiments (and even more so in future power producing fusion reactors) is prompting the development of new, advanced diagnostic systems. The detection of radiation emitted by the plasma in the X-ray spectral region is likely to play the role that visible or UV radiation have in present day experiments. GEM gas detectors, developed at CERN, are the natural evolution of Multiwire Proportional Chambers, with a number of advantages: higher counting rates, lower noise, good energy resolution, low sensitivity to background radiation. GEM's can be used in several different ways, but two specific applications are being explored in the framework of the Ignitor program, one for plasma position control and the other for high resolution spectroscopy. The diagnostic layout on the Ignitor machine is such that the detectors will not be in direct view of the plasma, at locations where they can be efficiently screened by the background radiation. Prototype detectors 10 x 10 cm^2 in area have been assembled and will be tested to assess the optimal geometrical parameters and operating conditions, regarding in particular the choice between Single and Triple GEM configurations, the gas mixture, and the problem of fan-out associated with the high number of output channels required for high resolution crystal spectrometers.

Luminescence properties and molecular mechanics calculation of bis-β-diketonate Eu3+ complex/polymer hybrid fibers

NASA Astrophysics Data System (ADS)

Bai, Jinyuan; Gu, Huiquan; Hou, Yanjun; Wang, Shuhong

2018-05-01

Two series of bis-β-diketonate Eu3+ complex/polymer hybrid fibers, namely, Eu2(BTP)3(H2O)4/PMMA (Eu/PMMA) and Eu2(BTP)3(H2O)4/PVP (Eu/PVP) have been prepared by electrospinning technology (BTP = 1,3-bis(4,4,4-trifluoro-1,3-dioxobutyl)phenyl, PVP = poly (vinyl pyrrolidone) and PMMA = poly (methyl methacrylate)). The effect of complex Eu2(BTP)3(H2O)4 on the luminescence, thermal stability and morphology of composite fibers were studied by characterization techniques. The Judd-Ofelt theory was applied to this study for explaining the effect of the distribution of Eu2(BTP)3(H2O)4 and the mutual effect of the Eu2(BTP)3(H2O)4 coordination compound and neighboring chain segments of PMMA and PVP polymer matrix.

Discovery of phosphonic acid natural products by mining the genomes of 10,000 actinomycetes.

PubMed

Ju, Kou-San; Gao, Jiangtao; Doroghazi, James R; Wang, Kwo-Kwang A; Thibodeaux, Christopher J; Li, Steven; Metzger, Emily; Fudala, John; Su, Joleen; Zhang, Jun Kai; Lee, Jaeheon; Cioni, Joel P; Evans, Bradley S; Hirota, Ryuichi; Labeda, David P; van der Donk, Wilfred A; Metcalf, William W

2015-09-29

Although natural products have been a particularly rich source of human medicines, activity-based screening results in a very high rate of rediscovery of known molecules. Based on the large number of natural product biosynthetic genes in microbial genomes, many have proposed "genome mining" as an alternative approach for discovery efforts; however, this idea has yet to be performed experimentally on a large scale. Here, we demonstrate the feasibility of large-scale, high-throughput genome mining by screening a collection of over 10,000 actinomycetes for the genetic potential to make phosphonic acids, a class of natural products with diverse and useful bioactivities. Genome sequencing identified a diverse collection of phosphonate biosynthetic gene clusters within 278 strains. These clusters were classified into 64 distinct groups, of which 55 are likely to direct the synthesis of unknown compounds. Characterization of strains within five of these groups resulted in the discovery of a new archetypical pathway for phosphonate biosynthesis, the first (to our knowledge) dedicated pathway for H-phosphinates, and 11 previously undescribed phosphonic acid natural products. Among these compounds are argolaphos, a broad-spectrum antibacterial phosphonopeptide composed of aminomethylphosphonate in peptide linkage to a rare amino acid N(5)-hydroxyarginine; valinophos, an N-acetyl l-Val ester of 2,3-dihydroxypropylphosphonate; and phosphonocystoximate, an unusual thiohydroximate-containing molecule representing a new chemotype of sulfur-containing phosphonate natural products. Analysis of the genome sequences from the remaining strains suggests that the majority of the phosphonate biosynthetic repertoire of Actinobacteria has been captured at the gene level. This dereplicated strain collection now provides a reservoir of numerous, as yet undiscovered, phosphonate natural products.

Discovery of phosphonic acid natural products by mining the genomes of 10,000 actinomycetes

PubMed Central

Ju, Kou-San; Gao, Jiangtao; Doroghazi, James R.; Wang, Kwo-Kwang A.; Thibodeaux, Christopher J.; Li, Steven; Metzger, Emily; Fudala, John; Su, Joleen; Zhang, Jun Kai; Lee, Jaeheon; Cioni, Joel P.; Evans, Bradley S.; Hirota, Ryuichi; Labeda, David P.; van der Donk, Wilfred A.; Metcalf, William W.

2015-01-01

Although natural products have been a particularly rich source of human medicines, activity-based screening results in a very high rate of rediscovery of known molecules. Based on the large number of natural product biosynthetic genes in microbial genomes, many have proposed “genome mining” as an alternative approach for discovery efforts; however, this idea has yet to be performed experimentally on a large scale. Here, we demonstrate the feasibility of large-scale, high-throughput genome mining by screening a collection of over 10,000 actinomycetes for the genetic potential to make phosphonic acids, a class of natural products with diverse and useful bioactivities. Genome sequencing identified a diverse collection of phosphonate biosynthetic gene clusters within 278 strains. These clusters were classified into 64 distinct groups, of which 55 are likely to direct the synthesis of unknown compounds. Characterization of strains within five of these groups resulted in the discovery of a new archetypical pathway for phosphonate biosynthesis, the first (to our knowledge) dedicated pathway for H-phosphinates, and 11 previously undescribed phosphonic acid natural products. Among these compounds are argolaphos, a broad-spectrum antibacterial phosphonopeptide composed of aminomethylphosphonate in peptide linkage to a rare amino acid N5-hydroxyarginine; valinophos, an N-acetyl l-Val ester of 2,3-dihydroxypropylphosphonate; and phosphonocystoximate, an unusual thiohydroximate-containing molecule representing a new chemotype of sulfur-containing phosphonate natural products. Analysis of the genome sequences from the remaining strains suggests that the majority of the phosphonate biosynthetic repertoire of Actinobacteria has been captured at the gene level. This dereplicated strain collection now provides a reservoir of numerous, as yet undiscovered, phosphonate natural products. PMID:26324907

gem-Difluoroolefination of diaryl ketones and enolizable aldehydes with difluoromethyl 2-pyridyl sulfone: new insights into the Julia-Kocienski reaction.

PubMed

Gao, Bing; Zhao, Yanchuan; Hu, Mingyou; Ni, Chuanfa; Hu, Jinbo

2014-06-16

The direct conversion of diaryl ketones and enolizable aliphatic aldehydes into gem-difluoroalkenes has been a long-standing challenge in organofluorine chemistry. Herein, we report efficient strategies to tackle this problem by using difluoromethyl 2-pyridyl sulfone as a general gem-difluoroolefination reagent. The gem-difluoroolefination of diaryl ketones proceeds by acid-promoted Smiles rearrangement of the carbinol intermediate; the gem-difluoroolefination is otherwise difficult to achieve through a conventional Julia-Kocienski olefination protocol under basic conditions due to the retro-aldol type decomposition of the key intermediate. Efficient gem-difluoroolefination of aliphatic aldehydes was achieved by the use of an amide base generated in situ (from CsF and tris(trimethylsilyl)amine), which diminishes the undesired enolization of aliphatic aldehydes and provides a powerful synthetic method for chemoselective gem-difluoroolefination of multi-carbonyl compounds. Our results provide new insights into the mechanistic understanding of the classical Julia-Kocienski reaction. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Gem GTP-binding protein promotes morphological differentiation in neuroblastoma.

PubMed

Leone, A; Mitsiades, N; Ward, Y; Spinelli, B; Poulaki, V; Tsokos, M; Kelly, K

2001-05-31

Gem is a small GTP-binding protein within the Ras superfamily whose function has not been determined. We report here that ectopic Gem expression is sufficient to stimulate cell flattening and neurite extension in N1E-115 and SH-SY5Y neuroblastoma cells, suggesting a role for Gem in cytoskeletal rearrangement and/or morphological differentiation of neurons. Consistent with this potential function, in clinical samples of neuroblastoma, Gem protein was most highly expressed within cells which had differentiated to express ganglionic morphology. Gem was also observed in developing trigeminal nerve ganglia in 12.5 day mouse embryos, demonstrating that Gem expression is a property of normal ganglionic development. Although Gem expression is rare in epithelial and hematopoietic cancer cell lines, constitutive Gem levels were detected in several neuroblastoma cell lines and could be further induced as much as 10-fold following treatment with PMA or the acetylcholine muscarinic agonist, carbachol.

Synthesis, spectroscopy, magnetic and redox behaviors of copper(II) complexes with tert-butylated salen type ligands bearing bis(4-aminophenyl)ethane and bis(4-aminophenyl)amide backbones.

PubMed

Kasumov, Veli T; Yerli, Yusuf; Kutluay, Aysegul; Aslanoglu, Mehmet

2013-03-01

New salen type ligands, N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-ethylenedianiline [(X=H (1), 5-tert-butyl (2)] and N,N'-bis(X-3-tert-butylsalicylidene)-4,4'-amidedianiline [X=H (3), 5-tert (4)] and their copper(II) complexes 5-8, have been synthesized. Their spectroscopic (IR, (1)H NMR, UV/vis, ESR) properties, as well as magnetic and redox-reactivity behavior are reported. IR spectra of 7 and 8 indicate the coordination of amide oxygen atoms of 3 and 4 ligands to Cu(II). The solid state ESR spectra of 5-8 exhibits less informative exchange narrowed isotropic or anisotropic signals with weak unresolved low field patterns. The magnetic moments of 5 (2.92 μ(B) per Cu(II)) and 6 (2.79 μ(B) per Cu(II)) are unusual for copper(II) complexes and considerably higher than those for complexes 7 and 8. Cryogenic measurements (300-10 K) show weak antiferromagnetic exchange interactions between the copper(II) centers in complexes 6 and 8. The results of electrochemical and chemical redox-reactivity studies are discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

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

Manna, Kuntal

The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C 5Hmore » 5)(Ox R) 2] [Ox R = Ox 4S-iPr,Me2, Ox 4R-iPr,Me2, Ox 4S-tBu]. These optically active proligands react with an equivalent of M(NMe 2) 4 (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C 5H 4)(Ox R) 2}M(NMe 2) 2 in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C-N/C-H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C 5H 4)(Ox4 S-iPr,Me2) 2}Zr(NMe 2) 2 ({S-2}Zr(NMe 2) 2) displays highest activity and enantioselectivity. Interestingly, S-2Zr(NMe 2) 2 also desymmetrizes olefin moieties of achiral non-conjugated aminodienes and aminodiynes during cyclization. The cyclization of aminodienes catalyzed by S-2Zr(NMe 2) 2 affords diastereomeric mixture of cis and trans cylic amines

Comparison of Zirconium Phosphonate-Modified Surfaces for Immobilizing Phosphopeptides and Phosphate-Tagged Proteins.

PubMed

Forato, Florian; Liu, Hao; Benoit, Roland; Fayon, Franck; Charlier, Cathy; Fateh, Amina; Defontaine, Alain; Tellier, Charles; Talham, Daniel R; Queffélec, Clémence; Bujoli, Bruno

2016-06-07

Different routes for preparing zirconium phosphonate-modified surfaces for immobilizing biomolecular probes are compared. Two chemical-modification approaches were explored to form self-assembled monolayers on commercially available primary amine-functionalized slides, and the resulting surfaces were compared to well-characterized zirconium phosphonate monolayer-modified supports prepared using Langmuir-Blodgett methods. When using POCl3 as the amine phosphorylating agent followed by treatment with zirconyl chloride, the result was not a zirconium-phosphonate monolayer, as commonly assumed in the literature, but rather the process gives adsorbed zirconium oxide/hydroxide species and to a lower extent adsorbed zirconium phosphate and/or phosphonate. Reactions giving rise to these products were modeled in homogeneous-phase studies. Nevertheless, each of the three modified surfaces effectively immobilized phosphopeptides and phosphopeptide tags fused to an affinity protein. Unexpectedly, the zirconium oxide/hydroxide modified surface, formed by treating the amine-coated slides with POCl3/Zr(4+), afforded better immobilization of the peptides and proteins and efficient capture of their targets.

3D Observation of GEMS by Electron Tomography

NASA Technical Reports Server (NTRS)

Matsuno, Junya; Miyake, Akira; Tsuchiyama, Akira; Nakamura-Messenger, Keiko; Messenger, Scott

2014-01-01

Amorphous silicates in chondritic porous interplanetary dust particles (CP-IDPs) coming from comets are dominated by glass with embedded metal and sulfides (GEMS). GEMS grains are submicron-sized rounded objects (typically 100-500) nm in diameter) with anaometer-sized (10-50 nm) Fe-Ni metal and sulfide grains embedded in an amorphous silicate matrix. Several formation processes for GEMS grains have been proposed so far, but these models are still being debated [2-5]. Bradley et al. proposed that GEMS grains are interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk and that they are amorphiation products of crystalline silicates in the interstellar medium by sputter-deposition of cosmic ray irradiation, similar to space weathering [2,4]. This consideration is based on the observation of nano-sized crystals (approximately 10 nm) called relict grains in GEMS grains and their shapes are pseudomorphs to the host GEMS grains. On the other hand, Keller and Messenger proposed that most GEMS formed in the protoplanetary disk as condensates from high temperature gas [3,5]. This model is based on the fact that most GEMS grains have solar isotopic compositions and have extremely heterogeneous and non-solar elemental compositions. Keller and Messenger (2011) also reported that amorphous silicates in GEMS grains are surrounded by sulfide grains, which formed as sulfidization of metallic iron grains located on the GEMS surface. The previous studies were performed with 2D observation by using transmission electron microscopy (TEM) or scanning TEM (STEM). In order to understand the structure of GEMS grains described above more clearly, we observed 3D structure of GEMS grains by electron tomography using a TEM/STEM (JEM-2100F, JEOL) at Kyoto University. Electron tomography gives not only 3D structures but also gives higher spatial resolution (approximately a few nm) than that in conventional 2D image, which is restricted by

Hydrogenation of CO 2 in Water Using a Bis(diphosphine) Ni–H Complex

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

Burgess, Samantha A.; Kendall, Alexander J.; Tyler, David R.

2017-03-17

The water soluble Ni bis(diphosphine) complex [NiL2](BF4)2 (L = 1,2- bis(di(methoxypropyl)phosphino)ethane) and the corresponding hydride, [HNiL2]BF4, were synthesized and characterized. For HNiL2+, the hydricity was determined to be 23.2(3) kcal/mol in aqueous solution. Based on the hydricity of formate of 24.1 kcal/mol, the transfer of a hydride from HNiL2 + to CO2 to produce formate is favorable by 1 kcal/mol. Starting from either NiL2 2+ or HNiL2 + in water, catalytic hydrogenation of CO2 was observed with NaHCO3 (0.8 M) as the only additive. A maximum turnover frequency of 3.6(8) h–1 was observed at 80 °C and 51 atm ofmore » a 1:1 mixture of CO2 and H2.« less

Synthesis, Spectroscopic, and Antimicrobial Studies on Bivalent Nickel and Copper Complexes of Bis(thiosemicrbazone)

PubMed Central

Chandra, Sulekh; Raizada, Smriti; Tyagi, Monika; Gautam, Archana

2007-01-01

A series of metal complexes of Cu(II) and Ni(II) having the general composition [M(L)X2] with benzil bis(thiosemicarbazone) has been prepared and characterized by element chemical analysis, molar conductance, magnetic susceptibility measurements, and spectral (electronic, IR, EPR, mass) studies. The IR spectral data suggest the involvement of sulphur and azomethane nitrogen in coordination to the central metal ion. On the basis of spectral studies, an octahedral geometry has been assigned for Ni(II) complexes but a tetragonal geometry for Cu(II) complexes. The free ligand and its metal complexes have been tested in vitro against a number of microorganisms in order to assess their antimicrobial properties. PMID:18273385

Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(III) amine-bis(phenolate) complex.

PubMed

Dean, Rebecca K; Devaine-Pressing, Katalin; Dawe, Louise N; Kozak, Christopher M

2013-07-07

A diamine-bis(phenolate) chromium(III) complex, {CrCl[O2NN'](BuBu)}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.

Gravity model improvement using GEOS-3 (GEM 9 and 10)

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Klosko, S. M.; Laubscher, R. E.; Wagner, C. A.

1977-01-01

The use of collocation permitted GEM 9 to be a larger field than previous derived satellite models, GEM 9 having harmonics complete to 20 x 20 with selected higher degree terms. The satellite data set has approximately 840,000 observations, of which 200,000 are laser ranges taken on 9 satellites equipped with retroreflectors. GEM 10 is complete to 22 x 22 with selected higher degree terms out to degree and order 30 amounting to a total of 592 coefficients. Comparisons with surface gravity and altimeter data indicate a substantial improvement in GEM 9 over previous satellite solutions; GEM 9 is in even closer agreement with surface data than the previously published GEM 6 solution which contained surface gravity. In particular the free air gravity anomalies calculated from GEM 9 and a surface gravity solution are in excellent agreement for the high degree terms.

GEM Detector Performance Assessment in the BM@N Experiment

NASA Astrophysics Data System (ADS)

Kapishin, Mikhail; Karjavin, Vladimir; Kulish, Elena; Lenivenko, Vasilisa; Makankin, Alexander; Maksymchuk, Anna; Palichik, Vladimir; Vasiliev, Sergey

2018-02-01

The Gas Electron Multiplier (GEM) chambers are developed for modern purposes in the elementary particle physics. In the BM@N experiment, a GEM system is used for the reconstruction of the trajectories of the charged particles. The investigation of GEM performance (efficiency and spatial resolution) is presented.

Two-Electron Carbon Dioxide Reduction Catalyzed by Rhenium(I) Bis(imino)acenaphthene Carbonyl Complexes

PubMed Central

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-01-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile–water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. PMID:24737649

Perfluoroalkyl phosphonic and phosphinic acids as proton conductors for anhydrous proton-exchange membranes.

PubMed

Herath, Mahesha B; Creager, Stephen E; Kitaygorodskiy, Alex; DesMarteau, Darryl D

2010-09-10

A study of proton-transport rates and mechanisms under anhydrous conditions using a series of acid model compounds, analogous to comb-branch perfluorinated ionomers functionalized with phosphonic, phosphinic, sulfonic, and carboxylic acid protogenic groups, is reported. Model compounds are characterized with respect to proton conductivity, viscosity, proton, and anion (conjugate base) self-diffusion coefficients, and Hammett acidity. The highest conductivities, and also the highest viscosities, are observed for the phosphonic and phosphinic acid model compounds. Arrhenius analysis of conductivity and viscosity for these two acids reveals much lower activation energies for ion transport than for viscous flow. Additionally, the proton self-diffusion coefficients are much higher than the conjugate-base self-diffusion coefficients for these two acids. Taken together, these data suggest that anhydrous proton transport in the phosphonic and phosphinic acid model compounds occurs primarily by a structure-diffusion, hopping-based mechanism rather than a vehicle mechanism. Further analysis of ionic conductivity and ion self-diffusion rates by using the Nernst-Einstein equation reveals that the phosphonic and phosphinic acid model compounds are relatively highly dissociated even under anhydrous conditions. In contrast, sulfonic and carboxylic acid-based systems exhibit relatively low degrees of dissociation under anhydrous conditions. These findings suggest that fluoroalkyl phosphonic and phosphinic acids are good candidates for further development as anhydrous, high-temperature proton conductors.

Solution structure of a DNA complex with the fluorescent bis-intercalator TOTO determined by NMR spectroscopy.

PubMed

Spielmann, H P; Wemmer, D E; Jacobsen, J P

1995-07-11

We have used two-dimensional 1H NMR spectroscopy to determine the solution structure of the DNA oligonucleotide d(5'-CGCTAGCG-3')2 complexed with the bis-intercalating dye 1,1'-(4,4,8,8-tetramethyl-4,8-diazaundecamethylene)bis[4-(3-methyl -2,3- dihydrobenzo-1,3-thiazolyl-2-methylidene)qui nolinium] tetraiodide (TOTO). The determination of the structure was based on total relaxation matrix analysis of the NOESY cross-peak intensities using the program MARDIGRAS. Improved procedures to consider the experimental "noise" in NOESY spectra during these calculations have been employed. The NOE-derived distance restraints were applied in restrained molecular dynamics calculations. Twenty final structures each were generated for the TOTO complex from both A-form and B-form dsDNA starting structures. The root-mean-square (rms) deviation of the coordinates for the 40 structures of the complex was 1.45 A. The local DNA structure is distorted in the complex. The helix is unwound by 60 degrees and has an overall helical repeat of 12 base pairs, caused by bis-intercalation of TOTO. The poly(propylenamine) linker chain is located in the minor groove of dsDNA. Calculations indicate that the benzothiazole ring system is twisted relative to the quinoline in the uncomplexed TOTO molecule. The site selectivity of TOTO for the CTAG-CTAG site is explained by its ability to adapt to the base pair propeller twist of dsDNA to optimize stacking and the hydrophobic interaction between the thymidine methyl group and the benzothiazole ring. There is a 3000-fold fluorescence enhancement upon binding of TOTO to dsDNA. Rotation about the cyanine methine bonds is possible in free TOTO, allowing relaxation nonradiatively. When bound to dsDNA, the benzothiazole ring and the quinolinium ring are clamped by the nucleobases preventing this rotation, and the chromophore loses excitation energy by fluorescence instead.

Removal of phosphonates from industrial wastewater with UV/FeII, Fenton and UV/Fenton treatment.

PubMed

Rott, Eduard; Minke, Ralf; Bali, Ulusoy; Steinmetz, Heidrun

2017-10-01

Phosphonates are an important group of phosphorus-containing compounds due to their increasing industrial use and possible eutrophication potential. This study involves investigations into the methods UV/Fe II , Fenton and UV/Fenton for their removal from a pure water matrix and industrial wastewaters. It could be shown that the degradability of phosphonates by UV/Fe II (6 kWh/m 3 ) in pure water crucially depended on the pH and was higher the less phosphonate groups a phosphonate contains. The UV/Fe II method is recommended in particular for the treatment of concentrates with nitrogen-free phosphonates, only little turbidity and a low content of organic compounds. Using Fenton reagent, the degradation of polyphosphonates was relatively weak in a pure water matrix (<20% transformation to o-PO 4 3- ). By means of the Photo-Fenton method (6 kWh/m 3 ), those phosphonates with the smallest numbers of phosphonate groups were easier degraded as well at pH 3.5 in a pure water matrix (o-PO 4 3- formation rates of up to 80%). Despite an incomplete transformation of organically bound phosphorus to o-PO 4 3- with Fenton reagent in an organically highly polluted wastewater (max. 15%), an almost total removal of the total P occurred. The most efficient total P elimination rates were achieved in accordance with the following Fenton implementation: reaction → sludge separation (acidic) → neutralization of the supernatant → sludge separation (neutral). Accordingly, a neutralization directly after the reaction phase led to a lower total P removal extent. Copyright © 2017 Elsevier Ltd. All rights reserved.

40 CFR 721.10370 - Phosphonic acid, p-octyl-, lanthanum (3+) salt (2:1).

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Phosphonic acid, p-octyl-, lanthanum... New Uses for Specific Chemical Substances § 721.10370 Phosphonic acid, p-octyl-, lanthanum (3+) salt... substance identified as phosphinic acid, p-octyl-, lanthanum (3+) salt (2:1) (PMN P-10-99; CAS No. 1186211...

40 CFR 721.10370 - Phosphonic acid, p-octyl-, lanthanum (3+) salt (2:1).

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Phosphonic acid, p-octyl-, lanthanum... New Uses for Specific Chemical Substances § 721.10370 Phosphonic acid, p-octyl-, lanthanum (3+) salt... substance identified as phosphinic acid, p-octyl-, lanthanum (3+) salt (2:1) (PMN P-10-99; CAS No. 1186211...

40 CFR 721.10370 - Phosphonic acid, p-octyl-, lanthanum (3+) salt (2:1).

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Phosphonic acid, p-octyl-, lanthanum... New Uses for Specific Chemical Substances § 721.10370 Phosphonic acid, p-octyl-, lanthanum (3+) salt... substance identified as phosphinic acid, p-octyl-, lanthanum (3+) salt (2:1) (PMN P-10-99; CAS No. 1186211...

Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations

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

Eedugurala, Naresh; Hovey, Megan; Ho, Hung -An

Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(Ox Me2) 2C 5H 5 (Bo MCpH; Ox Me2 = 4,4-dimethyl-2-oxazoline) and MeC(Ox Me2) 2C 5Me 4H (Bo MCp tetH) are synthesized from C 5R 4HI (R = H, Me) and MeC(Ox Me2) 2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. Bo MCpH and Bo MCp tetH react with MgMe 2(O 2C 4H 8)more » 2 to give the magnesium methyl complexes {Bo MCp}MgMe and {Bo MCp tet}MgMe. Bo MCpH and Bo MCp tetH are converted to Bo MCpTl and Bo MCp tetTl by reaction with TlOEt. The thallium derivatives react with TiCl 3(THF) 3 to provide [{Bo MCp}TiCl(μ-Cl)] 2 and [{Bo MCptet}TiCl(μ-Cl)] 2, the former of which is crystallographically characterized as a dimeric species. Bo MCpH and Zr(NMe 2) 4 react to eliminate dimethylamine and afford {Bo MCp}Zr(NMe 2) 3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {Bo MCp}Zr(NMe 2) 3, {Bo MCp}MgMe, and {Bo MCp tet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.« less

Cyclopentadienyl-bis(oxazoline) magnesium and zirconium complexes in aminoalkene hydroaminations

DOE PAGES

Eedugurala, Naresh; Hovey, Megan; Ho, Hung -An; ...

2015-11-25

Here, a new class of cyclopentadiene-bis(oxazoline) compounds and their piano-stool-type organometallic complexes have been prepared as catalysts for hydroamination of aminoalkenes. The two compounds MeC(Ox Me2) 2C 5H 5 (Bo MCpH; Ox Me2 = 4,4-dimethyl-2-oxazoline) and MeC(Ox Me2) 2C 5Me 4H (Bo MCp tetH) are synthesized from C 5R 4HI (R = H, Me) and MeC(Ox Me2) 2Li. These cyclopentadiene-bis(oxazolines) are converted into ligands that support a variety of metal centers in piano-stool-type geometries, and here we report the preparation of Mg, Tl, Ti, and Zr compounds. Bo MCpH and Bo MCp tetH react with MgMe 2(O 2C 4H 8)more » 2 to give the magnesium methyl complexes {Bo MCp}MgMe and {Bo MCp tet}MgMe. Bo MCpH and Bo MCp tetH are converted to Bo MCpTl and Bo MCp tetTl by reaction with TlOEt. The thallium derivatives react with TiCl 3(THF) 3 to provide [{Bo MCp}TiCl(μ-Cl)] 2 and [{Bo MCptet}TiCl(μ-Cl)] 2, the former of which is crystallographically characterized as a dimeric species. Bo MCpH and Zr(NMe 2) 4 react to eliminate dimethylamine and afford {Bo MCp}Zr(NMe 2) 3, which is crystallographically characterized as a monomeric four-legged piano-stool compound. {Bo MCp}Zr(NMe 2) 3, {Bo MCp}MgMe, and {Bo MCp tet}MgMe are efficient catalysts for the hydroamination/cyclization of aminoalkenes under mild conditions.« less

A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

PubMed

Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

2013-03-01

The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

ATR-FTIR spectroscopic investigation of the cis- and trans-bis-(α-amino acids) copper(II) complexes

NASA Astrophysics Data System (ADS)

Berestova, Tatyana V.; Kuzina, Lyudmila G.; Amineva, Natalya A.; Faizrakhmanov, Ilshat S.; Massalimov, Ismail A.; Mustafin, Akhat G.

2017-06-01

The crystalline phases of the trans-(a) and cis-(b)-isomers of bis-(α-amino acids) copper(II) complexes [Cu(bL)2] 1-5 (bL - bidentate ligand: gly (1), S-ala (2), R,S-val (3), (±)-thr (4), R,S-phe (5)) were studied by ATR-FTIR spectroscopy in the mid region IR spectrum. It was established that asymmetric νas(COO) and symmetric νs(COO) stretching vibrations of carboxylic groups of 1-5 are sensitive to change of the geometric structure and have a different maxima for the trans(a)- and cis(b)-isomers. It found that νas(COO) and νs(COO) stretching vibrations of cis-isomers are broadened and shifted to longer wavelengths (b) as compared with trans-isomers (a). Shown that peculiarities of crystal packing molecules of geometric isomers may affect on carboxylate stretching vibration bis-α-amino acids complexes copper(II) 1-5 a,b.

Measurement Of Gas Electron Multiplier (GEM) Detector Characteristics

NASA Astrophysics Data System (ADS)

Park, Seongtae; Baldelomar, Edwin; Park, Kwangjune; Sosebee, Mark; White, Andy; Yu, Jaehoon

2011-06-01

The High Energy Physics group of the University of Texas at Arlington has been developing gas electron multiplier detectors to use them as sensitive gap detectors in digital hadron calorimeters for the International Linear Collider, a future high energy particle accelerator. For this purpose, we constructed numerous GEM detectors that employ double GEM layers. In this study, two kinds of prototype GEM detectors were tested; one with 28×28 cm2 active area double GEM structure with a 3 mm drift gap, a 1 mm transfer gap and a 1 mm induction gap and the other with two 3×3 cm2 GEM foils in the amplifier stage with a 5 mm drift gap, a 2 mm transfer gap and a 1 mm induction gap. The detectors' characteristics from exposure to high-energy charged particles and other radiations were measured using cosmic rays and 55Fe radioactive source. From the 55Fe tests, we observed two well separated characteristic X-ray emission peaks and confirmed the detectors' functionality. We also measured chamber gains to be over 6000 at a high voltage of 395 V across each GEM electrode. The responses to cosmic rays show the spectra that fit well to Landau distributions as expected from minimum ionizing particles.

Syntheses, crystal structures and characterizations of new zinc (II) and lead (II) carboxylate-phosphonates

NASA Astrophysics Data System (ADS)

Song, Jun-Ling; Mao, Jiang-Gao

2005-04-01

The syntheses, crystal structures and characterizations of two new divalent metal carboxylate-phosphonates, namely, Zn(H 3L)·2H 2O ( 1) and Pb(H 3L)(H 2O) 2 ( 2) (H 5L dbnd6 4-HO 2C-C 6H 4-CH 2N(CH 2PO 3H 2) 2) have been reported. Compound 1 features a 1D column structure in which the Zn(II) ions are tetrahedrally coordinated by four phosphonate oxygen atoms from four phosphonate ligands, and neighboring such 1D building blocks are further interconnected via hydrogen bonds into a 3D network. The carboxylate group of H 3L anion remains non-coordinated. Compound 2 has a 2D layer structure. Pb(II) ion is 7-coordinated by four phosphonate oxygen atoms from four phosphonate ligands and three aqua ligands. The interconnection of Pb(II) ions via bridging H 3L anions results in a <001> layer. The carboxylate group of the H 3L anion also remains non-coordinated and is oriented toward the interlayer space. Solid state luminescent spectrum of compound 1 exhibits a strong broad blue fluorescent emission band at 455 nm under excitation at 365 nm at room temperature.

openBIS: a flexible framework for managing and analyzing complex data in biology research

PubMed Central

2011-01-01

Background Modern data generation techniques used in distributed systems biology research projects often create datasets of enormous size and diversity. We argue that in order to overcome the challenge of managing those large quantitative datasets and maximise the biological information extracted from them, a sound information system is required. Ease of integration with data analysis pipelines and other computational tools is a key requirement for it. Results We have developed openBIS, an open source software framework for constructing user-friendly, scalable and powerful information systems for data and metadata acquired in biological experiments. openBIS enables users to collect, integrate, share, publish data and to connect to data processing pipelines. This framework can be extended and has been customized for different data types acquired by a range of technologies. Conclusions openBIS is currently being used by several SystemsX.ch and EU projects applying mass spectrometric measurements of metabolites and proteins, High Content Screening, or Next Generation Sequencing technologies. The attributes that make it interesting to a large research community involved in systems biology projects include versatility, simplicity in deployment, scalability to very large data, flexibility to handle any biological data type and extensibility to the needs of any research domain. PMID:22151573

The GEMS-2 SEIS Experiment

NASA Astrophysics Data System (ADS)

Tillier, S.; De Raucourt, S.; Mimoun, D.; Lognonne, P.; Giardini, D.; Christensen, U. R.; Pike, W. T.; Banerdt, B.; Laudet, P.; Kerjean, L.; Hurst, K. J.; Zweifel, P.; Mance, D.; Roll, R.; Bierwirth, M.; Gagnepain-Beyneix, J.; Nibut, T.; Robert, O.; Gabsi, T.; Pot, O.; Lecomte, B.; Schibler, P.; Mocquet, A.; Garcia, R.

2011-12-01

overall mass of the SEIS instrument is about 9.6 kg, including all sensors, data control processors and installation devices, while power consumption is not exceeding 2W. The proposed instrument has been developed up to PDR in the frame of the ExoMars Humbold payload, and further developments were achieved in the frame of the Japanese SELENE2 project. Most critical parts have been tested, including shock tests for pivots, electronics components and displacement sensors. TRL 6 is expected at the end of 2011. The GEMS phase A will end by March 2012, and the final NASA continuation decision is due in June 2012. GEMS is planned to be launched in 2016.

Complete Tem-Tomography: 3D Structure of Gems Cluster

NASA Technical Reports Server (NTRS)

Matsuno, J.; Miyake, A.; Tsuchiyama, A.; Messenger, S.; Nakamura-Messenger, K.

2015-01-01

GEMS (glass with embedded metal and sulfide) grains in interplanetary dust particles (IDPs) are considered to be one of the ubiquitous and fundamental building blocks of solids in the Solar System. They have been considered to be interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk but the elemental and isotopic composition measurements suggest that most of them have been formed in the protoplanetary disk as condensates from high temperature gas. This formation model is also supported by the formation of GEMS-like grains with respect to the size, mineral assemblage, texture and infrared spectrum by condensation experiments from mean GEMS composition materials. Previous GEMS studies were performed only with 2D observation by transmission electron microscopy (TEM) or scanning TEM (STEM). However, the 3D shape and structure of GEMS grains and the spatial distribution of Fe/FeS's has critical information about their formation and origin. Recently, the 3D structure of GEMS grains in ultrathin sections of cluster IDPs was revealed by electron tomography using a TEM/STEM (JEM-2100F, JEOL). However, CT images of thin sections mounted on Cu grids acquired by conventional TEM-tomography are limited to low tilt angles (e. g., less than absolute value of 75 deg. In fact, previous 3D TEM observations of GEMS were affected by some artifacts related to the limited tilt range in the TEM used. Complete tomographic images should be acquired by rotating the sample tilt angle over a range of more than absolute value of 80 deg otherwise the CT images lose their correct structures. In order to constrain the origin and formation process of GEMS grains more clearly, we performed complete electron tomography for GEMS grains. Here we report the sample preparation method we have developed for this study, and the preliminary results.

Intermediate temperature proton conductors for PEM fuel cells based on phosphonic acid as protogenic group: a progress report.

PubMed

Steininger, H; Schuster, M; Kreuer, K D; Kaltbeitzel, A; Bingöl, B; Meyer, W H; Schauff, S; Brunklaus, G; Maier, J; Spiess, H W

2007-04-21

The melting behaviour and transport properties of straight chain alkanes mono- and difunctionalized with phosphonic acid groups have been investigated as a function of their length. The increase of melting temperature and decrease of proton conductivity with increasing chain length is suggested to be the consequence of an increasing ordering of the alkane segments which constrains the free aggregation of the phosphonic acid groups. However, the proton mobility is reduced to a greater extent than the proton diffusion coefficient indicating an increasing cooperativity of proton transport with increasing length of the alkane segment. The results clearly indicate that the "spacer concept", which had been proven successful in the optimization of the proton conductivity of heterocycle based systems, fails in the case of phosphonic acid functionalized polymers. Instead, a very high concentration of phosphonic acid functional groups forming "bulky" hydrogen bonded aggregates is suggested to be essential for obtaining very high proton conductivity. Aggregation is also suggested to reduce condensation reactions generally observed in phosphonic acid containing systems. On the basis of this understanding, the proton conductivities of poly(vinyl phosphonic acid) and poly(meta-phenylene phosphonic acid) are discussed. Though both polymers exhibit a substantial concentration of phosphonic acid groups, aggregation seems to be constrained to such an extent that intrinsic proton conductivity is limited to values below sigma = 10(-3) S cm(-1) at T = 150 degrees C. The results suggest that different immobilization concepts have to be developed in order to minimize the conductivity reduction compared to the very high intrinsic proton conductivity of neat phosphonic acid under quasi dry conditions. In the presence of high water activities, however, (as usually present in PEM fuel cells) the very high ion exchange capacities (IEC) possible for phosphonic acid functionalized ionomers (IEC

The determination of the orbit of the Japanese satellite Ajisai and the GEM-T1 and GEM-T2 gravity field models

NASA Technical Reports Server (NTRS)

Sanchez, Braulio V.

1990-01-01

The Japanese Experimental Geodetic Satellite Ajisai was launched on August 12, 1986. In response to the TOPEX-POSEIDON mission requirements, the GSFC Space Geodesy Branch and its associates are producing improved models of the Earth's gravitational field. With the launch of Ajisai, precise laser data is now available which can be used to test many current gravity models. The testing of the various gravity field models show improvements of more than 70 percent in the orbital fits when using GEM-T1 and GEM-T2 relative to results obtained with the earlier GEM-10B model. The GEM-T2 orbital fits are at the 13-cm level (RMS). The results of the tests with the various versions of the GEM-T1 model indicate that the addition of satellite altimetry and surface gravity anomalies as additional data types should improve future gravity field models.

Probing the interaction of U (VI) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy

DOE PAGES

Uribe, Eva C.; Mason, Harris E.; Shusterman, Jennifer A.; ...

2016-05-30

The fundamental interaction of U (VI) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U (VI) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse 31P NMR on U (VI) contacted samples revealed that U (VI)only interacts with a fraction of the ligands present on the surface. At pH 4 the U (VI) extraction capacity of the material is limited to 27–37% of the theoretical capacity, based on ligand loading. We combined single pulse 31Pmore » NMR on U (VI)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U (VI) binds to deprotonated phosphonate and/or silanol sites. We use 31P– 31P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U (VI)-complexed and non-complexed ligand environments. Furthermore, these measurements reveal that U (VI) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.« less

Probing the interaction of U (VI) with phosphonate-functionalized mesoporous silica using solid-state NMR spectroscopy

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

Uribe, Eva C.; Mason, Harris E.; Shusterman, Jennifer A.

The fundamental interaction of U (VI) with diethylphosphatoethyl triethoxysilane functionalized SBA-15 mesoporous silica is studied by macroscopic batch experiments and solid-state NMR spectroscopy. DPTS-functionalized silica has been shown to extract U (VI) from nitric acid solutions at or above pH 3. Extraction is dependent on pH and ionic strength. Single-pulse 31P NMR on U (VI) contacted samples revealed that U (VI)only interacts with a fraction of the ligands present on the surface. At pH 4 the U (VI) extraction capacity of the material is limited to 27–37% of the theoretical capacity, based on ligand loading. We combined single pulse 31Pmore » NMR on U (VI)-contacted samples with batch studies to measure a ligand-to-metal ratio of approximately 2 : 1 at pH 3 and 4. Batch studies and cross-polarization NMR measurements reveal that U (VI) binds to deprotonated phosphonate and/or silanol sites. We use 31P– 31P DQ-DRENAR NMR studies to compare the average dipolar coupling between phosphorus spins for both U (VI)-complexed and non-complexed ligand environments. Furthermore, these measurements reveal that U (VI) extraction is not limited by inadequate surface distribution of ligands, but rather by low stability of the surface phosphonate complex.« less

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

PubMed

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

2010-10-18

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

Phosphonic Acids on an Atomically Defined Oxide Surface: The Binding Motif Changes with Surface Coverage.

PubMed

Schuschke, Christian; Schwarz, Matthias; Hohner, Chantal; Silva, Thais N; Fromm, Lukas; Döpper, Tibor; Görling, Andreas; Libuda, Jörg

2018-04-19

We have studied the anchoring mechanism of a phosphonic acid on an atomically defined oxide surface. Using time-resolved infrared reflection absorption spectroscopy, we investigated the reaction of deuterated phenylphosphonic acid (DPPA, C 6 H 5 PO 3 D 2 ) with an atomically defined Co 3 O 4 (111) surface in situ during film growth by physical vapor deposition. We show that the binding motif of the phosphonate anchor group changes as a function of coverage. At low coverage, DPPA binds in the form of a chelating tridentate phosphonate, while a transition to a chelating bidentate occurs close to monolayer saturation coverage. However, the coverage-dependent change in the binding motif is not associated with a major change of the molecular orientation, suggesting that the rigid phosphonate linker always maintains the DPPA in a strongly tilted orientation irrespective of the surface coverage.

Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.

PubMed

Melomedov, Jascha; Wünsche von Leupoldt, Anica; Meister, Michael; Laquai, Frédéric; Heinze, Katja

2013-07-14

New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy in combination with DFT/PCM calculations on diamagnetic neutral bis(porphyrins) 4 and on respective charged mixed-valent radicals 4(+/-). The interaction via the -C6H4-NHCO-C6H4- bridge, the site of oxidation and reduction and the lowest excited singlet state S1, is tuned by the substituents on the individual porphyrins and the metalation state.

Gas electron multiplier (GEM) foil test, repair and effective gain calculation

NASA Astrophysics Data System (ADS)

Tahir, Muhammad; Zubair, Muhammad; Khan, Tufail A.; Khan, Ashfaq; Malook, Asad

2018-06-01

The focus of my research is based on the gas electron multiplier (GEM) foil test, repairing and effective gain calculation of GEM detector. During my research work define procedure of GEM foil testing short-circuit, detection short-circuits in the foil. Study different ways to remove the short circuits in the foils. Set and define the GEM foil testing procedures in the open air, and with nitrogen gas. Measure the leakage current of the foil and applying different voltages with specified step size. Define the Quality Control (QC) tests and different components of GEM detectors before assembly. Calculate the effective gain of GEM detectors using 109Cd and 55Fe radioactive source.

GEM at 10: a decade's experience with the Guideline Elements Model.

PubMed

Hajizadeh, Negin; Kashyap, Nitu; Michel, George; Shiffman, Richard N

2011-01-01

The Guideline Elements Model (GEM) was developed in 2000 to organize the information contained in clinical practice guidelines using XML and to represent guideline content in a form that can be understood by human readers and processed by computers. In this work, we systematically reviewed the literature to better understand how GEM was being used, potential barriers to its use, and suggestions for improvement. Fifty external and twelve internally produced publications were identified and analyzed. GEM was used most commonly for modeling and ontology creation. Other investigators applied GEM for knowledge extraction and data mining, for clinical decision support for guideline generation. The GEM Cutter software-used to markup guidelines for translation into XML- has been downloaded 563 times since 2000. Although many investigators found GEM to be valuable, others critiqued its failure to clarify guideline semantics, difficulties in markup, and the fact that GEM files are not usually executable.

Mono- and bis-tolylterpyridine iridium(III) complexes

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

Hinkle, Lindsay M.; Young, Jr., Victor G.; Mann, Kent R.

The first structure report of trichlorido[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl{sub 3}(C{sub 22}H{sub 17}N{sub 3})] {center_dot} C{sub 2}H{sub 6}OS, (I), is presented, along with a higher-symmetry setting of previously reported bis[4'-(p-tolyl)-2,2':6',2{double_prime}-terpyridine]iridium(III) tris(hexafluoridophosphate) acetonitrile disolvate, [Ir(C{sub 22}H{sub 17}N{sub 3})2](PF{sub 6}){sub 3} {center_dot} 2C{sub 2}H{sub 3}N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007). Eur. J. Inorg. Chem. pp. 1911-1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent molecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group.more » The iridium complex and one PF{sub 6}{sup -} anion lie on twofold axes in this structure, making half of the molecule unique.« less

Developmental Toxicity of Perfluorinated Phosphonic Acids in Mice

EPA Science Inventory

Perfluorinated phosphonic acids (PFPAs) are a third member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. PFPAs are used primarily as a surfactant defoaming agent in pesticide production. Re...

Method and apparatus for detecting gem-polyhalogenated hydrocarbons

DOEpatents

Anderson, deceased, William G.; Anderson, legal representative, Johanna S.

1990-01-01

A method and optrode for detecting gem polyhalogenated hydrocarbons in a sample fluid based on a single phase Fujiwara reaction as provided. The method comprises contacting a reaction mixture with a sample fluid which contains the gem-polyhalogenated hydrocarbons. The reaction mixture comprises an aqueous solution of pyridine or derivative thereof and a hindered nitrogen base. Upon contact a fluorescent and/or chromgenic reaction product forms whose fluorescence and/or absorbance is related to the concentration of gem-polyhalogenated hydrocarbons in the sample fluid.

Seasonal Expression of the Picocyanobacterial Phosphonate Transporter Gene phnD in the Sargasso Sea

PubMed Central

Ilikchyan, Irina N.; McKay, Robert Michael L.; Kutovaya, Olga A.; Condon, Rob; Bullerjahn, George S.

2010-01-01

In phosphorus-limited marine environments, picocyanobacteria (Synechococcus and Prochlorococcus spp.) can hydrolyze naturally occurring phosphonates as a P source. Utilization of 2-aminoethylphosphonate (2-AEP) is dependent on expression of the phn genes, encoding functions required for uptake, and C–P bond cleavage. Prior work has indicated that expression of picocyanobacterial phnD, encoding the phosphonate binding protein of the phosphonate ABC transporter, is a proxy for the assimilation of phosphonates in natural assemblages of Synechococcus spp. and Prochlorococcus spp (Ilikchyan et al., 2009). In this study, we expand this work to assess seasonal phnD expression in the Sargasso Sea. By RT-PCR, our data confirm that phnD expression is constitutive for the Prochlorococcus spp. detected, but in Synechococcus spp. phnD transcription follows patterns of phosphorus availability in the mixed layer. Specifically, our data suggest that phnD is repressed in the spring when P is bioavailable following deep winter mixing. In the fall, phnD expression follows a depth-dependent pattern reflecting depleted P at the surface following summertime drawdown, and elevated P at depth. PMID:21687717

Development of Resistive Electrode Gas Electron Multiplier (RE-GEM)

NASA Technical Reports Server (NTRS)

Yoshikawa, A.; Tamagawa, T.; Iwahashi, T.; Asami, F.; Takeuchi, Y.; Hayato, A.; Hamagaki, H.; Gunji, T.; Akimoto, R.; Nukariya, A.;

Gravitational field modes GEM 3 and 4

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Wagner, C. A.; Putney, B. H.; Sandson, M. L.; Brownd, J. E.; Richardson, J. A.; Taylor, W. A.

