Synthesis of cis - and trans-diisothiocyanato-bis(NHC) complexes of nickel(II) and applications in the Kumada-Corriu reaction

KAUST Repository

Jothibasu, Ramasamy

2010-09-13

Metathetical reaction of AgSCN with a series of trans-dihalido-bis(carbene) nickel(II) complexes in CH3CN readily afforded the novel diisothiocyanato-bis(carbene) complexes [Ni(NCS)2(NHC)2] (trans-2a, NHC = 1,3-diisopropylbenzimidazolin-2-ylidene; trans-2b, NHC = 1,3-diisobutylbenzimidazolin-2-ylidene; trans-2c, NHC = 1,3- dibenzylbenzimidazolin-2-ylidene; cis-2d, NHC = 1,3-di(2-propenyl) benzimidazolin-2-ylidene; cis-2e, NHC = 1-propyl-3-methylbenzimidazolin-2- ylidene) as greenish-yellow powders in moderate to good yields. While dihalido-bis(carbene) Ni(II) complexes exclusively form trans-complexes, a trans-cis isomerization occurs upon halido-isothiocyanato exchange with complexes bearing less bulky carbene ligands, i.e., cis-2d/e. DFT calculations indicated that this isomerization can be attributed to a reduced energy difference between trans- and cis-isomers of diisothiocyanato complexes. All complexes have been characterized by multinuclear NMR spectroscopy, ESI mass spectrometry, and X-ray diffraction analysis. A catalytic study revealed that cis-complexes generally exhibit greater activities in the Kumada-Corriu coupling reaction. © 2010 American Chemical Society.

Differential Effects of Munc18s on Multiple Degranulation-Relevant Trans-SNARE Complexes.

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Hao Xu

Full Text Available Mast cell exocytosis, which includes compound degranulation and vesicle-associated piecemeal degranulation, requires multiple Q- and R- SNAREs. It is not clear how these SNAREs pair to form functional trans-SNARE complexes and how these trans-SNARE complexes are selectively regulated for fusion. Here we undertake a comprehensive examination of the capacity of two Q-SNARE subcomplexes (syntaxin3/SNAP-23 and syntaxin4/SNAP-23 to form fusogenic trans-SNARE complexes with each of the four granule-borne R-SNAREs (VAMP2, 3, 7, 8. We report the identification of at least six distinct trans-SNARE complexes under enhanced tethering conditions: i VAMP2/syntaxin3/SNAP-23, ii VAMP2/syntaxin4/SNAP-23, iii VAMP3/syntaxin3/SNAP-23, iv VAMP3/syntaxin4/SNAP-23, v VAMP8/syntaxin3/SNAP-23, and vi VAMP8/syntaxin4/SNAP-23. We show for the first time that Munc18a operates synergistically with SNAP-23-based non-neuronal SNARE complexes (i to iv in lipid mixing, in contrast to Munc18b and c, which exhibit no positive effect on any SNARE combination tested. Pre-incubation with Munc18a renders the SNARE-dependent fusion reactions insensitive to the otherwise inhibitory R-SNARE cytoplasmic domains, suggesting a protective role of Munc18a for its cognate SNAREs. Our findings substantiate the recently discovered but unexpected requirement for Munc18a in mast cell exocytosis, and implicate post-translational modifications in Munc18b/c activation.

Synthesis, solvatochromism and crystal structure of trans-[Cu(Et2NCH2CH2NH2)2.H2O](NO3)2 complex: Experimental with DFT combination

Science.gov (United States)

Warad, Ismail; Musameh, Sharif; Badran, Ismail; Nassar, Nashaat N.; Brandao, Paula; Tavares, Carlos Jose; Barakat, Assem

2017-11-01

In this study, two dicationic asymmetrical diamine/copper(II) nitrate salt complexes of the general formula trans-[CuII(NN‧)2.H2O](NO3)2 were successfully synthesized using N,N-dimethylethylenediamine and N,N-diethylethylenediamine as asymmetrical diamine ligands. The structure of complex 2 was identified by X-ray single crystal diffraction analysis confirming that the bidentate ligand N,N-dimethylethylenediamine forms a penta-coordinated complex with an H2O molecule located around the copper(II) ion in a trans configuration. It was found that the metal centre is coordinated in a distorted square pyramidal fashion with a τ value of 0.274. The desired complexes were fully characterized using, MS, UV-Vis, CV, FTIR, TG/DTA, and Hirshfeld surface computational analysis. High level theoretical calculations were also performed in order to investigate the complexes structure, conformers, vibrational frequencies, and their excited states.

Proton magnetic resonance spectra of metal ammine complexes, 8

International Nuclear Information System (INIS)

Taura, Toshiaki; Sakaguchi, Ushio; Yoneda, Hayami

1976-01-01

The rates of amine hydrogen isotopic exchange in the [Co(O) 2 (N) 4 ] + complex ions, where (O) 2 represents carbonate, oxalate, or malonate ions, and (N) 4 , tetraamine, bis(ethylenediamine), or bis(trimethylenediamine), were measured in D 2 O at 35 0 C by the PMR technique. It was found that: (1) the rates for trans (to oxygen) amines are faster than those for cis amines; (2) the rates, especially for trans amines, in the carbonato complexes are slower than those in the oxalato and malonato analogs, and (3) the difference between the rates for cis and trans amines is smaller in the bis(diamine) complexes than in the tetraammine complexes. These results are discussed in terms of the influence of the chelate geometry in the complex on the exchange reaction. (auth.)

Structural Elucidation of cis / trans Dicaffeoylquinic Acid Photoisomerization Using Ion Mobility Spectrometry-Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Zheng, Xueyun; Renslow, Ryan S.; Makola, Mpho M.; Webb, Ian K.; Deng, Liulin; Thomas, Dennis G.; Govind, Niranjan; Ibrahim, Yehia M.; Kabanda, Mwadham M.; Dubery, Ian A.; Heyman, Heino M.; Smith, Richard D.; Madala, Ntakadzeni E.; Baker, Erin S.

2017-03-15

Due to the recently uncovered health benefits and anti-HIV activities of dicaffeoylquinic acids (diCQAs), understanding their structures and functions is of great interest for drug discovery efforts. DiCQAs are analytically challenging to identify and quantify since they commonly exist as a diverse mixture of positional and geometric (cis/trans) isomers. In this work, we utilized ion mobility spectrometry coupled with mass spectrometry to separate the various isomers before and after UV irradiation. The experimental collision cross sections were then compared with theoretical structures to differentiate and identify the diCQA isomers. Our analyses found that naturally the diCQAs existed predominantly as trans/trans isomers, but after 3 h of UV irradiation, cis/cis, cis/trans, trans/cis, and trans/trans isomers were all present in the mixture. This is the first report of successful differentiation of cis/trans diCQA isomers individually, which shows the great promise of IMS coupled with theoretical calculations for determining the structure and activity relationships of different isomers in drug discovery studies.

Calderas and mineralization: volcanic geology and mineralization in the Chianti caldera complex, Trans-Pecos Texas

Energy Technology Data Exchange (ETDEWEB)

Duex, T.W.; Henry, C.D.

1981-01-01

This report describes preliminary results of an ongoing study of the volcanic stratigraphy, caldera activity, and known and potential mineralization of the Chinati Mountains area of Trans-Pecos Texas. Many ore deposits are spatially associated with calderas and other volcanic centers. A genetic relationship between calderas and base and precious metal mineralization has been proposed by some and denied by others. Steven and others have demonstrated that calderas provide an important setting for mineralization in the San Juan volcanic field of Colorado. Mineralization is not found in all calderas but is apparently restricted to calderas that had complex, postsubsidence igneous activity. A comparison of volcanic setting, volcanic history, caldera evolution, and evidence of mineralization in Trans-Pecos to those of the San Juan volcanic field, a major mineral producer, indicates that Trans-Pecos Texas also could be an important mineralized region. The Chianti caldera complex in Trans-Pecos Texas contains at least two calderas that have had considerable postsubsidence activity and that display large areas of hydrothermal alteration and mineralization. Abundant prospects in Trans-Pecos and numerous producing mines immediately south of the Trans-Pecos volcanic field in Mexico are additional evidence that ore-grade deposits could occur in Texas.

Isotopic Ligand Exchange of Some Hexa-Coordinated Inorganic Complexes with Halide Ions in Solution and in Crystals; Echanges Isotopiques de Coordinats de Complexes Inorganiques Hexacoordonnes Avec des Ions Halogenures en Solution et dans les Cristaux; Izotopnyj obmen ligand v nekotorykh geksakoordinirovannykh ne- organicheskikh kompleksakh s ionami galoidov v rastvore i kristallakh; Intercambio Isotopico de Ligandos de Complejos Inorganicos Hexacoordinados y Iones Haluro en Solucion y en Cristales

Energy Technology Data Exchange (ETDEWEB)

Schmidt, G. B. [Institut fuer Kernchemie der Universitaet Koeln, Cologne, Federal Republic of Germany (Germany)

1965-10-15

The kinetics of isotopic exchange reactions give information about the lability of complexes in solution and about the mechanisms of substitution. The exchange of {sup 82}Br-labelled [Rh(NH{sub 3}){sub 5}Br]{sup 2+} and [Ii(NH{sub 3}){sub 5}Br]{sup 2+} complexes with Br{sup -} ions, of trans-[Rh(en){sub 2}Cl{sub 2}]{sup +} and trans- [Co(en){sub 2} Cl{sub 2}]{sup +}]+ with Cl{sup -} ions, of trans- [Co(en){sub 2}Br{sub 2}]{sup +} with Br{sup -} and of [OSCl{sub 6}]{sup 2-} and [OsI{sub 6}]{sup 2-} with Cl{sup -} and I{sup -} ions, respectively, was investigated in acid solutions. The iridium pentamminebromo complex exchanges about 60 times slower than the corresponding rhodium pentamminebromo complex. The rate constant for the Rh- complex was found to be k = (1.03 {+-} 0,02) x 10{sup -2} min{sup -1} at 100 Degree-Sign C, for the Ir-complex k{sub 100 Degree-Sign C} = 1.7 x 10{sup -4} min{sup -1}. For both complexes the exchange rate R is first-order in the complex concentration; in acid solution R is nearly independent of the bromide and hydrogen concentration as well as of the ionic strength. This indicates that the exchange takes place by a dissociation mechanism. Activation energies of 24 and 23 kcal/ mole forthe Rh- and Ir-complex, respectively, were calculated. Rate constants of the {sup 36}Cl isotopic exchange between 60 and 100 Degree-Sign C were measured for the trans- [Rh(en){sub 2} Cl{sub 2}]{sup +} complex and an Arrhenius activation energy of 25 kcal/mole was determined. Here again the increase of the rate R is of first order in the complex concentration; but it is only slightly dependent on the hydrogen and chloride concentration. The exchange seems to occur by aquation. In methanolic HCl solution the exchange rate of this complex is immeasurably slow at 60 Degree-Sign C. The halide exchanges of trans-[Co(en){sub 2} Cl{sub 2}]{sup +} and trans [Co(en){sub 2} Br{sub 2}]{sup +} were measured in methanolic solutions between 30 and 60 Degree-Sign C. Further

Stereospecific control of peptide gas-phase ion chemistry with cis and trans cyclo ornithine residues

Czech Academy of Sciences Publication Activity Database

Marek, Aleš; Nguyen, H. T. H.; Brož, Břetislav; Tureček, F.

2018-01-01

Roč. 53, č. 2 (2018), s. 124-137 ISSN 1076-5174 Institutional support: RVO:61388963 Keywords : cis and trans isomers * cyclo ornithine * peptide dissociations * peptide ion structures * stereochemistry Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 2.422, year: 2016

Understanding the complexity of trans fatty acid reduction in the American diet: American Heart Association Trans Fat Conference 2006: report of the Trans Fat Conference Planning Group.

Science.gov (United States)

Eckel, Robert H; Borra, Susan; Lichtenstein, Alice H; Yin-Piazza, Shirley Y

2007-04-24

A 2-day forum was convened to discuss the current status and future implications of reducing trans fatty acids without increasing saturated fats in the food supply while maintaining functionality and consumer acceptance of packaged, processed, and prepared foods. Attendees represented the agriculture and oilseed industry and oil processing, food manufacturing, food service, government, food technology, and health and nutrition disciplines. Presentations included food science behind fatty acid technology, the health science of dietary fatty acids, alternatives to trans fatty acids, and the use of alternatives in food manufacturing and food service. The reduction of trans fatty acids in the food supply is a complex issue involving interdependent and interrelated stakeholders. Actions to reduce trans fatty acids need to carefully consider both intended and unintended consequences related to nutrition and public health. The unintended consequence of greatest concern is that fats and oils high in saturated fats, instead of the healthier unsaturated fats, might be used to replace fats and oils with trans fatty acids. Many different options of alternative oils and fats to replace trans fatty acids are available or in development. Decisions on the use of these alternatives need to consider availability, health effects, research and development investments, reformulated food quality and taste, supply-chain management, operational modifications, consumer acceptance, and cost. The conference demonstrated the value of collaboration between the food industry and health and nutrition professionals, and this conference model should be used to address other food development, processing, and/or technology issues.

Synthesis and characterization of technetium(III) complexes containing 2,2'-bipyridine and 1,10-phenanthroline. X-ray crystal structures of cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(bpy)]B(C6H5)4, cis (Cl),trans(P)-[TcCl2(P(CH3)2C6H5)2(phen)]B(C6H5)4, and cis (Cl),trans(P)-[TcCl2(P(CH3CH2)(C6H5)2)2(bpy)]SO3CF3

International Nuclear Information System (INIS)

Wilcox, B.E.; Ho, D.M.; Deutsch, E.

1989-01-01

Technetium(III) complexes of the general formula cis(Cl),trans(P)-[TcCl 2 (P) 2 L] + , where (P) is dimethylphenylphosphine (PMe 2 Ph) or ethyldiphenylphosphine (PEtPh 2 ) and L is 2,2'-bipyridine (bpy), 4,4'-dimethyl-2,2'-bipyridine (Me 2 bpy), or 1,10-phenanthroline (phen), have been synthesized and characterized. They are prepared by L substitution onto, with concomitant displacement of one chloride and one phosphine ligand from, the mer-TcCl 3 (P) 3 starting material in refluxing ethanol. Analysis of these complexes by fast atom bombardment mass spectrometry (in the positive ion mode) provides fingerprint mass spectra that exhibit peaks assigned to the molecular ion M + as well as peaks assigned to M + minus one or more monodentate ligands. Results of single-crystal x-ray structure determinations of cis(Cl),trans(P)-[TcCl 2 (PMe 2 Ph) 2 (bpy)]BPh 4 (A), cis(Cl),trans(P)-[TcCl 2- (PMe 2 Ph) 2 (phen)]BPh 4 (B), and cis(Cl),trans(P)-[TcCl 2 (PEtPh 2 ) 2 (bpy)]SO 3 CF 3 (C), with formula weights of 921.62, 945.64, and 903.65, respectively are reported. 26 refs., 5 figs., 5 tabs

Spectroscopic manifestation of trans- effect in tungsten (6) octahedral complexes

Energy Technology Data Exchange (ETDEWEB)

Buslaev, Yu A; Tsivadze, A Yu; Kharitonov, Yu Ya; Kokunov, Yu V; Gustyakova, M P [AN SSSR, Moscow. Inst. Obshchej i Neorganicheskoj Khimii

1977-10-01

The vibration spectra are studied of the following WOF/sub 4/ acetonitrile solutions in the presence of L ligands: formamide, acetamide, propioamide, butyric acid amide, dimethyl formamide, dimethyl acetamide, oxymethyl nicotinamide, diethyl nicotinamide, benzamide, salicylic acid amide, acetal acetamide, hydrorubean acid, hexamethyl phosphorus triamide, tetramethyl urea, TBP, DMSO and diethyl amine, molar ratio of WOF/sub 4/:L = 1:1. Infrared absorption spectra (400-4000 cm/sup -1/) and combination scattering spectra (50-4000 cm/sup -1/) were recorded. A decline in the vibration frequency ..nu..(WO) was caused by a lesser strength constant in the WO bond during exchange of CH/sub 3/CN for L. A slight weakening of the WO bond depending on the nature of the trans-ligands of L on the L-W-O coordinate is representative of the trans-effect of coordinated ligands in the octahedral complexes of tungsten, WOF/sub 4/xL.

Trans-sphenoidal encephalocele in association with Dandy-Walker complex and cardiovascular anomalies

Energy Technology Data Exchange (ETDEWEB)

Joy, H.M.; Barker, C.S. [Wessex Neurological Centre, Southampton (United Kingdom); Small, J.H. [Dept. of Radiology, Royal Bournemouth Hospital (United Kingdom); Armitage, M. [Bournemouth Diabetes and Endocrine Centre, Royal Bournemouth Hospital (United Kingdom)

2001-01-01

We present a case of trans-sphenoidal encephalomeningocele in association with a posterior cranial fossa malformation which fulfils the criteria for the Dandy-Walker complex. Congenital cardiovascular defects were also present. An abnormality of neural crest development may be responsible for the combined occurrence of these anomalies. (orig.)

Acetylcholinesterase Inhibition and Antioxidant Activity of N-trans-Caffeoyldopamine and N-trans-Feruloyldopamine

Directory of Open Access Journals (Sweden)

Muamer Dizdar

2018-04-01

Full Text Available Phenolic acids and their derivatives found in nature are well-known for their potential biological activity. In this study, two amides derived from trans-caffeic/ferulic acid and dopamine were synthesized and characterized by Fourier-transform infrared spectroscopy (FTIR, mass spectrometry, proton and carbon-13 nuclear magnetic resonance spectroscopy. The compounds were tested for the inhibition of acetylcholinesterase (AChE from Electrophorus electricus and for antioxidant activity by scavenging 2,2-diphenyl-1-pycrylhydrazyl free radical (DPPH• and 2,2′-azinobis(3-ethylbenzothiazoline-6-sulphonic acid radical cation (ABTS•+, reducing ferric ions, and ferrous ions chelation. N-trans-Feruloyldopamine displayed the highest inhibitory effect on AChE with half-maximal inhibitory concentration (IC50 values of 8.52 μM. In addition, an in silico study was done to determine the most favorable AChE cluster with the synthesized compounds. Further, these clusters were investigated for binding positions at the lowest free binding energy. Both synthesized hydroxycinnamates were found to be better antioxidants than the parent acids in in vitro tests applied. N-trans-Caffeoyldopamine showed the best antioxidant activity in the three tested methods—against non-biological stable free radicals IC50 5.95 μM for DPPH•, 0.24 μM for the ABTS•+ method, and for reducing power (ascorbic acid equivalent (AAE 822.45 μmol/mmol—while for chelation activity against Fe2+ ions N-trans-feruloyldopamine had slightly better antioxidant activity (IC50 3.17 mM.

Using Ion Exchange Chromatography to Separate and Quantify Complex Ions

Science.gov (United States)

Johnson, Brian J.

2014-01-01

Ion exchange chromatography is an important technique in the separation of charged species, particularly in biological, inorganic, and environmental samples. In this experiment, students are supplied with a mixture of two substitution-inert complex ions. They separate the complexes by ion exchange chromatography using a "flash"…

Photogeneration of metastable side-on N2 linkage isomers in [Ru(NH3)5N2]Cl2, [Ru(NH3)5N2]Br2 and [Os(NH3)5N2]Cl2.

Science.gov (United States)

Schaniel, Dominik; Woike, Theo; Delley, Bernard; Boskovic, Colette; Güdel, Hans-Ueli

2008-09-28

Photogeneration of side-on N2 linkage isomers in [Ru(NH3)5N2]2+ and [Os(NH3)5N2]2+ is achieved by irradiation with lambda = 325 nm of powder samples at T = 80 K and detected by the downshift of the nu(N-N) vibration and by the heat release at elevated temperature due to the back switching of the side-on configuration to the ground state. The concentration of the transferred molecules is evaluated by the decrease of the area of the nu(N-N) or 2nu(N-N) vibrational bands. All characteristic changes between the linear Ru-N-N and side-on configuration are predicted by DFT calculations: the structure of the anion, shifts of the vibrations, electronic excitation energy, energetic position and sequence of the electronic orbitals, the potentials of the ground and relaxed metastable state with the activation energy, saddle points and energetic position of the minimum.

Electrochemical Sensing of Casein Based on the Interaction between Its Phosphate Groups and a Ruthenium(III) Complex.

Science.gov (United States)

Inaba, Iku; Kuramitz, Hideki; Sugawara, Kazuharu

2016-01-01

A reaction to casein, along with β-lactoglobulin, is a main cause of milk allergies, and also is a useful indicator of protein in allergic analyses. In the present study, a simple casein sensor was developed based on the interaction between a phosphate group of casein and electroactive [Ru(NH3)6](3+). We evaluated the voltammetric behavior of a casein-[Ru(NH3)6](3+) complex using a glassy carbon electrode. When the ruthenium(III) complex was combined with the phosphate groups of casein, the structure of the casein was changed. Since the hydrophobicity of casein was increased due to the binding, the casein was adsorbed onto the electrode. Furthermore, we modified an electrode with a ruthenium(III) ions/collagen film. When the sensor was applied to the detection of the casein contained in milk, the values coincided with those indicated by the manufacturer. Accordingly, this electrode could be a powerful sensor for the determination of casein in several foods.

Ion pairing of radical ions of aromatic alkenes and alkynes studied by pulse radiolysis

International Nuclear Information System (INIS)

Yamamoto, Satoshi; Yamamoto, Yukio; Hayashi, Koichiro

1991-01-01

Pulse radiolysis of 1,2-dichloroethane solutions of trans,trans-1,4-bis(2-phenylethenyl)benzene and 1,4-bis(2-phenylethynyl)benzene was undertaken in the presence of Bu 4 NPF 6 (Bu=butyl) to investigate the effect of ion pairing of the solute radical cations with PF 6 - . It was also undertaken for the tetrahydrofuran solutions of the above compounds in the presence of Bu 4 NPF 6 and NaBPh 4 , where the solute radical anions are generated and form ion pairs with Bu 4 N + and Na + . The decay of the radical ions, which is due to neutralization, is retarded by the ion pairing. The rate constants for the neutralization reactions in the free-ion and ion-paired states were determined. Also presented are the data for the radical ions of trans-stilbene, diphenylacetylene, trans,trans-1,4-diphenyl-1,3-butadiene, and diphenylbutadiene. The radical ions of the aromatic alkynes are less stabilized by the ion pairing than those of the aromatic alkenes having the same carbon skeletons probably because of more extensive charge delocalization of the former radical ions. Spectral shifts to shorter wavelengths caused by the ion pairing are appreciable for the radical anions. Dependence of the spectral shifts on the size of the radical anions is described. (author)

"There's no chasing involved": cis/trans relationships, "tranny chasers," and the future of a sex-positive trans politics.

Science.gov (United States)

Tompkins, Avery Brooks

2014-01-01

This article adds to a small, but growing, body of work on trans sexualities and partnerships, and provides a much-needed inquiry into the complex and contested politics of desire when we take trans identities, bodies, and sexualities into account. Using digital ethnographic data from YouTube videos along with in-person observational data from LGBTQ and trans conferences in the U.S., Tompkins argues that a sex-positive trans politics cannot emerge in trans and trans-allied communities if the rhetoric of the "tranny chaser" continues to inform discourses of desire and attraction to trans people.

Thiolato-technetium complexes. 5. Synthesis, characterization, and electrochemical properties of bis(o-phenylenebis(dimethylarsine))technetium(II) and -technetium(III) complexes with thiolato ligands. Single-crystal structural analyses of trans-[Tc(SCH3)2(DIARS)2]PF6 and trans-[Tc(SC6H5)2(DIARS)2]0

International Nuclear Information System (INIS)

Konno, Takumi; Heineman, W.R.; Deutsch, E.; Kirchhoff, J.R.; Heeg, M.J.; Stuckey, J.A.

1992-01-01

Three different thiols have been brought into reaction with trans-[Tc(OH)(O)(DIARS) 2 ] 2+ to produce initially the Tc(II) complex, [Tc(SR) 2 (DIARS) 2 ] 0 , which can be oxidized to the Tc(III) complex, [Tc(SR) 2 (DIARS) 2 ] + (DIARS = o-phenylenebis(dimethylarsine)). In the case of SR = SCH 3 and SCH 2 C 6 H 5 , the Tc(II) and Tc(III) products were found to be in the trans geometry, while for SR = SC 6 H 5 , both cis and trans isomers were generated. Two of the complexes were structurally characterized by X-ray diffraction. trans-[Tc(SCH 3 ) 2 (DIARS) 2 ]PF 6 , chemical formula TcAs 4 S 2 PF 6 C 22 H 38 , crystallizes in the monoclinic space group. The Tc atom occupies an inversion center. Representative elemental analyses, FAB mass spectra, and visible-UV spectra are reported. Electrochemical and spectroelectrochemical measurements were taken on trans-[Tc(SCH 3 ) 2 (DIARS) 2 ] + , trans-[Tc(SCH 2 C 6 H 5 ) 2 (DIARS) 2 ] + , and cis-[Tc(SC 6 H 5 ) 2 (DIARS) 2 ] + , which exhibit a reversible Tc(III/II) redox couple in the range -0.32 to -0.47 V vs. Ag/AgCl. Another redox couple is present in the range -1.22 to -1.70 V; this is ascribed to Tc(II/I) and is reversible only for SR = SCH 2 C 6 H 5 at 20C. At room temperature, chemically irreversible couples are exhibited at ca. +1.0 V for Tc(IV/III)

Therapeutic Targeting of the IL-6 Trans-Signaling/Mechanistic Target of Rapamycin Complex 1 Axis in Pulmonary Emphysema.

Science.gov (United States)

Ruwanpura, Saleela M; McLeod, Louise; Dousha, Lovisa F; Seow, Huei J; Alhayyani, Sultan; Tate, Michelle D; Deswaerte, Virginie; Brooks, Gavin D; Bozinovski, Steven; MacDonald, Martin; Garbers, Christoph; King, Paul T; Bardin, Philip G; Vlahos, Ross; Rose-John, Stefan; Anderson, Gary P; Jenkins, Brendan J

2016-12-15

The potent immunomodulatory cytokine IL-6 is consistently up-regulated in human lungs with emphysema and in mouse emphysema models; however, the mechanisms by which IL-6 promotes emphysema remain obscure. IL-6 signals using two distinct modes: classical signaling via its membrane-bound IL-6 receptor (IL-6R), and trans-signaling via a naturally occurring soluble IL-6R. To identify whether IL-6 trans-signaling and/or classical signaling contribute to the pathogenesis of emphysema. We used the gp130 F/F genetic mouse model for spontaneous emphysema and cigarette smoke-induced emphysema models. Emphysema in mice was quantified by various methods including in vivo lung function and stereology, and terminal deoxynucleotidyl transferase dUTP nick end labeling assay was used to assess alveolar cell apoptosis. In mouse and human lung tissues, the expression level and location of IL-6 signaling-related genes and proteins were measured, and the levels of IL-6 and related proteins in sera from emphysematous mice and patients were also assessed. Lung tissues from patients with emphysema, and from spontaneous and cigarette smoke-induced emphysema mouse models, were characterized by excessive production of soluble IL-6R. Genetic blockade of IL-6 trans-signaling in emphysema mouse models and therapy with the IL-6 trans-signaling antagonist sgp130Fc ameliorated emphysema by suppressing augmented alveolar type II cell apoptosis. Furthermore, IL-6 trans-signaling-driven emphysematous changes in the lung correlated with mechanistic target of rapamycin complex 1 hyperactivation, and treatment of emphysema mouse models with the mechanistic target of rapamycin complex 1 inhibitor rapamycin attenuated emphysematous changes. Collectively, our data reveal that specific targeting of IL-6 trans-signaling may represent a novel treatment strategy for emphysema.

Organodioxygen complexes of some heavy metal ions and their oxygen transfer reactions

International Nuclear Information System (INIS)

Tarafder, M.T.H.; Mei Ling; Gino Mariotto

2003-09-01

Several novel organodioxygen complexes of lanthanide ions, viz., lanthanum(m) and cerium(IV) have been synthesized containing a number of organic co- ligands. The complexes characterized were, [La(0 2 )(det)(N0 3 ) 2 ] (1), [La(O 2 )(tet)(NO 3 ) 2 ] (2), [La(O 2 )(C 5 H 5 N)2NO 3 ] (3), [La(O 2 )(C 6 H 18 N 3 PO) 2 (NO 3 ) 2 ] (4), [La(0 2 )(OPPh 3 ) 2 (N0 3 ) 2 ] (5), [La(O 2 ) 2 (NH 2 CH 2 CH 2 NH 2 ) 2 NO 3 ] (6), [La(O 2 )(PPh 3 ) 2 (NO 3 ) 2 ] (7) and [Ce(O 2 )(C 6 H 18 N 3 PO) 2 (NO 3 ) 3 ] (8). IR and Raman spectra revealed that (3) was a peroxo complex while the others were, in particular, superoxo type. The IR spectrum of (3) gives V 1 (O-O) at 851 cm -1 while the Raman spectra of (4), (5), (7) and (8) give V 1 (O 2 ) bands at 1046 cm -1 , 1032 cm 1 , 1100 cm -1 and 1046 cm -1 , respectively. The oxygen transfer reactions of two selected complexes were carried out under stoichiometric conditions. The complex containing a bidentate ligand, (6), was found to oxidize triphenylphosphine and trans-stilbene to their oxides while the complex containing tridentate ligand (1) was stable and inert towards oxidation. (author)

Complexes of vanadyl and uranyl ions with the chelating groups of humic matter

International Nuclear Information System (INIS)

Goncalves, M.L.S.; Mota, A.M.

1987-01-01

The uranyl and vanadyl complexes formed with salicylic, phthalic and 3,4-dihydroxybenzoic acids have been studied by potentiometry in order to determine the stability constants of the Msub(m) Lsub(n) species formed in solution, and the constants for hydrolysis and polymeric complexes, at 25.0 0 , in 0.10, 0.40 and 0.70M sodium perchlorate. MINIQUAD was used in process the data to find the best models for the species in solution, and calculate the formation constants. The uranyl-salicylic acid sytem was also studied by spectrophotometry and the program SQUAD used to process the data obtained. The best models for these systems show that co-ordination of the uranyl ion by carboxylate groups is easier than for the vanadyl ion, whereas the vanadyl ion seems to form more stable complexes with phenolate groups. Both oxo-cations seem to tend to hydrolyse rather than form complexes when the L:M ratios are greater than unity. Although the change in the constants with ionic strength is small, the activity coefficients of the salicylate and phthalate species have been calculated at ionic strengths 0.40 and 0.70M, along with the interaction parameters with Na + , from the stability constants found for the species ML and H 2 L, according to the Bronsted-Guggenheim expression. (author)

An integrated view of complex landscapes: a big data-model integration approach to trans-disciplinary science

Science.gov (United States)

The Earth is a complex system comprised of many interacting spatial and temporal scales. Understanding, predicting, and managing for these dynamics requires a trans-disciplinary integrated approach. Although there have been calls for this integration, a general approach is needed. We developed a Tra...

Phosphate barrier on pore-filled cation-exchange membrane for blocking complexing ions in presence of non-complexing ions

Science.gov (United States)

Chavan, Vivek; Agarwal, Chhavi; Shinde, Rakesh N.

2018-06-01

In present work, an approach has been used to form a phosphate groups bearing surface barrier on a cation-exchange membrane (CEM). Using optimized conditions, the phosphate bearing monomer bis[2-(methacryloyloxy)ethyl] phosphate has been grafted on the surface of the host poly(ethersulfone) membranes using UV light induced polymerization. The detailed characterizations have shown that less than a micron layer of phosphate barrier is formed without disturbing the original microporous structure of the host membrane. The pores of thus formed membrane have been blocked by cationic-gel formed by in situ UV-initiator induced polymerization of 2-acrylamido-2-methyl-1-propane sulphonic acid along with crosslinker ethylene glycol dimethacrylate in the pores of the membrane. UV-initiator is required for pore-filling as UV light would not penetrate the interior matrix of the membrane. The phosphate functionalized barrier membrane has been examined for permselectivity using a mixture of representative complexing Am3+ ions and non-complexing Cs+ ions. This experiment has demonstrated that complex forming Am3+ ions are blocked by phosphate barrier layer while non-complexing Cs+ ions are allowed to pass through the channels formed by the crosslinked cationic gel.

Synthesis, spectral characterization and biological studies of some organotin(IV) complexes of L-proline, trans-hydroxy- L-proline and L-glutamine

Science.gov (United States)

Nath, Mala; Jairath, Ruchi; Eng, George; Song, Xueqing; Kumar, Ashok

2005-12-01

New organotin(IV) complexes of the general formula R 3Sn(L) (where R = Me, n-Bu and HL = L-proline; R = Me, Ph and HL = trans-hydroxy- L-proline and L-glutamine) and R 2Sn(L) 2 (where R = n-Bu, Ph and HL = L-proline; R = Ph, HL = trans-hydroxy- L-proline) have been synthesized by the reaction of R nSnCl 4- n (where n = 2 or 3) with sodium salt of the amino acid (HL). n-Bu 2Sn(Pro) 2 was synthesized by the reaction of n-Bu 2SnO with L-proline under azeotropic removal of water. The bonding and coordination behavior in these complexes have been discussed on the basis of IR and 119Sn Mössbauer spectroscopic studies in the solid-state. Their coordination behavior in solution has been discussed with the help of multinuclear ( 1H, 13C and 119Sn) NMR spectral studies. The 119Sn Mössbauer and IR studies indicate that L-proline and trans-hydroxy- L-proline show similar coordination behavior towards organotin(IV) compounds. Pentacoordinate trigonal-bipyramidal and hexacoordinate octahedral structures, respectively, have been proposed for the tri- and diorganotin(IV) complexes of L-proline and trans-hydroxy- L-proline, in which the carboxylate group acts as bidentate group. L-Glutamine shows different coordination behavior towards organotin(IV) compounds, it acts as monoanionic bidentate ligand coordinating through carboxylate and amino group. The triorganotin(IV) complexes of L-glutamine have been proposed to have trigonal-bipyramidal environment around tin. The newly synthesized complexes have been tested for their antiinflammatory and cardiovascular activities. Their LD 50 values are >1000 mg kg -1.

Anion-assisted trans-cis isomerization of palladium(II) phosphine complexes containing acetanilide functionalities through hydrogen bonding interactions.

Science.gov (United States)

Lu, Xiao-Xia; Tang, Hau-San; Ko, Chi-Chiu; Wong, Jenny Ka-Yan; Zhu, Nianyong; Yam, Vivian Wing-Wah

2005-03-28

The anion-assisted shift of trans-cis isomerization equilibrium of a palladium(II) complex containing acetanilide functionalities brought about by allosteric hydrogen bonding interactions has been established by UV/Vis, 1H NMR, 31P NMR and ESI-MS studies.

Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

KAUST Repository

Gong, Dirong; Jia, Xiaoyu; Wang, Baolin; Zhang, Xuequan; Huang, Kuo-Wei

2014-01-01

Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

KAUST Repository

Gong, Dirong

2014-09-01

Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

Production and sympathetic cooling of complex molecular ions

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chaobo

2008-06-24

This thesis reports on experimental and theoretical studies of the sympathetic cooling of complex molecular ions demonstrating that this general method for cooling atomic and molecular ions is reliable and efficient. For this purpose, complex molecular ions and barium ions have been confined simultaneously in a linear Paul trap. The complex molecular ions are generated in an electrospray ionization system and transferred to the trap via a 2 m long octopole ion guide. These molecular ions are pre-cooled by room temperature helium buffer gas so that they can be captured by the trap. The atomic barium ions are loaded from a barium evaporator oven and are laser-cooled by a 493 nm cooling laser and a 650 nm repumping laser. Due to the mutual Coulomb interaction among these charged particles, the kinetic energy of the complex molecular ions can be reduced significantly. In our experiments we have demonstrated the sympathetic cooling of various molecules (CO{sub 2}, Alexa Fluor 350, glycyrrhetinic acid, cytochrome c) covering a wide mass range from a few tens to 13000 amu. In every case the molecular ions could be cooled down to millikelvin temperatures. Photo-chemical reactions of the {sup 138}Ba{sup +} ions in the ({sup 2}P{sub 1/2}) excited state with gases such as O{sub 2}, CO{sub 2}, or N{sub 2}O, could be observed. If the initial {sup 138}Ba{sup +} ion ensemble is cold, the produced {sup 138}BaO{sup +} ions are cold as well, with a similar temperature as the laser-cooled barium ions (a few tens of millikelvin). The back-reaction of {sup 138}BaO{sup +} ions with neutral CO to {sup 138}Ba{sup +} is possible and was observed in our experiments as well. A powerful molecular dynamics (MD) simulation program has been developed. With this program dynamic properties of ion ensembles, such as sympathetic interactions or heating effects, have been investigated and experimental results have been analyzed to obtain, for example, ion numbers and temperatures. Additionally, the

Production and sympathetic cooling of complex molecular ions

International Nuclear Information System (INIS)

Zhang, Chaobo

2008-01-01

This thesis reports on experimental and theoretical studies of the sympathetic cooling of complex molecular ions demonstrating that this general method for cooling atomic and molecular ions is reliable and efficient. For this purpose, complex molecular ions and barium ions have been confined simultaneously in a linear Paul trap. The complex molecular ions are generated in an electrospray ionization system and transferred to the trap via a 2 m long octopole ion guide. These molecular ions are pre-cooled by room temperature helium buffer gas so that they can be captured by the trap. The atomic barium ions are loaded from a barium evaporator oven and are laser-cooled by a 493 nm cooling laser and a 650 nm repumping laser. Due to the mutual Coulomb interaction among these charged particles, the kinetic energy of the complex molecular ions can be reduced significantly. In our experiments we have demonstrated the sympathetic cooling of various molecules (CO 2 , Alexa Fluor 350, glycyrrhetinic acid, cytochrome c) covering a wide mass range from a few tens to 13000 amu. In every case the molecular ions could be cooled down to millikelvin temperatures. Photo-chemical reactions of the 138 Ba + ions in the ( 2 P 1/2 ) excited state with gases such as O 2 , CO 2 , or N 2 O, could be observed. If the initial 138 Ba + ion ensemble is cold, the produced 138 BaO + ions are cold as well, with a similar temperature as the laser-cooled barium ions (a few tens of millikelvin). The back-reaction of 138 BaO + ions with neutral CO to 138 Ba + is possible and was observed in our experiments as well. A powerful molecular dynamics (MD) simulation program has been developed. With this program dynamic properties of ion ensembles, such as sympathetic interactions or heating effects, have been investigated and experimental results have been analyzed to obtain, for example, ion numbers and temperatures. Additionally, the feasibility of nondestructive spectroscopy via an optical dipole excitation

[Partitioning of taxifolin-iron ions complexes in octanol-water system].

Science.gov (United States)

Shatalin, Iu V; Shubina, V S

2014-01-01

The composition of taxifolin-iron ions complexes in an octanol-water biphasic system was studied using the method of absorption spectrophotometry. It was found that at pH 5.0 in an aqueous biphasic system the complex of [Tf2 x Fe x (OH)k(H2O)8-k] is present, but at pH 7.0 and 9.0 the complexes of [Tf2 x Fe x (OH)k(H2O)2-k] and [Tf x Fe x OH)k(H2O)4-k] are predominantly observed. The formation of a stable [Tf3 x Fe] complex occurred in octanol phase. The charged iron ion of this complex is surrounded by taxifolin molecules, which shield the iron ion from lipophilic solvent. During transition from water to octanol phase the changes of the composition of complexes are accompanied by reciprocal changes in portion of taxifolin and iron ions in these phases. It was shown that the portion of taxifolin in aqueous solution in the presence of iron ions is increased at high pH values, and the portion of iron ions is minimal at pH 7.0. In addition, the parameters of solubility limits of taxifolin-iron ions complexes in an aqueous solution were determined. The data obtained gain a better understanding of the role of complexation of polyphenol with metal of variable valency in passive transport of flavonoids and metal ions across lipid membranes.

Mass transport and chloride ion complexes in occluded cell

International Nuclear Information System (INIS)

Tsuru, T.; Hashimoto, K.; Nishikata, A.; Haruyama, S.

1989-01-01

Changes in the transport and the concentration of ions in a model occluded cell are traced during galvanostatic anodic polarization of a mild steel and a stainless steel. Apparent transport numbers of anions and cations, which were estimated from chemical analysis of solution, were different from those calculated from known mobility data. At the initial stage of the polarization, the transport number of chloride ion was almost unity, and then decreased gradually. For the mild steel, the concentration of total chloride ion accumulated in the occluded compartment increased with the anodic charge passed, and the amount of chloride ion complexed with cations also increased. The chloride complex was estimated as FeCl + . For SUS304 stainless steel, the total chloride ion increased, however, the free chloride ion, which responded to an Ag/AgCl electrode remained approximately 2 mol/dm 3 . Therefore, most of the chloride ions transferred into the occluded cell formed complex ions, such as CrCl n 3-n . The number of chloride ion coordinated to ferrous and chromic ions was estimated from the data fo mass transport for the case of the mild steel and the stainless steel. (author) 9 refs., 14 figs

PUTAS Y TRANS. ¿ESTÁN LAS MUJERES TRANS EN LAS NARRATIVAS SOBRE LA PROSTITUCIÓN?

Directory of Open Access Journals (Sweden)

Liza García Reyes

2015-06-01

Full Text Available Este artículo evidencia los principales resultados de la investigación cualitativa titulada: Putas y trans. Narrativas sobre mujeres trans en España –desarrollada en 2010–, la cual estudió su presencia en textos académicos sobre prostitución en España, producidos entre los años 2000-2009. El análisis de contenido de 34 narrativas evidenció que las referencias a mujeres trans resulta escasa en ellas, aun siendo ellas quienes tienen mayor presencia en la prostitución, en proporción con las mujeres biológicas. Solo nueve textos mencionan la experiencia trans al interior de la prostitución y, entre estos, el asunto solo aparece asertivamente descrito cuando son las propias mujeres trans quienes escriben. AbstractThis paper shows the results of a qualitative research entitled: Hookers and Trans Women: Narratives about trans women in Spain. This study was developed in 2010 and it is based on presence of trans women in the academic texts of prostitution in Spain produced between 2000 and 2009. The content analysis of thirty four narratives showed that the references to in transsexual women in these texts were few, although they have more presence into prostitution, in relation to the biological women. Only nine texts show an experience of prostitution and among these, transexperience only is described assertively when transsexual women write the texts themselves.

Trans-acting RNAs as molecular probes for monitoring time-dependent structural change of an RNA complex adapting two structures.

Science.gov (United States)

Maeda, Yuri; Furuta, Hiroyuki; Ikawa, Yoshiya

2011-03-01

As dynamic structural changes are pivotal for the functions of some classes of RNA molecule, it is important to develop methods to monitor structural changes in RNA in a time-dependent manner without chemical modification. Based on previous reports that trans-acting RNAs can be used as probes for analysis and control of 3D structures of target RNAs, we applied this method to monitor time-dependent structural changes in RNA. We designed and performed a proof-of-principle study using a simple model RNA complex that adopts two different structures as a target. The time-dependent structural changes in the target RNA were successfully monitored using two trans-acting RNAs, which stably form a ternary complex with the bimolecular target RNA and act as a catalyst to join two RNA fragments of the target complex, respectively. Copyright © 2010 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Synthesis and Crystal Structures of Luminescent Mononuclear Ni(ii and Cd(ii Complexes with 1,10-phenanthroline

Directory of Open Access Journals (Sweden)

Ecaterina Tocana

2017-12-01

Full Text Available New supramolecular systems of Ni(II and Cd(II with 1,10-phenanthroline constructed by non-covalent interactions have been synthesized and characterized by single-crystal X-ray diffractometry. The smaller nickel(II ion forms a cis complex with outer-sphere perchlorates, while the cadmium(II ion forms a trans complex involving inner-sphere perchlorates. Both compoundsrevealintraligand-basedluminescentproperties.

Analysis of Trans Fat in Edible Oils with Cooking Process

Science.gov (United States)

Song, Juhee; Park, Joohyeok; Jung, Jinyeong; Lee, Chankyu; Gim, Seo Yeoung; Ka, HyeJung; Yi, BoRa; Kim, Mi-Ja; Kim, Cho-il

2015-01-01

Trans fat is a unsaturated fatty acid with trans configuration and separated double bonds. Analytical methods have been introduced to analyze trans fat content in foods including infrared (IR) spectroscopy, gas chromatography (GC), Fourier transform-infrared (FT-IR) spectroscopy, reverses-phase silver ion high performance liquid chromatography, and silver nitrate thin layer chromatography. Currently, FT-IR spectroscopy and GC are mostly used methods. Trans fat content in 6 vegetable oils were analyzed and processing effects including baking, stir-frying, pan-frying, and frying on the formation of trans fat in corn oil was evaluated by GC. Among tested vegetable oils, corn oil has 0.25 g trans fat/100 g, whereas other oils including rapeseed, soybean, olive, perilla, and sesame oils did not have detectable amount of trans fat content. Among cooking methods, stir-frying increased trans fat in corn oil whereas baking, pan-frying, and frying procedures did not make changes in trans fat content compared to untreated corn oils. However, the trans fat content was so low and food label can be declared as ‘0’ trans based on the regulation of Ministry of Food ad Drug Safety (MFDS) (edible oil). PMID:26483890

Trans- and cis-2-phenylindole platinum(II) complexes as cytotoxic agents against human breast adenocarcinoma cell lines

Science.gov (United States)

Tomé, Maria; López, Concepción; González, Asensio; Ozay, Bahadir; Quirante, Josefina; Font-Bardía, Mercè; Calvet, Teresa; Calvis, Carme; Messeguer, Ramon; Baldomá, Laura; Badía, Josefa

2013-09-01

The synthesis and characterization of the new 2-phenylindole derivative: C8H3N-2-C6H5-3NOMe-5OMe (3c) and the trans- and cis-isomers of [Pt(3c)Cl2(DMSO)] complexes (4c and 5c, respectively) are described. The crystal structures of 4c·CH2Cl2 and 5c confirm: (a) the existence of a Pt-Nindole bond, (b) the relative arrangement of the Cl- ligands [trans- (in 4c) or cis- (in 5c)] and (c) the anti-(E) configuration of the oxime. The cytotoxic assessment of C8H3N-2-(C6H4-4‧R1)-3NOMe-5R2 [with R1 = R2 = H (3a); R1 = Cl, R2 = H (3b) and R1 = H, R2 = OMe (3c)] and the geometrical isomers of [Pt(L)Cl2(DMSO)] with L = 3a-3c [trans- (4a-4c) and cis- (5a-5c), respectively] against human breast adenocarcinoma cell lines (MDA-MB231 and MCF-7) is also reported and reveals that all the platinum(II) complexes (except 4a) are more cytotoxic than cisplatin in front of the MCF7 cell line. Electrophoretic DNA migration studies of the synthesized compounds in the absence and in the presence of topoisomerase-I have been performed, in order to get further insights into their mechanism of action.

Synthesis, characterization and crystal structure determination of a new Zn(II Schiff base complex derived from condensation of a new asymmetrical tripodal amine, 3-((4-aminobutyl(pyridin-2-ylmethylaminopropan-1-ol and 2-hydroxy-3-methoxybenzaldehyde

Directory of Open Access Journals (Sweden)

Majid Rezaeivala

2017-05-01

Full Text Available A new tripodal amine, 3-((4-aminobutyl(pyridin-2-ylmethylaminopropan-1-ol (HL has been prepared. This has been used to synthesize a new Schiff base complex by template condensation with 2-hydroxy-3-methoxybenzaldehyde in the presence of Zn(II metal ion in methanol. The complex has been characterized using spectroscopic methods and the crystal structure of [ZnL]BF4, L:3-((4-aminobutyl(pyridin-2-ylmethylaminopropan-1-ol was confirmed by single crystal X-ray diffraction studies. Single crystal X-ray structure analysis showed that in the mononuclear Zn(II complex, [ZnL]BF4 the Zn(II ion is in a distorted square pyramidal environment.

Synthesis, crystal structures and thermodynamic properties of two novel lanthanide complexes based on 3,4-diethoxybenzoic acid and 2,2′-bipyridine

International Nuclear Information System (INIS)

Jin, Cheng-Wei; Wang, Ye; Ren, Ning; Geng, Li-Na; Zhang, Jian-Jun

2016-01-01

Highlights: • Two novel complexes crystal structures are obtained. • The 1-D chain and 2D layer structures were formed via π–π stacking interactions. • The pathway of thermal decomposition for title complexes were investigated. • The molar heat capacities and thermodynamic functions were calculated. - Abstract: Two binuclear lanthanide complexes [Ln(3,4,-DEOBA) 3 DIPY] 2 DIPY (Ln = Tb (1), Dy (2); 3,4,-DEOBA = 3,4-diethoxybenzoate; DIPY = 2,2′-bipyridine) have been synthesized and characterized. The single crystals of complexes 1 and 2 were obtained. And the two complexes are isostructural with a coordination number of eight to form a distorted square antiprism. Carboxylic groups adopt two modes coordinating with Ln(III) ions: bidentate chelate, and bridging bidentate. Binuclear complexes 1 and 2 are stitched together via π–π stacking interactions to form 1D chain and 2D layer supramolecular structures. The two complexes were characterized by elemental analysis, IR spectra, and powder X-ray diffraction. The luminescence spectra of complexes 1 and 2 show the characteristic emissions of Tb 3+ ( 5 D 4 → 7 F 6-3 ) and Dy 3+ ( 4 F 9/2 → 6 H 15/2 , 6 H 13/2 ). The thermal decomposition mechanisms for title complexes were studied by the technology of TG-FTIR. And the heat capacities of two complexes were measured by DSC in the temperature range from 258.15 to 343.15 K. The smoothed heat capacities and thermodynamic functions for complexes 1 and 2 were calculated by fitted polynomial and thermodynamic equations.

Sequential analysis of trans-SNARE formation in intracellular membrane fusion.

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Kannan Alpadi

2012-01-01

Full Text Available SNARE complexes are required for membrane fusion in the endomembrane system. They contain coiled-coil bundles of four helices, three (Q(a, Q(b, and Q(c from target (t-SNAREs and one (R from the vesicular (v-SNARE. NSF/Sec18 disrupts these cis-SNARE complexes, allowing reassembly of their subunits into trans-SNARE complexes and subsequent fusion. Studying these reactions in native yeast vacuoles, we found that NSF/Sec18 activates the vacuolar cis-SNARE complex by selectively displacing the vacuolar Q(a SNARE, leaving behind a Q(bcR subcomplex. This subcomplex serves as an acceptor for a Q(a SNARE from the opposite membrane, leading to Q(a-Q(bcR trans-complexes. Activity tests of vacuoles with diagnostic distributions of inactivating mutations over the two fusion partners confirm that this distribution accounts for a major share of the fusion activity. The persistence of the Q(bcR cis-complex and the formation of the Q(a-Q(bcR trans-complex are both sensitive to the Rab-GTPase inhibitor, GDI, and to mutations in the vacuolar tether complex, HOPS (HOmotypic fusion and vacuolar Protein Sorting complex. This suggests that the vacuolar Rab-GTPase, Ypt7, and HOPS restrict cis-SNARE disassembly and thereby bias trans-SNARE assembly into a preferred topology.

Few atom chemistry of the trans actinide element rutherfordium (Rf)

International Nuclear Information System (INIS)

Nagame, Y.

2002-01-01

Studies of chemical properties of the trans actinide elements - starting with element 104 (Rf) - offer the unique opportunity to obtain information about trends in the Periodic Table at the limits of nuclear stability and to assess the magnitude of the influence of relativistic effects on chemical properties. To explore experimentally the influence of relativistic effects of electron shell structure, we study the chemical properties of the trans actinide elements. So far, we have developed some experimental apparatuses for the study of chemical properties of the trans actinide elements: a beam-line safety system for the usage of the gas-jet coupled radioactive 248 Cm target chamber for the production of trans actinides, a rotating wheel catcher apparatus for the measurement of α particles and spontaneous fission decay of trans actinides and an automated rapid chemical separation apparatus based on high performance liquid chromatography. The trans actinide nuclide, the element 104, 261 Rf (t 1/2 = 78 s) has been successfully produced via the reactions of 248 Cm( 18 O,5n) at the JAERI (Japan Atomic Energy Research Institute) tandem accelerator. The evaluated production cross section was about 10 nb, indicating that the production rate was approximately 2 atoms per min. Because of the short half-life and the low production rate of Rf, each atom produced decays before a new atom is synthesized. It means that any chemistry to be performed must be done on an 'atom-at-a-time' basis. Therefore rapid, very efficient and selective chemical procedures are indispensable to isolate the desired trans actinide 261 Rf. To perform fast and repetitive ion-exchange separation of Rf, we have developed the apparatus AIDA (Automated Ion exchange separation system coupled with the Detection apparatus for Alpha spectroscopy). Recently, ion-exchange behavior of Rf in acidic solutions has been studied with AIDA, and the results indicate that anion-exchange behavior of Rf is quite similar

Nitric oxide production by visible light irradiation of aqueous solution of nitrosyl ruthenium complexes.

Science.gov (United States)

Sauaia, Marília Gama; de Lima, Renata Galvão; Tedesco, Antonio Claudio; da Silva, Roberto Santana

2005-12-26

[Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](PF(6))(5) (L is NH(3), py, or 4-acpy) was prepared with good yields in a straightforward way by mixing an equimolar ratio of cis-[Ru(NO(2))(bpy)(2)(NO)](PF(6))(2), sodium azide (NaN(3)), and trans-[RuL(NH(3))(4)(pz)] (PF(6))(2) in acetone. These binuclear compounds display nu(NO) at ca. 1945 cm(-)(1), indicating that the nitrosyl group exhibits a sufficiently high degree of nitrosonium ion (NO(+)). The electronic spectrum of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex in aqueous solution displays the bands in the ultraviolet and visible regions typical of intraligand and metal-to-ligand charge transfers, respectively. Cyclic voltammograms of the binuclear complexes in acetonitrile give evidence of three one-electron redox processes consisting of one oxidation due to the Ru(2+/3+) redox couple and two reductions concerning the nitrosyl ligand. Flash photolysis of the [Ru(II)L(NH(3))(4)(pz)Ru(II)(bpy)(2)(NO)](5+) complex is capable of releasing nitric oxide (NO) upon irradiation at 355 and 532 nm. NO production was detected and quantified by an amperometric technique with a selective electrode (NOmeter). The irradiation at 532 nm leads to NO release as a consequence of a photoinduced electron transfer. All species exhibit similar photochemical behavior, a feature that makes their study extremely important for their future application in the upgrade of photodynamic therapy in living organisms.

trans-Methylpyridine cyclen versus cross-bridged trans-methylpyridine cyclen. Synthesis, acid-base and metal complexation studies (metal = Co2+, Cu2+, and Zn2+).

Science.gov (United States)

Bernier, Nicolas; Costa, Judite; Delgado, Rita; Félix, Vítor; Royal, Guy; Tripier, Raphaël

2011-05-07

The synthesis of the cross-bridged cyclen CRpy(2) {4,10-bis((pyridin-2-yl)methyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane}, a constrained analogue of the previously described trans-methylpyridine cyclen Cpy(2) is reported. The additional ethylene bridge confers to CRpy(2) proton-sponge type behaviour which was explored by NMR and potentiometric studies. Transition metal complexes have been synthesized (by complexation of both ligands with Co(2+), Cu(2+) and Zn(2+)) and characterized in solution and in the solid state. The single crystal X-ray structures of [CoCpy(2)](2+), [CuCpy(2)](2+) and [ZnCpy(2)](2+) complexes were determined. Stability constants of the complexes, including those of the cross-bridged derivative, were determined using potentiometric titration data and the kinetic inertness of the [CuCRpy(2)](2+) complex in an acidic medium (half-life values) was evaluated by spectrophotometry. The pre-organized structure of the cross-bridged ligand imposes an additional strain for the complexation leading to complexes with smaller thermodynamic stability in comparison with the related non-bridged ligand. The electrochemical study involving cyclic voltammetry underlines the importance of the ethylene cross-bridge on the redox properties of the transition metal complexes.

Studies on mixed ligand complexes of lanthanide (III) ions

International Nuclear Information System (INIS)

Rajendran, G.; Usha Devi, K.G.

2002-01-01

As part of our research programme, we have prepared and characterized a few nitrato, thiocyanato and perchlorato complexes of lanthanide(III) ions with ligands, viz., a Schiff base derived from p-anisidine and vanillin and diphenyl sulphoxide. The complexes were characterized by the measurement of electrical conductances and magnetic susceptibilities, molecular mass and metal percentage and spectral analysis. The thermal decompositions were studied by TG and DTG techniques. The thiocyanato complexes were prepared by substitution method from nitrato complexes. p-Anisidine-vanillin (HDDA) and diphenyl sulphoxide (DPSO) are coordinated to the metal ion in unidentate fashion. All the anions were involved in coordination in these complexes. Thus they were found to have non- electrolytic behaviour with composition [Ln(HDDA) 2 (DPSO)X 3 ] where X = NO 3 ) or SCN perchlorato complexes were prepared from metal perchlorate as done in the case of nitrato complexes. They were found to have electrical conductance which corresponds to 1 : 1 electrolyte. Hence one of the perchlorate ions is outside the coordination sphere. The composition of this complex is found to be [Ln(HDDA) 3 (DPSO)(ClO 4 ) 2 ]ClO 4 . (author)

Resolution of limonene 1,2-epoxide diastereomers by mercury(II) ions

NARCIS (Netherlands)

Werf, M. van der; Jongejan, H.; Franssen, M.C.R.

2001-01-01

When HgCl2 was added to a diastereomeric mixture of cis- and trans-(4S)-limonene 1,2-epoxide, the Hg(II) ions stereoselectively complexed to the cis epoxide, enabling ring opening by water. The resulting mercuric salt could be demetalated by treatment with NaBH4, giving a mixture of diastereomeric

Target-induced formation of gold amalgamation on DNA-based sensing platform for electrochemical monitoring of mercury ion coupling with cycling signal amplification strategy.

Science.gov (United States)

Chen, Jinfeng; Tang, Juan; Zhou, Jun; Zhang, Lan; Chen, Guonan; Tang, Dianping

2014-01-31

Heavy metal ion pollution poses severe risks in human health and environmental pollutant, because of the likelihood of bioaccumulation and toxicity. Driven by the requirement to monitor trace-level mercury ion (Hg(2+)), herein we construct a new DNA-based sensor for sensitive electrochemical monitoring of Hg(2+) by coupling target-induced formation of gold amalgamation on DNA-based sensing platform with gold amalgamation-catalyzed cycling signal amplification strategy. The sensor was simply prepared by covalent conjugation of aminated poly-T(25) oligonucleotide onto the glassy carbon electrode by typical carbodiimide coupling. Upon introduction of target analyte, Hg(2+) ion was intercalated into the DNA polyion complex membrane based on T-Hg(2+)-T coordination chemistry. The chelated Hg(2+) ion could induce the formation of gold amalgamation, which could catalyze the p-nitrophenol with the aid of NaBH4 and Ru(NH3)6(3+) for cycling signal amplification. Experimental results indicated that the electronic signal of our system increased with the increasing Hg(2+) level in the sample, and has a detection limit of 0.02nM with a dynamic range of up to 1000nM Hg(2+). The strategy afforded exquisite selectivity for Hg(2+) against other environmentally related metal ions. In addition, the methodology was evaluated for the analysis of Hg(2+) in spiked tap-water samples, and the recovery was 87.9-113.8%. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis, Photophysical and Electrochemical Properties of a Mixed Bipyridyl-Phenanthrolyl Ligand Ru(II Heteroleptic Complex Having trans-2-Methyl-2-butenoic Acid Functionalities

Directory of Open Access Journals (Sweden)

Adewale O. Adeloye

2011-09-01

Full Text Available In this work, two ligands: 4-(trans-2-Methyl-2-butenoic acid-2,2'-bipyridine (L1 and 5-(trans-2-methyl-2-butenoic acid-1,10-phenanthroline (L2, with the corresponding mixed-ligand heteroleptic Ru(II complex were synthesized and characterized by FT-IR, 1H-, 13C-NMR spectroscopy and elemental analysis. The influence of the mixed functionalized polypyridyl ruthenium(II complex on the photophysical and electrochemical properties were investigated and compared to individual single-ligand homoleptic complexes. Interestingly, the mixed-ligand complex formulated as [RuL1L2(NCS2] exhibits broad and intense metal-to-ligand charge transfer (MLCT absorption with a high molar extinction coefficient (λmax = 514 nm, ε = 69,700 M−1 cm−1, better than those of individual single-ligand complexes, [Ru(L12(NCS2] and [Ru(L22(NCS2], and a strong photoluminescence intensity ratio in the red region at λem = 686 nm. The electrochemical properties of the complex indicated that the redox processes are ligand-based.

Metal ion-improved complexation countercurrent chromatography for enantioseparation of dihydroflavone enantiomers.

Science.gov (United States)

Han, Chao; Wang, Wenli; Xue, Guimin; Xu, Dingqiao; Zhu, Tianyu; Wang, Shanshan; Cai, Pei; Luo, Jianguang; Kong, Lingyi

2018-01-12

Cu(II) ion was selected as an additive to improve the enantioseparation efficiency of three dihydroflavone enantiomers in high-speed counter-current chromatography (HSCCC), using hydroxypropyl-β-cyclodextrin (HP-β-CyD) as the chiral selector. The influences of important parameters, including the metal ion, the concentrations of HP-β-CyD and the Cu(II) ion, and the sample size were investigated. Under optimal conditions, three dihydroflavone enantiomers, including (±)-hesperetin, (±)-naringenin, and (±)-farrerol, were successfully enantioseparated. The chiral recognition mechanism was investigated. The enantioseparation was attributed to the different thermodynamic stabilities of the binary complexes of HP-β-CyD and (±)-hesperetin, and Cu(II) ion could enhance this difference by forming ternary complexes with the binary complexes. This Cu(II) ion-improved complexation HSCCC system exhibited improved performance for chiral separation, and therefore it has great application potential in the preparative enantioseparation of other compounds with similar skeletons. Copyright © 2017 Elsevier B.V. All rights reserved.

New polymer-supported ion-complexing agents: Design, preparation and metal ion affinities of immobilized ligands

International Nuclear Information System (INIS)

Alexandratos, Spiro D.

2007-01-01

Polymer-supported reagents are comprised of crosslinked polymer networks that have been modified with ligands capable of selective metal ion complexation. Applications of these polymers are in environmental remediation, ion chromatography, sensor technology, and hydrometallurgy. Bifunctional polymers with diphosphonate/sulfonate ligands have a high selectivity for actinide ions. The distribution coefficient for the uranyl ion from 1 M nitric acid is 70,000, compared to 900 for the monophosphonate/sulfonate polymer and 200 for the sulfonic acid ion-exchange resin. A bifunctional trihexyl/triethylammonium polymer has a high affinity and selectivity for pertechnetate and perchlorate anions from groundwater. In one example, its distribution coefficient for perchlorate ions in the presence of competing anions is 3,300,000, compared to 203,180 for a commercially available anion-exchange resin. Polystyrene modified with N-methyl-D-glucamine ligands is capable of selectively complexing arsenate from groundwater. It complexes 99% of the arsenate present in a solution of 100 mg/L arsenate with 560 mg/L sulfate ions. Its selectivity is retained even in the presence of 400 mg/L phosphate. There is no affinity for arsenate above pH 9, allowing for the polymer to be regenerated with moderate alkali solution. In studies aimed at developing a Hg(II)-selective resin, simple amine resins were found to have a high Hg(II) affinity and that affinity is dependent upon the solution pH and the counterion

Electronic communication in phosphine substituted bridged dirhenium complexes - clarifying ambiguities raised by the redox non-innocence of the C4H2- and C4-bridges.

Science.gov (United States)

Li, Yan; Blacque, Olivier; Fox, Thomas; Luber, Sandra; Polit, Walther; Winter, Rainer F; Venkatesan, Koushik; Berke, Heinz

2016-04-07

The mononuclear rhenium carbyne complex trans-[Re(C[triple bond, length as m-dash]CSiMe3)([triple bond, length as m-dash]C-Me)(PMe3)4][PF6] (2) was prepared in 90% yield by heating a mixture of the dinitrogen complex trans-[ReCl(N2)(PMe3)4] (1), TlPF6, and an excess of HC[triple bond, length as m-dash]CSiMe3. 2 could be deprotonated with KOtBu to the vinylidene complex trans-[Re(C[triple bond, length as m-dash]CSiMe3)([double bond, length as m-dash]C[double bond, length as m-dash]CH2)(PMe3)4] (3) in 98% yield. Oxidation of 3 with 1.2 equiv. of [Cp2Fe][PF6] at -78 °C gave the Cβ-C'β coupled dinuclear rhenium biscarbyne complex trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[triple bond, length as m-dash]C-CH2-CH2-C[triple bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)][PF6]2 (5) in 92% yield. Deprotonation of 5 with an excess of KOtBu in THF produced the diamagnetic trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[double bond, length as m-dash]C[double bond, length as m-dash]CH-CH[double bond, length as m-dash]C[double bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)] complex (E-6(S)) in 87% yield with an E-butadienediylidene bridge. Density functional theory (DFT) calculations of E-6(S) confirmed its singlet ground state. The Z-form of 6 (Z-6(S)) could not be observed, which is in accord with its DFT calculated 17.8 kJ mol(-1) higher energy. Oxidation of E-6 with 2 equiv. of [Cp2Fe][PF6] resulted in the stable diamagnetic dicationic trans-[(Me3SiC[triple bond, length as m-dash]C)(PMe3)4Re[triple bond, length as m-dash]C-CH[double bond, length as m-dash]CH-C[triple bond, length as m-dash]Re(PMe3)4(C[triple bond, length as m-dash]CSiMe3)][PF6]2 complex (E-6[PF6]2) with an ethylenylidene dicarbyne structure of the bridge. The paramagnetic mixed-valence (MV) complex E-6[PF6] was obtained by comproportionation of E-6(S) and E-6[PF6]2 or by oxidation of E-6(S) with 1 equiv. of [Cp2Fe][PF6]. The

Synthesis and characterization of templated ion exchange resins for the selective complexation of actinide ions. 1998 annual progress report

International Nuclear Information System (INIS)

Murray, G.M.; Uy, O.M.

1998-01-01

'The purpose of this research is to develop polymeric extractants for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions (lakes, streams, waste tanks and body fluids). Selectivity for a specific actinide ion is obtained by providing polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide metal ion. These cavity-containing polymers will be produced using a specific actinide ion (or surrogate) as a template around which monomeric complexing ligands will be polymerized. The polymers will provide useful sequestering agents for removing actinide ions from wastes and will form the basis for a variety of analytical techniques for actinide determinations.'

Combining results of two GC separations partly achieves determination of all cis and trans 16:1, 18:1, 18:2 and 18:3 except CLA isomers of milk fat as demonstrated using Ag-ion SPE fractionation.

Science.gov (United States)

Kramer, John K G; Hernandez, Marta; Cruz-Hernandez, Cristina; Kraft, Jana; Dugan, Michael E R

2008-03-01

Milk fat is a complex mixture of geometric and positional isomers of monounsaturated and polyunsaturated, including short-, long- and branch-chain fatty acids (FAs). There has been partial success to resolve this mixture of FAs using different GC temperature programs, or a combination of GC isothermal and temperature programs. To overcome the problem associated with overlapping isomers prior silver-ion separation was recommended. However, this procedure is time consuming and not practical for routine analysis. In addition, previous methods focused mainly on the trans and cis isomers of 18:1. The present method takes advantage of differences in the relative elution times between different types of FAs. The method involved analyzing each milk fat using the same highly polar 100-m capillary column and GC instrument, and conducting two separations using temperature programs that plateau at 175 and 150 degrees C. The relative shift among the geometric and positional isomers at these two temperature settings was enough to permit identification of most of the trans and cis 16:1, 18:1 and 20:1, the c/t-18:2 and the c/c/t-18:3 isomers found in milk fat. The identity of these FAs was confirmed by prior separation of the total fatty acid methyl esters (FAMEs) of milk fat using Ag(+)-SPE columns, and comparing the fractions to the total milk fat. The Ag(+)-SPE technique was modified to obtain pure saturated, trans- and cis-monounsaturated and diunsaturated FAMEs. By combining the results from these two separate GC analyses, knowing the elution order, it was possible to determine most of the geometric and positional isomers of 16:1, 18:1, 20:1, 18:2 and 18:3 without a prior silver-ion separation. Only few minor FAs could not be resolved, notable the conjugated linoleic acid isomers that still required the complimentary Ag(+)-HPLC separation. The two GC temperature programs have been successfully used to routinely analyze most FA isomers in total milk and beef fats in about 200

Polarographic investigation of complexing kinetics of polyacrylate anions with cadmium ions

International Nuclear Information System (INIS)

Avlyanov, Zh.K.; Kabanov, N.M.; Zezin, A.B.; Askarov, M.A.

1990-01-01

The processes which occur during the reduction of cadmium ions from polymer-metallic complexes (PMC) are studied for the purposes of polarographic investigation of complexing kinetics of polyacrylate anions (PAA) of different molecular masses with cadmium ions in KCl aqueous solutions. An expression is derived for establishing semiwave potential. PMC formation and dissociation reduction rate constants are calculated. It is shown that intramolecular reorderings required for the formation of a two-coordinate complex proceed much slower as compared to the diffusion of free ions

Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl₃(C₂H₄)^- with Heavier Halides (Br^–, I^- )

Energy Technology Data Exchange (ETDEWEB)

Hou, Gao-Lei [Physical; Govind, Niranjan [Environmental; Xantheas, Sotiris S. [Advanced; Department; Wang, Xue-Bin [Physical

2018-01-16

Four new Zeise’s family ions with mixed-halide ligands, i.e., PtCl_nX_3-n(C₂H₄)^- (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl₃(C₂H₄) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl₃) > 4.56 (–Cl₂Br) > 4.53 (–ClBr₂) > 4.34 (–Cl₂I) > 4.30 eV (–ClI₂). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl₂X, and the trans-isomer for –ClX₂ slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.

Repair pathways for heavy ion-induced complex DNA double strand breaks

International Nuclear Information System (INIS)

Yajima, Hirohiko; Nakajima, Nakako; Hirakawa, Hirokazu; Murakami, Takeshi; Okayasu, Ryuichi; Fujimori, Akira

2012-01-01

DNA double strand break (DSB) induced by ionizing radiation (IR) is a deleterious damage leading to cell death and genome instability if not properly repaired. It is well known that DSB is repaired by two major pathways, non-homologous end-joining (NHEJ) and homologous recombination (HR). It is also known that NHEJ is dominant throughout the cell cycle after X- or gamma-ray irradiation in mammalian cells, Meanwhile, it is thought that heavy-ion radiation (e.g., carbon-ions, iron-ions) gives rise to clustered DNA damages consisting of not only strand breaks but also aberrant bases in the vicinity of DSBs (complex DSBs). Our previous work suggested that the efficiency of NHEJ is diminished for repair of complex DSBs induced by heavy-ion radiation. We thought that this difficulty in NHEJ process associated with heavy ion induced complex DNA damage might be extended to HR process in cells exposed to heavy ions. In order to find out if this notion is true or not, exposed human cells to X-rays and heavy-ions, and studied HR associated processes at the molecular level. Our result indicates that complex DSBs induced by heavy ions effectively evoke DNA end resection activity during the HR process. Together with our results, a relevant recent progress in the field of DNA DSB repair will be discussed. (author)

Shifting Paradigms: Moving beyond "Trans 101" in Sexuality Education

Science.gov (United States)

Green, Eli R.

2010-01-01

Trans-inclusive sexuality education can be complex, confusing, and outright intimidating for even the most seasoned sexuality educator to teach. Historically, standalone "Trans 101" sessions have successfully raised awareness about the highly marginalized transgender community. However, their potential success has been limited by being taught in…

A heavy ion linac complex for RI beams

International Nuclear Information System (INIS)

Arai, Shigeaki

1995-01-01

A heavy ion linac complex for RI-beams has been under construction since fiscal year 1992 at INS. The linac complex comprises following accelerating structures: a 25.5-MHz split coaxial RFQ (SCRFQ), a 51-MHz interdigital-H (IH) linac, and a 25.5-MHz rebuncher cavity. The SCRFQ with modulated vanes accelerates ions with a charge-to-mass ratio (q/A) greater than 1/30 from 2 to 170 keV/u. The IH linac comprises four cavities and three magnetic quadrupole triplets placed between cavities, accelerates ions with q/A≥1/10, and varies the output energy continuously in the range 0.17 ∼1.05 MeV/u. The rebuncher cavity with six accelerating gaps is a double coaxial λ/4 resonator, and the total accelerating voltage is 200 kV. (author)

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

International Nuclear Information System (INIS)

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-01-01

Highlights: ► The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. ► The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature ► The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. ► A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 × 10 3 J mol −1 . The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

Electron spin resonance and electron spin echo modulation studies of Cu(II) ions in the aluminosilicate chabazite: A comparison of Cu(II) cation location and adsorbate interaction with isostructural silicoaluminophosphate-34

International Nuclear Information System (INIS)

Zamadics, M.; Kevan, L.

1992-01-01

This study focuses on Cu(II) ions exchanged in the aluminosilicate zeolite chabazite. The various Cu(II) species formed after dehydration, rehydration, and exposure to adsorbates are characterized by electron spin resonance and electron spin echo modulation spectroscopies. These results are interpreted in terms of Cu(II) ion location and adsorbate interaction. The results of this study are compared to the results found earlier for SAPO-34, chabazite's structural analog from the silicoaluminophosphate group. In a hydrated sample of chabazite the Cu(II) ions are found to be in a near octahedral environment coordinated to three nonequivalent water molecules and three framework oxygens. The most probable location of the Cu(II) ion in a hydrated sample is above the plane of the six-membered ring slightly displaced into the ellipsoidal cavity. A somewhat similar location and coordination is found for Cu(II) ions in H-SAPO-34. A feature common to both CuH-chabazite and CuH-SAPO-34 is the generation of two distinct Cu(II) species upon dehydration. It is found that Cu(II) cations in chabazite interact with the various adsorbate molecules in a similar manner as Cu(II) cation in H-chabazite and three molecules of ethanol and three propanol molecules. Only the Cu(II) ions located in the hexagonal rings after dehydration were found to complex with ethylene. The differences observed in the interaction of the Cu(II) in with water, propanol, and ehtylene between SAPO-34 and chabazite can be related to the differing cation densities of these two materials. 32 refs., 7 figs., 21 tabs

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Kim, Kwang-Wook, E-mail: nkwkim@kaeri.re.kr [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon [Korea Atomic Energy Research Institute, 1045 Daedeok daero, Yuseong, Daejeon 305-353 (Korea, Republic of); Shin, Dong-Woo [Gyeongsang National University, 900 Gajwa, Jinju 660-701 (Korea, Republic of)

2012-09-30

Highlights: Black-Right-Pointing-Pointer The stability of peroxide in uranyl peroxo carbonato complex solutions with different temperatures was characterized. Black-Right-Pointing-Pointer The decomposition rate of uranyl peroxo carbonato complex ion to uranyl tris-carbonato complex ion was observed to increase with temperature Black-Right-Pointing-Pointer The decomposition kinetics of uranyl peroxo carbonato complex ions was evaluated by absorption and Raman spectroscopies. Black-Right-Pointing-Pointer A precipitate of uranyl peroxo carbonato complex solution was evaluated with XRD. - Abstract: This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144 Multiplication-Sign 10{sup 3} J mol{sup -1}. The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature.

X-Ray K Absorption Edge Structures of Ligand Chlorine Ion in Some Cobalt Coordination Compounds

Science.gov (United States)

Obashi, Masayoshi; Matsukawa, Tokuo

1983-03-01

The X-ray Cl K absorption spectra in [Co(NH3)6]Cl3, [Co(NH3)5Cl]Cl2, trans-[Co(NH3)4Cl2]Cl and Cs2[CoCl4] are measured with a high-resolution vacuum two-crystal spectrometer. The spectra, except that of [Co(NH3)6]Cl3, show an extremely narrow absorption line at the absorption threshold. The result is interpreted on the basis of molecular orbital theory and it is proposed that the intensity of these narrow absorption lines depends on the chemical state between the cobalt and ligand chlorine ions. The narrow absorption line may well be attributed to transitions of the Cl 1s electron into the eg* antibonding orbitals having partially the 3p character of chlorine in [Co(NH3)5Cl]Cl2 and trans-[Co(NH3)4Cl2]Cl. In Cs2[CoCl4] it may be ascribed to the Cl 1s-t2* transitions.

Isolation of nitrosylruthenium nitrato complexes by ion exchange and extraction chromatography

International Nuclear Information System (INIS)

Huang, H.; Liu, L.

TBP Levextrel and cation exchange resins were used to separate RuNO nitrato complexes of different nitric acid concentrations. 7402 quaternary ammonium salt Levextrel was used instead of an anionic exchange resin to separate anionic and neutral complex ions. The results indicated that D 3 and D 4 , which can easily be extracted by TBP, were anionic and neutral complex ions

Assembling Metal Ions Induced Cyanide-Bridged Heterometallic 1D and Ion-Pair Complexes: Synthesis, Crystal Structures and Magnetic Properties

International Nuclear Information System (INIS)

Kong, Lingqian; Zhao, Zengdian; Chen, Kexun; Wang, Ping; Zhang, Daopeng

2013-01-01

We obtained a heterobimetallic one-dimensional cyanide-bridged Mn(II)-Ni(II) complex and an Co(III)-Ni(II) ion-pair complex with [Ni(CN) 4 ] 2- as building block and M(II)-phenanthroline (M = Mn, Co) compounds as assembling segment. The different structural types of complexes 1 and 2 indicate that the property of the metal ions the assembling segment contained have obvious influence on the structure of the cyanide-bridged complex. Investigation over the magnetic properties of complex 1 reveals an overall weak antiferromagnetic coupling between the adjacent Mn(II) ions bridged by the antiferromagnetic [-NC-Ni-CN-] unit. Among of all the molecular magnetism systems, for the well known reasons, cyanide-containing complexes have been widely employed as bridges to assemble homo/hetero-metallic molecular magnetic materials by using the cyanide bridge transferring magnetic coupling between the neighboring paramagnetic ions, in whichsome showed interesting magnetic properties, such as high-Tc magnets, spin crossover materials, single-molecule magnets (SMMs) and single-chain magnets (SCMs)

Preparation, physicochemical characterization and release behavior of the inclusion complex of trans-anethole and β-cyclodextrin.

Science.gov (United States)

Zhang, Wenwen; Li, Xinying; Yu, Taocheng; Yuan, Lun; Rao, Gang; Li, Defu; Mu, Changdao

2015-08-01

Trans-anethole (AT) has a variety of antimicrobial properties and is widely used as food functional ingredient. However, the applications of AT are limited due to its low water solubility, strong odor and low physicochemical stability. Therefore, the aim of this work was to encapsulate AT with β-cyclodextrin (β-CD) for obtaining inclusion complex by co-precipitation method. The measurements effectively confirmed the formation of inclusion complex between AT and β-CD. The results showed that the inclusion complex presented new solid crystalline phases and was more thermally stable than the physical mixture and β-CD. The phase solubility study showed that the aqueous solubility of AT was increased by being included in β-CD. The calculated stability constant of inclusion complex was 1195M -1 , indicating the strong interaction between AT and β-CD. Furthermore, the release study suggested that β-CD provided the protection for AT against evaporation. The release behavior of AT from the inclusion complex was controlled. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluation of the stability of uranyl peroxo-carbonato complex ions in carbonate media at different temperatures.

Science.gov (United States)

Kim, Kwang-Wook; Lee, Keun-Young; Chung, Dong-Yong; Lee, Eil-Hee; Moon, Jei-Kwon; Shin, Dong-Woo

2012-09-30

This work studied the stability of peroxide in uranyl peroxo carbonato complex ions in a carbonate solution with hydrogen peroxide using absorption and Raman spectroscopies, and evaluated the temperature dependence of the decomposition characteristics of uranyl peroxo carbonato complex ions in the solution. The uranyl peroxo carbonato complex ions self-decomposed more rapidly into uranyl tris-carbonato complex ions in higher temperature carbonate solutions. The concentration of peroxide in the solution without free hydrogen peroxide represents the concentration of uranyl peroxo carbonato complex ions in a mixture of uranyl peroxo carbonato complex and uranyl tris-carbonato complex ions. The self-decomposition of the uranyl peroxo carbonato complex ions was a first order reaction, and its activation energy was evaluated to be 7.144×10(3) J mol(-1). The precipitation of sodium uranium oxide hydroxide occurred when the amount of uranyl tris-carbonato complex ions generated from the decomposition of the uranyl peroxo carbonato complex ions exceeded the solubility of uranyl tris-carbonato ions in the solution at the solution temperature. Copyright © 2012 Elsevier B.V. All rights reserved.

Mixed-mode solid-phase extraction followed by acetylation and gas chromatography mass spectrometry for the reliable determination of trans-resveratrol in wine samples

Energy Technology Data Exchange (ETDEWEB)

Montes, R.; Garcia-Lopez, M. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain); Rodriguez, I., E-mail: isaac.rodriguez@usc.es [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain); Cela, R. [Departamento de Quimica Analitica, Nutricion y Bromatologia, Instituto de Investigacion y Analisis Alimentario, Universidad de Santiago de Compostela, Santiago de Compostela 15782 (Spain)

2010-07-12

This work presents an advantageous analytical procedure for the accurate determination of free trans-resveratrol in red and white wines. The proposed method involves solid-phase extraction (SPE), acetylation of the analyte in aqueous media and further determination by gas chromatography (GC) with mass spectrometry detection (MS). The use of a mixed-mode SPE sorbent provides an improvement in the selectivity of the extraction step; moreover, the presence of several intense ions in the electron impact mass spectra of its acetyl derivative guarantees the unambiguous identification of trans-resveratrol. Considering a sample intake of 10 mL, the method provides a limit of quantification (LOQ) of 0.8 ng mL{sup -1} and linear responses for concentrations up to 2.5 {mu}g mL{sup -1}, referred to wine samples. The average recovery, estimated with samples fortified at different concentrations in the above range, was 99.6% and the inter-day precision stayed below 8%. Trans-resveratrol levels in the analyzed wines varied from 3.4 to 1810 ng mL{sup -1}. Cis-resveratrol was also found in all samples. In most cases, equal or higher responses were measured for this latter form than for the trans-isomer. The reduced form of resveratrol, dihydro-resveratrol, was systematically identified in red wines.

Mixed-mode solid-phase extraction followed by acetylation and gas chromatography mass spectrometry for the reliable determination of trans-resveratrol in wine samples

International Nuclear Information System (INIS)

Montes, R.; Garcia-Lopez, M.; Rodriguez, I.; Cela, R.

2010-01-01

This work presents an advantageous analytical procedure for the accurate determination of free trans-resveratrol in red and white wines. The proposed method involves solid-phase extraction (SPE), acetylation of the analyte in aqueous media and further determination by gas chromatography (GC) with mass spectrometry detection (MS). The use of a mixed-mode SPE sorbent provides an improvement in the selectivity of the extraction step; moreover, the presence of several intense ions in the electron impact mass spectra of its acetyl derivative guarantees the unambiguous identification of trans-resveratrol. Considering a sample intake of 10 mL, the method provides a limit of quantification (LOQ) of 0.8 ng mL -1 and linear responses for concentrations up to 2.5 μg mL -1 , referred to wine samples. The average recovery, estimated with samples fortified at different concentrations in the above range, was 99.6% and the inter-day precision stayed below 8%. Trans-resveratrol levels in the analyzed wines varied from 3.4 to 1810 ng mL -1 . Cis-resveratrol was also found in all samples. In most cases, equal or higher responses were measured for this latter form than for the trans-isomer. The reduced form of resveratrol, dihydro-resveratrol, was systematically identified in red wines.

Stability constants of the Europium complexes with the chloride ions

International Nuclear Information System (INIS)

Jimenez R, M.; Solache R, M.; Rojas H, A.

2000-01-01

The stability constants of lanthanides complexes with chloride ions which were determined at the same ionic force but in different media, are significantly different. It does not exist a systematic study over these stability constants. The purpose of this work is to determine the stability constants of the europium complexes with chloride ions at 303 K, by the solvents extraction method. (Author)

Visualization of complex DNA damage along accelerated ions tracks

Science.gov (United States)

Kulikova, Elena; Boreyko, Alla; Bulanova, Tatiana; Ježková, Lucie; Zadneprianetc, Mariia; Smirnova, Elena

2018-04-01

The most deleterious DNA lesions induced by ionizing radiation are clustered DNA double-strand breaks (DSB). Clustered or complex DNA damage is a combination of a few simple lesions (single-strand breaks, base damage etc.) within one or two DNA helix turns. It is known that yield of complex DNA lesions increases with increasing linear energy transfer (LET) of radiation. For investigation of the induction and repair of complex DNA lesions, human fibroblasts were irradiated with high-LET 15N ions (LET = 183.3 keV/μm, E = 13MeV/n) and low-LET 60Co γ-rays (LET ≈ 0.3 keV/μm) radiation. DNA DSBs (γH2AX and 53BP1) and base damage (OGG1) markers were visualized by immunofluorecence staining and high-resolution microscopy. The obtained results showed slower repair kinetics of induced DSBs in cells irradiated with accelerated ions compared to 60Co γ-rays, indicating induction of more complex DNA damage. Confirming previous assumptions, detailed 3D analysis of γH2AX/53BP1 foci in 15N ions tracks revealed more complicated structure of the foci in contrast to γ-rays. It was shown that proteins 53BP1 and OGG1 involved in repair of DNA DSBs and modified bases, respectively, were colocalized in tracks of 15N ions and thus represented clustered DNA DSBs.

Effects of complexing compounds on sorption of metal ions to cement

Energy Technology Data Exchange (ETDEWEB)

Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry

2005-12-15

This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

Trans-Binding Mechanism of Ubiquitin-like Protein Activation Revealed by a UBA5-UFM1 Complex

Directory of Open Access Journals (Sweden)

Walaa Oweis

2016-09-01

Full Text Available Modification of proteins by ubiquitin or ubiquitin-like proteins (UBLs is a critical cellular process implicated in a variety of cellular states and outcomes. A prerequisite for target protein modification by a UBL is the activation of the latter by activating enzymes (E1s. Here, we present the crystal structure of the non-canonical homodimeric E1, UBA5, in complex with its cognate UBL, UFM1, and supporting biochemical experiments. We find that UBA5 binds to UFM1 via a trans-binding mechanism in which UFM1 interacts with distinct sites in both subunits of the UBA5 dimer. This binding mechanism requires a region C-terminal to the adenylation domain that brings UFM1 to the active site of the adjacent UBA5 subunit. We also find that transfer of UFM1 from UBA5 to the E2, UFC1, occurs via a trans mechanism, thereby requiring a homodimer of UBA5. These findings explicitly elucidate the role of UBA5 dimerization in UFM1 activation.

Behaviour of the homologues of Rf and Db in complexing media

International Nuclear Information System (INIS)

Trubert, D.; Monroy Guzman, F.; Hussonnois, M.; Brillard, L.; Le Naour, C.; Servajean, V.; Constantinescu, O.; Constantinescu, M.; Ardisson, G.; Barci, V.; Weiss, B.

1999-01-01

In order to study the chemical behaviour of the trans-actinide elements, the chemical properties of their most probable homologues have been investigated by ion exchange methods in various complexing media. A new chromatographic method allowing the determination of distribution coefficients in the case o short-lived isotopes has been developed and successfully tested with the RACHEL device. (authors)

The chemistry of polypyridine complexes of ruthenium. Communication 5. Electronic structure of mixed-ligand bipyridyl-diphosphine complexes of ruthenium(2)

International Nuclear Information System (INIS)

Sizova, O.V.; Ivanova, N.V.; Ershov, A.Yu.

2001-01-01

Comparative analysis of donor-acceptor abilities of diphosphine ligands for two series of complex compounds: cis-[Ru(bpy) 2 (LL) q+ [LL=2,2'-bipyridyl(bpy), o-benzoquinonediimine (bqdi), cis-1,2-bis(diphenylphosphino)ethane, cis-1,2-bis(diphenylphosphino)ethylene (dppen), (NH 3 ) 2 and (CO) 2 ] and [Ru(NH 3 ) 4 (LL)] 2+ (LL = bpy, dppen and bqdi) was carried out on the basis of results of quantum chemical calculations. It is shown that diphosphines are the strongest σ-donors; their π-acceptor abilities stemming from d-orbitals of phosphorus are comparable in value with π-acceptor abilities of 2,2'-bipyridyl, being essentially lower than those of o-benzoquinonediimine and carbonyl [ru

Identification of absolute geometries of cis and trans molecular isomers by Coulomb Explosion Imaging.