1972-01-01

A refinement in the satellite geopotential solution for a Goddard Earth Model (GEM 3) was obtained. The solution includes the addition of two low inclination satellites, SAS at 3 deg and PEOLE at 15 deg, and is based upon 27 close earth satellites containing some 400,000 observations of electronic, laser, and optical data. In addition, a new combination satellite/gravimetry solution (GEM 4) was derived. The new model includes 61 center of mass tracking station locations with data from GRARR, Laser, MOTS, Baker-Nunn, and NWL Tranet Doppler tracking sites. Improvement was obtained for the zonal coefficients of the new models and is shown by tests on the long period perturbations of the orbits. Individual zonal coefficients agree very closely among different models that contain low inclination satellites. Tests of models with surface gravity data show that the GEM 3 satellite model has significantly better agreement with the gravimetry data than the GEM 1 satellite model, and that it also has better agreement with the gravimetry data than the 1969 SAO Standard Earth 2 model.

Synthesis, characterization and properties of copper(I) complexes with bis(diphenylphosphino)-ferrocene ancillary ligand

NASA Astrophysics Data System (ADS)

Liu, Xinfang; Zhang, Songlin; Ding, Yuqiang

2012-06-01

Three copper(I) complexes (2-4) containing dppf ancillary ligand (dppf = bis(diphenylphosphino)-ferrocene) were synthesized when chloride-bridged copper(I) complex 1 reacted with acetanilide and characterized by IR, element analysis and NMR spectrum. And the crystal structures of complexes 2 and 4 have been determined by X-ray diffraction method. Complex 2, an acetate-bridged copper(I) complex, was obtained under N2 atmosphere in un-dried solvent; the acetate ion came from the hydrolysis reaction of acetanilide due to residual water in solvent. Acetanilide was deprotonated and coordinated with the copper(I) centre to form a copper(I) amidate complex 3 when reacted in pre-dried solvent. In addition, a known complex 4, the oxidation product of dppf, was isolated from the same reaction system when reacted in air atmosphere. CV and TG experiments were carried out to check the electron transfer properties and thermal stabilities of complexes 2-3. Finally, the arylation reaction of complex 3 with iodobenzene was performed to study the reaction mechanism of copper(I) catalyzed Goldberg reaction.

Sulfide Oxidation by O2: Synthesis, Structure and Reactivity of Novel Sulfide-Incorporated Fe(II) Bis(imino)pyridine Complexes

PubMed Central

Widger, Leland R.; Siegler, Maxime A.

2013-01-01

The unsymmetrical iron(II) bis(imino)pyridine complexes [FeII(LN3SMe)(H2O)3](OTf)2 (1), and [FeII(LN3SMe)Cl2] (2) were synthesized and their reactivity with O2 was examined. Complexes 1 and 2 were characterized by single crystal X-ray crystallography, LDI-MS, 1H-NMR and elemental analysis. The LN3SMe ligand was designed to incorporate a single sulfide donor and relies on the bis(imino)pyridine scaffold. This scaffold was selected for its ease of synthesis and its well-precedented ability to stabilize Fe(II) ions. Complexes 1 and 2 ware prepared via a metal-assisted template reaction from the unsymmetrical pyridyl ketone precursor 2-(O=CMe)-6-(2,6-(iPr2-C6H3N=CMe)-C5H3N. Reaction of 1 with O2 was shown to afford the S-oxygenated sulfoxide complex [Fe(LN3S(O)Me)(OTf)]2+(3), whereas compound 2, under the same reaction conditions, afforded the corresponding sulfone complex [Fe(LN3S(O2)Me)Cl]2+ (4). PMID:23878411

GEMS Revealed: Spectrum Imaging of Aggregate Grains in Interplanetary Dust

NASA Technical Reports Server (NTRS)

Keller, L. P.; Messenger, S.; Christoffersen, R.

2005-01-01

Anhydrous interplanetary dust particles (IDPs) of cometary origin contain abundant materials that formed in the early solar nebula. These materials were transported outward and subsequently mixed with molecular cloud materials and presolar grains in the region where comets accreted [1]. GEMS (glass with embedded metal and sulfides) grains are a major component of these primitive anhydrous IDPs, along with crystalline Mg-rich silicates, Fe-Ni sulfides, carbonaceous material, and other trace phases. Some GEMS grains (5%) are demonstrably presolar based on their oxygen isotopic compositions [2]. However, most GEMS grains are isotopically solar and have bulk chemical compositions that are incompatible with inferred compositions of interstellar dust, suggesting a solar system origin [3]. An alternative hypothesis is that GEMS grains represent highly irradiated interstellar grains whose oxygen isotopic compositions were homogenized through processing in the interstellar medium (ISM) [4]. We have obtained the first quantitative X-ray maps (spectrum images) showing the distribution of major and minor elements in individual GEMS grains. Nanometer-scale chemical maps provide critical data required to evaluate the differing models regarding the origin of GEMS grains.

Vanadium(V) Complexes with Substituted 1,5-bis(2-hydroxybenzaldehyde)carbohydrazones and Their Use As Catalyst Precursors in Oxidation of Cyclohexane.

PubMed

Dragancea, Diana; Talmaci, Natalia; Shova, Sergiu; Novitchi, Ghenadie; Darvasiová, Denisa; Rapta, Peter; Breza, Martin; Galanski, Markus; Kožı́šek, Jozef; Martins, Nuno M R; Martins, Luísa M D R S; Pombeiro, Armando J L; Arion, Vladimir B

2016-09-19

Six dinuclear vanadium(V) complexes have been synthesized: NH4[(VO2)2((H)LH)] (NH4[1]), NH4[(VO2)2((t-Bu)LH)] (NH4[2]), NH4[(VO2)2((Cl)LH)] (NH4[3]), [(VO2)(VO)((H)LH)(CH3O)] (4), [(VO2)(VO)((t-Bu)LH)(C2H5O)] (5), and [(VO2)(VO)((Cl)LH)(CH3O)(CH3OH/H2O)] (6) (where (H)LH4 = 1,5-bis(2-hydroxybenzaldehyde)carbohydrazone, (t-Bu)LH4 = 1,5-bis(3,5-di-tert-butyl-2-hydroxybenzaldehyde)carbohydrazone, and (Cl)LH4 = 1,5-bis(3,5-dichloro-2-hydroxybenzaldehyde)carbohydrazone). The structures of NH4[1] and 4-6 have been determined by X-ray diffraction (XRD) analysis. In all complexes, the triply deprotonated ligand accommodates two V ions, using two different binding sites ONN and ONO separated by a diazine unit -N-N-. In two pockets of NH4[1], two identical VO2(+) entities are present, whereas, in those of 4-6, two different VO2(+) and VO(3+) are bound. The highest oxidation state of V ions was corroborated by X-ray data, indicating the presence of alkoxido ligand bound to VO(3+) in 4-6, charge density measurements on 4, magnetic susceptibility, NMR spectroscopy, spectroelectrochemistry, and density functional theory (DFT) calculations. All four complexes characterized by XRD form dimeric associates in the solid state, which, however, do not remain intact in solution. Compounds NH4[1], NH4[2], and 4-6 were applied as alternative selective homogeneous catalysts for the industrially significant oxidation of cyclohexane to cyclohexanol and cyclohexanone. The peroxidative (with tert-butyl hydroperoxide, TBHP) oxidation of cyclohexane was performed under solvent-free and additive-free conditions and under low-power microwave (MW) irradiation. Cyclohexanol and cyclohexanone were the only products obtained (high selectivity), after 1.5 h of MW irradiation. Theoretical calculations suggest a key mechanistic role played by the carbohydrazone ligand, which can undergo reduction, instead of the metal itself, to form an active reduced form of the catalyst.

GEM1: First-year modeling and IT activities for the Global Earthquake Model

NASA Astrophysics Data System (ADS)

Anderson, G.; Giardini, D.; Wiemer, S.

2009-04-01

GEM is a public-private partnership initiated by the Organisation for Economic Cooperation and Development (OECD) to build an independent standard for modeling and communicating earthquake risk worldwide. GEM is aimed at providing authoritative, open information about seismic risk and decision tools to support mitigation. GEM will also raise risk awareness and help post-disaster economic development, with the ultimate goal of reducing the toll of future earthquakes. GEM will provide a unified set of seismic hazard, risk, and loss modeling tools based on a common global IT infrastructure and consensus standards. These tools, systems, and standards will be developed in partnership with organizations around the world, with coordination by the GEM Secretariat and its Secretary General. GEM partners will develop a variety of global components, including a unified earthquake catalog, fault database, and ground motion prediction equations. To ensure broad representation and community acceptance, GEM will include local knowledge in all modeling activities, incorporate existing detailed models where possible, and independently test all resulting tools and models. When completed in five years, GEM will have a versatile, penly accessible modeling environment that can be updated as necessary, and will provide the global standard for seismic hazard, risk, and loss models to government ministers, scientists and engineers, financial institutions, and the public worldwide. GEM is now underway with key support provided by private sponsors (Munich Reinsurance Company, Zurich Financial Services, AIR Worldwide Corporation, and Willis Group Holdings); countries including Belgium, Germany, Italy, Singapore, Switzerland, and Turkey; and groups such as the European Commission. The GEM Secretariat has been selected by the OECD and will be hosted at the Eucentre at the University of Pavia in Italy; the Secretariat is now formalizing the creation of the GEM Foundation. Some of GEM's global

Phosphonic acid functionalization of nanostructured Ni-W coatings on steel

NASA Astrophysics Data System (ADS)

Orrillo, P. A.; Ribotta, S. B.; Gassa, L. M.; Benítez, G.; Salvarezza, R. C.; Vela, M. E.

2018-03-01

The functionalization of nanocrystalline Ni-W coatings, formed by galvanostatic pulsed electrodeposition on steel, by thermal treatment of octadecylphosphonic acid self-assembled on the oxidized alloy surface is studied by Raman spectroscopy, contact angle measurements, X-ray photoelectron spectroscopy, AFM and electrochemical techniques. Results show that this procedure preserves the surface topography and the optimum mechanical properties of the alloy. More importantly, it turns the alloy surface highly hydrophobic and markedly improves its corrosion resistance, in particular to pitting corrosion in aggressive solutions containing chloride anions. The ability of the phosphonate layer to improve surface properties arises from the barrier properties introduced by the hydrocarbon chains and the strong bonds between the phosphonate head and the underlying surface oxides.

Synthesis and characterization of 5-bis(benzyl thio)-1, 3, 4-thiadiazole complexes with fac-ReBr3(CO) 32-

USDA-ARS?s Scientific Manuscript database

Reactions of 2,5-bis(benzylthio)-1,3,4-thiadiazole (Compound 1) with a common organometallic rhenium starting material [NEt4]2[fac-[Re(I)Br3(CO)3] yielded two distinct types of complexes. Both complexes coordinate only through the nitrogen of the thiadiazole ring. Reaction of Compound 1 with the rhe...

Carbonate formation within a nickel dimer: synthesis of a coordinatively unsaturated bis(mu-hydroxo) dinickel complex and its reactivity toward carbon dioxide.

PubMed

Wikstrom, Jeffrey P; Filatov, Alexander S; Mikhalyova, Elena A; Shatruk, Michael; Foxman, Bruce M; Rybak-Akimova, Elena V

2010-03-14

The tridentate aminopyridine ligand bearing a bulky tert-butyl substituent at the amine nitrogen, tert-butyl-dipicolylamine (tBuDPA), occupies three coordination sites in six-coordinate complexes of nickel(ii), leaving the remaining three sites available for additional ligand binding and activation. New crystallographically characterized complexes include two mononuclear species with 1:1 metal:ligand complexation: a trihydrate solvate (1.3H(2)O) and a monohydrate biacetonitrile solvate (1.H(2)O.2CH(3)CN). Complexation in the presence of sodium hydroxide results in a bis(mu-hydroxo) complex (2), the bridging hydroxide anions of which are labile and become displaced by methoxide anions in methanol solvent, affording bis-methoxo-bridged (4). Nickel(II) centers in 2 are five-coordinate and antiferromagnetically coupled (with J = -31.4(5) cm(-1), H = -2JS(1)S(2), in agreement with Ni-O-Ni angle of 103.7 degrees). Bridging hydroxide or alkoxide anions in coordinatively unsaturated dinuclear nickel(II) complexes with tBuDPA react as active nucleophiles. 2 readily performs carbon dioxide fixation, resulting in the formation of a bis(mu-carbonato) tetrameric complex (3), which features a novel binding geometry in the form of an inverted butterfly-type nickel-carbonate core. Temperature-dependent magnetic measurements of tetranuclear carbonato-bridged revealed relatively weak antiferromagnetic coupling (J(1) = -3.1(2) cm(-1)) between the two nickel centers in the core of the cluster, as well as weak antiferromagnetic pairwise interactions (J(2) = J(3) = -4.54(5) cm(-1)) between central and terminal nickel ions.

Readout electronics for the GEM detector

NASA Astrophysics Data System (ADS)

Kasprowicz, G.; Czarski, T.; Chernyshova, M.; Czyrkowski, H.; Dabrowski, R.; Dominik, W.; Jakubowska, K.; Karpinski, L.; Kierzkowski, K.; Kudla, I. M.; Pozniak, K.; Rzadkiewicz, J.; Salapa, Z.; Scholz, M.; Zabolotny, W.

2011-10-01

A novel approach to the Gas Electron Multiplier (GEM) detector readout is presented. Unlike commonly used methods, based on discriminators[2],[3] and analogue FIFOs[1], the method developed uses simultaneously sampling high speed ADCs and advanced FPGA-based processing logic to estimate the energy of every single photon. Such method is applied to every GEM strip signal. It is especially useful in case of crystal-based spectrometers for soft X-rays, where higher order reflections need to be identified and rejected[5].

Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

PubMed Central

2016-01-01

Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this paper, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (ϕNpm) values ranging from 0.13 to 0.44 and dispersity (Đ) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Dry samples with ϕNpm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. We demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers. PMID:27134312

The Mitochondrial GTPase Gem1 Contributes to the Cell Wall Stress Response and Invasive Growth of Candida albicans.

PubMed

Koch, Barbara; Tucey, Timothy M; Lo, Tricia L; Novakovic, Stevan; Boag, Peter; Traven, Ana

2017-01-01

The interactions of mitochondria with the endoplasmic reticulum (ER) are crucial for maintaining proper mitochondrial morphology, function and dynamics. This enables cells to utilize their mitochondria optimally for energy production and anabolism, and it further provides for metabolic control over developmental decisions. In fungi, a key mechanism by which ER and mitochondria interact is via a membrane tether, the protein complex ERMES (ER-Mitochondria Encounter Structure). In the model yeast Saccharomyces cerevisiae , the mitochondrial GTPase Gem1 interacts with ERMES, and it has been proposed to regulate its activity. Here we report on the first characterization of Gem1 in a human fungal pathogen. We show that in Candida albicans Gem1 has a dominant role in ensuring proper mitochondrial morphology, and our data is consistent with Gem1 working with ERMES in this role. Mitochondrial respiration and steady state cellular phospholipid homeostasis are not impacted by inactivation of GEM1 in C. albicans . There are two major virulence-related consequences of disrupting mitochondrial morphology by GEM1 inactivation: C. albicans becomes hypersusceptible to cell wall stress, and is unable to grow invasively. In the gem1 Δ / Δ mutant, it is specifically the invasive capacity of hyphae that is compromised, not the ability to transition from yeast to hyphal morphology, and this phenotype is shared with ERMES mutants. As a consequence of the hyphal invasion defect, the gem1 Δ / Δ mutant is drastically hypovirulent in the worm infection model. Activation of the mitogen activated protein (MAP) kinase Cek1 is reduced in the gem1 Δ / Δ mutant, and this function could explain both the susceptibility to cell wall stress and lack of invasive growth. This result establishes a new, respiration-independent mechanism of mitochondrial control over stress signaling and hyphal functions in C. albicans . We propose that ER-mitochondria interactions and the ER-Mitochondria Organizing

The Mitochondrial GTPase Gem1 Contributes to the Cell Wall Stress Response and Invasive Growth of Candida albicans

PubMed Central

Koch, Barbara; Tucey, Timothy M.; Lo, Tricia L.; Novakovic, Stevan; Boag, Peter; Traven, Ana

2017-01-01

The interactions of mitochondria with the endoplasmic reticulum (ER) are crucial for maintaining proper mitochondrial morphology, function and dynamics. This enables cells to utilize their mitochondria optimally for energy production and anabolism, and it further provides for metabolic control over developmental decisions. In fungi, a key mechanism by which ER and mitochondria interact is via a membrane tether, the protein complex ERMES (ER-Mitochondria Encounter Structure). In the model yeast Saccharomyces cerevisiae, the mitochondrial GTPase Gem1 interacts with ERMES, and it has been proposed to regulate its activity. Here we report on the first characterization of Gem1 in a human fungal pathogen. We show that in Candida albicans Gem1 has a dominant role in ensuring proper mitochondrial morphology, and our data is consistent with Gem1 working with ERMES in this role. Mitochondrial respiration and steady state cellular phospholipid homeostasis are not impacted by inactivation of GEM1 in C. albicans. There are two major virulence-related consequences of disrupting mitochondrial morphology by GEM1 inactivation: C. albicans becomes hypersusceptible to cell wall stress, and is unable to grow invasively. In the gem1Δ/Δ mutant, it is specifically the invasive capacity of hyphae that is compromised, not the ability to transition from yeast to hyphal morphology, and this phenotype is shared with ERMES mutants. As a consequence of the hyphal invasion defect, the gem1Δ/Δ mutant is drastically hypovirulent in the worm infection model. Activation of the mitogen activated protein (MAP) kinase Cek1 is reduced in the gem1Δ/Δ mutant, and this function could explain both the susceptibility to cell wall stress and lack of invasive growth. This result establishes a new, respiration-independent mechanism of mitochondrial control over stress signaling and hyphal functions in C. albicans. We propose that ER-mitochondria interactions and the ER-Mitochondria Organizing Network

Nebraska NativeGEM (Geospatial Extension Model)

NASA Technical Reports Server (NTRS)

Bowen, Brent

2004-01-01

This proposal, Nebraska NativeGEM (Geospatial Extension Model) features a unique diversity component stemming from the exceptional reputation NNSGC has built by delivering geospatial science experiences to Nebraska s Native Americans. For 7 years, NNSGC has partner4 with the 2 tribal colleges and 4 reservation school districts in Nebraska to form the Nebraska Native American Outreach Program (NNAOP), a partnership among tribal community leaders, academia, tribal schools, and industry reaching close to 1,OOO Native American youth, over 1,200 community members (Lehrer & Zendajas, 2001).NativeGEM addresses all three key components of Cooperative State Research, Education, and Extension Service (CSREES) goals for advancing decision support, education, and workforce development through the GES. The existing long term commitments that the NNSGC and the GES have in these areas allow for the pursuit of a broad range of activities. NativeGEM builds upon these existing successful programs and collaborations. Outcomes and metrics for each proposed project are detailed in the Approach section of this document.

A gravity model for crustal dynamics (GEM-L2)

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Klosko, S. M.; Patel, G. B.; Wagner, C. A.

1985-01-01

The Laser Geodynamics Satellite (Lageos) was the first NASA satellite which was placed into orbit exclusively for laser ranging applications. Lageos was designed to permit extremely accurate measurements of the earth's rotation and the movement of the tectonic plates. The Goddard earth model, GEM-L2, was derived mainly on the basis of the precise laser ranging data taken on many satellites. Douglas et al. (1984) have demonstrated the utility of GEM-L2 in detecting the broadest ocean circulations. As Lageos data constitute the most extensive set of satellite laser observations ever collected, the incorporation of 2-1/2 years of these data into the Goddard earth models (GEM) has substantially advanced the geodynamical objectives. The present paper discusses the products of the GEM-L2 solution.

Psychometric validation of the Growth and Empowerment Measure (GEM) applied with Indigenous Australians.

PubMed

Haswell, Melissa R; Kavanagh, David; Tsey, Komla; Reilly, Lyndon; Cadet-James, Yvonne; Laliberte, Arlene; Wilson, Andrew; Doran, Chris

2010-09-01

Empowerment is a complex process of psychological, social, organizational and structural change. It allows individuals and groups to achieve positive growth and effectively address the social and psychological impacts of historical oppression, marginalization and disadvantage. The Growth and Empowerment Measure (GEM) was developed to measure change in dimensions of empowerment as defined and described by Aboriginal Australians who participated in the Family Well Being programme. The GEM has two components: a 14-item Emotional Empowerment Scale (EES14) and 12 Scenarios (12S). It is accompanied by the Kessler 6 Psychological Distress Scale (K6), supplemented by two questions assessing frequency of happy and angry feelings. For validation, the measure was applied with 184 Indigenous Australian participants involved in personal and/or organizational social health activities. Psychometric analyses of the new instruments support their validity and reliability and indicate two-component structures for both the EES (Self-capacity; Inner peace) and the 12S (Healing and enabling growth, Connection and purpose). Strong correlations were observed across the scales and subscales. Participants who scored higher on the newly developed scales showed lower distress on the K6, particularly when the two additional questions were included. However, exploratory factor analyses demonstrated that GEM subscales are separable from the Kessler distress measure. The GEM shows promise in enabling measurement and enhancing understanding of both process and outcome of psychological and social empowerment within an Australian Indigenous context.

GEM Building Taxonomy (Version 2.0)

USGS Publications Warehouse

Brzev, S.; Scawthorn, C.; Charleson, A.W.; Allen, L.; Greene, M.; Jaiswal, Kishor; Silva, V.

2013-01-01

/7/8/IRRE9/10/RSH3+RWO211/FW12/13/ which can be read as (1) Direction = [DX or DY] (the building has the same lateral load-resisting system in both directions); (2) Material = [Unreinforced Masonry + solid fired clay bricks + cement: lime mortar]; (3) Lateral Load-Resisting System = [Wall]; (4) Date of construction = [pre-1939]; (5) Heaight = [exactly 2 storeys]; (6) Occupancy = [residential, unknown type]; (7) Building Position = [unknown = no entry]; (8) Shape of building plan = [unknown = no entry]; (9) Structural irregularity = [regular]; (10) Exterior walls = [unknown = no entry]; (11) Roof = [Shape: pitched and hipped, Roof covering: clay tiles, Roof system material: wood, Roof system type: wood trusses]; (12) Floor = [Floor system: Wood, unknown]; (13) Foundation = [unknown = no entry]. Mapping of GEM Building Taxonomy to selected taxonomies is included in the report -- for example, the above building would be referenced by previous structural taxonomies as: PAGER-STR as UFB or UFB4, by the World Housing Encyclopedia as 7 or 8 and by the European Macroseismic Scale (98) as M5. The Building Taxonomy data model is highly flexible and has been incorporated within a relational database architecture. Due to its ability to represent building typologies using a shorthand form, it is also possible to use the taxonomy for non-database applications, and we discuss possible application of adaptation for Building Information Modelling (BIM) systems, and for the insurance industry. The GEM Building Taxonomy was independently evaluated and tested by the Earthquake Engineering Research Institute (EERI), which received 217 TaxT reports from 49 countries, representing a wide range of building typologies, including single and multi-storey buildings, reinforced and unreinforced masonry, confined masonry, concrete, steel, wood, and earthern buildings used for residential, commercial, industrial, and educational occupancy. Based on these submissions and other feedback, the EERI

A Hidden GEM

ERIC Educational Resources Information Center

Khan, Samia

2012-01-01

The internet abounds with free science education applications. But, on their own, these applications have limited capacity to teach students curricular concepts or skills. The author integrated several free web-based applications into a broader pedagogical approach called T-GEM, in which the teacher guides student investigations. In this article,…

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

NASA Astrophysics Data System (ADS)

Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

2017-02-01

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes.

PubMed

Gregson, Matthew; Lu, Erli; Mills, David P; Tuna, Floriana; McInnes, Eric J L; Hennig, Christoph; Scheinost, Andreas C; McMaster, Jonathan; Lewis, William; Blake, Alexander J; Kerridge, Andrew; Liddle, Stephen T

2017-02-03

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal-ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle.

The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes

PubMed Central

Gregson, Matthew; Lu, Erli; Mills, David P.; Tuna, Floriana; McInnes, Eric J. L.; Hennig, Christoph; Scheinost, Andreas C.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Kerridge, Andrew; Liddle, Stephen T.

2017-01-01

Across the periodic table the trans-influence operates, whereby tightly bonded ligands selectively lengthen mutually trans metal–ligand bonds. Conversely, in high oxidation state actinide complexes the inverse-trans-influence operates, where normally cis strongly donating ligands instead reside trans and actually reinforce each other. However, because the inverse-trans-influence is restricted to high-valent actinyls and a few uranium(V/VI) complexes, it has had limited scope in an area with few unifying rules. Here we report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data suggest the presence of an inverse-trans-influence. Studies of hypothetical praseodymium(IV) and terbium(IV) analogues suggest the inverse-trans-influence may extend to these ions but it also diminishes significantly as the 4f orbitals are populated. This work suggests that the inverse-trans-influence may occur beyond high oxidation state 5f metals and hence could encompass mid-range oxidation state actinides and lanthanides. Thus, the inverse-trans-influence might be a more general f-block principle. PMID:28155857

Phosphonated Near-Infrared Fluorophores for Biomedical Imaging of Bone**

PubMed Central

Hyun, Hoon; Wada, Hideyuki; Bao, Kai; Gravier, Julien; Yadav, Yogesh; Laramie, Matt; Henary, Maged; Frangioni, John V.

2014-01-01

The conventional method for creating targeted contrast agents is to conjugate separate targeting and fluorophore domains. In this study we report a new strategy based on incorporation of targeting moieties into the non-resonant structure of pentamethine and heptamethine indocyanines. Using the known affinity of phosphonates for bone minerals as a model system, we have synthesized two families of bifunctional molecules that target bone without the need for a traditional bisphosphonate. With peak fluorescence emission at ≈ 700 nm or ≈ 800 nm, these molecules can be used for FLARE dual-channel imaging. Longitudinal FLARE studies in mice demonstrate that phosphonated near-infrared fluorophores remain stable in bone for over 5 weeks, and histological analysis demonstrates incorporation into bone matrix. Taken together, we describe a new strategy for creating ultracompact, targeted, near-infrared fluorophores for various bioimaging applications. PMID:25139079

Synthesis and characterization of poly(phenylacetylene)s with Ru(II) bis-terpyridine complexes in the side-chain.

PubMed

Breul, Alexander M; Kübel, Joachim; Häupler, Bernhard; Friebe, Christian; Hager, Martin D; Winter, Andreas; Dietzek, Benjamin; Schubert, Ulrich S

2014-04-01

An alkyne-functionalized ruthenium(II) bis-terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size-exclusion chromatography (SEC), (1) H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV-vis absorption spectroscopy. In addition, spectro-electrochemical measurements are carried out. Time-resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)2 (2+) model complex. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward improved guideline quality: using the COGS statement with GEM.

PubMed

Shiffman, Richard N; Michel, Georges

2004-01-01

The Conference on Guideline Standardization (COGS) was convened to create a standardized documentation checklist for clinical practice guidelines in an effort to promote guideline quality and facilitate implementation. The statement was created by a multidisciplinary panel using a rigorous consensus development methodology. The Guideline Elements Model (GEM) provides a standardized approach to representing guideline documents using XML. In this work, we demonstrate the sufficiency of GEM for describing COGS components. Using the mapping between COGS and GEM elements we built an XSLT application to examine a guideline's adherence (or non-adherence) to the COGS checklist. Once a guideline has been marked up according to the GEM hierarchy, its knowledge content can be reused in multiple ways.

Gd-Complexes of New Arylpiperazinyl Conjugates of DTPA-Bis(amides): Synthesis, Characterization and Magnetic Relaxation Properties.

PubMed

Ba-Salem, Abdullah O; Ullah, Nisar; Shaikh, M Nasiruzzaman; Faiz, Mohamed; Ul-Haq, Zaheer

2015-04-29

Two new DTPA-bis(amide) based ligands conjugated with the arylpiperazinyl moiety were synthesized and subsequently transformed into their corresponding Gd(III) complexes 1 and 2 of the type [Gd(L)H2O]·nH2O. The relaxivity (R1) of these complexes was measured, which turned out to be comparable with that of Omniscan®, a commercially available MRI contrast agent. The cytotoxicity studies of these complexes indicated that they are non-toxic, which reveals their potential and physiological suitability as MRI contrast agents. All the synthesized ligands and complexes were characterized with the aid of analytical and spectroscopic methods, including elemental analysis, 1H-NMR, FT-IR, XPS and fast atom bombardment (FAB) mass spectrometry.

Synthesis, characterization, and reactivity of the first uranium metallocene 1,2 bis(diphenylphosphino)acetylene complexes.

DOE PAGES

Pagano, Justin Kane; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

2018-06-09

Two new uranium metallacyclopropenes, (C 5Me 4R) 2U(η 2-Ph 2PC=CPPh 2) (R = Me, Et) were prepared by reducing the corresponding (C 5Me 4R) 2UCl 2 complexes with KC 8 in the presence of 1,2-bis(diphenylphosphino)acetylene (Ph 2P–C≡C–PPh 2). Both compounds were fully characterized by a combination of elemental analysis and multinuclear NMR, UV–visible–NIR, and IR spectroscopies. Differences in the electronic spectra of these novel compounds and the known (C 5Me 5) 2U(η 2-Me 3SiC=CSiMe 3) are discussed. Finally, also presented is the solid-state structure of (C 5Me 4Et) 2U(η 2-Ph 2PC=CPPh 2), which reveals significant distortions of the coordinated 1,2-bis(diphenylphosphino)acetylenemore » (Ph 2P–C≡C–PPh 2) ligand.« less

Synthesis, characterization, and reactivity of the first uranium metallocene 1,2 bis(diphenylphosphino)acetylene complexes.

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

Pagano, Justin Kane; Scott, Brian Lindley; Kiplinger, Jaqueline Loetsch

Two new uranium metallacyclopropenes, (C 5Me 4R) 2U(η 2-Ph 2PC=CPPh 2) (R = Me, Et) were prepared by reducing the corresponding (C 5Me 4R) 2UCl 2 complexes with KC 8 in the presence of 1,2-bis(diphenylphosphino)acetylene (Ph 2P–C≡C–PPh 2). Both compounds were fully characterized by a combination of elemental analysis and multinuclear NMR, UV–visible–NIR, and IR spectroscopies. Differences in the electronic spectra of these novel compounds and the known (C 5Me 5) 2U(η 2-Me 3SiC=CSiMe 3) are discussed. Finally, also presented is the solid-state structure of (C 5Me 4Et) 2U(η 2-Ph 2PC=CPPh 2), which reveals significant distortions of the coordinated 1,2-bis(diphenylphosphino)acetylenemore » (Ph 2P–C≡C–PPh 2) ligand.« less

Gold nanoparticle assemblies stabilized by bis(phthalocyaninato)lanthanide(III) complexes through van der Waals interactions

NASA Astrophysics Data System (ADS)

Noda, Yuki; Noro, Shin-Ichiro; Akutagawa, Tomoyuki; Nakamura, Takayoshi

2014-01-01

Gold nanoparticle assemblies possess diverse application potential, ranging from industrial nanotechnology to medical biotechnology. Because the structures and properties of assemblies are directly affected by the stabilization mechanism between the organic molecules serving as protecting ligands and the gold nanoparticle surface, it is crucial to find and investigate new stabilization mechanisms. Here, we report that π-conjugated phthalocyanine rings can serve as stabilizing ligands for gold nanoparticles. Bis(phthalocyaninato)lutetium(III) (LuPc2) or bis(phthalocyaninato)terbium(III) (TbPc2), even though complex, do not have specific binding units and stabilize gold nanoparticles through van der Waals interaction between parallel adsorbed phthalocyanine ligands and the gold nanoparticle surface. AC magnetic measurements and the electron-transport properties of the assemblies give direct evidence that the phthalocyanines are isolated from each other. Each nanoparticle shows weak electronic coupling despite the short internanoparticle distance (~1 nm), suggesting Efros-Shklovskii-type variable-range hopping and collective single-electron tunnelling behaviours.

pH-Dependence of Binding Constants and Desorption Rates of Phosphonate- and Hydroxamate-Anchored [Ru(bpy)3]2+ on TiO2 and WO3.

PubMed

Esarey, Samuel L; Bartlett, Bart M

2018-04-17

The binding constants and rate constants for desorption of the modified molecular dye [Ru(bpy) 3 ] 2+ anchored by either phosphonate or hydroxamate on the bipyridine ligand to anatase TiO 2 and WO 3 have been measured. In aqueous media at pH 1-10, repulsive electrostatic interactions between the negatively charged anchor and the negatively charged surface govern phosphonate desorption under neutral and basic conditions for TiO 2 anatase due to the high acidity of phosphonic acid (p K a,4 = 5.1). In contrast, the lower acidity of hydroxamate (p K a,1 = 6.5, p K a,2 = 9.1) leads to little change in adsorption/desorption properties as a function of pH from 1 to 7. The binding constant for hydroxamate is 10 3 in water, independent of pH in this range. These results are true for WO 3 as well, but are not reported at pH > 4 due to its Arrhenius acidity. Kinetics for desorption as a function of pH are reported, with a proposed mechanism for phosphonate desorption at high pH being the electrostatic repulsion of negative charges between the surface and the anionic anchor. Further, the hydroxamic acid anchor itself is likely the site of quasi-reversible redox activity in [Ru(bpy) 2 (2,2'-bpy-4,4'-(C(O)N(OH)) 2 )] 2+ , which does not lead to any measurable deterioration of the complex within 2 h of dark cyclic voltammogram scans in aqueous media. These results posit phosphonate as the preferred anchoring group under acidic conditions and hydroxamate for neutral/basic conditions.

An efficient preparation of isosteric phosphonate analogues of sphingolipids by opening of oxirane and cyclic sulfamidate intermediates with alpha-lithiated alkylphosphonic esters.

PubMed

Sun, Chaode; Bittman, Robert

2004-10-29

D-erythro-(2S,3R,4E)-Sphingosine-1-phosphonate (1), the isosteric phosphonate analogue of naturally occurring sphingosine 1-phosphate (1a), and D-ribo-phytosphingosine 1-phosphonate (2), the isosteric phosphonate analogue of D-ribo-phytosphingosine-1-phosphate (2a), were synthesized starting with methyl 2,3-O-isopropylidene-d-glycerate (4) and D-ribo-phytosphingosine (3), respectively. Oxirane 12 was formed in eight steps from 4, and cyclic sulfamidate 22 was formed in five steps from 3. The phosphonate group was introduced via regioselective ring-opening reactions of oxirane 12 and cyclic sulfamidate 22 with lithium dialkyl methylphosphonate, affording 13 and 23, respectively. The synthesis of 1 was completed by S(N)2 displacement of chloromesylate intermediate 14b with azide ion, followed by conversion of the resulting azido group to a NHBoc group and deprotection. The synthesis of 2 was completed by cleavage of the acetal, N-benzyl, and alkyl phosphonate ester groups.

Morphology and Proton Transport in Humidified Phosphonated Peptoid Block Copolymers

DOE PAGES

Sun, Jing; Jiang, Xi; Siegmund, Aaron; ...

2016-04-04

Polymers that conduct protons in the hydrated state are of crucial importance in a wide variety of clean energy applications such as hydrogen fuel cells and artificial photosynthesis. Phosphonated and sulfonated polymers are known to conduct protons at low water content. In this study, we report on the synthesis phosphonated peptoid diblock copolymers, poly-N-(2-ethyl)hexylglycine-block-poly-N-phosphonomethylglycine (pNeh-b-pNpm), with volume fractions of pNpm (Φ Npm) values ranging from 0.13 to 0.44 and dispersity (¯D) ≤ 1.0003. The morphologies of the dry block copolypeptoids were determined by transmission electron microscopy and in both the dry and hydrated states by synchrotron small-angle X-ray scattering. Drymore » samples with Φ Npm > 0.13 exhibited a lamellar morphology. Upon hydration, the lowest molecular weight sample transitioned to a hexagonally packed cylinder morphology, while the others maintained their dry morphologies. Water uptake of all of the ordered samples was 8.1 ± 1.1 water molecules per phosphonate group. In spite of this, the proton conductivity of the ordered pNeh-b-pNpm copolymers ranged from 0.002 to 0.008 S/cm. Finally, we demonstrate that proton conductivity is maximized in high molecular weight, symmetric pNeh-b-pNpm copolymers.« less

Possible Gems and Ultra-Fine Grained Polyphase Units in Comet Wild 2.

NASA Technical Reports Server (NTRS)

Gainsforth, Z.; Butterworth, A. L.; Jilly-Rehak, C. E.; Westphal, A. J.; Brownlee, D. E.; Joswiak, D.; Ogliore, R. C.; Zolensky, M. E.; Bechtel, H. A.; Ebel, D. S.;

Performance of GEM Detectors in the DarkLight Experiment at LERF

NASA Astrophysics Data System (ADS)

Mohammed Prem Nazeer, Sahara Jesmin; DarkLight Collaboration

2017-01-01

The DarkLight experiment has been proposed to search for a heavy photon A' in the mass range of 10-100 MeV/c2 produced in electron-proton collisions. Phase-I of DarkLight has started to take place in 2016 at the Low Energy Recirculator Facility (LERF) at Jefferson Lab. LERF delivered a 100 MeV electron beam onto a windowless hydrogen gas target. The phase-I detector tracks leptons inside the DarkLight solenoid with a set of Gas Electron Multiplier (GEM) detectors, combined with segmented scintillators for triggering. The GEM telescope consists of four 10 × 10 cm2 triple layer GEM chambers with 2D readout strips, mounted in a slightly angled fixed frame about 12 cm tall. The GEM data are read out with analog pipeline front-end cards (APV-25) each of which can process 128 readout channels. Each GEM chamber has 250 channels for each coordinate axis, read out with two APVs on each side, resulting in 2000 readout channels for the GEM stack, processed by 16 APVs. One Multi Purpose Digitizer (MPD) module is used to read out all of the 16 APV-25 cards. The current run status of DarkLight experiment and the performance of GEMs in the experiment will be discussed. This work has been supported by NSF PHY-1436680 and PHY-1505934.

Two isomeric lead(II) carboxylate-phosphonates: syntheses, crystal structures and characterizations

NASA Astrophysics Data System (ADS)

Lei, Chong; Mao, Jiang-Gao; Sun, Yan-Qiong

2004-07-01

Two isomeric layered lead(II) carboxylate-phosphonates of N-(phosphonomethyl)- N-methyl glycine ([MeN(CH 2CO 2H)(CH 2PO 3H 2)]=H 3L), namely, monoclinic Pb 3L 2·H 2O 1 and triclinic Pb 3L 2·H 2O 2, have been synthesized and structurally determined. Compound 1 synthesized by hydrothermal reaction at 150°C is monoclinic, space group C2/ c with a=19.9872(6), b=11.9333(1) and c=15.8399(4) Å, β=110.432(3)°, V=3540.3(1) Å 3, and Z=8. The structure of compound 1 features a <400> layer in which the lead(II) ions are bridged by both phosphonate and carboxylate groups. The lattice water molecules are located between the layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Compound 2 with a same empirical formula as compound 1 was synthesized by hydrothermal reaction at 170°C. It has a different layer structure from that of compound 1 due to the adoption of a different coordination mode for the ligand. It crystallizes in the triclinic system, space group P 1¯ with cell parameters of a=7.1370(6), b=11.522(1), c=11.950(1) Å, α=110.280(2), β=91.625(2), γ=95.614(2)°, V=915.3(1) Å 3 and Z=2. The structure of compound 2 features a <020> metal carboxylate-phosphonate double layer built from 1D lead(II) carboxylate chains interconnected with 1D lead(II) phosphonate double chains. XRD powder patterns of compounds 1 and 2 indicate that each compound exists as a single phase.

Comparative verification between GEM model and official aviation terminal forecasts

NASA Technical Reports Server (NTRS)

Miller, Robert G.

1988-01-01

The Generalized Exponential Markov (GEM) model uses the local standard airways observation (SAO) to predict hour-by-hour the following elements: temperature, pressure, dew point depression, first and second cloud-layer height and amount, ceiling, total cloud amount, visibility, wind, and present weather conditions. GEM is superior to persistence at all projections for all elements in a large independent sample. A minute-by-minute GEM forecasting system utilizing the Automated Weather Observation System (AWOS) is under development.

A Bis-Triazacyclononane Tris-Pyridyl N9 -Azacryptand "Beer Can" Receptor for Complexation of Alkali Metal and Lead(II) Cations.

PubMed

Brown, Asha; Bunchuay, Thanthapatra; Crane, Christopher G; White, Nicholas G; Thompson, Amber L; Beer, Paul D

2018-04-18

A new bis-triazacyclononane tris-pyridyl N 9 -azacryptand ligand is prepared via a convenient one-pot [2+3] condensation reaction between triazacyclononane and 2,6-bis(bromomethyl) pyridine in the presence of M 2 CO 3 (M=Li, Na, K). The proton, lithium, sodium, potassium and lead(II) complexes of the ligand are characterised in the solid state. Preliminary solution-phase competition experiments indicate that the cryptand ligand preferentially binds lead(II) in the presence of sodium, calcium, potassium and zinc cations in methanol solution. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ chemical functionalization of gallium nitride with phosphonic acid derivatives during etching.

PubMed

Wilkins, Stewart J; Greenough, Michelle; Arellano, Consuelo; Paskova, Tania; Ivanisevic, Albena

2014-03-04

In situ functionalization of polar (c plane) and nonpolar (a plane) gallium nitride (GaN) was performed by adding (3-bromopropyl) phosphonic acid or propyl phosphonic acid to a phosphoric acid etch. The target was to modulate the emission properties and oxide formation of GaN, which was explored through surface characterization with atomic force microscopy, X-ray photoelectron spectroscopy, photoluminescence (PL), inductively coupled plasma-mass spectrometry, and water contact angle. The use of (3-bromopropyl) phosphonic acid and propyl phosphonic acid in phosphoric acid demonstrated lower amounts of gallium oxide formation and greater hydrophobicity for both sample sets, while also improving PL emission of polar GaN samples. In addition to crystal orientation, growth-related factors such as defect density in bulk GaN versus thin GaN films residing on sapphire substrates were investigated as well as their responses to in situ functionalization. Thin nonpolar GaN layers were the most sensitive to etching treatments due in part to higher defect densities (stacking faults and threading dislocations), which accounts for large surface depressions. High-quality GaN (both free-standing bulk polar and bulk nonpolar) demonstrated increased sensitivity to oxide formation. Room-temperature PL stands out as an excellent technique to identify nonradiative recombination as observed in the spectra of heteroepitaxially grown GaN samples. The chemical methods applied to tune optical and physical properties of GaN provide a quantitative framework for future novel chemical and biochemical sensor development.

Equilibrium and NMR studies on GdIII, YIII, CuII and ZnII complexes of various DTPA-N,N''-bis(amide) ligands. Kinetic stabilities of the gadolinium(III) complexes.

PubMed

Jászberényi, Zoltán; Bányai, István; Brücher, Ernö; Király, Róbert; Hideg, Kálmán; Kálai, Tamás

2006-02-28

Three DTPA-derivative ligands, the non-substituted DTPA-bis(amide) (L(0)), the mono-substituted DTPA-bis(n-butylamide) (L(1)) and the di-substituted DTPA-bis[bis(n-butylamide)] (L(2)) were synthesized. The stability constants of their Gd3+ complexes (GdL) have been determined by pH-potentiometry with the use of EDTA or DTPA as competing ligands. The endogenous Cu2+ and Zn2+ ions form ML, MHL and M(2)L species. For the complexes CuL(0) and CuL(1) the dissociation of the amide hydrogens (CuLH(-1)) has also been detected. The stability constants of complexes formed with Gd3+, Cu2+ and Zn2+ increase with an increase in the number of butyl substituents in the order ML(0) < ML(1) < ML(2). NMR studies of the diamagnetic YL(0) show the presence of four diastereomers formed by changing the chirality of the terminal nitrogens of their enantiomers. At 323 K, the enantiomerization process, involving the racemization of central nitrogen, falls into the fast exchange range. By the assignment and interpretation of 1H and 13C NMR spectra, the fractions of the diastereomers were found to be equal at pH = 5.8 for YL(0). The kinetic stabilities of GdL(0), GdL(1) and GdL(2) have been characterized by the rates of the exchange reactions occurring between the complexes and Eu3+, Cu2+ or Zn2+. The rates of reaction with Eu3+ are independent of the [Eu3+] and increase with increasing [H+], indicating the rate determining role of the proton assisted dissociation of complexes. The rates of reaction with Cu2+ and Zn2+ increase with rising metal ion concentration, which shows that the exchange can take place with direct attack of Cu2+ or Zn2+ on the complex, via the formation of a dinuclear intermediate. The rates of the proton, Cu2+ and Zn2+ assisted dissociation of Gd3+ complexes decrease with increasing number of the n-butyl substituents, which is presumably the result of steric hindrance hampering the formation or dissociation of the intermediates. The kinetic stabilities of GdL(0) and Gd

Luminescence enhancement of terbium(III) perchlorate by 2,2'-dipyridyl on bis(benzylsulfinyl)methane complex and luminescence mechanism.