Science.gov (United States)

Ablikim, Utuq; Bomme, Cédric; Xiong, Hui; Savelyev, Evgeny; Obaid, Razib; Kaderiya, Balram; Augustin, Sven; Schnorr, Kirsten; Dumitriu, Ileana; Osipov, Timur; Bilodeau, René; Kilcoyne, David; Kumarappan, Vinod; Rudenko, Artem; Berrah, Nora; Rolles, Daniel

2016-12-02

An experimental route to identify and separate geometric isomers by means of coincident Coulomb explosion imaging is presented, allowing isomer-resolved photoionization studies on isomerically mixed samples. We demonstrate the technique on cis/trans 1,2-dibromoethene (C 2 H 2 Br 2 ). The momentum correlation between the bromine ions in a three-body fragmentation process induced by bromine 3d inner-shell photoionization is used to identify the cis and trans structures of the isomers. The experimentally determined momentum correlations and the isomer-resolved fragment-ion kinetic energies are matched closely by a classical Coulomb explosion model.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non-Polar Solvents by using Conductometry.

Science.gov (United States)

Iseda, Kazuya; Kokado, Kenta; Sada, Kazuki

2018-03-01

In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride ( TBACl ) ion-pair salt to the free ions through complexation with meso -octamethylcalix[4]pyrrole ( CP ), which is a well-known receptor for chloride anions. In the presence of CP , the conductivity of TBACl increases in various non-polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non-polar solvents. In other words, CP recognizes chloride as an ion-paired salt as well as a free anion in non-polar solvents. Additionally, the TBA(CP - Cl ) complex exhibited a considerably lower ion-pairing constant ( K ip ) than TBACl in non-polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli-responsive soft materials in organic solvents using coulombic forces.

Assembling Metal Ions Induced Cyanide-Bridged Heterometallic 1D and Ion-Pair Complexes: Synthesis, Crystal Structures and Magnetic Properties

Energy Technology Data Exchange (ETDEWEB)

Kong, Lingqian [Liaocheng Univ., Liaocheng (China); Zhao, Zengdian; Chen, Kexun; Wang, Ping; Zhang, Daopeng [Shandong Univ. of Technology, Zibo (China)

2013-07-15

We obtained a heterobimetallic one-dimensional cyanide-bridged Mn(II)-Ni(II) complex and an Co(III)-Ni(II) ion-pair complex with [Ni(CN){sub 4}]{sup 2-} as building block and M(II)-phenanthroline (M = Mn, Co) compounds as assembling segment. The different structural types of complexes 1 and 2 indicate that the property of the metal ions the assembling segment contained have obvious influence on the structure of the cyanide-bridged complex. Investigation over the magnetic properties of complex 1 reveals an overall weak antiferromagnetic coupling between the adjacent Mn(II) ions bridged by the antiferromagnetic [-NC-Ni-CN-] unit. Among of all the molecular magnetism systems, for the well known reasons, cyanide-containing complexes have been widely employed as bridges to assemble homo/hetero-metallic molecular magnetic materials by using the cyanide bridge transferring magnetic coupling between the neighboring paramagnetic ions, in whichsome showed interesting magnetic properties, such as high-Tc magnets, spin crossover materials, single-molecule magnets (SMMs) and single-chain magnets (SCMs)

Complex formation constant and hydration number change of aqua-rare earth ions

International Nuclear Information System (INIS)

Kanno, H.

1998-01-01

Full text: It is now well established that the inner-sphere hydration number of aqua-rare earth ions changes from nine to eight in the middle of the rare earth series. This hydration number change greatly affects the complex formation of rare earth ions as we observe irregular variations in most series behaviours of the complex formation constant (K) in aqueous solution systems when K being plotted against 1/r or r (r is ionic radius of rare earth ion). Furthermore, it shows very anomalous concentration dependence in the sense that nona-aqua Ln 3+ ion increases in number with increase in salt concentration in aqueous rare earth salt solution (salt chloride, perchlorate). In this report, a theoretical derivation of the formation constant (K) for the inner-sphere complex formation of rare earth ions with a monodentate ligand was made by taking account of both the hydration number change in the middle of the series and its anomalous salt concentration dependence. The series behaviour of the formation constant against 1/r (or r) is successfully explained with using the empirical finding that K varies almost linearly with 1/r (or r) in the region where only one hydration number dominates. This success is also taken as evidence that the anomalous salt concentration dependence of the hydration number change is caused by the outer-sphere complex formation of rare earth ions with the condition that nona-aqua rare earth ions form outer-sphere complexes more easily than octa-aqua ions

Traveling-wave ion mobility mass spectrometry of protein complexes

DEFF Research Database (Denmark)

Salbo, Rune; Bush, Matthew F; Naver, Helle

2012-01-01

The collision cross-section (Ω) of a protein or protein complex ion can be measured using traveling-wave (T-wave) ion mobility (IM) mass spectrometry (MS) via calibration with compounds of known Ω. The T-wave Ω-values depend strongly on instrument parameters and calibrant selection. Optimization ...

Target-induced formation of gold amalgamation on DNA-based sensing platform for electrochemical monitoring of mercury ion coupling with cycling signal amplification strategy

International Nuclear Information System (INIS)

Chen, Jinfeng; Tang, Juan; Zhou, Jun; Zhang, Lan; Chen, Guonan; Tang, Dianping

2014-01-01

Graphical abstract: -- Highlights: •We report a new electrochemical sensing protocol for the detection of mercury ion. •Gold amalgamation on DNA-based sensing platform was used as nanocatalyst. •The signal was amplified by cycling signal amplification strategy. -- Abstract: Heavy metal ion pollution poses severe risks in human health and environmental pollutant, because of the likelihood of bioaccumulation and toxicity. Driven by the requirement to monitor trace-level mercury ion (Hg 2+ ), herein we construct a new DNA-based sensor for sensitive electrochemical monitoring of Hg 2+ by coupling target-induced formation of gold amalgamation on DNA-based sensing platform with gold amalgamation-catalyzed cycling signal amplification strategy. The sensor was simply prepared by covalent conjugation of aminated poly-T (25) oligonucleotide onto the glassy carbon electrode by typical carbodiimide coupling. Upon introduction of target analyte, Hg 2+ ion was intercalated into the DNA polyion complex membrane based on T–Hg 2+ –T coordination chemistry. The chelated Hg 2+ ion could induce the formation of gold amalgamation, which could catalyze the p-nitrophenol with the aid of NaBH 4 and Ru(NH 3 ) 6 3+ for cycling signal amplification. Experimental results indicated that the electronic signal of our system increased with the increasing Hg 2+ level in the sample, and has a detection limit of 0.02 nM with a dynamic range of up to 1000 nM Hg 2+ . The strategy afforded exquisite selectivity for Hg 2+ against other environmentally related metal ions. In addition, the methodology was evaluated for the analysis of Hg 2+ in spiked tap-water samples, and the recovery was 87.9–113.8%

Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

Science.gov (United States)

Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

2002-01-01

The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

Finding trans-regulatory genes and protein complexes modulating meiotic recombination hotspots of human, mouse and yeast.

Science.gov (United States)

Wu, Min; Kwoh, Chee-Keong; Li, Xiaoli; Zheng, Jie

2014-09-11

The regulatory mechanism of recombination is one of the most fundamental problems in genomics, with wide applications in genome wide association studies (GWAS), birth-defect diseases, molecular evolution, cancer research, etc. Recombination events cluster into short genomic regions called "recombination hotspots". Recently, a zinc finger protein PRDM9 was reported to regulate recombination hotspots in human and mouse genomes. In addition, a 13-mer motif contained in the binding sites of PRDM9 is found to be enriched in human hotspots. However, this 13-mer motif only covers a fraction of hotspots, indicating that PRDM9 is not the only regulator of recombination hotspots. Therefore, the challenge of discovering other regulators of recombination hotspots becomes significant. Furthermore, recombination is a complex process. Hence, multiple proteins acting as machinery, rather than individual proteins, are more likely to carry out this process in a precise and stable manner. Therefore, the extension of the prediction of individual trans-regulators to protein complexes is also highly desired. In this paper, we introduce a pipeline to identify genes and protein complexes associated with recombination hotspots. First, we prioritize proteins associated with hotspots based on their preference of binding to hotspots and coldspots. Second, using the above identified genes as seeds, we apply the Random Walk with Restart algorithm (RWR) to propagate their influences to other proteins in protein-protein interaction (PPI) networks. Hence, many proteins without DNA-binding information will also be assigned a score to implicate their roles in recombination hotspots. Third, we construct sub-PPI networks induced by top genes ranked by RWR for various species (e.g., yeast, human and mouse) and detect protein complexes in those sub-PPI networks. The GO term analysis show that our prioritizing methods and the RWR algorithm are capable of identifying novel genes associated with

Multiheteromacrocycles that complex metal ions. Third progress report, 1 May 1976--30 April 1977

International Nuclear Information System (INIS)

Cram, D.J.

1977-01-01

The overall objective of this research is to design, synthesize and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes and clusters. Host organic compounds consist of strategically placed solvating, coordinating and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The specific compounds synthesized and their complexing and lipophilizing properties are summarized

Preparation and voltammetric characterization of electrodes coated with Langmuir-Schaefer ultrathin films of Nafion®

Directory of Open Access Journals (Sweden)

Bertoncello Paolo

2003-01-01

Full Text Available Ultrathin films of Nafion® perfluorinated polymer were deposited on indium-tin oxide electrodes (ITO by using Langmuir-Schaefer (LS technique, after optimization of the subphase composition conditions. Morphological characteristics of these coatings were obtained by Atomic Force Microscopy (AFM. Nafion® LS films showed a good uniformity and complete coverage of the electrode surface, however a different organization degree of the polymer layer was evidenced with respect to thin films deposited by spin-coating. ITO electrodes modified with Nafion® LS coatings preconcentrate by ion-exchange electroactive cations, such as Ru[(NH36]3+, dissolved in diluted solutions. The electroactive species is retained by the Nafion® LS coated ITO also after transfer of the modified electrode into pure supporting electrolyte. This allowed the use of the ruthenium complex as voltammetric probe to test diffusion phenomena within the Nafion® LS films. Apparent diffusion coefficients (Dapp of Ru[(NH36]3+ incorporated in Nafion® LS films were obtained by voltammetric measurements. Dapp values decrease slightly by increasing the amount of ruthenium complex incorporated in the ultrathin film. They are significantly lower than values typical for recasted Nafion® films, in agreement with the highly condensed nature of the Nafion® LS fims.

COMPLEX OF NUMERICAL MODELS FOR COMPUTATION OF AIR ION CONCENTRATION IN PREMISES

Directory of Open Access Journals (Sweden)

M. M. Biliaiev

2016-04-01

Full Text Available Purpose. The article highlights the question about creation the complex numerical models in order to calculate the ions concentration fields in premises of various purpose and in work areas. Developed complex should take into account the main physical factors influencing the formation of the concentration field of ions, that is, aerodynamics of air jets in the room, presence of furniture, equipment, placement of ventilation holes, ventilation mode, location of ionization sources, transfer of ions under the electric field effect, other factors, determining the intensity and shape of the field of concentration of ions. In addition, complex of numerical models has to ensure conducting of the express calculation of the ions concentration in the premises, allowing quick sorting of possible variants and enabling «enlarged» evaluation of air ions concentration in the premises. Methodology. The complex numerical models to calculate air ion regime in the premises is developed. CFD numerical model is based on the use of aerodynamics, electrostatics and mass transfer equations, and takes into account the effect of air flows caused by the ventilation operation, diffusion, electric field effects, as well as the interaction of different polarities ions with each other and with the dust particles. The proposed balance model for computation of air ion regime indoors allows operative calculating the ions concentration field considering pulsed operation of the ionizer. Findings. The calculated data are received, on the basis of which one can estimate the ions concentration anywhere in the premises with artificial air ionization. An example of calculating the negative ions concentration on the basis of the CFD numerical model in the premises with reengineering transformations is given. On the basis of the developed balance model the air ions concentration in the room volume was calculated. Originality. Results of the air ion regime computation in premise, which

Density functional study of isoguanine tetrad and pentad sandwich complexes with alkali metal ions.

Science.gov (United States)

Meyer, Michael; Steinke, Thomas; Sühnel, Jürgen

2007-02-01

Isoguanine tetraplexes and pentaplexes contain two or more stacked polyads with intercalating metal ions. We report here the results of a density functional study of sandwiched isoguanine tetrad and pentad complexes consisting of two polyads with Na(+), K(+) and Rb(+) ions at the B3LYP level. In comparison to single polyad metal ion complexes, there is a trend towards increased non-planarity of the polyads in the sandwich complexes. In general, the pentad sandwiches have relatively planar polyad structures, whereas the tetrad complexes contain highly non-planar polyad building blocks. As in other sandwich complexes and in metal ion complexes with single polyads, the metal ion-base interaction energy plays an essential role. In iG sandwich structures, this interaction energy is slightly larger than in the corresponding guanine sandwich complexes. Because the base-base interaction energy is even more increased in passing from guanine to isoguanine, the isoguanine sandwiches are thus far the only examples where the base-base interaction energy is larger than the base-metal ion interaction energy. Stacking interactions have been studied in smaller models consisting of two bases, retaining the geometry from the complete complex structures. From the data obtained at the B3LYP and BH&H levels and with Møller-Plesset perturbation theory, one can conclude that the B3LYP method overestimates the repulsion in stacked base dimers. For the complexes studied in this work, this is only of minor importance because the direct inter-tetrad or inter-pentad interaction is supplemented by a strong metal ion-base interaction. Using a microsolvation model, the metal ion preference K(+) approximately Rb(+) > Na(+) is found for tetrad complexes. On the other hand, for pentads the ordering is Rb(+) > K(+) > Na(+). In the latter case experimental data are available that agree with this prediction.

Better faster cheaper: TransCanada PipeLines Ltd. 2000 annual report

International Nuclear Information System (INIS)

2000-01-01

Financial information from TransCanada was presented along with a review of their operations throughout 2000, including a summary of actions in the area of management, strategy, and policy. The company's efforts in 2000 were directed at restoring and strengthening their financial position by strengthening their balance sheet, restoring earnings, establishing a growth platform for future earnings and positioning the company with discretionary cash flow. In 2000, TransCanada substantially completed its divestiture program and sold assets for proceeds of nearly $3.4 billion. These proceeds have been used mainly to reduce debt and associated financial charges. TransCanada also made successful bids in Alberta's power auctions, increased ownership in Ocean State power and TransCanada Power, L.P. In addition, the company began development of two new power plants in Alberta. These initiatives are expected to contribute to an increase in earnings. tabs., figs

Investigation of different-ligand complexes of holmium and erbium with NTA and carbonate ion

International Nuclear Information System (INIS)

Nazarenko, N.A.; Bel'tyukova, S.V.; Poluehktov, N.S.

1979-01-01

Found out have been the optimum conditions for the formation of the lantanides (Ln) multiligand complexes with the nitriletriacetic acid (NTA) and the carbonate-ion. It has been established that the components correlation in complex compounds is equal to 1:1:1. Computed have been the values of the oscillator forces of the absorption bands, that conform to the ''supersensitive'' migration of the multiligand complexes, It is shown that the increment in the oscillator forces, the induced entering of one carbonate-ion into the Ln-NTA complex molecule conforms to about 1/4 of the oscillator forces increment during the migration from the aquo ion to the [Ln(CO 3 ) 4 ] 5- complex carbonaceous ion

Complex fluids with mobile charge-regulating macro-ions

Science.gov (United States)

Markovich, Tomer; Andelman, David; Podgornik, Rudi

2017-10-01

We generalize the concept of charge regulation of ionic solutions, and apply it to complex fluids with mobile macro-ions having internal non-electrostatic degrees of freedom. The suggested framework provides a convenient tool for investigating systems where mobile macro-ions can self-regulate their charge (e.g., proteins). We show that even within a simplified charge-regulation model, the charge dissociation equilibrium results in different and notable properties. Consequences of the charge regulation include a positional dependence of the effective charge of the macro-ions, a non-monotonic dependence of the effective Debye screening length on the concentration of the monovalent salt, a modification of the electric double-layer structure, and buffering by the macro-ions of the background electrolyte.

Development of complexation ion chromatography for the determination of metal ions

OpenAIRE

Bashir, Wasim

2002-01-01

A simple ion chromatographic method was developed for the determination of Pb(II) in river and polluted water samples. The method was based upon the use of a colourforming complexing eluent and direct visible detection of the eluting Pb(II) complex. Using the combination of a strong cation exchange column and an eluent consisting of 20 mM sodium acetate-acetic acid buffer and 0.2 mM xylenol orange (XO) (~pH = 4.2), Pb(II) was detected at 572 nm eluting in under 6.5 min. The developed method p...

miR-34 and p53: New Insights into a Complex Functional Relationship.

Directory of Open Access Journals (Sweden)

Francisco Navarro

Full Text Available miR-34, a tumor suppressor miRNA family transcriptionally activated by p53, is considered a critical mediator of p53 function. However, knockout of the mouse miR-34 family has little or no effect on the p53 response. The relative contribution of different miR-34 family members to p53 function or how much p53 relies on miR-34 in human cells is unclear. Here we show that miR-34a has a complex effect on the p53 response in human cells. In HCT116 cells miR-34a overexpression enhances p53 transcriptional activity, but the closely related family members, miR-34b and miR-34c, even when over-expressed, have little effect. Both TP53 itself and MDM4, a strong p53 transactivation inhibitor, are direct targets of miR-34a. The genes regulated by miR-34a also include four other post-translational inhibitors of p53. miR-34a overexpression leads to variable effects on p53 levels in p53-sufficient human cancer cell lines. In HCT116, miR-34a overexpression increases p53 protein levels and stability. About a quarter of all mRNAs that participate in the human p53 network bind to biotinylated miR-34a, suggesting that many are direct miR-34a targets. However, only about a fifth of the mRNAs that bind to miR-34a also bind to miR-34b or miR-34c. Two human cell lines knocked out for miR-34a have unimpaired p53-mediated responses to genotoxic stress, like mouse cells. The complex positive and negative effects of miR-34 on the p53 network suggest that rather than simply promoting the p53 response, miR-34a might act at a systems level to stabilize the robustness of the p53 response to genotoxic stress.

Synthesis of Fe–C{sub 60} complex by ion irradiation

Energy Technology Data Exchange (ETDEWEB)

Minezaki, Hidekazu, E-mail: dn1000012@toyo.jp [Graduate School of Engineering, Toyo University, 2100 Kujirai, Kawagoe, Saitama 350-8585 (Japan); Oshima, Kosuke [Graduate School of Engineering, Toyo University, 2100 Kujirai, Kawagoe, Saitama 350-8585 (Japan); Uchida, Takashi; Mizuki, Toru [Bio-Nano Electronics Research Centre, Toyo University, 2100 Kujirai, Kawagoe, Saitama 350-8585 (Japan); Racz, Richard [Institute of Nuclear Research (ATOMKI), H-4026, Debrecen, Bem tér 18/C (Hungary); Muramatsu, Masayuki [National Institute of Radiological Sciences (NIRS), 4-9-1 Anagawa, Inage-ku, Chiba-shi, Chiba 263-8555 (Japan); Asaji, Toyohisa [Oshima National College of Maritime Technology, 1091-1 Komatsu Suou Oshima City, Oshima, Yamaguchi 742-2193 (Japan); Kitagawa, Atsushi [National Institute of Radiological Sciences (NIRS), 4-9-1 Anagawa, Inage-ku, Chiba-shi, Chiba 263-8555 (Japan); Kato, Yushi [Graduate School of Engineering, Osaka University, 2-1 Yamada-oka, Suita-shi, Osaka 565-0871 (Japan); Biri, Sandor [Institute of Nuclear Research (ATOMKI), H-4026, Debrecen, Bem tér 18/C (Hungary); Yoshida, Yoshikazu [Graduate School of Engineering, Toyo University, 2100 Kujirai, Kawagoe, Saitama 350-8585 (Japan); Bio-Nano Electronics Research Centre, Toyo University, 2100 Kujirai, Kawagoe, Saitama 350-8585 (Japan)

2013-09-01

Highlights: •The Fe{sup +} beam was irradiated to the C{sub 60} thin films. •The Fe{sup +}-irradiated C{sub 60} thin films were analyzed by LDI-TOF-MS and by HPLC. •The peak with mass/charge of 776 was observed in the Fe{sup +}-irradiated C{sub 60} thin film. •We could synthesize the Fe–C{sub 60} complex as a new material. -- Abstract: In order to synthesize the Fe@C{sub 60} complex, iron ion beam irradiated to C{sub 60} thin films. The energy of the irradiated iron ions was controlled from 50 eV to 250 eV. The dose of that was controlled from 6.67 × 10{sup 12} to 6.67 × 10{sup 14} ions/cm{sup 2}. By the analysis of the surface of the iron ion irradiated C{sub 60} thin films using laser desorption/ionization time-of-flight mass spectrometry, we could confirm the peak with mass/charge of 776. The mass/charge of 776 corresponds to Fe + C{sub 60}. We obtained the maximum intensity of the peak with mass/charge of 776 under the irradiation iron ion energy and the dose were 50 eV and 3.30 × 10{sup 13} ions/cm{sup 2}, respectively. Then, the separation of the material with mass of 776 was performed by using high performance liquid chromatography. We could separate the Fe + C{sub 60} from the iron ion irradiated C{sub 60} thin film. As a result, we could synthesize the Fe + C{sub 60} complex as a new material.

Ion-Exchanged SAPO-34 Membranes for Krypton-Xenon Separation: Control of Permeation Properties and Fabrication of Hollow Fiber Membranes.

Science.gov (United States)

Kwon, Yeon Hye; Min, Byunghyun; Yang, Shaowei; Koh, Dong-Yeun; Bhave, Ramesh R; Nair, Sankar

2018-02-21

Separation of radioisotope 85 Kr from 136 Xe is of importance in used nuclear fuel reprocessing. Membrane separation based on zeolite molecular sieves such as chabazite SAPO-34 is an attractive alternative to energy-intensive cryogenic distillation. We report the synthesis of SAPO-34 membranes with considerably enhanced performance via thickness reduction based upon control of a steam-assisted vapor-solid conversion technique followed by ion exchange with alkali metal cations. The reduction of membrane thickness leads to a large increase in Kr permeance from 7.5 to 26.3 gas permeation units (GPU) with ideal Kr/Xe selectivities >20 at 298 K. Cation-exchanged membranes show large (>50%) increases in selectivity at ambient or slight subambient conditions. The adsorption, diffusion, and permeation characteristics of ion-exchanged SAPO-34 materials and membranes are investigated in detail, with potassium-exchanged SAPO-34 membranes showing particularly attractive performance. We then demonstrate the fabrication of selective SAPO-34 membranes on α-alumina hollow fibers.

Regular square planer bis-(4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione)/copper(II) complex: Trans/cis-DFT isomerization, crystal structure, thermal, solvatochromism, hirshfeld surface and DNA-binding analysis

Science.gov (United States)

Hema, M. K.; Karthik, C. S.; Warad, Ismail; Lokanath, N. K.; Zarrouk, Abdelkader; Kumara, Karthik; Pampa, K. J.; Mallu, P.

2018-04-01

Trans-[Cu(O∩O)2] complex, O∩O = 4,4,4-trifluoro-1-(thiophen-2-yl)butane-1,3-dione was reported with high potential toward CT-DNA binder. The solved XRD-structure of complex indicated a perfect regular square-planer geometry around the Cu(II) center. The trans/cis-DFT-isomerization calculation supported the XRD seen in reflecting the trans-isomer as the kinetic-favor isomer. The desired complex structure was also characterized by conductivity measurement, CHN-elemental analyses, MS, EDX, SEM, UV-Vis., FT-IR, HAS and TG/DTG. The Solvatochromism behavior of the complex was evaluated using four different polar solvents. MPE and Hirshfeld surface analysis (HSA) come to an agreement that fluoride and thiophene protons atoms are with suitable electro-potential environment to form non-classical H-bonds of type CThsbnd H⋯F. The DNA-binding properties were investigated by viscosity tests and spectrometric titrations, the results revealed the complex as strong calf-thymus DNA binder. High intrinsic-binding constants value ∼1.8 × 105 was collected.

Complexation ion-exchange chromatography of some metal ions on papers impregnated with Ti(IV)-based inorganic ion exchangers.

Science.gov (United States)

Sharma, S D; Gupta, R

2000-02-01

The chromatographic behavior of 40 metal ions is studied on titanium (IV) arsenate, titanium (IV) phosphate-, titanium (IV) molybdate-, titanium(IV) tungstate-, and titanium(IV) selenite-impregnated papers in 0.1M oxalic, citric, and tartaric acid as mobile phases. Similar studies are carried out on Whatman No. 1 papers for comparison. The ion-exchange capacity of these papers is determined, and their selectivity for different cations is discussed. The mechanism of migration is explained in terms of ion-exchange, precipitation, and adsorption. The prediction of elution sequence from RF values is also checked. The average Ri is found to be almost linearly dependent on the charge of the metal ions. The effect of the pKa of complexing acids on average RF values of 3d series metal ions is explained. A number of binary and ternary separations are achieved.

A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions

Energy Technology Data Exchange (ETDEWEB)

Chen, Junying; Lee, Yong-Min; Davis, Katherine M.; Wu, Xiujuan; Seo, Mi Sook; Cho, Kyung-Bin; Yoon, Heejung; Park, Young Jun; Fukuzumi, Shunichi; Pushkar, Yulia N.; Nam, Wonwoo [Ewha; (Purdue); (Osaka)

2013-05-29

Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N₅ ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc³⁺ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

The piroxicam complex of copper(II), trans-[Cu(Pir)2(THF)2], and its interaction with DNA

Science.gov (United States)

Hadadzadeh, Hassan; Salimi, Mona; Weil, Matthias; Jannesari, Zahra; Darabi, Farivash; Abdi, Khatereh; Khalaji, Aliakbar Dehno; Sardari, Soroush; Ahangari, Reza

2012-08-01

The mononuclear Cu(II) complex, trans-[Cu(Pir)2(THF)2], where Pir is 4-hydroxy-2-methyl-N-2-pyridyl-2H-1,2-benzothiazine-3-carboxamide-1,1-dioxide (piroxicam), has been prepared and characterized by elemental analysis, spectroscopic methods (UV-Vis, IR, and 1H NMR) and single crystal X-ray structure analysis. The molecular structure of the centrosymmetric complex is made up of two monoanionic bidentate Pir ligands coordinated to the Cu(II) atom through the pyridyl N atom and the carbonyl O atom of the amide group in equatorial positions. The elongated rhombic octahedral (ERO) coordination of the CuNONOO2″ chromophore is completed by the O atoms of two THF molecules in axial positions. A strong intramolecular hydrogen bond between the amide N-H function and the enolate O atom confirms the ZZZ conformation of piroxicam. In addition, CD spectroscopy and gel electrophoresis assays have been used to investigate the interaction of the complex with DNA. The results revealed that the binding of the complex with DNA led to DNA backbone distortion.

transPLANT Resources for Triticeae Genomic Data

Directory of Open Access Journals (Sweden)

Manuel Spannagl

2016-03-01

Full Text Available The genome sequences of many important Triticeae species, including bread wheat ( L. and barley ( L., remained uncharacterized for a long time because their high repeat content, large sizes, and polyploidy. As a result of improvements in sequencing technologies and novel analyses strategies, several of these have recently been deciphered. These efforts have generated new insights into Triticeae biology and genome organization and have important implications for downstream usage by breeders, experimental biologists, and comparative genomicists. transPLANT ( is an EU-funded project aimed at constructing hardware, software, and data infrastructure for genome-scale research in the life sciences. Since the Triticeae data are intrinsically complex, heterogenous, and distributed, the transPLANT consortium has undertaken efforts to develop common data formats and tools that enable the exchange and integration of data from distributed resources. Here we present an overview of the individual Triticeae genome resources hosted by transPLANT partners, introduce the objectives of transPLANT, and outline common developments and interfaces supporting integrated data access.

Complexation-induced supramolecular assembly drives metal-ion extraction.

Science.gov (United States)

Ellis, Ross J; Meridiano, Yannick; Muller, Julie; Berthon, Laurence; Guilbaud, Philippe; Zorz, Nicole; Antonio, Mark R; Demars, Thomas; Zemb, Thomas

2014-09-26

Combining experiment with theory reveals the role of self-assembly and complexation in metal-ion transfer through the water-oil interface. The coordinating metal salt Eu(NO3)3 was extracted from water into oil by a lipophilic neutral amphiphile. Molecular dynamics simulations were coupled to experimental spectroscopic and X-ray scattering techniques to investigate how local coordination interactions between the metal ion and ligands in the organic phase combine with long-range interactions to produce spontaneous changes in the solvent microstructure. Extraction of the Eu(3+)-3(NO3(-)) ion pairs involves incorporation of the "hard" metal complex into the core of "soft" aggregates. This seeds the formation of reverse micelles that draw the water and "free" amphiphile into nanoscale hydrophilic domains. The reverse micelles interact through attractive van der Waals interactions and coalesce into rod-shaped polynuclear Eu(III) -containing aggregates with metal centers bridged by nitrate. These preorganized hydrophilic domains, containing high densities of O-donor ligands and anions, provide improved Eu(III) solvation environments that help drive interfacial transfer, as is reflected by the increasing Eu(III) partitioning ratios (oil/aqueous) despite the organic phase approaching saturation. For the first time, this multiscale approach links metal-ion coordination with nanoscale structure to reveal the free-energy balance that drives the phase transfer of neutral metal salts. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complexation of metal ions with humic acid: charge neutralization model

International Nuclear Information System (INIS)

Kim, J.I.; Czerwinski, K.R.

1995-01-01

A number of different approaches are being used for describing the complexation equilibrium of actinide ions with humic or fulvic acid. The approach chosen and verified experimentally by Tu Muenchen will be discussed with notable examples from experiment. This approach is based on the conception that a given actinide ion is neutralized upon complexation with functional groups of humic or fulvic acid, e.g. carboxylic and phenolic groups, which are known as heterogeneously cross-linked polyelectrolytes. The photon energy transfer experiment with laser light excitation has shown that the actinide ion binding with the functional groups is certainly a chelation process accompanied by metal ion charge neutralization. This fact is in accordance with the experimental evidence of the postulated thermodynamic equilibrium reaction. The experimental results are found to be independent of origin of humic or fulvic acid and applicable for a broad range of pH. (authors). 23 refs., 7 figs., 1 tab

New 3,4-diaminobenzoic acid Schiff base compounds and their complexes: synthesis, characterization and thermodynamics.

Science.gov (United States)

Mohammadi, Khosro; Niad, Mahmood; Jafari, Tahereh

2014-03-25

Some new tetradentate Schiff base ligands (H3L) were prepared via condensation of 3,4-diaminobenzoic acid with 2-hydroxybenzaldehyde derivatives, such as 3,4-bis((E)-2,4-dihydroxybenzylideneamino)benzoic acid (H3L(1)), 3,4-bis((E)-2-hydroxy-3-methoxybenzylideneamino)benzoic acid (H3L(2)) and 3,4-bis((E)-5-bromo-2-hydroxybenzylideneamino)benzoic acid (H3L(4)). Additionally, a tetradentate Schiff base ligand 3,4-bis((E)-2-hydroxybenzylideneamino)benzoic acid (H3L(3)) and its complexes were synthesized. Their metal complexes of Co(II), Ni(II), Cu(II) and Zn(II) were prepared in good yields from the reaction of the ligands with the corresponding metal acetate. They were characterized based on IR, (1)H NMR, Mass spectroscopy and UV-Vis spectroscopy. Also, the formation constants of the complexes were measured by UV-Vis spectroscopic titration at constant ionic strength 0.1M (NaClO4), at 25 °C in dimethylformamide (DMF) as a solvent. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

Science.gov (United States)

Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

2017-07-01

Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4±0.05, 7±0.05 and 9±0.05) and three different temperatures (15±0.5°C, 30±0.5°C and 45±0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

KAUST Repository

Kaur, Sukhmanpreet

2017-07-04

Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions

KAUST Repository

Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

2017-01-01

Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

Science.gov (United States)

Cram, D. J.

1980-01-15

Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

Metal-ion complexes of functionalised 1,10-Phenanthrolines as hydrolytic synzymes

NARCIS (Netherlands)

Weijnen, J.G.J.

1993-01-01

In this thesis metal-ion complexes of functionalised 1,10-phenanthroline derivatives have been studied as model systems for hydrolytic metallo-enzymes. Amphiphilic metallo- complexes incorporated into micelles or vesicles and water-soluble complexes in pure aqueous buffer solutions, have

Fragmentation of deuteronated aromatic derivatives: The role of ion-neutral complexes

Science.gov (United States)

Harrison, Alex G.; Wang, Jian-Yao

1997-01-01

The low-energy collision-induced dissociation reactions of the MD+ ions of a number of alkyl phenyl ethers, alkylbenzenes, acetophenones and benzaldehyde have been studied as a function of collision energy to establish qualitatively the dependence of the fragmentation reactions observed on internal energy. Deuteronated alkyl phenyl ethers (ROC6H5·D+, R = C3H7, C4H9) fragment at low collision energies to form C6H5OHD+ + (R-H), the thermochemically favoured products; with increasing collision energy (and, hence, internal energy) formation of the alkyl ion R+ increases significantly in importance. Deuteronated alkylbenzenes (RC6H5, RC6H4R', R = C2H5, C3H7) similarly form the deuteronated benzene (the thermochemically favoured product) at low collision energies with formation of the alkyl ion R+ being observed at higher collision energies. The results for both systems are consistent with a fragmentation mechanism involving initial formation of an R+/aromatic ion/neutral complex. At low internal energies proton transfer occurs within this complex to form an ion/neutral complex consisting of the deuteronated aromatic and a neutral olefin; this complex fragments to the thermochemically favoured products. Since the transition state leading to these products is a "tight" transition state involving loss of rotational degrees of freedom, the proton transfer reaction is unfavourable entropically with respect to simple dissociation of the R+/aromatic complex to R+ + ArD. Consequently, these products increase in importance as the internal energy is increased. The fragmentation of deuteronated aromatic carbonyl compounds can also be rationalized by similar mechanisms involving the intermediacy of ion/neutral complexes. Deuteronated acetophenone forms only CH3CO+ at all collision energies; this is both the thermochemically and entropically favoured product. However, deuteronated p-aminoacetophenone forms deuteronated aniline, the thermochemically favoured product at low collision

Trans-generational responses to low pH depend on parental gender in a calcifying tubeworm

OpenAIRE

Lane, Ackley; Campanati, Camilla; Dupont, Sam; Thiyagarajan, Vengatesen

2015-01-01

The uptake of anthropogenic CO2 emissions by oceans has started decreasing pH and carbonate ion concentrations of seawater, a process called ocean acidification (OA). Occurring over centuries and many generations, evolutionary adaptation and epigenetic transfer will change species responses to OA over time. Trans-generational responses, via genetic selection or trans-generational phenotypic plasticity, differ depending on species and exposure time as well as differences between individuals su...

Membranes linked by trans-SNARE complexes require lipids prone to non-bilayer structure for progression to fusion.

Science.gov (United States)

Zick, Michael; Stroupe, Christopher; Orr, Amy; Douville, Deborah; Wickner, William T

2014-01-01

Like other intracellular fusion events, the homotypic fusion of yeast vacuoles requires a Rab GTPase, a large Rab effector complex, SNARE proteins which can form a 4-helical bundle, and the SNARE disassembly chaperones Sec17p and Sec18p. In addition to these proteins, specific vacuole lipids are required for efficient fusion in vivo and with the purified organelle. Reconstitution of vacuole fusion with all purified components reveals that high SNARE levels can mask the requirement for a complex mixture of vacuole lipids. At lower, more physiological SNARE levels, neutral lipids with small headgroups that tend to form non-bilayer structures (phosphatidylethanolamine, diacylglycerol, and ergosterol) are essential. Membranes without these three lipids can dock and complete trans-SNARE pairing but cannot rearrange their lipids for fusion. DOI: http://dx.doi.org/10.7554/eLife.01879.001.

A study on complex formation of cadmium(II) ions, 8

International Nuclear Information System (INIS)

Matsui, Haruo; Hirabayashi, Yoshihiro

1984-01-01

In the potentiometric titration of the solution containing a cadmium(II) ion and an amino acid, white precipitates often appear in the test solution, and they disturb the emf measurements. Such precipitates were formes in the solutions, pH ranging 7.5--8.5, during the course of titrations of the test solutions containing cadmium(II) ion and amino acid such as glycine, α-alanine. 2-aminobutanoic acid, 3-aminobutanoic acid, 4-aminobutanoic acid, 2-aminopentanoic acid, 5-aminopentanoic acid, 2-aminohexanoic acid, 6-aminohexanoic acid, aspartic acid, glutamic acid, asparagine, or glutamine. The identification of the precipitates obtained from the solutions containing cadmium(II) ion and L-aspartic acid, 4-aminobutanoic acid, or 6-aminohexanoic acid were carried out by both of elemental analysis and the infrared spectroscopy. These results indicated that the precipitate obtained from the solution containing cadmium(II) ion and L-aspartic acid was 1:1 cadmium(II)-L-aspartic acid complex and did not contain any cadmium(II) hydroxide, and other two precipitates were mostly cadmium(II) hydroxide and contained a little cadmium(II)-amino acid complexes. (author)

Resisting Coherence: Trans Men's Experiences and the Use of Grounded Theory Methods

Science.gov (United States)

Catalano, D. Chase J.

2017-01-01

In this methodological reflective manuscript, I explore my decision to use a grounded theoretical approach to my dissertation study on trans* men in higher education. Specifically, I question whether grounded theory as a methodology is capable of capturing the complexity and capaciousness of trans*-masculine experiences. Through the lenses of…

Reactivity at the film/solution interface of ex situ prepared bismuth film electrodes: A scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM) investigation

International Nuclear Information System (INIS)

Hocevar, Samo B.; Daniele, Salvatore; Bragato, Carlo; Ogorevc, Bozidar

2007-01-01

Bismuth film electrodes (BiFEs) prepared ex situ with and without complexing bromide ions in the modification solution were investigated using scanning electrochemical microscopy (SECM) and atomic force microscopy (AFM). A feedback mode of the SECM was employed to examine the conductivity and reactivity of a series of thin bismuth films deposited onto disk glassy carbon substrate electrodes (GCEs) of 3 mm in diameter. A platinum micro-electrode (φ = 25 μm) was used as the SECM tip, and current against tip/substrate distance was recorded in solutions containing either Ru(NH 3 ) 6 3+ or Fe(CN) 6 4- species as redox mediators. With both redox mediators positive feedback approach curves were recorded, which indicated that the bismuth film deposition protocol associated with the addition of bromide ions in the modification solution did not compromise the conductivity of the bismuth film in comparison with that prepared without bromide. However, at the former Bi film a slight kinetic hindering was observed in recycling Ru(NH 3 ) 6 3+ , suggesting a different surface potential. On the other hand, the approach curves recorded by using Fe(CN) 6 4- showed that both types of the aforementioned bismuth films exhibited local reactivity with the oxidised form of the redox mediator, and that bismuth film obtained with bromide ions exhibited slightly lower reactivity. The use of SECM in the scanning operation mode allowed us to ascertain that the bismuth deposits were uniformly distributed across the whole surface of the glassy carbon substrate electrode. Comparative AFM measurements corroborated the above findings and additionally revealed a denser growth of smaller bismuth crystals over the surface of the substrate electrode in the presence of bromide ions, while the crystals were bigger but sparser in the absence of bromide ions in the modification solution

Synthesis, characterization and DFT studies of two new silver(I) complexes with 3,4-lutidine

Science.gov (United States)

Soliman, Saied M.; Assem, Rania; Abu-Youssef, Morsy A. M.; Kassem, Taher S.

2015-04-01

The synthesis, characterization and molecular structure of two new Ag(I) complexes with 3,4-lutidine (34lut) have been reported. The [Ag(34lut)3(OAC)]; 1 and [Ag(34lut)2(TFA)]; 2 complexes, where OAC and TFA are acetate and trifluoroacetate respectively, have been characterized using elemental analysis, FTIR, NMR and mass spectra. Their molecular structures were calculated using DFT quantum chemical calculations. Both 1 and 2 were found to have distorted tetrahedral geometry around the Ag(I). The spectroscopic properties of the studied complexes have been calculated using the same level of theory. The Infrared vibrational frequencies of the COO stretches confirmed that the OAC is monodentate in 1 while the TFA is bidentate in 2. The calculated polarizability (α0) and HOMO-LUMO energy gap (ΔE) values indicated that 1 has higher NLO activity than 2. The electronic spectra of these complexes are calculated using the TD-DFT calculations. The calculated 1H NMR chemical shift values using GIAO approach showed good correlations with the experimental data. The interaction energies using the second order perturbation theory have been used to study the different intramolecular charge transfer interactions in the studied complexes. The NBO calculations indicated that both the Agsbnd O bonds are almost identical in 2 but not in 1.

Oxidation of nitrite by a trans-dioxoruthenium(VI) complex: direct evidence for reversible oxygen atom transfer.

Science.gov (United States)

Man, Wai-Lun; Lam, William W Y; Wong, Wai-Yeung; Lau, Tai-Chu

2006-11-15

Reaction of trans-[Ru(VI)(L)(O)(2)](2+) (1, L = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane, a tetradentate macrocyclic ligand with N(2)O(2) donor atoms) with nitrite in aqueous solution or in H(2)O/CH(3)CN produces the corresponding (nitrato)oxoruthenium(IV) species, trans-[Ru(IV)(L)(O)(ONO(2))](+) (2), which then undergoes relatively slow aquation to give trans-[Ru(IV)(L)(O)(OH(2))](2+). These processes have been monitored by both ESI/MS and UV/vis spectrophotometry. The structure of trans-[Ru(IV)(L)(O)(ONO(2))](+) (2) has been determined by X-ray crystallography. The ruthenium center adopts a distorted octahedral geometry with the oxo and the nitrato ligands trans to each other. The Ru=O distance is 1.735(3) A, the Ru-ONO(2) distance is 2.163(4) A, and the Ru-O-NO(2) angle is 138.46(35) degrees . Reaction of trans-[Ru(VI)(L)((18)O)(2)](2+) (1-(18)O(2)) with N(16)O(2)(-) in H(2)O/CH(3)CN produces the (18)O-enriched (nitrato)oxoruthenium(IV) species 2-(18)O(2). Analysis of the ESI/MS spectrum of 2-(18)O(2) suggests that scrambling of the (18)O atoms has occurred. A mechanism that involves linkage isomerization of the nitrato ligand and reversible oxygen atom transfer is proposed.

An azine based sensor for selective detection of Cu2 + ions and its copper complex for sensing of phosphate ions in physiological conditions and in living cells

Science.gov (United States)

Tiwari, Karishma; Kumar, Sumit; Kumar, Vipan; Kaur, Jeevanjot; Arora, Saroj; Mahajan, Rakesh Kumar

2018-02-01

A simple and cost effective unsymmetrical azine based Schiff base, 5-diethylamino-2-[(2-hydroxy-benzylidene)hydrazonomethyl]-phenol (1) was synthesized which selectively detect Cu2 + ions in the presence of other competitive ions through ;naked eye; in physiological conditions (EtOH-buffer (1:1, v/v, HEPES 10 mM, pH = 7.4)). The presence of Cu2 + induce color change from light yellow green to yellow with the appearance of a new band at 450 nm in UV-Vis spectra of Schiff base 1. The fluorescence of Schiff base 1 (10 μM) was quenched completely in the presence of 2.7 equiv. of Cu2 + ions. Sub-micromolar limit of detection (LOD = 3.4 × 10- 7 M), efficient Stern-Volmer quenching constant (KSV = 1.8 × 105 L mol- 1) and strong binding constant (log Kb = 5.92) has been determined with the help of fluorescence titration profile. Further, 1 - Cu2 + complex was employed for the detection of phosphate ions (PO43 -, HPO42 - and H2PO4-) at micromolar concentrations in EtOH-buffer of pH 7.4 based on fluorescence recovery due to the binding of Cu2 + with phosphate ions. Solubility at low concentration in aqueous medium, longer excitation (406 nm) and emission wavelength (537 nm), and biocompatibility of Schiff base 1 formulates its use in live cell imaging.

Complexometric determination: Part I - EDTA and complex formation with the Cu2+ ion

Directory of Open Access Journals (Sweden)

Rajković Miloš B.