PubMed

Feng, Shu-Yan; Li, Wen-Xian; Guo, Feng; Cao, Xiao-Fang

2014-11-01

A novel ternary complex, Tb(2)L4 · L'·(ClO4)6 · 8H2O, has been synthesized using bis(benzylsulfinyl)methane as the first ligand L and 2,2'-dipyridyl as the second ligand L'. The ternary complex was characterized by element analysis, molar conductivity, coordination titration analysis, infrared, thermogravimetric-differential scanning calorimetric and ultraviolet spectra. The results indicated that the composition of the complex was Tb2 L4 · L'·(ClO4)6 · 8H2O (L = C(6)H(5)CH(2) SOCH(2)SOCH(2)C(6)H(5); L' = Dipy). Fourier transform infrared results revealed that the perchlorate group was bonded with the Tb(III) ion by the oxygen atom, and the coordination was bidentate. The fluorescent spectra illustrated that the complex displayed characteristic fluorescence in the solid state. After the introduction of the second ligand, 2,2-dipyridyl, the relative emission intensity and fluorescence lifetime of the ternary complex Tb(2)L(4) · L'·(ClO(4))(6) · 8H2O were enhanced compared to the binary complex TbL(2.5)(ClO4)3 · 3H2O. This indicated that the presence of both organic ligand bis(benzylsulfinyl)methane and the second ligand 2,2-dipyridyl could sensitize the fluorescence intensity of Tb(III) ion, and introduction of the 2,2-dipyridyl group resulted in an enhancement of the fluorescence of the Tb(III) ternary rare earth complex. The strongest characteristic fluorescence emission intensity of the ternary complex was 9.36 times that of the binary complex. The phosphorescence spectra and fluorescence lifetime of the complex were also measured. Copyright © 2014 John Wiley & Sons, Ltd.

Synthesis, characterization, and photophysical properties of a thiophene-functionalized bis(pyrazolyl) pyridine (BPP) tricarbonyl rhenium(I) complex.

PubMed

Lytwak, Lauren A; Stanley, Julie M; Mejía, Michelle L; Holliday, Bradley J

2010-09-07

A bromo tricarbonyl rhenium(I) complex with a thiophene-functionalized bis(pyrazolyl) pyridine ligand (L), ReBr(L)(CO)(3) (1), has been synthesized and characterized by variable temperature and COSY 2-D (1)H NMR spectroscopy, single-crystal X-ray diffraction, and photophysical methods. Complex 1 is highly luminescent in both solution and solid-state, consistent with phosphorescence from an emissive (3)MLCT excited state with an additional contribution from a LC (3)(pi-->pi*) transition. The single-crystal X-ray diffraction structure of the title ligand is also reported.

Phase Behavior and Conductivity of Phosphonated Block Copolymers Containing Ionic Liquids

NASA Astrophysics Data System (ADS)

Jung, Ha Young; Kim, Sung Yeon; Park, Moon Jeong

2015-03-01

As the focus on proton exchange fuel cells continues to escalate in the era of alternative energy systems, the rational design of sulfonated polymers has emerged as a key technique for enhancing device efficiency. While the sulfonic acid group guarantees high proton conductivity of membranes under humidified conditions, the growing need for high temperature operation has discouraged their practical uses in fuel cells. In this respect, phosphonated polymers have drawn intensive attention in recent years owing to their self-dissociation ability. In this study, we have synthesized a set of phosphonated block copolymers, poly(styrenephosphonate-methylbutylene) (PSP- b - PMB), by varying phosphonation level (PL). A wide variety of self-assembled morphologies, i.e., disordered, lamellar, hexagonally perforated lamellae and hexagonally packed cylindrical phases, were observed with PL. Remarkably, upon comparing the morphology of PSP- b-PMB and that of sulfonated analog, we found distinctly dissimilar domain sizes at the same molecular weight and composition. A range of ionic liquids (ILs) were incorporated into the PSP- b-PMB block copolymers and their ion transport properties were examined. It has been revealed that the degree of confinement of ionic phases (domain size) impacts the ion mobility and proton dissociation efficiency of IL-containing polymers.

The Ozone Layer. UNEP/GEMS Environment Library No. 2.

ERIC Educational Resources Information Center

United Nations Environment Programme, Nairobi (Kenya).

Since the United Nations Environment Program (UNEP) was created, more than a dozen years ago, public understanding of the environmental issues confronting our planet has increased enormously. The Global Environment Monitoring System (GEMS) has provided several environmental assessments. The aim of the UNEP/GEMS Environment Library is to provide…

Functionalization of SBA-15 mesoporous silica by Cu-phosphonate units: Probing of synthesis route

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

Laskowski, Lukasz, E-mail: lukasz.laskowski@kik.pcz.pl; Czestochowa University of Technology, Institute of Physics, Al. Armii Krajowej 19, 42-201 Czestochowa; Laskowska, Magdalena, E-mail: magdalena.laskowska@onet.pl

2014-12-15

Mesoporous silica SBA-15 containing propyl-copper phosphonate units was investigated. The structure of mesoporous samples was tested by N{sub 2} isothermal sorption (BET and BHJ analysis), TEM microscopy and X-Ray scattering. Quantitative analysis EDX has given information about proportions between component atoms in the sample. Quantitative elemental analysis has been carried out to support EDX. To examine bounding between copper atoms and phosphonic units the Raman spectroscopy was carried out. As a support of Raman scattering, the theoretical calculations were made based on density functional theory, with the B3LYP method. By comparison of the calculated vibrational spectra of the molecule withmore » experimental results, distribution of the active units inside silica matrix has been determined. - Graphical abstract: The present study is devoted to mesoporous silica SBA-15 containing propyl-copper phosphonate units. The species were investigated to confirm of synthesis procedure correctness by the micro-Raman technique combined with DFT numerical simulations. Complementary research was carried out to test the structure of mesoporous samples. - Highlights: • SBA-15 silica functionalized with propyl-copper phosphonate units was synthesized. • Synthesis efficiency probed by Raman study supported with DFT simulations. • Homogenous distribution of active units was proved. • Synthesis route enables precise control of distance between copper ions.« less

Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes

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

Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa Jennifer

The terminal actinide fluoride bonds in (C 5Me 5) 2ThF 2(py) (py = pyridine) and (C 5Me 5) 2UF 2(O=PR 3) (R = Me, Ph) react with two equivalents of Me 3SiN 3 in toluene to form the polymeric thorium bis(azide), [(C 5Me 5) 2Th(N 3)2] ∞, and a new class of monometallic uranium bis(azide) complexes, (C 5Me 5) 2U(N 3)2(O=PR 3), respectively. Full characterization of the novel complexes (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2UF 2(O=PR 3) are reported, including the solid-state structures of (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2U(N 3) 2(O=PPhmore » 3). Lastly, electronic absorption spectral data are also reported for (C 5Me 5) 2AnF 2(py) (An = Th, U) and (C 5Me 5) 2U(N 3) 2(O=PR 3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.« less

Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes

DOE PAGES

Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa Jennifer; ...

2017-11-04

The terminal actinide fluoride bonds in (C 5Me 5) 2ThF 2(py) (py = pyridine) and (C 5Me 5) 2UF 2(O=PR 3) (R = Me, Ph) react with two equivalents of Me 3SiN 3 in toluene to form the polymeric thorium bis(azide), [(C 5Me 5) 2Th(N 3)2] ∞, and a new class of monometallic uranium bis(azide) complexes, (C 5Me 5) 2U(N 3)2(O=PR 3), respectively. Full characterization of the novel complexes (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2UF 2(O=PR 3) are reported, including the solid-state structures of (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2U(N 3) 2(O=PPhmore » 3). Lastly, electronic absorption spectral data are also reported for (C 5Me 5) 2AnF 2(py) (An = Th, U) and (C 5Me 5) 2U(N 3) 2(O=PR 3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.« less

Morphology and water resistance of mixed silane films of bis[3-(triethoxysilyl) propyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine

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

Pan, Guirong; Schaefer, Dale W.; van Ooij, Wim J.

2010-12-03

Functional organosilanes are powerful interface-active agents that find applications as adhesion promoters as well as optical, dielectric and protective coatings. Bis-silanes are of particular interest because they are highly crosslinked leading to very robust films. In almost all applications, the water resistance of the films is a critical performance measure. Here we use neutron reflectivity to address the effect of bridging group on the hydrothermal response of bis-silane films prepared using bis[3-(triethoxysilyl) propyl]tetrasulfide and bis-[trimethoxysilylpropyl]amine. Neat and mixed films are examined as-prepared, after exposure to water vapor and then in the re-dried state. The bridging group is the key factormore » that controls the morphology and water resistance of silane films. Although bis-sulfur silane is not as condensed as bis-amino silane, bis-sulfur swells less in water because of the hydrophobic nature of bridging group. The reflectivity of bis-sulfur silane film is reversible after room-temperature water conditioning but not at 80 C, indicating chemical alternation of the film at 80 C. The water resistance of mixed silane is roughly that of both components weighted by their volume fraction. But based on the enhanced shrinkage that occurs following water-vapor conditioning of the mixed film, condensation is accelerated in the mixed silane. Regarding the precursor solution, bis-amino silane may act as a catalyst in the hydrolysis of bis-sulfur silane leading to more silanols in the solution and further condensation in the film. Variation in the structure normal to the substrate is also examined by swelling the film with d-nitrobenzene, a non-reacting swelling agent.« less

Phenyl substitution of cationic bis-cyclometalated iridium(iii) complexes for iTMC-LEECs.

PubMed

Suhr, Kristin J; Bastatas, Lyndon D; Shen, Yulong; Mitchell, Lauren A; Frazier, Gary A; Taylor, David W; Slinker, Jason D; Holliday, Bradley J

2016-11-28

A series of seven cationic bis-cyclometalated iridium(iii) complexes of the form [(C^N) 2 (N^N)Ir][PF 6 ] has been designed in order to examine the effect of bulky, hydrophobic phenyl substituents on the structure-property relationship of these ionic transition metal complexes (iTMCs) in light-emitting electrochemical cells (LEECs). Capping phenyl substituents on the cyclometalating and ancillary ligands allows for individual tuning of the HOMO and LUMO energy levels, respectively, yielding an emission range from yellow to red. The complexes in this series exhibit increased quantum yields, up to 70% higher than the unoptimized, archetypal [(2-phenylpyridine) 2 (2,2'-bipyridine)Ir][PF 6 ]. Among these, one complex, C3, was recently reported to produce devices with superior luminance and efficiency. Simultaneous measure of the series of complexes enabled the clear discernment of trends in device performance connected to fundamental structure-property relationships that elucidate the origin of enhanced luminance. In general, phenyl substitution of the 2-phenylpyridine ligands of the parent complex produced higher luminance and faster device response than phenyl substitution of the 2,2'-bipyridine ligand. Overall, complex design and device engineering produce competitive LEECs from simple, single-layer architectures. The synthesis, crystallographic, photophysical, and electrochemical properties of the iTMCs, along with the electroluminescence properties of the LEEC devices are reported herein.

Geopotential models of the Earth from satellite tracking, altimeter and surface gravity observations: GEM-T3 and GEM-T3S

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Nerem, R. S.; Putney, B. H.; Felsentreger, T. L.; Sanchez, B. V.; Klosko, S. M.; Patel, G. B.; Williamson, R. G.; Chinn, D. S.; Chan, J. C.

1992-01-01

Improved models of the Earth's gravitational field have been developed from conventional tracking data and from a combination of satellite tracking, satellite altimeter and surface gravimetric data. This combination model represents a significant improvement in the modeling of the gravity field at half-wavelengths of 300 km and longer. Both models are complete to degree and order 50. The Goddard Earth Model-T3 (GEM-T3) provides more accurate computation of satellite orbital effects as well as giving superior geoidal representation from that achieved in any previous GEM. A description of the models, their development and an assessment of their accuracy is presented. The GEM-T3 model used altimeter data from previous satellite missions in estimating the orbits, geoid, and dynamic height fields. Other satellite tracking data are largely the same as was used to develop GEM-T2, but contain certain important improvements in data treatment and expanded laser tracking coverage. Over 1300 arcs of tracking data from 31 different satellites have been used in the solution. Reliable estimates of the model uncertainties via error calibration and optimal data weighting techniques are discussed.

Hydrothermal synthesis for new multifunctional materials: A few examples of phosphates and phosphonate-based hybrid materials

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

Rueff, Jean-Michel, E-mail: jean-michel.rueff@ensicaen.fr; Poienar, Maria; Guesdon, Anne

Novel physical or chemical properties are expected in a great variety of materials, in connection with the dimensionality of their structures and/or with their nanostructures, hierarchical superstructures etc. In the search of new advanced materials, the hydrothermal technique plays a crucial role, mimicking the nature able to produce fractal, hyperbranched, urchin-like or snow flake structures. In this short review including new results, this will be illustrated by examples selected in two types of materials, phosphates and phosphonates, prepared by this method. The importance of the synthesis parameters will be highlighted for a magnetic iron based phosphates and for hybrids containingmore » phosphonates organic building units crystallizing in different structural types. - Graphical abstract: Phosphate dendrite like and phosphonate platelet crystals.« less

Development of Oseltamivir Phosphonate Congeners as Anti-Influenza Agents

PubMed Central

Cheng, Ting-Jen R.; Weinheimer, Steven; Tarbet, E. Bart; Jan, Jia-Tsrong; Cheng, Yih-Shyun E.; Shie, Jiun-Jie; Chen, Chun-Lin; Chen, Chih-An; Hsieh, Wei-Che; Huang, Pei-Wei; Lin, Wen-Hao; Wang, Shi-Yun; Fang, Jim-Min; Hu, Oliver Yoa-Pu; Wong, Chi-Huey

2012-01-01

Oseltamivir phosphonic acid (tamiphosphor, 3a), its monoethyl ester (3c), guanidino-tamiphosphor (4a) and its monoethyl ester (4c) are potent inhibitors of influenza neuraminidases. They inhibit the replication of influenza viruses, including the oseltamivir-resistant H275Y strain, at low nM to pM levels, and significantly protect mice from infection with lethal doses of influenza viruses when orally administered with 1 mg/kg or higher doses. These compounds are stable in simulated gastric fluid, liver microsomes and human blood, and are largely free from binding to plasma proteins. Pharmacokinetic properties of these inhibitors are thoroughly studied in dogs, rats and mice. The absolute oral bioavailability of these compounds was lower than 12%. No conversion of monoester 4c to phosphonic acid 4a was observed in rats after intravenous administration, but partial conversion of 4c was observed with oral administration. Advanced formulation may be investigated to develop these new anti-influenza agents for better therapeutic use. PMID:23009169

Structure and Order of Phosphonic Acid-Based Self-Assembled Monolayers on Si(100)

PubMed Central

Dubey, Manish; Weidner, Tobias; Gamble, Lara J.; Castner, David G.

2010-01-01

Organophosphonic acid self-assembled monolayers (SAMs) on oxide surfaces have recently seen increased use in electrical and biological sensor applications. The reliability and reproducibility of these sensors require good molecular organization in these SAMs. In this regard, packing, order and alignment in the SAMs is important, as it influences the electron transport measurements. In this study, we examine the order of hydroxyl- and methyl- terminated phosphonate films deposited onto silicon oxide surfaces by the tethering by aggregation and growth method using complementary, state-of-art surface characterization tools. Near edge x-ray absorption fine structure (NEXAFS) spectroscopy and in situ sum frequency generation (SFG) spectroscopy are used to study the order of the phosphonate SAMs in vacuum and under aqueous conditions, respectively. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectrometry results show that these samples form chemically intact monolayer phosphonate films. NEXAFS and SFG spectroscopy showed that molecular order exists in the octadecylphosphonic acid and 11-hydroxyundecylphosphonic acid SAMs. The chain tilt angles in these SAMs were approximately 37° and 45°, respectively. PMID:20735054

Gallium(III) chelates of mixed phosphonate-carboxylate triazamacrocyclic ligands relevant to nuclear medicine: Structural, stability and in vivo studies.

PubMed

Prata, Maria I M; André, João P; Kovács, Zoltán; Takács, Anett I; Tircsó, Gyula; Tóth, Imre; Geraldes, Carlos F G C

2017-12-01

Three triaza macrocyclic ligands, H 6 NOTP (1,4,7-triazacyclononane-N,N',N″-trimethylene phosphonic acid), H 4 NO2AP (1,4,7-triazacyclononane-N-methylenephosphonic acid-N',N″-dimethylenecarboxylic acid), and H 5 NOA2P (1,4,7-triazacyclononane-N,N'-bis(methylenephosphonic acid)-N″-methylene carboxylic acid), and their gallium(III) chelates were studied in view of their potential interest as scintigraphic and PET (Positron Emission Tomography) imaging agents. A 1 H, 31 P and 71 Ga multinuclear NMR study gave an insight on the structure, internal dynamics and stability of the chelates in aqueous solution. In particular, the analysis of 71 Ga NMR spectra gave information on the symmetry of the Ga 3+ coordination sphere and the stability of the chelates towards hydrolysis. The 31 P NMR spectra afforded information on the protonation of the non-coordinated oxygen atoms from the pendant phosphonate groups and on the number of species in solution. The 1 H NMR spectra allowed the analysis of the structure and the number of species in solution. 31 P and 1 H NMR titrations combined with potentiometry afforded the measurement of the protonation constants (log K Hi ) and the microscopic protonation scheme of the triaza macrocyclic ligands. The remarkably high thermodynamic stability constant (log K GaL =34.44 (0.04) and stepwise protonation constants of Ga(NOA2P) 2- were determined by potentiometry and 69 Ga and 31 P NMR titrations. Biodistribution and gamma imaging studies have been performed on Wistar rats using the radiolabeled 67 Ga(NO2AP) - and 67 Ga(NOA2P) 2- chelates, having both demonstrated to have renal excretion. The correlation of the molecular properties of the chelates with their pharmacokinetic properties has been analysed. Copyright © 2017 Elsevier Inc. All rights reserved.

Properties of the Flight Model Gas Electron Multiplier for the GEMS Mission

NASA Technical Reports Server (NTRS)

Takeuchi, Yoko; Kitaguchi, Takao; Hayato, Asami; Tamagawa, Toru; Iwakiri, Wataru; Asami, Fumi; Yoshikawa, Akifumi; Kaneko, Kenta; Enoto, Teruaki; Black, Kevin;

Trace elemental analysis of Indian natural moonstone gems by PIXE and XRD techniques.

PubMed

Venkateswara Rao, R; Venkateswarulu, P; Kasipathi, C; Sivajyothi, S

2013-12-01

A selected number of Indian Eastern Ghats natural moonstone gems were studied with a powerful nuclear analytical and non-destructive Proton Induced X-ray Emission (PIXE) technique. Thirteen elements, including V, Co, Ni, Zn, Ga, Ba and Pb, were identified in these moonstones and may be useful in interpreting the various geochemical conditions and the probable cause of their inceptions in the moonstone gemstone matrix. Furthermore, preliminary XRD studies of different moonstone patterns were performed. The PIXE technique is a powerful method for quickly determining the elemental concentration of a substance. A 3MeV proton beam was employed to excite the samples. The chemical constituents of moonstones from parts of the Eastern Ghats geological formations of Andhra Pradesh, India were determined, and gemological studies were performed on those gems. The crystal structure and the lattice parameters of the moonstones were estimated using X-Ray Diffraction studies, trace and minor elements were determined using the PIXE technique, and major compositional elements were confirmed by XRD. In the present work, the usefulness and versatility of the PIXE technique for research in geo-scientific methodology is established. © 2013 Elsevier Ltd. All rights reserved.

Dinuclear Cu(II) complexes of isomeric bis-(3-acetylacetonate)benzene ligands: synthesis, structure, and magnetic properties.

PubMed

Rancan, Marzio; Dolmella, Alessandro; Seraglia, Roberta; Orlandi, Simonetta; Quici, Silvio; Sorace, Lorenzo; Gatteschi, Dante; Armelao, Lidia

2012-05-07

Highly versatile coordinating ligands are designed and synthesized with two β-diketonate groups linked at the carbon 3 through a phenyl ring. The rigid aromatic spacer is introduced in the molecules to orient the two acetylacetone units along different angles and coordination vectors. The resulting para, meta, and ortho bis-(3-acetylacetonate)benzene ligands show efficient chelating properties toward Cu(II) ions. In the presence of 2,2'-bipyridine, they promptly react and yield three dimers, 1, 2, and 3, with the bis-acetylacetonate unit in bridging position between two metal centers. X-ray single crystal diffraction shows that the compounds form supramolecular chains in the solid state because of intermolecular interactions. Each of the dinuclear complexes shows a magnetic behavior which is determined by the combination of structural parameters and spin polarization effects. Notably, the para derivative (1) displays a moderate antiferromagnetic coupling (J = -3.3 cm(-1)) along a remarkably long Cu···Cu distance (12.30 Å).

Luminescent Dinuclear Ruthenium Terpyridine Complexes with a Bis-Phenylbenzimidazole Spacer.

PubMed

Mondal, Debiprasad; Biswas, Sourav; Paul, Animesh; Baitalik, Sujoy

2017-07-17

A conjugated bis-terpyridine bridging ligand, 2-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)-6-(2-(4-(2,6-di(pyridin-2-yl)pyridin-4-yl)phenyl)-1H-benzo[d]imidazol-6-yl)-1H-benzo[d] imidazole (tpy-BPhBzimH 2 -tpy), was designed in this work by covalent coupling of 3,3'-diaminobenzidine and two 4'-(p-formylphenyl)-2,2':6',2″-terpyridine units to synthesize a new series of bimetallic Ru(II)-terpyridine light-harvesting complexes. Photophysical and electrochemical properties were modulated by the variation of the terminal ligands in the complexes. The new compounds were thoroughly characterized by 1 H NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis. Absorption spectra of the complexes consist of very strong ligand-centered π-π* and n-π* transitions in the UV, metal-to-ligand, and intraligand charge transfer bands in the visible regions. Steady-state and time-resolved emission spectral measurements indicate that the complexes exhibit moderately intense luminescence at room temperature within the spectral domain of 653-687 nm having luminescence lifetimes in the range between 6.3 and 55.2 ns, depending upon terminal tridentate ligand and solvent. Variable-temperature luminescence measurements suggest substantial increase of the energy gap between luminescent 3 metal-to-ligand charge transfer state and nonluminescent 3 metal centered in the complexes compared to the parent [Ru(tpy) 2 ] 2+ . Each of the three bimetallic complexes exhibits only one reversible couple in the positive potential window with almost no detectable splitting corresponding to simultaneous oxidation of the two remote Ru centers. All the complexes possess a number of imidazole NH protons, which became sufficiently acidic upon metal ion coordination. By utilizing these NH protons, we thoroughly studied anion recognition properties of the complexes in pure organic as well as predominantly aqueous media through multiple optical channels and spectroscopic methods. Finally

Microwave gallium-68 radiochemistry for kinetically stable bis(thiosemicarbazone) complexes: structural investigations and cellular uptake under hypoxia.

PubMed

Alam, Israt S; Arrowsmith, Rory L; Cortezon-Tamarit, Fernando; Twyman, Frazer; Kociok-Köhn, Gabriele; Botchway, Stanley W; Dilworth, Jonathan R; Carroll, Laurence; Aboagye, Eric O; Pascu, Sofia I

2016-01-07

We report the microwave synthesis of several bis(thiosemicarbazones) and the rapid gallium-68 incorporation to give the corresponding metal complexes. These proved kinetically stable under 'cold' and 'hot' biological assays and were investigated using laser scanning confocal microscopy, flow cytometry and radioactive cell retention studies under normoxia and hypoxia. (68)Ga complex retention was found to be 34% higher in hypoxic cells than in normoxic cells over 30 min, further increasing to 53% at 120 min. Our data suggests that this class of gallium complexes show hypoxia selectivity suitable for imaging in living cells and in vivo tests by microPET in nude athymic mice showed that they are excreted within 1 h of their administration.

Synthesis and strong photooxidation power of a supramolecular hybrid comprising a polyoxometalate and Ru(II) polypyridyl complex with zinc(II).

PubMed

Ohashi, Kenji; Takeda, Hiroyuki; Koike, Kazuhide; Ishitani, Osamu

2015-01-01

A novel method for constructing supramolecular hybrids composed of polyoxometalates and photofunctional metal complexes was developed. A Ru(II) complex with phosphonate groups (RuP) strongly interacted with Zn(II) to afford a 2 : 1 trinuclear metal complex ([(RuP)2Zn](3+)). In dimethylsulfoxide, [(RuP)2Zn](3+) strongly interacted with a Keggin-type heteropolyoxometalate (Si-WPOM) to form a 1 : 1 hybrid ([(RuP)2Zn]-POM). Irradiation of [(RuP)2Zn]-POM in the presence of diethanolamine caused rapid accumulation of the one-electron reduced hybrid with a quantum yield of 0.99.

Hubble Finds a Little Gem

NASA Image and Video Library

2015-08-07

This colorful bubble is a planetary nebula called NGC 6818, also known as the Little Gem Nebula. It is located in the constellation of Sagittarius (The Archer), roughly 6,000 light-years away from us. The rich glow of the cloud is just over half a light-year across — humongous compared to its tiny central star — but still a little gem on a cosmic scale. When stars like the sun enter "retirement," they shed their outer layers into space to create glowing clouds of gas called planetary nebulae. This ejection of mass is uneven, and planetary nebulae can have very complex shapes. NGC 6818 shows knotty filament-like structures and distinct layers of material, with a bright and enclosed central bubble surrounded by a larger, more diffuse cloud. Scientists believe that the stellar wind from the central star propels the outflowing material, sculpting the elongated shape of NGC 6818. As this fast wind smashes through the slower-moving cloud it creates particularly bright blowouts at the bubble’s outer layers. Hubble previously imaged this nebula back in 1997 with its Wide Field Planetary Camera 2, using a mix of filters that highlighted emission from ionized oxygen and hydrogen. This image, while from the same camera, uses different filters to reveal a different view of the nebula. Image credit: ESA/Hubble & NASA, Acknowledgement: Judy Schmidt NASA image use policy. NASA Goddard Space Flight Center enables NASA’s mission through four scientific endeavors: Earth Science, Heliophysics, Solar System Exploration, and Astrophysics. Goddard plays a leading role in NASA’s accomplishments by contributing compelling scientific knowledge to advance the Agency’s mission. Follow us on Twitter Like us on Facebook Find us on Instagram

The current status of the Gas Electron Multiplier (GEM) research at Kasetsart University, Thailand

NASA Astrophysics Data System (ADS)

Kumpiranon, P.; Kulasri, K.; Rittirong, A.; Saenboonruang, K.

2017-06-01

During the past decade, Gas Electron Multiplier (GEM) detectors have been greatly developed and utilized in numbers of applications including advanced nuclear and particle researches, medical imaging, astrophysics, and neutron detection for national security. Our GEM research group at the Department of Applied Radiation and Isotopes, Faculty of Science, Kasetsart University, Thailand, realized in its excellent properties/potentials and started extensive researches on GEM detectors. To build a strong foundation on our research group, two 10 cm × 10 cm triple GEM detectors were characterized on their important properties including absolute gains and detection uniformity. Moreover, to widen applications of the GEM detector, our group had modified the GEM detector by introducing either solid or gaseous neutron converters to the detector so that the detector could effectively detect neutrons. These modifications included coating a thin film of 10B and natB to the GEM drift cathode for thermal neutron detection and flowing a gas mixture of He/CO2 (80:20 and 70:30) and C4H10/He/CO2 (7:70:23) for fast neutron detection. Results showed that the modified GEM-based neutron detector could detect both types of neutrons with different relative efficiencies and gains depending on thicknesses and types of neutron converters. This article discusses basic knowledge of the GEM detector, construction and testing procedures, results, and discussion.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands.

PubMed

El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO(3)) using a potentiometric technique. The order of -ΔG(0) and -ΔH(0) was found to obey Co(2+) < Ni(2+) < Cu(2+) > Zn(2+), in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands

PubMed Central

El-Sherif, Ahmed A.; Shehata, Mohamed R.; Shoukry, Mohamed M.; Barakat, Mohammad H.

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO3) using a potentiometric technique. The order of –ΔG0 and –ΔH0 was found to obey Co2+ < Ni2+ < Cu2+ > Zn2+, in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K. PMID:23226992

The mononuclear nickel(II) complex bis(azido-κN)bis[2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole-κ2 N2 ,N3 ]nickel(II) protects tomato from Verticillium dahliae by inhibiting fungal growth and activating plant defences.

PubMed

Zine, Hanane; Rifai, Lalla Aicha; Koussa, Tayeb; Bentiss, Fouad; Guesmi, Salaheddine; Laachir, Abdelhakim; Makroum, Kacem; Belfaiza, Malika; Faize, Mohamed

2017-01-01

The antifungal properties of the nickel(II) complex bis(azido-κN)bis[2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole-κ 2 N 2 ,N 3 ]nickel(II) [NiL 2 (N 3 ) 2 ] and its parental ligand 2,5-bis(pyridin-2-yl)-1,3,4-thiadiazole were examined to evaluate their ability to protect tomato plants against Verticillium dahliae. Our main objectives were to determine their effects on the in vitro growth of the pathogen, and their aptitude for controlling verticillium wilt and activating plant defence responses in the greenhouse. NiL 2 (N 3 ) 2 exhibited in vitro an elevated inhibition of radial growth of three strains of the pathogen. According to the strain, the EC 50 values ranged from 10 to 29 µg mL -1 for NiL 2 (N 3 ) 2 . In the greenhouse, it induced an elevated protection against V. dahliae when it was applied twice as foliar sprays at 50 µg mL -1 . It reduced the leaf alteration index by 85% and vessel browning by 96%. In addition, its protective ability was associated with the accumulation of H 2 O 2 and the activation of total phenolic content, as well as potentiation of the activity of peroxidase and polyphenol oxidase. These results demonstrated that the coordination of the ligand with Ni associated with the azide as a coligand resulted in an improvement in its biological activity by both inhibiting the growth of V. dahliae and activating plant defence responses. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

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

PubMed

Shebl, Magdy

2009-07-15

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

Yield Improvement and Energy Savings Uing Phosphonates as Additives in Kraft pulping

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

Ulrike W. Tschirner; Timothy Smith

2007-03-31

Project Objective: Develop a commercially viable modification to the Kraft process resulting in energy savings, increased yield and improved bleachability. Evaluate the feasibility of this technology across a spectrum of wood species used in North America. Develop detailed fundamental understanding of the mechanism by which phosphonates improve KAPPA number and yield. Evaluate the North American market potential for the use of phosphonates in the Kraft pulping process. Examine determinants of customer perceived value and explore organizational and operational factors influencing attitudes and behaviors. Provide an economic feasibility assessment for the supply chain, both suppliers (chemical supply companies) and buyers (Kraftmore » mills). Provide background to most effectively transfer this new technology to commercial mills.« less

Two-electron carbon dioxide reduction catalyzed by rhenium(I) bis(imino)acenaphthene carbonyl complexes.

PubMed

Portenkirchner, Engelbert; Kianfar, Elham; Sariciftci, Niyazi Serdar; Knör, Günther

2014-05-01

Rhenium(I) carbonyl complexes carrying substituted bis(arylimino)acenaphthene ligands (BIAN-R) have been tested as potential catalysts for the two-electron reduction of carbon dioxide. Cyclic voltammetric studies as well as controlled potential electrolysis experiments were performed using CO2-saturated solutions of the complexes in acetonitrile and acetonitrile-water mixtures. Faradaic efficiencies of more than 30 % have been determined for the electrocatalytic production of CO. The effects of ligand substitution patterns and water content of the reaction medium on the catalytic performance of the new catalysts are discussed. © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

16 CFR 23.25 - Misuse of the word “gem.”

Code of Federal Regulations, 2014 CFR

2014-01-01

... stones possess the necessary qualifications to properly be termed “gems.” Imitation diamonds and other imitation stones should not be described as “gems.” Not all diamonds or natural stones, including those...

16 CFR 23.25 - Misuse of the word “gem.”

Code of Federal Regulations, 2013 CFR

2013-01-01

... stones possess the necessary qualifications to properly be termed “gems.” Imitation diamonds and other imitation stones should not be described as “gems.” Not all diamonds or natural stones, including those...

16 CFR 23.25 - Misuse of the word “gem.”

Code of Federal Regulations, 2011 CFR

2011-01-01

... stones possess the necessary qualifications to properly be termed “gems.” Imitation diamonds and other imitation stones should not be described as “gems.” Not all diamonds or natural stones, including those...

16 CFR 23.25 - Misuse of the word “gem.”

Code of Federal Regulations, 2012 CFR

2012-01-01

... stones possess the necessary qualifications to properly be termed “gems.” Imitation diamonds and other imitation stones should not be described as “gems.” Not all diamonds or natural stones, including those...

The structure of the GemC1 coiled coil and its interaction with the Geminin family of coiled-coil proteins

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

Caillat, Christophe; Fish, Alexander; Pefani, Dafni-Eleftheria

The GemC1 coiled-coil structure has subtle differences compared with its homologues Geminin and Idas. Co-expression experiments in cells and biophysical stability analysis of the Geminin-family coiled coils suggest that the GemC1 coiled coil alone is unstable. GemC1, together with Idas and Geminin, an important regulator of DNA-replication licensing and differentiation decisions, constitute a superfamily sharing a homologous central coiled-coil domain. To better understand this family of proteins, the crystal structure of a GemC1 coiled-coil domain variant engineered for better solubility was determined to 2.2 Å resolution. GemC1 shows a less typical coiled coil compared with the Geminin homodimer and themore » Geminin–Idas heterodimer structures. It is also shown that both in vitro and in cells GemC1 interacts with Geminin through its coiled-coil domain, forming a heterodimer that is more stable that the GemC1 homodimer. Comparative analysis of the thermal stability of all of the possible superfamily complexes, using circular dichroism to follow the unfolding of the entire helix of the coiled coil, or intrinsic tryptophan fluorescence of a unique conserved N-terminal tryptophan, shows that the unfolding of the coiled coil is likely to take place from the C-terminus towards the N-terminus. It is also shown that homodimers show a single-state unfolding, while heterodimers show a two-state unfolding, suggesting that the dimer first falls apart and the helices then unfold according to the stability of each protein. The findings argue that Geminin-family members form homodimers and heterodimers between them, and this ability is likely to be important for modulating their function in cycling and differentiating cells.« less

Combined readout of a triple-GEM detector

NASA Astrophysics Data System (ADS)

Antochi, V. C.; Baracchini, E.; Cavoto, G.; Di Marco, E.; Marafini, M.; Mazzitelli, G.; Pinci, D.; Renga, F.; Tomassini, S.; Voena, C.

2018-05-01

Optical readout of GEM based devices by means of high granularity and low noise CMOS sensors allows to obtain very interesting tracking performance. Space resolution of the order of tens of μm were measured on the GEM plane along with an energy resolution of 20%÷30%. The main limitation of CMOS sensors is represented by their poor information about time structure of the event. In this paper, the use of a concurrent light readout by means of a suitable photomultiplier and the acquisition of the electric signal induced on the GEM electrode are exploited to provide the necessary timing informations. The analysis of the PMT waveform allows a 3D reconstruction of each single clusters with a resolution on z of 100 μm. Moreover, from the PMT signals it is possible to obtain a fast reconstruction of the energy released within the detector with a resolution of the order of 25% even in the tens of keV range useful, for example, for triggering purpose.

Heteroleptic Copper(I) Complexes of "Scorpionate" Bis-pyrazolyl Carboxylate Ligand with Auxiliary Phosphine as Potential Anticancer Agents: An Insight into Cytotoxic Mode.

PubMed

Khan, Rais Ahmad; Usman, Mohammad; Dhivya, Rajakumar; Balaji, Perumalsamy; Alsalme, Ali; AlLohedan, Hamad; Arjmand, Farukh; AlFarhan, Khalid; Akbarsha, Mohammad Abdulkader; Marchetti, Fabio; Pettinari, Claudio; Tabassum, Sartaj

2017-03-24

New copper(I) complexes [CuCl(PPh 3 )(L)] (1: L = L A  = 4-carboxyphenyl)bis(3,5-dimethylpyrazolyl)methane; (2: L = L B  = 3-carboxyphenyl)bis(3,5-dimethylpyrazolyl)methane) were prepared and characterised by elemental analysis and various spectroscopic techniques such as FT-IR, NMR, UV-Vis, and ESI-MS. The molecular structures of complexes 1 and 2 were analyzed by theoretical B3LYP/DFT method. Furthermore, in vitro DNA binding studies were carried out to check the ability of complexes 1 and 2 to interact with native calf thymus DNA (CT-DNA) using absorption titration, fluorescence quenching and circular dichroism, which is indicative of more avid binding of the complex 1. Moreover, DNA mobility assay was also conducted to study the concentration-dependent cleavage pattern of pBR322 DNA by complex 1, and the role of ROS species to have a mechanistic insight on the cleavage pattern, which ascertained substantial roles by both hydrolytic and oxidative pathways. Additionally, we analyzed the potential of the interaction of complex 1 with DNA and enzyme (Topo I and II) with the aid of molecular modeling. Furthermore, cytotoxic activity of complex 1 was tested against HepG2 cancer cell lines. Thus, the potential of the complex 1 is promising though further in vivo investigations may be required before subjecting it to clinical trials.

Mono- and bis-tolyl­terpyridine iridium(III) complexes

PubMed Central

Hinkle, Lindsay M.; Young, Victor G.; Mann, Kent R.

2010-01-01

The first structure report of trichlorido[4′-(p-tolyl)-2,2′:6′,2′′-terpyridine]iridium(III) dimethyl sulfoxide solvate, [IrCl3(C22H17N3)]·C2H6OS, (I), is presented, along with a higher-symmetry setting of previously reported bis­[4′-(p-tolyl)-2,2′:6′,2′′-terpyridine]iridium(III) tris­(hexa­fluorido­phosphate) acetonitrile disolvate, [Ir(C22H17N3)2](PF6)3·2C2H3N, (II) [Yoshikawa, Yamabe, Kanehisa, Kai, Takashima & Tsukahara (2007 ▶). Eur. J. Inorg. Chem. pp. 1911–1919]. For (I), the data were collected with synchrotron radiation and the dimethyl sulfoxide solvent mol­ecule is disordered over three positions, one of which is an inversion center. The previously reported structure of (II) is presented in the more appropriate C2/c space group. The iridium complex and one PF6 − anion lie on twofold axes in this structure, making half of the mol­ecule unique. PMID:20203396

Limitations and opportunities of whole blood bilirubin measurements by GEM premier 4000®.

PubMed

Wang, Li; Albert, Arianne Y K; Jung, Benjamin; Hadad, Keyvan; Lyon, Martha E; Basso, Melanie

2017-03-29

Neonatal hyperbilirubinemia has traditionally been screened by either total serum bilirubin or transcutaneous bilirubin. Whole blood bilirubin (TwB) by the GEM Premier 4000® blood gas analyzer (GEM) is a relatively new technology and it provides fast bilirubin results with a small sample volume and can measure co-oximetry and other analytes. Our clinical study was to evaluate the reliability of TwB measured by the GEM and identify analytical and clinical factors that may contribute to possible bias. 440 consecutive healthy newborn samples that had plasma bilirubin ordered for neonatal hyperbilirubinemia screening were included. TwB was first measured using the GEM, after which the remainder of the blood was spun and plasma neonatal bilirubin was measured using the VITROS 5600® (VITROS). 62 samples (14%) were excluded from analysis due to failure in obtaining GEM results. Passing-Bablok regression suggested that the GEM results were negatively biased at low concentrations of bilirubin and positively biased at higher concentrations relative to the VITROS results (y = 1.43x-61.13). Bland-Altman plots showed an overall negative bias of the GEM bilirubin with a wide range of differences compared to VITROS. Both hemoglobin concentration and hemolysis affected the accuracy of the GEM results. Clinically, male infants had higher mean bilirubin levels, and infants delivered by caesarean section had lower hemoglobin levels. When comparing the number of results below the 40th percentile and above the 95th percentile cut-offs in the Bhutani nomogram which would trigger discharge or treatment, GEM bilirubin exhibited poor sensitivity and poor specificity in contrast to VITROS bilirubin. An imperfect correlation was observed between whole blood bilirubin measured on the GEM4000® and plasma bilirubin on the VITROS 5600®. The contributors to the observed differences between the two instruments were specimen hemolysis and the accuracy of hemoglobin measurements, the latter

Preliminary assessment of developmental toxicity of Perfluorinated Phosphonic Acid in mice

EPA Science Inventory

Perfluorinated phosphonic acids (PFPAs) are a third member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. These emerging chemicals have recently been detected in the environment, particularl...

Gaseous Elemental Mercury (GEM) Emissions from Snow Surfaces in Northern New York

PubMed Central

Maxwell, J. Alexander; Holsen, Thomas M.; Mondal, Sumona

2013-01-01

Snow surface-to-air exchange of gaseous elemental mercury (GEM) was measured using a modified Teflon fluorinated ethylene propylene (FEP) dynamic flux chamber (DFC) in a remote, open site in Potsdam, New York. Sampling was conducted during the winter months of 2011. The inlet and outlet of the DFC were coupled with a Tekran Model 2537A mercury (Hg) vapor analyzer using a Tekran Model 1110 two port synchronized sampler. The surface GEM flux ranged from −4.47 ng m−2 hr−1 to 9.89 ng m−2 hr−1. For most sample periods, daytime GEM flux was strongly correlated with solar radiation. The average nighttime GEM flux was slightly negative and was not well correlated with any of the measured meteorological variables. Preliminary, empirical models were developed to estimate GEM emissions from snow surfaces in northern New York. These models suggest that most, if not all, of the Hg deposited with and to snow is reemitted to the atmosphere. PMID:23874951

Gaseous elemental mercury (GEM) emissions from snow surfaces in northern New York.

PubMed

Maxwell, J Alexander; Holsen, Thomas M; Mondal, Sumona

2013-01-01

Snow surface-to-air exchange of gaseous elemental mercury (GEM) was measured using a modified Teflon fluorinated ethylene propylene (FEP) dynamic flux chamber (DFC) in a remote, open site in Potsdam, New York. Sampling was conducted during the winter months of 2011. The inlet and outlet of the DFC were coupled with a Tekran Model 2537A mercury (Hg) vapor analyzer using a Tekran Model 1110 two port synchronized sampler. The surface GEM flux ranged from -4.47 ng m(-2) hr(-1) to 9.89 ng m(-2) hr(-1). For most sample periods, daytime GEM flux was strongly correlated with solar radiation. The average nighttime GEM flux was slightly negative and was not well correlated with any of the measured meteorological variables. Preliminary, empirical models were developed to estimate GEM emissions from snow surfaces in northern New York. These models suggest that most, if not all, of the Hg deposited with and to snow is reemitted to the atmosphere.

Novel bis-(−)-nor-meptazinol derivatives act as dual binding site AChE inhibitors with metal-complexing property

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

Zheng, Wei; NPFPC Key Laboratory of Contraceptives and Devices, Shanghai Institute of Planned Parenthood Research, 2140 Xietu Road, Shanghai 200032; Li, Juan

The strategy of dual binding site acetylcholinesterase (AChE) inhibition along with metal chelation may represent a promising direction for multi-targeted interventions in the pathophysiological processes of Alzheimer's disease (AD). In the present study, two derivatives (ZLA and ZLB) of a potent dual binding site AChE inhibitor bis-(−)-nor-meptazinol (bis-MEP) were designed and synthesized by introducing metal chelating pharmacophores into the middle chain of bis-MEP. They could inhibit human AChE activity with IC{sub 50} values of 9.63 μM (for ZLA) and 8.64 μM (for ZLB), and prevent AChE-induced amyloid-β (Aβ) aggregation with IC{sub 50} values of 49.1 μM (for ZLA) and 55.3more » μM (for ZLB). In parallel, molecular docking analysis showed that they are capable of interacting with both the catalytic and peripheral anionic sites of AChE. Furthermore, they exhibited abilities to complex metal ions such as Cu(II) and Zn(II), and inhibit Aβ aggregation triggered by these metals. Collectively, these results suggest that ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency, and may be potential leads of value for further study on disease-modifying treatment of AD. -- Highlights: ► Two novel bis-(−)-nor-meptazinol derivatives are designed and synthesized. ► ZLA and ZLB may act as dual binding site AChEIs with metal-chelating potency. ► They are potential leads for disease-modifying treatment of Alzheimer's disease.« less

Quantitative structure-property relationship (correlation analysis) of phosphonic acid-based chelates in design of MRI contrast agent.

PubMed

Tiwari, Anjani K; Ojha, Himanshu; Kaul, Ankur; Dutta, Anupama; Srivastava, Pooja; Shukla, Gauri; Srivastava, Rakesh; Mishra, Anil K

2009-07-01

Nuclear magnetic resonance imaging is a very useful tool in modern medical diagnostics, especially when gadolinium (III)-based contrast agents are administered to the patient with the aim of increasing the image contrast between normal and diseased tissues. With the use of soft modelling techniques such as quantitative structure-activity relationship/quantitative structure-property relationship after a suitable description of their molecular structure, we have studied a series of phosphonic acid for designing new MRI contrast agent. Quantitative structure-property relationship studies with multiple linear regression analysis were applied to find correlation between different calculated molecular descriptors of the phosphonic acid-based chelating agent and their stability constants. The final quantitative structure-property relationship mathematical models were found as--quantitative structure-property relationship Model for phosphonic acid series (Model 1)--log K(ML) = {5.00243(+/-0.7102)}- MR {0.0263(+/-0.540)}n = 12 l r l = 0.942 s = 0.183 F = 99.165 quantitative structure-property relationship Model for phosphonic acid series (Model 2)--log K(ML) = {5.06280(+/-0.3418)}- MR {0.0252(+/- .198)}n = 12 l r l = 0.956 s = 0.186 F = 99.256.

Effects of Perfluorinated Phosphonic Acid Exposure during pregnancy in the mouse

EPA Science Inventory

Perfluorinated phosphonic acids (PFPAs) are a member of the perfluoroalkyl acid (PFAA) family, and are structurally similar to the perfluoroalkyl sulfonates and perfluoroalkyl carboxylates. These chemicals have recently been detected in the environment, particularly in surface wa...

Performance Evaluation of the COBRA GEM for the Application of the TPC

NASA Astrophysics Data System (ADS)

Terasaki, Kohei; Hamagaki, Hideki; Gunji, Taku; Yamaguchi, Yorito

2014-09-01

Suppression of the back-drifting ions from avalanche region to drift space (IBF: Ion Backflow) is the key for a Time Projection Chamber (TPC) since IBF easily distorts the drift field. To suppress IBF, Gating Grid system is widely used for the TPC but this limits the data taking rate. Gas Electron Multiplier (GEM) has advantages in the reduction of IBF and high rate capability. By adopting GEM, it is possible to run a TPC continuously under high rate and high multiplicity conditions. Motivated by the study of IBF reduction for RICH with Thick COBRA, which has been developed by F. A. Amero et al., we developed COBRA GEMs for the application of a TPC. With a stack configuration, IBF reaches about 0.1 ~ 0.5%, which is ×5--10 better IBF than the standard GEMs. However, the measured energy resolution with COBRA is 20% (σ) and this is much worse than the resolution with standard GEMs. Measurement of long-time stability of gain indicates that gain of COBRA varies significantly due to charging up effect. Simulation studies based on Garfield++ are performed for understanding quantitatively the reasons of worse energy resolution and instability of gain. In this presentation, we will report the simulation studies together with the measured performance of the COBRA GEM.