2002-01-01

Full Text Available Compounds forming very stable complexes - chelates, have a wide field of application in analytical chemistry. The most famous group of these compounds are complexons. Complexons represent organic polyaminocarbonic acids as for example ethylenediaminetetraacetic acid (EDTA and its salts. The EDTA molecule has six coordinative sites. It is a hexadentate ligands i.e. it has two binding nitrogen atoms and four oxygen atoms from carboxyl groups and it forms complexes with almost all metal ions. EDTA as a tetraprotonic acid, H4Y disociates through four steps, yielding the ions HsY-, H2Y2-, HY3- and Y4-. Which of the EDTA forms will be encountered in a solution, depends on the pH. Due to the poor solubility of EDTA in pure water, as well as in most organic solvents, the disodium salt of EDTA Na2H2Y-2H2O, under the commercial name complexon III, is utilized for analytical determinations. In water, EDTA forms soluble, stabile chelate complexes with all cations, at the molar ratio 1:1, regardless of the charge of the metal ion. In contrast to other equilibria, which are mainly defined by Le Chatellier's principle, equilibria related to metal-EDTA complex formation are also dependent on the influence of the secondary equilibria of EDTA complex formation. Complexing reactions, which are equilibrium reactions, are simultaneously influenced by the following factors: solution pH and the presence of complexing agents which may also form a stabile complex with metal ions. The secondary reaction influence may be viewed and monitored through conditional stability constants. In the first part of the paper, the reaction of the formation of the Cu2+-ion complex with EDTA is analyzed beginning from the main reaction through various influences of secondary reactions on the complex Cu2+-EDTA: pH effect, complexation effect and hydrolysis effect. The equations are given for conditional stability constants, which include equilibrium reactions under actual conditions.

Characterization of inclusion complexes of organic ions with hydrophilic hosts by ion transfer voltammetry with solvent polymeric membranes.

Science.gov (United States)

Olmos, José Manuel; Laborda, Eduardo; Ortuño, Joaquín Ángel; Molina, Ángela

2017-03-01

The quantitative characterization of inclusion complexes formed in aqueous phase between organic ions and hydrophilic hosts by ion-transfer voltammetry with solvent polymeric membrane ion sensors is studied, both in a theoretical and experimental way. Simple analytical solutions are presented for the determination of the binding constant of the complex from the variation with the host concentration of the electrochemical signal. These solutions are valid for any voltammetric technique and for solvent polymeric membrane ion sensors comprising one polarisable interface (1PI) and also, for the first time, two polarisable interfaces (2PIs). Suitable experimental conditions and data analysis procedures are discussed and applied to the study of the interactions of a common ionic liquid cation (1-octyl-3-metyl-imidazolium) and an ionisable drug (clomipramine) with two hydrophilic cyclodextrins: α-cyclodextrin and 2-hydroxypropyl-β-cyclodextrin. The experimental study is performed via square wave voltammetry with 2PIs and 1PI solvent polymeric membranes and in both cases the electrochemical experiments enable the detection of inclusion complexes and the determination of the corresponding binding constant. Copyright © 2016 Elsevier B.V. All rights reserved.

Design and Beam Dynamics Studies of a Multi-Ion Linac Injector for the JLEIC Ion Complex

Energy Technology Data Exchange (ETDEWEB)

Ostroumov, P. N.; Plastun, A. S.; Mustapha, B.; Conway, Z. A.

2016-01-01

The electron-ion collider (JLEIC) being proposed at JLab requires a new ion accelerator complex which includes a linac capable of delivering any ion beam from hydrogen to lead to the booster. We are currently developing a linac which consists of several ion sources, a normal conducting (NC) front end, up to 5 MeV/u, and a SC section for energies > 5 MeV/u. This design work is focused on the beam dynamics and electrodynamics studies performed to design efficient and cost-effective accelerating structures for both the NC and SC sections of the linac. Currently, we are considering two separate RFQs for the heavy-ion and light-ion beams including polarized beams, and different types of NC accelerating structures downstream of the RFQ. Quarter-wave and half-wave resonators can be effectively used in the SC section.

Theoretical study of the nucleophilic addition of oximes to the nitrile complexes trans-/cis-[ReCl4(NCCH3)2

International Nuclear Information System (INIS)

Klestova-Nadeeva, E. A.; Kuznetsov, M. L.; Dement'ev, A. I.

2005-01-01

The reaction of nucleophilic addition of oximes (HON=CRR 1 ) to organic nitriles coordinated in the rhenium complexes trans-/cis-[ReCl 4 (NCCH 3 ) 2 ] was theoretically studied by the Hartree-Fock and density functional theory (B3LYP) methods. The reaction mechanism involves (I) the initial change of the oxime conformation; (II) the formation of the orientation complex with the coordinated nitrile molecule, which transforms into a four-membered transition state; (III) the formation of the addition product in a less stable conformation; and (IV) the formation of the ultimate addition product. The calculations make it possible to interpret the activation of nitriles in terms of the activated complex theory as a result of stabilization of the transition state in going from the free to the coordinated nitrile [ru

Trans-acting translational regulatory RNA binding proteins.

Science.gov (United States)

Harvey, Robert F; Smith, Tom S; Mulroney, Thomas; Queiroz, Rayner M L; Pizzinga, Mariavittoria; Dezi, Veronica; Villenueva, Eneko; Ramakrishna, Manasa; Lilley, Kathryn S; Willis, Anne E

2018-05-01

The canonical molecular machinery required for global mRNA translation and its control has been well defined, with distinct sets of proteins involved in the processes of translation initiation, elongation and termination. Additionally, noncanonical, trans-acting regulatory RNA-binding proteins (RBPs) are necessary to provide mRNA-specific translation, and these interact with 5' and 3' untranslated regions and coding regions of mRNA to regulate ribosome recruitment and transit. Recently it has also been demonstrated that trans-acting ribosomal proteins direct the translation of specific mRNAs. Importantly, it has been shown that subsets of RBPs often work in concert, forming distinct regulatory complexes upon different cellular perturbation, creating an RBP combinatorial code, which through the translation of specific subsets of mRNAs, dictate cell fate. With the development of new methodologies, a plethora of novel RNA binding proteins have recently been identified, although the function of many of these proteins within mRNA translation is unknown. In this review we will discuss these methodologies and their shortcomings when applied to the study of translation, which need to be addressed to enable a better understanding of trans-acting translational regulatory proteins. Moreover, we discuss the protein domains that are responsible for RNA binding as well as the RNA motifs to which they bind, and the role of trans-acting ribosomal proteins in directing the translation of specific mRNAs. This article is categorized under: RNA Interactions with Proteins and Other Molecules > RNA-Protein Complexes Translation > Translation Regulation Translation > Translation Mechanisms. © 2018 Medical Research Council and University of Cambridge. WIREs RNA published by Wiley Periodicals, Inc.

Iodine K-edge EXAFS analysis of iodide ion-cyclodextrin inclusion complexes in aqueous solution

International Nuclear Information System (INIS)

Kaneko, T; Ueda, M; Nagamatsu, S; Konishi, T; Fujikawa, T; Mizumaki, M

2009-01-01

We study the structure of inclusion complexes of α-, β-, γ-cyclodextrin with mono-iodide ion in aqueous solution by means of iodine K-edge EXAFS spectroscopy. The analysis is based on the assumption that two kinds of iodide ions exist in KI-cyclodextrin aqueous solution i.e. hydrated mono-iodide ions and one-one mono-iodide-cyclodextrin inclusion complexes. In KI-α-cyclodextrin system, iodine K-edge EXAFS analyse show that the average coordination number of the oxygen atoms in water molecules in the first hydration shell decreases as the fraction of included ions increases. This result suggests that dehydration process accompanies the formation of the inclusion complex. This is not found in the case of β-cyclodextrin, indicating that in this case the iodide ions are included together with the whole first hydration shell.

Decomposition of uranyl peroxo-carbonato complex ion in the presence of metal oxides in carbonate media

International Nuclear Information System (INIS)

Dong-Yong Chung; Min-Sung Park; Keun-Young Lee; Eil-Hee Lee; Kwang-Wook Kim; Jei-Kwon Moon

2015-01-01

Uranium oxide was dissolved in the form of the uranyl peroxo-carbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- in carbonate solutions with hydrogen peroxide. When UO 2 (O 2 )(CO 3 ) 2 4- ions lose their peroxide component, they become a stable species of uranyl tricarbonato complex ion, UO 2 (O 2 )(CO 3 ) 2 4- . The uranyl peroxo-carbonato complex self-decomposed more rapidly into the uranyl tricarbonato complex ion in the presence of a metal oxide in the carbonate solution. In this study, decomposition of the uranyl peroxo-carbonato complex in a carbonate solution was investigated in the presence of several metal oxides using absorption spectroscopy. (author)

Reaction of Non-Symmetric Schiff Base Metallo-Ligand Complexes Possessing an Oxime Function with Ln Ions

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Jean-Pierre Costes

2018-03-01

Full Text Available The preparation of non-symmetric Schiff base ligands possessing one oxime function that is associated to a second function such as pyrrole or phenol function is first described. These ligands, which possess inner N4 or N3O coordination sites, allow formation of cationic or neutral non-symmetric CuII or NiII metallo-ligand complexes under their mono- or di-deprotonated forms. In presence of Lanthanide ions the neutral complexes do not coordinate to the LnIII ions, the oxygen atom of the oxime function being only hydrogen-bonded to a water molecule that is linked to the LnIII ion. This surprising behavior allows for the isolation of LnIII ions by non-interacting metal complexes. Reaction of cationic NiII complexes possessing a protonated oxime function with LnIII ions leads to the formation of original and dianionic (Gd(NO352− entities that are well separated from each other. This work highlights the preparation of well isolated mononuclear LnIII entities into a matrix of diamagnetic metal complexes. These new complexes complete our previous work dealing with the complexing ability of the oxime function toward Lanthanide ions. It could open the way to the synthesis of new entities with interesting properties, such as single-ion magnets for example.

Study on complexed lead and cadmium ions removal from aqueous solutions by means of ion exchange method

International Nuclear Information System (INIS)

Dudzinska, M.

1992-01-01

The possibility of simultaneous removal of heavy metal ions and organic chelates from waste water has been studied. The experimental work has been preceded by extensive theoretical considerations and calculations of physico-chemical parameters of the process for model and real waste water systems. The negative influence of the presence of sulfate anions on cadmium and lead complexes removal in ion exchange process has been experimentally proved. In the systems free of sulfate anions or when their concentrations were low, the purification process conducted on Amberlite IRA-68 was very effective for cadmium and lead complexes removal. 112 refs, 78 figs, 15 tabs

Images of Complex Interactions of an Intense Ion Beam with Plasma Electrons

International Nuclear Information System (INIS)

Kaganovich, Igor D.; Startsev, Edward; Davidson, Ronald C.

2004-01-01

Ion beam propagation in a background plasma is an important scientific issue for many practical applications. The process of ion beam charge and current neutralization is complex because plasma electrons move in strong electric and magnetic fields of the beam. Computer simulation images of plasma interaction with an intense ion beam pulse are presented

Stability complexes of lanthanide ions with some macrocyclic polyethers

International Nuclear Information System (INIS)

Poluehktov, N.S.; Malinka, E.V.; Meshkova, S.B.; Bel'tyukova, S.V.; Danilkovich, M.M.

1984-01-01

Stability of lanthanide complexes with macrocyclic polyethers has been studied versus the number of f-electrons, spin- and orbital angular momenta of the Lu 3+ ion ground states. The following compounds were used as macrocyclic complexones: 12-crown-4 (12C4), tert-bulylbenzo-15-crown-5(BB15C5), 18-crown-6 (18C6), ditert-butylbenzo-18-crown-6(DBB18C6), dibenzo-30-crown-10 (DB30C10), cryptand [2, 2, 1] (Cr[2, 2, 1]). It is shoWn that the stability constants of the studied lanthanide complexes can be described rather satisfactorily by an expression suggested earlier that relates their values with the number of 4f-electrons and the S and L quantum numbers of the ground states of the lantharide ions

Trans fatty acid isomers and the trans-9/trans-11 index in fat containing foods

Science.gov (United States)

Kuhnt, Katrin; Baehr, Melanie; Rohrer, Carsten; Jahreis, Gerhard

2011-01-01

To determine trans fatty acid (TFA) distribution of contemporary foods, especially regarding individual trans octadecenoic acids (trans C18:1), 339 German foods of six categories (semi-solid fats, deep-fried potato products, bakery products, confectioneries, instant products and butter) were analysed using two GC methods. Results showed a high variation of TFA content between and within the categories containing between 0 and 40.5% of FAME except in butter, which is a source of natural TFA. The mean TFA values were below 2.0% of FAME, however, bakery products contained 4.5% and butter fat 3.2%, respectively. In addition, the distribution of individual trans C18:1 differed. In samples containing ruminant fat (butter and various confectioneries), vaccenic acid (t11-C18:1, t11) predominated, while in foods containing industrially hydrogenated fats, elaidic acid (trans-9, t9-) and t10-C18:1 were the major trans isomers.. This was reflected by a low t9/t11 index of 0.3 and 0.5 in butter and ruminant fat containing confectioneries, respectively, whilst the highest index was observed in shortenings and deep-fried potato products at 5.2 and 6.8, respectively. In conclusion, the TFA content of foods available on the German market is generally declining, but substantial variations are present. The t9/t11 index could be used as an indicator to determine ruminant fat. Practical applications: A number of studies provide evidence that a high TFA intake, particularly of industrial origin, adversely affects human health. The TFA content of foods could be reduced due to the introduction of several mandatory regulations and modifications regarding the hydrogenation process of oils. The most abundant dietary TFA are the isomers of trans C18:1. Unfortunately, the differentiation of these isomers is not yet very common, though the trans C18:1 profile differs depending on its origin (bacterial hydrogenation in the rumen or industrial hydrogenation). To date, data for TFA content

Investigation of Uranyl Nitrate Ion Pairs Complexed with Amide Ligands using Electrospray Ionization Ion Trap Mass Spectrometry and Density Functional Theory

International Nuclear Information System (INIS)

Groenewold, Gary S.; Dinescu, Adriana; Benson, Michael T.; Gresham, Garold L.; van Stipdonk, Michael J.

2011-01-01

Ion populations formed from electrospray of uranyl nitrate solutions containing different amides vary depending on ligand nucleophilicity and steric crowding at the metal center. The most abundant species were ion pair complexes having the general formula (UO2(NO3)(amide)n=2,3)+, and complexes containing the amide conjugate base, reduced uranyl UO2+, and a 2+ charge were also formed. The formamide experiment produced the greatest diversity of species that stems from weaker amide binding leading to dissociation and subsequent solvent coordination or metal reduction. Experiments using methyl formamide, dimethyl formamide, acetamide, and methyl acetamide produced ion pair and doubly charged complexes that were more abundant, and less abundant complexes containing solvent or reduced uranyl. This pattern is reversed in the dimethylacetamide experiment, which displayed reduced doubly charged complexes and augmented reduced uranyl complexes. DFT investigations of the tris-amide ion pair complexes showed that inter-ligand repulsion distorts the amide ligands out of the uranyl equatorial plane, and that complex stabilities do not increase with increasing amide nucleophilicity. Elimination of an amide ligand largely relieves the interligand repulsion, and the remaining amide ligands become closely aligned with the equatorial plane in the structures of the bis-amide ligands. The studies show that the phenomenological distribution of coordination complexes in a metal-ligand electrospray experiment is a function of both ligand nucleophilicity and interligand repulsion, and that the latter factor begins exerting influence even in the case of relatively small ligands like the substituted methyl-formamide and methyl-acetamide ligands.

X-ray Lβ215 emission spectrum of Ru in Ru(NH3)6Cl3

International Nuclear Information System (INIS)

Perera, R.C.C.; Barth, J.; LaVilla, R.E.; Nordling, C.

1984-07-01

One of the broader applications of synchrotron radiation has been to EXAFS studies for material structure determination, i.e., for an analysis of x-ray absorption over an extended energy region beyond a core ionization limit. Studies of the near edge structure (XANES) give a different type of information, characteristic of the local symmetry and electronic configuration of the absorbing atom. This type of information is reflected also in the x-ray emission spectra, in particular for transitions involving the valence levels. Examination of the near edge absorption or the emission spectrum does not require an instrument capable of scanning a wide energy range with high counting statistics, as does EXAFS; the needs are rather for good resolution and a reliable calibration of the energy scale. Some of the problems of near edge spectra were particularly evident in our investigation of Ru-Lβ 2 15 emission from Ru(NH 3 ) 6 Cl 3 . The Ru-Lβ 2 15 emission was measured with a laboratory Rowland circle x-ray spectrometer with a curved quartz (1010) crystal (radius = 22 inches) in a fixed position appropriate to the energy range, and a position sensitive detector which can be positioned along the Rowland circle. The Ru spectrum was excited mainly by Sn-L/sub α/ primary radiation from a Sn anode in a demountable x-ray tube operating at 13 kV and 120 mA. The resolution of the instrument in this region is 1.5 eV. An accurate calibration of the energy scale was conveniently obtained by measuring a reference x-ray emission line in the same instrumental configuration. In the present case the Pd-L/sub α/ emission line at 2838 eV was used to establish the energy scale. The energy dispersion of the instrument was determined from the Cl-K/sub β/ emission spectrum of CH 3 Cl between 2810 eV and 2830 eV and Pd-Lα 1 2 and extrapolated to the energy region of the recorded emission spectrum. 6 references, 1 figure

Theoretical level energies and transition data for 4p64d4, 4p64d34f and 4p54d5 configurations of W34+ ion

Science.gov (United States)

Karpuškienė, R.; Bogdanovich, P.; Kisielius, R.

2017-05-01

The ab initio quasirelativistic approach developed specifically for the calculation of spectral parameters of highly charged ions was used to derive transition data for the tungsten ion W34+. The configuration interaction method was applied to include electron correlation effects. The relativistic effects were taken into account in the Breit-Pauli approximation. The level energies, radiative lifetimes τ, Landé g-factors are determined for the ground configuration 4p64d4 and two excited configurations 4p64d34f and 4p54d5. The radiative transition wavelengths λ and emission transition probabilities A for the electric dipole, electric quadrupole, electric octupole, magnetic dipole, and magnetic quadrupole transitions among the levels of these configurations are produced.

Trans-Planckian wimpzillas

CERN Document Server

Kolb, E W; Tkachev, I I

2007-01-01

Two previously proposed conjectures--gravitational trans-Planckian particle creation in the expanding universe, and the existence of ultra-heavy stable particles with masses up to the Planck scale (wimpzillas)--are combined in a proposal for trans-Planckian particle creation of wimpzillas. It is shown that the trans-Planckian particle creation parameter should be rather small to avoid overproduction of such particles. This ensures that wimpzillas are mainly created at the end of primordial inflation. Conditions under which trans-Planckian wimpzillas can constitute the present dark matter are determined.

Effect of Trans, Trans-Farnesol on Pseudogymnoascus destructans and Several Closely Related Species.

Science.gov (United States)

Raudabaugh, Daniel B; Miller, Andrew N

2015-12-01

Bat white-nose syndrome, caused by the psychrophilic fungus Pseudogymnoascus destructans, has dramatically reduced the populations of many hibernating North American bat species. The search for effective biological control agents targeting P. destructans is of great importance. We report that the sesquiterpene trans, trans-farnesol, which is also a Candida albicans quorum sensing compound, prevented in vitro conidial germination for at least 14 days and inhibited growth of preexisting hyphae of five P. destructans isolates in filtered potato dextrose broth at 10 °C. Depending on the inoculation concentrations, both spore and hyphal inhibition occurred upon exposure to concentrations as low as 15-20 µM trans, trans-farnesol. In contrast, most North American Pseudogymnoascus isolates were more tolerant to the exposure of trans, trans-farnesol. Our results suggest that some Candida isolates may have the potential to inhibit the growth of P. destructans and that the sesquiterpene trans, trans-farnesol has the potential to be utilized as a biological control agent.

A simplified study of trans-mitral Doppler patterns

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Thomas George

2008-11-01

Full Text Available Abstract Background Trans-mitral Doppler produces complex patterns with a great deal of variability. There are several confusing numerical measures and indices to study these patterns. However trans-mitral Doppler produces readymade data visualization by pattern generation which could be interpreted by pattern analysis. By following a systematic approach we could create an order and use this tool to study cardiac function. Presentation of the hypothesis In this new approach we eliminate the variables and apply pattern recognition as the main criterion of study. Proper terminologies are also devised to avoid confusion. In this way we can get some meaningful information. Testing the hypothesis Trans-mitral Doppler should be seen as patterns rather than the amplitude. The hypothesis can be proven by logical deduction, extrapolation and elimination of variables. Trans-mitral flow is also analyzed vis-à-vis the Starling's Law applied to the left atrium. Implications of the hypothesis Trans-mitral Doppler patterns are not just useful for evaluating diastolic function. They are also useful to evaluate systolic function. By following this schema we could get useful diagnostic information and therapeutic options using simple pattern recognition with minimal measurements. This simplified but practical approach will be useful in day to day clinical practice and help in understanding cardiac function better. This will also standardize research and improve communication.

Kinetics and mechanisms of the oxidation of iodide and bromide in aqueous solutions by a trans-dioxoruthenium(VI) complex.

Science.gov (United States)

Lam, William W Y; Man, Wai-Lun; Wang, Yi-Ning; Lau, Tai-Chu

2008-08-04

The kinetics and mechanisms of the oxidation of I (-) and Br (-) by trans-[Ru (VI)(N 2O 2)(O) 2] (2+) have been investigated in aqueous solutions. The reactions have the following stoichiometry: trans-[Ru (VI)(N 2O 2)(O) 2] (2+) + 3X (-) + 2H (+) --> trans-[Ru (IV)(N 2O 2)(O)(OH 2)] (2+) + X 3 (-) (X = Br, I). In the oxidation of I (-) the I 3 (-)is produced in two distinct phases. The first phase produces 45% of I 3 (-) with the rate law d[I 3 (-)]/dt = ( k a + k b[H (+)])[Ru (VI)][I (-)]. The remaining I 3 (-) is produced in the second phase which is much slower, and it follows first-order kinetics but the rate constant is independent of [I (-)], [H (+)], and ionic strength. In the proposed mechanism the first phase involves formation of a charge-transfer complex between Ru (VI) and I (-), which then undergoes a parallel acid-catalyzed oxygen atom transfer to produce [Ru (IV)(N 2O 2)(O)(OHI)] (2+), and a one electron transfer to give [Ru (V)(N 2O 2)(O)(OH)] (2+) and I (*). [Ru (V)(N 2O 2)(O)(OH)] (2+) is a stronger oxidant than [Ru (VI)(N 2O 2)(O) 2] (2+) and will rapidly oxidize another I (-) to I (*). In the second phase the [Ru (IV)(N 2O 2)(O)(OHI)] (2+) undergoes rate-limiting aquation to produce HOI which reacts rapidly with I (-) to produce I 2. In the oxidation of Br (-) the rate law is -d[Ru (VI)]/d t = {( k a2 + k b2[H (+)]) + ( k a3 + k b3[H (+)]) [Br (-)]}[Ru (VI)][Br (-)]. At 298.0 K and I = 0.1 M, k a2 = (2.03 +/- 0.03) x 10 (-2) M (-1) s (-1), k b2 = (1.50 +/- 0.07) x 10 (-1) M (-2) s (-1), k a3 = (7.22 +/- 2.19) x 10 (-1) M (-2) s (-1) and k b3 = (4.85 +/- 0.04) x 10 (2) M (-3) s (-1). The proposed mechanism involves initial oxygen atom transfer from trans-[Ru (VI)(N 2O 2)(O) 2] (2+) to Br (-) to give trans-[Ru (IV)(N 2O 2)(O)(OBr)] (+), which then undergoes parallel aquation and oxidation of Br (-), and both reactions are acid-catalyzed.

Sustained release of antibiotic complexed by multivalent ion: in vitro and in vivo study for the treatment of peritonitis.

Science.gov (United States)

Na, Seung Yeon; Oh, Se Heang; Kim, Tae Ho; Yoon, Jin A; Lee, In Soo; Lee, Jin Ho

2014-12-10

The main aims of this study are (i) the development of an antibiotic complexed with multivalent ion, which can allow sustained release of the antibiotic without any additional matrix or difficult process and (ii) the feasibility study of the ion-complexed antibiotic as a therapeutic technique for peritonitis treatment. An ion-complexed antibiotic is prepared by simple mixing of two aqueous solutions containing an ionized (water-soluble) drug (tetracycline) and a multivalent counter ionic compound. The ion-complexed antibiotic shows a continuous release of the antibiotic up to 21 days, and thus prolonged anti-bacterial effect by gradual ionic exchange between the multivalent ions in the complex and same-charged monovalent ions in surrounding medium. From the in vivo animal study using a cecum perforated peritonitis mouse model, the ion-complexed antibiotic group shows sufficient anti-bacterial effect and thus effectively treat the peritonitis because of the extermination of the contaminated enteric bacteria in the peritoneum during wound healing of injury cecum (by the sustained release of antibiotic from the ion complex). These results suggest that the ion-complexed antibiotic system may be promising for the effective treatment of the peritonitis caused by frequent gastrointestinal defect in clinical fields. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis, spectral, thermal studies and electrical conductivity of Co (II) and Ni (II) complexes 3-[4-dimethylaminophenyl]-1-(2-pyridyl) prop-2-en-1-one (DMAPP)

Energy Technology Data Exchange (ETDEWEB)

Gaber, Mohamed, E-mail: abuelazm@yahoo.com [Chemistry Department, Faculty of Science, Tanta University, 31527 Tanta (Egypt); Al-Daly, Samy; Fayed, Tarek [Chemistry Department, Faculty of Science, Tanta University, 31527 Tanta (Egypt); El-Sayed, Yousif [Department of Chemistry, Faculty of Science, Tanta University, Tanta (Egypt)

2015-01-15

Co(II) and Ni(II) complexes of 3-[4-dimethylaminophenyl]-1-(2-pyridyl)prop-2-en-1-one have been prepared and characterized on the basis of elemental analyses, molar conductance, magnetic susceptibility measurements, IR, electronic spectra as well as thermal studies. The magnetic and spectral studies suggested the octahedral geometry for Co(II) and Ni(II) complexes. The kinetic parameters of the thermal decomposition stages have been evaluated using Coats–Redfern method. The electrical conductivity of the titled ligand and its Co(II) complexes was studied. The effects of different alcoholic solvents, pH and temperature on the complexation formation were considered. Also, the effect of Co(II) and Ni(II) ions on the emission spectrum of the free DMAPP was assigned. The stoichiometry of the metal complexes, the conditional formation constant, free energy, Beer{sup '}s law, molar extinction coefficient as well as specific absorptivity were evaluated. The ability of using the titled ligand as metalochromic indicator in complexometric titration was studied.

Confined Li ion migration in the silicon-graphene complex system: An ab initio investigation

Science.gov (United States)

Wang, Guoqing; Xu, Bo; Shi, Jing; Lei, Xueling; Ouyang, Chuying

2018-04-01

Silicon-Carbon complex systems play an important role in enhancing the performance of Si-based anode materials for Li ion batteries. In this work, the Li migration property of the Silicon-Graphene (Si-Gr) complex systems are investigated by using first-principles calculations. Especially, the effects of graphene coating on the migration of Li ions are discussed in detail. The distance between Si surface and graphene in the Si-Gr system significantly affects the lateral migration of Li ions. With the decrease of the distance from 4.715 to 3.844 Å, the energy barrier of Li ion migration also decreases from 0.115 to 0.067 eV, which are all lower than that of the case without graphene d(0.135 eV). However, smaller distance (3.586 Å) brings the high energy barrier (0.237 eV). Through AIMD calculations, it is found that the graphene coating in the Si-Gr complex system would result in the larger intercalation depths, more uniform distributions, and higher migration coefficients of Li ions. Further calculations of migration coefficients of Li ions at different temperature are used to obtained the activation energy for Li ions migration in the Si-Gr system, which is as low as 0.028 eV. This low activation energy shows that it is easy for Li ions migrating in the Si-Gr system. Our study provided the basically information to understand the migration mechanism of Li ions in Si-C system.

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

Science.gov (United States)

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

Trans labilization of am(m)ine ligands from platinum(II) complexes by cancer cell extracts.

Science.gov (United States)

Kasherman, Yonit; Sturup, Stefan; Gibson, Dan

2009-03-01

Cisplatin, cis-[Pt(NH(3))(2)Cl(2)], is an effective anticancer agent in wide clinical use whose efficacy is affected by cellular interactions with sulfur-containing nucleophiles. These interactions can potentially enhance the efficacy of the drug by mediating its delivery to nuclear DNA or inactivate the drug by binding to it irreversibly or by labilizing the NH(3) ligands. Despite the potential importance of trans-labilization reactions in the mechanism of action of the drug, few detailed studies on trans labilization of the ammines have been conducted. We used 2D NMR to show that some trans labilization occurs in proliferating cells and that aqueous extracts of cancer cells labilized 20% of the amine ligands of cis-[PtCl(2)((13)CH(3)NH(2))(2)] after a 12-h incubation. Both low molecular mass nucleophiles (less than 3 kDa) and high molecular mass nucleophiles (more than 3 kDa) labilize the amines with similar efficiency. Studies with model compounds show that thiols and thioethers bind to platinum(II) at similar rates, but thioethers are significantly more efficient at labilizing the am(m)ine at lower pH. N-Acetylcysteine is a more efficient trans-labilizer than glutathione, suggesting that the displacement of the amine proceeds through an associative mechanism. The lag time, the time that elapses from the formation of the Pt-S bond till the release of the amine trans to the sulfur, depends on the pH (for thiols), increasing at lower pH. Quantification of the platinum adducts obtained from incubation of cisplatin with cell extracts indicates that two thirds of the platinum is bound to cellular components with molecular mass greater than 3 kDa.

Rpa4, a homolog of the 34-kilodalton subunit of the replication protein A complex.

OpenAIRE

Keshav, K F; Chen, C; Dutta, A

1995-01-01

Replication protein A (RPA) is a complex of three polypeptides of 70, 34, and 13 kDa isolated from diverse eukaryotes. The complex is a single-stranded DNA-binding protein essential for simian virus 40-based DNA replication in vitro and for viability in the yeast Saccharomyces cerevisiae. We have identified a new 30-kDa human protein which interacts with the 70- and 13-kDa subunits of RPA, with a yeast two-hybrid/interaction trap method. This protein, Rpa4, has 47% identity with Rpa2, the 34-...

Double hydrogen atom transfer in lactamide radical cations via ion-neutral complexes

Science.gov (United States)

Friedrichs, Heike; McGibbon, Graham A.; Schwarz, Helmut

1996-02-01

Tandem mass spectrometry experiments on lactamide and deuterium-labelled isotopomers show that the reaction of metastable ions CH3CH(OH)CONH2·+ --> CH3CO· + HC(OH)NH2+ occurs via ion-neutral complexes. The experimental findings are complemented by density functional theory calculations.

9,10-phenanthrenesemiquinone radical complexes of ruthenium(III), osmium(III) and rhodium(III) and redox series.

Science.gov (United States)

Biswas, Manas Kumar; Patra, Sarat Chandra; Maity, Amarendra Nath; Ke, Shyue-Chu; Weyhermüller, Thomas; Ghosh, Prasanta

2013-05-14

parameters well prompting the coordination of PQ(˙-) to the M(III) ions. The comparatively shorter C-O lengths, 1.268(4) and 1.266(5) Å and the longer C-C length, 1.466(6) Å, are consistent with the PQ chelation to osmium(II) ion in 4(+). The reversible anodic waves at 0.22, 0.22, and 0.18 V of 1-3, referenced by the Fc(+)/Fc couple, are assigned to the PQ(˙-)/PQ couple forming PQ complexes as trans/cis-[M(III)(PQ)(PPh3)2X2](+) while the cathodic waves at -0.92 and -0.89 V of 2 and 3 are due to formations of PQ(2-) complexes as trans-[M(III)(PQ(2-))(PPh3)2X2](-). 1 displays two overlapping cathodic waves at -0.72(89), -1.0(120) V. EPR spectrum of the frozen glass of 1(-) along with DFT calculations detected the contribution of both the valence tautomers, trans-[Ru(III)(PQ(2-))(PPh3)2Cl2](-) (g1 = g2 = 2.456; g3 = 1.983) and trans-[Ru(II)(PQ(˙-))(PPh3)2X2](-) (g(iso) = 1.999) in the anion. The characteristic lower energy absorption bands of 1 and 2 at 700 nm were assigned to CSS-OSS perturbation MLCT those are absent in paramagnetic 3, 1(+), 2(+), 1(-), 2(-) and 4(+) complexes, investigated by spectro-electrochemical measurements and time dependent (TD) DFT calculations on 1Me, 2Me, 1Me(+) and 1Me(-).

Proton transfer and complex formation of angiotensin I ions with gaseous molecules at various temperature

International Nuclear Information System (INIS)

Nonose, Shinji; Yamashita, Kazuki; Sudo, Ayako; Kawashima, Minami

2013-01-01

Highlights: • Proton transfer from angiotensin I ions (z = 2, 3) to gaseous molecules was studied. • Temperature dependence of absolute reaction rate constants was measured. • Remarkable changes were obtained for distribution of product ions and reaction rate constants. • Proton transfer reaction was enhanced and reduced by complex formation. • Conformation changes are induced by complex formation and or by thermal collision with He. - Abstract: Proton transfer reactions of angiotensin I ions for +2 charge state, [M + 2H] 2+ , to primary, secondary and aromatic amines were examined in the gas phase. Absolute reaction rate constants for proton transfer were determined from intensities of parent and product ions in the mass spectra. Temperature dependence of the reaction rate constants was measured. Remarkable change was observed for distribution of product ions and reaction rate constants. Proton transfer reaction was enhanced or reduced by complex formation of [M + 2H] 2+ with gaseous molecules. The results relate to conformation changes of [M + 2H] 2+ with change of temperature, which are induced by complex formation and or by thermal collision with He. Proton transfer reactions of angiotensin I ions for +3 charge state, [M + 3H] 3+ , were also studied. The reaction rates did not depend on temperature so definitely

Superconducting racetrack booster for the ion complex of MEIC

Energy Technology Data Exchange (ETDEWEB)

Filatov, Yu [Joint Inst. for Nuclear Research (JINR), Dubna (Russian Federation); Moscow Inst. of Physics and Technology (MIPT), Moscow (Russian Federation); Kondratenko, A. M. [Science and Technique Laboratory ' Zaryad' , 630090, Novosibirsk, Russia; Kondratenko, M. A. [Science and Technique Laboratory ' Zaryad' , 630090, Novosibirsk, Russia; Kovalenko, A. [Joint Inst. for Nuclear Research (JINR), Dubna (Russian Federation); Derbenev, Yaroslav S. [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States); Lin, Fanglei [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States); Morozov, Vasiliy S. [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States); Zhang, Yuhong [Thomas Jefferson National Accelerator Facility (TJNAF), Newport News, VA (United States)

2016-02-01

The current design of the Medium-energy Electron-Ion Collider (MEIC) project at Jefferson lab features a single 8 GeV/c figure-8 booster based on super-ferric magnets. Reducing the circumference of the booster by switching to a racetrack design may improve its performance by limiting the space charge effect and lower its cost. We consider problems of preserving proton and deuteron polarizations in a superconducting racetrack booster. We show that using magnets based on hollow high-current NbTi composite superconducting cable similar to those designed at JINR for the Nuclotron guarantees preservation of the ion polarization in a racetrack booster up to 8 GeV/c. The booster operation cycle would be a few seconds that would improve the operating efficiency of the MEIC ion complex.

Structural Information Inference from Lanthanoid Complexing Systems: Photoluminescence Studies on Isolated Ions

Science.gov (United States)

Greisch, Jean Francois; Harding, Michael E.; Chmela, Jiri; Klopper, Willem M.; Schooss, Detlef; Kappes, Manfred M.

2016-06-01

The application of lanthanoid complexes ranges from photovoltaics and light-emitting diodes to quantum memories and biological assays. Rationalization of their design requires a thorough understanding of intramolecular processes such as energy transfer, charge transfer, and non-radiative decay involving their subunits. Characterization of the excited states of such complexes considerably benefits from mass spectrometric methods since the associated optical transitions and processes are strongly affected by stoichiometry, symmetry, and overall charge state. We report herein spectroscopic measurements on ensembles of ions trapped in the gas phase and soft-landed in neon matrices. Their interpretation is considerably facilitated by direct comparison with computations. The combination of energy- and time-resolved measurements on isolated species with density functional as well as ligand-field and Franck-Condon computations enables us to infer structural as well as dynamical information about the species studied. The approach is first illustrated for sets of model lanthanoid complexes whose structure and electronic properties are systematically varied via the substitution of one component (lanthanoid or alkali,alkali-earth ion): (i) systematic dependence of ligand-centered phosphorescence on the lanthanoid(III) promotion energy and its impact on sensitization, and (ii) structural changes induced by the substitution of alkali or alkali-earth ions in relation with structures inferred using ion mobility spectroscopy. The temperature dependence of sensitization is briefly discussed. The focus is then shifted to measurements involving europium complexes with doxycycline an antibiotic of the tetracycline family. Besides discussing the complexes' structural and electronic features, we report on their use to monitor enzymatic processes involving hydrogen peroxide or biologically relevant molecules such as adenosine triphosphate (ATP).

Stability constants of the Europium complexes with the chloride ions; Constantes de estabilidad de los complejos del europio con los iones cloruro

Energy Technology Data Exchange (ETDEWEB)

Jimenez R, M.; Solache R, M.; Rojas H, A. [Instituto Nacional de Investigaciones Nucleares, Departamento de Quimica, A.P. 18-1027, C.P. 11801 Mexico D.F. (Mexico)

2000-07-01

The stability constants of lanthanides complexes with chloride ions which were determined at the same ionic force but in different media, are significantly different. It does not exist a systematic study over these stability constants. The purpose of this work is to determine the stability constants of the europium complexes with chloride ions at 303 K, by the solvents extraction method. (Author)

Complexation and extraction of series 4f, 5f and 4d ions by dialkyldithiophosphoric acids

International Nuclear Information System (INIS)

Fitoussi, Richard.

1982-04-01

A study was carried out on the complexing and extracting properties of various dialkyldithiophosphoric acids towards ions of the 4f, 5f and 4d series. Sulphurated donors complex and extract ions of the 4f and 5f series less strongly than their oxygenated homologues. However the affinity of trivalent actinide ions for dialkythiophosphate ions is shown to be greater than that of lanthanides. The conditions of ruthenium extraction from nitric acid are defined [fr

Spectrophotometric study of neptunium (VI) complexation by nitrate ions; Etude par spectrophotometrie de la complexation du neptunium au degre d'oxydation (VI) par les ions nitrates

Energy Technology Data Exchange (ETDEWEB)

Pochon, P. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification (DRRV), 30 - Marcoule (France)]|[Conservatoire National des Arts et Metiers (CNAM), 75 - Paris (France)]|[Centre Regional Associe de Lyon, 69 (France)

2000-07-01

Neptunium(VI) complexation by nitrate ions was investigated by visible and near-infrared spectrophotometry, a technique suitable for observing the appearance and evolution of the species in solution. In the absence of reference spectra for Np(VI) nitrate- complexes, mathematical (factor analysis) tools were used to interpret the spectra. These chemo-metric techniques were first tested and validated on a simpler chemical system: Np(VI)complexation by the SiW{sub 11}O{sub 39}{sup 8-} anion. The test media used to investigate Np(VI) nitrate- complexes generally contain nitrate and perchlorate salts at high concentrations (high ionic strength). Media effects arising from the presence of cations, acidity or the perchlorate ion concentration are therefore significant, and no doubt account for the scattered values of the complexation constants published in the literature. The evolution of the neptunium spectra according to the parameters of the reaction medium illustrated these effects and allowed them to be quantified by a global 'perturbation constant'. In order to minimize the spectrum modifications due to media effects, the neptunium nitrate-complexes were studied at constant ionic strength in weak acidic media (2 mol.kg{sup -1}{sub H2O}) in the presence of sodium salts. The bulk formation constants and the spectrum of the NpO{sub 2}(NO{sub 3}){sup +} complex were determined for ionic strength values of 2.2, 4, 6 and 8 mol.kg{sup -1}{sub H2O}. The constants remained on the same order of magnitude regardless of the ionic strength; the thermodynamic constant {beta}{sub 1}{sup 0} determined from them according to specific interaction theory is thus probably of little significance. Conversely, the bulk constants can be corrected for the effects of the perchlorate ions by taking the global 'perturbation constant' into account. (author)

On the possibility of removing of transition metal ions from sewage using polymeric complexes

International Nuclear Information System (INIS)

Tazhibaeva, S.M.; Abilov, Zh.A.; Musabekov, K.V.

1997-01-01

The possibility of using of complexation in the system polyethylene-imine transition metal ions (Cu 2+ , Ni 2+ , Co 2+ )-surface active substance for removing of metal ions from solution and sewage has been investigated. It is shown, that pH of medium, hydro-fugitive of system and ratio between component of the triply complex effect on purification of solution. (author)

Theory Meets Experiment: Metal Ion Effects in HCV Genomic RNA Kissing Complex Formation

Directory of Open Access Journals (Sweden)

Li-Zhen Sun

2017-12-01

Full Text Available The long-range base pairing between the 5BSL3. 2 and 3′X domains in hepatitis C virus (HCV genomic RNA is essential for viral replication. Experimental evidence points to the critical role of metal ions, especially Mg2+ ions, in the formation of the 5BSL3.2:3′X kissing complex. Furthermore, NMR studies suggested an important ion-dependent conformational switch in the kissing process. However, for a long time, mechanistic understanding of the ion effects for the process has been unclear. Recently, computational modeling based on the Vfold RNA folding model and the partial charge-based tightly bound ion (PCTBI model, in combination with the NMR data, revealed novel physical insights into the role of metal ions in the 5BSL3.2-3′X system. The use of the PCTBI model, which accounts for the ion correlation and fluctuation, gives reliable predictions for the ion-dependent electrostatic free energy landscape and ion-induced population shift of the 5BSL3.2:3′X kissing complex. Furthermore, the predicted ion binding sites offer insights about how ion-RNA interactions shift the conformational equilibrium. The integrated theory-experiment study shows that Mg2+ ions may be essential for HCV viral replication. Moreover, the observed Mg2+-dependent conformational equilibrium may be an adaptive property of the HCV genomic RNA such that the equilibrium is optimized to the intracellular Mg2+ concentration in liver cells for efficient viral replication.

Trans-Cultural, Trans-Language Practices: Potentialities for Rethinking Doctoral Education Pedagogies

Directory of Open Access Journals (Sweden)

Sarojni Choy

2017-01-01

Full Text Available Over the last decade, there has been a rapid increase in doctoral enrolments of Asian international students in Australian universities. While policies have been developed to meet the needs of these students, there seems to be some confusion around the terms internationalisation, globalisation, bi-cultural, inter-cultural, multi-cultural, and trans-cultural within these policies. In this paper, we define these terms and advocate for a policy position which orients to a futurist definition of culture. We then review the work of Michael Singh and his research team at Western Sydney University who have responded to this rapid increase in Asian international student doctoral enrolments in Australian universities by developing pedagogic principles around notions of trans-language and trans-cultural practices. In the final section of the paper, we then draw on our own experiences of doctoral supervision in Australian universities to reflect on our positioning within the pedagogic principles around trans-language and trans-cultural practices.

Complex versus simple models: ion-channel cardiac toxicity prediction.

Science.gov (United States)

Mistry, Hitesh B

2018-01-01

There is growing interest in applying detailed mathematical models of the heart for ion-channel related cardiac toxicity prediction. However, a debate as to whether such complex models are required exists. Here an assessment in the predictive performance between two established large-scale biophysical cardiac models and a simple linear model B net was conducted. Three ion-channel data-sets were extracted from literature. Each compound was designated a cardiac risk category using two different classification schemes based on information within CredibleMeds. The predictive performance of each model within each data-set for each classification scheme was assessed via a leave-one-out cross validation. Overall the B net model performed equally as well as the leading cardiac models in two of the data-sets and outperformed both cardiac models on the latest. These results highlight the importance of benchmarking complex versus simple models but also encourage the development of simple models.

Complex versus simple models: ion-channel cardiac toxicity prediction

Directory of Open Access Journals (Sweden)

Hitesh B. Mistry

2018-02-01

Full Text Available There is growing interest in applying detailed mathematical models of the heart for ion-channel related cardiac toxicity prediction. However, a debate as to whether such complex models are required exists. Here an assessment in the predictive performance between two established large-scale biophysical cardiac models and a simple linear model Bnet was conducted. Three ion-channel data-sets were extracted from literature. Each compound was designated a cardiac risk category using two different classification schemes based on information within CredibleMeds. The predictive performance of each model within each data-set for each classification scheme was assessed via a leave-one-out cross validation. Overall the Bnet model performed equally as well as the leading cardiac models in two of the data-sets and outperformed both cardiac models on the latest. These results highlight the importance of benchmarking complex versus simple models but also encourage the development of simple models.

Template Synthesis, Crystal Structure, and Magnetic Properties of a Dinuclear Copper(II) Complex with Cooperative Hydrogen Bonding

International Nuclear Information System (INIS)

Kang, Shin Geol; Nam, Kwang Hee; Min, Kil Sik; Lee, Uk

2011-01-01

The dinuclear complex with cooperative hydrogen bonds can be prepared by the metal-directed reaction of Eq. This work shows that the coordinated hydroxyl group trans to the secondary amino group is deprotonated more readily than that trans to the tertiary amino group and acts as the hydrogen-bond accepter. The lattice water molecules in act as bridges between the two mononuclear units through hydrogen bonds. The complex is quite stable as the dimeric form even in various polar solvents. The complex exhibits a weak antiferromagnetic interaction between the metal ions in spite of relatively long Cu···Cu distance. This strongly supports the suggestion that the antiferromagnetic behavior is closely related to the cooperative hydrogen bonds. The design and synthesis of polynuclear transition metal complexes have received much attention because of their potential applications in various fields, such as catalysis, supramolecular chemistry, and materials chemistry. Until now, various types of dinuclear copper(II) complexes have been prepared and investigated. Some dinuclear copper(II) complexes resulting from cooperative hydrogen bonding, such as containing two N_2O_2 donor sets, are also reported

The Possibility of Ce3+ and Mn2+ Complex Ions Formation With Iodine Species in a Dushman Reaction

Directory of Open Access Journals (Sweden)

Iurie Ungureanu

2018-06-01

Full Text Available This contribution presents investigations into possible effects of Ce3+ and Mn2+ on the reduction of UV-spectral signal for I3- observed e.g. in the Dushman reaction. The potential of the metal ions to form complexes with iodine-containing species was analysed. It was shown that no complex ions are formed between Ce3+ and Mn2+ metals ions with IO3-, I-, I2 species. Only the formation of a very weak CeI32+ complex ion was found to occur. An effect of a complex formation on the studied systems could be excluded.

Dimeric Complexes of Tryptophan with M2+ Metal Ions

NARCIS (Netherlands)

Dunbar, R. C.; Steill, J. D.; Polfer, N. C.; Oomens, J.

2009-01-01

IRMPD spectroscopy using the FELIX free electron laser and a Fourier transform ICR mass spectrometer was used to characterize the structures of electrosprayed dimer complexes M(2+)Trp(2) of tryptophan with a series of eight doubly charged metal ions, including alkaline earths Ca, Sr, and Ba, and

Trans* Leadership.

Science.gov (United States)

Jourian, T J; Simmons, Symone L

2017-06-01

Focusing on emerging literature on trans* and gender-nonconforming students and their leadership, this chapter outlines the ways trans* students are engaged in leadership in educational institutions and outside of them and discusses implications for staff and faculty regarding how to support and engage these students and their leadership. © 2017 Wiley Periodicals, Inc., A Wiley Company.

The study of Cr(III) complexation in the xylem sap using ion exchange and radiotracer

International Nuclear Information System (INIS)

Juneja, Shikha; Prakash, Satya

2003-01-01

Radiotracer was employed to carry out ion exchange experiments to study the chromium speciation in the in vitro samples of xylem sap of maize stem of 60 days old plants. Cr(III) radiolabelled with its radioactive isotope ( 51 Cr) was mixed with both the ion exchange fraction of the sap which represented the carboxylic acids, as well as the whole sap and was analysed for complexation after 10 and 30 days at 25 degC. Prior to this, the ion exchange elution chromatography of Cr(III), and the Cr(III) complexes with oxalic and citric acid were used to compare the complexes being formed in the in vitro studies. The in vitro Cr(III) complexation results indicated that Cr(III) was vitally present as anionic species. The elution curve trend was similar to that of citric acid complexation. Citric acid was also found to be the major complexing acid in the xylem sap as determined by HPLC. The results indicate the transportation of Cr(III) as a citrate complex in the xylem sap of maize plants. (author)

Ion chromatographic determination of vanadium (4) and vanadium (5) in the form of EDTA complexes

International Nuclear Information System (INIS)

Komarova, T.V.; Obrezkov, O.N.; Shpigun, O.A.

1991-01-01

Ion chromatographic behaviour of V 4+ and V 5+ -EDTA complexes (1,2) and V 5+ -EDTA monoperoxo complexes (3) has been studied. The regularities of ion exchange are obeyed for 1 and 3 complexes. These complex anions are strongly retained on HIX-1 anion exchanger. The chromatographic characteristics of 2 change in time, therefore its determination is impossible under the conditions studied. A method has been developed of the simultaneous determination of V 4+ and V 5+ which is based on retarded formation of the V 5+ -EDTA monoperoxo complex in a system of V 4+ -EDTA - H 2 O 2

Structure and luminescent property of complexes of aryl carboxylic acid-functionalized polystyrene with Eu(III) and Tb(III) ions.

Science.gov (United States)

Gao, Baojiao; Shi, Nan; Qiao, Zongwen

2015-11-05

Via polymer reactions, naphthoic acid (NA) and benzoic acid (BA) were bonded onto the side chains of polystyrene (PS), respectively, and two aryl carboxylic acid-functionalized polystyrenes, PSNA and PSBA, were obtained. Using PSNA and PSBA as macromolecule ligands and Eu(3+) and Tb(3+) ions as central ions, various luminescent binary polymer-rare earth complexes were prepared. At the same time, with 1,10-phenanthroline (Phen) and 4,4'-bipyridine (Bipy) as small-molecule co-ligands, various ternary polymer-rare earth complexes were also prepared. On the basis of characterizing PSNA, PSBA and complexes, the relationship between structure and luminescent property for these prepared complexes were mainly investigated. The study results show that the macromolecule ligands PSNA and PSBA, or the bonded NA and BA ligands, can strongly sensitize the fluorescence emissions of Eu(3+) ion or Tb(3+) ion, but the sensitization effect is strongly dependent on the structure of the ligands and the property of the central ions, namely it is strongly dependent on the matching degree of energy levels. The fluorescence emission of the binary complex PS-(NA)3-Eu(III) is stronger than that PS-(BA)3-Eu(III), indicating ligand NA has stronger sensitization action for Eu(3+) ion than ligand BA; the binary complex PS-(BA)3-Tb(III) emit strong characteristic fluorescence of Tb(3+) ion, displaying that ligand BA can strongly sensitize Tb(3+) ion, whereas the binary complex PS-(NA)3-Tb(III) nearly does not emit the characteristic fluorescence of Tb(3+) ion, showing that ligand NA does not sensitize Tb(3+) ion. The fluorescence intensity of the ternary complexes is much stronger than that of the binary complexes in the same series. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation and characterization of trans-RhCl(CO)(TPPTS)2-intercalated layered double hydroxides

International Nuclear Information System (INIS)

Zhang Xian; Wei Min; Pu Min; Li Xianjun; Chen Hua; Evans, David G.; Duan Xue

2005-01-01

trans-RhCl(CO)(TPPTS) 2 (TPPTS=tris(m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and 31 P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS) 2 was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS) 2 is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins

Functions of chalcogenide electrodes in solutions of complexing reagents and interfering ions

International Nuclear Information System (INIS)

Kiyanskij, V.V.

1990-01-01

The possibility to modify chalcogenide electrodes and their behaviour in solutions of complexing reagents for the development of new methods of potentiometric titration has been studied. It is shown that complexing reagents (EDTA, cupferron, 8-hydroxyquinoline, sodium dithiocarbaminate) and Cu(2), Hg(2) produce a strong effect on the functions of Ag, Cu, Cd, Pb - selective electrodes, which is used for titration of potential-determining and non-potential-determining ions ions (Sr 2+ , La 3+ etc.) and also for modification of sulfide-selecting electrode. A method of potentiometric titration of sulfates and chlorides with modified Cd- and Ag-selective electrodes is suggested

Inner- and outer-sphere complexation of ions at the goethite-solution interface

NARCIS (Netherlands)

Rahnemaie, R.; Hiemstra, T.; Riemsdijk, van W.H.

2006-01-01

Formation of inner- and outer-sphere complexes of environmentally important divalent ions on the goethite surface was examined by applying the charge distribution CD model for inner- and outer-sphere complexation. The model assumes spatial charge distribution between the surface (0-plane) and the

Biotransformation of trans-1-chloro-3,3,3-trifluoropropene (trans-HCFO-1233zd)

International Nuclear Information System (INIS)

Schmidt, Tobias; Bertermann, Rüdiger; Rusch, George M.; Tveit, Ann; Dekant, Wolfgang

2013-01-01

trans-1-Chloro-3,3,3-trifluoropropene (trans-HCFO-1233zd) is a novel foam blowing and precision cleaning agent with a very low impact for global warming and ozone depletion. trans-HCFO-1233zd also has a low potential for toxicity in rodents and is negative in genotoxicity testing. The biotransformation of trans-HCFO-1233zd and kinetics of metabolite excretion with urine were assessed in vitro and in animals after inhalation exposures. For in vitro characterization, liver microsomes from rats, rabbits and humans were incubated with trans-HCFO-1233zd. Male Sprague Dawley rats and female New Zealand White rabbits were exposed to 2,000, 5,000 and 10,000 ppm for 6 h and urine was collected for 48 h after the end of the exposure. Study specimens were analyzed for metabolites using 19 F NMR, LC-MS/MS and GC/MS. S-(3,3,3-trifluoro-trans-propenyl)-glutathione was identified as predominant metabolite of trans-HCFO-1233zd in all microsomal incubation experiments in the presence of glutathione. Products of the oxidative biotransformation of trans-HCFO-1233zd were only minor metabolites when glutathione was present. In rats, both 3,3,3-trifluorolactic acid and N-acetyl-(3,3,3-trifluoro-trans-propenyl)-L-cysteine were observed as major urinary metabolites. 3,3,3-Trifluorolactic acid was not detected in the urine of rabbits. Quantitation showed rapid excretion of both metabolites in both species (t 1/2 1/2 < 6 h). ► Glutathione adduct as predominant in vitro metabolite in all tested species. ► Toxic metabolites could not be detected in any great extent

Monoclonal antibodies to DNA modified with cis- or trans-diamminedichloroplatinum(II)

International Nuclear Information System (INIS)

Sundquist, W.I.; Lippard, S.J.; Stollar, B.D.

1987-01-01

Murine monoclonal antibodies that bind selectively to adducts formed on DNA by the antitumor drug cis-diamminedichloroplatinum(II), cis-DDP, or to the chemothrapeutically inactive trans isomer trans-DDP were elicited by immunization with calf thymus DNA modified with either cis- or trans-DDP at ratios of bound platinum per nucleotide, (D/N)/sub b/, of 0.06-0.08. The binding of two monoclonal antibodies to cis-DDP-modified DNA was competitively inhibited in an enzyme-linked immunosorbent assay (ELISA) by 4-6 nM concentrations of cis-DDP bound to DNA. Adducts formed by cis-DDP on other synthetic DNA polymers did not inhibit antibody binding to cis-DDP-DNA. The biologically active compounds [Pt(en)Cl 2 ], [Pt(dach)Cl 2 ], and [Pt(NH 3 ) 2 (cbdca)] (carboplatin) all formed antibody-detectable adducts on DNA, whereas the inactive platinum complexes trans-DDP and [Pt(dien)Cl]Cl (dien, diethylenetriamine) did not. The monoclonal antibodies therefore recognize a bifunctional Pt-DNA adduct with cis stereochemistry in which platinum is coordinated by two adjacent guanines or, to a lesser degree, by adjacent adenine and guanine. A monoclonal antibody raised against trans-DDP-DNA was competitively inhibited in an ELISA by 40 nM trans-DDP bound to DNA. This antibody crossreacted with unmodified, denatured DNA. The recognition of cis- or trans-DDP-modified DNAs by monoclonal antibodies thus parallels the known modes of DNA binding of these compounds and may correlate with their biological activities

Biotransformation of trans-1-chloro-3,3,3-trifluoropropene (trans-HCFO-1233zd)

Energy Technology Data Exchange (ETDEWEB)

Schmidt, Tobias [Institut für Toxikologie, Universität Würzburg, Versbacher Str. 9, 97078 Würzburg (Germany); Bertermann, Rüdiger [Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg (Germany); Rusch, George M.; Tveit, Ann [Honeywell, P.O. Box 1057, Morristown, NJ 07962-1057 (United States); Dekant, Wolfgang, E-mail: dekant@toxi.uni-wuerzburg.de [Institut für Toxikologie, Universität Würzburg, Versbacher Str. 9, 97078 Würzburg (Germany)

2013-05-01

trans-1-Chloro-3,3,3-trifluoropropene (trans-HCFO-1233zd) is a novel foam blowing and precision cleaning agent with a very low impact for global warming and ozone depletion. trans-HCFO-1233zd also has a low potential for toxicity in rodents and is negative in genotoxicity testing. The biotransformation of trans-HCFO-1233zd and kinetics of metabolite excretion with urine were assessed in vitro and in animals after inhalation exposures. For in vitro characterization, liver microsomes from rats, rabbits and humans were incubated with trans-HCFO-1233zd. Male Sprague Dawley rats and female New Zealand White rabbits were exposed to 2,000, 5,000 and 10,000 ppm for 6 h and urine was collected for 48 h after the end of the exposure. Study specimens were analyzed for metabolites using {sup 19}F NMR, LC-MS/MS and GC/MS. S-(3,3,3-trifluoro-trans-propenyl)-glutathione was identified as predominant metabolite of trans-HCFO-1233zd in all microsomal incubation experiments in the presence of glutathione. Products of the oxidative biotransformation of trans-HCFO-1233zd were only minor metabolites when glutathione was present. In rats, both 3,3,3-trifluorolactic acid and N-acetyl-(3,3,3-trifluoro-trans-propenyl)-L-cysteine were observed as major urinary metabolites. 3,3,3-Trifluorolactic acid was not detected in the urine of rabbits. Quantitation showed rapid excretion of both metabolites in both species (t{sub 1/2} < 6 h) and the extent of biotransformation of trans-HCFO-1233zd was determined as approximately 0.01% of received dose in rabbits and approximately 0.002% in rats. trans-HCFO-1233zd undergoes both oxidative biotransformation and glutathione conjugation at very low rates. The low extent of biotransformation and the rapid excretion of metabolites formed are consistent with the very low potential for toxicity of trans-HCFO-1233zd in mammals. - Highlights: ► No lethality and clinical signs were observed. ► Glutathione S-transferase and cytochrome P-450 dependent

Investigation of complexing of vitamine B-6 with rare earth ions by PMR and luminescent spectroscopy

International Nuclear Information System (INIS)

Buiklinskij, V.D.; Zelenov, V.I.; Zolin, V.F.; Koreneva, L.G.; Panyushkin, V.T.

1981-01-01

To investigate the complexing of pyridoxine (P), pyridoxal (PL) and pyridoxamine (PM) with lanthanide ions the changes of PMR spectra of ligands in the presence of cerium, praseodymium, neodymium, europium, gadolinium ions, as well as luminescence and absorption spectra of europium in the presence of ligands are used. Using the optical spectroscopy it has been shown that the PL and PM complexes do not have axial symmetry. The values of parameters of the crystalline field of the second order, determining the anisotropy of magnetic susceptibility of europium complexes are evaluated. With an aid of PMR and luminescence spectroscopy it is shown that lanthanide ions coordinate the hydroxy groups of ligands. In the case of P and especially PL oxygen of the substituent in position 4 takes part in the coordination. Using the PMR spectroscopy the difference of the substituent location near C4 in the PM complex from its location in the P and PL complexes as well as the difference in the position of lanthanide ion in the complexes of all the three ligands are detected. The reasons for the differences above are discussed [ru

Powdered activated carbon adsorption of two fishy odorants in water: Trans,trans-2,4-heptadienal and trans,trans-2,4-decadienal.

Science.gov (United States)

Li, Xin; Wang, Jun; Zhang, Xiaojian; Chen, Chao

2015-06-01

Powdered activated carbon (PAC) adsorption of two fishy odorants, trans,trans-2,4-heptadienal (HDE) and trans,trans-2,4-decadienal (DDE), was investigated. Both the pseudo first-order and the pseudo second-order kinetic models well described the kinetics curves, and DDE was more readily removed by PAC. In isotherm tests, both Freundlich and Modified Freundlich isotherms fitted the experimental data well. PAC exhibited a higher adsorption capacity for DDE than for HDE, which could be ascribed to the difference in their hydrophobicity. The calculated thermodynamic parameters (ΔG0, ΔH0, and ΔS0) indicated an exothermic and spontaneous adsorption process. PAC dosage, pH, and natural organic matter (NOM) presence were found to influence the adsorption process. With increasing PAC dosage, the pseudo first-order and pseudo second-order rate constants both increased. The value of pH had little influence on HDE or DDE molecules but altered the surface charge of PAC, and the maximum adsorption capacity occurred at pH9. The presence of NOM, especially the fraction with molecular weight less than 1k Dalton, hindered the adsorption. The study showed that preloaded NOM impaired the adsorption capacity of HDE or DDE more severely than simultaneously fed NOM did. Copyright © 2015. Published by Elsevier B.V.

SupraTrans II. Test drive facility for a superconductor-based maglev train; SupraTrans II. Fahrversuchsanlage fuer eine Magnetbahn mit Supraleitern

Energy Technology Data Exchange (ETDEWEB)

Kuehn, Lars; Haas, Oliver de [evico GmbH, Dresden (Germany); Berger, Dietmar; Schultz, Ludwig [IFW Dresden (Germany); Olsen, Henning; Roehlig, Steffen [ELBAS Elektrische Bahnsysteme Ingenieur-Gesellschaft mbH, DNV company, Dresden (Germany)

2012-08-15

The SupraTrans system was further developed and a test drive facility built up in Dresden. The latter permits complex drive tests to be made as well as the testing of components. Compared to the demonstrator, the facility is characterized by a higher loadability, higher speeds and a completely contactless energy transmission. (orig.)

A response of L-α-alanine and standard bone powder on 3.4 MeV/amu 59Co ion beams

International Nuclear Information System (INIS)

Stuglik, Z.; Sadlo, J.

1997-01-01

Dosimetric response of microcrystaline L-α-alanine and standard bovine bone powder on 3.4 MeV/amu 59 Co ions (LET ∼5500 eV/nm) was investigated. The long-lived paramagnetic centers created by ion beams were measured after 51 and 420 days. Relative sensitivity compared to gamma rays was estimated at 0.2 for L-α-alanine and 0.15 for standard bovine bone powder. (Author)

EPR study of complex formation between copper (II) ions and sympathomimetic amines in aqueous solution

Energy Technology Data Exchange (ETDEWEB)

Preoteasa, E.A. [Inst. of Atomic Physics, IFIN, Bucharest (Romania); Duliu, O.G.; Grecu, V.V. [Bucharest, Univ. (Romania). Dept. of Atomic and Nuclear Physics

1997-07-01

The complex formation between sympathomimetic amines (SA): adrenaline (AD), noradrenaline (NA), dopamine (DA), ephedrine (ED) and p-tyramine (pTA), and Cu(II) ion in aqueous solution has been studied by X-band EPR at room temperature. Excepting pTA, all investigated SA yielded two types of complexes in different pH domains. All complexes consistent with a ligand fields having a distorted octahedral symmetry, i.e., hexacoordination of Cu(II). The covalence coefficient calculated from the isotropic g and A values has shown strong ionic sigma-type ligand bonds. A structural model with the Cu(II) ion bound by four catecholic O(hydroxy) atoms for the low pH complexes of AD, NA and DA is proposed. For the high pH complexes of the former compounds as well as for both Ed complexes, the authors suppose Cu(II) bound by two N (amino) and two O (hydroxy) atoms. The spectra are consistent to water binding on the longitudinal octahedron axis in all compounds excepting the high pH complex of Ed, where OH2- ions are bound. Possible implications for the SA-cell receptors interactions are discussed.

trans-Bis(perchlorato-κOtetrakis(1H-pyrazole-κN2copper(II

Directory of Open Access Journals (Sweden)

Viktor Zapol'skii

2008-10-01

Full Text Available The title compound, [Cu(ClO42(C3H4N24], was obtained unexpectedly by the reaction of copper(II perchlorate hexahydrate with equimolar amounts of 1-chloro-1-nitro-2,2,2-tripyrazolylethane in methanol solution. The crystal structure comprises octahedrally coordinated Cu2+ ions, located on an inversion centre, with four pyrazole ligands in the equatorial plane. The average Cu—N distance is 2.000 (1 Å. Two perchlorate ions are coordinated to copper in trans positions [Cu—O = 2.4163 (11 Å].

Survey of the trans-resveratrol and trans-piceid content of cocoa-containing and chocolate products.

Science.gov (United States)

Hurst, W Jeffrey; Glinski, Jan A; Miller, Kenneth B; Apgar, Joan; Davey, Matthew H; Stuart, David A

2008-09-24

Dietary resveratrol (3,4',5-trihydroxystilbene) has been implicated in the health benefits associated with grapes and red wine, more specifically with potential benefits for metabolic syndrome, energy use, and increased endurance. Levels of trans-resveratrol and its glucoside, trans-piceid, were determined in 19 top selling commercially available cocoa-containing and chocolate products from the U.S. market. Amounts of trans-resveratrol and trans-piceid were closely correlated with the amount of nonfat cocoa solids (NFCS) in the cocoa-containing products. Among these products, trans-resveratrol levels were highest in cocoa powders (1.85 +/- 0.43 microg/g), followed by unsweetened baking chocolates (1.24 +/- 0.22), semisweet chocolate baking chips (0.52 +/- 0.14), dark chocolates (0.35 +/- 0.08), milk chocolates (0.10 +/- 0.05), and chocolate syrups (0.09 +/- 0.02). These cocoa-containing and chocolate products have about 3-5 times more trans-piceid than trans-resveratrol. Levels of trans-piceid were highest in the cocoa powders (7.14 +/- 0.80 microg/g), followed by unsweetened baking chocolates (4.04 +/- 0.14), semisweet chocolate baking chips (2.01 +/- 0.18), dark chocolates (1.82 +/- 0.36), milk chocolates (0.44 +/- 0.06), and chocolate syrups (0.35 +/- 0.06). On an equal weight basis, cocoa powder had about half as much trans-resveratrol as the average California red wine. On a per serving basis, cocoa-containing and chocolate products had less trans-resveratrol than red wine and grape juice but more than roasted peanuts. Overall, these cocoa-containing and chocolate products rank second after red wines and grape juice in foods with the highest levels of total trans-resveratrol in the diet.

Complexes of trivalent lanthanide ions with schiff base derived from vanillin and triethylenetetraamine

International Nuclear Information System (INIS)

Shahma, A.; Athar, M.; Ahmad, N.

1982-01-01

Complexes of lanthanide(III) ions with the schiff base derived from vanillin and triethylenetetraamine have been synthesised and characterised on the basis of elemental analyses, molar conductance, magnetic moment, IR and thermal analysis data. The thermograms show the elimination (OH)(OCH 3 )C 6 H 3 CH-group at low temperatures before the elimination of triethylenetetraamine part corroborating the observation made on the basis of IR spectral data. This is a clear indication of the non-coordination of the phenolic hydroxyl groups. The lanthanide ions in the complexes exhibit eight coordination numbers. (author)

Effect of swift heavy Kr ions on complex permittivity of silicon PIN diode

Energy Technology Data Exchange (ETDEWEB)

Li, Yun [Key Laboratory of Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); College of Physical Science and Technology, Sichuan University, Chengdu, Sichuan 610064 (China); Su, Ping, E-mail: pingsu@scu.edu.cn [Key Laboratory of Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Key Lab of Microelectronics Sichuan Province, Sichuan University, Chengdu, Sichuan 610064 (China); College of Physical Science and Technology, Sichuan University, Chengdu, Sichuan 610064 (China); Yang, Zhimei; Ma, Yao [Key Lab of Microelectronics Sichuan Province, Sichuan University, Chengdu, Sichuan 610064 (China); College of Physical Science and Technology, Sichuan University, Chengdu, Sichuan 610064 (China); Gong, Min, E-mail: mgong@scu.edu.cn [Key Laboratory of Radiation Physics and Technology of Ministry of Education, Sichuan University, Chengdu 610064 (China); Key Lab of Microelectronics Sichuan Province, Sichuan University, Chengdu, Sichuan 610064 (China); College of Physical Science and Technology, Sichuan University, Chengdu, Sichuan 610064 (China)

2016-12-01

Highlights: • The complex permittivity has been studied on Si PIN irradiated by heavy Kr ions. • DLTS was used to investigate damages formed in PIN diode during irradiation. • The recombination of carriers has important influence on the complex permittivity. - Abstract: The complex permittivity has been researched on silicon PIN diodes irradiated by 2150 MeV heavy Kr ions in this article. The difference of complex permittivity spectra from 1 to 10^7 Hz between irradiated and unirradiated were observed and discussed. The current-voltage (I-V) and capacitance-voltage (C-V) characteristics were measured at room temperature (300 K) to study the change of electrical properties in diode after irradiation. Deep level transient spectroscopy (DLTS) was used to investigate damages caused by 2150 MeV heavy Kr ions in diode. Two extra electron traps were observed, which were located at E{sub C}-0.31 eV and E{sub C}-0.17 eV. It indicated that new defects have been formed in PIN diode during irradiation. A comparison of the results illustrated that not only the carrier density but also the recombination of electron-hole pair have important influences on the properties of complex permittivity. These results offer a further indication of the mechanism about the complex permittivity property of semiconductor device, which could help to make the applications for the semiconductor device controlled by electric signals come true in the fields of optoelectronic integrated circuits, plasma antenna and so on.

Effect of swift heavy Kr ions on complex permittivity of silicon PIN diode

International Nuclear Information System (INIS)

Li, Yun; Su, Ping; Yang, Zhimei; Ma, Yao; Gong, Min

2016-01-01

Highlights: • The complex permittivity has been studied on Si PIN irradiated by heavy Kr ions. • DLTS was used to investigate damages formed in PIN diode during irradiation. • The recombination of carriers has important influence on the complex permittivity. - Abstract: The complex permittivity has been researched on silicon PIN diodes irradiated by 2150 MeV heavy Kr ions in this article. The difference of complex permittivity spectra from 1 to 10^7 Hz between irradiated and unirradiated were observed and discussed. The current-voltage (I-V) and capacitance-voltage (C-V) characteristics were measured at room temperature (300 K) to study the change of electrical properties in diode after irradiation. Deep level transient spectroscopy (DLTS) was used to investigate damages caused by 2150 MeV heavy Kr ions in diode. Two extra electron traps were observed, which were located at E C -0.31 eV and E C -0.17 eV. It indicated that new defects have been formed in PIN diode during irradiation. A comparison of the results illustrated that not only the carrier density but also the recombination of electron-hole pair have important influences on the properties of complex permittivity. These results offer a further indication of the mechanism about the complex permittivity property of semiconductor device, which could help to make the applications for the semiconductor device controlled by electric signals come true in the fields of optoelectronic integrated circuits, plasma antenna and so on.

[Trans fatty acids in the nutrition of children with neurological disorders].

Science.gov (United States)

Cortés, E; Aguilar, M J; Rizo, M M; Hidalgo, M J

2013-01-01

Trans-fatty acids are present in various foods, being the only source of the same in humans. Its presence in high concentrations is a risk factor for health, being involved in a series of events, cardiovascular, inflammatory, etc. Therefore, steps have been taken for its decrease in the diet. The aim is to determine serum and phospholipids of membranes in healthy children and neurological alterations. It has analyzed the fatty acids trans in 34 healthy children and 374 with various neurological pathologies. Serum and blood cells, making the lipid extraction, samples have been separation of the phospholipids of cells membranes, methylation of fatty acids, separation by gas chromatography and quantification using mass detector. The data have been processed statistically. The distribution of trans fatty acids and their sum is not normally distributed, so its nonparemetric tests were used. The values are higher than in serum phospholipids and membrane with a weak but significant correlation. The tC18: 1 is in a double proportion in children with neurological disorders in healthy children, both in serum and membrane phospholipids, with significant differences. The highest proportion of trans-fatty acids in the group of children with neurological disorders is caused no doubt by an increase in intake, due to less adequate food. Copyright © AULA MEDICA EDICIONES 2013. Published by AULA MEDICA. All rights reserved.

Rôle des complexes ion/neutre dans les décompositions unimoléculaires d'ions [beta]-hydroxy acylium

Science.gov (United States)

Morizur, J.-P.; Chapon, E.

1994-06-01

Résumé Les réactions des ions [beta]-hydroxy acylium métastables CH3CH(OH)CH2CO+ (1) formés en phase gazeuse par perte de CH3O à partir du méthyl 3-hydroxy butyrate ionisé sont présentées et discutées. Le marquage aux isotopes stables a montré que la formation des ions CH2=CHCH2CO+ et CH3CO+ est précédée d'échanges d'atomes d'hydrogène et d'oxygène. L'utilisation des techniques de spectrométrie de masse a fourni des preuves expérimentales sur les isomérisations et dissociations de l'ion 1. On propose que la perte d'eau s'effectue à partir de CH2=CHCH2C(=O)OH+2, la formation de CH3CO+ implique un complexe ion/neutre [CH3CHO/CH3CO+]. L'interprétation des résultats est étayée par des données thermodynamiques. The reactions of metastable [beta]-hydroxy acylium ions CH3CH(OH)CH2CO+ (1) generated in the gas phase by loss of CH3O from ionized methyl 3-hydroxy butyrate are reported and discussed. Isotopic labelling shows that the dissociation, which produces the acylium ions CH2=CHCH2CO+ and CH3CO+, is preceded by hydrogen and oxygen atom exchange. Mass spectrometry techniques have provided experimental information of the isomerization and dissociation of ion 1. Loss of water is proposed to occur from CH2=CHCH2C(=O)OH+2; formation of CH3CO+ involves an ion/neutral complex [CH3CHO/CH3CO+]. Interpretation of data is supported by thermochemistry.

Irradiation characteristics of metal-cluster-complex ions containing diverse multi-elements with large mass differences

International Nuclear Information System (INIS)

Fujiwara, Yukio; Kondou, Kouji; Teranishi, Yoshikazu; Nonaka, Hidehiko; Saito, Naoaki; Fujimoto, Toshiyuki; Kurokawa, Akira; Ichimura, Shingo; Tomita, Mitsuhiro

2007-01-01

Tetrairidium dodecacarbonyl, Ir 4 (CO) 12 , is a metal cluster complex which has a molecular weight of 1104.9. Using a metal-cluster-complex ion source, the interaction between Ir 4 (CO) n + ions (n=0-12) and silicon substrates was studied at a beam energy ranging from 2keV to 10keV at normal incidence. By adjusting Wien-filter voltage, the influence of CO ligands was investigated. Experimental results showed that sputtering yield of silicon bombarded with Ir 4 (CO) n + ions at 10keV decreased with the number of CO ligands. In the case of 2keV, deposition tended to be suppressed by removing CO ligands from the impinging cluster ions. The influence of CO ligands was explained by considering changes in surface properties caused by the irradiation of Ir 4 (CO) n + ions. It was also found that the bombardment with Ir 4 (CO) 7 + ions at 2.5keV caused deposition on silicon target

Homologous SV40 RNA trans-splicing: Special case or prime example of viral RNA trans-splicing?

Directory of Open Access Journals (Sweden)

Sushmita Poddar

2014-06-01

Full Text Available To date the Simian Virus 40 (SV40 is the only proven example of a virus that recruits the mechanism of RNA trans-splicing to diversify its sequences and gene products. Thereby, two identical viral transcripts are efficiently joined by homologous trans-splicing triggering the formation of a highly transforming 100 kDa super T antigen. Sequences of other viruses including HIV-1 and the human adenovirus type 5 were reported to be involved in heterologous trans-splicing towards cellular or viral sequences but the meaning of these events remains unclear. We computationally and experimentally investigated molecular features associated with viral RNA trans-splicing and identified a common pattern: Viral RNA trans-splicing occurs between strong cryptic or regular viral splice sites and strong regular or cryptic splice sites of the trans-splice partner sequences. The majority of these splice sites are supported by exonic splice enhancers. Splice sites that could compete with the trans-splicing sites for cis-splice reactions are weaker or inexistent. Finally, all but one of the trans-splice reactions seem to be facilitated by one or more complementary binding domains of 11 to 16 nucleotides in length which, however occur with a statistical probability close to one for the given length of the involved sequences. The chimeric RNAs generated via heterologous viral RNA trans-splicing either did not lead to fusion proteins or led to proteins of unknown function. Our data suggest that distinct viral RNAs are highly susceptible to trans-splicing and that heterologous viral trans-splicing, unlike homologous SV40 trans-splicing, represents a chance event.

Electronic structure, fluorescence and photochemistry of the uranyl ion, and comparison with octahedral uranium (VI), ruthenyl (VI), rhenium (V) and osmium (VI) complexes

Energy Technology Data Exchange (ETDEWEB)

Joergensen, C K [Geneva Univ. (Switzerland)

1977-01-01

The highly anisotropic uranyl complexes (with very short U-O distances and very long distances to the ligating atoms in the equatorial plane) are compared with trans-dioxo complexes of 4d/sup 2/Ru(VI) and 5d/sup 2/Re(V) and Os(VI). A major difference is the low-lying empty 5f orbitals, and the first excited state is highly oxidizing, and sufficiently long-lived to abstract hydrogen atoms from most organic molecules. It is argued that even the low concentrations of uranyl carbonate present in sea water is excited by solar radiation roughly every 10 minutes. Octahedral U(VI)O/sub 6/ in perovskites and UF/sub 6/ are also discussed, as well as trans-lawrencium chemistry.

Complexation of trivalent actinide ions (Am3+, Cm3+) with humic acid: a comparison of different experimental methods

International Nuclear Information System (INIS)

Kim, J.I.; Rhee, D.S.; Wimmer, H.; Buckau, G.; Klenze, R.

1993-01-01

The complexation of trivalent metal ions with humic acid has been studied at pH 4 and 5 in 0.1 M NaClO 4 by three different experimental methods, i.e. UV spectroscopy, time resolved laser fluorescence spectroscopy (TRLFS) and ultrafiltration. The direct speciation of the metal ion and its humate complex in the reaction process has been made by UV spectroscopy for Am(III) in the micromolar concentration range and by TRLFS for Cm(III) in the nanomolar concentration range. The ultrafiltration is used with the lowest pore size of filter (ca. 1 nm) to separate the uncomplexed metal ion from its complexed species. The concentrations of both metal ion and humic acid are varied in such a manner that the effective functional groups of the humic acid becomes loaded with metal ions from 1% to nearly 100%. The loading capacity of the humic acid for the trivalent metal ion, determined separately at each pH, is introduced into the evaluation of complexation constants. The variation of the metal ion concentration from 6 x 10 -8 mol/l to 4 x 10 -5 mol/l does not show any effect on the complexation reaction. The three different methods give rise to constants being comparable with one another. The average value of the constants thus determined is log β = 6.24±0.28 for the trivalent actinide ions. (orig.)

Stability and kinetics of uranyl ion complexation by macrocycles in propylene carbonate

International Nuclear Information System (INIS)

Fux, P.

1984-06-01

A thermodynamic study of uranyl ion complexes formation with different macrocyclic ligands was realized in propylene carbonate as solvent using spectrophotometric and potentiometric techniques. Formation kinetics of two UO 2 complexes: a crown ether (18C6) and a coronand (22) was studied by spectrophotometry in propylene carbonate with addition of tetraethylammonium chlorate 0.1M at 25 0 C. Possible structures of complexes in solution are discussed [fr

An optimized method for fatty acid analysis, including quantification of trans fatty acids, in human adipose tissue by gas-liquid chromatography

DEFF Research Database (Denmark)

Bysted, Anette; Cold, S; Hølmer, Gunhild Kofoed

1999-01-01

Considering the need for a quick direct method for measurement of the fatty acid composition including trans isomers ofhuman adipose tissue we have developed a procedure using gas-liquid chromatography (GLC) alone, which is thussuitable for validation of fatty acid status in epidemiological studies...... for 25 min, and finally raised at 25 degrees C/min to 225 degrees C. The trans and cis isomers of18:1 were well separated from each other, as shown by silver-ion thin-layer chromatography. Verification by standardsshowed that the trans 18:1 isomers with a double bond in position 12 or lower were...

Engineering of a calcium-ion binding site into the RC-LH1-PufX complex of Rhodobacter sphaeroides to enable ion-dependent spectral red-shifting.

Science.gov (United States)

Swainsbury, David J K; Martin, Elizabeth C; Vasilev, Cvetelin; Parkes-Loach, Pamela S; Loach, Paul A; Neil Hunter, C

2017-11-01

The reaction centre-light harvesting 1 (RC-LH1) complex of Thermochromatium (Tch.) tepidum has a unique calcium-ion binding site that enhances thermal stability and red-shifts the absorption of LH1 from 880nm to 915nm in the presence of calcium-ions. The LH1 antenna of mesophilic species of phototrophic bacteria such as Rhodobacter (Rba.) sphaeroides does not possess such properties. We have engineered calcium-ion binding into the LH1 antenna of Rba. sphaeroides by progressively modifying the native LH1 polypeptides with sequences from Tch. tepidum. We show that acquisition of the C-terminal domains from LH1 α and β of Tch. tepidum is sufficient to activate calcium-ion binding and the extent of red-shifting increases with the proportion of Tch. tepidum sequence incorporated. However, full exchange of the LH1 polypeptides with those of Tch. tepidum results in misassembled core complexes. Isolated α and β polypeptides from our most successful mutant were reconstituted in vitro with BChl a to form an LH1-type complex, which was stabilised 3-fold by calcium-ions. Additionally, carotenoid specificity was changed from spheroidene found in Rba. sphaeroides to spirilloxanthin found in Tch. tepidum, with the latter enhancing in vitro formation of LH1. These data show that the C-terminal LH1 α/β domains of Tch. tepidum behave autonomously, and are able to transmit calcium-ion induced conformational changes to BChls bound to the rest of a foreign antenna complex. Thus, elements of foreign antenna complexes, such as calcium-ion binding and blue/red switching of absorption, can be ported into Rhodobacter sphaeroides using careful design processes. Copyright © 2017 The Author(s). Published by Elsevier B.V. All rights reserved.

Minimally invasive endoscope-assisted trans-oral excision of huge parapharyngeal space tumors.

Science.gov (United States)

Li, Shang-Yi; Hsu, Ching-Hui; Chen, Mu-Kuan

2015-04-01

Parapharyngeal space tumors are rare head and neck neoplasms, and most are benign lesions. Complete excision of these tumors is difficult because of the complexity of the surrounding anatomic structures. The algorithm for excision of these tumors is typically based on the tumor's characteristics; excision is performed via approaches such as the trans-oral route, the trans-cervical route, and even a combination of the trans-parotid route and mandibulotomy. However, each of these approaches is associated with some complications. Endoscope-assisted minimally invasive surgery is being increasingly employed for surgeries in the head and neck regions. It has the advantage of leaving no facial scars, and ensures better patient comfort after the operation. Here, we report the use of endoscope-assisted trans-oral surgery for excision of parapharyngeal space tumors. The technique yields an excellent outcome and should be a feasible, safe, and economic method for these patients. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

A theoretical view on the thermodynamic cis-trans equilibrium of dihalo ruthenium olefin metathesis (pre-)catalysts

KAUST Repository

Pump, Eva

2015-02-24

Abstract: This work was conducted to provide an overview on the position of the thermodynamic cis–trans equilibrium of 85 conventional and X-chelated alkylidene-ruthenium complexes (X=O, S, Se, N, P, Cl, I, Br). The reported energies (ΔE) were obtained through single-point calculations with M06 functional and TZVP basis set from BP86/SVP-optimized cis- and trans-dichloro geometries and using the polarizable continuum model to simulate the influence of the solvent. Dichloromethane and toluene were selected as examples for solvents with high and low dielectric constants. The obtained relative stabilities of the cis- and trans-dihalo derivatives of the respective alkylidene complexes will serve for a better explanation of their catalytic activity as has been disclosed herein with selected examples.Graphical abstract: [Figure not available: see fulltext.

Oxygen atom transfer from a trans-dioxoruthenium(VI) complex to nitric oxide.

Science.gov (United States)

Man, Wai-Lun; Lam, William W Y; Ng, Siu-Mui; Tsang, Wenny Y K; Lau, Tai-Chu

2012-01-02

In aqueous acidic solutions trans-[Ru(VI)(L)(O)(2)](2+) (L=1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) is rapidly reduced by excess NO to give trans-[Ru(L)(NO)(OH)](2+). When ≤1 mol equiv NO is used, the intermediate Ru(IV) species, trans-[Ru(IV)(L)(O)(OH(2))](2+), can be detected. The reaction of [Ru(VI)(L)(O)(2)](2+) with NO is first order with respect to [Ru(VI)] and [NO], k(2)=(4.13±0.21)×10(1) M(-1) s(-1) at 298.0 K. ΔH(≠) and ΔS(≠) are (12.0±0.3) kcal mol(-1) and -(11±1) cal mol(-1) K(-1), respectively. In CH(3)CN, ΔH(≠) and ΔS(≠) have the same values as in H(2)O; this suggests that the mechanism is the same in both solvents. In CH(3)CN, the reaction of [Ru(VI)(L)(O)(2)](2+) with NO produces a blue-green species with λ(max) at approximately 650 nm, which is characteristic of N(2)O(3). N(2)O(3) is formed by coupling of NO(2) with excess NO; it is relatively stable in CH(3)CN, but undergoes rapid hydrolysis in H(2)O. A mechanism that involves oxygen atom transfer from [Ru(VI)(L)(O)(2)](2+) to NO to produce NO(2) is proposed. The kinetics of the reaction of [Ru(IV)(L)(O)(OH(2))](2+) with NO has also been investigated. In this case, the data are consistent with initial one-electron O(-) transfer from Ru(IV) to NO to produce the nitrito species [Ru(III)(L)(ONO)(OH(2))](2+) (k(2)>10(6) M(-1) s(-1)), followed by a reaction with another molecule of NO to give [Ru(L)(NO)(OH)](2+) and NO(2)(-) (k(2)=54.7 M(-1) s(-1)). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A study on complex formation of cadmium (II) ions, 9

International Nuclear Information System (INIS)

Matsui, Haruo

1984-01-01

Formation constants of cadmium (11) complexes with dicarboxylic acids such as oxalic, malonic, methylmalonic, succinic, and glutaric acids were determined in aqueous solutions containing 3 mol.dm -3 LiClO 4 as a constan ionic medium at 25 0 C by potentiometric titrations. It was reported in the previous works that cadmium (11)- aspartic acid complexes contained two chelate rings. However, a problem remained whether the second chelate ring could be formed by six membered-ring containing -O-Cd-N- bond or by seven membered-ring containing -O-Cd-O- bond. The results of the present work suggested that it would be formed by a six membered ring. Cadmium (11) ions were coordinated with a carboxylic group of the dicarboxylic acids studied, and formed no chelate ring within the complexes. The white precipitate appeared in the solution containing cadmium (11) ion and oxalic acid, in the pH range below 3.0, therefore, the chelate formation was not ascertained in this case. The formation constants, log βsub(pr)= log([Cdsub(p)Lsub(r)sup((2p-2r)+)]/([Cd 2+ ]sup(p)[L 2- ]sup(r))), of the complexes were: log β 11 = 1.98, log β 12 = 3.05 for cadmium (11)-malonic acid; log β 11 = 2.28, log β 12 = 3.06 for cadmium (11)-methylmalonic acid; log β 11 = 1.78, log β 12 = 3.08 for cadmium (11)-succinic acid; log β 11 = 1.85, log β 12 = 3.28 for cadmium (11)-glutaric acid complexes. (author)

Study on rare earths complexes separation by means of different type of ion exchangers

International Nuclear Information System (INIS)

Hubicka, H.

1990-01-01

The applicability of different types of ion exchangers for purification and separation of rare earths complexes has been examined. The experimental work has been carried out on 14 chelating ion exchangers. The investigation results proved the great usefulness chelating ion exchangers especially of amino acid and phosphorus-type. Application of that type ion exchangers in column chromatographic process gave the excellent rare earths separation as well as enabled to obtain their preparates of high purity. 218 refs, 21 figs, 27 tabs

Clinical role of a modified seton technique for the treatment of trans-sphincteric and supra-sphincteric anal fistulas.

Science.gov (United States)

Tokunaga, Yukihiko; Sasaki, Hirokazu; Saito, Tohru

2013-03-01

We have devised a modified seton technique that resects the external fistula tract while preserving the anal sphincter muscle. This study assessed the technique when used for the management of complex anal fistulas. Between January 2006 and December 2007, 239 patients (208 males and 31 females, median age: 41 years) underwent surgery for complex anal fistulas using the technique. Of the 239 patients, 198 patients had trans-sphincteric fistula and 41 patients had supra-sphincteric fistula. The durations of the surgeries were 17 min (47, 13) [median (range, interquartile range)] for trans-sphincteric fistulas and 38 (44, 16) for supra-sphincteric fistulas. The durations of the surgeries were significantly (P trans-sphincteric fistula. The hospital stays were 4 (13, 2) days and 5 (14, 3) days, respectively, for trans- and supra-sphincteric fistulas. The durations of seton placement until the spontaneous dropping of the seton were 42 (121, 48) and 141 (171, 55) days respectively. The recurrence rate was 0 % in patients with trans-sphincteric fistulas and 4.9 % (2 of 41) in patients with supra-sphincteric fistulas (P < 0.01). Serious incontinence was not observed. The technique provided favorable results for the treatment of complex anal fistulas and could be safely applied while preserving the sphincter function and conserving fecal continence.