Gem and mineral identification using GL Gem Raman and comparison with other portable instruments

NASA Astrophysics Data System (ADS)

Culka, Adam; Hyršl, Jaroslav; Jehlička, Jan

2016-11-01

Several mainly silicate minerals in their gemstone varieties have been analysed by the Gem Raman portable system by Gemlab R&T, Vancouver, Canada, in order to ascertain the general performance of this relatively non-expensive tool developed exactly for the purpose of gemstone identification. The Raman spectra of gemstones acquired by this system have been subsequently critically compared with the data obtained by several other portable or handheld Raman instruments. The Raman spectra acquired with the Gem Raman instrument were typically of lesser quality when compared with the spectra taken by other instruments. Characteristic features such as steep baseline probably due to the fluorescence of the minerals, Raman bands much broader and therefore less resolved closely located Raman bands, and generally greater shifts of the band positions from the reference values were encountered. Some gemstone groups such as rubies did not provide useful Raman spectra at all. Nevertheless, general identification of gemstones was possible for a selection of gemstones.

New Gem-Dicyanocyclobutane-Containing Hydroxyesters

DTIC Science & Technology

1989-04-01

polar saponification conditions, the cyclobutanes underwent ring opening to unidentified products. When in one case we obtained a carboxylic acid, it...polar saponification conditions also favored ionization of the cyclobutane back to the tetramethylenes. We conclude that the proposed route to gem

GAS eleven node thermal model (GEM)

NASA Technical Reports Server (NTRS)

Butler, Dan

1988-01-01

The Eleven Node Thermal Model (GEM) of the Get Away Special (GAS) container was originally developed based on the results of thermal tests of the GAS container. The model was then used in the thermal analysis and design of several NASA/GSFC GAS experiments, including the Flight Verification Payload, the Ultraviolet Experiment, and the Capillary Pumped Loop. The model description details the five cu ft container both with and without an insulated end cap. Mass specific heat values are also given so that transient analyses can be performed. A sample problem for each configuration is included as well so that GEM users can verify their computations. The model can be run on most personal computers with a thermal analyzer solution routine.

Experimental and Theoretical Progress on the GEM Theory

NASA Astrophysics Data System (ADS)

Brandenburg, J. E.

This paper reports experimental and theoretical progress on the GEM unification theory. In theoretical progress, the derivation of the GEM theory using it in a fully covariant form is achieved based on the principle of self-cancellation of the ZPF EM stress-momentum tensor. This derivation reveals that the final Gravity-EM system obeys a Helmholtz-like equation resembling that governing sound propagation. Finally an improved derivation of the formula for the Newton Gravitation constant is shown, qresulting in the formula G = e2/(4πɛ0 me mp) α exp (-2 (α-.86/σ2…) = 6.673443 x10-11 N-m2 kg-2 that agrees with experimental values to 3 parts per 100,000. Experiments have found parity violating weight reductions in gyroscopes driven by rotating EM fields. These experiments appear to confirm gravity modification using electromagnetism predicted by the GEM theory through the Vacuum Bernoulli Equation.

The GEMS Model of Volunteer Administration.

ERIC Educational Resources Information Center

Culp, Ken, III; Deppe, Catherine A.; Castillo, Jaime X.; Wells, Betty J.

1998-01-01

Describes GEMS, a spiral model that profiles volunteer administration. Components include Generate, Educate, Mobilize, and Sustain, four sets of processes that span volunteer recruitment and selection to retention or disengagement. (SK)

Unexpected complexes from meta-phenylene bis(tert-butyl nitroxides) and gadolinium(III) 1,1,1,5,5,5-hexafluoropentane-2,4-dionate

NASA Astrophysics Data System (ADS)

Sekine, Hiroyasu; Ishida, Takayuki

2018-01-01

Coordination reaction of the stable ground triplet biradical biphenyl-3,5-diyl bis(tert-butyl nitroxide) and [Gd(hfac)3(H2O)2] unexpectedly gave complexes containing a dimerized diamagnetic ligand via a [3+3] cycloaddition of the benzene rings (hfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dionate). To avoid such dimerization, we introduced a bulkier substituent into the ligand; namely, a new ground triplet biradical 5-mesityl-1,3-phenylene bis(tert-butyl nitroxide) was applied to this complexation scheme. However, an unexpected complex was again obtained in a different way, and the magnetic study revealed that the novel ligand involved was diamagnetic. The crystallographic analysis of the product clarified isomerization from the paramagnetic ligand to a diamagnetic N-tert-butylaminoquinone imine N-oxide ligand as a result of disproportionation from two open-shell nitroxide groups to closed-shell groups, an amine and a nitrone. The present paper reports the first structural evidence for a diamagnetic isomer of m-phenylene-bridged bisnitroxde compounds.

FPGA based charge fast histogramming for GEM detector

NASA Astrophysics Data System (ADS)

Poźniak, Krzysztof T.; Byszuk, A.; Chernyshova, M.; Cieszewski, R.; Czarski, T.; Dominik, W.; Jakubowska, K.; Kasprowicz, G.; Rzadkiewicz, J.; Scholz, M.; Zabolotny, W.

2013-10-01

This article presents a fast charge histogramming method for the position sensitive X-ray GEM detector. The energy resolved measurements are carried out simultaneously for 256 channels of the GEM detector. The whole process of histogramming is performed in 21 FPGA chips (Spartan-6 series from Xilinx) . The results of the histogramming process are stored in an external DDR3 memory. The structure of an electronic measuring equipment and a firmware functionality implemented in the FPGAs is described. Examples of test measurements are presented.

A large ungated TPC with GEM amplification

NASA Astrophysics Data System (ADS)

Berger, M.; Ball, M.; Fabbietti, L.; Ketzer, B.; Arora, R.; Beck, R.; Böhmer, F. V.; Chen, J.-C.; Cusanno, F.; Dørheim, S.; García, F.; Hehner, J.; Herrmann, N.; Höppner, C.; Kaiser, D.; Kis̆, M.; Kleipa, V.; Konorov, I.; Kunkel, J.; Kurz, N.; Leifels, Y.; Müllner, P.; Münzer, R.; Neubert, S.; Rauch, J.; Schmidt, C. J.; Schmitz, R.; Soyk, D.; Vandenbroucke, M.; Voss, B.; Walther, D.; Zmeskal, J.

2017-10-01

A Time Projection Chamber (TPC) is an ideal device for the detection of charged particle tracks in a large volume covering a solid angle of almost 4 π. The high density of hits on a given particle track facilitates the task of pattern recognition in a high-occupancy environment and in addition provides particle identification by measuring the specific energy loss for each track. For these reasons, TPCs with Multiwire Proportional Chamber (MWPC) amplification have been and are widely used in experiments recording heavy-ion collisions. A significant drawback, however, is the large dead time of the order of 1 ms per event generated by the use of a gating grid, which is mandatory to prevent ions created in the amplification region from drifting back into the drift volume, where they would severely distort the drift path of subsequent tracks. For experiments with higher event rates this concept of a conventional TPC operating with a triggered gating grid can therefore not be applied without a significant loss of data. A continuous readout of the signals is the more appropriate way of operation. This, however, constitutes a change of paradigm with considerable challenges to be met concerning the amplification region, the design and bandwidth of the readout electronics, and the data handling. A mandatory prerequisite for such an operation is a sufficiently good suppression of the ion backflow from the avalanche region, which otherwise limits the tracking and particle identification capabilities of such a detector. Gas Electron Multipliers (GEM) are a promising candidate to combine excellent spatial resolution with an intrinsic suppression of ions. In this paper we describe the design, construction and the commissioning of a large TPC with GEM amplification and without gating grid (GEM-TPC). The design requirements have driven innovations in the construction of a light-weight field-cage, a supporting media flange, the GEM amplification and the readout system, which are

Structure based design, synthesis and biological evaluation of amino phosphonate derivatives as human glucokinase activators.

PubMed

Yellapu, Nanda Kumar; Kilaru, Ravendra Babu; Chamarthi, Nagaraju; Pvgk, Sarma; Matcha, Bhaskar

2017-06-01

Glucokinase (GK) is a potential therapeutic target of type 2 diabetes and GK activators (GKAs) represent a promising class of small organic molecules which enhance GK activity. Based on the configuration and conformation of the allosteric site of GK, we have designed a novel class of amino phosphonate derivatives in order to develop potent GKAs. The QSAR model developed using numerous descriptors revealed its potential with the best effective statistical values of RMSE=1.52 and r 2 =0.30. Moreover, application of this model on the present test set GKAs proved to be worthy to predict their activities as a better linear relationship was observed with RMSE=0.14 and r 2 =0.88. ADME studies and Lipinski filters encouraged them as safer therapeutics. The molecular dynamics and docking studies against the GK allosteric site revealed that all GKAs bind with best affinities and the complexes are strengthened by H-bonding, phosphonate salt bridges, hydrophobic and arene cat ionic interactions. Finally, in vitro evaluation with human liver GK revealed their potential to increase the GK activity by different folds. The results from QSAR, ADME, molecular docking and in vitro assays strongly suggested that the present molecules could be used as effective and safer therapeutics to control and manage type 2 diabetes. Copyright © 2017. Published by Elsevier Ltd.

DEGRADATION OF NITRILOTRIS (METHYLENEPHOSPHONIC ACID) AND RELATED (AMINO) PHOSPHONATE CHELATING AGENTS IN THE PRESENCE OF MANGANESE AND MOLECULAR OXYGEN. (R826376)

EPA Science Inventory

Phosphonates are used in an increasing variety of industrial and household
applications including cooling waters systems, oil production, textile industry,
and detergents. Phosphonates are not biodegraded during wastewater treatment but
instead are removed by adsor...

Investigations into the synthesis and fluorescence properties of Eu(III), Tb(III), Sm(III) and Gd(III) complexes of a novel bis- β-diketone-type ligand

NASA Astrophysics Data System (ADS)

Luo, Yi-Ming; Chen, Zhe; Tang, Rui-Ren; Xiao, Lin-Xiang; Peng, Hong-Jian

2008-02-01

A novel bis- β-diketon ligand, 1,1'-(2,6-bispyridyl)bis-3-phenyl-1,3-propane-dione (L), was designed and synthesized and its complexes with Eu(III), Tb(III), Sm(III) and Gd(III) ions were successfully prepared. The ligand and the corresponding metal complexes were characterized by elemental analysis, and infrared, mass and proton nuclear magnetic resonance spectroscopy. Analysis of the IR spectra suggested that each of the lanthanide metal ions coordinated to the ligand via the carbonyl oxygen atoms and the nitrogen atom of the pyridine ring. The fluorescence properties of these complexes in solid state were investigated and it was discovered that all of the lanthanide ions could be sensitized by the ligand (L) to some extent. In particular, the Tb(III) complex was an excellent green-emitter and would be a potential candidate material for applications in organic light-emitting devices (OLEDs) and medical diagnosis.

Editorial: Reviewer Selection Process and New Areas of Expertise in GEMS

NASA Technical Reports Server (NTRS)

Liemohn, Michael W.; Balikhin, Michael; Kepko, Larry; Rodger, Alan; Wang, Yuming

2016-01-01

One method of selecting potential reviewers for papers submitted to the Journal of Geophysical Research Space Physics is to filter the user database within the Geophysical Electronic Manuscript System (GEMS) by areas of expertise. The list of these areas in GEMS can be self selected by users in their profile settings. The Editors have added 18 new entries to this list, an increase of 33 more than the previous 55 entries. All space physicists are strongly encouraged to update their profile settings in GEMS, especially their areas of expertise selections, and details of how to do this are provided.

Editorial: Reviewer selection process and new areas of expertise in GEMS

NASA Astrophysics Data System (ADS)

Liemohn, Michael W.; Balikhin, Michael; Kepko, Larry; Rodger, Alan; Wang, Yuming

2016-06-01

One method of selecting potential reviewers for papers submitted to the Journal of Geophysical Research Space Physics is to filter the user database within the Geophysical Electronic Manuscript System (GEMS) by areas of expertise. The list of these areas in GEMS can be self selected by users in their profile settings. The Editors have added 18 new entries to this list, an increase of 33% more than the previous 55 entries. All space physicists are strongly encouraged to update their profile settings in GEMS, especially their areas of expertise selections, and details of how to do this are provided.

Gemcitabine-loaded albumin nanospheres (GEM-ANPs) inhibit PANC-1 cells in vitro and in vivo

NASA Astrophysics Data System (ADS)

Li, Ji; Di, Yang; Jin, Chen; Fu, Deliang; Yang, Feng; Jiang, Yongjian; Yao, Lie; Hao, Sijie; Wang, Xiaoyi; Subedi, Sabin; Ni, Quanxing

2013-04-01

With the development of nanotechnology, special attention has been given to the nanomaterial application in tumor treatment. Here, a modified desolvation-cross-linking method was successfully applied to fabricate gemcitabine-loaded albumin nanospheres (GEM-ANPs), with 110 and 406 nm of mean diameter, respectively. The aim of this study was to assess the drug distribution, side effects, and antitumor activity of GEM-ANPs in vivo. The metabolic viability and flow cytometry analysis revealed that both GEM-ANPs, especially 406-nm GEM-ANPs, could effectively inhibit the metabolism and proliferation and promote the apoptosis of human pancreatic carcinoma (PANC-1) in vitro. Intravenous injection of 406-nm GEM-ANPs exhibited a significant increase of gemcitabine in the pancreas, liver, and spleen of Sprague-Dawley rats ( p < 0.05). Moreover, no signs of toxic side effects analyzed by blood parameter changes were observed after 3 weeks of administration although a high dose (200 mg/kg) of GEM-ANPs were used. Additionally, in PANC-1-induced tumor mice, intravenous injection of 406-nm GEM-ANPs also could effectively reduce the tumor volume by comparison with free gemcitabine. With these findings, albumin nanosphere-loading approach might be efficacious to improve the antitumor activity of gemcitabine, and the efficacy is associated with the size of GEM-ANPs.

The cylindrical GEM detector of the KLOE-2 experiment

NASA Astrophysics Data System (ADS)

Bencivenni, G.; Branchini, P.; Ciambrone, P.; Czerwinski, E.; De Lucia, E.; Di Cicco, A.; Domenici, D.; Felici, G.; Fermani, P.; Morello, G.

2017-07-01

The KLOE-2 experiment started its data taking campaign in November 2014 with an upgraded tracking system at the DAΦNE electron-positron collider at the Frascati National Laboratory of INFN. The new tracking device, the Inner Tracker, operated together with the KLOE-2 Drift Chamber, has been installed to improve track and vertex reconstruction capabilities of the experimental apparatus. The Inner Tracker is a cylindrical GEM detector composed of four cylindrical triple-GEM detectors, each provided with an X-V strips-pads stereo readout. Although GEM detectors are already used in high energy physics experiments, this device is considered a frontier detector due to its fully-cylindrical geometry: KLOE-2 is the first experiment benefiting of this novel detector technology. Alignment and calibration of this detector will be presented together with its operating performance and reconstruction capabilities.

Identifying the Source of Gem Diamonds: Requirements for a Certification System

NASA Astrophysics Data System (ADS)

Shigley, J. E.

2002-05-01

Recent civil conflicts in several countries, in which profits from the sales of gem diamonds have supported the rival factions, have forced the jewelry industry to confront the need to certify the geographic sources of gem diamonds. The goals of this program are to prohibit the sale of so-called "conflict diamonds", and to prevent the loss of consumer confidence. Efforts to identify unique characteristics of gem diamonds have been hampered so far by the absence of chemical or physical features that are diagnostic of particular sources, and the lack of a representative collection of diamonds from major producing areas that would be required for a rigorous scientific study. The jewelry industry has therefore adopted plans to track gem diamonds from the mine through the manufacturing process to the consumer. Practical requirements for implementation of such a certification system will be summarized. Any proposed solutions for determining the sources of gem diamonds by some analytical technique, or for following diamonds from the mine, must take into account the annual production of several tens of millions of carats of rough diamonds, which are transformed during manufacturing into several hundreds of millions of polished gemstones (with an average weight of only about 0.03 carat, or 0.006 gram).

What a difference a 5f element makes: trivalent and tetravalent uranium halide complexes supported by one and two bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) ligands.

PubMed

Cantat, Thibault; Scott, Brian L; Morris, David E; Kiplinger, Jaqueline L

2009-03-02

The coordination behavior of the bis[2-(diisopropylphosphino)-4-methylphenyl]amido ligand (PNP) toward UI3(THF)4 and UCl4 has been investigated to access new uranium(III) and uranium(IV) halide complexes supported by one and two PNP ligands. The reaction between (PNP)K (6) and 1 equiv of UI3(THF)4 afforded the trivalent halide complex (PNP)UI2(4-tBu-pyridine)2 (7) in the presence of 4-tert-butylpyridine. The same reaction carried out with UCl4 and no donor ligand gave [(PNP)UCl3]2 (8), in which the uranium coordination sphere in the (PNP)UCl3 unit is completed by a bridging chloride ligand. When UCl4 is reacted with 1 equiv (PNP)K (6) in the presence of THF, trimethylphosphine oxide (TMPO), or triphenylphosphineoxide (TPPO), the tetravalent halide complexes (PNP)UCl3(THF) (9), (PNP)UCl3(TMPO)2 (10), and (PNP)UCl3(TPPO) (11), respectively, are formed in excellent yields. The bis(PNP) complexes of uranium(III), (PNP)2UI (12), and uranium(IV), (PNP)2UCl2 (13), were easily isolated from the analogous reactions between 2 equiv of 6 and UI3(THF)4 or UCl4, respectively. Complexes 12 and 13 represent the first examples of complexes featuring two PNP ligands coordinated to a single metal center. Complexes 7-13 have been characterized by single-crystal X-ray diffraction and 1H and 31P NMR spectroscopy. The X-ray structures demonstrate the ability of the PNP ligand to adopt new coordination modes upon coordination to uranium. The PNP ligand can adopt both pseudo-meridional and pseudo-facial geometries when it is kappa3-(P,N,P) coordinated, depending on the steric demand at the uranium metal center. Additionally, its hemilabile character was demonstrated with an unusual kappa2-(P,N) coordination mode that is maintained in both the solid-state and in solution. Comparison of the structures of the mono(PNP) and bis(PNP) complexes 7, 9, 11-13 with their respective C5Me5 analogues 1-4 undoubtedly show that a more sterically congested environment is provided by the PNP ligand. The

The mechanism of action of piperazine-phosphonates derivatives in cotton fabric

USDA-ARS?s Scientific Manuscript database

Piperazine-phosphonates additives are known to be very effective flame retardants on different polymeric systems, especially cotton cellulose. In order to understand their mechanism of action, we carried out the investigation of their thermal behavior on cotton fabric by, first, employing the attenu...

Impaired clinical utility of sequential patient GEM blood gas measurements associated with calibration schedule.

PubMed

Cembrowski, George S; Xu, Qian; Cembrowski, Adam R; Mei, Junyi; Sadrzadeh, Hossein

2017-11-01

Within- and/or between-instrument variation may falsely indicate patient trends or obscure real trends. We employ a methodology that transforms sequential intra-patient results into estimates of biologic and analytic variation. We previously derived realistic biologic variation (s b ) of blood gas (BG) and hematology analytes. We extend this methodology to derive the imprecision of two GEM 4000 BG analyzers. A laboratory data repository provided arterial BG, electrolyte and metabolite results generated by two GEM 4000s on ICU patients in 2012-2013. We tabulated consecutive pairs of intra-patient results separated by increasing time interval between consecutive tests. The average between pair variations were regressed against time with the y-intercept representing the sum of the biologic variation and short term analytic variation: y o 2 =s b 2 +s a 2 . Using an equivalent equation for the Radiometer ABL, the imprecision of the two GEMs was calculated: s aGEM =(y oGEM 2 -y oABL 2 +s aABL 2 ) 1/2 . This analysis was performed for nearly all measurements, regardless of time as well for values obtained over two 12h mutually exclusive periods, starting either at 2am or 2pm. Regression graphs were derived from 1800 patients' blood gas results with least 10,000 data pairs grouped into 2h intervals. The calculated s aGEM exceed the directly measured s aABL with many GEM sigma ratios of biologic variation/analytic variation being close to unity. All of the afternoon s aGEM exceeded their morning counterparts with pH, pCO 2 , K and bicarbonate being statistically significant. For many analytes, the average analytical variation of tandem GEMs approximates the biologic variation, indicating impaired clinical usefulness of tandem sequential measurements. A significant component of this variation is due to increased variation of the GEMs between 2pm and 2am. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Two-photon absorption properties of cationic 1,4-bis(styryl)benzene derivative and its inclusion complexes with cyclodextrins.

PubMed

Nag, Okhil Kumar; Nayak, Rati Ranjan; Lim, Chang Su; Kim, In Hong; Kyhm, Kwangseuk; Cho, Bong Rae; Woo, Han Young

2010-07-29

Two-photon absorption properties of 1,4-bis{4'-[N,N-bis(6''-trimethylammoniumhexyl)amino]styryl}benzene tetrabromide (C1) and its inclusion complexes (ICs) with cyclodextrins (CDs) have been studied. Upon complexation with CDs, the absorption spectra of C1 showed a slight red shift, whereas the emission spectra showed a blue shift with concomitant increase in the fluorescence quantum efficiency. A Stern-Volmer study using K(3)Fe(CN)(6) as a quencher revealed significant reduction in the photoinduced charge transfer quenching, in accord with the IC formation. Comparison of the spectroscopic results reveals that C1 forms increasingly more stable ICs in the order C1/beta-CD < C1/gamma-CD < C1/(3gamma:beta)-CD (gamma-CD/beta-CD 3:1, mole ratio). Moreover, the two-photon action cross section of C1 increased from 200 GM for C1 to 400 GM for C1/beta-CD, 460 GM for C1/gamma-CD, and 650 GM for C1/(3gamma:beta)-CD, respectively. Furthermore, the two-photon microscopy images of HeLa cells stained with C1 emitted strong two-photon excited fluorescence in the plasma membrane. These results provide a useful guideline for the development of efficient two-photon materials for bioimaging applications.

Botanicals and Phosphonate Show Potential to Replace Copper for Control of Potato Late Blight

PubMed Central

Forrer, Hans-Rudolf

2017-01-01

Potato late blight (PLB) caused by Phytophthora infestans (Pi) is the most harmful disease in potato production worldwide. In organic farming, copper is used despite its persistence in soil and toxicity to soil organisms. To replace copper, suspensions of powders from three promising botanicals, including bark of buckthorn (Frangula alnus, FA), roots of medicinal rhubarb (Rheum palmatum) and galls of the nutgall tree (Galla chinensis), were tested in multi-year field experiments. The current study shows for the first time that botanicals could replace copper under field conditions and best PLB reduction on leaves was achieved with FA, reaching a level close to that of 2 to 3 kg copper per hectare and year. Better results than with copper were achieved with Phosfik® (Ph), a phosphonate-based product. For both FA and Ph, the mode of action is based on induced resistance, for Ph also on direct fungicidal effects. A disadvantage of Ph is the accumulation of residues in potato tubers. Nevertheless, two to three applications with 2 to 3 L/ha of Ph would be feasible to not exceed a minimal risk level (MLR) of 20 mg/kg of phosphorous acid as proposed by the European Food Safety Authority. Due to an excellent environmental profile and a complex mode of action counteracting Pi resistance, phosphonate-based products would be most suitable for sustainable PLB management in integrated pest management (IPM) programmes. PMID:29371580

Phosphonate Analogs of 2-Oxoglutarate Perturb Metabolism and Gene Expression in Illuminated Arabidopsis Leaves

PubMed Central

Araújo, Wagner L.; Tohge, Takayuki; Nunes-Nesi, Adriano; Daloso, Danilo M.; Nimick, Mhairi; Krahnert, Ina; Bunik, Victoria I.; Moorhead, Greg B. G.; Fernie, Alisdair R.

2012-01-01

Although the role of the 2-oxoglutarate dehydrogenase complex (2-OGDHC) has previously been demonstrated in plant heterotrophic tissues its role in photosynthetically active tissues remains poorly understood. By using a combination of metabolite and transcript profiles we here investigated the function of 2-OGDHC in leaves of Arabidopsis thaliana via use of specific phosphonate inhibitors of the enzyme. Incubation of leaf disks with the inhibitors revealed that they produced the anticipated effects on the in situ enzyme activity. In vitro experiments revealed that succinyl phosphonate (SP) and a carboxy ethyl ester of SP are slow-binding inhibitors of the 2-OGDHC. Our results indicate that the reduced respiration rates are associated with changes in the regulation of metabolic and signaling pathways leading to an imbalance in carbon-nitrogen metabolism and cell homeostasis. The inducible alteration of primary metabolism was associated with altered expression of genes belonging to networks of amino acids, plant respiration, and sugar metabolism. In addition, by using isothermal titration calorimetry we excluded the possibility that the changes in gene expression resulted from an effect on 2-oxoglutarate (2OG) binding to the carbon/ATP sensing protein PII. We also demonstrated that the 2OG degradation by the 2-oxoglutarate dehydrogenase strongly influences the distribution of intermediates of the tricarboxylic acid (TCA) cycle and the GABA shunt. Our results indicate that the TCA cycle activity is clearly working in a non-cyclic manner upon 2-OGDHC inhibition during the light period. PMID:22876250

Preparation of polyvinyl alcohol graphene oxide phosphonate film and research of thermal stability and mechanical properties.

PubMed

Li, Jihui; Song, Yunna; Ma, Zheng; Li, Ning; Niu, Shuai; Li, Yongshen

2018-05-01

In this article, flake graphite, nitric acid, peroxyacetic acid and phosphoric acid are used to prepare graphene oxide phosphonic and phosphinic acids (GOPAs), and GOPAs and polyvinyl alcohol (PVA) are used to synthesize polyvinyl alcohol graphene oxide phosphonate and phosphinate (PVAGOPs) in the case of faint acidity and ultrasound irradiation, and PVAGOPs are used to fabricate PVAGOPs film, and the structure and morphology of GOPAs, PVAGOPs and PVAGOPs film are characterized, and the thermal stability and mechanical properties of PVAGOPs film are investigated. Based on these, it has been proved that GOPAs consist of graphene oxide phosphonic acid and graphene oxide phosphinic acid, and there are CP covalent bonds between them, and PVAGOPs are composed of GOPAs and PVA, and there are six-member lactone rings between GOPAs and PVA, and the thermal stability and mechanical properties of PVAGOPs film are improved effectively. Copyright © 2018 Elsevier B.V. All rights reserved.

The GEM-Mars general circulation model for Mars: Description and evaluation

NASA Astrophysics Data System (ADS)

Neary, L.; Daerden, F.

2018-01-01

GEM-Mars is a gridpoint-based three-dimensional general circulation model (GCM) of the Mars atmosphere extending from the surface to approximately 150 km based on the GEM (Global Environmental Multiscale) model, part of the operational weather forecasting and data assimilation system for Canada. After the initial modification for Mars, the model has undergone considerable changes. GEM-Mars is now based on GEM 4.2.0 and many physical parameterizations have been added for Mars-specific atmospheric processes and surface-atmosphere exchange. The model simulates interactive carbon dioxide-, dust-, water- and atmospheric chemistry cycles. Dust and water ice clouds are radiatively active. Size distributed dust is lifted by saltation and dust devils. The model includes 16 chemical species (CO2, Argon, N2, O2, CO, H2O, CH4, O3, O(1D), O, H, H2, OH, HO2, H2O2 and O2(a1Δg)) and has fully interactive photochemistry (15 reactions) and gas-phase chemistry (31 reactions). GEM-Mars provides a good simulation of the water and ozone cycles. A variety of other passive tracers can be included for dedicated studies, such as the emission of methane. The model has both a hydrostatic and non-hydrostatic formulation, and together with a flexible grid definition provides a single platform for simulations on a variety of horizontal scales. The model code is fully parallelized using OMP and MPI. Model results are evaluated by comparison to a selection of observations from instruments on the surface and in orbit, relating to atmosphere and surface temperature and pressure, dust and ice content, polar ice mass, polar argon, and global water and ozone vertical columns. GEM-Mars will play an integral part in the analysis and interpretation of data that is received by the NOMAD spectrometer on the ESA-Roskosmos ExoMars Trace Gas Orbiter. The present paper provides an overview of the current status and capabilities of the GEM-Mars model and lays the foundations for more in-depth studies in support

Geostationary Environment Monitoring Spectrometer (gems) Over the Korea Peninsula and Asia-Pacific Region

NASA Astrophysics Data System (ADS)

Lasnik, J.; Stephens, M.; Baker, B.; Randall, C.; Ko, D. H.; Kim, S.; Kim, Y.; Lee, E. S.; Chang, S.; Park, J. M.; SEO, S. B.; Youk, Y.; Kong, J. P.; Lee, D.; Lee, S. H.; Kim, J.

2014-12-01

Introduction: The Geostationary Environment Monitoring Spectrometer (GEMS) is one of two instruments manifested aboard the South Korean Geostationary Earth Orbit KOrea Multi-Purpose SATellite-2B (GEO-KOMPSAT-2B or GK2B), which is scheduled to launch in 2018. Jointly developed/built by KARI and Ball Aerospace, GEMS is a geostationary UV-Vis hyperspectral imager designed to monitor trans-boundary tropospheric pollution events over the Korean peninsula and Asia-Pacific region. The spectrometer provides high temporal and spatial resolution (3.5 km N/S by 7.2 km E/W) measurements of ozone, its precursors, and aerosols. Over the short-term, hourly measurements by GEMS will improve early warnings for potentially dangerous pollution events and monitor population exposure. Over the 10-year mission-life, GEMS will serve to enhance our understanding of long-term climate change and broader air quality issues on both a regional and global scale. The GEMS sensor design and performance are discussed, which includes an overview of measurement capabilities and the on-orbit concept of operations. GEMS Sensor Overview: The GEMS hyperspectral imaging system consists of a telescope and Offner grating spectrometer that feeds a single CCD detector array. A spectral range of 300-500 nm and sampling of 0.2 nm enables NO2, SO2, HCHO, O3, and aerosol retrieval. The GEMS field of regard (FOR), which extends from 5°S to 45°N in latitude and 75°E to 145°E in longitude, is operationally achieved using an onboard two-axis scan mirror. On-orbit, the radiometric calibration is maintained using solar measurements, which are performed using two onboard diffusers: a working diffuser that is deployed routinely for the purpose of solar calibration, and a reference diffuser that is deployed sparingly for the purpose of monitoring working diffuser performance degradation.

Antimicrobial activity of organotin(IV) complexes with the ligand benzil bis(benzoylhydrazone) and 4,4'-bipyridyl as coligand.

PubMed

López-Torres, Elena; Zani, Franca; Mendiola, M Antonia

2011-05-01

Several methyltin(IV) and butyltin(IV) complexes with the ligand benzil bis(benzoylhydrazone) and 4,4'-bipyridyl as coligand were synthesised and characterized by elemental analysis and by IR, (1)H, (13)C and (119)Sn NMR spectroscopies. Some of them were also analyzed using single crystal X-ray diffraction. The title compounds were evaluated for their in vitro antimicrobial properties. All buthyltin complexes showed significant inhibition of Gram positive bacteria, resulting Bacillus subtilis, Sarcina lutea and both methicillin-susceptible and methicillin-resistant Staphylococcus epidermidis the most sensitive strains. Furthermore, they were able to inhibit the growth of Gram negative bacteria, especially Proteus vulgaris, whereas no activity was exhibited against fungi. All methyltin complexes were devoid of antimicrobial properties. Copyright © 2011 Elsevier Inc. All rights reserved.

Student involvement in the Geospace Environment Modeling (GEM) workshop

NASA Astrophysics Data System (ADS)

Allen, R. C.; Cohen, I. J.

2014-12-01

The Geospace Environment Modeling (GEM) workshop is a unique venue for students to begin to integrate into the magnetospheric community. GEM, an annual workshop funded by the NSF, allows students to present their research in a collaborative atmosphere and to engage with senior scientists as peers. This builds confidence in the students, while also allowing them to share ideas and strengthen their research. Each GEM workshop starts with a student-run and organized "student day", in which older students volunteer to present tutorials on different magnetospheric systems and processes. These tutorials strive to put the upcoming week of talks and posters in context while providing an overarching base understanding of the magnetospheric system. By starting the week with student taught tutorials, as well as icebreaker activities, the students become comfortable with asking questions and set the tone for the less formal student and discussion-oriented workshop.

3D simulation of electron and ion transmission of GEM-based detectors

NASA Astrophysics Data System (ADS)

Bhattacharya, Purba; Mohanty, Bedangadas; Mukhopadhyay, Supratik; Majumdar, Nayana; da Luz, Hugo Natal

2017-10-01

Time Projection Chamber (TPC) has been chosen as the main tracking system in several high-flux and high repetition rate experiments. These include on-going experiments such as ALICE and future experiments such as PANDA at FAIR and ILC. Different R&D activities were carried out on the adoption of Gas Electron Multiplier (GEM) as the gas amplification stage of the ALICE-TPC upgrade version. The requirement of low ion feedback has been established through these activities. Low ion feedback minimizes distortions due to space charge and maintains the necessary values of detector gain and energy resolution. In the present work, Garfield simulation framework has been used to study the related physical processes occurring within single, triple and quadruple GEM detectors. Ion backflow and electron transmission of quadruple GEMs, made up of foils with different hole pitch under different electromagnetic field configurations (the projected solutions for the ALICE TPC) have been studied. Finally a new triple GEM detector configuration with low ion backflow fraction and good electron transmission properties has been proposed as a simpler GEM-based alternative suitable for TPCs for future collider experiments.

Development, characterization and qualification of first GEM foils produced in India

NASA Astrophysics Data System (ADS)

Shah, Aashaq; Ahmed, Asar; Gola, Mohit; Sharma, Ram Krishna; Malhotra, Shivali; Kumar, Ashok; Naimuddin, Md.; Menon, Pradeep; Srinivasan, K.

2018-06-01

The increasing demand for Gas Electron Multiplier (GEM) foils has been driven by their application in many current and proposed high-energy physics experiments. Micropack, a Bengaluru-based company, has established and commercialized GEM foils for the first time in India. Micropack used the double-mask etching technique to successfully produce 10 cm × 10 cm GEM foil. In this paper, we report on the development as well as the geometrical and electrical properties of these foils, including the size uniformity of the holes and leakage current measurements. Our characterization studies show that the foils are of good quality and satisfy all the necessary quality control criteria.

GenomeGems: evaluation of genetic variability from deep sequencing data

PubMed Central

2012-01-01

Background Detection of disease-causing mutations using Deep Sequencing technologies possesses great challenges. In particular, organizing the great amount of sequences generated so that mutations, which might possibly be biologically relevant, are easily identified is a difficult task. Yet, for this assignment only limited automatic accessible tools exist. Findings We developed GenomeGems to gap this need by enabling the user to view and compare Single Nucleotide Polymorphisms (SNPs) from multiple datasets and to load the data onto the UCSC Genome Browser for an expanded and familiar visualization. As such, via automatic, clear and accessible presentation of processed Deep Sequencing data, our tool aims to facilitate ranking of genomic SNP calling. GenomeGems runs on a local Personal Computer (PC) and is freely available at http://www.tau.ac.il/~nshomron/GenomeGems. Conclusions GenomeGems enables researchers to identify potential disease-causing SNPs in an efficient manner. This enables rapid turnover of information and leads to further experimental SNP validation. The tool allows the user to compare and visualize SNPs from multiple experiments and to easily load SNP data onto the UCSC Genome browser for further detailed information. PMID:22748151

Galium Electromagnetic (GEM) Thruster Concept and Design

NASA Technical Reports Server (NTRS)

Polzin, Kurt A.; Markusic, Thomas E.

2005-01-01

We describe the design of a new type of two-stage pulsed electromagnetic accelerator, the gallium electromagnetic (GEM) thruster. A schematic illustration of the GEM thruster concept is given. In this concept, liquid gallium propellant is pumped into the first stage through a porous metal electrode using an electromagnetic pump. At a designated time, a pulsed discharge (approx. 10-50 J) is initiated in the first stage, ablating the liquid gallium from the porous electrode surface and ejecting a dense thermal gallium plasma into the second state. The presence of the gallium plasma in the second stage serves to trigger the high-energy (approx. 500 J), second-stage pulse which provides the primary electromagnetic (j x B) acceleration.

Synthesis of GEMS from Shock-accelerated Crystalline Dust in Superbubbles: Model and Predictions

NASA Technical Reports Server (NTRS)

Westphal, Andrew J.; Bradley, John P.

2005-01-01

GEMS (Glass Embedded with Metals and Sulfides) are highly enigmatic yet common components of anhydrous IDPs. We have recently proposed a model of GEMS formation from shock-accelerated crystalline dust in superbubbles[1] which explains the three most perplexing properties of GEMS: pseudomorphism[2], their chemistry[3], and their size range. In this Abstract, we briefly review the main points of the model, and suggest tests that will either prove or rule out this hypothesis.

The Effects of Phosphonic Acids in Dye-Sensitized Solar Cells

NASA Astrophysics Data System (ADS)

James, Keith Edward

Novel methods for the construction of dye-sensitized solar cells (DSSCs) were developed. A thin dense underlayer of TiO2 was applied on fluorine-doped tin oxide (FTO) glass using as a precursor Tyzor AA-105. Subsequently a mesoporous film of P-25 TiO2 was applied by spreading a suspension uniformly over the surface of the underlayer and allowing the plate to slowly dry while resting on a level surface. After sintering at 500° C slides were treated with TCPP as a sensitizing dye and assembled into DSSCs. A novel method was used to seal the cells; strips of ParafilmRTM were used as spacers between the electrodes and to secure the electrodes together. The cells were filled with a redox electrolyte and sealed by dipping into molten paraffin. A series of phosphonic acids and one arsonic acid were employed as coadsorbates in DSSCs. The coadsorbates were found to compete for binding sites, resulting in lower levels of dye adsorption. The resulting loss of photocurrent was not linear with the reduction of dye loading, and in some cases photocurrent and efficiency were higher for cells with lower levels of dye loading. Electrodes were treated with coadsorbates by procedures including pre-adsorption, simultaneous (sim-adsorption), and post-adsorption, using a range of concentrations and treatment times and a variety of solvents. Most cells were tested using an iodide-triiodide based electrolyte (I3I-1) but some cells were tested using electrolytes based on a Co(II)/Co(III) redox couple (CoBpy electrolytes). Phosphonic acid post-adsorbates increased the Voc of cells using CoBpy electrolytes but caused a decrease in the Voc of cells using I3I-1 electrolyte. Phosphonic acids as sim-adsorbates resulted in a significant increase in efficiency and Jsc, and they show promise as a treatment for TCPP DSSCs.

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.

Copper-Catalyzed SN2'-Selective Allylic Substitution Reaction of gem-Diborylalkanes.

PubMed

Zhang, Zhen-Qi; Zhang, Ben; Lu, Xi; Liu, Jing-Hui; Lu, Xiao-Yu; Xiao, Bin; Fu, Yao

2016-03-04

A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted gem-diborylalkanes and allylic electrophiles can be employed in this reaction, and various synthetic valuable functional groups can be tolerated. The asymmetric version of this reaction was initially researched with chiral N-heterocyclic carbene (NHC) ligands.

Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

USDA-ARS?s Scientific Manuscript database

Phosphonates were synthesized on a medium scale (~200 g) from three lipids: methyl linoleate (MeLin), high-oleic sunflower oil (HOSO), and soybean oil (SBO), and three dialkyl phosphites: methyl, ethyl, and n-butyl, using radical initiator. A staged addition of the lipid and the initiator was needed...

Computer-Aided Molecular Design of Bis-phosphine Oxide Lanthanide Extractants

DOE PAGES

McCann, Billy W.; Silva, Nuwan De; Windus, Theresa L.; ...

2016-02-17

Computer-aided molecular design and high-throughput screening of viable host architectures can significantly reduce the efforts in the design of novel ligands for efficient extraction of rare earth elements. This paper presents a computational approach to the deliberate design of bis-phosphine oxide host architectures that are structurally organized for complexation of trivalent lanthanides. Molecule building software, HostDesigner, was interfaced with molecular mechanics software, PCModel, providing a tool for generating and screening millions of potential R 2(O)P-link-P(O)R 2 ligand geometries. The molecular mechanics ranking of ligand structures is consistent with both the solution-phase free energies of complexation obtained with density functional theorymore » and the performance of known bis-phosphine oxide extractants. For the case where link is -CH 2-, evaluation of the ligand geometry provides the first characterization of a steric origin for the ‘anomalous aryl strengthening’ effect. The design approach has identified a number of novel bis-phosphine oxide ligands that are better organized for lanthanide complexation than previously studied examples.« less

Gaseous elemental mercury (GEM) fluxes over canopy of two typical subtropical forests in south China

NASA Astrophysics Data System (ADS)

Yu, Qian; Luo, Yao; Wang, Shuxiao; Wang, Zhiqi; Hao, Jiming; Duan, Lei

2018-01-01

Mercury (Hg) exchange between forests and the atmosphere plays an important role in global Hg cycling. The present estimate of global emission of Hg from natural source has large uncertainty, partly due to the lack of chronical and valid field data, particularly for terrestrial surfaces in China, the most important contributor to global atmospheric Hg. In this study, the micrometeorological method (MM) was used to continuously observe gaseous elemental mercury (GEM) fluxes over forest canopy at a mildly polluted site (Qianyanzhou, QYZ) and a moderately polluted site (Huitong, HT, near a large Hg mine) in subtropical south China for a full year from January to December in 2014. The GEM flux measurements over forest canopy in QYZ and HT showed net emission with annual average values of 6.67 and 0.30 ng m-2 h-1, respectively. Daily variations of GEM fluxes showed an increasing emission with the increasing air temperature and solar radiation in the daytime to a peak at 13:00, and decreasing emission thereafter, even as a GEM sink or balance at night. High temperature and low air Hg concentration resulted in the high Hg emission in summer. Low temperature in winter and Hg absorption by plant in spring resulted in low Hg emission, or even adsorption in the two seasons. GEM fluxes were positively correlated with air temperature, soil temperature, wind speed, and solar radiation, while it is negatively correlated with air humidity and atmospheric GEM concentration. The lower emission fluxes of GEM at the moderately polluted site (HT) when compared with that in the mildly polluted site (QYZ) may result from a much higher adsorption fluxes at night in spite of a similar or higher emission fluxes during daytime. This shows that the higher atmospheric GEM concentration at HT restricted the forest GEM emission. Great attention should be paid to forests as a crucial increasing Hg emission source with the decreasing atmospheric GEM concentration in polluted areas because of Hg

Gallium Electromagnetic (GEM) Thrustor Concept and Design

NASA Technical Reports Server (NTRS)

Polzin, Kurt A.; Markusic, Thomas E.

2006-01-01

We describe the design of a new type of two-stage pulsed electromagnetic accelerator, the gallium electromagnetic (GEM) thruster. A schematic illustration of the GEM thruster concept is given in Fig. 1. In this concept, liquid gallium propellant is pumped into the first stage through a porous metal electrode using an electromagneticpump[l]. At a designated time, a pulsed discharge (approx.10-50 J) is initiated in the first stage, ablating the liquid gallium from the porous electrode surface and ejecting a dense thermal gallium plasma into the second state. The presence of the gallium plasma in the second stage serves to trigger the high-energy (approx.500 I), send-stage puke which provides the primary electromagnetic (j x B) acceleration.

Performance verification of the Gravity and Extreme Magnetism Small explorer (GEMS) x-ray polarimeter

NASA Astrophysics Data System (ADS)

Enoto, Teruaki; Black, J. Kevin; Kitaguchi, Takao; Hayato, Asami; Hill, Joanne E.; Jahoda, Keith; Tamagawa, Toru; Kaneko, Kenta; Takeuchi, Yoko; Yoshikawa, Akifumi; Marlowe, Hannah; Griffiths, Scott; Kaaret, Philip E.; Kenward, David; Khalid, Syed

2014-07-01

Polarimetry is a powerful tool for astrophysical observations that has yet to be exploited in the X-ray band. For satellite-borne and sounding rocket experiments, we have developed a photoelectric gas polarimeter to measure X-ray polarization in the 2-10 keV range utilizing a time projection chamber (TPC) and advanced micro-pattern gas electron multiplier (GEM) techniques. We carried out performance verification of a flight equivalent unit (1/4 model) which was planned to be launched on the NASA Gravity and Extreme Magnetism Small Explorer (GEMS) satellite. The test was performed at Brookhaven National Laboratory, National Synchrotron Light Source (NSLS) facility in April 2013. The polarimeter was irradiated with linearly-polarized monochromatic X-rays between 2.3 and 10.0 keV and scanned with a collimated beam at 5 different detector positions. After a systematic investigation of the detector response, a modulation factor >=35% above 4 keV was obtained with the expected polarization angle. At energies below 4 keV where the photoelectron track becomes short, diffusion in the region between the GEM and readout strips leaves an asymmetric photoelectron image. A correction method retrieves an expected modulation angle, and the expected modulation factor, ~20% at 2.7 keV. Folding the measured values of modulation through an instrument model gives sensitivity, parameterized by minimum detectable polarization (MDP), nearly identical to that assumed at the preliminary design review (PDR).

Self-assembled titanium phosphonate nanomaterial having a mesoscopic void space and its optoelectronic application.

PubMed

Pramanik, Malay; Patra, Astam K; Bhaumik, Asim

2013-04-14

Here we report the synthesis of a new crystalline titanium phosphonate material (HTiP-7) having a self-assembled nanostructure and a mesoscopic void space without the aid of any surfactant or templating agent. The material has been synthesized hydrothermally through the reaction between benzene-1,3,5-triphosphonic acid (BTPA) and titanium(iv) isopropoxide at neutral pH at 453 K for 24 h. This hybrid phosphonate material has been thoroughly characterized by powder X-ray diffraction, N2 sorption, HR TEM, FE SEM, TG-DTA, FT IR and UV-Vis diffuse reflectance spectroscopic studies. Two very well-known software packages, REFLEX and CELSIZ unit cell refinement programs, are employed to establish the triclinic crystal phase of this hybrid material (HTiP-7). Very tiny nanocrystals of HTiP-7 self-aggregated to form spherical nanoparticles of dimension ca. 25 nm together with a mesoscopic void space and good BET surface area (255 m(2) g(-1)). The framework is thermally stable up to 650 K. The material showed excellent carrier mobility for photocurrent generation in the presence of a photosensitizer molecule (Rose Bengal). To the best of our knowledge this is the first report of a photon-to-electron energy transfer process over a dye doped titanium phosphonate nanomaterial.

Catalytic hydrogenation activity and electronic structure determination of bis(arylimidazol-2-ylidene)pyridine cobalt alkyl and hydride complexes.

PubMed

Yu, Renyuan Pony; Darmon, Jonathan M; Milsmann, Carsten; Margulieux, Grant W; Stieber, S Chantal E; DeBeer, Serena; Chirik, Paul J

2013-09-04

The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, ((iPr)CNC)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 °C and 4 atm of H2 pressure, ((iPr)CNC)CoCH3 is an effective precatalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene, and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, ((iPr)CNC)CoH, was accomplished by hydrogenation of ((iPr)CNC)CoCH3. Over the course of 3 h at 22 °C, migration of the metal hydride to the 4-position of the pyridine ring yielded (4-H2-(iPr)CNC)CoN2. Similar alkyl migration was observed upon treatment of ((iPr)CNC)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redox-active, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic, and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity, and suggest that a wide family of pyridine-based pincers may also be redox-active.

Structure-activity relationship of (N)-Methanocarba phosphonate analogues of 5'-AMP as cardioprotective agents acting through a cardiac P2X receptor.

PubMed

Kumar, T Santhosh; Zhou, Si-Yuan; Joshi, Bhalchandra V; Balasubramanian, Ramachandran; Yang, Tiehong; Liang, Bruce T; Jacobson, Kenneth A

2010-03-25

P2X receptor activation protects in heart failure models. MRS2339 3, a 2-chloro-AMP derivative containing a (N)-methanocarba (bicyclo[3.1.0]hexane) system, activates this cardioprotective channel. Michaelis-Arbuzov and Wittig reactions provided phosphonate analogues of 3, expected to be stable in vivo due to the C-P bond. After chronic administration via a mini-osmotic pump (Alzet), some analogues significantly increased intact heart contractile function in calsequestrin-overexpressing mice (genetic model of heart failure) compared to vehicle-infused mice (all inactive at the vasodilatory P2Y(1) receptor). Two phosphonates, (1'S,2'R,3'S,4'R,5'S)-4'-(6-amino-2-chloropurin-9-yl)-2',3'-(dihydroxy)-1'-(phosphonomethylene)-bicyclo[3.1.0]hexane, 4 (MRS2775), and its homologue 9 (MRS2935), both 5'-saturated, containing a 2-Cl substitution, improved echocardiography-derived fractional shortening (20.25% and 19.26%, respectively, versus 13.78% in controls), while unsaturated 5'-extended phosphonates, all 2-H analogues, and a CH(3)-phosphonate were inactive. Thus, chronic administration of nucleotidase-resistant phosphonates conferred a beneficial effect, likely via cardiac P2X receptor activation. Thus, we have greatly expanded the range of carbocyclic nucleotide analogues that represent potential candidates for the treatment of heart failure.

Synthesis, kinetic evaluation, and utilization of a biotinylated dipeptide proline diphenyl phosphonate for the disclosure of dipeptidyl peptidase IV-like serine proteases.

PubMed

Gilmore, Brendan F; Carson, Louise; McShane, Laura L; Quinn, Derek; Coulter, Wilson A; Walker, Brian

2006-08-18

In this study, we report on the synthesis, kinetic characterisation, and application of a novel biotinylated and active site-directed inactivator of dipeptidyl peptidase IV (DPP-IV). Thus, the dipeptide-derived proline diphenyl phosphonate NH(2)-Glu(biotinyl-PEG)-Pro(P)(OPh)(2) has been prepared by a combination of classical solution- and solid-phase methodologies and has been shown to be an irreversible inhibitor of porcine DPP-IV, exhibiting an over all second-order rate constant (k(i)/K(i)) for inhibition of 1.57 x 10(3) M(-1) min(-1). This value compares favourably with previously reported rates of inactivation of DPP-IV by dipeptides containing a P(1) proline diphenyl phosphonate grouping [B. Boduszek, J. Oleksyszyn, C.M. Kam, J. Selzler, R.E. Smith, J.C. Powers, Dipeptide phophonates as inhibitors of dipeptidyl peptidase IV, J. Med. Chem. 37 (1994) 3969-3976; B.F. Gilmore, J.F. Lynas, C.J. Scott, C. McGoohan, L. Martin, B. Walker, Dipeptide proline diphenyl phosphonates are potent, irreversible inhibitors of seprase (FAPalpha), Biochem, Biophys. Res. Commun. 346 (2006) 436-446.], thus demonstrating that the incorporation of the side-chain modified (N-biotinyl-3-(2-(2-(3-aminopropyloxy)-ethoxy)-ethoxy)-propyl) glutamic acid residue at the P(2) position is compatible with inhibitor efficacy. The utilisation of this probe for the detection of both purified dipeptidyl peptidase IV and the disclosure of a dipeptidyl peptidase IV-like activity from a clinical isolate of Porphyromonas gingivalis, using established electrophoretic and Western blotting techniques previously developed by our group, is also demonstrated.

Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

USDA-ARS?s Scientific Manuscript database

Phosphonates were synthesized on a medium scale (~200 g) from three lipids: methyl linoleate (MeLin), high-oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites: methyl, ethyl and n-butyl, using a radical initiator. A staged addition of the lipid and the initiator to the dia...

Synthesis and characterization of phosphonates from methyl linoleate and vegetable oils

USDA-ARS?s Scientific Manuscript database

Phosphonates were synthesized on a medium scale (~200 g) from three lipids–methyl linoleate (MeLin), high-oleic sunflower oil (HOSO) and soybean oil (SBO), and three dialkyl phosphites–methyl, ethyl and n-butyl, using a radical initiator. A staged addition of the lipid and the initiator was used to ...

Reentrant and Isostructural Transitions in the Cluster-Crystal Forming GEM-4

NASA Astrophysics Data System (ADS)

Zhang, Kai; Charbonneau, Patrick; Mladek, Bianca

2011-03-01

Systems governed by soft, bounded, purely repulsive interactions show two possible equilibrium behaviors under compression: reentrant melting, as in the Gaussian core model (GCM), or clustering, as in the penetrable sphere model (PSM). The generalized exponential model of power 4 (GEM-4), which is the intermedia of the GCM and PSM with a simple isotropic pair interaction u (r) ~e-r4 , is thought to belong to the second family and was indeed found to form clusters at sufficiently high densities at high temperatures. Here, we present the low-temperature behavior of GEM-4 through Monte Carlo simulations using a specially developed free energy integration scheme. We find the phase behavior to be hybrid between the GCM and the PSM limits, showing a surprisingly rich phase behavior in spite of the simplicity of the interaction form. For instance, S- shaped doubly reentrant phase sequences and evidence of a cascade of critical isostructural transitions between crystals of different average lattice site occupancy are observed. The possible annihilation of lattice sites and accompanying clustering moreover leads to an unusual softening upon compression, which suggest that these materials may have interesting mechanical properties. We discuss possible experimental realizations and challenges of this class of materials.

Simulation of the GEM detector for BM@N experiment

NASA Astrophysics Data System (ADS)

Baranov, Dmitriy; Rogachevsky, Oleg

2017-03-01

The Gas Electron Multiplier (GEM) detector is one of the basic parts of the BM@N experiment included in the NICA project. The simulation model that takes into account features of signal generation process in an ionization GEM chamber is presented in this article. Proper parameters for the simulation were extracted from data retrieved with the help of Garfield++ (a toolkit for the detailed simulation of particle detectors). Due to this, we are able to generate clusters in layers of the micro-strip readout that correspond to clusters retrieved from a real physics experiment.

Modelling two-way interactions between atmospheric pollution and weather using high-resolution GEM-MACH

NASA Astrophysics Data System (ADS)

Makar, Paul; Gong, Wanmin; Pabla, Balbir; Cheung, Philip; Milbrandt, Jason; Gravel, Sylvie; Moran, Michael; Gilbert, Samuel; Zhang, Junhua; Zheng, Qiong

2013-04-01

The Global Environmental Multiscale (GEM) model is the source of the Canadian government's operational numerical weather forecast guidance, and GEM-MACH is the Canadian operational air-quality forecast model. GEM-MACH comprises GEM and the 'Modelling Air-quality and Chemistry' module, a gas-phase, aqueous-phase and aerosol chemistry and microphysics subroutine package called from within GEM's physics module. The present operational GEM-MACH model is "on-line" (both chemistry and meteorology are part of the same modelling structure) but is not fully coupled (weather variables are provided as inputs to the chemistry, but the chemical variables are not used to modify the weather). In this work, we describe modifications made to GEM-MACH as part of the 2nd phase of the Air Quality Model Evaluation International Initiative, in order to bring the model to a fully coupled status and present the results of initial tests comparing uncoupled and coupled versions of the model to observations for a high-resolution forecasting system. Changes to GEM's cloud microphysics and radiative transfer packages were carried out to allow two-way coupling. The cloud microphysics package used here is the Milbrandt-Yau 2-moment (MY2) bulk microphysics scheme, which solves prognostic equations for the total droplet number concentration and the mass mixing ratios of six hydrometeor categories. Here, we have replaced the original cloud condensation nucleation parameterization of MY2 (empirically relating supersaturation and CCN number) with the aerosol activation scheme of Abdul-Razzak and Ghan (2002). The latter scheme makes use of the particle size and speciation distribution of GEM-MACH's chemistry code as well as meteorological inputs to predict the number of aerosol particles activated to form cloud droplets, which is then used in the MY2 microphysics. The radiative transfer routines of GEM assume a default constant concentration aerosol profile between the surface and 1500m, and a single

16 CFR 23.25 - Misuse of the word “gem.”

Code of Federal Regulations, 2010 CFR

2010-01-01

... 16 Commercial Practices 1 2010-01-01 2010-01-01 false Misuse of the word âgem.â 23.25 Section 23... JEWELRY, PRECIOUS METALS, AND PEWTER INDUSTRIES § 23.25 Misuse of the word “gem.” (a) It is unfair or deceptive to use the word “gem” to describe, identify, or refer to a ruby, sapphire, emerald, topaz, or...

Luminescent low-valent rhenium complexes with 1,2-bis(dialkylphosphino)ethane ligands. synthesis and X-ray crystallographic, electrochemical, and spectroscopic characterization.

PubMed

Messersmith, Stephania J; Kirschbaum, Kristin; Kirchhoff, Jon R

2010-04-19

A series of low-valent rhenium phosphine complexes with the general formula [Re(dmpe)(3-x)(depe)(x)](2+/+) (x = 0-3), where dmpe is 1,2-bis(dimethylphosphino)ethane and depe is 1,2-bis(diethylphosphino)ethane, were synthesized and characterized. The reaction of [Re(benzil)(PPh(3))Cl(3)] with the appropriate phosphine yielded the homoleptic tris complexes [Re(dmpe)(3)](+) and [Re(depe)(3)](2+), while the mixed-ligand complexes [Re(dmpe)(2)(depe)](+) and [Re(dmpe)(depe)(2)](2+) were prepared from [Re(dmpe)(2)Cl(2)](+) and [Re(depe)(2)Cl(2)](+), respectively. The oxidation state of the final product strongly depends on the donating properties of the ligand. Each complex, however, exhibits a diffusion-controlled, reversible one-electron transfer between Re(I) and Re(II) with formal reduction potentials, E degrees ', ranging from -0.09 to -0.28 V versus a ferrocene external standard. Subsequent oxidation to Re(III) was found to be chemically irreversible. UV-vis and luminescence spectroelectrochemical techniques were used to study the spectral properties of the Re(I) and Re(II) forms. The Re(II) complexes are red in color and exhibit absorption features from 350 to 600 nm; the lowest-energy transition was assigned as a sigma(P) to dpi(Re) ligand-to-metal charge-transfer (LMCT) transition. Excitation into the lowest-energy absorption band revealed rare examples of luminescent (Phi approximately 0.07) LMCT excited states from d(5) transition-metal complexes in a room temperature solution. Structural characterization of salts of both oxidation states of [Re(dmpe)(2)(depe)](2+/+) was also performed.

Water oxidation by Ruthenium complexes incorporating multifunctional biipyridyl diphosphonate ligands

DOE PAGES

Xie, Yan; Shaffer, David W.; Lewandowska-Andralojc, Anna; ...

2016-05-11

Here, we describe herein the synthesis and characterization of ruthenium complexes with multifunctional bipyridyl diphosphonate ligands as well as initial water oxidation studies. In these complexes, the phosphonate groups provide redox-potential leveling through charge compensation and σ donation to allow facile access to high oxidation states. These complexes display unique pH-dependent electrochemistry associated with deprotonation of the phosphonic acid groups. The position of these groups allows them to shuttle protons in and out of the catalytic site and reduce activation barriers. A mechanism for water oxidation by these catalysts is proposed on the basis of experimental results and DFT calculations.more » The unprecedented attack of water at a neutral six-coordinate [Ru IV] center to yield an anionic seven-coordinate [Ru IV–OH] – intermediate is one of the key steps of a single-site mechanism in which all species are anionic or neutral. These complexes are among the fastest single-site catalysts reported to date.« less

Noninvasive positron emission tomography imaging of cell death using a novel small-molecule probe, (18)F labeled bis(zinc(II)-dipicolylamine) complex.

PubMed

Wang, Hongliang; Tang, Xiaolan; Tang, Ganghua; Huang, Tingting; Liang, Xiang; Hu, Kongzhen; Deng, Huaifu; Yi, Chang; Shi, Xinchong; Wu, Kening

2013-08-01

The synthetic bis(zinc(II)-dipicolylamine) (DPAZn2) coordination complexes are known to have a high specific and selective affinity to target the exposed phosphatidylserine (PS) on the surface of dead and dying cells. An (18)F-labeled DPAZn2 complex (4-(18)F-Fluoro-benzoyl-bis(zinc(II)-dipicolylamine), (18)F-FB-DPAZn2) as positron emission tomography (PET) tracer was developed and evaluated for in vivo imaging of tumor treated with a chemical agent. The in vitro cell stain studies revealed that fluorescent DPAZn2 complexes (Dansyl-DPAZn2) stained the same cells (apoptotic and necrotic cells) as fluorescein isothiocyanate (FITC) labeled Annexin V (FITC-Annexin V). The radiosynthesis of (18)F-FB-DPAZn2 was achieved through the amidation the precursor bis(2,2'-dipicolylamine) derivative (DPA2) with the prosthetic group N-succinimidyl-4-[(18)F]-fluorobenzoate ((18)F-SFB) and chelation with zinc nitrate. In the biodistribution study, the fast clearance of (18)F-FB-DPAZn2 from blood and kidney was observed and high uptake in liver and intestine within 90 min postinjection was also found. For the PET imaging, significantly higher tumor uptake of (18)F-FB-DPAZn2 was observed in the adriamycin (ADM)-treated Hepa1-6 hepatocellular carcinoma-bearing mice than that in the untreated tumor-model mice, while a slightly decreased tumor uptake of (18)F-FDG was found in the ADM-treated tumor-bearing mice. The results indicate that (18)F-FB-DPAZn2 has the similar capability of apoptosis detection as FITC-Annexin V and seems to be a potential PET tracer for noninvasive evaluation and monitoring of anti-tumor chemotherapy. The high uptake of (18)F-FB-DPAZn2 in the abdomen needs to optimize the structure for improving its pharmacokinetics characteristics in the future work.

Gd-complexes of macrocyclic DTPA conjugates of 1,1'-bis(amino)ferrocenes as high relaxivity MRI blood-pool contrast agents (BPCAs).

PubMed

Kim, Hee-Kyung; Park, Ji-Ae; Kim, Kyeong Min; Nasiruzzaman, Sk Md; Kang, Duk-Sik; Lee, Jongmin; Chang, Yongmin; Kim, Tae-Jeong

2010-11-28

We report the synthesis of macrocyclic DTPA conjugates of 1,1'-bis(amino)ferrocenes (1a-b) and their Gd-complexes [Gd(L)(H(2)O)] (2a-b, L = 1a-b) for use as new MRI blood-pool contrast agents. High R(1) relaxivity in HSA as well as high thermodynamic and kinetic stabilities is observed for 2a.

Synthesis, X-ray crystal structures, and phosphate ester cleavage properties of bis(2-pyridylmethyl)amine copper(II) complexes with guanidinium pendant groups.

PubMed

Belousoff, Matthew J; Tjioe, Linda; Graham, Bim; Spiccia, Leone

2008-10-06

Three new derivatives of bis(2-pyridylmethyl)amine (DPA) featuring ethylguanidinium (L (1)), propylguanidinium (L (2)), or butylguanidinium (L (3)) pendant groups have been prepared by the reaction of N, N- bis(2-pyridylmethyl)alkane-alpha,omega-diamines with 1 H-pyrazole-1-carboxamidine hydrochloride. The corresponding mononuclear copper(II) complexes were prepared by reacting the ligands with copper(II) nitrate and were isolated as [Cu(LH (+))(OH 2)](ClO 4) 3. xNaClO 4. yH 2O ( C1: L = L (1), x = 2, y = 3; C2: L = L (2), x = 2, y = 4; C3: L = L (3), x = 1, y = 0) following cation exchange purification. Recrystallization yielded crystals of composition [Cu(LH (+))(X)](ClO 4) 3.X ( C1': L = L (1), X = MeOH; C2': L = L (2), X = H 2O; C3': L = L (3), X = H 2O), which were suitable for X-ray crystallography. The crystal structures of C1', C2', and C3' indicate that the DPA moieties of the ligands coordinate to the copper(II) centers in a meridional fashion, with a water or methanol molecule occupying the fourth basal position. Weakly bound perchlorate anions located in the axial positions complete the distorted octahedral coordination spheres. The noncoordinating, monoprotonated guanidinium groups project away from the Cu(II)-DPA units and are involved in extensive charge-assisted hydrogen-bonding interactions with cocrystallized water/methanol molecules and perchlorate anions within the crystal lattices. The copper(II) complexes were tested for their ability to promote the cleavage of two model phosphodiesters, bis( p-nitrophenyl)phosphate (BNPP) and uridine-3'- p-nitrophenylphosphate (UpNP), as well as supercoiled plasmid DNA (pBR 322). While the presence of the guanidine pendants was found to be detrimental to BNPP cleavage efficiency, the functionalized complexes were found to cleave plasmid DNA and, in some cases, the model ribose phosphate diester, UpNP, at a faster rate than the parent copper(II) complex of DPA.

An improved model of the Earth's gravity field - GEM-T3

NASA Technical Reports Server (NTRS)

Nerem, R. S.; Lerch, F. J.; Putney, B. H.; Klosko, S. M.; Patel, G. B.; Williamson, R. G.; Pavlis, E. C.

1992-01-01

An improved model of the Earth's gravitational field is developed from a combination of conventional satellite tracking, satellite altimeter measurements, and surface gravimetric data (GEM-T3). This model gives improved performance for the computation of satellite orbital effects as well as a superior representation of the geoid from that achieved in any previous Goddard Earth Model. The GEM-T3 model uses altimeter data directly to define the orbits, geoid, and dynamic height fields. Altimeter data acquired during the GEOS-3 (1975-1976), SEASAT (1978), and GEOSAT (1986-1987) missions were used to compute GEM-T3. In order to accommodate the non-gravitational signal mapped by these altimeters, spherical harmonic models of the dynamic height of the ocean surface were recovered for each mission simultaneously with the gravitational field. The tracking data utilized in the solution includes more than 1300 arcs of data encompassing 31 different satellites. The observational data base is highly dependent on SLR, but also includes TRANET Doppler, optical, S-Band average range-rate and satellite-to-satellite tracking acquired between ATS-6 and GEOS-3. The GEM-T3 model has undergone extensive error calibration.

GEM detector performance and efficiency in Proton Charge Radius (PRad) Experiment

NASA Astrophysics Data System (ADS)

Bai, Xinzhan; PRad Collaboration

2017-09-01

The PRad experiment (E12-11-106) was performed in 2016 at Jefferson Lab in Hall B. It aims to investigate the proton charge radius puzzle through electron proton elastic scattering process. The experiment used a non-magnetic spectrometer method, and reached a very small ep scattering angle and thus an unprecedented small four-momentum transfer squared region, Q2 from 2 ×10-4 to 0.06(GeV / c) 2 . PRad experiment was designed to measure the proton charge radius within a sub-percent precision. Gas Electron Multiplier (GEM) detectors have contributed to reach the experimental goal. A pair of large area GEM detectors, and a large acceptance, high resolution calorimeter(HyCal) were utilized in the experiment to detect the scattered electrons. The precision requirements of the experiment demands a highly accurate understanding of efficiency and stability of GEM detectors. In this talk, we will present the preliminary results on the performance and efficiency of GEM detectors. This work is supported in part by NSF MRI award PHY-1229153, the U.S. Department of Energy under Contract No. DE-FG02-07ER41528, No. DE-FG02-03ER41240 and Thomas Jefferson National Laboratory.

An improved error assessment for the GEM-T1 gravitational model

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Marsh, J. G.; Klosko, S. M.; Pavlis, E. C.; Patel, G. B.; Chinn, D. S.; Wagner, C. A.

1988-01-01

Several tests were designed to determine the correct error variances for the Goddard Earth Model (GEM)-T1 gravitational solution which was derived exclusively from satellite tracking data. The basic method employs both wholly independent and dependent subset data solutions and produces a full field coefficient estimate of the model uncertainties. The GEM-T1 errors were further analyzed using a method based upon eigenvalue-eigenvector analysis which calibrates the entire covariance matrix. Dependent satellite and independent altimetric and surface gravity data sets, as well as independent satellite deep resonance information, confirm essentially the same error assessment. These calibrations (utilizing each of the major data subsets within the solution) yield very stable calibration factors which vary by approximately 10 percent over the range of tests employed. Measurements of gravity anomalies obtained from altimetry were also used directly as observations to show that GEM-T1 is calibrated. The mathematical representation of the covariance error in the presence of unmodeled systematic error effects in the data is analyzed and an optimum weighting technique is developed for these conditions. This technique yields an internal self-calibration of the error model, a process which GEM-T1 is shown to approximate.

Simulation of the West African monsoon onset using the HadGEM3-RA regional climate model

NASA Astrophysics Data System (ADS)

Diallo, Ismaïla; Bain, Caroline L.; Gaye, Amadou T.; Moufouma-Okia, Wilfran; Niang, Coumba; Dieng, Mame D. B.; Graham, Richard

2014-08-01

The performance of the Hadley Centre Global Environmental Model version 3 regional climate model (HadGEM3-RA) in simulating the West African monsoon (WAM) is investigated. We focus on performance for monsoon onset timing and for rainfall totals over the June-July-August (JJA) season and on the model's representation of the underlying dynamical processes. Experiments are driven by the ERA-Interim reanalysis and follow the CORDEX experimental protocol. Simulations with the HadGEM3 global model, which shares a common physical formulation with HadGEM3-RA, are used to gain insight into the causes of HadGEM3-RA simulation errors. It is found that HadGEM3-RA simulations of monsoon onset timing are realistic, with an error in mean onset date of two pentads. However, the model has a dry bias over the Sahel during JJA of 15-20 %. Analysis suggests that this is related to errors in the positioning of the Saharan heat low, which is too far south in HadGEM3-RA and associated with an insufficient northward reach of the south-westerly low-level monsoon flow and weaker moisture convergence over the Sahel. Despite these biases HadGEM3-RA's representation of the general rainfall distribution during the WAM appears superior to that of ERA-Interim when using Global Precipitation Climatology Project or Tropical Rain Measurement Mission data as reference. This suggests that the associated dynamical features seen in HadGEM3-RA can complement the physical picture available from ERA-Interim. This approach is supported by the fact that the global HadGEM3 model generates realistic simulations of the WAM without the benefit of pseudo-observational forcing at the lateral boundaries; suggesting that the physical formulation shared with HadGEM3-RA, is able to represent the driving processes. HadGEM3-RA simulations confirm previous findings that the main rainfall peak near 10°N during June-August is maintained by a region of mid-tropospheric ascent located, latitudinally, between the cores of

Discriminating cosmic muons and X-rays based on rise time using a GEM detector

NASA Astrophysics Data System (ADS)

Wu, Hui-Yin; Zhao, Sheng-Ying; Wang, Xiao-Dong; Zhang, Xian-Ming; Qi, Hui-Rong; Zhang, Wei; Wu, Ke-Yan; Hu, Bi-Tao; Zhang, Yi

2016-08-01

Gas electron multiplier (GEM) detectors have been used in cosmic muon scattering tomography and neutron imaging over the last decade. In this work, a triple GEM device with an effective readout area of 10 cm × 10 cm is developed, and a method of discriminating between cosmic muons and X-rays based on rise time is tested. The energy resolution of the GEM detector is tested by 55Fe ray source to prove the GEM detector has a good performance. Analysis of the complete signal-cycles allows us to get the rise time and pulse heights. The experiment result indicates that cosmic muons and X-rays can be discriminated with an appropriate rise time threshold. Supported by National Natural Science Foundation of China (11135002, 11275235, 11405077, 11575073)

Great Explorations in Math and Science[R] (GEMS[R]) Space Science. What Works Clearinghouse Intervention Report

ERIC Educational Resources Information Center

What Works Clearinghouse, 2012

2012-01-01

"Great Explorations in Math and Science[R] (GEMS[R]) Space Science" is an instructional sequence for grades 3-5 that covers fundamental concepts, including planetary sizes and distance, the Earth's shape and movement, gravity, and moon phases and eclipses. Part of the "GEMS"[R] core curriculum, "GEMS[R] Space Science"…

A refined gravity model from Lageos /GEM-L2/

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Klosko, S. M.; Patel, G. B.

1982-01-01

Lageos satellite laser ranging (SLR) data taken over a 2.5 yr period were employed to develop the Goddard Earth Model GEM-L2, a refined gravity field model. Additional data was gathered with 30 other satellites, resulting in spherical harmonics through degree and order 20, based on over 600,000 measurements. The Lageos data was accurate down to 10 cm, after which the GEM 9 data were used to make adjustments past order 7. The resolution of long wavelength activity, through degree and order 4, was made possible by the Lageos data. The GEM-L2 model features a 20 x 20 geopotential, tracking station coordinates (20), 5-day polar motion and A1-UT1 values, and a GM value of 398,600.607 cu km/sq sec. The accuracy of station positioning has been raised to within 6 cm total position globally and within 1.8 cm in baselines. It is concluded that SLR is useful for measuring tectonic plate motions and inter-plate deformations.

Development of near infrared spectrometer for gem materials study

NASA Astrophysics Data System (ADS)

Jindata, W.; Meesiri, W.; Wongkokua, W.

2015-07-01

Most of gem materials can be characterized by infrared absorption spectroscopy. Normally, mid infrared absorption technique has been applied for investigating fundamental vibrational modes. However, for some gem materials, such as tourmaline, NIR is a better choice due to differentiation. Most commercial NIR spectrometers employ complicated dispersive grating or Fourier transform techniques. In this work, we developed a filter type NIR spectrometer with the availability of high efficiency and low-cost narrow bandpass NIR interference filters to be taught in a physics laboratory. The instrument was designed for transmission-mode configuration. A 50W halogen lamp was used as NIR source. There were fourteen NIR filters mounted on a rotatory wheel for wavelength selection ranging from 1000-1650 nm with steps of 50 nm. A 1.0 mm diameter of InGaAs photodiode was used as the detector for the spectrometer. Hence, transparent gem materials can be used as samples for experiment. Student can learn vibrational absorption spectroscopy as well as Beer-Lambert law from the development of this instrument.

Ethylglyoxal bis(guanylhydrazone) as an inhibitor of polyamine biosynthesis in L1210 leukemia cells.

PubMed

Seppänen, P; Ruohola, H; Jänne, J

1984-04-16

Ethylglyoxal bis(guanylhydrazone), a close derivative of the known anti-cancer drug methylglyoxal bis(guanylhydrazone), is also a powerful inhibitor of S-adenosylmethionine decarboxylase (EC 4.1.1.50), the enzyme needed for the synthesis of spermidine and spermine. There were, however, marked differences between the ethyl and methyl derivatives of glyoxal bis(guanylhydrazone) when tested in cultured L1210 cells. The cellular accumulation of ethylglyoxal bis(guanylhydrazone) represented only a fraction (20-25%) of that of the methyl derivative. Moreover, polyamine depletion, which is known to strikingly stimulate the uptake of methylglyoxal bis(guanylhydrazone), decreased, if anything, the uptake of ethylglyoxal bis(guanylhydrazone) by L1210 cells. The compound produced spermidine and spermine depletion fully comparable to that achieved with methylglyoxal bis(guanylhydrazone) at micromolar concentrations. Ethylglyoxal bis(guanylhydrazone) was growth-inhibitory to L1210 cells and produced an additive antiproliferative action when used together with 2-difluoromethylornithine. Ethylglyoxal bis(guanylhydrazone) was distinctly less effective than methylglyoxal bis(guanylhydrazone) in releasing bound polyamines from isolated cell organelles in vitro. Ethylglyoxal bis(guanylhydrazone) was also devoid of the early and profound mitochondrial toxicity typical to methylglyoxal bis(guanylhydrazone). These findings may indicate that this compound is a more specific inhibitor of polyamine biosynthesis with less intracellular polyamine 'receptor-site' activity than methylglyoxal bis(guanylhydrazone).

Synthesis, structural, and biological evaluation of bis-heteroarylmaleimides and bis-heterofused imides.

PubMed

Ferri, Nicola; Radice, Tiziano; Antonino, Manuela; Beccalli, Egle Maria; Tinelli, Stella; Zunino, Franco; Corsini, Alberto; Pratesi, Graziella; Ragg, Enzio M; Gelmi, Maria Luisa; Contini, Alessandro

2011-09-15

Bis-2,3-heteroarylmaleimides and polyheterocondensed imides joined through nitrogen atoms of the N,N'-bis(ethyl)-1,3-propanediamine linker were prepared from substituted maleic anhydrides and symmetrical diamines in good to satisfactory yields and short reaction times using microwave heating. The novel molecules were shown to inhibit proliferation of human tumor cells (NCI-H460 lung carcinoma) and rat aortic smooth muscle cells (SMCs) with variable potencies. Compound 11a, the most potent one of the series, showed IC(50) values comparable to those observed for the leading molecule elinafide in both cell lines, but with a higher selectivity toward human tumor cells. Compound 11a affected G1/S phase transition of the cell cycle, showed in vitro DNA intercalating activity and in vivo antitumor activity. A thorough structural analysis of the 11a-DNA complex was also made by mean of NMR and computational techniques. Copyright © 2011 Elsevier Ltd. All rights reserved.

Behavioural Inhibition System (BIS) sensitivity differentiates EEG theta responses during goal conflict in a continuous monitoring task.

PubMed

Moore, Roger A; Mills, Matthew; Marshman, Paul; Corr, Philip J

2012-08-01

Previous research has revealed that EEG theta oscillations are affected during goal conflict processing. This is consistent with the behavioural inhibition system (BIS) theory of anxiety (Gray & McNaughton, 2000). However, studies have not attempted to relate these BIS-related theta effects to BIS personality measures. Confirmation of such an association would provide further support for BIS theory, especially as it relates to trait differences. EEG was measured (32 electrodes) from extreme groups (low/high trait BIS) engaged in a target detection task. Goal conflicts were introduced throughout the task. Results show that the two groups did not differ in behavioural performance. The major EEG result was that a stepwise discriminant analysis indicated discrimination by 6 variables derived from coherence and power, with 5 of the 6 in the theta range as predicted by BIS theory and one in the beta range. Also, across the whole sample, EEG theta coherence increased at a variety of regions during primary goal conflict and showed a general increase during response execution; EEG theta power, in contrast, was primarily reactive to response execution. This is the first study to reveal a three-way relationship between the induction of goal conflict, the induction of theta power and coherence, and differentiation by psychometrically-defined low/high BIS status. Copyright © 2012 Elsevier B.V. All rights reserved.

Gravity model improvement using GEOS 3 /GEM 9 and 10/. [and Seasat altimetry data

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Wagner, C. A.; Klosko, S. M.; Laubscher, R. E.

1979-01-01

Although errors in previous gravity models have produced large uncertainties in the orbital position of GEOS 3, significant improvement has been obtained with new geopotential solutions, Goddard Earth Model (GEM) 9 and 10. The GEM 9 and 10 solutions for the potential coefficients and station coordinates are presented along with a discussion of the new techniques employed. Also presented and discussed are solutions for three fundamental geodetic reference parameters, viz. the mean radius of the earth, the gravitational constant, and mean equatorial gravity. Evaluation of the gravity field is examined together with evaluation of GEM 9 and 10 for orbit determination accuracy. The major objectives of GEM 9 and 10 are achieved. GEOS 3 orbital accuracies from these models are about 1 m in their radial components for 5-day arc lengths. Both models yield significantly improved results over GEM solutions when compared to surface gravimetry, Skylab and GEOS 3 altimetry, and highly accurate BE-C (Beacon Explorer-C) laser ranges. The new values of the parameters discussed are given.

Promoting microbiology education through the iGEM synthetic biology competition.

PubMed

Kelwick, Richard; Bowater, Laura; Yeoman, Kay H; Bowater, Richard P

2015-08-01

Synthetic biology has developed rapidly in the 21st century. It covers a range of scientific disciplines that incorporate principles from engineering to take advantage of and improve biological systems, often applied to specific problems. Methods important in this subject area include the systematic design and testing of biological systems and, here, we describe how synthetic biology projects frequently develop microbiology skills and education. Synthetic biology research has huge potential in biotechnology and medicine, which brings important ethical and moral issues to address, offering learning opportunities about the wider impact of microbiological research. Synthetic biology projects have developed into wide-ranging training and educational experiences through iGEM, the International Genetically Engineered Machines competition. Elements of the competition are judged against specific criteria and teams can win medals and prizes across several categories. Collaboration is an important element of iGEM, and all DNA constructs synthesized by iGEM teams are made available to all researchers through the Registry for Standard Biological Parts. An overview of microbiological developments in the iGEM competition is provided. This review is targeted at educators that focus on microbiology and synthetic biology, but will also be of value to undergraduate and postgraduate students with an interest in this exciting subject area. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Evaluation of phosphonate treatments for control of phytophthora crown rot of walnut

USDA-ARS?s Scientific Manuscript database

Foliar and soil applications of phosphonate were evaluated in a factorial manner for control of trunk cankers caused by Phytophthora citricola in a Persian walnut orchard, cultivar ‘Chandler’. In each of two experiments, the foliar treatment was applied once in the second week of September, whereas...

Phosphorus sorption on marine carbonate sediment: phosphonate as model organic compounds.

PubMed

Huang, Xiao-Lan; Zhang, Jia-Zhong

2011-11-01

Organophosphonate, characterized by the presence of a stable, covalent, carbon to phosphorus (C-P) bond, is a group of synthetic or biogenic organophosphorus compounds. The fate of these organic phosphorus compounds in the environment is not well studied. This study presents the first investigation on the sorption of phosphorus (P) in the presence of two model phosphonate compounds, 2-aminothylphosphonoic acid (2-AEP) and phosphonoformic acid (PFA), on marine carbonate sediments. In contrast to other organic P compounds, no significant inorganic phosphate exchange was observed in seawater. P was found to adsorb on the sediment only in the presence of PFA, not 2-AEP. This indicated that sorption of P from phosphonate on marine sediment was compound specific. Compared with inorganic phosphate sorption on the same sediments, P sorption from organic phosphorus is much less in the marine environment. Further study is needed to understand the potential role of the organophosphonate compounds in biogeochemical cycle of phosphorus in the environment. Copyright © 2011 Elsevier Ltd. All rights reserved.

OSG-GEM: Gene Expression Matrix Construction Using the Open Science Grid.

PubMed

Poehlman, William L; Rynge, Mats; Branton, Chris; Balamurugan, D; Feltus, Frank A

2016-01-01

High-throughput DNA sequencing technology has revolutionized the study of gene expression while introducing significant computational challenges for biologists. These computational challenges include access to sufficient computer hardware and functional data processing workflows. Both these challenges are addressed with our scalable, open-source Pegasus workflow for processing high-throughput DNA sequence datasets into a gene expression matrix (GEM) using computational resources available to U.S.-based researchers on the Open Science Grid (OSG). We describe the usage of the workflow (OSG-GEM), discuss workflow design, inspect performance data, and assess accuracy in mapping paired-end sequencing reads to a reference genome. A target OSG-GEM user is proficient with the Linux command line and possesses basic bioinformatics experience. The user may run this workflow directly on the OSG or adapt it to novel computing environments.

Determination of Fosetyl and Phosphonic Acid at 0.010 mg/kg Level by Ion Chromatography Tandem Mass Spectrometry.

PubMed

Bauer, Anna; Luetjohann, Jens; Rohn, Sascha; Kuballa, Juergen; Jantzen, Eckard

2018-01-10

A new sensitive, fast, and robust method using ion chromatography tandem mass spectrometry (IC-MS/MS) for the determination of fosetyl and phosphonic acid in plant-derived matrices was developed. For compensation of matrix effects and differences in recovery rates the isotopically labeled internal standard (ILIS) 18 O 3 -labeled phosphonic acid was added to the samples prior to the extraction of the target compounds. The validation of the method for the matrices tomato, apple, lemon, sultana, avocado, and wheat was performed according to the actual EU guidance document SANTE/11945/2015. The precision and accuracy were determined in five replicates at spiking levels of 0.010 and 0.100 mg/kg with recovery rates between 76 and 105% and RSDs between 1.2 and 17.8%. In this paper, it was achieved for the first time to detect both fosetyl and phosphonic acid at the reporting level of 0.010 mg/kg most relevant for organic plant food commodities.

The use of functionalized monoalkyl phosphates and phosphonates in the colloidal processing of oxide ceramic powders

NASA Astrophysics Data System (ADS)

Radsick, Timothy Carl

The purpose of this study was to develop phosphorous-based chemicals that could be used to modify the interparticle pair potential of several oxide ceramic particles, thereby enabling their use in colloidal processing schemes. Several procedures for the synthesis of 11-12 carbon alpha,o-functionalized monoalkyl phosphates and phosphonates were developed. Because of its simplicity and its use of mild reagents, a procedure based on the Michaelis-Arbuzov rearrangement was selected to produce the bulk of the chemicals used in this study. Carboxyl- and hydroxyl-terminated monoalkyl phosphonates were adsorbed onto alumina and zirconia powders using either aqueous-based or solvent-based methods to produce a monolayer of "brushlike" steric molecules. In the aqueous-based methods, powders were processed at pH values below their isoelectric point in order to produce a positive charge on the powder, thereby attracting the negatively charged phosphate or phosphonate group onto the powder surface to form the steric monolayer. In solvent-based methods, powder was suspended in an acetone solution of the phosphonates, heated at reflux, washed, dried and heat treated at 120°C under vacuum. The zeta potential of the coated powders was measured to quantify the degree of steric layer adsorption and the shift in the isoelectric point. Slurries of coated alumina and zirconia were prepared having 20 vol % powder. Rheological behavior was studied by measuring viscosity as a function of shear rate for slurries of various pH values and counterion concentrations. Slurries with powder processed via the solvent method were the least sensitive to changes in slurry pH and were straightforward to prepare. It is thought that the solvent-based coating procedure produced a stronger, multi-dentate powder-phosphonate bond than that of the aqueous-based procedure. Dispersed and coagulated slurries were able to be prepared over a wide pH range, including at the isoelectric point of the uncoated powders

Python based integration of GEM detector electronics with JET data acquisition system

NASA Astrophysics Data System (ADS)

Zabołotny, Wojciech M.; Byszuk, Adrian; Chernyshova, Maryna; Cieszewski, Radosław; Czarski, Tomasz; Dalley, Simon; Hogben, Colin; Jakubowska, Katarzyna L.; Kasprowicz, Grzegorz; Poźniak, Krzysztof; Rzadkiewicz, Jacek; Scholz, Marek; Shumack, Amy

2014-11-01

This paper presents the system integrating the dedicated measurement and control electronic systems for Gas Electron Multiplier (GEM) detectors with the Control and Data Acquisition system (CODAS) in the JET facility in Culham, England. The presented system performs the high level procedures necessary to calibrate the GEM detector and to protect it against possible malfunctions or dangerous changes in operating conditions. The system also allows control of the GEM detectors from CODAS, setting of their parameters, checking their state, starting the plasma measurement and to reading the results. The system has been implemented using the Python language, using the advanced libraries for implementation of network communication protocols, for object based hardware management and for data processing.

Overview of the Gems Model of Volunteer Administration (Generate, Educate, Mobilize and Sustain)

ERIC Educational Resources Information Center

Culp, Ken, III

2012-01-01

To organize and coordinate the efforts of many volunteers, a framework for volunteer engagement is needed. The "GEMS" Model of volunteer administration was developed to assist Extension professionals and volunteer coordinators to effectively administer volunteer programs without delivering the program themselves. The GEMS Model is…

Catalytic Hydrogenation Activity and Electronic Structure Determination of Bis(arylimidazol-2-ylidene)pyridine Cobalt Alkyl and Hydride Complexes

PubMed Central

Yu, Renyuan Pony; Darmon, Jonathan M.; Milsmann, Carsten; Margulieux, Grant W.; E. Stieber, S. Chantal; DeBeer, Serena

2013-01-01

The bis(arylimidazol-2-ylidene)pyridine cobalt methyl complex, (iPrCNC)CoCH3, was evaluated for the catalytic hydrogenation of alkenes. At 22 °C and 4 atm of H2 pressure, (iPrCNC)CoCH3 is an effective pre-catalyst for the hydrogenation of sterically hindered, unactivated alkenes such as trans-methylstilbene, 1-methyl-1-cyclohexene and 2,3-dimethyl-2-butene, representing one of the most active cobalt hydrogenation catalysts reported to date. Preparation of the cobalt hydride complex, (iPrCNC)CoH was accomplished by hydrogenation of (iPrCNC)CoCH3. Over the course of 3 hours at 22 °C, migration of the metal-hydride to the 4-position of the pyridine ring yielded (4-H2-iPrCNC)CoN2. Similar alkyl migration was observed upon treatment of (iPrCNC)CoH with 1,1-diphenylethylene. This reactivity raised the question as to whether this class of chelate is redoxactive, engaging in radical chemistry with the cobalt center. A combination of structural, spectroscopic and computational studies was conducted and provided definitive evidence for bis(arylimidazol-2-ylidene)pyridine radicals in reduced cobalt chemistry. Spin density calculations established that the radicals were localized on the pyridine ring, accounting for the observed reactivity and suggest a wide family of pyridine-based pincers may also be redox active. PMID:23968297

Multi-GEM Detectors in High Particle Fluxes

NASA Astrophysics Data System (ADS)

Thuiner, P.; Resnati, F.; Franchino, S.; Gonzalez Diaz, D.; Hall-Wilton, R.; Müller, H.; Oliveri, E.; Pfeiffer, D.; Ropelewski, L.; Van Stenis, M.; Streli, C.; Veenhof, R.

2018-02-01

Gaseous Electron Multipliers (GEM) are well known for stable operation at high particle fluxes. We present a study of the intrinsic limits of GEMdetectors when exposed to very high particle fluxes of the order of MHz/mm2. We give an interpretation to the variations of the effective gain, which, as a function of the particle flux, first increases and then decreases. We also discuss the reduction of the ion back-flow with increasing flux. We present measurements and simulations of a triple GEM detector, describing its behaviour in terms of accumulation of positive ions that results in changes of the transfer fields and the amplification fields. The behaviour is expected to be common to all multi-stage amplification devices where the efficiency of transferring the electrons from one stage to the next one is not 100%.

Energetic Salts Based on 3,5-Bis(dinitromethyl)-1,2,4-triazole Monoanion and Dianion: Controllable Preparation, Characterization, and High Performance.

PubMed

Zhang, Jiaheng; Dharavath, Srinivas; Mitchell, Lauren A; Parrish, Damon A; Shreeve, Jean'ne M

2016-06-22

Molecular modification of known explosives is considered to be an efficient route to design new energetic materials. A new family of energetic salts based on the 3,5-bis(dinitromethyl)-1,2,4-triazole monoanion and dianion were controllably synthesized by using 1-diamino-2,2-dinitroethene as a precursor. X-ray structure determination of monohydrazinium 3,5-bis(dinitromethyl)-1,2,4-triazolate (5) and monoammonium (6) and diammonium 3,5-bis(dinitromethyl)-1,2,4-triazolate hydrate (8·H2O) further confirmed the structures of these anions. In addition, as supported by X-ray data, in the monoanion system, the roving proton on the ring nitrogen rather than on the gem-dinitro carbon results in extensive hydrogen-bonding interactions and higher packing coefficients. Interestingly, 5 and 6 possess the highest calculated crystal densities, 1.965 and 1.957 g cm(-3) at 150 K, for hydrazinium and ammonium energetic salts, respectively. Energetic evaluation indicates that 5 (detonation velocity vD = 9086 m s(-1); detonation pressure P = 38.7 GPa) and 6 (vD, 9271 m s(-1); P = 41.0 GPa) exhibit great detonation properties, superior to those of current highly explosive benchmarks, such as 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX).

Complex formation equilibria of binary and ternary complexes involving 3,3-bis(1-methylimidazol-2yl)propionic acid and bio-relevant ligands as 1-aminocyclopropane carboxylic acid with reference to plant hormone

NASA Astrophysics Data System (ADS)

Shoukry, Mohamed M.; Hassan, Safaa S.

2014-01-01

The formation equilibria for the binary complexes of Cu(II) with 1-aminocyclopropane carboxylic acid (ACC) and 3,3-bis(1-methylimidazol-2-yl)propionic acid (BIMP) were investigated. ACC and BIMP form the complexes 1 1 0, 1 2 0 and 1 1 -1. The ternary complexes of Cu(II) with BIMP and biorelevant ligands as some selected amino acids, peptides and DNA constituents are formed in a stepwise mechanism. The stability constants of the complexes formed were determined and their distribution diagrams were evaluated. The kinetics of hydrolysis of glycine methyl ester in presence of [Cu(BIMP)]+ was investigated by pH-stat technique and the mechanism was discussed.

MeerLICHT and BlackGEM: custom-built telescopes to detect faint optical transients

NASA Astrophysics Data System (ADS)

Bloemen, Steven; Groot, Paul; Woudt, Patrick; Klein Wolt, Marc; McBride, Vanessa; Nelemans, Gijs; Körding, Elmar; Pretorius, Margaretha L.; Roelfsema, Ronald; Bettonvil, Felix; Balster, Harry; Bakker, Roy; Dolron, Peter; van Elteren, Arjen; Elswijk, Eddy; Engels, Arno; Fender, Rob; Fokker, Marc; de Haan, Menno; Hagoort, Klaas; de Hoog, Jasper; ter Horst, Rik; van der Kevie, Giel; Kozłowski, Stanisław; Kragt, Jan; Lech, Grzegorz; Le Poole, Rudolf; Lesman, Dirk; Morren, Johan; Navarro, Ramon; Paalberends, Willem-Jelle; Paterson, Kerry; Pawłaszek, Rafal; Pessemier, Wim; Raskin, Gert; Rutten, Harrie; Scheers, Bart; Schuil, Menno; Sybilski, Piotr W.