Differential effect of corn oil-based low trans structured fat on the plasma and hepatic lipid profile in an atherogenic mouse model: comparison to hydrogenated trans fat

Directory of Open Access Journals (Sweden)

Kim Hye-Jin

2011-01-01

Full Text Available Abstract Background Trans fat are not desirable in many aspects on health maintenance. Low trans structured fats have been reported to be relatively more safe than trans fats. Methods We examined the effects of low trans structured fat from corn oil (LC, compared with high trans fat shortening, on cholesterol and fatty acid metabolism in apo E deficient mice which is an atherogenic animal model. The animals were fed a high trans fat (10% fat: commercial shortening (CS or a low trans fat (LC diet for 12 weeks. Results LC decreased apo B and hepatic cholesterol and triglyceride concentration compared to the CS group but significantly increased plasma total cholesterol and triglyceride concentration and fecal lipids with a simultaneous increase in HDL-cholesterol level, apo A-I, and the ratio of HDL-cholesterol to total cholesterol (HTR. Reduction of hepatic lipid levels by inclusion of LC intake was observed alongside modulation of hepatic enzyme activities related to cholesterol esterification, fatty acid metabolism and fecal lipids level compared to the CS group. The differential effects of LC intake on the plasma and hepatic lipid profile seemed to be partly due to the fatty acid composition of LC which contains higher MUFA, PUFA and SFA content as well as lower content of trans fatty acids compared to CS. Conclusions We suggest that LC may exert a dual effect on plasma and hepatic lipid metabolism in an atherogenic animal model. Accordingly, LC, supplemented at 10% in diet, had an anti-atherogenic effect on these apo E-/- mice, and increased fecal lipids, decreased hepatic steatosis, but elevated plasma lipids. Further studies are needed to verify the exact mode of action regarding the complex physiological changes and alteration in lipid metabolism caused by LC.

Differential effect of corn oil-based low trans structured fat on the plasma and hepatic lipid profile in an atherogenic mouse model: comparison to hydrogenated trans fat

Science.gov (United States)

2011-01-01

Background Trans fat are not desirable in many aspects on health maintenance. Low trans structured fats have been reported to be relatively more safe than trans fats. Methods We examined the effects of low trans structured fat from corn oil (LC), compared with high trans fat shortening, on cholesterol and fatty acid metabolism in apo E deficient mice which is an atherogenic animal model. The animals were fed a high trans fat (10% fat: commercial shortening (CS)) or a low trans fat (LC) diet for 12 weeks. Results LC decreased apo B and hepatic cholesterol and triglyceride concentration compared to the CS group but significantly increased plasma total cholesterol and triglyceride concentration and fecal lipids with a simultaneous increase in HDL-cholesterol level, apo A-I, and the ratio of HDL-cholesterol to total cholesterol (HTR). Reduction of hepatic lipid levels by inclusion of LC intake was observed alongside modulation of hepatic enzyme activities related to cholesterol esterification, fatty acid metabolism and fecal lipids level compared to the CS group. The differential effects of LC intake on the plasma and hepatic lipid profile seemed to be partly due to the fatty acid composition of LC which contains higher MUFA, PUFA and SFA content as well as lower content of trans fatty acids compared to CS. Conclusions We suggest that LC may exert a dual effect on plasma and hepatic lipid metabolism in an atherogenic animal model. Accordingly, LC, supplemented at 10% in diet, had an anti-atherogenic effect on these apo E-/- mice, and increased fecal lipids, decreased hepatic steatosis, but elevated plasma lipids. Further studies are needed to verify the exact mode of action regarding the complex physiological changes and alteration in lipid metabolism caused by LC. PMID:21247503

Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

Science.gov (United States)

Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

2017-02-01

Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission ;turn-on; bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

Conserving Coherence and Storing Energy during Internal Conversion: Photoinduced Dynamics of cis- and trans-Azobenzene Radical Cations

KAUST Repository

Munkerup, Kristin

2017-10-24

Light harvesting via energy storage in azobenzene has been a key topic for decades, and the process of energy distribution over the molecular degrees of freedom following photoexcitation remains to be understood. Dynamics of a photoexcited system can exhibit high degrees of non-ergodicity when it is driven by just a few degrees of freedom. Typically, an internal conversion leads to the loss of such localization of dynamics, as the intramolecular energy becomes statistically redistributed over all molecular degrees of freedom. Here, we present a unique case where the excitation energy remains localized even subsequent to internal conversion. Strong-field ionization is used to prepare cis- and trans-azobenzene radical cations on the D1 surface with little excess energy, at the equilibrium neutral geometry. These D1 ions are preferably formed because in this case D1 and D0 switch place in the presence of the strong laser field. The post-ionization dynamics is dictated by the potential energy landscape. The D1 surface is steep downhill along the cis/trans isomerization coordinate and towards a common minimum shared by the two isomers in the region of D1/D0 conical intersection. Coherent cis/trans torsional motion along this coordinate is manifested in the ion transients by a cosine modulation. In this scenario, D0 becomes populated with molecules that are energized mainly along the cis-trans isomerization coordinate, with the kinetic energy above the cis-trans inter-conversion barrier. These activated azobenzene molecules easily cycle back and forth along the D0 surface, and give rise to several periods of modulated signal before coherence is lost. This persistent localization of the internal energy during internal conversion is provided by the steep downhill potential energy surface, small initial internal energy content, and a strong hole-lone pair interaction that drives the molecule along the cis-trans isomerization coordinate to facilitate the transition between

Mono- and dinuclear bioxazoline-palladium complexes for the stereocontrolled synthesis of CO/styrene polyketones.

Science.gov (United States)

Scarel, Alessandro; Durand, Jérôme; Franchi, Davide; Zangrando, Ennio; Mestroni, Giovanni; Carfagna, Carla; Mosca, Luca; Seraglia, Roberta; Consiglio, Giambattista; Milani, Barbara

2005-10-07

The coordination chemistry of the chiral bioxazoline ligand (4S,4'S)-2,2'-bis(4-isopropyl-4,5-dihydrooxazole) to Pd(II) provides evidence that the ligand bonding can occur either through chelation of one Pd(II) ion leading to a mononuclear species with the expected cis geometry, or by double bridging of two Pd(II) ions giving a dinuclear complex with trans geometry. The species in solution are identified by 1H NMR spectroscopy. Both the mononuclear and the dinuclear complexes promote the CO/styrene copolymerization, yielding the corresponding polyketone with a fully or a predominantly isotactic microstructure, depending on the reaction medium. The nature of the anion present in the palladium precatalysts affects the polyketone stereochemistry. MALDI-TOF analysis of the copolymers synthesized reveals the presence of p-hydroxyphenolic end-groups, thus confirming and explaining the role of 1,4-hydroquinone as a molecular weight regulator.

Trans and cis influences and effects in cobalamins and in their simple models.

Science.gov (United States)

De March, Matteo; Demitri, Nicola; Geremia, Silvano; Hickey, Neal; Randaccio, Lucio

2012-11-01

The interligand interactions in coordination compounds have been principally interpreted in terms of cis and trans influences and effects, which can be defined as the ability of a ligand X to affect the bond of another ligand, cis or trans to X, to the metal. This review analyzes these effects/influences in cobalamins (XCbl) and their simple models cobaloximes, LCo(chel)X. Important properties of these complexes, such as geometry, stability, and reactivity, can be rationalized in terms of steric and electronic factors of the ligands. Experimental evidence of normal and inverse trans influence is described in alkylcobaloximes for the first time. The study of simple B(12) models has complemented that on the more complex cobalamins, with particular emphasis on the properties of the axial L-Co-X moiety. Some of the conclusions reached for the axial fragment of simple models have also been qualitatively detected in cobalamins and have furnished new insight into the as yet unestablished mechanism for the homolytic cleavage of the Co - C bond in the AdoCbl-based enzymes. Copyright © 2012 Elsevier Inc. All rights reserved.

Position of coordination of the lithium ion determines the regioselectivity of demethylations of 3,4-dimethoxymorphinans with L-selectride.

Science.gov (United States)

Wu, Huifang; Thatcher, Linn N; Bernard, Denzil; Parrish, Damon A; Deschamps, Jeffrey R; Rice, Kenner C; MacKerell, Alexander D; Coop, Andrew

2005-06-23

[reaction: see text] L-Selectride is an efficient agent for the 3-O-demethylation of opioids and is known to cleave the least hindered methoxyl group in a molecule. The treatment of a 3,4-dimethoxymorphinan containing a 6-ketal with L-Selectride gave selective 4-O-demethylation, rather than cleavage of the less hindered 3-methoxyl. In contrast, a 3,4-dimethoxymorphinan lacking a 6-ketal gave selective 3-O-demethylation, suggesting that the regiochemistry of L-Selectride-mediated O-demethylation can be manipulated through altering the position of coordination of the lithium ion.

TransAlta: More than a utility

International Nuclear Information System (INIS)

Mikalson, D.A.

1991-01-01

TransAlta Utilities Corporation is Canada's largest privately owned utility and is also a major coal mining company. In 1989, TransAlta produced 20.9% of all coal mined in Canada. A brief history of TransAlta is presented along with TransAlta's present coal operations and plans for the next three years. An overview is presented of how TransAlta Fuel Supply is organized to utilize contracted mining operation, engineering and environmental services and in-house capabilities. Recent strategic initiatives to improve organizational efficiency and the mining operations are discussed. These range from developing a common departmental vision to modifying major mining equipment. TransAlta's proactive role in clean coal combustion such as low NOx-SOx burner, integrated combined cycle gasification, and other energy research projects is reviewed. A summary is provided of recent participation of TransAlta in environmental management initiatives. Recent successes of TransAlta's unregulated subsidiary in the development of cogeneration facilities and the future of this area of business are discussed. 8 refs., 4 figs

Predicting the stability constants of metal-ion complexes from first principles

Czech Academy of Sciences Publication Activity Database

Gutten, Ondrej; Rulíšek, Lubomír

2013-01-01

Roč. 52, č. 18 (2013), s. 10347-10355 ISSN 0020-1669 Institutional support: RVO:61388963 Keywords : stability constants * solvation energy * metal-ion complexation * theoretical calculations * DFT methods Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.794, year: 2013

Interaction of Cr (III), Ni (II), Pb (II) with DTPA complexes of essential metal ions

International Nuclear Information System (INIS)

Gulzar, S.; Zahida; Maqsood, T.; Naqvi, R.R.

2002-01-01

With the increase of anthropogenic activities in the environment, heavy metal toxicity (Chromium, Nickel and Lead) is more common now. DTPA (diethylene triamine pentaacetic acid) a polyamino carboxylic acid is widely used to form hydrophilic and stable complexes with most of the metal ions. In this spectrophotometric study, concentration of Cr(III), Ni(II) and Pb(II) (toxic metal ions) exchanged with Fe(III), Zn(II) and Ca(II) from their DTPA complexes were estimated at pH 4,7 and 9. Concentration of added metal was varied from 1-4 times to that of complexed metal. (author)

Imaging and structural studies of DNA–protein complexes and membrane ion channels

KAUST Repository

Marini, Monica; Limongi, Tania; Falqui, Andrea; Genovese, Alessandro; Allione, Marco; Moretti, Manola; Lopatin, Sergei; Tirinato, Luca; Das, Gobind; Torre, Bruno; Giugni, Andrea; Cesca, F.; Benfenati, F.; Di Fabrizio, Enzo M.

2017-01-01

In bio-imaging by electron microscopy, damage of the sample and limited contrast are the two main hurdles for reaching high image quality. We extend a new preparation method based on nanofabrication and super-hydrophobicity to the imaging and structural studies of nucleic acids, nucleic acid-protein complexes (DNA/Rad51 repair protein complex) and neuronal ion channels (gap-junction, K+ and GABA(A) channels) as paradigms of biological significance and increasing complexity. The preparation method is based on the liquid phase and is compatible with physiological conditions. Only in the very last stage, samples are dried for TEM analysis. Conventional TEM and high-resolution TEM (HRTEM) were used to achieve a resolution of 3.3 and 1.5 angstrom, respectively. The EM dataset quality allows the determination of relevant structural and metrological information on the DNA structure, DNA-protein interactions and ion channels, allowing the identification of specific macromolecules and their structure.

Imaging and structural studies of DNA–protein complexes and membrane ion channels

KAUST Repository

Marini, Monica

2017-01-17

In bio-imaging by electron microscopy, damage of the sample and limited contrast are the two main hurdles for reaching high image quality. We extend a new preparation method based on nanofabrication and super-hydrophobicity to the imaging and structural studies of nucleic acids, nucleic acid-protein complexes (DNA/Rad51 repair protein complex) and neuronal ion channels (gap-junction, K+ and GABA(A) channels) as paradigms of biological significance and increasing complexity. The preparation method is based on the liquid phase and is compatible with physiological conditions. Only in the very last stage, samples are dried for TEM analysis. Conventional TEM and high-resolution TEM (HRTEM) were used to achieve a resolution of 3.3 and 1.5 angstrom, respectively. The EM dataset quality allows the determination of relevant structural and metrological information on the DNA structure, DNA-protein interactions and ion channels, allowing the identification of specific macromolecules and their structure.

Equilibrium studies on mixed ligand complexes of some tripositive rare earth ions

International Nuclear Information System (INIS)

Vimal, Rashmi; Singh, Mamta; Ram Nayan

1996-01-01

Interaction of the rare earth ions, La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ and Eu 3+ with the pair of ligands 1-amino-2-naphthol-4-sulphonic acid (an, H 2 A) and o-aminophenol (ap, HB) have been studied in aqueous solution at 25 degC (μ=0.1 M KNO 3 /NaCl). Equilibrium constants of the reactions involving the formations of the mixed ligand species MAB, MA 2 B 2- , MB 2 A - (M = metal ion) and the binary complexes containing up to three ligand molecules have been evaluated from the pH-metric data, and coordinating behaviour of the ligands in the formation of the mixed ligand complexes has been discussed. (author). 10 refs., 1 tab., 1 fig

The trans influence in mer-trichloronitridobis(triphenylarsine)ruthenium(VI)

DEFF Research Database (Denmark)

Magnussen, Magnus; Bendix, Jesper

2003-01-01

The title compound, mer-[RuCl(3)N(C(18)H(15)As)(2)], is the first structurally characterized example of a nitride complex in which ruthenium is six-coordinated to monodentate ligands only. The Ru[triple-bond]N bond length [1.6161 (15) A] is relatively long, and the trans influence of the nitride...

Homogeneous conversion of methane to methanol. 2. Catalytic activation of methane by cis- and trans-platin: A density functional study of the Shilov type reaction

Energy Technology Data Exchange (ETDEWEB)

Mylvaganam, K.; Bacskay, G.B.; Hush, N.S.

2000-03-08

The C-H activation of methane catalyzed by cis- and trans-platin in aqueous solution has been studied by density functional based computational methods. By analogy with the Shilov reaction, the initial step is the replacement of an ammonia ligand by methane, followed by the formation of a methyl complex and the elimination o a proton. The computations utilize the B3LYP hybrid functionals, effective core potentials, and double-{zeta} to polarized double-{zeta} basis sets and include solvation effects by a dielectric continuum method. In contrast with the Shilov reaction studied by Seigbahn and Crabtree (J.Am.Chem.Soc. 1996, 118, 4443), in the platins the replacement of an ammonia ligand by methane is found to be effectively rate determining, in that the energy barriers to C-H activation are comparable with those of the initial substitution reaction, viz. {approximately} 34 and 44 kcal/mol for cis- and trans-platin, respectively. Several reaction pathways for C-H activation and subsequent proton elimination were identified. For cis-platin the energy barriers associated with the oxidative addition and {sigma}-bond metathesis type mechanisms were found to be comparable, while for trans-platin oxidative addition is predicted to be strongly preferred over {sigma}-bond metathesis, which, interestingly, also proceeds through a Pt(IV) methyl hydrido complex as reaction intermediate. In line with accepted ideas on trans influence, the methyl and hydride ligands in the Pt(IV) complexes that arise in the oxidative addition reactions were always found to be cis to each other. On the basis of the population analyses on the Pt(IV) complexes it is suggested that the Pt-H and Pt-CH{sub 3} bonds are best described as covalent bonds and, further, that the preference of the hydride and methyl anions to be cis to each other is a consequence of such covalent bonding. In light of these findings, the energies of several methyl Pt(IV) hydrido bisulfate complexes were also recalculated

Role of ion chromatograph in nuclear fuel fabrication process at Nuclear Fuel Complex

International Nuclear Information System (INIS)

Balaji Rao, Y.; Prasada Rao, G.; Prahlad, B.; Saibaba, N.

2012-01-01

The present paper discusses the different applications of ion chromatography followed in nuclear fuel fabrication process at Nuclear Fuel Complex. Some more applications of IC for characterization of nuclear materials and which are at different stages of method development at Control Laboratory, Nuclear Fuel Complex are also highlighted

Novel product ions of 2-aminoanilide and benzimidazole Ag(I) complexes using electrospray ionization with multi-stage tandem mass spectrometry.

Science.gov (United States)

Johnson, Byron S; Burinsky, David J; Burova, Svetlana A; Davis, Roman; Fitzgerald, Russ N; Matsuoka, Richard T

2012-05-15

The 2-aminoaniline scaffold is of significant value to the pharmaceutical industry and is embedded in a number of pharmacophores including 2-aminoanilides and benzimidazoles. A novel application of coordination ion spray mass spectrometry (CIS-MS) for interrogating the silver ion (Ag(+)) complexes of a homologous series of these compounds using multi-stage tandem mass spectrometry is described. Unlike the ubiquitous alkali metal ion complexes, Ag(+) complexes of 2-aminoanilides and benzimidazoles were found to yield [M - H](+) ions in significant abundance via gas-phase elimination of the metal hydride (AgH) resulting in unique product ion cascades. Sample introduction was by liquid chromatography with mass spectrometry analysis performed on a hybrid linear ion trap/orbitrap instrument capable of high-resolution measurements. Rigorous structural characterization by multi-stage tandem mass spectrometry using [M +  H](+), [M - H](-) and [M - H](+) precursor ions derived from ESI and CIS experiments was performed for the homologous series of 2-aminoanilide and benzimidazole compounds. A full tabular comparison of structural information resulting from these product ion cascades was produced. Multi-stage tandem mass spectrometry of [M - H](+) ions resulting from Ag(+) complexes of 2-aminoanilides and benzimidazoles in CIS-MS experiments produced unique product ion cascades that exhibited complementary structural information to that obtained from tandem mass spectrometry of [M  +  H](+) and [M - H](-) ions by electrospray ionization (ESI). These observations may be broadly applicable to other compounds that are observed to form Ag(+) complexes and eliminate AgH. Copyright © 2012 John Wiley & Sons, Ltd.

Determination of aminoglycoside antibiotics using complex compounds of chromotropic acid bisazoderivatives with rare earth ions

International Nuclear Information System (INIS)

Alykov, N.M.

1981-01-01

Studies of complex formation of bisazo derivatives of chromotropic acid with rare earth ions and aminoglycoside antibiotics have made it possible to choose carboxyarsenazo, orthanyl R and carboxynitrazo as highly sensitive reagents for determining aminoglycoside antibiotics. Conditions have been found for the formation of precipitates of different-ligand complexes containing rare earth ions, bisazo derivatives of chromotropic acid and aminogylcoside antibiotics. A procedure has been worked out of determining the antibiotics in biological samples with carboxyarsenazo [ru

Preliminary evidence for association of genetic variants in pri-miR-34b/c and abnormal miR-34c expression with attention deficit and hyperactivity disorder.

Science.gov (United States)

Garcia-Martínez, I; Sánchez-Mora, C; Pagerols, M; Richarte, V; Corrales, M; Fadeuilhe, C; Cormand, B; Casas, M; Ramos-Quiroga, J A; Ribasés, M

2016-08-30

Attention deficit and hyperactivity disorder (ADHD) is a prevalent neurodevelopmental disorder characterized by impairment to sustain attention and inability to control impulses and activity level. The etiology of ADHD is complex, with an estimated heritability of 70-80%. Under the hypothesis that alterations in the processing or target binding of microRNAs (miRNAs) may result in functional alterations predisposing to ADHD, we explored whether common polymorphisms potentially affecting miRNA-mediated regulation are involved in this psychiatric disorder. We performed a comprehensive association study focused on 134 miRNAs in 754 ADHD subjects and 766 controls and found association between the miR-34b/c locus and ADHD. Subsequently, we provided preliminary evidence for overexpression of the miR-34c-3p mature form in peripheral blood mononuclear cells of ADHD subjects. Next, we tested the effect on gene expression of single-nucleotide polymorphisms within the ADHD-associated region and found that rs4938923 in the promoter of the pri-miR-34b/c tags cis expression quantitative trait loci for both miR-34b and miR-34c and has an impact on the expression levels of 681 transcripts in trans, including genes previously associated with ADHD. This gene set was enriched for miR-34b/c binding sites, functional categories related to the central nervous system, such as axon guidance or neuron differentiation, and serotonin biosynthesis and signaling canonical pathways. Our results provide preliminary evidence for the contribution to ADHD of a functional variant in the pri-miR-34b/c promoter, possibly through dysregulation of the expression of mature forms of miR-34b and miR-34c and some target genes. These data highlight the importance of abnormal miRNA function as a potential epigenetic mechanism contributing to ADHD.

EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose.

Science.gov (United States)

Pacławski, K; Zajac, D A; Borowiec, M; Kapusta, Cz; Fitzner, K

2010-11-11

EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time.

Electrochemical Grafting of Graphene Nano Platelets with Aryl Diazonium Salts.

Science.gov (United States)

Qiu, Zhipeng; Yu, Jun; Yan, Peng; Wang, Zhijie; Wan, Qijin; Yang, Nianjun

2016-10-26

To vary interfacial properties, electrochemical grafting of graphene nano platelets (GNP) with 3,5-dichlorophenyl diazonium tetrafluoroborate (aryl-Cl) and 4-nitrobenzene diazonium tetrafluoroborate (aryl-NO 2 ) was realized in a potentiodynamic mode. The covalently bonded aryl layers on GNP were characterized using atomic force microscopy and X-ray photoelectron spectroscopy. Electrochemical conversion of aryl-NO 2 into aryl-NH 2 was conducted. The voltammetric and impedance behavior of negatively and positively charged redox probes (Fe(CN) 6 3-/4- and Ru(NH 3 ) 6 2+/3+ ) on three kinds of aryl layers grafted on GNP reveal that their interfacial properties are determined by the charge states of redox probes and reactive terminal groups (-Cl, -NO 2 , -NH 2 ) in aryl layers. On aryl-Cl and aryl-NH 2 garted GNP, selective and sensitive monitoring of positively charged lead ions as well as negatively charged nitrite and sulfite ions was achieved, respectively. Such a grafting procedure is thus a perfect way to design and control interfacial properties of graphene.

Trans-methylation reactions in plants: focus on the activated methyl cycle.

Science.gov (United States)

Rahikainen, Moona; Alegre, Sara; Trotta, Andrea; Pascual, Jesús; Kangasjärvi, Saijaliisa

2018-02-01

Trans-methylation reactions are vital in basic metabolism, epigenetic regulation, RNA metabolism, and posttranslational control of protein function and therefore fundamental in determining the physiological processes in all living organisms. The plant kingdom is additionally characterized by the production of secondary metabolites that undergo specific hydroxylation, oxidation and methylation reactions to obtain a wide array of different chemical structures. Increasing research efforts have started to reveal the enzymatic pathways underlying the biosynthesis of complex metabolites in plants. Further engineering of these enzymatic machineries offers significant possibilities in the development of bio-based technologies, but necessitates deep understanding of their potential metabolic and regulatory interactions. Trans-methylation reactions are tightly coupled with the so-called activated methyl cycle (AMC), an essential metabolic circuit that maintains the trans-methylation capacity in all living cells. Tight regulation of the AMC is crucial in ensuring accurate trans-methylation reactions in different subcellular compartments, cell types, developmental stages and environmental conditions. This review addresses the organization and posttranslational regulation of the AMC and elaborates its critical role in determining metabolic regulation through modulation of methyl utilization in stress-exposed plants. © 2017 Scandinavian Plant Physiology Society.

Studies on mixed ligand complexes of adenine and xanthine with some rare earth ions

International Nuclear Information System (INIS)

Rastogi, P.R.; Singh, Mamta; Nayan, Ram

1993-01-01

Interactions of 6-aminopurine (adenine, HA) and 2,6-dihydroxypurine (xanthine, HB) with trivalent rare earth ions Y, Tb, Dy, Ho, Er and Tm, have been studied by pH-titration methods in aqueous solution at 20 o (μ = 0.1 M KNO 3 ). The ligands in their mixtures with tripositive rare earth ions (M 3+ ) form a number of mixed ligand complexes, M 3+ -adenine-xanthine, M 3+ -(adenine) 2 -xanthine, M 3+ -adenine-(xanthine) 2 in addition to the binary complexes, M 3+ -(adenine), M 3+ -(adenine) 2 , M 3+ -(adenine) 3 , M 3+ -(xanthine), M 3+ -(xanthine) 2 and M 3+ -(xanthine) 3 . The stability constants of these complexes have been evaluated and the results discussed. (author). 13 refs., 1 fig., 1 tab

Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

Science.gov (United States)

Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

2014-02-15

The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

Identifying cis-mediators for trans-eQTLs across many human tissues using genomic mediation analysis.

Science.gov (United States)

Yang, Fan; Wang, Jiebiao; Pierce, Brandon L; Chen, Lin S

2017-11-01

The impact of inherited genetic variation on gene expression in humans is well-established. The majority of known expression quantitative trait loci (eQTLs) impact expression of local genes ( cis -eQTLs). More research is needed to identify effects of genetic variation on distant genes ( trans -eQTLs) and understand their biological mechanisms. One common trans -eQTLs mechanism is "mediation" by a local ( cis ) transcript. Thus, mediation analysis can be applied to genome-wide SNP and expression data in order to identify transcripts that are " cis -mediators" of trans -eQTLs, including those " cis -hubs" involved in regulation of many trans -genes. Identifying such mediators helps us understand regulatory networks and suggests biological mechanisms underlying trans -eQTLs, both of which are relevant for understanding susceptibility to complex diseases. The multitissue expression data from the Genotype-Tissue Expression (GTEx) program provides a unique opportunity to study cis -mediation across human tissue types. However, the presence of complex hidden confounding effects in biological systems can make mediation analyses challenging and prone to confounding bias, particularly when conducted among diverse samples. To address this problem, we propose a new method: Genomic Mediation analysis with Adaptive Confounding adjustment (GMAC). It enables the search of a very large pool of variables, and adaptively selects potential confounding variables for each mediation test. Analyses of simulated data and GTEx data demonstrate that the adaptive selection of confounders by GMAC improves the power and precision of mediation analysis. Application of GMAC to GTEx data provides new insights into the observed patterns of cis -hubs and trans -eQTL regulation across tissue types. © 2017 Yang et al.; Published by Cold Spring Harbor Laboratory Press.

Complexes with charge transfer and ion-radical salts in catalysis

Energy Technology Data Exchange (ETDEWEB)

Krylov, O V [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1978-01-01

Considered are the data experimentally proving formation of complexes with charge transfer as intermediate complexes in homogeneous and heterogeneous catalysis. Catalytic activity correlations with charge transfer energy (and in heterogeneous catalysis with width of semiconductor forbidden band can be useful while selection of catalysts (MoO/sub 3//MgO; V/sub 2/O/sub 5//MgO; MoO/sub 3//Al/sub 2/O/sub 3/; V/sub 2/O/sub 5//Al/sub 2/O/sub 3/). A review of papers on catalytic activity of the previously prepared complexes with charge transfer and ion-radical salts is given. The use of alkali metal complexes with aromatic compounds showed their high activity in hydrogenation reactions and proved principle possibility of activation of hydrogen and hydrocarbons by the systems which do not contain transfer metals.

Facts about trans fats

Science.gov (United States)

Trans fat is a type of dietary fat . Of all the fats, trans fat is the worst for your health. Too much ... from solid margarine to soft margarine. Ask what type of fats foods are cooked in when you eat out ...

Selective transport of metal ions through cation exchange membrane in the presence of a complexing agent

Energy Technology Data Exchange (ETDEWEB)

Tingchia Huang; Jaukai Wang (National Cheng Kung Univ., Tainan (Taiwan, Province of China))

1993-01-01

Selective transport of metal ions through a cation exchange membrane was studied in stirred batch dialyzer for the systems Ni[sup 2+]-Cu[sup 2+] and Cu[sup 2+]-Fe[sup 3+]. Oxalic acid, malonic acid, citric acid, glycine, and ethylenediaminetetraacetic acid were employed as the complexing agents added in the feed solution in order to increase the permselectivity of metal ions. The experimental results show that the selective transport behavior of metal ions depends on the valence and the concentration of metal ions, the stoichiometric ratio of complexing agent to metal ions, and the pH value of the feed solution, but is independent of the concentration of counterion in the stripping phase. A theoretical approach was formulated on the basis of the Nernst-Planck equation and interface quasi-equilibrium. Theoretical solutions obtained from numerical calculation were in agreement with the experimental data.

Exploración estocástica de las superficies de energía potencial de dímeros cis-trans y trans-trans del ácido fórmico

Directory of Open Access Journals (Sweden)

Said F. Figueredo

2014-01-01

Full Text Available Potential energy surface (PES of cis-trans and trans-trans formic acid dimers were sampled using a stochastic method, and the geometries, energies, and vibrational frequencies were computed at B3LYP/6-311++G(3df,2p level of theory. The results show that molar free energy of dimerization deviated up to 108.4% when basis set superposition error (BSSE and zero-point energy (ZPE were not considered. For cis-trans dimers, C=O and O - H bond weakened, whereas C - O bonds strengthened due to dimerization. Also, trans-trans FA dimers did not show a trend regarding strengthening or weakening of the C=O, O - H and C - O bonds.

Radium removal from Canadian uranium mining effluents by a radium-selective ion exchange complexer

International Nuclear Information System (INIS)

1984-07-01

A laboratory test program was initiated by the Department of Energy, Mines and Resources as part of the National Uranium Tailings Program to investigate the applicability of a radium-selective ion exchange complexer for removing radium from Canadian uranium mining effluents. The ion exchange complexer was shown to be efficient in removing radium from contaminated water of uranium mining operations, with the ultimate loading capacity of the resin on one type of water treated being determined as approximately 1,600 Bq/cm 3 of new resin. The results showed that the resin was effective in removing radium but not any other contaminants

Metal ion complex formation in small lakes of the Western Siberian Arctic zone

Science.gov (United States)

Kremleva, Tatiana; Dinu, Marina

2017-04-01

The paper is based on joint investigation of the Tyumen State University (Russia, Tyumen) and the Geochemistry and Analytical Chemistry Vernadsky Institute of Russian Academy of Sciences (Moscow, Russia) during 2012-2014 period. It presents the results of research of chemical composition of about 70 small lakes located in the area of tundra and northern taiga of West Siberia (Russia, Yamal-Nenets and Khanty-Mansi Autonomous Districts of the Tyumen region). The investigation includes determination of different parameters of natural water samples: • content of trace elements (Al, Fe, Mn, Cr, Cu, Ni, Zn, Cd, Co, Pb, etc., total more than 60 elements) by emission method with an inductively coupled plasma (ICP-MS) using mass spektrometrometre Element 2 equipment; • content of inorganic and total carbon (TIC and TC) by elemental analysis and the difference between the total and inorganic carbon gives the organic carbon content (TOC); • pH value by potentiometric method; • content of basic ions (Na+, Ca2+, K+, Mg2+, NH4+, Cl-, SO42-, NO3-, PO43-) by ion chromatography. Determination of the chemical composition of samples was conducted in the accredited laboratory according to standard procedures with regular quality control of results. Heavy metals in natural waters can exist in various forms: free (hydrated) ions bound in complexes with organic or inorganic ligands, as well as in the form of suspensions. The form of metal existence has a significant influence on their availability to transport in aquatic organisms. Metal ions associated in stable complexes with organic substances are considered less toxic. From the previous investigations state that the most stable complexes are ligands with organic ions Fe3+, Al3+. The main conclusion of the present research states that if the total content of aluminum, iron and manganese ions (meq/dm3) is equal to or greater than the concentration of dissolved organic carbon (TOC, mg/dm3) in lakes water other heavy metals will

The complex formation-partition and partition-association models of solvent extraction of ions

International Nuclear Information System (INIS)

Siekierski, S.

1976-01-01

Two models of the extraction process have been proposed. In the first model it is assumed that the partitioning neutral species is at first formed in the aqueous phase and then transferred into the organic phase. The second model is based on the assumption that equivalent amounts of cations are at first transferred from the aqueous into the organic phase and then associated to form a neutral molecule. The role of the solubility parameter in extraction and the relation between the solubility of liquid organic substances in water and the partition of complexes have been discussed. The extraction of simple complexes and complexes with organic ligands has been discussed using the first model. Partition coefficients have been calculated theoretically and compared with experimental values in some very simple cases. The extraction of ion pairs has been discussed using the partition-association model and the concept of single-ion partition coefficients. (author)

Thermodynamic and structural properties in complexing media; Comportement chimique du protactinium (V) en presence d'ions sulfate

Energy Technology Data Exchange (ETDEWEB)

Di Giandomenico, M.V

2007-10-15

Protactinium is experiencing a renewal of interest in the frame of long-term energy production. Modelling the behaviour of this element in the geosphere requires thermodynamic and structural data relevant to environmental conditions. Now deep clayey formation are considered for the disposal of radioactive waste and high values of natural sulphate contents have been determined in pore water in equilibrium with clay surface. Because of its tendency to polymerisation, hydrolysis and sorption on all solid supports, the equilibria constants relative to monomer species were determined at tracer scale (ca. 10 - 12 M) with {sup 233}Pa. The complexation constants of Pa(V) and sulphate ions were calculated starting from a systematic study of the apparent distribution coefficient D in the system TTA/Toluene/H{sub 2}O/Na{sub 2}SO{sub 4}/HClO{sub 4}/NaClO{sub 4} and as a function of ionic strength, temperature, free sulphate, protons and chelatant concentration. First of all, the interaction between free species H{sup +}, SO{sub 4}{sup -}, Na{sup +} leads to the formation of HSO{sub 4}{sup -} and NaSO{sub 4}{sup -}, for which concentrations depend upon the related thermodynamic constants. For this purpose a computer code was developed in order to determine all free species concentration. This iterative code takes into account the influence of temperature and ionic strength (SIT modelling) on thermodynamic constants. The direct measure of Pa(V) in the organic and aqueous phase by g-spectrometry had conducted to estimate the apparent distribution coefficient D as function of free sulphate ions. Complexation constants have been determined after a mathematical treatment of D. The extrapolation of these constants at zero ionic strength have been realized by SIT modelling at different temperatures. Besides, enthalpy and entropy values were calculated. Parallelly, the structural study of Pa(V) was performed using 231 Pa. XANES and EXAFS spectra show unambiguously the absence of the

TransAtlasDB: an integrated database connecting expression data, metadata and variants

Science.gov (United States)

Adetunji, Modupeore O; Lamont, Susan J; Schmidt, Carl J

2018-01-01

Abstract High-throughput transcriptome sequencing (RNAseq) is the universally applied method for target-free transcript identification and gene expression quantification, generating huge amounts of data. The constraint of accessing such data and interpreting results can be a major impediment in postulating suitable hypothesis, thus an innovative storage solution that addresses these limitations, such as hard disk storage requirements, efficiency and reproducibility are paramount. By offering a uniform data storage and retrieval mechanism, various data can be compared and easily investigated. We present a sophisticated system, TransAtlasDB, which incorporates a hybrid architecture of both relational and NoSQL databases for fast and efficient data storage, processing and querying of large datasets from transcript expression analysis with corresponding metadata, as well as gene-associated variants (such as SNPs) and their predicted gene effects. TransAtlasDB provides the data model of accurate storage of the large amount of data derived from RNAseq analysis and also methods of interacting with the database, either via the command-line data management workflows, written in Perl, with useful functionalities that simplifies the complexity of data storage and possibly manipulation of the massive amounts of data generated from RNAseq analysis or through the web interface. The database application is currently modeled to handle analyses data from agricultural species, and will be expanded to include more species groups. Overall TransAtlasDB aims to serve as an accessible repository for the large complex results data files derived from RNAseq gene expression profiling and variant analysis. Database URL: https://modupeore.github.io/TransAtlasDB/ PMID:29688361

2006 marketplace survey of trans-fatty acid content of margarines and butters, cookies and snack cakes, and savory snacks.

Science.gov (United States)

Albers, Matthew J; Harnack, Lisa J; Steffen, Lyn M; Jacobs, David R

2008-02-01

In recent years, newer technologies have been developed to reduce the trans-fat content of fats and oils used in manufacturing food products. To examine the implications of these changes on foods in the marketplace, a survey was conducted to assess current levels of trans and saturated fat in three food categories: margarines and butters; cookies and snack cakes; and savory snacks. A sampling of products from each category was conducted at a Wal-Mart Supercenter in the Minneapolis-St Paul, MN, metropolitan area in July of 2006. All information was obtained from product labels, except price, which was recorded from price listings on product shelving. Most margarines and butters (21 of 29), cookies and snack cakes (34 of 44), and savory snacks (31 of 40) were labeled as containing 0 g trans fat. However, some products contained substantial amounts of trans fat. Most notably, 3 of 40 savory snack products were labeled as containing > or =3 g trans fat. Significant inverse correlations were found between product price and the saturated and trans-fat content of margarines (r=-0.45) and savory snacks (r=-0.32). In conclusion, it appears that the food industry has made progress in reducing the trans-fat content in a variety of products. Nonetheless, consumers need to read product labels because the trans-fat content of individual products can vary considerably. Products that are lower in trans and saturated fat tend to cost more, which may be a barrier to their purchase for price-conscious consumers.

trans-Diaquabis[2,5-bis(pyridin-2-yl-1,3,4-thiadiazole]cobalt(II bis(tetrafluoridoborate

Directory of Open Access Journals (Sweden)

Fouad Bentiss

2011-07-01

Full Text Available The bidentate 1,3,4-thiadiazole ligand substituted by two 2-pyridyl rings (denoted L has been found to produce the new monomeric title complex, [Co(C12H8N4S2(H2O2](BF42. The thiadiazole and pyridyl rings surrounding the Co atom are almost coplanar [dihedral angle = 4.35 (7°]. The mean plane defined by these heterocyclic moieties makes a dihedral angle of 18.72 (6° with the non-coordinated pyridyl ring. The Co2+ cation, located at a crystallographic center of symmetry, is bonded to two ligands and two water molecules in a trans configuration in an octahedral environment. The tetrafluoridoborate ions can be regarded as free anions in the crystal lattice. Nevertheless, they are involved in an infinite two-dimensional network along the [010] and [101] directions of O—H...F hydrogen bonds.

Komplexe zouten van trans-1-2-diaminocyclohexaan met driewaardig rhodium en kobalt

NARCIS (Netherlands)

Bijkerk, Lucas

1937-01-01

Some complex salts of trans-I-2-díominocyclohexane with trivalent cobaltum and rhodium were prepared and their properties described in detail. Diaminocyclohexanwe as obtained by the following series of reactions: cyclohexanone --> cyclohexanone-I-oxalylicester --> cyclohexonone-I-carboxylicester-2

Nickel complexes of o-amidochalcogenophenolate(2-)/o-iminochalcogenobenzosemiquinonate(1-) pi-radical: synthesis, structures, electron spin resonance, and x-ray absorption spectroscopic evidence.

Science.gov (United States)

Hsieh, Chung-Hung; Hsu, I-Jui; Lee, Chien-Ming; Ke, Shyue-Chu; Wang, Tze-Yuan; Lee, Gene-Hsiang; Wang, Yu; Chen, Jin-Ming; Lee, Jyh-Fu; Liaw, Wen-Feng

2003-06-16

The preparation of complexes trans-[Ni(-SeC(6)H(4)-o-NH-)(2)](-) (1), cis-[Ni(-TeC(6)H(4)-o-NH-)(2)](-) (2), trans-[Ni(-SC(6)H(4)-o-NH-)(2)](-) (3), and [Ni(-SC(6)H(4)-o-S-)(2)](-) (4) by oxidative addition of 2-aminophenyl dichalcogenides to anionic [Ni(CO)(SePh)(3)](-) proves to be a successful approach in this direction. The cis arrangement of the two tellurium atoms in complex 2 is attributed to the intramolecular Te.Te contact interaction (Te.Te contact distance of 3.455 A). The UV-vis electronic spectra of complexes 1 and 2 exhibit an intense absorption at 936 and 942 nm, respectively, with extinction coefficient epsilon > 10000 L mol(-)(1) cm(-)(1). The observed small g anisotropy, the principal g values at g(1) = 2.036, g(2) = 2.062, and g(3) = 2.120 for 1 and g(1) = 2.021, g(2) = 2.119, and g(3) = 2.250 for 2, respectively, indicates the ligand radical character accompanied by the contribution of the singly occupied d orbital of Ni(III). The X-ray absorption spectra of all four complexes show L(III) peaks at approximately 854.5 and approximately 853.5 eV. This may indicate a variation of contribution of the Ni(II)-Ni(III) valence state. According to the DFT calculation, the unpaired electron of complex 1 and 2 is mainly distributed on the 3d(xz)() orbital of the nickel ion and on the 4p(z)() orbital of selenium (tellurium, 5p(z)()) as well as the 2p(z)() orbital of nitrogen of the ligand. On the basis of X-ray structural data, UV-vis absorption, electron spin resonance, magnetic properties, DFT computation, and X-ray absorption (K- and L-edge) spectroscopy, the monoanionic trans-[Ni(-SeC(6)H(4)-o-NH-)(2)](-) and cis-[Ni(-TeC(6)H(4)-o-NH-)(2)](-) complexes are appositely described as a resonance hybrid form of Ni(III)-bis(o-amidochalcogenophenolato(2-)) and Ni(II)-(o-amidochalcogenophenolato(2-))-(o-iminochalcogenobenzosemiquinonato(1-) pi-radical; i.e., complexes 1 and 2 contain delocalized oxidation levels of the nickel ion and ligands.

TransDetect Identifies a New Regulatory Module Controlling Phosphate Accumulation.

Science.gov (United States)

Pal, Sikander; Kisko, Mushtak; Dubos, Christian; Lacombe, Benoit; Berthomieu, Pierre; Krouk, Gabriel; Rouached, Hatem

2017-10-01

Identifying transcription factor (TFs) cooperation controlling target gene expression is still an arduous challenge. The accuracy of current methods at genome scale significantly drops with the increase in number of genes, which limits their applicability to more complex genomes, like animals and plants. Here, we developed an algorithm, TransDetect, able to predict TF combinations controlling the expression level of a given gene. TransDetect was used to identify novel TF modules regulating the expression of Arabidopsis ( Arabidopsis thaliana ) phosphate transporter PHO1;H3 comprising MYB15, MYB84, bHLH35, and ICE1. These TFs were confirmed to interact between themselves and with the PHO1;H3 promoter. Phenotypic and genetic analyses of TF mutants enable the organization of these four TFs and PHO1;H3 in a new gene regulatory network controlling phosphate accumulation in zinc-dependent manner. This demonstrates the potential of TransDetect to extract directionality in nondynamic transcriptomes and to provide a blueprint to identify gene regulatory network involved in a given biological process. © 2017 American Society of Plant Biologists. All Rights Reserved.

Zinc and cadmium complexes of a plant metallothionein under radical stress: desulfurisation reactions associated with the formation of trans-lipids in model membranes.

Science.gov (United States)

Torreggiani, Armida; Domènech, Jordi; Orihuela, Ruben; Ferreri, Carla; Atrian, Sílvia; Capdevila, Mercè; Chatgilialoglu, Chryssostomos

2009-06-08

Metallothioneins (MTs) are sulfur-rich proteins capable of binding metal ions to give metal clusters. The metal-MT aggregates used in this work were Zn- and Cd-QsMT, where QsMT is an MT from the plant Quercus suber. Reactions of reductive reactive species (H(*) atoms and e(aq)(-)), produced by gamma irradiation of water, with Zn- and Cd-QsMT were carried out in both aqueous solutions and vesicle suspensions, and were characterized by different approaches. By using a biomimetic model based on unsaturated lipid vesicle suspensions, the occurrence of tandem protein/lipid damage was shown. The reactions of reductive reactive species with methionine residues and/or sulfur-containing ligands afford diffusible sulfur-centred radicals, which migrate from the aqueous phase to the lipid bilayer and transform the cis double bond of the oleate moiety into the trans isomer. Tailored experiments allowed the reaction mechanism to be elucidated in some detail. The formation of sulfur-centred radicals is accompanied by the modification of the metal-QsMT complexes, which were monitored by various spectroscopic and spectrometric techniques (Raman, CD, and ESI-MS). Attack of the H(*) atom and e(aq)(-) on the metal-QsMT aggregates can induce significant structural changes such as partial deconstruction and/or rearrangement of the metal clusters and breaking of the protein backbone. Substantial differences were observed in the behaviour of the Zn- and Cd-QsMT aggregates towards the reactive species, depending on the different folding of the polypeptide in these two cases.