2016-07-01

We present the MeerLICHT and BlackGEM telescopes, which are wide-field optical telescopes that are currently being built to study transient phenomena, gravitational wave counterparts and variable stars. The telescopes have 65 cm primary mirrors and a 2.7 square degree field-of-view. The MeerLICHT and BlackGEM projects have different science goals, but will use identical telescopes. The first telescope, MeerLICHT, will be commissioned at Sutherland (South Africa) in the first quarter of 2017. It will co-point with MeerKAT to collect optical data commensurate with the radio observations. After careful analysis of MeerLICHT's performance, three telescopes of the same type will be commissioned in La Silla (Chile) in 2018 to form phase I of the BlackGEM array. BlackGEM aims at detecting and characterizing optical counterparts of gravitational wave events detected by Advanced LIGO and Virgo. In this contribution we present an overview of the science goals, the design and the status of the two projects.

OSG-GEM: Gene Expression Matrix Construction Using the Open Science Grid

PubMed Central

Poehlman, William L.; Rynge, Mats; Branton, Chris; Balamurugan, D.; Feltus, Frank A.

2016-01-01

High-throughput DNA sequencing technology has revolutionized the study of gene expression while introducing significant computational challenges for biologists. These computational challenges include access to sufficient computer hardware and functional data processing workflows. Both these challenges are addressed with our scalable, open-source Pegasus workflow for processing high-throughput DNA sequence datasets into a gene expression matrix (GEM) using computational resources available to U.S.-based researchers on the Open Science Grid (OSG). We describe the usage of the workflow (OSG-GEM), discuss workflow design, inspect performance data, and assess accuracy in mapping paired-end sequencing reads to a reference genome. A target OSG-GEM user is proficient with the Linux command line and possesses basic bioinformatics experience. The user may run this workflow directly on the OSG or adapt it to novel computing environments. PMID:27499617

Metal phosphonate coordination networks and frameworks as precursors of electrocatalysts for the hydrogen and oxygen evolution reactions

NASA Astrophysics Data System (ADS)

Zhang, Rui; El-Refaei, Sayed M.; Russo, Patrícia A.; Pinna, Nicola

2018-05-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) play key roles in the conversion of energy derived from renewable energy sources into chemical energy. Efficient, robust, and inexpensive electrocatalysts are necessary for driving these reactions at high rates at low overpotentials and minimize energetic losses. Recently, electrocatalysts derived from hybrid metal phosphonate compounds have shown high activity for the HER or OER. We review here the utilization of metal phosphonate coordination networks and metal-organic frameworks as precursors/templates for transition-metal phosphides, phosphates, or oxyhydroxides generated in situ in alkaline solutions, and their electrocatalytic performance in HER or OER.

Geminal difunctionalization of α-diazo arylmethylphosphonates: synthesis of fluorinated phosphonates.

PubMed

Zhou, Yujing; Zhang, Yan; Wang, Jianbo

2016-11-08

A general approach towards diverse fluorinated phosphonates via geminal difunctionalization reactions of α-diazo arylmethylphosphonates is described. The diazo functionality (RR'C[double bond, length as m-dash]N 2 ) is successfully converted to RR'CF 2 , RR'CHF, RR'CFBr or RR'CFNR'' 2 groups by employing different fluorination reagents. A variety of fluorinated organophosphorus compounds were readily accessed in good to excellent yields from a common type of precursor.

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2012 CFR

2012-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

40 CFR 721.1630 - 1,2-Ethanediol bis(4-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate...

Code of Federal Regulations, 2014 CFR

2014-07-01

...-methylbenzenesulfonate); 2,2-oxybis-ethane bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis(2,1-ethanediyl oxy)]bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[oxybis (2,1-ethane diyloxy)] bis-, bis(4-methylbenzenesulfonate); ethanol, 2,2â²-[[1-[(2-propenyloxy) methyl]-1,2-ethanediyl] bis(oxy)]bis-, bis(4-methylbenzene...

The development and evaluation of mini-GEMs - short, focused, online e-learning videos in geriatric medicine.

PubMed

Garside, Mark J; Fisher, James M; Blundell, Adrian G; Gordon, Adam L

2018-01-01

Mini Geriatric E-Learning Modules (Mini-GEMs) are short, focused, e-learning videos on geriatric medicine topics, hosted on YouTube, which are targeted at junior doctors working with older people. This study aimed to explore how these resources are accessed and used. The authors analyzed the viewing data from 22 videos published over the first 18 months of the Mini-GEM project. We conducted a focus group of U.K. junior doctors considering their experiences with Mini-GEMS. The Mini-GEMs were viewed 10,291 times over 18 months, equating to 38,435 minutes of total viewing time. The average viewing time for each video was 3.85 minutes. Learners valued the brevity and focused nature of the Mini-GEMs and reported that they watched them in a variety of settings to supplement clinical experiences and consolidate learning. Watching the videos led to an increase in self-reported confidence in managing older patients. Mini-GEMs can effectively disseminate clinical teaching material to a wide audience. The videos are valued by junior doctors due to their accessibility and ease of use.

Cd(II)-coordination polymers based on tetracarboxylic acid and diverse bis(imidazole) ligands: Synthesis, structural diversity and photoluminescence properties

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

Arıcı, Mürsel, E-mail: marici@ogu.edu.tr; Yeşilel, Okan Zafer; Taş, Murat

Three new Cd(II)-coordination polymers, namely, ([Cd{sub 2}(μ{sub 6}-ao{sub 2}btc)(μ-1,5-bipe){sub 2}]·2H{sub 2}O){sub n} (1), ([Cd{sub 2}(μ{sub 6}-ao{sub 2}btc)(μ-1,4-bix){sub 2}]{sub n}·2DMF) (2) and ([Cd{sub 2}(μ{sub 8}-abtc)(μ-1,4-betix)]·DMF·H{sub 2}O){sub n} (3) (ao{sub 2}btc=di-oxygenated form of 3,3′,5,5′-azobenzenetetracarboxylate, 1,5-bipe: 1,5-bis(imidazol-1yl)pentane, 1,4-bix=1,4-bis(imidazol-1ylmethyl)benzene, 1,4-betix=1,4-bis(2-ethylimidazol-1ylmethyl)benzene) were synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1–3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the raremore » sqc27 topology. When semi-flexible substituted bis(imidazole) linker was used, 3D framework of complex 3 was obtained with the paddlewheel Cd{sub 2}(CO{sub 2}){sub 4}-type binuclear SBU. Moreover, thermal and photoluminescence properties of the complexes were determined in detailed. - Graphical abstract: In this study, three novel Cd(II)-coordination polymers were synthesized with 3,3′,5,5′-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1–3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the rare sqc27 topology

Binuclear ruthenium(III) bis(thiosemicarbazone) complexes: Synthesis, spectral, electrochemical studies and catalytic oxidation of alcohol

NASA Astrophysics Data System (ADS)

Mohamed Subarkhan, M.; Ramesh, R.

2015-03-01

A new series of binuclear ruthenium(III) thiosemicarbazone complexes of general formula [(EPh3)2(X)2Ru-L-Ru(X)2(EPh3)2] (where E = P or As; X = Cl or Br; L = NS chelating bis(thiosemicarbazone ligands) has been synthesized and characterized by analytical and spectral (FT-IR, UV-Vis and EPR). IR spectra show that the thiosemicarbazones behave as monoanionic bidentate ligands coordinating through the azomethine nitrogen and thiolate sulphur. The electronic spectra of the complexes indicate that the presence of d-d and intense LMCT transitions in the visible region. The complexes are paramagnetic (low spin d5) in nature and all the complexes show rhombic distortion around the ruthenium ion with three different 'g' values (gx ≠ gy ≠ gz) at 77 K. All the complexes are redox active and exhibit an irreversible metal centered redox processes (RuIII-RuIII/RuIV-RuIV; RuIII-RuIII/RuII-RuII) within the potential range of 0.38-0.86 V and -0.39 to -0.66 V respectively, versus Ag/AgCl. Further, the catalytic efficiency of one of the complexes [Ru2Cl2(AsPh3)4(L1)] (4) has been investigated in the case of oxidation of primary and secondary alcohols into their corresponding aldehydes and ketones in the presence of N-methylmorpholine-N-oxide(NMO) as co-oxidant. The formation of high valent RuVdbnd O species is proposed as catalytic intermediate for the catalytic cycle.

Optical characterization of synthetic faceted gem materials grown from hydrothermal solutions

NASA Astrophysics Data System (ADS)

Lu, Taijin; Shigley, James E.

1998-10-01

Various non-destructive optical characterization techniques have been used to characterize and identify synthetic gem materials grown from hydrothermal solutions, to include ruby, sapphire, emerald, amethyst and ametrine (amethyst-citrine), from their natural counterparts. The ability to observe internal features, such as inclusions, dislocations, twins, color bands, and growth zoning in gem materials is strongly dependent on the observation techniques and conditions, since faceted gemstones have many polished surfaces which can reflect and scatter light in various directions which can make observation difficult. However, diagnostic gemological properties of these faceted synthetic gem materials can be obtained by choosing effective optical characterization methods, and by modifying optical instruments. Examples of some of the distinctive features of synthetic amethyst, ametrine, pink quartz, ruby and emerald are presented to illustrate means of optical characterization of gemstones. The ability to observe defects by light scattering techniques is discussed.

Structural characterization of two solvates of a luminescent copper(II) bis­(pyridine)-substituted benzimidazole complex

PubMed Central

DeStefano, Matthew R.; Lewis, Robert A.

2017-01-01

Copper(II) complexes of benzimidazole are known to exhibit biological activity that makes them of inter­est for chemotherapeutic and other pharmaceutical uses. The complex bis­(acetato-κO){5,6-dimethyl-2-(pyridin-2-yl)-1-[(pyridin-2-yl)meth­yl]-1H-benzimidazole-κ2 N 2,N 3}copper(II), has been prepared. The absorption spectrum has features attributed to intra­ligand and ligand-field transitions and the complex exhibits ligand-centered room-temperature luminescence in solution. The aceto­nitrile monosolvate, [Cu(C2H3O2)2(C20H18N4)]·C2H3N (1), and the ethanol hemisolvate, [Cu(C2H3O2)2(C20H18N4)]·0.5C2H6O (2), have been structurally characterized. Compound 2 has two copper(II) complexes in the asymmetric unit. In both 1 and 2, distorted square-planar N2O2 coordination geometries are observed and the Cu—N(Im) bond distance is slightly shorter than the Cu—N(py) bond distance. Inter­molecular π–π inter­actions are found in 1 and 2. A weak C—H⋯π inter­action is observed in 1. PMID:29152336

Cd(II)-coordination polymers based on tetracarboxylic acid and diverse bis(imidazole) ligands: Synthesis, structural diversity and photoluminescence properties

NASA Astrophysics Data System (ADS)

Arıcı, Mürsel; Yeşilel, Okan Zafer; Taş, Murat

2017-01-01

Three new Cd(II)-coordination polymers, namely, {[Cd2(μ6-ao2btc)(μ-1,5-bipe)2]·2H2O}n (1), {[Cd2(μ6-ao2btc)(μ-1,4-bix)2]n·2DMF} (2) and {[Cd2(μ8-abtc)(μ-1,4-betix)]·DMF·H2O}n (3) (ao2btc=di-oxygenated form of 3,3‧,5,5‧-azobenzenetetracarboxylate, 1,5-bipe: 1,5-bis(imidazol-1yl)pentane, 1,4-bix=1,4-bis(imidazol-1ylmethyl)benzene, 1,4-betix=1,4-bis(2-ethylimidazol-1ylmethyl)benzene) were synthesized with 3,3‧,5,5‧-azobenzenetetracarboxylic acid and flexible, semi-flexible and semi-flexible substituted bis(imidazole) linkers. They were characterized by IR spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder X-ray diffractions (PXRD) and thermal analyses (TG/DTA). Complexes 1-3 exhibited structural diversities depending on flexible, semi-flexible and semi-flexible substituted bis(imidazole) ligands. Complex 1 was 2D structure with 3,6L18 topology. Complex 2 had a 3D pillar-layered framework with the rare sqc27 topology. When semi-flexible substituted bis(imidazole) linker was used, 3D framework of complex 3 was obtained with the paddlewheel Cd2(CO2)4-type binuclear SBU. Moreover, thermal and photoluminescence properties of the complexes were determined in detailed.

Synthesis and characterization of bright green terbium coordination complex derived from 1,4-bis(carbonylmethyl)terephthalate: Structure and luminescence properties

NASA Astrophysics Data System (ADS)

Ma, Mengjiao; Li, Congcong; Shu, Dengkun; Wang, Chaohua; Xi, Peng

2018-02-01

A photoluminescent terbium (Tb) complex involving a novel benzoic-acid compound with a unique coordinated structure, namely 1,4-bis(carbonylmethyl)terephthalate (BCMT), has been designed and synthesized. The new coordinate structure and energy-transfer mechanism between the ligand and Tb(III) ions were investigated in detail. The results demonstrated that the BCMT-Tb(III) complex shows strong fluorescence intensity (4 × 106 a.u.) and long fluorescence lifetime (1.302 ms), owing to the favorable degree of energy matching between the triplet excited level of the ligand and the resonant level of Tb(III) ions. Based on the analysis of three-dimensional luminescence spectra, the as-prepared Tb(III) complex can be effectively excited in the range of 250-310 nm, and it shows high color purity, with a bright green appearance.

A spin-crossover complex based on a 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligand functionalized with a carboxylate group.

PubMed

Abhervé, Alexandre; Clemente-León, Miguel; Coronado, Eugenio; Gómez-García, Carlos J; López-Jordà, Maurici

2014-07-07

Combining Fe(ii) with the carboxylate-functionalized 2,6-bis(pyrazol-1-yl)pyridine (bppCOOH) ligand results in the spin-crossover compound [Fe(bppCOOH)2](ClO4)2 which shows an abrupt spin transition with a T1/2 of ca. 380 K and a TLIESST of 60 K due to the presence of a hydrogen-bonded linear network of complexes.

Evaluation of a GEM and CAT-based detector for radiation therapy beam monitoring

NASA Astrophysics Data System (ADS)

Brahme, A.; Danielsson, M.; Iacobaeus, C.; Ostling, J.; Peskov, V.; Wallmark, M.

2000-11-01

We are developing a radiation therapy beam monitor for the Karolinska Institute. This monitor will consist of two consecutive detectors confined in one gas chamber: a "keV-photon detector", which will allow diagnostic quality visualization of the patient, and a "MeV-photon detector", that will measure the absolute intensity of the therapy beam and its position with respect to the patient. Both detectors are based on highly radiation resistant gas and solid photon to electron converters, combined with GEMs and a CAT as amplification structures. We have performed systematic studies of the high-rate characteristics of the GEM and the CAT, as well as tested the electron transfer through these electron multipliers and various types of converters. The tests show that the GEM and the CAT satisfy all requirements for the beam monitoring system. As a result of these studies we successfully developed and tested a full section of the beam monitor equipped with a MeV-photon converter placed between the GEM and the CAT.

The physiological basis of Glottal electromagnetic micropower sensors (GEMS) and their use in defining an excitation function for the human vocal tract

NASA Astrophysics Data System (ADS)

Burnett, Gregory Clell

1999-10-01

The definition, use, and physiological basis of Glottal Electromagnetic Micropower Sensors (GEMS) is presented. These sensors are a new type of low power (<20 milliwatts radiated) microwave regime (900 MHz to 2.5 GHz) multi-purpose motion sensor developed at the Lawrence Livermore National Laboratory. The GEMS are sensitive to movement in an adjustable field of view (FOV) surrounding the antennae. In this thesis, the GEMS has been utilized for speech research, targeted to receive motion signals from the subglottal region of the trachea. The GEMS signal is analyzed to determine the physiological source of the signal, and this information is used to calculate the subglottal pressure, effectively an excitation function for the human vocal tract. For the first time, an excitation function may be calculated in near real time using a noninvasive procedure. Several experiments and models are presented to demonstrate that the GEMS signal is representative of the motion of the subglottal posterior wall of the trachea as it vibrates in response to the pressure changes caused by the folds as they modulate the airflow supplied by the lungs. The vibrational properties of the tracheal wall are modeled using a lumped-element circuit model. Taking the output of the vocal tract to be the audio pressure captured by a microphone and the input to be the subglottal pressure, the transfer function of the vocal tract (including the nasal cavities) can be approximated every 10-30 milliseconds using an autoregressive moving-average model. Unlike the currently utilized method of transfer function approximation, this new method only involves noninvasive GEMS measurements and digital signal processing and does not demand the difficult task of obtaining precise physical measurements of the tract and subsequent estimation of the transfer function using its cross-sectional area. The ability to measure the physical motion of the trachea enables a significant number of potential applications

Depletion of pro-oncogenic RUNX2 enhances gemcitabine (GEM) sensitivity of p53-mutated pancreatic cancer Panc-1 cells through the induction of pro-apoptotic TAp63.

PubMed

Ozaki, Toshinori; Nakamura, Mizuyo; Ogata, Takehiro; Sang, Meijie; Yoda, Hiroyuki; Hiraoka, Kiriko; Sang, Meixiang; Shimozato, Osamu

2016-11-01

Recently, we have described that siRNA-mediated silencing of runt-related transcription factor 2 (RUNX2) improves anti-cancer drug gemcitabine (GEM) sensitivity of p53-deficient human pancreatic cancer AsPC-1 cells through the augmentation of p53 family TAp63-dependent cell death pathway. In this manuscript, we have extended our study to p53-mutated human pancreatic cancer Panc-1 cells. According to our present results, knockdown of mutant p53 alone had a marginal effect on GEM-mediated cell death of Panc-1 cells. We then sought to deplete RUNX2 using siRNA in Panc-1 cells and examined its effect on GEM sensitivity. Under our experimental conditions, RUNX2 knockdown caused a significant enhancement of GEM sensitivity of Panc-1 cells. Notably, GEM-mediated induction of TAp63 but not of TAp73 was further stimulated in RUNX2-depleted Panc-1 cells, indicating that, like AsPC-1 cells, TAp63 might play a pivotal role in the regulation of GEM sensitivity of Panc-1 cells. Consistent with this notion, forced expression of TAp63α in Panc-1 cells promoted cell cycle arrest and/or cell death, and massively increased luciferase activities driven by TAp63-target gene promoters such as p21WAF1 and NOXA. In addition, immunoprecipitation experiments indicated that RUNX2 forms a complex with TAp63 in Panc-1 cells. Taken together, our current observations strongly suggest that depletion of RUNX2 enhances the cytotoxic effect of GEM on p53-mutated Panc-1 cells through the stimulation of TAp63-dependent cell death pathway even in the presence of a large amount of pro-oncogenic mutant p53, and might provide an attractive strategy to treat pancreatic cancer patients with p53 mutations.

Depletion of pro-oncogenic RUNX2 enhances gemcitabine (GEM) sensitivity of p53-mutated pancreatic cancer Panc-1 cells through the induction of pro-apoptotic TAp63

PubMed Central

Ozaki, Toshinori; Nakamura, Mizuyo; Ogata, Takehiro; Sang, Meijie; Yoda, Hiroyuki; Hiraoka, Kiriko; Sang, Meixiang; Shimozato, Osamu

2016-01-01

Recently, we have described that siRNA-mediated silencing of runt-related transcription factor 2 (RUNX2) improves anti-cancer drug gemcitabine (GEM) sensitivity of p53-deficient human pancreatic cancer AsPC-1 cells through the augmentation of p53 family TAp63-dependent cell death pathway. In this manuscript, we have extended our study to p53-mutated human pancreatic cancer Panc-1 cells. According to our present results, knockdown of mutant p53 alone had a marginal effect on GEM-mediated cell death of Panc-1 cells. We then sought to deplete RUNX2 using siRNA in Panc-1 cells and examined its effect on GEM sensitivity. Under our experimental conditions, RUNX2 knockdown caused a significant enhancement of GEM sensitivity of Panc-1 cells. Notably, GEM-mediated induction of TAp63 but not of TAp73 was further stimulated in RUNX2-depleted Panc-1 cells, indicating that, like AsPC-1 cells, TAp63 might play a pivotal role in the regulation of GEM sensitivity of Panc-1 cells. Consistent with this notion, forced expression of TAp63α in Panc-1 cells promoted cell cycle arrest and/or cell death, and massively increased luciferase activities driven by TAp63-target gene promoters such as p21WAF1 and NOXA. In addition, immunoprecipitation experiments indicated that RUNX2 forms a complex with TAp63 in Panc-1 cells. Taken together, our current observations strongly suggest that depletion of RUNX2 enhances the cytotoxic effect of GEM on p53-mutated Panc-1 cells through the stimulation of TAp63-dependent cell death pathway even in the presence of a large amount of pro-oncogenic mutant p53, and might provide an attractive strategy to treat pancreatic cancer patients with p53 mutations. PMID:27713122

N,N'-Bis((6-methoxylpyridin-2-yl)methylene)-p-phenylenediimine based d(10) transition metal complexes and their utilization in co-sensitized solar cells.

PubMed

Wei, Liguo; Yang, Yulin; Fan, Ruiqing; Na, Yong; Wang, Ping; Dong, Yuwei; Yang, Bin; Cao, Wenwu

2014-08-07

N,N'-Bis((6-methoxylpyridin-2-yl)methylene)-p-phenylenediimine based four-coordinated d(10) transition metal complexes (named ML, M = Zn, Cd, Hg) were synthesized and employed as co-sensitizers and co-adsorbents in combination with a ruthenium complex N719 in dye sensitized solar cells. After co-sensitization, not only the incident-photon-to-current conversion efficiency is enhanced but also the dark current is reduced. A short circuit current density of 14.46 mA cm(-2), an open circuit voltage of 0.74 V and a fill factor of 0.62 corresponding to an overall conversion efficiency of 6.65% under AM 1.5 G solar irradiation were achieved when ZnL was used as a co-sensitizer, which are much higher than that for DSSCs only sensitized by N719 (5.22%) under the same conditions. The improvement in efficiency is attributed to the fact that N,N'-bis((6-methoxylpyridin-2-yl)methylene)-p-phenylenediimine coordinated complexes overcome the deficiency of N719 absorption in the low wavelength region of the visible spectrum, prevent its aggregation, offset competitive visible light absorption of I3(-) and reduce charge recombination due to formation of an effective cover layer of the dye molecules on the TiO2 surface. As a result, the synthesized complexes are promising candidates as co-adsorbents and co-sensitizers for highly efficient DSSCs.

Synthesis and crystal structure of the rhodium(I) cyclooctadiene complex with bis(3-tert-butylimidazol-2-ylidene)borate ligand

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

Chen, F.; Shao, K.-J.; Xiao, Y.-C.

2015-12-15

The rhodium(I) cyclooctadiene complex with the bis(3-tert-butylimidazol-2-ylidene)borate ligand [H{sub 2}B(Im{sup t}Bu){sup 2}]Rh(COD) C{sup 22}H{sup 36}BN{sup 4}Rh, has been prepared, and its crystal structure is determined by X-ray diffraction. Complex exhibits slightly distorted square planar configurations around the metal center, which is coordinated by the bidentate H{sup 2}B(Im{sup t}Bu){sub 2} and one cyclooctadiene group. The Rh–C{sub carbene} bond lengths are 2.043(4) and 2.074(4) Å, and the bond angle C–Rh1–C is 82.59°. The dihedral angle between two imidazol-2-ylidene rings is 67.30°.

Glyoxal bis(guanylhydrazone) as an inhibitor of polyamine biosynthesis in tumour cells.

PubMed Central

Seppänen, P; Fagerström, R; Alhonen-Hongisto, L; Elo, H; Lumme, P; Jänne, J

1984-01-01

Glyoxal bis(guanylhydrazone), the parent compound of methylglyoxal bis(guanylhydrazone), was synthesized and tested for its ability to inhibit the biosynthesis of polyamines. It was found to be a powerful competitive inhibitor of adenosylmethionine decarboxylase (EC 4.1.1.50), yet the lack of the methyl group at the glyoxal portion increased the apparent Ki value for the enzyme by about 30-fold in comparison with methylglyoxal bis(guanylhydrazone). Glyoxal bis(guanylhydrazone) inhibited diamine oxidase (EC 1.4.3.6) activity as effectively as did methylglyoxal bis(guanylhydrazone). The cellular accumulation curves of glyoxal bis(guanylhydrazone) in L1210 cells were practically superimposable with those of methylglyoxal bis(guanylhydrazone), and the uptake of both compounds was distinctly stimulated by a prior treatment with 2-difluoromethylornithine. The drug decreased the concentration of spermidine in a dose-dependent manner and, in contrast with methylglyoxal bis(guanylhydrazone), without a concomitant accumulation of putrescine. The fact that putrescine concentrations were decreased in cells exposed to glyoxal bis(guanylhydrazone) was, at least in part, attributable to an inhibition of ornithine decarboxylase (EC 4.1.1.17) activity in cells treated with the compound. Under these experimental conditions equivalent concentrations of methylglyoxal bis(guanylhydrazone) [1,1'-[(methylethanediylidine)dinitrilo]diguanidine] elicited large increases in the enzyme activity. When combined with difluoromethylornithine, glyoxal bis(guanylhydrazone) potentiated the growth-inhibitory effect of that drug. Taking into consideration the proven anti-leukaemic activity of glyoxal bis(guanylhydrazone), its effectiveness to inhibit spermidine biosynthesis (without raising the concentration of putrescine) as well as its suitability for combined use with inhibitors of ornithine decarboxylase, this drug is apparently worthy of further testing in tumour-bearing animals, especially in

Glyoxal bis(guanylhydrazone) as an inhibitor of polyamine biosynthesis in tumour cells.

PubMed

Seppänen, P; Fagerström, R; Alhonen-Hongisto, L; Elo, H; Lumme, P; Jänne, J

1984-07-15

Glyoxal bis(guanylhydrazone), the parent compound of methylglyoxal bis(guanylhydrazone), was synthesized and tested for its ability to inhibit the biosynthesis of polyamines. It was found to be a powerful competitive inhibitor of adenosylmethionine decarboxylase (EC 4.1.1.50), yet the lack of the methyl group at the glyoxal portion increased the apparent Ki value for the enzyme by about 30-fold in comparison with methylglyoxal bis(guanylhydrazone). Glyoxal bis(guanylhydrazone) inhibited diamine oxidase (EC 1.4.3.6) activity as effectively as did methylglyoxal bis(guanylhydrazone). The cellular accumulation curves of glyoxal bis(guanylhydrazone) in L1210 cells were practically superimposable with those of methylglyoxal bis(guanylhydrazone), and the uptake of both compounds was distinctly stimulated by a prior treatment with 2-difluoromethylornithine. The drug decreased the concentration of spermidine in a dose-dependent manner and, in contrast with methylglyoxal bis(guanylhydrazone), without a concomitant accumulation of putrescine. The fact that putrescine concentrations were decreased in cells exposed to glyoxal bis(guanylhydrazone) was, at least in part, attributable to an inhibition of ornithine decarboxylase (EC 4.1.1.17) activity in cells treated with the compound. Under these experimental conditions equivalent concentrations of methylglyoxal bis(guanylhydrazone) [1,1'-[(methylethanediylidine)dinitrilo]diguanidine] elicited large increases in the enzyme activity. When combined with difluoromethylornithine, glyoxal bis(guanylhydrazone) potentiated the growth-inhibitory effect of that drug. Taking into consideration the proven anti-leukaemic activity of glyoxal bis(guanylhydrazone), its effectiveness to inhibit spermidine biosynthesis (without raising the concentration of putrescine) as well as its suitability for combined use with inhibitors of ornithine decarboxylase, this drug is apparently worthy of further testing in tumour-bearing animals, especially in

Fast ADC based multichannel acquisition system for the GEM detector

NASA Astrophysics Data System (ADS)

Kasprowicz, G.; Czarski, T.; Chernyshova, M.; Dominik, W.; Jakubowska, K.; Karpinski, L.; Kierzkowski, K.; Pozniak, K.; Rzadkiewicz, J.; Scholz, M.; Zabolotny, W.

2012-05-01

A novel approach to the Gas Electron Multiplier1 (GEM) detector readout is presented. Unlike commonly used methods, based on discriminators, and analogue FIFOs,[ the method developed uses simultaneously sampling high speed ADCs and advanced FPGA-based processing logic to estimate the energy of every single photon. Such method is applied to every GEM strip signal. It is especially useful in case of crystal-based spectrometers for soft X-rays, where higher order reflections need to be identified and rejected. For the purpose of the detector readout, a novel conception of the measurement platform was developed.

An improved model of the Earth's gravitational field: GEM-T1

NASA Technical Reports Server (NTRS)

Marsh, J. G.; Lerch, F. J.; Christodoulidis, D. C.; Putney, B. H.; Felsentreger, T. L.; Sanchez, B. V.; Smith, D. E.; Klosko, S. M.; Martin, T. V.; Pavlis, E. C.

1987-01-01

Goddard Earth Model T1 (GEM-T1), which was developed from an analysis of direct satellite tracking observations, is the first in a new series of such models. GEM-T1 is complete to degree and order 36. It was developed using consistent reference parameters and extensive earth and ocean tidal models. It was simultaneously solved for gravitational and tidal terms, earth orientation parameters, and the orbital parameters of 580 individual satellite arcs. The solution used only satellite tracking data acquired on 17 different satellites and is predominantly based upon the precise laser data taken by third generation systems. In all, 800,000 observations were used. A major improvement in field accuracy was obtained. For marine geodetic applications, long wavelength geoidal modeling is twice as good as in earlier satellite-only GEM models. Orbit determination accuracy has also been substantially advanced over a wide range of satellites that have been tested.

A new design using GEM-based technology for the CMS experiment

NASA Astrophysics Data System (ADS)

Ressegotti, M.

2017-07-01

The muon system of the Compact Muon Solenoid (CMS) experiment at the LHC is currently not instrumented for pseudorapidity higher than |η|> 2.4. The main challenges to the installation of a detector in that position are the high particle flux to be sustained, a high level of radiation, and the ability to accomodate a multilevel detector into the small available space (less than 30 cm). A new back-to-back configuration of a Gas Electron Multiplier (GEM) detector is presented with the aim of developing a compact, multi-layer GEM detector. It is composed of two independent stacked triple-GEM detectors, positioned with the anodes toward the outside and sharing the same cathode plane, which is located at the center of the chamber, to reduce the total detector's thickness. A first prototype has been produced and tested with an X-Ray source and muon beam. First results on its performance are presented.

Creation of a genetic calcium channel blocker by targeted gem gene transfer in the heart.

PubMed

Murata, Mitsushige; Cingolani, Eugenio; McDonald, Amy D; Donahue, J Kevin; Marbán, Eduardo

2004-08-20

Calcium channel blockers are among the most commonly used therapeutic drugs. Nevertheless, the utility of calcium channel blockers for heart disease is limited because of the potent vasodilatory effect that causes hypotension, and other side effects attributable to blockade of noncardiac channels. Therefore, focal calcium channel blockade by gene transfer is highly desirable. With a view to creating a focally applicable genetic calcium channel blocker, we overexpressed the ras-related small G-protein Gem in the heart by somatic gene transfer. Adenovirus-mediated delivery of Gem markedly decreased L-type calcium current density in ventricular myocytes, resulting in the abbreviation of action potential duration. Furthermore, transduction of Gem resulted in a significant shortening of the electrocardiographic QTc interval and reduction of left ventricular systolic function. Focal delivery of Gem to the atrioventricular (AV) node significantly slowed AV nodal conduction (prolongation of PR and AH intervals), which was effective in the reduction of heart rate during atrial fibrillation. Thus, these results indicate that gene transfer of Gem functions as a genetic calcium channel blocker, the local application of which can effectively modulate cardiac electrical and contractile function.

A report on emergent uranyl binding phenomena by an amidoxime phosphonic acid co-polymer

DOE PAGES

Abney, C. W.; Das, S.; Mayes, R. T.; ...

2016-08-01

Development of technology to harvest the uranium dissolved in seawater would enable access to vast quantities of this critical metal for nuclear power generation. Amidoxime polymers are the most promising platform for achieving this separation, yet design of advanced adsorbents is hindered by uncertainty regarding the uranium binding mode. In this work we use XAFS to investigate the uranium coordination environment in an amidoxime-phosphonic acid copolymer adsorbent. In contrast to the binding mode predicted computationally and from small molecule studies, a cooperative chelating model is favoured, attributable to emergent behavior resulting from inclusion of amidoxime in a polymer. Samples exposedmore » to seawater also display a feature consistent with a 2-oxo-bridged transition metal, suggesting formation of an in situ specific binding site. As a result, these findings challenge long held assumptions and provide new opportunities for the design of advanced adsorbent materials.« less

Design of T-GEM detectors for X-ray diagnostics on JET

NASA Astrophysics Data System (ADS)

Rzadkiewicz, J.; Dominik, W.; Scholz, M.; Chernyshova, M.; Czarski, T.; Czyrkowski, H.; Dabrowski, R.; Jakubowska, K.; Karpinski, L.; Kasprowicz, G.; Kierzkowski, K.; Pozniak, K.; Salapa, Z.; Zabolotny, W.; Blanchard, P.; Tyrrell, S.; Zastrow, K.-D.; JET EFDA Contributors

2013-08-01

Upgraded high-resolution X-ray diagnostics on JET is expected to monitor the plasma radiation emitted by W46+ and Ni26+ ions at 2.4 keV and 7.8 keV photon energies, respectively. Both X-ray lines will be monitored by new generation energy-resolved micropattern gas detectors with 1-D position reconstruction capability. The detection structure is based on triple GEM (T-GEM) amplification structure followed by the strip readout electrode. This article presents a design of new detectors and prototype detector tests.

Study of complex formation of 5,5'-(2 E, 2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) (HYT) macrocyclic ligand with Cd2+ cation in non-aqueous solution by spectroscopic and conductometric methods

NASA Astrophysics Data System (ADS)

Mallaekeh, Hassan; Shams, Alireza; Shaker, Mohammad; Bahramzadeh, Ehsan; Arefi, Donya

2014-12-01

In this paper the complexation reaction of the 5,5'-(2 E,2' E)-2,2'-(ethane-1,2-diylidene)bis(hydrazine-1-yl-2-ylidene)bis(4-amino-4H-1,2,4-triazole-3-thiol) ligand (HYT) with Cd2+ education was studied in some binary mixtures of methanol (MeOH), n-propanol (PrOH) and dimethyl-formamide (DMF) at different temperatures using the conductometry and spectrophotometry. The stability constants of the complex was determined using a GENPLOT computer program. The conductance data and absorbance-mole ratio plots show that in all solvent systems, the stoichiometry of the complex formed between (HYT) and Cd2+ cation is 1: 1. The obtained results show that the stability of (HYT)-Cd complex is sensitive to the mixed solvents composition. The values of thermodynamic parameters (Δ G ∘, Δ H ∘, and Δ S ∘) for formation of (HYT)-Cd complex were obtained from temperature dependence of the stability constant using the van't Hoff plots. The results show that in most cases, the complex are enthalpy destabilized but entropy stabilized and the complex formation is affected by pH, time, temperature and the nature of the solvent.

The Landscape of Somatic Chromosomal Copy Number Aberrations in GEM Models of Prostate Carcinoma

PubMed Central

Bianchi-Frias, Daniella; Hernandez, Susana A.; Coleman, Roger; Wu, Hong; Nelson, Peter S.

2015-01-01

Human prostate cancer (PCa) is known to harbor recurrent genomic aberrations consisting of chromosomal losses, gains, rearrangements and mutations that involve oncogenes and tumor suppressors. Genetically engineered mouse (GEM) models have been constructed to assess the causal role of these putative oncogenic events and provide molecular insight into disease pathogenesis. While GEM models generally initiate neoplasia by manipulating a single gene, expression profiles of GEM tumors typically comprise hundreds of transcript alterations. It is unclear whether these transcriptional changes represent the pleiotropic effects of single oncogenes, and/or cooperating genomic or epigenomic events. Therefore, it was determined if structural chromosomal alterations occur in GEM models of PCa and whether the changes are concordant with human carcinomas. Whole genome array-based comparative genomic hybridization (CGH) was used to identify somatic chromosomal copy number aberrations (SCNAs) in the widely used TRAMP, Hi-Myc, Pten-null and LADY GEM models. Interestingly, very few SCNAs were identified and the genomic architecture of Hi-Myc, Pten-null and LADY tumors were essentially identical to the germline. TRAMP neuroendocrine carcinomas contained SCNAs, which comprised three recurrent aberrations including a single copy loss of chromosome 19 (encoding Pten). In contrast, cell lines derived from the TRAMP, Hi-Myc, and Pten-null tumors were notable for numerous SCNAs that included copy gains of chromosome 15 (encoding Myc) and losses of chromosome 11 (encoding p53). PMID:25298407

CtGEM typing: Discrimination of Chlamydia trachomatis ocular and urogenital strains and major evolutionary lineages by high resolution melting analysis of two amplified DNA fragments.

PubMed

Giffard, Philip M; Andersson, Patiyan; Wilson, Judith; Buckley, Cameron; Lilliebridge, Rachael; Harris, Tegan M; Kleinecke, Mariana; O'Grady, Kerry-Ann F; Huston, Wilhelmina M; Lambert, Stephen B; Whiley, David M; Holt, Deborah C

2018-01-01

Chlamydia trachomatis infects the urogenital tract (UGT) and eyes. Anatomical tropism is correlated with variation in the major outer membrane protein encoded by ompA. Strains possessing the ocular ompA variants A, B, Ba and C are typically found within the phylogenetically coherent "classical ocular lineage". However, variants B, Ba and C have also been found within three distinct strains in Australia, all associated with ocular disease in children and outside the classical ocular lineage. CtGEM genotyping is a method for detecting and discriminating ocular strains and also the major phylogenetic lineages. The rationale was facilitation of surveillance to inform responses to C. trachomatis detection in UGT specimens from young children. CtGEM typing is based on high resolution melting analysis (HRMA) of two PCR amplified fragments with high combinatorial resolving power, as defined by computerised comparison of 65 whole genomes. One fragment is from the hypothetical gene defined by Jali-1891 in the C. trachomatis B_Jali20 genome, while the other is from ompA. Twenty combinatorial CtGEM types have been shown to exist, and these encompass unique genotypes for all known ocular strains, and also delineate the TI and T2 major phylogenetic lineages, identify LGV strains and provide additional resolution beyond this. CtGEM typing and Sanger sequencing were compared with 42 C. trachomatis positive clinical specimens, and there were no disjunctions. CtGEM typing is a highly efficient method designed and tested using large scale comparative genomics. It divides C. trachomatis into clinically and biologically meaningful groups, and may have broad application in surveillance.

Effect of phosphonate treatments for sudden oak death on tanoaks in naturally infested forests

Treesearch

Matteo Garbelotto; Doug Schmidt

2013-01-01

Application of phosphonate compounds has been shown to be an effective preventive treatment for sudden oak death (SOD), caused by Phytophthora ramorum, in coast live oak (Quercus agrifolia Née) and tanoak (Notholithocarpus densiflorus Manos, Cannon & S.H. Oh). To test the effectiveness of...

Does GEM-Encoding Clinical Practice Guidelines Improve the Quality of Knowledge Bases? A Study with the Rule-Based Formalism

PubMed Central

Georg, Gersende; Séroussi, Brigitte; Bouaud, Jacques

2003-01-01

The aim of this work was to determine whether the GEM-encoding step could improve the representation of clinical practice guidelines as formalized knowledge bases. We used the 1999 Canadian recommendations for the management of hypertension, chosen as the knowledge source in the ASTI project. We first clarified semantic ambiguities of therapeutic sequences recommended in the guideline by proposing an interpretative framework of therapeutic strategies. Then, after a formalization step to standardize the terms used to characterize clinical situations, we created the GEM-encoded instance of the guideline. We developed a module for the automatic derivation of a rule base, BR-GEM, from the instance. BR-GEM was then compared to the rule base, BR-ASTI, embedded within the critic mode of ASTI, and manually built by two physicians from the same Canadian guideline. As compared to BR-ASTI, BR-GEM is more specific and covers more clinical situations. When evaluated on 10 patient cases, the GEM-based approach led to promising results. PMID:14728173

Does GEM-encoding clinical practice guidelines improve the quality of knowledge bases? A study with the rule-based formalism.

PubMed

Georg, Georg; Séroussi, Brigitte; Bouaud, Jacques

2003-01-01

The aim of this work was to determine whether the GEM-encoding step could improve the representation of clinical practice guidelines as formalized knowledge bases. We used the 1999 Canadian recommendations for the management of hypertension, chosen as the knowledge source in the ASTI project. We first clarified semantic ambiguities of therapeutic sequences recommended in the guideline by proposing an interpretative framework of therapeutic strategies. Then, after a formalization step to standardize the terms used to characterize clinical situations, we created the GEM-encoded instance of the guideline. We developed a module for the automatic derivation of a rule base, BR-GEM, from the instance. BR-GEM was then compared to the rule base, BR-ASTI, embedded within the critic mode of ASTI, and manually built by two physicians from the same Canadian guideline. As compared to BR-ASTI, BR-GEM is more specific and covers more clinical situations. When evaluated on 10 patient cases, the GEM-based approach led to promising results.

Cross-couplings in the elaboration of luminescent bis-terpyridyl iridium complexes: the effect of extended or inhibited conjugation on emission.

PubMed

Leslie, Wendy; Batsanov, Andrei S; Howard, Judith A K; Williams, J A Gareth

2004-02-21

The utility of Suzuki cross-coupling methodology for the in situ elaboration of bromo-functionalised bis-terpyridyl iridium(III) complexes has been explored. The complex [Ir(tpy)(tpy-phi-Br)]3+ [tpy-phi-Br = 4'-(4-bromophenyl)-2,2':6',2''-terpyridine] undergoes palladium-catalysed cross-coupling with aryl boronic acids to yield biaryl-substituted complexes directly. The biphenyl and 4-cyanobiphenyl-substituted products display relatively intense, long-lived (tau > 100 mus) yellow emission in degassed aqueous solution at room temperature, assigned to a 3pi-pi* state. A 4-aminobiphenyl-substituted analogue displays an additional low energy absorbance band, attributed to an intraligand charge-transfer (ILCT) excited state, and is scarcely emissive under the same conditions. The iridium(III) complex of 4'-mesityl-terpyridine is also reported. Its emission is much shorter-lived, with a spectral profile resembling that of unsubstituted [Ir(tpy)2]3+, confirming the need for the attainment of a roughly coplanar geometry for stabilisation of the 3pi-pi* excited state.

Targeting SMN to Cajal bodies and nuclear gems during neuritogenesis

PubMed Central

Navascues, Joaquin; Berciano, Maria T.; Tucker, Karen E.

2006-01-01

Neurite outgrowth is a central feature of neuronal differentiation. PC12 cells are a good model system for studying the peripheral nervous system and the outgrowth of neurites. In addition to the dramatic changes observed in the cytoplasm, neuronal differentiation is also accompanied by striking changes in nuclear morphology. The large and sustained increase in nuclear transcription during neuronal differentiation requires synthesis of a large number of factors involved in pre-mRNA processing. We show that the number and composition of the nuclear subdomains called Cajal bodies and gems changes during the course of N-ras-induced neuritogenesis in the PC12-derived cell line UR61. The Cajal bodies found in undifferentiated cells are largely devoid of the survival of motor neurons (SMN) protein product. As cells shift to a differentiated state, SMN is not only globally upregulated, but is progressively recruited to Cajal bodies. Additional SMN foci (also known as Gemini bodies, gems) can also be detected. Using dual-immunogold labeling electron microscopy and mouse embryonic fibroblasts lacking the coilin protein, we show that gems clearly represent a distinct category of nuclear body. PMID:15164213

Control of morphology and function of low band gap polymer–bis-fullerene mixed heterojunctions in organic photovoltaics with selective solvent vapor annealing

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

Chen, Huipeng; Hsiao, Yu-Che; Hu, Bin

2014-05-07

We reported how by replacing PCBM with a bis-adduct fullerene (i.e. ICBA) we significantly improve the open circuit voltage (VOC) and power conversion efficiency (PCE) in P3HT bulk heterojunctions. But, for the most promising low band-gap polymer (LBP) systems, replacing PCBM with ICBA results in very poor shortcircuit current (JSC) and PCE although the VOC is significantly improved. Therefore, in this work, we have completed small angle neutron scattering and neutron reflectometry experiments to study the impact of post-deposition solvent annealing (SA) with control of solvent quality on the morphology and performance of LBP bis-fullerene BHJ photovoltaics. Our results showmore » that SA in a solvent that is selective for the LBP results in a depletion of bis-fullerene near the air surface, which limits device performance. SA in a solvent vapor which has similar solubility for polymer and bis-fullerene results in a higher degree of polymer ordering, bis-fullerene phase separation, and segregation of the bis-fullerene to the air surface, which facilitates charge transport and increases power conversion efficiency (PCE) by 100%. The highest degree of polymer ordering combined with significant bis-fullerene phase separation and segregation of bis-fullerene to the air surface is obtained by SA in a solvent vapor that is selective for the bis-fullerene. The resultant morphology increases PCE by 190%. These results indicate that solvent annealing with judicious solvent choice provides a unique tool to tune the morphology of LBP bisfullerene BHJ system, providing sufficient polymer ordering, formation of a bis-fullerene pure phase, and segregation of bis-fullerene to the air surface to optimize the morphology of the active layer. Furthermore, this process is broadly applicable to improving current disappointing LBP bis-fullerene systems to optimize their morphology and OPV performance post-deposition, including higher VOC and power conversion efficiency.« less

OpenGeoSys-GEMS: Hybrid parallelization of a reactive transport code with MPI and threads

NASA Astrophysics Data System (ADS)

Kosakowski, G.; Kulik, D. A.; Shao, H.

2012-04-01

OpenGeoSys-GEMS is a generic purpose reactive transport code based on the operator splitting approach. The code couples the Finite-Element groundwater flow and multi-species transport modules of the OpenGeoSys (OGS) project (http://www.ufz.de/index.php?en=18345) with the GEM-Selektor research package to model thermodynamic equilibrium of aquatic (geo)chemical systems utilizing the Gibbs Energy Minimization approach (http://gems.web.psi.ch/). The combination of OGS and the GEM-Selektor kernel (GEMS3K) is highly flexible due to the object-oriented modular code structures and the well defined (memory based) data exchange modules. Like other reactive transport codes, the practical applicability of OGS-GEMS is often hampered by the long calculation time and large memory requirements. • For realistic geochemical systems which might include dozens of mineral phases and several (non-ideal) solid solutions the time needed to solve the chemical system with GEMS3K may increase exceptionally. • The codes are coupled in a sequential non-iterative loop. In order to keep the accuracy, the time step size is restricted. In combination with a fine spatial discretization the time step size may become very small which increases calculation times drastically even for small 1D problems. • The current version of OGS is not optimized for memory use and the MPI version of OGS does not distribute data between nodes. Even for moderately small 2D problems the number of MPI processes that fit into memory of up-to-date workstations or HPC hardware is limited. One strategy to overcome the above mentioned restrictions of OGS-GEMS is to parallelize the coupled code. For OGS a parallelized version already exists. It is based on a domain decomposition method implemented with MPI and provides a parallel solver for fluid and mass transport processes. In the coupled code, after solving fluid flow and solute transport, geochemical calculations are done in form of a central loop over all finite

Structure, vibrations and quantum chemical investigations of hydrogen bonded complex of bis(1-hydroxy-2-methylpropan-2-aminium)selenate

NASA Astrophysics Data System (ADS)

Thirunarayanan, S.; Arjunan, V.; Marchewka, M. K.; Mohan, S.

2017-04-01

The hydrogen bonded molecular complex bis(1-hydroxy-2-methylpropan-2-aminium)selenate (C8H24N2O6Se) has been prepared by the reaction of 2-amino-2-methyl propanol and selenic acid. The X-ray diffraction analysis revealed that the intermolecular proton transfer from selenic acid (SeO4H2) to 2-amino-2-methylpropanol results in the formation of bis(1-hydroxy-2-methylpropan-2-aminium)selenate (HMPAS) salt and the fragments are connected through H-bonding and ion pairing. The N-H⋯O and O-H⋯O interactions between 2-amino-2-methylpropanol and selenic acid determine the supramolecular arrangement in three-dimensional space. The salt crystallises in the space group P121/n1 of monoclinic system. The complete vibrational assignments of HMPAS have been performed by FTIR and FT-Raman spectroscopy. The experimental data are correlated with the structural properties namely the energy, thermodynamic parameters, atomic charges, hybridization concepts and vibrational frequencies determined by quantum chemical studies performed with B3LYP method using 6-311++G*, 6-31+G* and 6-31G** basis sets.

The BoNuS GEM-Based Radial Time-Projection Chamber

NASA Astrophysics Data System (ADS)

Fenker, Howard

2006-10-01

A special-purpose detector for measuring low-momentum spectator protons from e-d collisions has been developed. It is a radial time-projection chamber in which the gas-amplification elements are GEM foils formed into cylinders. This is believed to be the first application of curved GEMs. In a 4T magnetic field, this low-mass detector allows tracking of spectator protons with momentum as low as 70 MeV/c while covering a large solid angle. Physics data were taken using the system in late 2005. We report on the development of the detector, experience with operating it, and the data coming out of it.

Public release of the ISC-GEM Global Instrumental Earthquake Catalogue (1900-2009)

USGS Publications Warehouse

Storchak, Dmitry A.; Di Giacomo, Domenico; Bondára, István; Engdahl, E. Robert; Harris, James; Lee, William H.K.; Villaseñor, Antonio; Bormann, Peter

2013-01-01

The International Seismological Centre–Global Earthquake Model (ISC–GEM) Global Instrumental Earthquake Catalogue (1900–2009) is the result of a special effort to substantially extend and improve currently existing global catalogs to serve the requirements of specific user groups who assess and model seismic hazard and risk. The data from the ISC–GEM Catalogue would be used worldwide yet will prove absolutely essential in those regions where a high seismicity level strongly correlates with a high population density.

GEM System: automatic prototyping of cell-wide metabolic pathway models from genomes.

PubMed

Arakawa, Kazuharu; Yamada, Yohei; Shinoda, Kosaku; Nakayama, Yoichi; Tomita, Masaru

2006-03-23

Successful realization of a "systems biology" approach to analyzing cells is a grand challenge for our understanding of life. However, current modeling approaches to cell simulation are labor-intensive, manual affairs, and therefore constitute a major bottleneck in the evolution of computational cell biology. We developed the Genome-based Modeling (GEM) System for the purpose of automatically prototyping simulation models of cell-wide metabolic pathways from genome sequences and other public biological information. Models generated by the GEM System include an entire Escherichia coli metabolism model comprising 968 reactions of 1195 metabolites, achieving 100% coverage when compared with the KEGG database, 92.38% with the EcoCyc database, and 95.06% with iJR904 genome-scale model. The GEM System prototypes qualitative models to reduce the labor-intensive tasks required for systems biology research. Models of over 90 bacterial genomes are available at our web site.

Binarity and Accretion in AGB Stars: HST/STIS Observations of UV Flickering in Y Gem

NASA Astrophysics Data System (ADS)

Sahai, R.; Sánchez Contreras, C.; Mangan, A. S.; Sanz-Forcada, J.; Muthumariappan, C.; Claussen, M. J.

2018-06-01

Binarity is believed to dramatically affect the history and geometry of mass loss in AGB and post-AGB stars, but observational evidence of binarity is sorely lacking. As part of a project to search for hot binary companions to cool AGB stars using the GALEX archive, we discovered a late-M star, Y Gem, to be a source of strong and variable UV and X-ray emission. Here we report UV spectroscopic observations of Y Gem obtained with the Hubble Space Telescope that show strong flickering in the UV continuum on timescales of ≲20 s, characteristic of an active accretion disk. Several UV lines with P-Cygni-type profiles from species such as Si IV and C IV are also observed, with emission and absorption features that are red- and blueshifted by velocities of ∼500 {km} {{{s}}}-1 from the systemic velocity. Our model for these (and previous) observations is that material from the primary star is gravitationally captured by a companion, producing a hot accretion disk. The latter powers a fast outflow that produces blueshifted features due to the absorption of UV continuum emitted by the disk, whereas the redshifted emission features arise in heated infalling material from the primary. The outflow velocities support a previous inference by Sahai et al. that Y Gem’s companion is a low-mass main-sequence star. Blackbody fitting of the UV continuum implies an accretion luminosity of about 13 L ⊙, and thus a mass-accretion rate >5 × 10‑7 M ⊙ yr‑1 we infer that Roche-lobe overflow is the most likely binary accretion mode for Y Gem.

Computational Study of Formic Acid Dehydrogenation Catalyzed by Al(III)-Bis(imino)pyridine.

PubMed

Lu, Qian-Qian; Yu, Hai-Zhu; Fu, Yao

2016-03-18

The mechanism of formic acid dehydrogenation catalyzed by the bis(imino)pyridine-ligated aluminum hydride complex (PDI(2-))Al(THF)H (PDI=bis(imino)pyridine) was studied by density functional theory calculations. The overall transformation is composed of two stages: catalyst activation and the catalytic cycle. The catalyst activation begins with O-H bond cleavage of HCOOH promoted by aluminum-ligand cooperation, followed by HCOOH-assisted Al-H bond cleavage, and protonation of the imine carbon atom of the bis(imino)pyridine ligand. The resultant doubly protonated complex ((H,H) PDI)Al(OOCH)3 is the active catalyst for formic acid dehydrogenation. Given this, the catalytic cycle includes β-hydride elimination of ((H,H) PDI)Al(OOCH)3 to produce CO2, and the formed ((H,H) PDI)Al(OOCH)2 H mediates HCOOH to release H2. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

aGEM: an integrative system for analyzing spatial-temporal gene-expression information

PubMed Central

Jiménez-Lozano, Natalia; Segura, Joan; Macías, José Ramón; Vega, Juanjo; Carazo, José María

2009-01-01

Motivation: The work presented here describes the ‘anatomical Gene-Expression Mapping (aGEM)’ Platform, a development conceived to integrate phenotypic information with the spatial and temporal distributions of genes expressed in the mouse. The aGEM Platform has been built by extending the Distributed Annotation System (DAS) protocol, which was originally designed to share genome annotations over the WWW. DAS is a client-server system in which a single client integrates information from multiple distributed servers. Results: The aGEM Platform provides information to answer three main questions. (i) Which genes are expressed in a given mouse anatomical component? (ii) In which mouse anatomical structures are a given gene or set of genes expressed? And (iii) is there any correlation among these findings? Currently, this Platform includes several well-known mouse resources (EMAGE, GXD and GENSAT), hosting gene-expression data mostly obtained from in situ techniques together with a broad set of image-derived annotations. Availability: The Platform is optimized for Firefox 3.0 and it is accessed through a friendly and intuitive display: http://agem.cnb.csic.es Contact: natalia@cnb.csic.es Supplementary information: Supplementary data are available at http://bioweb.cnb.csic.es/VisualOmics/aGEM/home.html and http://bioweb.cnb.csic.es/VisualOmics/index_VO.html and Bioinformatics online. PMID:19592395

A New Bis(aquated) High Relaxivity Mn(II) Complex as an Alternative to Gd(III)-Based MRI Contrast Agent.

PubMed

Phukan, Bedika; Mukherjee, Chandan; Goswami, Upashi; Sarmah, Amrit; Mukherjee, Subhajit; Sahoo, Suban K; Moi, Sankar Ch

2018-03-05

Disclosed here are a piperazine, a pyridine, and two carboxylate groups containing pentadentate ligand H 2 pmpa and its corresponding water-soluble Mn(II) complex (1). DFT-based structural optimization implied that the complex had pentagonal bipyramidal geometry where the axial positions were occupied by two water molecules, and the equatorial plane was constituted by the ligand ON 3 O donor set. Thus, a bis(aquated) disc-like Mn(II) complex has been synthesized. The complex showed higher stability compared with Mn(II)-EDTA complex [log K MnL = 14.29(3)] and showed a very high r 1 relaxivity value of 5.88 mM -1 s -1 at 1.41 T, 25 °C, and pH = 7.4. The relaxivity value remained almost unaffected by the pH of the medium in the range of 6-10. Although the presence of 200 equiv of fluoride and bicarbonate anions did not affect the relaxivity value appreciably, an increase in the value was noticed in the presence of phosphate anion due to slow tumbling of the complex. Cell viability measurements, as well as phantom MR images using clinical MRI imager, consolidated the possible candidature of complex 1 as a positive contrast agent.

Characterization of a hybrid GEM-Micromegas detector with respect to its application in a continuously read out TPC

NASA Astrophysics Data System (ADS)

Ratza, Viktor; Ball, Markus; Liebtrau, M.; Ketzer, Bernhard

2018-02-01

In the context of the upgrade of the LHC during the second long shutdown the interaction rate of the ALICE experiment will be increased up to 50 kHz for Pb-Pb collisions. As a consequence, a continuous read-out of the Time Projection Chamber (TPC) will be required. To keep the space-charge distortions at a manageable size, the ion backflow of the charge amplification system has to be significantly reduced. At the same time an excellent detector performance and stability of the system has to be maintained. A solution with four Gaseous Electron Multipliers (GEMs) has been adopted as baseline solution for the upgraded chambers. As an alternative approach a hybrid GEM-Micromegas detector consisting of one Micromegas (MM) and two GEMs has been investigated. The recent results of the study of the hybrid GEM-Micromegas detector will be presented and compared to measurements with four GEM foils.

The 2.3 GHz continuum survey of the GEM project

NASA Astrophysics Data System (ADS)

Tello, C.; Villela, T.; Torres, S.; Bersanelli, M.; Smoot, G. F.; Ferreira, I. S.; Cingoz, A.; Lamb, J.; Barbosa, D.; Perez-Becker, D.; Ricciardi, S.; Currivan, J. A.; Platania, P.; Maino, D.

2013-08-01

Context. Determining the spectral and spatial characteristics of the radio continuum of our Galaxy is an experimentally challenging endeavour for improving our understanding of the astrophysics of the interstellar medium. This knowledge has also become of paramount significance for cosmology, since Galactic emission is the main source of astrophysical contamination in measurements of the cosmic microwave background (CMB) radiation on large angular scales. Aims: We present a partial-sky survey of the radio continuum at 2.3GHz within the scope of the Galactic Emission Mapping (GEM) project, an observational program conceived and developed to reveal the large-scale properties of Galactic synchrotron radiation through a set of self-consistent surveys of the radio continuum between 408MHz and 10GHz. Methods: The GEM experiment uses a portable and double-shielded 5.5-m radiotelescope in altazimuthal configuration to map 60-degree-wide declination bands from different observational sites by circularly scanning the sky at zenithal angles of 30° from a constantly rotating platform. The observations were accomplished with a total power receiver, whose front-end high electron mobility transistor (HEMT) amplifier was matched directly to a cylindrical horn at the prime focus of the parabolic reflector. The Moon was used to calibrate the antenna temperature scale and the preparation of the map required direct subtraction and destriping algorithms to remove ground contamination as the most significant source of systematic error. Results: We used 484 h of total intensity observations from two locations in Colombia and Brazil to yield 66% sky coverage from to . The observations in Colombia were obtained with a horizontal HPBW of and a vertical HPBW of . The pointing accuracy was and the RMS sensitivity was 11.42 mK. The observations in Brazil were obtained with a horizontal HPBW of and a vertical HPBW of . The pointing accuracy was and the RMS sensitivity was 8.24 mK. The zero

Large Fluorescence Response by Alcohol from a Bis(benzoxazole)-Zinc(II) Complex: The Role of Excited State Intramolecular Proton Transfer

PubMed Central

Wang, Junfeng; Chu, Qinghui; Liu, Xiumin; Wesdemiotis, Chrys

2013-01-01

The formation of a bis(HBO) anion is known to turn-on the fluorescence to give red emission, via controlling the excited-state intramolecular proton transfer (ESIPT). The poor stability of the formed anion, however, hampered its application. The anion stability is found to be greatly improved by attaching the anion to Zn2+ cation (i.e. forming zinc complex), whose emission is at λem ≈ 550 and 760 nm. Interestingly, addition of methanol to the zinc complex induces a remarkable red fluorescence (λem ≈ 630 nm, ϕfl ≈ 0.8). With the aid of spectroscopic studies (1H NMR, UV-vis, fluorescence, and mass spectra), the structures of the zinc complexes are characterized. The emission species is identified as a dimer-like structure. The study thus reveals an effective fluorescence switching mechanism that could further advance the application of ESIPT-based sensors. PMID:23514312

Understanding the mechanism of action of triazine-phosphonate derivatives as flame retardants for cotton fabrics

USDA-ARS?s Scientific Manuscript database

Countless hours of research and studies on triazine, phosphonate and their combination have provided insightful information into their flame retardant properties on polymeric systems. However, only limited number of studies shed light on the mechanism of flame retardant cotton fabrics. The purpose...

Plant RuBisCo assembly in E. coli with five chloroplast chaperones including BSD2.

PubMed

Aigner, H; Wilson, R H; Bracher, A; Calisse, L; Bhat, J Y; Hartl, F U; Hayer-Hartl, M

2017-12-08

Plant RuBisCo, a complex of eight large and eight small subunits, catalyzes the fixation of CO 2 in photosynthesis. The low catalytic efficiency of RuBisCo provides strong motivation to reengineer the enzyme with the goal of increasing crop yields. However, genetic manipulation has been hampered by the failure to express plant RuBisCo in a bacterial host. We achieved the functional expression of Arabidopsis thaliana RuBisCo in Escherichia coli by coexpressing multiple chloroplast chaperones. These include the chaperonins Cpn60/Cpn20, RuBisCo accumulation factors 1 and 2, RbcX, and bundle-sheath defective-2 (BSD2). Our structural and functional analysis revealed the role of BSD2 in stabilizing an end-state assembly intermediate of eight RuBisCo large subunits until the small subunits become available. The ability to produce plant RuBisCo recombinantly will facilitate efforts to improve the enzyme through mutagenesis. Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Metallosulfoxides and -sulfones: Sulfur oxygenates of [1,5-Bis(2-mercaptoethyl)-1,5-diazacyclooctanato]palladium (II)

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

Tuntulani, T.; Musie, G.; Reibenspies, J.H.

1995-12-06

Successive sulfur-site oxygenation of the dithiolate complex [1,5-bis(mercaptoethyl)-1,5 diazacyclooctanato]-palladium(II), Pd-1, using H{sub 2}O{sub 2} as an O atom source produced all but one member of the series of palladium(II) complexes containing sulfinate (metallosulfone) and sulfinate (metallosulfoxide) S-donor ligands: the monosulfoxide, PdS(=O)R or Pd-4; bis(sulfoxide), Pd(S(=O)R){sub 2} or Pd-5; sulfone/sulfoxide, Pd((SO{sub 2}R)S(=))R or Pd-6; and the bis(sulfone) Pd(SO{sub 2}R){sub 2} or Pd-3 complex. A unique site selectivity for the addition of a second O atom from H{sub 2}O{sub 2} to thiolate sulfur of Pd-4 producing the bis(sulfoxide), Pd-5, exclusively, precluded the preparation of the monosulfone complex, Pd(SO{sub 2}R)SR or Pd-2, viamore » that route. However, the dithiolate Pd-1 reacts with O{sub 2} photochemically in aprotic solvents, giving access to this last member of the series, Pd-2. Further reaction of Pd-2 with O{sub 2} under UV photolysis gives the bis(sulfone) complex, Pd-3. The oxygenates were characterized by various spectroscopies, electrochemistry, and X-ray crystallography. Mass spectrometry delineated a single O atom loss pathway for the sulfoxide species, while SO{sub 2} and O{sub 2} loss is found in sulfone cases. Electrochemical studies show that the addition of an O atom to a thiolate sulfur to create a sulfoxide S-donor results in a stabilization of the Pd{sup I} oxidation state in the range 50-70 mV, while the addition of an O atom to a sulfoxide sulfur to create a sulfone S-donor results in greater stabilization of the Pd{sup I} oxidation state in the range 190-220 mV.« less

Site-selective chemical modification of chymotrypsin using peptidyl derivatives bearing optically active diphenyl 1-amino-2-phenylethylphosphonate: Stereochemical effect of the diphenyl phosphonate moiety.

PubMed

Ono, Shin; Nakai, Takahiko; Kuroda, Hirofumi; Miyatake, Ryuta; Horino, Yoshikazu; Abe, Hitoshi; Umezaki, Masahito; Oyama, Hiroshi

2016-11-04

Diphenyl (α-aminoalkyl)phosphonates act as mechanism-based inhibitors against serine proteases by forming a covalent bond with the hydroxy group of the active center Ser residue. Because the covalent bond was found to be broken and replaced by 2-pyridinaldoxime methiodide (2PAM), we employed a peptidyl derivative bearing diphenyl 1-amino-2-phenylethylphosphonate moiety (Phe(p) (OPh)2 ) to target the active site of chymotrypsin and to selectively anchor to Lys175 in the vicinity of the active site. Previously, it was reported that the configuration of the α-carbon of phosphorus in diphenyl (α-aminoalkyl)phosphonates affects the inactivation reaction of serine proteases, i.e., the (R)-enantiomeric diphenyl phosphonate is comparable to l-amino acids and it effectively reacts with serine proteases, whereas the (S)-enantiomeric form does not. In this study, we evaluated the stereochemical effect of the phosphonate moiety on the selective chemical modification. Epimeric dipeptidyl derivatives, Ala-(R or S)-Phe(p) (OPh)2 , were prepared by separation with RP-HPLC. A tripeptidyl (R)-epimer (Ala-Ala-(R)-Phe(p) (OPh)2 ) exhibited a more potent inactivation ability against chymotrypsin than the (S)-epimer. The enzyme inactivated by the (R)-epimer was more effectively reactivated with 2PAM than the enzyme inactivated by the (S)-epimer. Finally, N-succinimidyl (NHS) active ester derivatives, NHS-Suc-Ala-Ala- (R or S)-Phe(p) (OPh)2 , were prepared, and we evaluated their action when modifying Lys175 in chymotrypsin. We demonstrated that the epimeric NHS derivative that possessed the diphenyl phosphonate moiety with the (R)-configuration effectively modified Lys175 in chymotrypsin, whereas that with the (S)-configuration did not. These results demonstrate the utility of peptidyl derivatives that bear an optically active diphenyl phosphonate moiety as affinity labeling probes in protein bioconjugation. © 2015 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 106: 521-530, 2016. �

Phospholipid imprinted polymers as selective endotoxin scavengers

NASA Astrophysics Data System (ADS)

Sulc, Robert; Szekely, Gyorgy; Shinde, Sudhirkumar; Wierzbicka, Celina; Vilela, Filipe; Bauer, David; Sellergren, Börje

2017-03-01

Herein we explore phospholipid imprinting as a means to design receptors for complex glycolipids comprising the toxic lipopolysaccharide endotoxin. A series of polymerizable bis-imidazolium and urea hosts were evaluated as cationic and neutral hosts for phosphates and phosphonates, the latter used as mimics of the phospholipid head groups. The bis-imidazolium hosts interacted with the guests in a cooperative manner leading to the presence of tight and well defined 1:2 ternary complexes. Optimized monomer combinations were subsequently used for imprinting of phosphatidic acid as an endotoxin dummy template. Presence of the aforementioned ternary complexes during polymerization resulted in imprinting of lipid dimers - the latter believed to crudely mimic the endotoxin Lipid A motif. The polymers were characterized with respect to template rebinding, binding affinity, capacity and common structural properties, leading to the identification of polymers which were thereafter subjected to an industrially validated endotoxin removal test. Two of the polymers were capable of removing endotoxin down to levels well below the accepted threshold (0.005 EU/mg API) in pharmaceutical production.

Development of a scintillating G-GEM detector for a 6-MeV X-band Linac for medical applications

NASA Astrophysics Data System (ADS)

Fujiwara, T.; Tanaka, S.; Mitsuya, Y.; Takahashi, H.; Tagi, K.; Kusano, J.; Tanabe, E.; Yamamoto, M.; Nakamura, N.; Dobashi, K.; Tomita, H.; Uesaka, M.

2013-12-01

We recently developed glass gas electron multipliers (G-GEMs) with an entirely new process using photo-etchable glass. The photo-etchable glass used for the substrate is called PEG3 (Hoya Corporation). Taking advantage of low outgassing material, we have envisioned a medical application of G-GEMs. A two-dimensional position-sensitive dosimetry system based on a scintillating gas detector is being developed for real-time dose distribution monitoring in X-ray radiation therapy. The dosimetry system consists of a chamber filled with an Ar/CF4 scintillating gas mixture, inside of which G-GEM structures are mounted. Photons produced by the excited Ar/CF4 gas molecules during the gas multiplication in the GEM holes are detected by a mirror-lens-CCD-camera system. We found that the intensity distribution of the measured light spot is proportional to the 2D dose distribution. In this work, we report on the first results from a scintillating G-GEM detector for a position-sensitive X-ray beam dosimeter.

Synthesis, structurale elucidation and antioxidant study of Ortho-substituted N,N’-bis(benzamidothiocarbonyl)hydrazine derivatives

NASA Astrophysics Data System (ADS)

Firdausiah, Syadza; Hasbullah, S. A.; Yamin, B. M.

2018-03-01

Some bis(thiourea) compounds have been reported to posses excellent performance in pharmaceutical and environmental fields because of their ability to form chelating complexes with various anions and metal ions. Structurally for carbonyl thiourea derivatives, to become a chelating agent, it must adopt cis-configuration. In the present study, four new bis(thiourea) derivatives namely N,N’-bis(o-fluorobenzamidothiocarbonyl)hydrazine (1), N,N’- bis(o-chloro-benzamidothiocarbonyl)hydrazine (2), N,N’-bis(o-nitrobenzamidothiocarbonyl)-hydrazine (3), and N,N’-bis(o-methylbenzamidothiocarbonyl)hydrazine (4) were successfully synthesized and characterized by CHNS microelemental analysis, FTIR, UV-Vis, and 1H and 13C NMR spectroscopy. However chemical crystallography study showed that both thiourea moieties in compound (2) and (3) adopt trans geometry. Therefore they are potential monodentate ligand with two active moieties. DPPH radical scavenging experiment showed that compound (1), (2), and (4) exhibited higher antioxidant activity than ascorbic acid (Vitamin C).

GEMS X-ray Polarimeter Performance Simulations

NASA Technical Reports Server (NTRS)

Baumgartner, Wayne H.; Strohmayer, Tod; Kallman, Tim; Black, J. Kevin; Hill, Joanne; Swank, Jean

2012-01-01

The Gravity and Extreme Magnetism Small explorer (GEMS) is an X-ray polarization telescope selected as a NASA small explorer satellite mission. The X-ray Polarimeter on GEMS uses a Time Projection Chamber gas proportional counter to measure the polarization of astrophysical X-rays in the 2-10 keV band by sensing the direction of the track of the primary photoelectron excited by the incident X-ray. We have simulated the expected sensitivity of the polarimeter to polarized X-rays. We use the simulation package Penelope to model the physics of the interaction of the initial photoelectron with the detector gas and to determine the distribution of charge deposited in the detector volume. We then model the charge diffusion in the detector,and produce simulated track images. Within the track reconstruction algorithm we apply cuts on the track shape and focus on the initial photoelectron direction in order to maximize the overall sensitivity of the instrument, using this technique we have predicted instrument modulation factors nu(sub 100) for 100% polarized X-rays ranging from 10% to over 60% across the 2-10 keV X-ray band. We also discuss the simulation program used to develop and model some of the algorithms used for triggering, and energy measurement of events in the polarimeter.

Construction, Structural Diversity and Properties of Five Coordination Polymers Based on 5-Nitroisophthalate and Bis(imidazole) Linkers

NASA Astrophysics Data System (ADS)

Arıcı, Mürsel

2018-06-01

Five coordination polymers, namely, [Cd(μ3-5-nip)(μ-obix)]n (1), [Co(μ3-5-nip)(μ-obix)]n (2), [Zn(μ-5-nip)(μ-obix)]n (3 and 4) and [Cd(μ-5-nip)(μ-bisobix)]n (5) (5-nip: 5-nitroisophthalate, obix: 1,2-bis(imidazol-1ylmethyl)benzene, bisobix: 1,2-bis(2-isopropylimidazol-1ylmethyl)benzene) were hydrothermally synthesized and characterized by IR spectroscopy, elemental analysis, single crystal and powder X-ray diffraction and thermal analysis (TG/DTA). X-ray results showed that the complexes displayed structural diversity depending on metal ions and conformations of bis(imidazole) linkers. Complexes 1 and 2 were 1D structures and obix ligand displayed cis-conformation. Complexes 3 and 4 exhibited 2D and 3D structures with same components depending on obix conformation. In complex 5, 3D+3D→3D interpenetrated structure was obtained with dia topology when bisobix having sterically hindered groups on imidazole rings was used. Moreover, thermal, photoluminescence and optical properties of the complexes were also investigated.

Gas Electron Multipler (GEM) detectors for parity-violating electron scattering experiments at Jefferson Lab

NASA Astrophysics Data System (ADS)

Matter, John; Gnanvo, Kondo; Liyanage, Nilanga; Solid Collaboration; Moller Collaboration

2017-09-01

The JLab Parity Violation In Deep Inelastic Scattering (PVDIS) experiment will use the upgraded 12 GeV beam and proposed Solenoidal Large Intensity Device (SoLID) to measure the parity-violating electroweak asymmetry in DIS of polarized electrons with high precision in order to search for physics beyond the Standard Model. Unlike many prior Parity-Violating Electron Scattering (PVES) experiments, PVDIS is a single-particle tracking experiment. Furthermore the experiment's high luminosity combined with the SoLID spectrometer's open configuration creates high-background conditions. As such, the PVDIS experiment has the most demanding tracking detector needs of any PVES experiment to date, requiring precision detectors capable of operating at high-rate conditions in PVDIS's full production luminosity. Developments in large-area GEM detector R&D and SoLID simulations have demonstrated that GEMs provide a cost-effective solution for PVDIS's tracking needs. The integrating-detector-based JLab Measurement Of Lepton Lepton Electroweak Reaction (MOLLER) experiment requires high-precision tracking for acceptance calibration. Large-area GEMs will be used as tracking detectors for MOLLER as well. The conceptual designs of GEM detectors for the PVDIS and MOLLER experiments will be presented.

Data Quality Monitoring System for New GEM Muon Detectors for the CMS Experiment Upgrade

NASA Astrophysics Data System (ADS)

King, Robert; CMS Muon Group Team

2017-01-01

The Gas Electron Multiplier (GEM) detectors are novel detectors designed to improve the muon trigger and tracking performance in CMS experiment for the high luminosity upgrade of the LHC. Partial installation of GEM detectors is planned during the 2016-2017 technical stop. Before the GEM system is installed underground, its data acquisition (DAQ) electronics must be thoroughly tested. The DAQ system includes several commercial and custom-built electronic boards running custom firmware. The front-end electronics are radiation-hard and communicate via optical fibers. The data quality monitoring (DQM) software framework has been designed to provide online verification of the integrity of the data produced by the detector electronics, and to promptly identify potential hardware or firmware malfunctions in the system. Local hits reconstruction and clustering algorithms allow quality control of the data produced by each GEM chamber. Once the new detectors are installed, the DQM will monitor the stability and performance of the system during normal data-taking operations. We discuss the design of the DQM system, the software being developed to read out and process the detector data, and the methods used to identify and report hardware and firmware malfunctions of the system.

Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

NASA Astrophysics Data System (ADS)

Chang, Hao

A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1

Revisiting RuBisCO.

PubMed

Yokota, Akiho

2017-11-01

Since the discovery of its role in the CO 2 fixation reaction in photosynthesis, RuBisCO has been one of the most extensively researched enzymes in the fields of biochemistry, molecular biology, and molecular genetics as well as conventional plant physiology, agricultural chemistry, and crop science. In addition, the RuBisCO and RuBisCO-like genes of more than 2000 organisms have been sequenced during the past 20 years. During the course of those studies, the origin of the RuBisCO gene began to be discussed. Recent studies have reported that the RuBisCO gene emerged in methanogenic bacteria long before photosynthetic organisms appeared. The origin of similar early genes might have allowed this gene to overcome changes in global environments during ancient and recent eras and to participate in the fixation of 200 GT of CO 2 annually. In this review, I focus on several points that have not been discussed at length in the literature thus far.

Secondary scintillation yield from GEM and THGEM gaseous electron multipliers for direct dark matter search

NASA Astrophysics Data System (ADS)

Monteiro, C. M. B.; Fernandes, L. M. P.; Veloso, J. F. C. A.; Oliveira, C. A. B.; dos Santos, J. M. F.

2012-07-01

The search for alternatives to PMTs as photosensors in optical TPCs for rare event detection has significantly increased in the last few years. In particular, in view of the next generation large volume detectors, the use of photosensors with lower natural radioactivity, such as large area APDs or GM-APDs, with the additional possibility of sparse surface coverage, triggered the intense study of secondary scintillation production in micropattern electron multipliers, such as GEMs and THGEMs, as alternatives to the commonly used uniform electric field region between two parallel meshes. The much higher scintillation output obtained from the electron avalanches in such microstructures presents an advantage in those situations. The accurate knowledge of the amount of such scintillation is important for correct detector simulation and optimization. It will also serve as a benchmark for software tools developed and/or under development for the calculation of the amount of such scintillation.The secondary scintillation yield, or electroluminescence yield, in the electron avalanches of GEMs and THGEMs operating in gaseous xenon and argon has been determined for different gas pressures. At 1 bar, THGEMs deliver electroluminescence yields that are more than one order of magnitude higher when compared to those achieved in GEMs and two orders of magnitude when compared to those achieved in a uniform field gap. The THGEM electroluminescence yield presents a faster decrease with pressure when comparing to the GEM electroluminescence yield, reaching similar values to what is achieved in GEMs for xenon pressures of 2.5 bar, but still one order of magnitude higher than that produced in a uniform field gap. Another exception is the GEM operating in argon, which presents an electroluminescence yield similar to that produced in a uniform electric field gap, while the THGEM achieves yields that are more than one order of magnitude higher.

GEM detectors for WEST and potential application for heavy impurity transport studies

NASA Astrophysics Data System (ADS)

Mazon, D.; Jardin, A.; Coston, C.; Faisse, F.; Chernyshova, M.; Czarski, T.; Kasprowicz, G.; Wojenski, A.

2016-08-01

In tokamaks equipped with metallic walls and in particular tungsten, the interplay between particle transport and MagnetoHydroDynamic (MHD) activity might lead to impurities accumulation and finally to sudden plasma termination called disruption. Studying such transport phenomena is thus essential if stationary discharges are to be achieved. On WEST a new SXR diagnostic is developed in collaboration with IPPLM (Poland) and the Warsaw University of Technology, based on a triple Gas Electron Multiplier (GEM) detector. Potential application of the WEST GEM detectors for tomographic reconstruction and subsequent transport analysis is presented.

Study of the spatial resolution of low-material GEM tracking detectors

NASA Astrophysics Data System (ADS)

Kudryavtsev, V. N.; Maltsev, T. V.; Shekhtman, L. I.

2018-02-01

The spatial resolution of GEM based tracking detectors has been simulated and measured. The simulation includes the GEANT4 based transport of high energy electrons with careful accounting for atomic relaxation processes including emission of fluorescent photons and Auger electrons and custom post-processing, including accounting for diffusion, gas amplification fluctuations, the distribution of signals on readout electrodes, electronics noise and a particular algorithm of the final coordinate calculation (center of gravity). The simulation demonstrates that a minimum of the spatial resolution of about 10 μm can be achieved with strip pitches from 250 μm to 300 μm. For larger pitches the resolution is quickly degrading reaching 80-100 μm at a pitch of 500 μm. The spatial resolution of low-material triple-GEM detectors for the DEUTRON facility at the VEPP-3 storage ring is measured at the extracted beam facility of the VEPP-4M collider. The amount of material in these detectors is reduced by etching the copper of the GEMs electrodes and using a readout structure on a thin kapton foil rather than on a glass fibre plate. The exact amount of material in one DEUTRON detector is measured by studying multiple scattering of 100 MeV electrons in it. The result of these measurements is X/X0 = 2.4×10-3 corresponding to a thickness of the copper layers of the GEM foils of 3 μm. The spatial resolution of one DEUTRON detector is measured with 500 MeV electrons and the measured value is equal to 35 ± 1 μm for orthogonal tracks.

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

PubMed

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

2008-08-18

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

A geopotential model from satellite tracking, altimeter, and surface gravity data: GEM-T3

NASA Technical Reports Server (NTRS)

Lerch, F. J.; Nerem, R. S.; Putney, B. H.; Felsentreger, T. L.; Sanchez, B. V.; Marshall, J. A.; Klosko, S. M.; Patel, G. B.; Williamson, R. G.; Chinn, D. S.

1994-01-01

An improved model of Earth's gravitational field, Goddard Earth Model T-3 (GEM-T3), has been developed from a combination of satellite tracking, satellite altimeter, and surface gravimetric data. GEM-T3 provides a significant improvement in the modeling of the gravity field at half wavelengths of 400 km and longer. This model, complete to degree and order 50, yields more accurate satellite orbits and an improved geoid representation than previous Goddard Earth Models. GEM-T3 uses altimeter data from GEOS 3 (1975-1976), Seasat (1978) and Geosat (1986-1987). Tracking information used in the solution includes more than 1300 arcs of data encompassing 31 different satellites. The recovery of the long-wavelength components of the solution relies mostly on highly precise satellite laser ranging (SLR) data, but also includes Tracking Network (TRANET) Doppler, optical, and satellite-to-satellite tracking acquired between the ATS 6 and GEOS 3 satellites. The main advances over GEM-T2 (beyond the inclusion of altimeter and surface gravity information which is essential for the resolution of the shorter wavelength geoid) are some improved tracking data analysis approaches and additional SLR data. Although the use of altimeter data has greatly enhanced the modeling of the ocean geoid between 65 deg N and 60 deg S latitudes in GEM-T3, the lack of accurate detailed surface gravimetry leaves poor geoid resolution over many continental regions of great tectonic interest (e.g., Himalayas, Andes). Estimates of polar motion, tracking station coordinates, and long-wavelength ocean tidal terms were also made (accounting for 6330 parameters). GEM-T3 has undergone error calibration using a technique based on subset solutions to produce reliable error estimates. The calibration is based on the condition that the expected mean square deviation of a subset gravity solution from the full set values is predicted by the solutions' error covariances. Data weights are iteratively adjusted until

A Muon Tomography Station with GEM Detectors for Nuclear Threat Detection

NASA Astrophysics Data System (ADS)

Staib, Michael; Gnanvo, Kondo; Grasso, Leonard; Hohlmann, Marcus; Locke, Judson; Costa, Filippo; Martoiu, Sorin; Muller, Hans

2011-10-01

Muon tomography for homeland security aims at detecting well-shielded nuclear contraband in cargo and imaging it in 3D. The technique exploits multiple scattering of atmospheric cosmic ray muons, which is stronger in dense, high-Z nuclear materials, e.g. enriched uranium, than in low-Z and medium-Z shielding materials. We have constructed and operated a compact Muon Tomography Station (MTS) that tracks muons with six to ten 30 cm x 30 cm Triple Gas Electron Multiplier (GEM) detectors placed on the sides of a 27-liter cubic imaging volume. The 2D strip readouts of the GEMs achieve a spatial resolution of ˜130 μm in both dimensions and the station is operated at a muon trigger rate of ˜20 Hz. The 1,536 strips per GEM detector are read out with the first medium-size implementation of the Scalable Readout System (SRS) developed specifically for Micro-Pattern Gas Detectors by the RD51 collaboration at CERN. We discuss the performance of this MTS prototype and present experimental results on tomographic imaging of high-Z objects with and without shielding.

Thermal decomposition reactions of cotton fabric treated with piperazine-phosphonates derivatives as a flame retardant

USDA-ARS?s Scientific Manuscript database

There has been a great scientific interest in exploring the great potential of the piperazine-phosphonates in flame retardant (FR) application on cotton fabric by investigating the thermal decomposition of cotton fabric treated with them. This research tries to understand the mode of action of the t...

Effect of bis(bilato)-1,2-cyclohexanediammineplatinum(II) complexes on lung metastasis of B16-F10 melanoma cells in mice.

PubMed

Maeda, M; Suga, T; Takasuka, N; Hoshi, A; Sasaki, T

1990-12-03

New platinum(II) complexes, bis(bilato)-1,2-cyclohexanediammineplatinum(II) which were lipophilic and water-miscible, were tested for antitumor activity against lung nodules from intravenously injected B16-F10 melanoma cells in C57BL/6 mice by intravenous administration of the complexes in water suspension form. Among them, DACHP(litho)2 and DACHP(urso)2 had high antitumor activity but others had no activity. The antitumor activity of DACHP(urso)2 was increased significantly by injecting it three times; T/C was over 280% with 100-day survivors of 3 of 6 mice tested. Large amounts of total platinum were found in lung and liver tissues by atomic absorption spectroscopy after single intravenous injection of DACHP(urso)2 suspension in ICR mice.

Large size GEM for Super Bigbite Spectrometer (SBS) polarimeter for Hall A 12GeV program at JLab

DOE PAGES

Gnanvo, Kondo; Liyanage, Nilanga; Nelyubin, Vladimir; ...

2015-05-01

We report on the R&D effort in the design and construction of a large size GEM chamber for the Proton Polarimeter of the Super Bigbite Spectrometer (SBS) in Hall A at Thomas Jefferson National Laboratory (JLab). The SBS Polarimeter trackers consist of two sets of four large chambers of size 200 cm x 60 cm 2. Each chamber is a vertical stack of four GEM modules with an active area of 60 cm x 50 cm. We have built and tested several GEM modules and we describe in this paper the design and construction of the final GEM as wellmore » as the preliminary results on performances from tests carried out in our detector lab and with test beams at (Fermilab).« less

Fast modular data acquisition system for GEM-2D detector

NASA Astrophysics Data System (ADS)

Kasprowicz, G.; Byszuk, Adrian; Wojeński, A.; Zienkiewicz, P.; Czarski, T.; Chernyshova, M.; Poźniak, K.; Rzadkiewicz, J.; Zabolotny, W.; Juszczyk, B.

2014-11-01

A novel approach to two dimensional Gas Electron Multiplier (GEM) detector readout is presented. Unlike commonly used methods, based on discriminators and analogue FIFOs, the method developed uses simulta- neously sampling high speed ADCs with fast hybrid integrator and advanced FPGA-based processing logic to estimate the energy of every single photon. Such a method is applied to every GEM strip / pixel signal. It is especially useful in case of crystal-based spectrometers for soft X-rays, 2D imaging for plasma tomography and all these applications where energy resolution of every single photon is required. For the purpose of the detector readout, a novel, highly modular and extendable conception of the measurement platform was developed. It is evolution of already deployed measurement system for JET Spectrometer.

AlgaGEM – a genome-scale metabolic reconstruction of algae based on the Chlamydomonas reinhardtii genome

PubMed Central

2011-01-01

Background Microalgae have the potential to deliver biofuels without the associated competition for land resources. In order to realise the rates and titres necessary for commercial production, however, system-level metabolic engineering will be required. Genome scale metabolic reconstructions have revolutionized microbial metabolic engineering and are used routinely for in silico analysis and design. While genome scale metabolic reconstructions have been developed for many prokaryotes and model eukaryotes, the application to less well characterized eukaryotes such as algae is challenging not at least due to a lack of compartmentalization data. Results We have developed a genome-scale metabolic network model (named AlgaGEM) covering the metabolism for a compartmentalized algae cell based on the Chlamydomonas reinhardtii genome. AlgaGEM is a comprehensive literature-based genome scale metabolic reconstruction that accounts for the functions of 866 unique ORFs, 1862 metabolites, 2249 gene-enzyme-reaction-association entries, and 1725 unique reactions. The reconstruction was compartmentalized into the cytoplasm, mitochondrion, plastid and microbody using available data for algae complemented with compartmentalisation data for Arabidopsis thaliana. AlgaGEM describes a functional primary metabolism of Chlamydomonas and significantly predicts distinct algal behaviours such as the catabolism or secretion rather than recycling of phosphoglycolate in photorespiration. AlgaGEM was validated through the simulation of growth and algae metabolic functions inferred from literature. Using efficient resource utilisation as the optimality criterion, AlgaGEM predicted observed metabolic effects under autotrophic, heterotrophic and mixotrophic conditions. AlgaGEM predicts increased hydrogen production when cyclic electron flow is disrupted as seen in a high producing mutant derived from mutational studies. The model also predicted the physiological pathway for H2 production and

Synthesis of α,α-Difluorinated Phosphonate pSer/pThr Mimetics via Rhodium-Catalyzed Asymmetric Hydrogenation of β-Difluorophosphonomethyl α-(Acylamino)acrylates.

PubMed

Chen, Hong-Xue; Kang, Jie; Chang, Rong; Zhang, Yun-Lai; Duan, Hua-Zhen; Li, Yan-Mei; Chen, Yong-Xiang

2018-06-01

A novel and facile synthetic strategy for α,α-difluorinated phosphonate mimetics of phosphoserine/phosphothreonine utilizing rhodium-catalyzed asymmetric hydrogenation was developed. The dehydrogenated substrate β-difluorophosphonomethyl α-(acylamino)acrylates were first prepared from protected serine/threonine followed by asymmetric hydrogenation using the rhodium-DuPhos catalytic system to generate the chiral center(s). These important phosphonate building blocks were successfully incorporated into phosphatase-resistant peptides, which displayed similar inhibition to the 14-3-3 ζ protein as the parent pSer/pThr peptides.

Single-electron transfer in palladium complexes of 1,4-naphthoquinone-containing bis(pyrazol-1-yl)methane ligands.

PubMed

Scheuermann, Sebastian; Sarkar, Biprajit; Bolte, Michael; Bats, Jan W; Lerner, Hans-Wolfram; Wagner, Matthias

2009-10-05

A 1,4-naphthoquinone-substituted bis(pyrazol-1-yl)methane ligand (N--N) has been synthesized and transformed into its corresponding Pd(II) chelate complex [(N--N)PdCl(2)]. Both N--N and [(N--N)PdCl(2)] have been fully characterized by NMR spectroscopy, spectro-electrochemistry, and X-ray crystallography. After treatment of [(N--N)PdCl(2)] with NEt(3), the signature of a 1,4-naphthosemiquinonate radical is visible in the UV-vis- and electron paramagnetic resonance (EPR) spectrum of the reaction mixture; the free ligand N--N does not react with NEt(3) under the conditions applied. It is therefore concluded that NEt(3) first reduces the Pd(II)-ion of [(N--N)PdCl(2)] to the zero-valent state and that this reaction is followed by a single-electron transfer from the metal atom to the 1,4-naphthoquinone moiety. The complex has been specifically designed to disfavor any direct Pd-to-naphthoquinone coordination. Electron transfer thus proceeds through space or, less likely, via sigma-bonds of the ligand framework.

Idealized climate change simulations with a high-resolution physical model: HadGEM3-GC2

NASA Astrophysics Data System (ADS)

Senior, Catherine A.; Andrews, Timothy; Burton, Chantelle; Chadwick, Robin; Copsey, Dan; Graham, Tim; Hyder, Pat; Jackson, Laura; McDonald, Ruth; Ridley, Jeff; Ringer, Mark; Tsushima, Yoko

2016-06-01

Idealized climate change simulations with a new physical climate model, HadGEM3-GC2 from The Met Office Hadley Centre are presented and contrasted with the earlier MOHC model, HadGEM2-ES. The role of atmospheric resolution is also investigated. The Transient Climate Response (TCR) is 1.9 K/2.1 K at N216/N96 and Effective Climate Sensitivity (ECS) is 3.1 K/3.2 K at N216/N96. These are substantially lower than HadGEM2-ES (TCR: 2.5 K; ECS: 4.6 K) arising from a combination of changes in the size of climate feedbacks. While the change in the net cloud feedback between HadGEM3 and HadGEM2 is relatively small, there is a change in sign of its longwave and a strengthening of its shortwave components. At a global scale, there is little impact of the increase in atmospheric resolution on the future climate change signal and even at a broad regional scale, many features are robust including tropical rainfall changes, however, there are some significant exceptions. For the North Atlantic and western Europe, the tripolar pattern of winter storm changes found in most CMIP5 models is little impacted by resolution but for the most intense storms, there is a larger percentage increase in number at higher resolution than at lower resolution. Arctic sea-ice sensitivity shows a larger dependence on resolution than on atmospheric physics.