Precipitation characteristics of uranyl ions at different pHs depending on the presence of carbonate ions and hydrogen peroxide.

Science.gov (United States)

Kim, Kwang-Wook; Kim, Yeon-Hwa; Lee, Se-yoon; Lee, Jae-Won; Joe, Kih-Soo; Lee, Eil-Hee; Kim, Jong-Seung; Song, Kyuseok; Song, Kee-Chan

2009-04-01

This work studied the dissolution of uranium dioxide and precipitation characteristics of uranyl ions in alkaline and acidic solutions depending on the presence of carbonate ions and H2O2 in the solutions at different pHs controlled by adding HNO3 or NaOH in the solution. The chemical structures of the precipitates generated in different conditions were evaluated and compared by using XRD, SEM, TG-DT, and IR analyses together. The sizes and forms of the precipitates in the solutions were evaluated, as well. The uranyl ions were precipitated in the various forms, depending on the solution pH and the presences of hydrogen peroxide and carbonate ions in the solution. In a 0.5 M Na2CO3 solution with H2O2, where the uranyl ions formed mixed uranyl peroxy-carbonato complexes, the uranyl ions were precipitated as a uranium peroxide of UO4(H20)4 at pH 3-4, and precipitated as a clarkeite of Na2U2Ox(OH)y(H2O)z above pH 13. In the same carbonate solution without H2O2, where the uranyl ions formed uranyl tris-carbonato complex, the uranyl ions were observed to be precipitated as a different form of clarkeite above pH 13. The precipitate of uranyl ions in a nitrate solution without carbonate ions and H2O2 at a high pH were studied together to compare the precipitate forms in the carbonate solutions.

Properties of grafted polymer metal complexes as ion exchangers and its electrical conductivity

International Nuclear Information System (INIS)

El-Arnaouty, M.B.; Abdel Ghaffar, A.M.; Eid, M.

2011-01-01

The polyelectrolyte has been prepared as a potential proton exchanger polymer by grafting of acrylic acid/acrylamide and acrylic acid/acrylonitrile comonomer onto low density polyethylene film via gamma radiation. The influence of grafting percent on the electrical conductivity was studied. The resulting polymers were then characterized by evaluating their physico-chemical properties such as ion exchange capacity, and electrical conductivity as a function of grafting yield. The grafted films at different compositions was characterized by FTIR, TGA and SEM. The ion exchange capacity (IEC) of the grafted film at grafting % (191) and monomer concentration ratio 50:50 for (LDPE-g-AAc/AAm) was found to be more than that for (LDPE-g-AAc/AN). The electrical conductivity was found to be greatly affected by the comonomer composition where it increased as the degree of grafting increased for all grafted films. After alkaline treatment with 3% KOH, the electrical conductivity of the grafted films found to be increased. The presence of potassium as counter ion maximized the electrical conductivity of the grafted films. The electrical conductivity of Cu-membrane complexes was higher than that of both Co and Ni complexes. The electrical conductivity increases by increasing both Cu ions content and temperature

Cis By Trans

OpenAIRE

Rodovalho,Amara Moira

2017-01-01

Cis, trans: above all, metaphors. Cisjordan, region skirting the Jordan River. Cisplatin, Uruguay’s ancient name, region occupying one of the banks of the Prata River. Trans- Amazonian, that which crosses the Amazon; transatlantic, that which crosses the Atlantic. Cisalpine, transalpine. The geometric isomerism of Organic Chemistry, where “cis” are atoms that, when molecules are divided in half, remain on the same side, and “trans” those remaining on opposite sides. Ev...

Crystallinity and the effect of ionizing radiation in polyethylene. V. Distribution of trans-vinylene and trans, trans conjugated double bonds in linear polyethylene

International Nuclear Information System (INIS)

Patel, G.N.

1975-01-01

Freeze-dried chain folded single crystals and the single crystals without amorphous surface layers (crystalline cores) of different thicknesses of linear polyethylene were irradiated with 60 Co γ-rays up to 600 Mrad. Concentration of trans-vinylene double bonds and conjugated diene produced during irradiation of the crystals was measured by infrared. Concentrations of trans-vinylene and of the conjugated diene were independent of thickness of crystalline core which suggest that the double bonds were randomly distributed in the crystalline parts of the crystals. Concentrations of trans-vinylene and of conjugated double bonds were lower in chain-folded crystals than in the crystalline cores and this suggests that the folds (amorphous surface layers) are less preferential sites for formation of the double bonds. The zero-order growth and first-order decay kinetics of trans-vinylene double bonds was studied by the equation derived by Dole et al. The equation is strictly obeyed up to 300 Mrad and the results then deviate. Since there is the decay of trans-vinylene double bonds and though there are no crosslinks in the crystalline cores, it has been suggested that the decay of the double bond does not result in the crosslinks

Noncovalent Complexation of Monoamine Neurotransmitters and Related Ammonium Ions by Tetramethoxy Tetraglucosylcalix[4]arene

Science.gov (United States)

Torvinen, Mika; Kalenius, Elina; Sansone, Francesco; Casnati, Alessandro; Jänis, Janne

2012-02-01

The noncovalent complexation of monoamine neurotransmitters and related ammonium and quaternary ammonium ions by a conformationally flexible tetramethoxy glucosylcalix[4]arene was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. The glucosylcalixarene exhibited highest binding affinity towards serotonin, norepinephrine, epinephrine, and dopamine. Structural properties of the guests, such as the number, location, and type of hydrogen bonding groups, length of the alkyl spacer between the ammonium head-group and the aromatic ring structure, and the degree of nitrogen substitution affected the complexation. Competition experiments and guest-exchange reactions indicated that the hydroxyl groups of guests participate in intermolecular hydrogen bonding with the glucocalixarene.

Preparation and properties of mononuclear and binuclear uranyl(VI), thorium(IV) and transition d ions complexes with multidentate Schiff bases

Energy Technology Data Exchange (ETDEWEB)

Vidali, M; Casellato, U; Vigato, P A; Doretti, L; Madalosso, F [Consiglio Nazionale delle Ricerche, Padua (Italy). Lab. di Chimica e Tecnologia dei Radioelementi

1977-01-01

The preparation, physical and chemical properties of a variety of mononuclear and binuclear complexes containing Schiff base ligands derived from 3-formylsalicylic acid and diamines are reported. The Schiff bases have six potential donor atoms and can function as tetrabasic ligands. In the mononuclear complexes the copper(II) and nickel(II) ions occupy the N/sub 2/O/sub 2/ donor set and the uranyl(VI) ion the O/sub 2/O/sub 2/ one. Both types of complexes can act as ligand toward transition metal ions to form complexes with a binuclear structure connected by two phenolic oxygens. The complexes have been characterized by magnetic measurements and by IR and visible spectral methods.

Complexation of Flavonoids with Iron: Structure and Optical Signatures

Science.gov (United States)

Ren, Jun; Meng, Sheng; Lekka, Ch. E.; Kaxiras, Efthimios

2008-03-01

Flavonoids exhibit antioxidant behavior believed to be related to their metal ion chelation ability. We investigate the complexation mechanism of several flavonoids, quercetin, luteolin, galangin, kaempferol and chrysin with iron, the most abundant type of metal ions in the body, through first- principles electronic structure calculations based on Density Functional Theory (DFT). We find that the most likely chelation site for Fe is the 3-hydroxyl-4-carbonyl group, followed by 4- carbonyl-5-hydroxyl group and the 3'-4' hydroxyl (if present) for all the flavonoid molecules studied. Three quercetin molecules are required to saturate the bonds of a single Fe ion by forming six orthogonal Fe-O bonds, though the binding energy per molecule is highest for complexes consisting of two quercetin molecules and one Fe atom, in agreement with experiment. Optical absorption spectra calculated with time- dependent DFT serve as signatures to identify various complexes. For the iron-quercetin complexes, we find a redshift of the first absorbance peak upon complexation in good agreement with experiment; this behavior is explained by the narrowing of the optical gap of quercetin due to Fe(d)--O(p) orbital hybridization.

Hair dye-incorporated poly-γ-glutamic acid/glycol chitosan nanoparticles based on ion-complex formation

Directory of Open Access Journals (Sweden)

Lee HY

2011-11-01

Full Text Available Hye-Young Lee1,*, Young-IL Jeong2,*, Ki-Choon Choi31Anyang Science University, Anyang, Gyeonggi, South Korea; 2Chonnam National University Hwasun Hospital, Jeonnam, South Korea; 3Grassland and Forages Research Center, National Institute of Animal Science, Rural Development Administration, Chungnam, South Korea*These authors contributed equally to this work.Background: p-Phenylenediamine (PDA or its related chemicals are used more extensively than oxidative hair dyes. However, permanent hair dyes such as PDA are known to have potent contact allergy reactions in humans, and severe allergic reactions are problematic.Methods: PDA-incorporated nanoparticles were prepared based on ion-complex formation between the cationic groups of PDA and the anionic groups of poly(γ-glutamic acid (PGA. To reinforce PDA/PGA ion complexes, glycol chitosan (GC was added. PDA-incorporated nanoparticles were characterized using field-emission scanning electron microscopy, Fourier-transform infrared (FT-IR spectroscopy, dynamic light scattering, and powder X-ray diffractometry (XRD.Results: Nanoparticles were formed by ion-complex formation between the amine groups of PDA and the carboxyl groups of PGA. PDA-incorporated nanoparticles are small in size (<100 nm, and morphological observations showed spherical shapes. FT-IR spectra results showed that the carboxylic acid peak of PGA decreased with increasing PDA content, indicating that the ion complexes were formed between the carboxyl groups of PGA and the amine groups of PDA. Furthermore, the intrinsic peak of the carboxyl groups of PGA was also decreased by the addition of GC. Intrinsic crystalline peaks of PDA were observed by XRD. This crystalline peak of PDA was completely nonexistent when nanoparticles were formed by ion complex between PDA, PGA, and GC, indicating that PDA was complexed with PGA and no free drug existed in the formulation. During the drug-release experiment, an initial burst release of PDA was

Radical feminists & trans activists truce

OpenAIRE

Mackay, F.

2014-01-01

#GenderWeek: Truce! When radical feminists and trans feminists empathise\\ud Feminist Times\\ud By Finn Mackay \\ud read all #GenderWeek articles.\\ud We wanted to explore the ground between the polarised, entrenched positions in the so-called “TERF-war”. Radical feminists on one pole, trans-inclusionary feminists and trans activists on the other. The disputed territory being women-only space, language and the ever changing legal framework surrounding gender.\\ud Entrenchment leads to stalemate. S...

Polarographic investigation of complexing kinetics of polyacrylate anions with cadmium ions. Polyarograficheskoe issledovanie kinetiki kompleksoobrazovaniya poliakrilat-anionov s ionami kadmiya

Energy Technology Data Exchange (ETDEWEB)

Avlyanov, Zh K; Kabanov, N M; Zezin, A B; Askarov, M A

1990-01-01

The processes which occur during the reduction of cadmium ions from polymer-metallic complexes (PMC) are studied for the purposes of polarographic investigation of complexing kinetics of polyacrylate anions (PAA) of different molecular masses with cadmium ions in KCl aqueous solutions. An expression is derived for establishing semiwave potential. PMC formation and dissociation reduction rate constants are calculated. It is shown that intramolecular reorderings required for the formation of a two-coordinate complex proceed much slower as compared to the diffusion of free ions.

Production of highly charged ion beams from ECR ion sources

International Nuclear Information System (INIS)

Xie, Z.Q.

1997-09-01

Electron Cyclotron Resonance (ECR) ion source development has progressed with multiple-frequency plasma heating, higher mirror magnetic fields and better technique to provide extra cold electrons. Such techniques greatly enhance the production of highly charged ions from ECR ion sources. So far at cw mode operation, up to 300 eμA of O 7+ and 1.15 emA of O 6+ , more than 100 eμA of intermediate heavy ions for charge states up to Ar 13+ , Ca 13+ , Fe 13+ , Co 14+ and Kr 18+ , and tens of eμA of heavy ions with charge states to Kr 26+ , Xe 28+ , Au 35+ , Bi 34+ and U 34+ have been produced from ECR ion sources. At an intensity of at least 1 eμA, the maximum charge state available for the heavy ions are Xe 36+ , Au 46+ , Bi 47+ and U 48+ . An order of magnitude enhancement for fully stripped argon ions (I ≥ 60 enA) also has been achieved. This article will review the ECR ion source progress and discuss key requirement for ECR ion sources to produce the highly charged ion beams

Tackling complex turbulent flows with transient RANS

NARCIS (Netherlands)

Kenjeres, S.; Hanjalic, K.

2009-01-01

This article reviews some recent applications of the transient-Reynoldsaveraged Navier–Stokes (T-RANS) approach in simulating complex turbulent flows dominated by externally imposed body forces, primarily by thermal buoyancy and the Lorentz force. The T-RANS aims at numerical resolving unsteady

Trans advanced surface laser ablation (TransPRK) outcomes using SmartPulseTechnology.

Science.gov (United States)

Aslanides, Ioannis M; Kymionis, George D

2017-02-01

To evaluate early visual rehabilitation, post-operative pain, epithelial healing and haze after transepithelial photorefractive keratectomy (TransPRK) using the SmartPulseTechnology (SPT) of Schwind Amaris (Schwind eye-tech-solutions GmbH, Kleinostheim, Germany). This was a retrospective comparative evaluation of a cohort of myopic patients undergoing TransPRK with SPT (group 1), with one matched control group that underwent conventional TransPRK (group 2). All cases had a 6-month post-operative follow-up including visual acuity and slit-lamp examination. Subjective evaluation of pain was recorded post-operatively. 49 eyes of 25 patients in group 1 and 40 eyes of 20 patients in group 2 were enrolled. The patients' visual rehabilitation was significantly faster in group 1, one day and one week post-operatively (P0.05). TransPRK using SPT provides promising results in the early post-operative period. Visual rehabilitation, re-epithelialization and pain were faster in the early post-operative period in group 1 in comparison with group 2. Haze formation was not significantly different between the two groups; however, it was consistently less in group 1. Copyright © 2016 British Contact Lens Association. Published by Elsevier Ltd. All rights reserved.

Trans as Contested Intelligibility

DEFF Research Database (Denmark)

Raun, Tobias

2014-01-01

Denne artikel rejser en række epistemologiske og metodologiske spørgsmål vedrørende læsningen af trans som identitetskategori. Disse spørgsmål er stærkt underbelyste i en skandinavisk akademisk kontekst, om end der el- lers i stigende grad produceres analyser af trans identitetsnarrativer. Artikl...

Highly sensitive colour change system within slight differences in metal ion concentrations based on homo-binuclear complex formation equilibrium for visual threshold detection of trace metal ions

International Nuclear Information System (INIS)

Mizuguchi, Hitoshi; Atsumi, Hiroshi; Hashimoto, Keigo; Shimada, Yasuhiro; Kudo, Yuki; Endo, Masatoshi; Yokota, Fumihiko; Shida, Junichi; Yotsuyanagi, Takao

2004-01-01

A new technique of expressing slight differences in metal ion concentrations by clear difference in colour was established for visual threshold detection of trace metal ions. The proposed method is based on rapid change of the mole fraction of the homo-binuclear complex (M 2 L) about a ligand in a narrow range of the total metal ion concentration (M T ) in a small excess, in case the second metal ion is bound to the reagent molecule which can bind two metal ions. Theoretical simulations showed that the highly sensitive colour change within slight differences in metal ion concentrations would be realized under the following conditions: (i) both of the stepwise formation constants of complex species are sufficiently large; (ii) the stepwise formation constant of the 1:1 complex (ML) is larger than that of M 2 L; and (iii) the absorption spectrum of M 2 L is far apart from the other species in the visible region. Furthermore, the boundary of the colour region in M T would be readily controlled by the total ligand concentration (L T ). Based on this theory, the proposed model was verified with the 3,3'-bis[bis(carboxymethyl)amino]methyl derivatives of sulphonephthalein dyes such as xylenol orange (XO), methylthymol blue (MTB), and methylxylenol blue (MXB), which can bind two metal ions at both ends of a π-electron conjugated system. The above-mentioned model was proved with the iron(III)-XO system at pH 2. In addition, MTB and MXB were suitable reagents for the visual threshold detection of trivalent metal ions such as iron(III), aluminium(III), gallium(III) and indium(III) ion in slightly acidic media. The proposed method has been applied successfully as a screening test for aluminium(III) ion in river water sampled at the downstream area of an old mine

Synthesis, characterization, and monoamine transporter activity of the new psychoactive substance 3',4'-methylenedioxy-4-methylaminorex (MDMAR).

Science.gov (United States)

McLaughlin, Gavin; Morris, Noreen; Kavanagh, Pierce V; Power, John D; Twamley, Brendan; O'Brien, John; Talbot, Brian; Dowling, Geraldine; Mahony, Olivia; Brandt, Simon D; Patrick, Julian; Archer, Roland P; Partilla, John S; Baumann, Michael H

2015-07-01

The recent occurrence of deaths associated with the psychostimulant cis-4,4'-dimethylaminorex (4,4'-DMAR) in Europe indicated the presence of a newly emerged psychoactive substance on the market. Subsequently, the existence of 3,4-methylenedioxy-4-methylaminorex (MDMAR) has come to the authors' attention and this study describes the synthesis of cis- and trans-MDMAR followed by extensive characterization by chromatographic, spectroscopic, mass spectrometric platforms and crystal structure analysis. MDMAR obtained from an online vendor was subsequently identified as predominantly the cis-isomer (90%). Exposure of the cis-isomer to the mobile phase conditions (acetonitrile/water 1:1 with 0.1% formic acid) employed for high performance liquid chromatography analysis showed an artificially induced conversion to the trans-isomer, which was not observed when characterized by gas chromatography. Monoamine release activities of both MDMAR isomers were compared with the non-selective monoamine releasing agent (+)-3,4-methylenedioxymethamphetamine (MDMA) as a standard reference compound. For additional comparison, both cis- and trans-4,4'-DMAR, were assessed under identical conditions. cis-MDMAR, trans-MDMAR, cis-4,4'-DMAR and trans-4,4'-DMAR were more potent than MDMA in their ability to function as efficacious substrate-type releasers at the dopamine (DAT) and norepinephrine (NET) transporters in rat brain tissue. While cis-4,4'-DMAR, cis-MDMAR and trans-MDMAR were fully efficacious releasing agents at the serotonin transporter (SERT), trans-4,4'-DMAR acted as a fully efficacious uptake blocker. Currently, little information is available about the presence of MDMAR on the market but the high potency of ring-substituted methylaminorex analogues at all three monoamine transporters investigated here might be relevant when assessing the potential for serious side-effects after high dose exposure. Copyright © 2014 John Wiley & Sons, Ltd.

Quantitative description and local structures of trivalent metal ions Eu(III) and Cm(III) complexed with poly-acrylic acid

International Nuclear Information System (INIS)

Montavon, G.; Huclier-Markai, S.; Grambow, B.; Bouby, M.; Geckeis, H.; Rabung, T.; Huclier-Markai, S.; Pashalidis, I.; Amekraz, B.; Moulin, C.

2008-01-01

The trivalent metal ion (M(III) = Cm, Eu)/poly-acrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L -1 -50 g L -1 ) and metal ion concentrations (2*10 -9 - 10 -3 M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)-PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFIFFF) coupled to ICP-MS evidenced that size distributions of Eu-PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(Ill)-PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant. (authors)

Mixed bilayer containing dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylserine: lipid complexation, ion binding, and electrostatics.

Science.gov (United States)

Pandit, Sagar A; Bostick, David; Berkowitz, Max L

2003-11-01

Two mixed bilayers containing dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylserine at a ratio of 5:1 are simulated in NaCl electrolyte solutions of different concentration using the molecular dynamics technique. Direct NH.O and CH.O hydrogen bonding between lipids was observed to serve as the basis of interlipid complexation. It is deduced from our results and previous studies that dipalmitoylphosphatidylcholine alone is less likely to form interlipid complexes than in the presence of bound ions or other bilayer "impurities" such as dipalmitoylphosphatidylserine. The binding of counterions is observed and quantitated. Based upon the calculated ion binding constants, the Gouy-Chapman surface potential (theta) is calculated. In addition we calculated the electrostatic potential profile (Phi) by twice integrating the system charge distribution. A large discrepancy between and the value of Phi at the membrane surface is observed. However, at "larger" distance from the bilayer surface, a qualitative similarity in the z-profiles of Phi and psi(GC) is seen. The discrepancy between the two potential profiles near the bilayer surface is attributed to the discrete and nonbulk-like nature of water in the interfacial region and to the complex geometry of this region.

Complexes in solution of o-phenanthroline with the ions of 4f and 5f elements at valencies II, III, V, VI

International Nuclear Information System (INIS)

Le Marois, Gilles.

1980-06-01

Slight differences between the complexation in aqueous solution of 4f and 5f series ions are revealed by the use of a soft, aromatic and chelating ligand of the o-phenanthroline type. Trivalent actinide ions are extrated selectively in the presence of a carboxylic acid. This extraction takes place at high pH and does not require large quantities of salts in aqueous solution, which increase the volume of radioactive wastes for storage. Only the first two o-phenanthroline complexes of these ions are obtained in aqueous solution. Determination of the constants of formation of such complexes shows the stronger affinity of the ligand for actinide ions. An inversion of the usual order of complexation of the different actinide valencies is also observed: pentavalent ions are most complexed than trivalent, o-phenanthroline stabilises actinide ions preferentially because they are more liable to form bonds with delocalised electrons. Finally a slight stabilisation of europium at valency II shows the participation of electrons by back bonding of the metal, due to the strong conjugation of the ligand π electrons [fr

The magnetic g-tensors for ion complexes with large spin-orbit coupling

International Nuclear Information System (INIS)

Chang, P.K.L.; Liu, Y.S.

1977-01-01

A nonperturbative method for calculating the magnetic g-tensors is presented and discussed for complexes of transition metal ions of large spin-orbit coupling, in the ground term 2 D. A numerical example for CuCl 2 .2H 2 O is given [pt

Behaviour at the indicator scale of the elements Zr, Hf and 104, Nb,Ta and Pa (105) in very complexation media; Comportement a l`echelle des indicateurs des elements Zr, Hf, et 104, Nb, Ta, et Pa (105) en milieux tres complexants

Energy Technology Data Exchange (ETDEWEB)

Monroy Guzman, F. [Institut de Physique Nucleaire, CNRS - IN2P3 Universite Paris Sud, 91406 Orsay Cedex (France)

1997-12-31

In order to determine the chemical properties of the trans-actinide elements of Z = 104 and 105 in aqueous solutions we studied their behaviour to ion exchange resin in different complex media. Due to the very short lifetimes (some tens of seconds) et to the low yield of these elements (a few atoms per irradiation hour) only very fast radiochemical techniques can be used. These severe constraints impose comparative studies of these elements with their most likely homologues to be carried out. The corresponding homologues were the elements of group 4 (Zr and Hf) for the element 104 and the elements of group 5 (Nb and Ta) and also Pa for the element 105. The complexation properties of the elements at indicator scale were determined in the media of HF, NH{sub 4}/HClO{sub 4}, NH{sub 4}SCN/HClO{sub 4}, NH{sub 4}SCN/HF and HCl/HF by ion exchange chromatography. The studies in fluorides media allowed us to identify the complexes in solution and to explain the shape of the experimentally observed sorption curves. The decrease of sorption for higher acid concentration in case of HF/HCl medium was interpreted by formation of chloro-fluoro-complexes. In case of the mixture NH{sub 4}SCN/HF, the particularly pronounced anti-synergic effects were observed and discussed. At the same time studies of the Hf and Ta short-lived isotopes were carried out by means of the RACHEL facility operating by the Orsay Tandem accelerator. These realistic simulations allowed optimization of different production, transportation and separation stages of the trans-actinide elements. The two experiments of 104 element production showed that this element forms in HF very stable anionic complexes similarly to its homologues Zr and Hf. (authors). 181 refs.

Behaviour at the indicator scale of the elements Zr, Hf and 104, Nb,Ta and Pa (105) in very complexation media; Comportement a l`echelle des indicateurs des elements Zr, Hf, et 104, Nb, Ta, et Pa (105) en milieux tres complexants

Energy Technology Data Exchange (ETDEWEB)

Monroy Guzman, F [Institut de Physique Nucleaire, CNRS - IN2P3 Universite Paris Sud, 91406 Orsay Cedex (France)

1998-12-31

In order to determine the chemical properties of the trans-actinide elements of Z = 104 and 105 in aqueous solutions we studied their behaviour to ion exchange resin in different complex media. Due to the very short lifetimes (some tens of seconds) et to the low yield of these elements (a few atoms per irradiation hour) only very fast radiochemical techniques can be used. These severe constraints impose comparative studies of these elements with their most likely homologues to be carried out. The corresponding homologues were the elements of group 4 (Zr and Hf) for the element 104 and the elements of group 5 (Nb and Ta) and also Pa for the element 105. The complexation properties of the elements at indicator scale were determined in the media of HF, NH{sub 4}/HClO{sub 4}, NH{sub 4}SCN/HClO{sub 4}, NH{sub 4}SCN/HF and HCl/HF by ion exchange chromatography. The studies in fluorides media allowed us to identify the complexes in solution and to explain the shape of the experimentally observed sorption curves. The decrease of sorption for higher acid concentration in case of HF/HCl medium was interpreted by formation of chloro-fluoro-complexes. In case of the mixture NH{sub 4}SCN/HF, the particularly pronounced anti-synergic effects were observed and discussed. At the same time studies of the Hf and Ta short-lived isotopes were carried out by means of the RACHEL facility operating by the Orsay Tandem accelerator. These realistic simulations allowed optimization of different production, transportation and separation stages of the trans-actinide elements. The two experiments of 104 element production showed that this element forms in HF very stable anionic complexes similarly to its homologues Zr and Hf. (authors). 181 refs.

The Danish trans-fatty acids ban

DEFF Research Database (Denmark)

Vallgårda, Signild

2017-01-01

In 2003 an executive order was issued banning industrially produced trans-fatty acids above a low level in food items in Denmark. To date, only a few other countries have followed Denmark’s example. The way health consequences of trans fats were translated by the different actors enabled the crea......In 2003 an executive order was issued banning industrially produced trans-fatty acids above a low level in food items in Denmark. To date, only a few other countries have followed Denmark’s example. The way health consequences of trans fats were translated by the different actors enabled...

Coordination kinetics of different metal ions with the amidoximated polyacrylonitrile nanofibrous membranes and catalytic behaviors of their complexes

Energy Technology Data Exchange (ETDEWEB)

Li, Fu; Dong, Yong Chun; Kang, Wei Min; Cheng, Bowen; Qu, Xiang; Cui, Guixin [School of Textiles, Tianjin Polytechnic University, Tianjin (China)

2016-12-15

Two transition metal ions (Fe{sup 3+} and Cu{sup 2+}) and a rare earth metal ion (Ce{sup 3+}) were selected to coordinate with amidoximated polyacrylonitrile (PAN) nanofibrous membrane for preparing three metal modified PAN nanofibrous membrane complexes (M-AO-n-PANs, M = Fe, Cu, or Ce) as the heterogeneous Fenton catalysts for the dye degradation in water under visible irradiation. The coordination kinetics of three metal ions with modified PAN nanofibrous membranes was studied and the catalytic properties of the resulting complexes were also compared. The results indicated that increasing metal ion concentrations in solution or higher coordination temperature led to a significant increase in metal content, particularly in Fe and Cu contents of the complexes. Their coordination process could be described using Langmuir isotherm and pseudo-second-order kinetic equations. Moreover, Fe-AO-n-PAN had the best photocatalytic efficiency for the dye degradation in acidic medium, but a lower photocatalytic activity than Cu-AO-n-PAN in alkali medium.

A highly selective and non-reaction based chemosensor for the detection of Hg2+ ions using a luminescent iridium(III complex.

Directory of Open Access Journals (Sweden)

Daniel Shiu-Hin Chan

Full Text Available We report herein a novel luminescent iridium(III complex with two hydrophobic carbon chains as a non-reaction based chemosensor for the detection of Hg(2+ ions in aqueous solution (<0.002% of organic solvent attributed to the probe solution. Upon the addition of Hg(2+ ions, the emission intensity of the complex was significantly enhanced and this change could be monitored by the naked eye under UV irradiation. The iridium(III complex shows high specificity for Hg(2+ ions over eighteen other cations. The system is capable of detecting micromolar levels of Hg(2+ ions, which is within the range of many chemical systems.

TransForm: TransAlta 2000 annual report

International Nuclear Information System (INIS)

2001-01-01

Financial information from TransAlta Corp. was presented along with a review of their operations throughout 2000 and a summary of the how the electric utility is doing in terms of power generation, independent power producers, transmission and energy marketing. The utility has changed from a regulated vertically integrated utility into one of Canada's largest non-regulated electric power generators. The utility sold its retail businesses in Alberta and New Zealand and now focuses on coal and hydro generation, gas generation, high-voltage transmission and energy marketing. The newly constructed Centralia, Washington generation facility was brought on line with 1,340 MW in May 2000, on time and on budget. This was the platform to diversify their generation into the United States. The utility reported a solid financial year with $177.9 million in earnings from continuing operations, an 83 per cent increase from 1999, driven mostly by the results of Centralia and power marketing and trading businesses. A financial loss was suffered when the Wabamum power plant in Alberta was shut down for several months to repair a boiler. The utility made excellent progress toward their goal of 15,000 megawatts by 2005 by starting with the construction of what will be one of Canada's largest cogeneration facilities at Sarnia, Ontario. TransAlta also commissioned a 360 MW cogeneration facility at Poplar Creek at Suncor's Fort McMurray oil sand facility. TransAlta also has an excellent track record in developing power generation projects internationally. refs., tabs., figs

Liquid-liquid extraction of ion-association complexes of cobalt(II-4-(2-pyridylazoresorcinol with ditetrazolium salts

Directory of Open Access Journals (Sweden)

Divarova Vidka V.

2015-01-01

Full Text Available The formation and liquid-liquid extraction of ion-association complexes between Co(II-4-(2-Pyridylazoresorcinol (PAR anionic chelates and cations of three ditetrazolium chlorides were studied: Blue Tetrazolium chloride (BTC, Neotetrazolium chloride (NTC and Nitro Blue Tetrazolium chloride (NBT. The optimum conditions for the formation and solvent extraction of the ion-association comlpex chelates were determined. It has been found that in the systems of Co(II-PAR-DTS, the reactants are reacted in molar ratios 1:2:1 and the general formula of complexes was suggested. The extraction equilibria were investigated and quantitatively characterized by the equilibrium constants and the recovery factors. The analytical characteristics of the complexes were calculated.

Analytical and Numerical Studies of the Complex Interaction of a Fast Ion Beam Pulse with a Background Plasma

International Nuclear Information System (INIS)

Kaganovich, Igor D.; Startsev, Edward A.; Davidson, Ronald C.

2003-01-01

Plasma neutralization of an intense ion beam pulse is of interest for many applications, including plasma lenses, heavy ion fusion, high energy physics, etc. Comprehensive analytical, numerical, and experimental studies are underway to investigate the complex interaction of a fast ion beam with a background plasma. The positively charged ion beam attracts plasma electrons, and as a result the plasma electrons have a tendency to neutralize the beam charge and current. A suite of particle-in-cell codes has been developed to study the propagation of an ion beam pulse through the background plasma. For quasi-steady-state propagation of the ion beam pulse, an analytical theory has been developed using the assumption of long charge bunches and conservation of generalized vorticity. The analytical results agree well with the results of the numerical simulations. The visualization of the data obtained in the numerical simulations shows complex collective phenomena during beam entry into and ex it from the plasma

Breaking down barriers: exploring the potential for social care practice with trans survivors of domestic abuse.

Science.gov (United States)

Rogers, Michaela

2016-01-01

There is increasing recognition that domestic abuse takes place outside the heteronormative paradigm of social life. This paper presents a discussion of the findings of doctoral research which explores trans people's experiences of domestic abuse, their social care needs and whether these are met by domestic abuse agencies. This paper foregrounds debate on the intersections of domestic abuse, trans communities and social care provision as this research, and previous studies, suggests that trans survivors do not seek out or benefit from social care intervention. Qualitative data, collected via narrative interviews, were collected during 2012 from participants mainly located in the United Kingdom (two participants were based in the United States). A total of 24 interviews were undertaken with trans people (n = 15) and social care practitioners (n = 9). Data were examined using a voice-centred relational technique. The findings reveal that barriers are multiple and complex but work could be undertaken to encourage help-seeking behaviours. Barriers include expectations of a transphobic response and 'Othering' practices; lack of entitlement felt by trans people; lack of knowledge/misunderstandings about trans social care needs; heteronormative bias of existing services; and practitioner attitudes fixed to notions about gender as binary. The paper ends by proposing a framework for practice with trans survivors which incorporates a person-centred, narrative approach. © 2015 John Wiley & Sons Ltd.

Ammonium boranes for the selective complexation of cyanide or fluoride ions in water.

Science.gov (United States)

Hudnall, Todd W; Gabbaï, François P

2007-10-03

With the recognition of aqueous fluoride and cyanide ions as an objective, we have investigated the anion binding properties of two isomeric ammonium boranes, namely [p-(Mes2B)C6H4(NMe3)]+ ([1]+) and [o-(Mes2B)C6H4(NMe3)]+ ([2]+). These cationic boranes, which could be obtained by reaction of the known 4- and 2-dimesitylboryl-N,N-dimethylaniline with MeOTf, have been investigated both experimentally and computationally. They both react with fluoride and cyanide ions in organic solvents to afford the corresponding fluoroborate/ or cyanoborate/ammonium zwitterions 1F, 1CN, 2F, and 2CN. In aqueous solution, however, these cationic boranes behave as remarkably selective receptors. Indeed, [1]+ only complexes cyanide ions while [2]+ only complexes fluoride ions. In H2O/DMSO 60:40 vol (HEPES 6 mM, pH 7), the cyanide binding constant of [1]+ and the fluoride binding constant of [2]+ are respectively equal to 3.9 (+/-0.1) x 108 and 910 (+/-50) M-1. Structural and computational studies indicate that both steric and electronic effects contribute to the unusual selectivity displayed by these cationic boranes. Owing to favorable Coulombic effects, the para-derivative [1]+ has a very high affinity for cyanide; yet these effects are not sufficiently intense to allow complexation of the more efficiently hydrated and less basic fluoride anion. In the case of the ortho-derivative [2]+, the proximity of the ammonium moiety leads to an increase in the Lewis acidity of the boron center thus making fluoride binding possible. However, steric effects prevent cyanide coordination to the boron center of [2]+. Finally, cation [1]+ and [2]+ bind their dedicated anions reversibly and show a negligible response in the presence of other common anions including Cl-, Br-, I-, NO3-, OAc-, H2PO4-, and HSO4-.

Magnetic properties of cyano-bridged Ln3+-M3+ complexes. Part I: trinuclear complexes (Ln3+ = La, Ce, Pr, Nd, Sm; M3+ = FeLS, Co) with bpy as blocking ligand.

Science.gov (United States)

Figuerola, Albert; Ribas, Joan; Llunell, Miquel; Casanova, David; Maestro, Miguel; Alvarez, Santiago; Diaz, Carmen

2005-10-03

The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions.

Trans-Disciplinary Education for Sustainable Marine and Coastal Management: A Case Study in Taiwan

Directory of Open Access Journals (Sweden)

Hsiao-Chien Lee

2016-10-01

Full Text Available The present study aims to investigate the effect of a trans-disciplinary design of curricula, deemed a powerful tool for teaching and research on complex environmental problems, with a goal to help solve the real problems that climate change has brought to the coastal environment in Taiwan. Three major real-life problems in southern Taiwan—declining mullet fisheries, flooding, and coral bleaching—were integrated into four courses. Adopting a qualitative case study method, the researchers investigated the student perceptions of the trans-disciplinary learning experiences, their attitudes toward marine and coastal environmental protection, and their capability of solving the problems related to marine and coastal environments. The researchers employed various methods to analyze the student reflection reports, student self-evaluation forms, and the tape-recorded class meetings. The findings suggest the following: the trans-disciplinary curriculum stands to be an innovative yet indispensable design for coastal management education; such a curriculum benefits students by equipping them with essential knowledge and skills to succeed in future marine conservation; action learning for marine and coastal sustainability serves as the final goal of trans-disciplinary learning project; a trans-disciplinary case study on the design of curricula provides effective knowledge integration of marine and coastal sustainability.

TransCanada PipeLines Limited 1998 annual report : TransCanada energy solutions

International Nuclear Information System (INIS)

1999-01-01

Financial information from TransCanada PipeLines Limited and a review of the company's 1998 operations was made available for the benefit of shareholders. TransCanada's pipeline system transports natural gas and crude oil from Western Canada Sedimentary Basin to North America's major energy markets. Net earnings from continuing operations for 1998, before unusual charges, were $575 million ($ 355 million after unusual charges) compared to $522 million for 1997. Solid performances from the energy transmission and international business, when compared to 1997, were more than offset by a decreased contribution from energy processing. TransCanada recorded integration costs of $166 million, after tax, related to the merger with NOVA in 1998, which was the major operational accomplishment during the year, creating a seamless economic energy delivery, processing and marketing system from the wellhead to the market. tabs., figs

Comparative evaluation of capillary electrophoresis and high-performance liquid chromatography for the separation of cis-cis, cis-trans, and trans-trans isomers of atracurium besylate.

Science.gov (United States)

de Moraes, M de L; Polakiewicz, B; Mattua, M F; Tavares, M F

1998-01-01

Atracurium besylate is a highly selective nondepolarizing neuromuscular blocking agent routinely used during anesthetic procedures. The commercial presentation of this drug is a mixture of positional isomers, cis-cis, cis-trans, and trans-trans. Reversed-phase high-performance liquid chromatography has been the technique of choice for the analysis of atracurium besylate formulations at the quality control laboratory of Núcleo de Desenvolvimento Cristália (São Paulo, Brazil), a local pharmaceutical company. HPLC analysis is usually conducted under gradient elution using acetonitrile/0.1 M phosphate buffer eluent mixture as mobile phase and an octadecyl silica (ODS)-packed column. The complete elution of the three isomers takes about 1 hr. In this work, an alternative capillary electrophoresis methodology was developed. The complete resolution of all three isomers was accomplished in about 13 min (+20 kV/72 cm, 211 nm direct detection) using a 60-mM phosphate buffer solution (pH 4) containing 20 mM beta-cyclodextrin and 4 M urea. The isomer ratio was found to be 59.1% cis-cis, 35.9% cis-trans, and 5.02% trans-trans (expected ratio: 59:35:6). Laudanosine, a major metabolite of atracurium besylate, was identified in two commercially available formulations, Tracur (Núcleo de Desenvolvimento Cristália) and Tracrium (Glaxo Wellcome, S.A., Rio de Janeiro, Brazil). Its concentration increases considerably during storage of the product, even if the product is stored at low temperatures.

Synthesis, characterization and reactivity of nitrite and nitrosyl derivates of phosphane complexes of tetraamminrethenium (II)

International Nuclear Information System (INIS)

Souza Santos, L. de.

1988-01-01

The substitution reaction: trans-[Ru(NH 3 ) 4 P(III) (H 2 O)] 2+ + NO - 2 K 1 K -1 trans-[Ru(NH 3 ) 4 P(III) (NO 2 ) + + H 2 O. The reaction product has been isolated as trans-[Ru(NH 3 ) 4 P(III) (NO 2 )] (PF 6 ) and characterized by using electronic and infrared spectroscopies and cyclic voltammetry, microanalysis and conductometry techniques. This nitrite complex can be converted into the nitrosyl complex in solution by adding H + , according to: trans-[Ru(NH 3 ) 4 P(III) (NO 2 )] + + 2H + →sup (K)1 trans-[Ru(NH 3 ) 4 P(III) (NO)] 3+ + H 2 O which can be converted back to the nitrite derivative by adding alkali: trans-[Ru(NH 3 ) 4 P(III) (NO)] 3+ + 2 OH - →sup (K)-1 trans-[Ru(NH 3 ) 4 P(III) (NO 2 )] + + H 2 O. The nitrosyl complexes have been synthesized by reaction of NO with trans-[Ru(NH 3 ) 4 P(III) ( 2 O)] 2+ or by reacting the nitrite derivative in acidic solutions, and characterized by eletronic and infrared spetroscopies, cyclic voltametry, microanalysis, eletron paramagnetic resonance (E.P.R.) and nuclear magnetic resonance (N.M.R.) techniques. E.P.R. and N.M.R. data suggest that these complexes are diamagnetic and better formulated as Ru(II)-NO + . (author) [pt

Electron-impact excitation of complex atoms and ions

International Nuclear Information System (INIS)

Burke, P.G.; Burke, V.M.; Dunseath, K.M.

1994-01-01

A new R-matrix approach for calculating cross sections and rate coefficients for electron-impact excitation of complex atoms and ions is described. This approach, based on an expansion of the total wavefunction in target configurations rather than in individual target states and taking advantage of the special status of the scattered electron in the collisional wavefunction, enables the angular integrals to be performed very much more efficiently than hitherto. It also enables electron correlation effects in the target and in the electron-target collision complex to be treated consistently, eliminating pseudo-resonances which have caused serious difficulties in some earlier work. A major new program package RMATRIX II has been written that implements this approach and, as an example, electron-impact excitation of Fe 2+ is considered where the four target configurations 3d 6 , 3d 5 4s, 3d 5 4p and 3d 5 4d are retained in the expansion of the total wavefunction. RMATRIX II is compared with the standard R-matrix program package and is found to be much more efficient showing that accurate electron scattering calculations involving complex targets, such as the astrophysically important low ionization stages of iron-peak elements, are now possible. (author)

Trans Ova Genetics, L.C.

Science.gov (United States)

The EPA is providing notice of a proposed Administrative Penalty Assessment against Trans Ova Genetics, L.C., a business located at 2938 380th Street Sioux Center, IA 51250, for alleged violations at the Trans Ova Genetics, L.C.’s facility located in 12425

Multi-scale approach to radiation damage induced by ion beams: complex DNA damage and effects of thermal spikes

International Nuclear Information System (INIS)

Surdutovich, E.; Yakubovich, A.V.; Solov'yov, A.V.; Surdutovich, E.; Yakubovich, A.V.; Solov'yov, A.V.

2010-01-01

We present the latest advances of the multi-scale approach to radiation damage caused by irradiation of a tissue with energetic ions and report the calculations of complex DNA damage and the effects of thermal spikes on biomolecules. The multi-scale approach aims to quantify the most important physical, chemical, and biological phenomena taking place during and following irradiation with ions and provide a better means for clinically-necessary calculations with adequate accuracy. We suggest a way of quantifying the complex clustered damage, one of the most important features of the radiation damage caused by ions. This quantification allows the studying of how the clusterization of DNA lesions affects the lethality of damage. We discuss the first results of molecular dynamics simulations of ubiquitin in the environment of thermal spikes, predicted to occur in tissue for a short time after an ion's passage in the vicinity of the ions' tracks. (authors)

Selective Decontamination Effect of Metal Ions in Soil Using Supercritical CO2 and TBP Complex

International Nuclear Information System (INIS)

Park, Jihye; Park, Kwangheon; Jung, Wonyoung

2014-01-01

Decontamination of soil pollution is difficult because the type of contamination largely depends on the characteristics of the pollutant and the area. Also, existing soil decontamination methods generate large quantities of secondary waste and additional process costs. For this reason, new decontamination methods are always under active investigation. A method involving the use of supercritical carbon dioxide with excellent permeability in place of chemical solvents is currently being studied. Unlike other heavy metals in fission products, uranium is used as fuel, and must be handled carefully. Therefore, in this paper, we studied a supercritical carbon dioxide method for decontaminating heavy metal ions in soil using tri-n-butyl phosphate(TBP), which is well known as a ligand for the extraction of metal ions of actinium. We investigated the decontamination effect of heavy metal ions in the soil using TBP-HNO 3 Complex and supercritical carbon dioxide. The study results showed that when heavy metals in soil are extracted using supercritical carbon dioxide, the extraction efficiency is different according to the type of pollutant metal ions in the soil. When TBP-HNO 3 Complex is used with an extractant, uranium extraction is very effective, but lithium, strontium, and cesium extraction is not effective. Therefore, in the case of a mixture of uranium and other metals such as lithium, strontium, cesium, and so on in soil contaminated by fission product leaks from nuclear power plants, we can selectively decontaminate uranium with supercritical carbon dioxide and TBP-HNO 3 Complex

A colorimetric and luminescent dual-modal assay for Cu(II ion detection using an iridium(III complex.