Measurement of basic characteristics and gain uniformity of a triple GEM detector

NASA Astrophysics Data System (ADS)

Patra, Rajendra Nath; Singaraju, Rama N.; Biswas, Saikat; Ahammed, Zubayer; Nayak, Tapan K.; Viyogi, Yogendra P.

2017-08-01

Large area Gas Electron Multiplier (GEM) detectors have been the preferred choice for tracking devices in major nuclear and particle physics experiments. Uniformity over surface of the detector in terms of gain, energy resolution and efficiency is crucial for the optimum performance of these detectors. In the present work, detailed performance study of a 10×10 cm2 triple GEM detector operated using Ar and CO2 gas mixtures in proportions of 70:30 and 90:10, has been made by making a voltage scan of the efficiency with 106Ru-Rh β-source and cosmic rays. The gain and energy resolution of the detector were studied using the X-ray spectrum of 55Fe source. The uniformity of the detector has been investigated by dividing the detector in 7×7 zones and measuring the gain and energy resolution at the centre of each zone. The variations of the gain and energy resolution have been found to be 8.8% and 6.7%, respectively. These studies are essential to characterise GEM detectors before their final use in the experiments.

A GEM readout with radial zigzag strips and linear charge-sharing response

DOE PAGES

Zhang, Aiwu; Hohlmann, Marcus; Azmoun, Babak; ...

2018-01-10

Here, we study the position sensitivity of radial zigzag strips intended to read out large GEM detectors for tracking at future experiments. Zigzag strips can cover a readout area with fewer strips than regular straight strips while maintaining good spatial resolution. Consequently, they can reduce the number of required electronic channels and related cost for large-area GEM detector systems. A non-linear relation between incident particle position and hit position measured from charge sharing among zigzag strips was observed in a previous study. We significantly reduce this non-linearity by improving the interleaving of adjacent physical zigzag strips. Zigzag readout structures aremore » implemented on PCBs and on a flexible foil and are tested using a 10 cm × 10 cm triple-GEM detector scanned with a strongly collimated X-ray gun on a 2D motorized stage. Lastly, angular resolutions of 60–84 μrad are achieved with a 1.37 mrad angular strip pitch at a radius of 784 mm. On a linear scale this corresponds to resolutions below 100 μm.« less

A GEM readout with radial zigzag strips and linear charge-sharing response

NASA Astrophysics Data System (ADS)

Zhang, Aiwu; Hohlmann, Marcus; Azmoun, Babak; Purschke, Martin L.; Woody, Craig

2018-04-01

We study the position sensitivity of radial zigzag strips intended to read out large GEM detectors for tracking at future experiments. Zigzag strips can cover a readout area with fewer strips than regular straight strips while maintaining good spatial resolution. Consequently, they can reduce the number of required electronic channels and related cost for large-area GEM detector systems. A non-linear relation between incident particle position and hit position measured from charge sharing among zigzag strips was observed in a previous study. We significantly reduce this non-linearity by improving the interleaving of adjacent physical zigzag strips. Zigzag readout structures are implemented on PCBs and on a flexible foil and are tested using a 10 cm × 10 cm triple-GEM detector scanned with a strongly collimated X-ray gun on a 2D motorized stage. Angular resolutions of 60-84 μrad are achieved with a 1.37 mrad angular strip pitch at a radius of 784 mm. On a linear scale this corresponds to resolutions below 100 μm.

Isomorphous rare-earth tris[bis(2,6-diisopropylphenyl) phosphate] complexes and their catalytic properties in 1,3-diene polymerization and in the inhibited oxidation of polydimethylsiloxane.

PubMed

Minyaev, Mikhail E; Tavtorkin, Alexander N; Korchagina, Sof'ya A; Bondarenko, Galina N; Churakov, Andrei V; Nifant'ev, Ilya E

2018-05-01

Crystals of mononuclear tris[bis(2,6-diisopropylphenyl) phosphato-κO]pentakis(methanol-κO)lanthanide methanol monosolvates of lanthanum, [La(C 24 H 34 O 4 P) 3 (CH 3 OH) 5 ]·CH 3 OH, (1), cerium, [Ce(C 24 H 34 O 4 P) 3 (CH 3 OH) 5 ]·CH 3 OH, (2), and neodymium, [Nd(C 24 H 34 O 4 P) 3 (CH 3 OH) 5 ]·CH 3 OH, (3), have been obtained by reactions between LnCl 3 (H 2 O) n (n = 6 or 7) and lithium bis(2,6-diisopropylphenyl) phosphate in a 1:3 molar ratio in methanol media. Compounds (1)-(3) crystallize in the monoclinic P2 1 /c space group and have isomorphous crystal structures. All three bis(2,6-diisopropylphenyl) phosphate ligands display a κO-monodentate coordination mode. The coordination number of the metal atom is 8. Each [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 3 (CH 3 OH) 5 ] molecular unit exhibits four intramolecular O-H...O hydrogen bonds, forming six-membered rings. The unit forms two intermolecular O-H...O hydrogen bonds with one noncoordinating methanol molecule. All six hydroxy H atoms are involved in hydrogen bonding within the [Ln{O 2 P(O-2,6- i Pr 2 C 6 H 3 ) 2 } 3 (CH 3 OH) 5 ]·CH 3 OH unit. This, along with the high steric hindrance induced by the three bulky diaryl phosphate ligands, prevents the formation of a hydrogen-bond network. Complexes (1)-(3) exhibit disorder of two of the isopropyl groups of the phosphate ligands. The cerium compound (2) demonstrates an essential catalytic inhibition in the thermal decomposition of polydimethylsiloxane in air at 573 K. Catalytic systems based on the neodymium complex tris[bis(2,6-diisopropylphenyl) phosphato-κO]neodymium, (3'), which was obtained as a dry powder of (3) upon removal of methanol, display a high catalytic activity in isoprene and butadiene polymerization.

[(S)-1-Carbamoylethyl]bis(dimethylglyoximato-kappa2N,N')[(S)-1-phenylethylamine]cobalt(III) and bis(dimethylglyoximato-kappa2N,N')[(R)-1-(N-methylcarbamoyl)ethyl][(R)-1-phenylethylamine]cobalt(III) monohydrate.

PubMed

Orisaku, Keiko Komori; Hagiwara, Mieko; Ohgo, Yoshiki; Arai, Yoshifusa; Ohgo, Yoshiaki

2005-04-01

The title complexes, [Co(C3H6NO)(C4H7N2O2)2(C8H11N)] and [Co(C4H8NO)(C4H7N2O2)2(C8H11N)].H2O, were resolved from [(RS)-1-carbamoylethyl]bis(dimethylglyoximato)[(S)-1-phenylethylamine]cobalt(III) and bis(dimethylglyoximato)[(RS)-1-(N-methylcarbamoyl)ethyl][(R)-1-phenylethylamine]cobalt(III), respectively, and their crystal structures were determined in order to reveal the absolute configuration of the major enantiomer produced in the photoisomerization of each series of 2-carbamoylethyl and 2-(N-methylcarbamoyl)ethyl cobaloxime complexes.

GEM: a dynamic tracking model for mesoscale eddies in the ocean

NASA Astrophysics Data System (ADS)

Li, Qiu-Yang; Sun, Liang; Lin, Sheng-Fu

2016-12-01

The Genealogical Evolution Model (GEM) presented here is an efficient logical model used to track dynamic evolution of mesoscale eddies in the ocean. It can distinguish between different dynamic processes (e.g., merging and splitting) within a dynamic evolution pattern, which is difficult to accomplish using other tracking methods. To this end, the GEM first uses a two-dimensional (2-D) similarity vector (i.e., a pair of ratios of overlap area between two eddies to the area of each eddy) rather than a scalar to measure the similarity between eddies, which effectively solves the "missing eddy" problem (temporarily lost eddy in tracking). Second, for tracking when an eddy splits, the GEM uses both "parent" (the original eddy) and "child" (eddy split from parent) and the dynamic processes are described as the birth and death of different generations. Additionally, a new look-ahead approach with selection rules effectively simplifies computation and recording. All of the computational steps are linear and do not include iteration. Given the pixel number of the target region L, the maximum number of eddies M, the number N of look-ahead time steps, and the total number of time steps T, the total computer time is O(LM(N + 1)T). The tracking of each eddy is very smooth because we require that the snapshots of each eddy on adjacent days overlap one another. Although eddy splitting or merging is ubiquitous in the ocean, they have different geographic distributions in the North Pacific Ocean. Both the merging and splitting rates of the eddies are high, especially at the western boundary, in currents and in "eddy deserts". The GEM is useful not only for satellite-based observational data, but also for numerical simulation outputs. It is potentially useful for studying dynamic processes in other related fields, e.g., the dynamics of cyclones in meteorology.

Quantitative analysis of trace element concentrations in some gem-quality diamonds

NASA Astrophysics Data System (ADS)

McNeill, J.; Pearson, D. G.; Klein-Ben David, O.; Nowell, G. M.; Ottley, C. J.; Chinn, I.

2009-09-01

The geochemical signature of diamond-forming fluids can be used to unravel diamond-forming processes and is of potential use in the detection of so-called 'conflict' diamonds. While fluid-rich fibrous diamonds can be analyzed by a variety of techniques, very few data have been published for fluid-poor, gem-quality diamonds because of their very low impurity levels. Here we present a new ICPMS-based (ICPMS: inductively coupled plasma mass spectrometry) method for the analysis of trace element concentrations within fluid-poor, gem-quality diamonds. The method employs a closed-system laser ablation cell. Diamonds are ablated and the products trapped for later pre-concentration into solutions that are analyzed by sector-field ICPMS. We show that our limits of quantification for a wide range of elements are at the sub-pg to low pg level. The method is applied to a suite of 10 diamonds from the Cullinan Mine (previously known as Premier), South Africa, along with other diamonds from Siberia (Mir and Udachnaya) and Venezuela. The concentrations of a wide range of elements for all the samples (expressed by weight in the solid) are very low, with rare earth elements along with Y, Nb, Cs ranging from 0.01 to 2 ppb. Large ion lithophile elements (LILE) such as Rb and Ba vary from 1 to 30 ppb. Ti ranges from ppb levels up to 2 ppm. From the combined, currently small data set we observe two kinds of diamond-forming fluids within gem diamonds. One group has enrichments in LILE over Nb, whereas a second group has normalized LILE abundances more similar to those of Nb. These two groups bear some similarity to different groups of fluid-rich diamonds, providing some supporting evidence of a link between the parental fluids for both fluid-inclusion-rich and gem diamonds.

Copper-catalyzed cross-coupling reactions of epoxides with gem-diborylmethane: access to γ-hydroxyl boronic esters.

PubMed

Ebrahim-Alkhalil, Ahmed; Zhang, Zhen-Qi; Gong, Tian-Jun; Su, Wei; Lu, Xiao-Yu; Xiao, Bin; Fu, Yao

2016-04-07

Herein, we describe a novel copper-catalyzed epoxide opening reaction with gem-diborylmethane. Aliphatic, aromatic epoxides as well as aziridines are converted to the corresponding γ-pinacolboronate alcohols or amines in moderate to excellent yields. This new reaction provides beneficial applications for classic epoxide substrates as well as interesting gem-diborylalkane reagents.

A Study of a Mini-Drift GEM Tracking Detector

NASA Astrophysics Data System (ADS)

Azmoun, B.; DiRuzza, B.; Franz, A.; Kiselev, A.; Pak, R.; Phipps, M.; Purschke, M. L.; Woody, C.

2016-06-01

A GEM tracking detector with an extended drift region has been studied as part of an effort to develop new tracking detectors for future experiments at RHIC and for the Electron Ion Collider that is being planned for BNL or JLAB. The detector consists of a triple GEM stack with a 1.6 cm drift region that was operated in a mini TPC type configuration. Both the position and arrival time of the charge deposited in the drift region were measured on the readout plane which allowed the reconstruction of a short vector for the track traversing the chamber. The resulting position and angle information from the vector could then be used to improve the position resolution of the detector for larger angle tracks, which deteriorates rapidly with increasing angle for conventional GEM tracking detectors using only charge centroid information. Two types of readout planes were studied. One was a COMPASS style readout plane with 400 μm pitch XY strips and the other consisted of 2 × 10 mm2 chevron pads. The detector was studied in test beams at Fermilab and CERN, along with additional measurements in the lab, in order to determine its position and angular resolution for incident track angles up to 45 degrees. Several algorithms were studied for reconstructing the vector using the position and timing information in order to optimize the position and angular resolution of the detector for the different readout planes. Applications for large angle tracking detectors at RHIC and EIC are also discussed.

A Study of a Mini-Drift GEM Tracking Detector

DOE PAGES

Azmoun, B.; DiRuzza, B.; Franz, A.; ...

2016-06-22

In this paper, a GEM tracking detector with an extended drift region has been studied as part of an effort to develop new tracking detectors for future experiments at RHIC and for the Electron Ion Collider that is being planned for BNL or JLAB. The detector consists of a triple GEM stack with a 1.6 cm drift region that was operated in a mini TPC type configuration. Both the position and arrival time of the charge deposited in the drift region were measured on the readout plane which allowed the reconstruction of a short vector for the track traversing themore » chamber. The resulting position and angle information from the vector could then be used to improve the position resolution of the detector for larger angle tracks, which deteriorates rapidly with increasing angle for conventional GEM tracking detectors using only charge centroid information. Two types of readout planes were studied. One was a COMPASS style readout plane with 400 μm pitch XY strips and the other consisted of 2 × 10 mm 2 chevron pads. The detector was studied in test beams at Fermilab and CERN, along with additional measurements in the lab, in order to determine its position and angular resolution for incident track angles up to 45 degrees. Several algorithms were studied for reconstructing the vector using the position and timing information in order to optimize the position and angular resolution of the detector for the different readout planes. Finally, applications for large angle tracking detectors at RHIC and EIC are also discussed.« less

A Study of a Mini-Drift GEM Tracking Detector

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

Azmoun, B.; DiRuzza, B.; Franz, A.

In this paper, a GEM tracking detector with an extended drift region has been studied as part of an effort to develop new tracking detectors for future experiments at RHIC and for the Electron Ion Collider that is being planned for BNL or JLAB. The detector consists of a triple GEM stack with a 1.6 cm drift region that was operated in a mini TPC type configuration. Both the position and arrival time of the charge deposited in the drift region were measured on the readout plane which allowed the reconstruction of a short vector for the track traversing themore » chamber. The resulting position and angle information from the vector could then be used to improve the position resolution of the detector for larger angle tracks, which deteriorates rapidly with increasing angle for conventional GEM tracking detectors using only charge centroid information. Two types of readout planes were studied. One was a COMPASS style readout plane with 400 μm pitch XY strips and the other consisted of 2 × 10 mm 2 chevron pads. The detector was studied in test beams at Fermilab and CERN, along with additional measurements in the lab, in order to determine its position and angular resolution for incident track angles up to 45 degrees. Several algorithms were studied for reconstructing the vector using the position and timing information in order to optimize the position and angular resolution of the detector for the different readout planes. Finally, applications for large angle tracking detectors at RHIC and EIC are also discussed.« less

Evolution in boron-based GEM detectors for diffraction measurements: from planar to 3D converters

NASA Astrophysics Data System (ADS)

Albani, Giorgia; Perelli Cippo, Enrico; Croci, Gabriele; Muraro, Andrea; Schooneveld, Erik; Scherillo, Antonella; Hall-Wilton, Richard; Kanaki, Kalliopi; Höglund, Carina; Hultman, Lars; Birch, Jens; Claps, Gerardo; Murtas, Fabrizio; Rebai, Marica; Tardocchi, Marco; Gorini, Giuseppe

2016-11-01

The so-called ‘3He-crisis’ has motivated the neutron detector community to undertake an intense R&D programme in order to develop technologies alternative to standard 3He tubes and suitable for neutron detection systems in future spallation sources such as the European spallation source (ESS). Boron-based GEM (gas electron multiplier) detectors are a promising ‘3He-free’ technology for thermal neutron detection in neutron scattering experiments. In this paper the evolution of boron-based GEM detectors from planar to 3D converters with an application in diffraction measurements is presented. The use of 3D converters coupled with GEMs allows for an optimization of the detector performances. Three different detectors were used for diffraction measurements on the INES instrument at the ISIS spallation source. The performances of the GEM-detectors are compared with those of conventional 3He tubes installed on the INES instrument. The conceptual detector with the 3D converter used in this paper reached a count rate per unit area of about 25% relative to the currently installed 3He tube. Its timing resolution is similar and the signal-to-background ratio (S/B) is 2 times lower.

Highly effective copper-mediated gem-difluoromethylenation of arylboronic acids.

PubMed

Ma, Guobin; Wan, Wen; Hu, Qingyang; Jiang, Haizhen; Wang, Jing; Zhu, Shizheng; Hao, Jian

2014-07-18

A copper-mediated gem-difluoromethylenation of aryl, heteroaryl and vinyl boronic acids with bromodifluoromethylated oxazole or thiazole derivatives has been developed. This novel reaction showed an excellent functional group tolerance and wide substrate scope, providing facile access to practical application in drug discovery and development.

The Greenhouse Gases. UNEP/GEMS Environment Library No. 1.

ERIC Educational Resources Information Center

United Nations Environment Programme, Nairobi (Kenya).

Since the United Nations Environment Program (UNEP) was created, more than a dozen years ago, public understanding of the environmental issues confronting our planet has increased enormously. The Global Environment Monitoring System (GEMS) has provided several environmental assessments including urban air pollution, climate modification,…

Radical-lanthanide ferromagnetic interaction in a T bIII bis-phthalocyaninato complex

NASA Astrophysics Data System (ADS)

Komijani, Dorsa; Ghirri, Alberto; Bonizzoni, Claudio; Klyatskaya, Svetlana; Moreno-Pineda, Eufemio; Ruben, Mario; Soncini, Alessandro; Affronte, Marco; Hill, Stephen

2018-02-01

Recent studies have highlighted the importance of organic ligands in the field of molecular spintronics, via which delocalized electron-spin density can mediate magnetic coupling to otherwise localized 4 f moments of lanthanide ions, which show tremendous potential for single-molecule device applications. To this end, high-field/high-frequency electron paramagnetic resonance (EPR) spectroscopy is employed to study a neutral terbium bis-phthalocyaninato metalorganic complex, [TbPc2 ] 0, with the aim of understanding the magnetic interaction between the Ising-like moment of the lanthanide ion and the unpaired spin density on the coordinating organic radical ligand. The measurements were performed on a previously unknown [TbPc2 ] 0 structural phase crystallizing in the Pnma space group. EPR measurements on powder samples of [TbPc2 ] 0 reveal an anisotropic spectrum, which is attributed to the spin-1/2 radical coupled weakly to the EPR-silent T bIII ion. Extensive double-axis rotation studies on a single crystal reveal two independent spin-1/2 signals with differently oriented (albeit identical) uniaxial g -tensors, in complete agreement with x-ray structural studies that indicate two molecular orientations within the unit cell. The easy-axis nature of the radical EPR spectra thus reflects the coupling to the Ising-like T bIII moment. This is corroborated by studies of the isostructural [YPc2 ] 0 analog (where Y is nonmagnetic yttrium), which gives a completely isotropic radical EPR signal. The experimental results for the terbium complex are well explained on the basis of an effective model that introduces a weak ferromagnetic Heisenberg coupling between an isotropic spin-1/2 and an anisotropic spin-orbital moment, J =6 , that mimics the known, strong easy-axis Tb ⋯P c2 crystal-field interaction.

Molecular structure, magnetic properties, cyclic voltammetry of the low-spin iron(III) Bis(4-ethylaniline) complex with the para-chloro substituted meso-tetraphenylporphyrin

NASA Astrophysics Data System (ADS)

Dhifaoui, Selma; Mchiri, Chadlia; Quatremare, Pierre; Marvaud, Valérie; Bujacz, Anna; Nasri, Habib

2018-02-01

In this study, the preparation of a new iron(III) hexacoordinated metalloporphyrin namely the bis(4-ethylaniline){meso-tetra(para-chlorophenyl)porphyrinato}iron(III) triflate hemi-4-ethylaniline monohydrate with the formula [FeIII(TClPP)(PhEtNH2)2]SO3CF3•1/2PhEtNH2•H2O (I) was reported. This is the first example of an iron(III) metalloporphyrin bis(primary amine) with an aryl group adjacent to the amino group. This species was characterized by elemental, spectroscopic analysis including UV-visible and IR data, cyclic voltammetry, SQUID measurements and X-ray molecular structure. The mean equatorial distance between the iron(III) and the nitrogens of the porphyrin is appropriate for a low-spin (S = 1/2) iron(III) porphyrin complex. The magnetic data confirm the low-spin state of our ferric derivative while the cyclic voltammetry indicates a shift of the half potential E1/2[Fe(III)/Fe(II)] of complex (I) toward more negative value. In the crystal of (I), the [FeIII(TClPP)(PhEtNH2)2]+ ions, the triflate counterions and the water molecules are involved in a number of O__H⋯O, N__H⋯O, C-H⋯O and C__H⋯π intermolecular interactions forming a three-dimension network.

Dipicolinate Complexes of Gallium(III) and Lanthanum(III).

PubMed

Weekes, David M; Ramogida, Caterina F; Jaraquemada-Peláez, Maria de Guadalupe; Patrick, Brian O; Apte, Chirag; Kostelnik, Thomas I; Cawthray, Jacqueline F; Murphy, Lisa; Orvig, Chris

2016-12-19

Three dipicolinic acid amine-derived compounds functionalized with a carboxylate (H 3 dpaa), phosphonate (H 4 dppa), and bisphosphonate (H 7 dpbpa), as well as their nonfunctionalized analogue (H 2 dpa), were successfully synthesized and characterized. The 1:1 lanthanum(III) complexes of H 2 dpa, H 3 dpaa, and H 4 dppa, the 1:2 lanthanum(III) complex of H 2 dpa, and the 1:1 gallium(III) complex of H 3 dpaa were characterized, including via X-ray crystallography for [La 4 (dppa) 4 (H 2 O) 2 ] and [Ga(dpaa)(H 2 O)]. H 2 dpa, H 3 dpaa, and H 4 dppa were evaluated for their thermodynamic stability with lanthanum(III) via potentiometric and either UV-vis spectrophotometric (H 3 dpaa) or NMR spectrometric (H 2 dpa and H 4 dppa) titrations, which showed that the carboxylate (H 3 dpaa) and phosphonate (H 4 dppa) containing ligands enhanced the lanthanum(III) complex stability by 3-4 orders of magnitude relative to the unfunctionalized ligand (comparing log β ML and pM values) at physiological pH. In addition, potentiometric titrations with H 3 dpaa and gallium(III) were performed, which gave significantly (8 orders of magnitude) higher thermodynamic stability constants than with lanthanum(III). This was predicted to be a consequence of better size matching between the dipicolinate cavity and gallium(III), which was also evident in the aforementioned crystal structures. Because of a potential link between lanthanum(III) and osteoporosis, the ligands were tested for their bone-directing properties via a hydroxyapatite (HAP) binding assay, which showed that either a phosphonate or bisphosphonate moiety was necessary in order to elicit a chemical binding interaction with HAP. The oral activity of the ligands and their metal complexes was also assessed by experimentally measuring log P o/w values using the shake-flask method, and these were compared to a currently prescribed osteoporosis drug (alendronate). Because of the potential therapeutic applications of the radionuclides

Trace elements in Gem-Quality Diamonds - Origin and evolution of diamond-forming fluid inclusions

NASA Astrophysics Data System (ADS)

Pearson, Graham; Krebs, Mandy; Stachel, Thomas; Woodland, Sarah; Chinn, Ingrid; Kong, Julie

2017-04-01

In the same way that melt inclusions in phenocrysts have expanded our idea of melt formation and evolution in basalts, studying fluids trapped in diamonds is providing important new constraints on the nature of diamond-forming fluids. Fibrous and cloudy diamonds trap a high but variable density of fluid inclusions and so have been extensively studied using major and trace element compositions. In contrast, constraining the nature of the diamond-forming fluid for high purity gem-quality diamonds has been restricted by the rarity of available high quality trace element data. This is due to the extremely low concentrations of impurities that gem diamonds contain - often in the ppt range. The recent discovery of fluids in gem diamonds showing similar major element chemistry to fluid-rich diamonds suggest that many diamonds may share a common spectrum of parental fluids. Here we test this idea further. Recent advances in analytical techniques, in particular the development of the "off-line" laser ablation pre-concentration approach, have allowed fully quantitative trace element data to be recovered from "fluid-poor", high quality gem diamonds. We present trace element data for gem diamonds from a variety of locations from Canada, S. Africa and Russia, containing either silicate or sulphide inclusions to examine possible paragenetic or genetic differences between fluids. REE abundance in the "gem" diamonds vary from 0.1 to 0.0001 x chondrite. To a first order, we observe the same spectrum of trace element compositions in the gem diamonds as that seen in fluid-rich "fibrous" diamonds, supporting a common origin for the fluids. REE patterns range from extremely flat (Ce/Yb)n 2.5 to 5 (commonly in sulphide-bearing diamonds) to >70, the latter having significantly greater inter-element HFSE/LILE fractionation. In general, the fluids from the sulphide-bearing diamonds are less REE-enriched than the silicate-bearing diamonds, but the ranges overlap significantly. The very

Phosphonate-anchored monolayers for antibody binding to magnetic nanoparticles.

PubMed

Benbenishty-Shamir, Helly; Gilert, Roni; Gotman, Irena; Gutmanas, Elazar Y; Sukenik, Chaim N

2011-10-04

Targeted delivery of magnetic iron oxide nanoparticles (IONPs) to a specific tissue can be achieved by conjugation with particular biological ligands on an appropriately functionalized IONP surface. To take best advantage of the unique magnetic properties of IONPs and to maximize their blood half-life, thin, strongly bonded, functionalized coatings are required. The work reported herein demonstrates the successful application of phosphonate-anchored self-assembled monolayers (SAMs) as ultrathin coatings for such particles. It also describes a new chemical approach to the anchoring of antibodies on the surface of SAM-coated IONPs (using nucleophilic aromatic substitution). This anchoring strategy results in stable, nonhydrolyzable, covalent attachment and allows the reactivity of the particles toward antibody binding to be activated in situ, such that prior to the activation the modified surface is stable for long-term storage. While the SAMs do not have the well-packed crystallinity of other such monolayers, their structure was studied using smooth model substrates based on an iron oxide layer on a double-side polished silicon wafer. In this way, atomic force microscopy, ellipsometry, and contact angle goniometry (tools that could not be applied to the nanoparticles' surfaces) could contribute to the determination of their monomolecular thickness and uniformity. Finally, the successful conjugation of IgG antibodies to the SAM-coated IONPs such that the antibodies retain their biological activity is verified by their complexation to a secondary fluorescent antibody. © 2011 American Chemical Society

Prediction of Exploration Target Areas for GEM Deposits in Mogok Stone Tract, Northern Myanmar by Integrating Remote Sensing and Geoscience Data

NASA Astrophysics Data System (ADS)

Oo, Tin Ko

2011-07-01

The Mogok Stone Tract area has long been known for world famous finest ruby since 1597. The Mogok area lies in northern Myanmar and is located at about 205.99km northeast from Mandalay, the second largest city of Myanmar. The Mogok Group of metasedimentary rocks is divided into four units: (1) Wabyudaung Marble, (2) Ayenyeinchantha Calc-silicate, (3) Gwebin Quartzite, and (4) Kabe Gneiss. Igneous rocks in the Mogok area are classified into two units: (1) Kabaing Granite and (2) Pingutaung Leucogranite. The Mogok area has a complex structure involving several folds and faults. Using marbles and calc-silicates as marker horizons, a series of anticline and syncline can be identified such as Mogok syncline, Ongaing anticline, Bawpadan syncline, and Kyatpyin anticline. All the foldings show a low-angle plunge to the south. The main precious stones of the Mogok area are ruby and sapphire; and the other important semi-precious stones are spinel, topaz, peridot, garnet, apatite, beryl, tourmaline (rubellite), quartz, diopside, fluorite, and enstatite. Geological and remote sensing data are processed to extract the indicative features of gem mineralized areas: lithology, structure, and hydrothermal alteration. Density slice version of Landsat ETM band ratios 5/7 is used to map clay alterations. Filtering Landsat ETM band 5 by using edge detection filter is applied for lineament mapping. Spatial integration of various geoscience and remote sensing data sets such as geological maps, Landsat ETM images, and the location map of gem mines show the distribution of alteration zones associated with the gem mineralization in the study area. Geographic Information System (GIS) model has been designed and implemented by ARCVIEW software package based on the overlay of lithologic, lineament, and alteration vector maps. This process has resulted in delineation of most promising areas of probable gem mineralized zones as on the output map.

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

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

Kumar, Sandeep; Andotra, Savit; Kaur, Mandeep

2016-09-15

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

Introducing parallelism to histogramming functions for GEM systems

NASA Astrophysics Data System (ADS)

Krawczyk, Rafał D.; Czarski, Tomasz; Kolasinski, Piotr; Pozniak, Krzysztof T.; Linczuk, Maciej; Byszuk, Adrian; Chernyshova, Maryna; Juszczyk, Bartlomiej; Kasprowicz, Grzegorz; Wojenski, Andrzej; Zabolotny, Wojciech

2015-09-01

This article is an assessment of potential parallelization of histogramming algorithms in GEM detector system. Histogramming and preprocessing algorithms in MATLAB were analyzed with regard to adding parallelism. Preliminary implementation of parallel strip histogramming resulted in speedup. Analysis of algorithms parallelizability is presented. Overview of potential hardware and software support to implement parallel algorithm is discussed.

Estimation of Item Parameters and the GEM Algorithm.

ERIC Educational Resources Information Center

Tsutakawa, Robert K.

The models and procedures discussed in this paper are related to those presented in Bock and Aitkin (1981), where they considered the 2-parameter probit model and approximated a normally distributed prior distribution of abilities by a finite and discrete distribution. One purpose of this paper is to clarify the nature of the general EM (GEM)…

Microwave assisted synthesis of bis and tris(ω-bromoacetophenones): versatile precursors for novel bis(imidazo[1,2-a]pyridines), bis(imidazo[1,2-a]pyrimidines) and their tris-analogs

PubMed Central

2013-01-01

Background α-Bromination of the side chain of aromatic ketones using NBS in the presence of p-toluenesulfonic acid (p-TsOH) in acetonitrile is very common. However, regioselective bromination of bis and tris(ω-bromoacetophenones) with NBS in the presence of p-TsOH in acetonitrile under microwave irradiation is quite novel. The bis- and tris(ω-bromoacetophenones) are used in synthesis of bis and tris(heterocycles). bis(heterocycles) have received a great deal of attention, because many biologically active natural and synthetic products have molecular symmetry. The use of the pressurized microwave irradiation is very advantageous to many syntheses and provide a large rate enhancement. Results Bis and tris(ω-bromoacetophenones) were obtained as single monobrominated derivatives in a shorter time than the conventional conditions. The results clearly demonstrate the better reactivity and selectivity of NBS/p-TsOH/CH3CN as a brominating mixture under microwave conditions. The reaction of bis and tris(ω-bromoacetophenone) with 2-aminopyridine and 2-aminopyrimidine proceeded smoothly in a mixture of anhydrous ethanol and DMF under reflux or using 300 W/105°C/ 20 min microwave irradiation conditions to afford the corresponding bis(imidazo[1,2-a]pyridine), bis(imidazo[1,2-a]pyrimidine) and tris(imidazo[1,2-a]pyridine) derivatives in moderate to excellent yields. The carbonyl analogue of the targeted bis(imidazopyridines) could be synthesized by the reaction of N,N-dimethyl-N'-(pyridin-2-yl)formimidamide with bis(ω-bromoacetophenone) in refluxing ethanol. The structures of the newly synthesized compounds were confirmed by their spectral data as well as their elemental analyses. Conclusion In conclusion, selective α-bromination of bis- and tris(acetophenones) has been accomplished efficiently utilizing NBS/p-TsOH/CH3CN under microwave irradiation. In addition, a facile synthesis of novel series of bis- and tris(imidazopyridine) and bis(imidazopyrimidine) derivatives

Fluorescence "turn on" detection of mercuric ion based on bis(dithiocarbamato)copper(II) complex functionalized carbon nanodots.

PubMed

Yuan, Chao; Liu, Bianhua; Liu, Fei; Han, Ming-Yong; Zhang, Zhongping

2014-01-21

A new "turn on" fluorescence nanosensor for selective Hg(2+) determination is reported based on bis(dithiocarbamato)copper(II) functionalized carbon nanodots (CuDTC2-CDs). The CuDTC2 complex was conjugated to the prepared amine-coated CDs by the condensation of carbon disulfide onto the nitrogen atoms in the surface amine groups, followed by the coordination of copper(II) to the resulting dithiocarbamate groups (DTC) and finally by the additional coordination of ammonium N-(dithicarbaxy) sarcosine (DTCS) to form the CuDTC2-complexing CDs. The CuDTC2 complex at surface strongly quenched the bright-blue fluorescence of the CDs by a combination of electron transfer and energy transfer mechanism. Hg(2+) could immediately switch on the fluorescence of the CuDTC2-CDs by promptly displacing the Cu(2+) in the CuDTC2 complex and thus shutting down the energy transfer pathway, in which the sensitive limit for Hg(2+) as low as 4 ppb was reached. Moreover, a paper-based sensor has been fabricated by printing the CuDTC2-CDs probe ink on a piece of cellulose acetate paper using a commercial inkjet printer. The fluorescence "turn on" on the paper provided the most conveniently visual detection of aqueous Hg(2+) ions by the observation with naked eye. The very simple and effective strategy reported here facilitates the development of portable and reliable fluorescence nanosensors for the determination of Hg(2+) in real samples.

Asthenopia (eyestrain) in working children of gem-polishing industries.

PubMed

Tiwari, Rajnarayan R; Saha, Asim; Parikh, Jagdish R

2011-04-01

Working children of gem-polishing units are exposed to poor illumination and improper workstations. Also processes require lot of visual and mental concentration for precision. This may result in eyestrain. The study included 432 exposed and 569 comparison group subjects. Self-reported eyestrain was recorded through personal interview. Eyestrain included symptoms like itching, burning, or irritated eyes; tired or heavy eyes; difficulty seeing clearly (including blurred or double vision); and headache. The study variables included age, gender, daily working hours, and duration of exposure. The prevalence of eyestrain in child labourers was 32.2%, which was significantly more than the comparison group subjects. Also, the working children of gem-polishing units were at 1.4 times higher risk of developing eyestrain. Age (3)14 years and female gender were significantly associated with the eyestrain. The prevalence of eyestrain in child labourers was 32.2% and was associated with age (3)14 years and female gender.

ISC-GEM: Global Instrumental Earthquake Catalogue (1900-2009), II. Location and seismicity patterns

NASA Astrophysics Data System (ADS)

Bondár, I.; Engdahl, E. Robert; Villaseñor, A.; Harris, James; Storchak, D.

2015-02-01

We present the final results of a two-year project sponsored by the Global Earthquake Model (GEM) Foundation. The ISC-GEM global catalogue consists of some 19 thousand instrumentally recorded, moderate to large earthquakes, spanning 110 years of seismicity. We relocated all events in the catalogue using a two-tier approach. The EHB location methodology (Engdahl et al., 1998) was applied first to obtain improved hypocentres with special focus on the depth determination. The locations were further refined in the next step by fixing the depths to those from the EHB analysis and applying the new International Seismological Centre (ISC) location algorithm (Bondár and Storchak, 2011) that reduces location bias by accounting for correlated travel-time prediction error structure. To facilitate the relocation effort, some one million seismic P and S wave arrival-time data were added to the ISC database for the period between 1904 and 1970, either from original station bulletins in the ISC archive or by digitizing the scanned images of the International Seismological Summary (ISS) bulletin (Villaseñor and Engdahl, 2005, 2007). Although no substantial amount of new phase data were acquired for the modern period (1964-2009), the number of phases used in the location has still increased by three millions, owing to fact that both the EHB and ISC locators use most well-recorded ak135 (Kennett et al., 1995) phases in the location. We show that the relocation effort yielded substantially improved locations, especially in the first half of the 20th century; we demonstrate significant improvements in focal depth estimates in subduction zones and other seismically active regions; and we show that the ISC-GEM catalogue provides an improved view of 110 years of global seismicity of the Earth. The ISC-GEM Global Instrumental Earthquake Catalogue represents the final product of one of the ten global components in the GEM program, and is available to researchers at the ISC (http://www.isc.ac.uk).

Graphing Powers and Roots of Complex Numbers.

ERIC Educational Resources Information Center

Embse, Charles Vonder

1993-01-01

Using De Moivre's theorem and a parametric graphing utility, examines powers and roots of complex numbers and allows students to establish connections between the visual and numerical representations of complex numbers. Provides a program to numerically verify the roots of complex numbers. (MDH)

A Ni(II) Bis(diphosphine)-Hydride Complex Containing Proton Relays - Structural Characterization and Electrocatalytic Studies

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

Das, Partha Pratim; Stolley, Ryan M.; Van Der Eide, Edwin F.

The syntheses of the new 1,5-diphenyl-3,7-di(isopropyl)-1,5-diaza-3,7-diphosphacyclooctane ligand, PiPr2NPh2, is reported. The two equivalents of the ligand react with [Ni(CH3CN)6](BF4)2 to form the bis-diphosphine Ni(II)-complex [Ni(PiPr2NPh2)2](BF4)2, which acts as a proton reduction electrocatalyst. In addition to [Ni(PiPr2NPh2)2]2+, we report the syntheses and structural characterization of the Ni(0)-complex Ni(PiPr2NPh2)2, and the Ni(II)-hydride complex [HNi(PiPr2NPh2)2]BF4. The [HNi(PiPr2NPh2)2]BF4 complex represents the first Ni(II)-hydride in the [Ni(PR2NR'2)2]2+ family of compounds to be isolated and structurally characterized. In addition to the experimental data, the mechanism of electrocatalysis facilitated by [Ni(PiPr2NPh2)2]2+ is analyzed using linear free energy relationships recently established for the [Ni(PR2NR'2)2]2+ family. We thank Dr.more » Aaron Appel, Dr. Simone Raugei and Dr. Eric Wiedner for helpful discussions. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Mass spectrometry was provided at W. R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy’s office of Biological and Environmental Research located at Pacific Northwest National Laboratory. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

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

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

Fabrication of phosphonic acid films on nitinol nanoparticles by dynamic covalent assembly

DOE PAGES

Quinones, Rosalynn; Garretson, Samantha; Behnke, Grayce; ...

2017-09-25

Nitinol (NiTi) nanoparticles are a valuable metal alloy due to many unique properties that allow for medical applications. NiTi nanoparticles have the potential to form nanofluids, which can advance the thermal conductivity of fluids by controlling the surface functionalization through chemical attachment of organic acids to the surface to form self-assembled alkylphosphonate films. In this study, phosphonic functional head groups such as 16-phosphonohexadecanoic acid, octadecylphosphonic acid, and 12-aminododecylphosphonic acid were used to form an ordered and strongly chemically bounded film on the NiTi nanopowder. The surface of the NiTi nanoparticles was modified in order to tailor the chemical and physicalmore » properties to the desired application. The modified NiTi nanoparticles were characterized using infrared spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, and 31P solid-state nuclear magnetic resonance. The interfacial bonding was identified by spectroscopic data suggesting the phosphonic head group adsorbs in a mixed bidentate/monodentate binding motif on the NiTi nanoparticles. Dynamic light scattering and scanning electron microscopy-energy dispersive X-ray spectroscopy revealed the particle sizes. Differential scanning calorimetry was used to examine the phase transitions. Zeta potential determination as a function of pH was examined to investigate the surface properties of charged nanoparticles. In conclusion, the influence of environmental stability of the surface modifications was also assessed.« less

Gains in the Education of Mathematics and Science GEMS: Teaching Robotics to High School Students

DTIC Science & Technology

2013-01-01

find amusing but that we find of less educational value, like having the robots say comical things. Those who have more teaching time would doubtless...Gains in the Education of Mathematics and Science GEMS: Teaching Robotics to High School Students by Edward M. Measure and Edward Creegan...TR-6220 January 2013 Gains in the Education of Mathematics and Science (GEMS): Teaching Robotics to High School Students Edward M

The application of a monolithic triphenylphosphine reagent for conducting Ramirez gem-dibromoolefination reactions in flow.

PubMed

Roper, Kimberley A; Berry, Malcolm B; Ley, Steven V

2013-01-01

The application of a monolithic form of triphenylphosphine to the Ramirez gem-dibromoolefination reaction using flow chemistry techniques is reported. A variety of gem-dibromides were synthesised in high purity and excellent yield following only removal of solvent and no further off-line purification. It is also possible to perform the Appel reaction using the same monolith and the relationship between the mechanisms of the two reactions is discussed.

Application of phosphonate to prevent sudden oak death in south-western Oregon tanoak (Notholithocarpus densiflorus) forests

Treesearch

Alan Kanaskie; Everett Hansen; Wendy Sutton; Paul Reeser; Carolyn Choquette

2011-01-01

We conducted four experiments to evaluate the effectiveness of phosphonate application to tanoak (Notholithocarpus densiflorus (Hook. & Arn.) Manos, Cannon & S.H.Oh) forests in south-western Oregon: (1) aerial application to forest stands; (2) trunk injection; (3) foliar spray of potted seedlings; and (4) foliar spray of stump...

Symmetrically tetrasubstituted [2.2]paracyclophanes: their systematization and regioselective synthesis of several types of bis-bifunctional derivatives by double electrophilic substitution.

PubMed

Vorontsova, Natalia V; Rozenberg, Valeria I; Sergeeva, Elena V; Vorontsov, Evgenii V; Starikova, Zoya A; Lyssenko, Konstantin A; Hopf, Henning

2008-01-01

The possible number of chiral and achiral tetrasubstituted [2.2]paracyclophanes possessing different types of symmetry (C(2), C(i), C(s), C(2v), C(2h)) is evaluated and a unified independent trivial naming descriptor system is introduced. The reactivity and regioselectivity of the electrophilic substitution of the chiral pseudo-meta- and achiral pseudo-para-disubstituted [2.2]paracyclophanes are investigated in an approach suggested to be general for the synthesis of bis-bifunctional [2.2]paracyclophanes. The mono- and diacylation of chiral pseudo-meta-dihydroxy[2.2]paracyclophane 14 with acetylchloride occur ortho-regioselectively to produce tri- 22, 23 and symmetrically 21 tetrasubstituted acyl derivatives. The same reaction with benzoylchloride is neither regio-, nor chemoselective, and gives rise to a mixture of ortho-/para-, mono-/diacylated compounds 27-31. The double acylation of pseudo-meta-dimethoxy[2.2]paracyclophane 18 is completely para-regioselective. Electrophilic substitution of pseudo-meta-bis(methoxycarbonyl)[2.2]paracyclophane 20 regioselectively generates the pseudo-gem-substitution pattern. Formylation of this substrate produces the monocarbonyl derivatives 35 only, whereas the Fe-catalyzed bromination may be directed towards mono- 36 or disubstitution 37 products chemoselectively by varying the reactions conditions. The diacylation and dibromination reactions of the respective achiral diphenol 12 and bis(methoxycarbonyl) 40 derivatives of the pseudo-para-structure retain regioselectivities which are characteristic for their pseudo-meta-regioisomers. Imino ligands 26, 25, and 39, which were obtained from monoacyl- 22 and diacyldihydroxy[2.2]paracyclophanes 21, 38, are tested as chiral ligands in stereoselective Et(2)Zn addition to benzaldehyde producing 1-phenylpropanol with ee values up to 76 %.

Covalent heterogenization of discrete bis(8-quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes by a metal-template/metal-exchange method: Cyclooctene epoxidation catalysts with enhanced performances

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

Yang, Ying; Chattopadhyay, Soma; Shibata, Tomohiro

A metal-template/metal-exchange method was used to imprint covalently attached bis(8- quinolinolato)dioxomolybdenum(VI) and dioxotungsten(VI) complexes onto large surface-area, mesoporous SBA-15 silica to obtain discrete MoO2 VIT and WO2 VIT catalysts bearing different metal loadings, respectively. Homogeneous counterparts, MoO2 VIN and WO2 VIN, as well as randomly ligandgrafted heterogeneous analogues, MoO2 VIG and WO2 VIG, were also prepared for comparison. X-ray absorption fine structure (XAFS), pair distribution function (PDF) and UV–vis data demonstrate that MoO2 VIT and WO2 VIT adopt a more solution-like bis(8-quinolinol) coordination environment than MoO2 VIG and WO2 VIG, respectively. Correspondingly, the templated MoVI and WVI catalysts show superiormore » performances to their randomly grafted counterparts and neat analogues in the epoxidation of cyclooctene. It is found that the representative MoO2 VIT-10% catalyst can be recycled up to five times without significant loss of reactivity, and heterogeneity test confirms the high stability of MoO2 VIT-10% catalyst against leaching of active species into solution. The homogeneity of the discrete bis(8-quinolinol) metal spheres templated on SBA-15 should be responsible for the superior performances.« less

Synthesis, characterization and cytotoxicity of rare earth metal ion complexes of N,N‧-bis-(2-thiophenecarboxaldimine)-3,3‧-diaminobenzidene, Schiff base ligand

NASA Astrophysics Data System (ADS)

Shakir, Mohammad; Abbasi, Ambreen; Faraz, Mohammad; Sherwani, Asif

2015-12-01

Lanthanide complexes of La3+, Pr3+, Nd3+, Gd3+, Er3+ of general formula [Ln2 L(H2O)4(NO3)4](NO3)2·2H2O have been synthesized from Schiff base, N,N‧-bis-(2-thiophenecarboxaldimine)-3,3‧-diaminobenzidene. The complexes were characterized by elemental analysis, molar conductance, UV-Vis, fluorescence, FT-IR,1H NMR, mass spectroscopy, EDX, SEM and thermal analysis. FT-IR spectral data suggested that ligand coordinate with metal ions through azomethine nitrogen and uncondensed amino group. Molar conductance data revealed 1:2 electrolytic nature of complexes. From the analytical data, the stoichiometry of the complexes was found to be 1:2 (ligand:metal). Thephysico-chemical data suggested eight coordination number for Ln(III)Schiffbase complexes. SEM analysis shows morphological changes in the surfaces of complexes as compared to free ligand. Thermal decomposition profiles were consistent with proposed formulations. The anticancer activity of the complexes and theSchiffbase ligand has been studied towards human cervical cancer celllines (HeLa) and human breast cancer cell lines (MCF-7) and it was found that complexes exhibited greater activity than theSchiffbase.