Directory of Open Access Journals (Sweden)

Dik-Lung Ma

Full Text Available A novel iridium(III complex-based chemosensor bearing the 5,6-bis(salicylideneimino-1,10-phenanthroline ligand receptor was developed, which exhibited a highly sensitive and selective color change from colorless to yellow and a visible turn-off luminescence response upon the addition of Cu(II ions. The interactions of this iridium(III complex with Cu2+ ions and thirteen other cations have been investigated by UV-Vis absorption titration, emission titration, and 1H NMR titration.

Differential genotoxic effects of antitumor trans-[PtCl2(E-iminoether)2] and cisplatin in Escherichia coli

Czech Academy of Sciences Publication Activity Database

Janovská, Eva; Nováková, Olga; Natile, G.; Brabec, Viktor

2002-01-01

Roč. 90, 3/4 (2002), s. 155-158 ISSN 0162-0134 R&D Projects: GA ČR GA305/02/1552; GA AV ČR IAA5004101; GA MZd NL6069 Institutional research plan: CEZ:AV0Z5004920 Keywords : cisplatin * trans-platinum drugs * antitumor Subject RIV: BO - Biophysics Impact factor: 2.204, year: 2002

Spectroscopic and density functional theory studies of trans-3-(trans-4-imidazolyl)acrylic acid.

Science.gov (United States)

Arjunan, V; Remya, P; Sathish, U; Rani, T; Mohan, S

2014-08-14

The structural parameters, thermodynamic properties and vibrational frequencies of the optimised geometry of trans-3-(trans-4-imidazolyl)acrylic acid have been determined from B3LYP methods with 6-311++G(**) and cc-pVTZ basis sets. The effects of substituents (acrylyl group) on the imidazole vibrational frequencies are analysed. The vibrational frequencies of the fundamental modes of trans-3-(trans-4-imidazolyl)acrylic acid have been precisely assigned and analysed and the theoretical results are compared with the experimental vibrations. (1)H and (13)C NMR isotropic chemical shifts are calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound are also determined from DFT method. The total electron density and electrostatic potential of the compound are determined by natural bond orbital analysis. Various reactivity and selectivity descriptors such as chemical hardness, chemical potential, softness, electrophilicity, nucleophilicity and the appropriate local quantities employing natural population analysis (NPA) are calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Degradation of trans-ferulic acid in acidic aqueous medium by anodic oxidation, electro-Fenton and photoelectro-Fenton

Energy Technology Data Exchange (ETDEWEB)

Flores, Nelly; Sirés, Ignasi; Garrido, José Antonio; Centellas, Francesc; Rodríguez, Rosa María; Cabot, Pere Lluís; Brillas, Enric, E-mail: brillas@ub.edu

2016-12-05

Highlights: • trans-Ferulic acid degradation by EAOPs using a stirred BDD/air-diffusion cell. • Slow substrate abatement and poor mineralization by AO-H{sub 2}O{sub 2}. • 98% Mineralization by PEF, but with rapid and similar substrate decay than by EF. • Quicker degradation by SPEF due to the more potent photolytic action of sunlight. • Reaction pathway with four primary aromatic products and three final carboxylic acids. - Abstract: Solutions of pH 3.0 containing trans-ferulic acid, a phenolic compound in olive oil mill wastewater, have been comparatively degraded by anodic oxidation with electrogenerated H{sub 2}O{sub 2} (AO-H{sub 2}O{sub 2}), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were performed with a BDD/air-diffusion cell, where oxidizing ·OH was produced from water discharge at the BDD anode and/or in the solution bulk from Fenton’s reaction between cathodically generated H{sub 2}O{sub 2} and added catalytic Fe{sup 2+}. The substrate was very slowly removed by AO-H{sub 2}O{sub 2}, whereas it was very rapidly abated by EF and PEF, at similar rate in both cases, due to its fast reaction with ·OH in the bulk. The AO-H{sub 2}O{sub 2} process yielded a slightly lower mineralization than EF, which promoted the accumulation of barely oxidizable products like Fe(III) complexes. In contrast, the fast photolysis of these latter species under irradiation with UVA light in PEF led to an almost total mineralization with 98% total organic carbon decay. The effect of current density and substrate concentration on the performance of all treatments was examined. Several solar PEF (SPEF) trials showed its viability for the treatment of wastewater containing trans-ferulic acid at larger scale. Four primary aromatic products were identified by GC–MS analysis of electrolyzed solutions, and final carboxylic acids like fumaric, acetic and oxalic were detected by ion-exclusion HPLC. A reaction sequence for trans-ferulic acid mineralization

Mixed complex combinations with a new schiff base used as membranes ion-selective for copper and nickel ions, analytical applications)

International Nuclear Information System (INIS)

Mitu, L.; Tigae, C.

2009-01-01

Four electrodes with liquid membrane, Cu/sup 2+/ -selective and Ni/sup 2+/ -selective, not previously described in the literature, were prepared and characterized. Electrodes 1 and 2 are based on mixed complexes of Cu(II) and Ni(II) with isonicotinoylhydrazone-2-aldehyde pyrrole (INH2AP= HL/sup 1/) as ligand and electrodes 3 and 4 are based on the mixed complexes with isonicotinoyl- hydrazone-2-hydroxy-l-naphthaldehyde (INH2HNA = H/sub 2/L/sup 2/ ) Cu/sup 2+/. selective and Ni/sup 2+/ -selective electrodes have been used to determine the copper and nickel ions in aqueous solutions, by both direct potentiometric and potentiometric titration with EDTA. They have also been used for determining the Cu/sup 2+/ and Ni/sup 2+/ ions in industrial waters by direct potentiometry. The analytical results obtained have been checked by the standard addition method and by comparison with determinations through atomic absorption spectrometry. (author)

Trans-Saharan geopolitics. The game and the stakes

International Nuclear Information System (INIS)

Chegrouche, L.

2010-01-01

The geopolitics of energy exports from the trans-Saharan region are similar to the Caspian great game' at the end of the last century. In North/West Africa as in West/Central Asia, the question of control over hydrocarbon reserves and lines of access to those reserves lies at the source of various conflicts. Rivalries are expressed through open and complex conflicts in which powers confront one another over oil-rich zones through proxy ethnic, religious or cultural groups, as dictated by the colossal economic interests at stake. The increasing number of conflicts - the Niger Delta, Darfur, the Azawak, etc. - is an illustration of this. The shock waves from this rivalry undermine regional peace and security, as well as the security of international energy supplies. The question here is to understand the game and the stakes of this trans-Saharan chess-board, to study its principal features and its energetic consequences. The national oil companies and states of the region can work around or through the geopolitical rifts caused by local rivalries and extra-regional appetites. There is therefore a need to understand the ways in which the players in the trans-Saharan 'great game' interact with one another, an to identifies the effects these interactions may have in the field of energy, in terms of potential reserves and transport projects. The TSGP is presented as an illustration of this geopolitical dynamics. (author)

Complexation of biological ligands with lanthanides(III) for MRI: Structure, thermodynamic and methods; Complexation des cations lanthanides trivalents par des ligands d'origine biologique pour l'IRM: Structure, thermodynamique et methodes

Energy Technology Data Exchange (ETDEWEB)

Bonnet, C

2006-07-15

New cyclic ligands derived from sugars and amino-acids form a scaffold carrying a coordination sphere of oxygen atoms suitable to complex Ln(III) ions. In spite of their rather low molecular weights, the complexes display surprisingly high relaxivity values, especially at high field. The ACX and BCX ligands, which are acidic derivatives of modified and cyclo-dextrins, form mono and bimetallic complexes with Ln(III). The LnACX and LnBCX complexes show affinities towards Ln(III) similar to those of tri-acidic ligands. In the bimetallic Lu2ACX complex, the cations are deeply embedded in the cavity of the ligand, as shown by the X-ray structure. In aqueous solution, the number of water molecules coordinated to the cation in the LnACX complex depends on the nature and concentration of the alkali ions of the supporting electrolyte, as shown by luminescence and relaxometric measurements. There is only one water molecule coordinated in the LnBCX complex, which enables us to highlight an important second sphere contribution to relaxivity. The NMR study of the RAFT peptidic ligand shows the complexation of Ln(III), with an affinity similar to those of natural ligands derived from calmodulin. The relaxometric study also shows an important second sphere contribution to relaxivity. To better understand the intricate molecular factors affecting relaxivity, we developed new relaxometric methods based on probe solutes. These methods allow us to determine the charge of the complex, weak affinity constants, trans-metallation constants, and the electronic relaxation rate. (author)

Selective transport and incorporation of highly charged metal and metal complex ions in self-assembled polyelectrolyte multilayer membranes

International Nuclear Information System (INIS)

Toutianoush, Ali; Tieke, Bernd

2002-01-01

The transport of aqueous salts containing mono-, di- and trivalent metal and tetravalent metal complex ions across ultrathin polyvinylammonium/polyvinylsulphate (PVA/PVS) membranes is described. The membranes were prepared by electrostatic layer-by-layer (LBL) assembly of the two polyelectrolytes. Using spectroscopic measurements and permeability studies, it is demonstrated that the transport of copper(II) chloride, lanthanum(III) chloride, barium chloride and potassium hexacyanoferrate(II) is accompanied by the permanent incorporation of the metal and metal complex ions in the membrane. Upon the uptake of copper, lanthanum and hexacyanoferrate ions, the membranes become cross-linked so that the permeation rates of other salts not taken up by the membrane, e.g. sodium chloride, potassium chloride and magnesium chloride, are decreased. The uptake of barium ions leads to a decrease of the cross-linking density of the membrane so that the permeation rate of NaCl is increased. Possible mechanisms for the ion uptake are discussed

Epoxidation of the methamphetamine pyrolysis product, trans-phenylpropene, to trans-phenylpropylene oxide by CYP enzymes and stereoselective glutathione adduct formation

International Nuclear Information System (INIS)

Sanga, Madhu; Younis, Islam R.; Tirumalai, Padma S.; Bland, Tina M.; Banaszewska, Monica; Konat, Gregory W.; Tracy, Timothy S.; Gannett, Peter M.; Callery, Patrick S.

2006-01-01

Pyrolytic products of smoked methamphetamine hydrochloride are well established. Among the various degradation products formed, trans-phenylpropene (trans-β-methylstyrene) is structurally similar to styrene analogues known to be bioactivated by CYP enzymes. In human liver microsomes, trans-phenylpropene was converted to the epoxide trans-phenylpropylene oxide (trans-2-methyl-3-phenyloxirane) and cinnamyl alcohol. Incubation of trans-phenylpropene with microsomes in the presence of enzyme-specific P450 enzyme inhibitors indicated the involvement of CYP2E1, CYP1A2, and CYP3A4 enzymes. Both (R,R)-phenylpropylene oxide and (S,S)-phenylpropylene oxide were formed in human liver microsomal preparations. Enantiomers of trans-phenylpropylene oxide were stereoselectively and regioselectively conjugated in a Phase II drug metabolism reaction catalyzed by human liver cytosolic enzymes consisting of conjugation with glutathione. The structure of the phenylpropylene oxide-glutathione adduct is consistent with nucleophilic ring-opening by attack at the benzylic carbon. Exposure of cultured C6 glial cells to (S,S)-phenylpropylene oxide produced a cytotoxic response in a concentration-dependent manner based on cell degeneration and death

Infrared Spectroscopy of Gas-Phase M+(CO2)n (M = Co, Rh, Ir) Ion-Molecule Complexes.

Science.gov (United States)

Iskra, Andreas; Gentleman, Alexander S; Kartouzian, Aras; Kent, Michael J; Sharp, Alastair P; Mackenzie, Stuart R

2017-01-12

The structures of gas-phase M + (CO 2 ) n (M = Co, Rh, Ir; n = 2-15) ion-molecule complexes have been investigated using a combination of infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy and density functional theory. The results provide insight into fundamental metal ion-CO 2 interactions, highlighting the trends with increasing ligand number and with different group 9 ions. Spectra have been recorded in the region of the CO 2 asymmetric stretch around 2350 cm -1 using the inert messenger technique and their interpretation has been aided by comparison with simulated infrared spectra of calculated low-energy isomeric structures. All vibrational bands in the smaller complexes are blue-shifted relative to the asymmetric stretch in free CO 2 , consistent with direct binding to the metal center dominated by charge-quadrupole interactions. For all three metal ions, a core [M + (CO 2 ) 2 ] structure is identified to which subsequent ligands are less strongly bound. No evidence is observed in this size regime for complete activation or insertion reactions.

TransCut: interactive rendering of translucent cutouts.

Science.gov (United States)

Li, Dongping; Sun, Xin; Ren, Zhong; Lin, Stephen; Tong, Yiying; Guo, Baining; Zhou, Kun

2013-03-01

We present TransCut, a technique for interactive rendering of translucent objects undergoing fracturing and cutting operations. As the object is fractured or cut open, the user can directly examine and intuitively understand the complex translucent interior, as well as edit material properties through painting on cross sections and recombining the broken pieces—all with immediate and realistic visual feedback. This new mode of interaction with translucent volumes is made possible with two technical contributions. The first is a novel solver for the diffusion equation (DE) over a tetrahedral mesh that produces high-quality results comparable to the state-of-art finite element method (FEM) of Arbree et al. but at substantially higher speeds. This accuracy and efficiency is obtained by computing the discrete divergences of the diffusion equation and constructing the DE matrix using analytic formulas derived for linear finite elements. The second contribution is a multiresolution algorithm to significantly accelerate our DE solver while adapting to the frequent changes in topological structure of dynamic objects. The entire multiresolution DE solver is highly parallel and easily implemented on the GPU. We believe TransCut provides a novel visual effect for heterogeneous translucent objects undergoing fracturing and cutting operations.

Direct Detection of the Ion Pair to Free Ions Transformation upon Complexation with an Ion Receptor in Non‐Polar Solvents by using Conductometry

Science.gov (United States)

Iseda, Kazuya

2018-01-01

Abstract In this study, we performed conductometry in various organic solvents to directly detect the transformation from tetrabutylammonium chloride (TBACl) ion‐pair salt to the free ions through complexation with meso‐octamethylcalix[4]pyrrole (CP), which is a well‐known receptor for chloride anions. In the presence of CP, the conductivity of TBACl increases in various non‐polar solvents, indicating that complexation with CP enhances the ionic dissociation of TBACl in such non‐polar solvents. In other words, CP recognizes chloride as an ion‐paired salt as well as a free anion in non‐polar solvents. Additionally, the TBA(CP–Cl) complex exhibited a considerably lower ion‐pairing constant (K ip) than TBACl in non‐polar solvents, resulting in enhanced conductivity. Based on these findings, we can conclude that complexation of an anion with a hydrophobic anion receptor will be useful for creating functional and stimuli‐responsive soft materials in organic solvents using coulombic forces. PMID:29610717

A comparison of trans-cranial and trans-sphenoidal approaches for vision improvement due to pitutary adenomas

Directory of Open Access Journals (Sweden)

Fakhr Tabatabai SA

1997-07-01

Full Text Available To improve visual disturbance, optic nerve decompression can be performed via transcranial or tran-sphenoidal approaches. Although the surgical exposure in transcranial approach is favourable, yet the optic nerve's presence in the field may make it vulnerable to damage. Of fighty patients with different types of pituitary adenomas, 35 cases with medium-sized (1-3 cm tumors have been studied in a randomized clinical trial during a three year period, to compare the applicability of these approaches. While short hospital stay with better visual outcome was observed in fifteen trans-sphenoidal cases, in comparison to 20 trans-cranial cases, however the preoperative visual status and underlying disorders were similar in both groups. Decompressing the optic apparatus, trans-sphenoidally, seems beneficial, where there are no contraindications for the procedure in medium-sized pituitary adenomas

Reasons for decision in the matter of Trans Mountain Pipeline Inc. (formerly Terasen Pipelines (Trans Mountain) Inc.) : tariffs

International Nuclear Information System (INIS)

2007-01-01

In 2006 and 2007 Terasen Pipelines (Trans Mountain) Inc. (now Trans Mountain Pipeline Inc.) submitted a series of applications to the National Energy Board for revisions to the Trans Mountain Tariffs. They were filed in response to apportionment concerns on the Trans Mountain pipeline. Four of the applications involved pronounced and contentious changes to the capacity allocation procedures on the pipeline system. For ease of reference, the Board amalgamated its 4 decisions on these applications into a single document. A map of the Trans Mountain pipeline system as a whole was presented along with a detailed map indicating the delivery locations served by the system in the lower mainland of British Columbia and the state of Washington. The issues considered by the Board in each of these decisions included capacity allocation for Westridge Dock; capacity allocations to export destinations; common carriage requirements; and the need for creating a new barge subcategory. Relevant sections of the National Energy Board Act referred to in the decisions were highlighted. This document also listed the Trans Mountain Tariffs that have introduced notable revisions to the capacity allocation procedures on the system since September 2003. 16 refs., 2 figs., 3 appendices

Chemodynamics of metal ion complexation by charged nanoparticles: a dimensionless rationale for soft, core-shell and hard particle types.

Science.gov (United States)

Duval, Jérôme F L

2017-05-17

Soft nanoparticulate complexants are defined by a spatial confinement of reactive sites and electric charges inside their 3D body. In turn, their reactivity with metal ions differs significantly from that of simple molecular ligands. A revisited form of the Eigen mechanism recently elucidated the processes leading to metal/soft particle pair formation. Depending on e.g. particle size and metal ion nature, chemodynamics of nanoparticulate metal complexes is controlled by metal conductive diffusion to/from the particles, by intraparticulate complex formation/dissociation kinetics, or by both. In this study, a formalism is elaborated to achieve a comprehensive and systematic identification of the rate-limiting step governing the overall formation and dissociation of nanoparticulate metal complexes. The theory covers the different types of spherical particulate complexants, i.e. 3D soft/permeable and core-shell particles, and hard particles with reactive sites at the surface. The nature of the rate-limiting step is formulated by a dynamical criterion involving a power law function of the ratio between particle radius and an intraparticulate reaction layer thickness defined by the key electrostatic, diffusional and kinetic components of metal complex formation/dissociation. The analysis clarifies the intertwined contributions of particle properties (size, soft or hard type, charge, density or number of reactive sites) and aqueous metal ion dehydration kinetics in defining the chemodynamic behavior of nanoparticulate metal complexes. For that purpose, fully parameterized chemodynamic portraits involving the defining features of particulate ligand and metal ion as well as the physicochemical conditions in the local intraparticulate environment, are constructed and thoroughly discussed under conditions of practical interest.

Micro-Sugar-Snap and -Wire-Cut Cookie Baking with Trans- and Zero-Trans-Fat Shortenings

Science.gov (United States)

The effect of trans- and zero-trans-fat shortenings on cookie-baking performance was evaluated, using the two AACC micro-cookie-baking methods. Regardless of fat type, sugar-snap cookies made with a given flour were larger in diameter, smaller in height, and greater in weight loss during baking tha...

Chiral recognition of proteins having L-histidine residues on the surface with lanthanide ion complex incorporated-molecularly imprinted fluorescent nanoparticles

International Nuclear Information System (INIS)

Uzun, Lokman; Uzek, Recep; Şenel, Serap; Say, Ridvan; Denizli, Adil

2013-01-01

In this study, lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles were synthesized. A combination of three novel approaches was applied for the purpose. First, lanthanide ions [Terbium(III)] were complexed with N-methacryloyl-L-histidine (MAH), polymerizable derivative of L-histidine amino acid, in order to incorporate the complex directly into the polymeric backbone. At the second stage, L-histidine molecules imprinted nanoparticles were utilized instead of whole protein imprinting in order to avoid whole drawbacks such as fragility, complexity, denaturation tendency, and conformation dependency. At the third stage following the first two steps mentioned above, imprinted L-histidine was coordinated with cupric ions [Cu(II)] to conduct the study under mild conditions. Then, molecularly imprinted fluorescent nanoparticles synthesized were used for L-histidine adsorption from aqueous solution to optimize conditions for adsorption and fluorimetric detection. Finally, usability of nanoparticles was investigated for chiral biorecognition using stereoisomer, D-histidine, racemic mixture, D,L-histidine, proteins with surface L-histidine residue, lysozyme, cytochrome C, or without ribonuclease A. The results revealed that the proposed polymerization strategy could make significant contribution to the solution of chronic problems of fluorescent component introduction into polymers. Additionally, the fluorescent nanoparticles reported here could be used for selective separation and fluorescent monitoring purposes. Highlights: • Lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles • Direct incorporation of the fluorescent complex into polymeric backbone. • Imprinting by assistance of cupric ion coordination into nanoparticles • Evaluation of the chiral biorecognition ability of nanoparticles • Simultaneous selective separation and fluorescent monitoring

Chiral recognition of proteins having L-histidine residues on the surface with lanthanide ion complex incorporated-molecularly imprinted fluorescent nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Uzun, Lokman, E-mail: lokman@hacettepe.edu.tr [Hacettepe University, Department of Chemistry, 06381, Ankara (Turkey); Uzek, Recep; Şenel, Serap [Hacettepe University, Department of Chemistry, 06381, Ankara (Turkey); Say, Ridvan [Anadolu University, Department of Chemistry, 26470, Eskisehir (Turkey); Denizli, Adil [Hacettepe University, Department of Chemistry, 06381, Ankara (Turkey)

2013-08-01

In this study, lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles were synthesized. A combination of three novel approaches was applied for the purpose. First, lanthanide ions [Terbium(III)] were complexed with N-methacryloyl-L-histidine (MAH), polymerizable derivative of L-histidine amino acid, in order to incorporate the complex directly into the polymeric backbone. At the second stage, L-histidine molecules imprinted nanoparticles were utilized instead of whole protein imprinting in order to avoid whole drawbacks such as fragility, complexity, denaturation tendency, and conformation dependency. At the third stage following the first two steps mentioned above, imprinted L-histidine was coordinated with cupric ions [Cu(II)] to conduct the study under mild conditions. Then, molecularly imprinted fluorescent nanoparticles synthesized were used for L-histidine adsorption from aqueous solution to optimize conditions for adsorption and fluorimetric detection. Finally, usability of nanoparticles was investigated for chiral biorecognition using stereoisomer, D-histidine, racemic mixture, D,L-histidine, proteins with surface L-histidine residue, lysozyme, cytochrome C, or without ribonuclease A. The results revealed that the proposed polymerization strategy could make significant contribution to the solution of chronic problems of fluorescent component introduction into polymers. Additionally, the fluorescent nanoparticles reported here could be used for selective separation and fluorescent monitoring purposes. Highlights: • Lanthanide ion complex incorporated molecularly imprinted fluorescent nanoparticles • Direct incorporation of the fluorescent complex into polymeric backbone. • Imprinting by assistance of cupric ion coordination into nanoparticles • Evaluation of the chiral biorecognition ability of nanoparticles • Simultaneous selective separation and fluorescent monitoring.

A double salt of iodobismuthate: cis-aquaiodidobis(1,10-phenanthrolinecobalt(II tris(1,10-phenanthrolinecobalt(II trans-hexa-μ2-iodido-hexaiodidotribismuthate(III

Directory of Open Access Journals (Sweden)

Jiongke Chen

2011-09-01

Full Text Available In the title complex, [Co(C12H8N23][CoI(C12H8N22(H2O][Bi3I12], conventionally abbreviated [Co(phen3][CoI(phen2(H2O][Bi3I12], where phen is 1,10-phenanthroline, the CoII atom in one cation is coordinated by six N atoms from three phen ligands in an octahedral coordination while the CoII atom in the other cation is coordinated octahedrally by four N atoms from two phen ligands, one water O atom and one I atom. In the anion, three BiIII ions adopt an octahedral coordination constructed by six I− ligands. The three BiI6 octahedra are fused together through trans face-sharing.

Effect of secondary electron emission on Jean's instability in a complex plasma in the presence of nonthermal ions

International Nuclear Information System (INIS)

Sarkar, Susmita; Maity, Saumyen; Banerjee, Soumyajyoti

2011-01-01

In this paper, we have investigated the role of secondary electron emission on Jean's instability in a complex plasma in the presence of nonthermal ions. The equilibrium dust surface potential has been considered negative and hence primary and secondary electron temperatures are equal. Such plasma consists of three components: Boltzman distributed electrons, nonthermal ions and negatively charged inertial dust grains. From the linear dispersion relation, we have calculated the real frequency and growth rate of Jean's instability. Numerically, we have shown that for strong ion nonthermality Jean's mode is unstable. Growth of the instability reduces and the real part of the wave frequency increases with increasing secondary electron emission from dust grains. Hence, strong secondary electron emission suppresses Jean's instability in a complex plasma even when ion nonthermality is strong and equilibrium dust charge is negative.

GADD34 Function in Protein Trafficking Promotes Adaptation to Hyperosmotic Stress in Human Corneal Cells

Directory of Open Access Journals (Sweden)

Dawid Krokowski

2017-12-01

Full Text Available Summary: GADD34, a stress-induced regulatory subunit of the phosphatase PP1, is known to function in hyperosmotic stress through its well-known role in the integrated stress response (ISR pathway. Adaptation to hyperosmotic stress is important for the health of corneal epithelial cells exposed to changes in extracellular osmolarity, with maladaptation leading to dry eye syndrome. This adaptation includes induction of SNAT2, an endoplasmic reticulum (ER-Golgi-processed protein, which helps to reverse the stress-induced loss of cell volume and promote homeostasis through amino acid uptake. Here, we show that GADD34 promotes the processing of proteins synthesized on the ER during hyperosmotic stress independent of its action in the ISR. We show that GADD34/PP1 phosphatase activity reverses hyperosmotic-stress-induced Golgi fragmentation and is important for cis- to trans-Golgi trafficking of SNAT2, thereby promoting SNAT2 plasma membrane localization and function. These results suggest that GADD34 is a protective molecule for ocular diseases such as dry eye syndrome. : Here, Krokowski et al. show that GADD34/PP1 protects the microtubule network, prevents Golgi fragmentation, and preserves protein trafficking independent of its action in the integrated stress response (ISR. In osmoadaptation, GADD34 facilitates trans-Golgi-mediated processing of the endoplasmic reticulum (ER-synthesized amino acid transporter SNAT2, which in turn increases amino acid uptake. Keywords: SNAT2, GADD34, hyperosmotic stress, amino acid transport, Golgi fragmentation, ISR

Evidence that Autophosphorylation of the Major Sporulation Kinase in Bacillus subtilis Is Able To Occur in trans.

Science.gov (United States)

Devi, Seram Nganbiton; Kiehler, Brittany; Haggett, Lindsey; Fujita, Masaya

2015-08-01

Entry into sporulation in Bacillus subtilis is governed by a multicomponent phosphorelay, a complex version of a two-component system which includes at least three histidine kinases (KinA to KinC), two phosphotransferases (Spo0F and Spo0B), and a response regulator (Spo0A). Among the three histidine kinases, KinA is known as the major sporulation kinase; it is autophosphorylated with ATP upon starvation and then transfers a phosphoryl group to the downstream components in a His-Asp-His-Asp signaling pathway. Our recent study demonstrated that KinA forms a homotetramer, not a dimer, mediated by the N-terminal domain, as a functional unit. Furthermore, when the N-terminal domain was overexpressed in the starving wild-type strain, sporulation was impaired. We hypothesized that this impairment of sporulation could be explained by the formation of a nonfunctional heterotetramer of KinA, resulting in the reduced level of phosphorylated Spo0A (Spo0A∼P), and thus, autophosphorylation of KinA could occur in trans. To test this hypothesis, we generated a series of B. subtilis strains expressing homo- or heterogeneous KinA protein complexes consisting of various combinations of the phosphoryl-accepting histidine point mutant protein and the catalytic ATP-binding domain point mutant protein. We found that the ATP-binding-deficient protein was phosphorylated when the phosphorylation-deficient protein was present in a 1:1 stoichiometry in the tetramer complex, while each of the mutant homocomplexes was not phosphorylated. These results suggest that ATP initially binds to one protomer within the tetramer complex and then the γ-phosphoryl group is transmitted to another in a trans fashion. We further found that the sporulation defect of each of the mutant proteins is complemented when the proteins are coexpressed in vivo. Taken together, these in vitro and in vivo results reinforce the evidence that KinA autophosphorylation is able to occur in a trans fashion

Specific Noncovalent Association of Chiral Large-Ring Hexaimines: Ion Mobility Mass Spectrometry and PM7 Study.

Science.gov (United States)

Troć, Anna; Gajewy, Jadwiga; Danikiewicz, Witold; Kwit, Marcin

2016-09-05

Ion mobility mass spectrometry and PM7 semiempirical calculations are effective complementary methods to study gas phase formation of noncovalent complexes from vaselike macrocycles. The specific association of large-ring chiral hexaimines, derived from enantiomerically pure trans-1,2-diaminocyclohexane and various isophthaldehydes, is driven mostly by CH-π and π-π stacking interactions. The isotrianglimine macrocycles are prone to form two types of aggregates: tail-to-tail and head-to-head (capsule) dimers. The stability of the tail-to-tail dimers is affected by the size and electronic properties of the substituents at the C-5 position of the aromatic ring. Electron-withdrawing groups stabilize the aggregate, whereas bulky or electron-donating groups destabilize the complexes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Becoming lesbian: Monique Wittig's queer-trans-feminism.

Science.gov (United States)

Henderson, Kevin

2018-04-03

Inspired by Lynne Huffer's queer feminist genealogy, this article explores queer-trans-feminism as a project that would bring together queer, feminist, and transgender theory and politics into a shared critical lineage. I suggest that Monique Wittig is a neglected thinker who could re-enliven connections and debates within queer, feminist, and trans theory and politics. Utilizing recent historiographies of queer and feminist theory, I imagine what it would mean to hold on to the figure of the lesbian as a figure for queer-trans-feminist politics rather than render the lesbian anachronistic. I then explore the implications of Wittig's notion that "lesbians are not women" for a queer-trans-feminism. I argue that Wittig's critique of the language of the social sciences offers queer-trans-feminist scholars a source for contemporary self-critique and coalition.

Synthesis, Structure, and Magnetism of Tris(amide) {Ln[N(SiMe3)2]3}1- Complexes of the Non-Traditional +2 Lanthanide Ions.

Science.gov (United States)

Ryan, Austin Jack; Darago, Lucy E; Balasubramini, Sree Ganesh; Chen, Guo P; Ziller, Joseph W; Furche, Filipp; Long, Jeffrey R; Evans, William J

2018-02-28

A new series of Ln2+ complexes has been synthesized that overturns two previous generalizations in rare-earth metal reduction chemistry: that amide ligands do not form isolable complexes of the highly-reducing non-traditional Ln2+ ions and that yttrium is a good model for the late lanthanides in these reductive reactions. Reduction of Ln(NR2)3 (R = SiMe3) complexes in THF under Ar with M = K or Rb in the presence of 2.2.2-cryptand (crypt) forms crystallographically-characterizable [M(crypt)][Ln(NR2)3] complexes not only for the traditional Tm2+ ion and the configurational crossover ions, Nd2+ and Dy2+, but also for the non-traditional Gd2+, Tb2+, Ho2+, and Er2+ ions. Crystallographic data as well as UV-visible, magnetic susceptibility, and density functional theory studies are consistent with the accessibility of 4fn5d1 configurations for Ln2+ ions in this tris(silylamide) ligand environment. The Dy2+ complex, [K(crypt)][Dy(NR2)3], has a higher magnetic moment than previously observed for any monometallic complex: 11.67 µB. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trans-polychlorinated azobenzenes (PCABs) - new possibly ''dioxin-like'' environmental pollutants. Multidimensional analysis of the structural feature space of congener set

Energy Technology Data Exchange (ETDEWEB)

Falandysz, J.; Wilczynska, A.; Piliszek, S.; Puzyn, T. [Univ. of Gdansk (Poland)

2004-09-15

Introduction Azoxybenzene is molecule composed of two benzene ring fused to azoxy group (- N(O)=N-). Trans-PCAOBs consist at 399 congeners, and some of them can be formed as unwanted byproduct in the manufacture of 3,4-dichloroaniline (DCA) and its derivatives, and can be found in herbicides such as Diuron {sup registered}, Linuron {sup registered}, Methazole {sup registered} and Propanil {sup registered}. Degradation of chloroaniline herbicides is also a source of environmental pollution with PCAOBs as well as photolysis and biolysis of DCA. Trans-PCAOBs are planar compounds and can be considered as stereoisomers to highly toxic 2,3,7,8-tetrachlorodibenzo-p-dioxin. They is lack or very limited number of data available regarding to sources, possible mechanism of formation, environmental occurence and fate, analytical chemistry, properties, and effects of trans-PCAOBs. In this work some selected thermodynamic and quantum-mechanical properties of trans- PCAOBs were computed using ab initio methods. Presented property data of trans-PCAOBs can be useful as structural descriptors in further QSAR/QSPR studies of those compounds.

Trans-Kullo jagatakse tükkideks / Kadrin Karner

Index Scriptorium Estoniae

Karner, Kadrin

2008-01-01

Primos OÜ omanik ja Trans-Kullo osanik Endel Siff ütles, et Trans-Kullo on aktsionäride erinevate ärihuvide tõttu läinud jagunemisele, mis võib lõppeda ettevõtte likvideerimisega. Lisa: Trans-Kullo

Sexual desire in trans persons: associations with sex reassignment treatment.

Science.gov (United States)

Wierckx, Katrien; Elaut, Els; Van Hoorde, Birgit; Heylens, Gunter; De Cuypere, Griet; Monstrey, Stan; Weyers, Steven; Hoebeke, Piet; T'Sjoen, Guy

2014-01-01

Sex steroids and genital surgery are known to affect sexual desire, but little research has focused on the effects of cross-sex hormone therapy and sex reassignment surgery on sexual desire in trans persons. This study aims to explore associations between sex reassignment therapy (SRT) and sexual desire in a large cohort of trans persons. A cross-sectional single specialized center study including 214 trans women (male-to-female trans persons) and 138 trans men (female-to-male trans persons). Questionnaires assessing demographics, medical history, frequency of sexual desire, hypoactive sexual desire disorder (HSDD), and treatment satisfaction. In retrospect, 62.4% of trans women reported a decrease in sexual desire after SRT. Seventy-three percent of trans women never or rarely experienced spontaneous and responsive sexual desire. A third reported associated personal or relational distress resulting in a prevalence of HSDD of 22%. Respondents who had undergone vaginoplasty experienced more spontaneous sexual desire compared with those who planned this surgery but had not yet undergone it (P = 0.03). In retrospect, the majority of trans men (71.0%) reported an increase in sexual desire after SRT. Thirty percent of trans men never or rarely felt sexual desire; 39.7% from time to time, and 30.6% often or always. Five percent of trans men met the criteria for HSDD. Trans men who were less satisfied with the phalloplasty had a higher prevalence of HSDD (P = 0.02). Trans persons who were more satisfied with the hormonal therapy had a lower prevalence of HSDD (P = 0.02). HSDD was more prevalent in trans women compared with trans men. The majority of trans women reported a decrease in sexual desire after SRT, whereas the opposite was observed in trans men. Our results show a significant sexual impact of surgical interventions and both hormonal and surgical treatment satisfaction on the sexual desire in trans persons. © 2013 International Society for Sexual

Complexation of biological ligands with lanthanides(III) for MRI: Structure, thermodynamic and methods; Complexation des cations lanthanides trivalents par des ligands d'origine biologique pour l'IRM: Structure, thermodynamique et methodes

Energy Technology Data Exchange (ETDEWEB)

Bonnet, C

2006-07-15

New cyclic ligands derived from sugars and amino-acids form a scaffold carrying a coordination sphere of oxygen atoms suitable to complex Ln(III) ions. In spite of their rather low molecular weights, the complexes display surprisingly high relaxivity values, especially at high field. The ACX and BCX ligands, which are acidic derivatives of modified and cyclo-dextrins, form mono and bimetallic complexes with Ln(III). The LnACX and LnBCX complexes show affinities towards Ln(III) similar to those of tri-acidic ligands. In the bimetallic Lu2ACX complex, the cations are deeply embedded in the cavity of the ligand, as shown by the X-ray structure. In aqueous solution, the number of water molecules coordinated to the cation in the LnACX complex depends on the nature and concentration of the alkali ions of the supporting electrolyte, as shown by luminescence and relaxometric measurements. There is only one water molecule coordinated in the LnBCX complex, which enables us to highlight an important second sphere contribution to relaxivity. The NMR study of the RAFT peptidic ligand shows the complexation of Ln(III), with an affinity similar to those of natural ligands derived from calmodulin. The relaxometric study also shows an important second sphere contribution to relaxivity. To better understand the intricate molecular factors affecting relaxivity, we developed new relaxometric methods based on probe solutes. These methods allow us to determine the charge of the complex, weak affinity constants, trans-metallation constants, and the electronic relaxation rate. (author)

Investigation into complexing of phthalexone S with praseodymium ions and some aminoglycoside antibiotics

International Nuclear Information System (INIS)

Alykov, N.M.

1981-01-01

Complex formation of phthalexone S (Phth) with praseodymium ion and some aminoglycoside antibiotics (Ab) in aqueous ethanol solutions (1:1) has been examined photometrically at 619 mm. It has been shown that compounds with the ratios of Ab:Pr:Phth=1:2:8, 1:1:4, 1:1:3 are formed depending on the number of amino groups and structure of the antibiotics. The molar absorptivities and solubility products for the complexes have been calculated. The complex formation scheme is given. A procedure has been developed of determining 0.01-10 μg of antibiotics in 1 ml of a biological material with a relative error of less than 10% [ru

Effect of bisquaternary ammonium salts on complexing of metal ions with pyrocatechol violet

International Nuclear Information System (INIS)

Tananajko, M.M.; Kofanova, N.K.

1984-01-01

Conditions for the improvement of contrast and sensitivity of reactions of high-charge ions of metals (Mo, W, La, Cd, Zr, Hf, Th) in the process of their photometric determination with pyrocatechol violet (PV), using bisquaternary ammonium salts (BQAS), have been studied. It is shown that in the systems investigated the BQAS play the role of ''shifting'' reagents, shifting bathochromically the absorption bands of different ligand complexes as compared with absorption bands of the Me-PV binary complexes. The effect of the BQAS on complexing with PV in aqueous and organic phases (chloroform) is studied and potential flotation of the compounds in the phase interface is considered

Studies on chelation properties of ampicillin with trace metal ions and comparison with penicillin complexes

International Nuclear Information System (INIS)

Rehmani, F.S.; Hameed, W.

2003-01-01

The penicillin is highly effective antibiotic with extremely wide margin of safety. Ampicillin e is the penicillin group of antibiotic in which side chain is phenyl group i.e. D-amino benzyl penicillin. The side chain determines many of anti bacterial and pharmacological characteristics. They inhibit the protein synthesis in bacterial cell wall. The chelating properties of the antibiotic may be used in the metal transport across the membrane. The present investigations are helpful in drug metabolism and their effects on minerals contents of the body. The complex formation between Ampicillin and penicillin with trace metal ions such as Fe(III), Cr(III), Al(III), Mn(II), Ni(II), Co(II), Ca(II), Mg(II), Cu(III) and Zn(II) were studied by potentiometric titrations and spectrophotometric methods. Stoichiometry of these complexes were studied by mole ratio method. It was found that the Fe(III) and Cu(II) ions form most stable complexes near physiological pH and the mole ratio was 1:1. (author)

Reliability of trans-abdominal ultrasonography in determining exact location of placenta in patients of placenta previa major

International Nuclear Information System (INIS)

Zafar, M.; Hayat, N; Gul, U.

2017-01-01

Objective: To determine the reliability of trans-abdominal ultrasonographical localization of placenta in cases of placenta previa major, by taking peroperative finding as gold standard. Study Design: Validation study. Place and Duration of Study: Maternity ward, Obstetrics and Gynecology department, Military Hospital Rawalpindi from 2007 to 2008. Patients and Methods: A total of 100 patients fulfilling the inclusion and exclusion criteria were recruited for the study. These patients were admitted to the maternity ward, where trans-abdominal ultrasound was performed, site of the placenta and its relation to the internal os was documented. These patients under went elective cesarean section, during which the site and relation of the placenta to the internal os was confirmed. Results: The mean age of patients was 34.23 +- 6.76 years. Transabdominal ultrasound had a sensitivity of 93.4 percent in localizing major placenta previa while the specificity was 83 percent. Positive predictive value was 94.7 percent, negative predictive value was 80 percent and accuracy 91 percent. Conclusion: Trans-abdominal ultrasound was found highly effective in diagnosing and localizing placenta previa. (author)

Actinide uptake onto zeolite-L and SAPO-34

International Nuclear Information System (INIS)

Amini, S.; Dyer, A.

1994-01-01

The characteristics of ion exchange of uranyl and americium, which are α-emitting radioactive nuclides, were examined by batch and column methods. SAPO-34 showed good selectivity for uranyl ion at pH 2-3.5, and distribution coefficients of Am 3+ and UO 2 2+ increased with equilibrium pH. γ irradiation (2 MGy) did not show any significant effect on the uptake of both of actinide ions onto L and SAPO-34. Higher doses of γ-irradiation (up to 10 MGy) created a change of equilibrium pH, and hence uptake, due to radiolysis of water and heat localization generated by γ-radiation and annealing processes. (author) 19 refs.; 15 figs.; 3 tabs

PENYUSUNAN SKENARIO KEBIJAKAN UNTUK PENGEMBANGAN BRT TRANS SEMARANG DENGAN PENDEKATAN SISTEM DINAMIK

Directory of Open Access Journals (Sweden)

Aries Susanty

2014-10-01

Full Text Available [Preparation for Policy Scenarios for Developing the Bus Rapid Transit (BRT Trans Semarang with Dynamic System Approach] Related to the complexity of the problem faced by Bus Rapid Transit (BRT Trans Semarang, this research attempts to develop a framework for dynamic development of BRT Trans Semarang and provide a platform to support policy making related to performance improvement of BRT Trans Semarang. This research use system dynamics (SD methodology. There are three scenarios constructed in this research and then a system dynamics model built based on them for the next five years. The first scenario is providing some feeder that will take the passenger on the bus, the second scenario is providing some new bus, and the third scenario is a combination of providing a number of feeders and also some new bus. There are three criteria which are used to evaluate the result of each scenario, i. e the achievement of the target of load factor (greater than 70%, the amount of total subsidy for operational of BRT, and percentage of the number of people that change their moda of transportation, from using private vehicles to BRT. The result of simulation with system dynamic indicated that scenario 1 is better than the existing condition; scenario 1 also better than scenario 2 or scenario 3. By providing some feeder, operational BRT can achieve the target of load factor at month 15, the government also does not need to issue subsidies for operational of BRT Trans Semarang, as well as the percentage of the number of people who moved from using private vehicles reached 26%.

Starch plus sunflower oil addition to the diet of dry dairy cows results in a trans-11 to trans-10 shift of biohydrogenation.

Science.gov (United States)

Zened, A; Enjalbert, F; Nicot, M C; Troegeler-Meynadier, A

2013-01-01

Trans fatty acids (FA), exhibit different biological properties. Among them, cis-9,trans-11 conjugated linoleic acid has some interesting putative health properties, whereas trans-10,cis-12 conjugated linoleic acid has negative effects on cow milk fat production and would negatively affect human health. In high-yielding dairy cows, a shift from trans-11 to trans-10 pathway of biohydrogenation (BH) can occur in the rumen of cows receiving high-concentrate diets, especially when the diet is supplemented with unsaturated fat sources. To study this shift, 4 rumen-fistulated nonlactating Holstein cows were assigned to a 4×4 Latin square design with 4 different diets during 4 periods. Cows received 12 kg of dry matter per day of 4 diets based on corn silage during 4 successive periods: a control diet (22% starch, diet supplemented with wheat plus barley (35% starch, diet supplemented with 5% of sunflower oil (20% starch, 7.6% crude fat), and a high-starch plus sunflower oil diet (33% starch, 7.3% crude fat). Five hours after feeding, proportions of trans-11 BH isomers greatly increased in the rumen content with the addition of sunflower oil, without change in ruminal pH compared with the control diet. Addition of starch to the control diet had no effect on BH pathways but decreased ruminal pH. The addition of a large amount of starch in association with sunflower oil increased trans-10 FA at the expense of trans-11 FA in the rumen content, revealing a trans-11 to trans-10 shift. Interestingly, with this latter diet, ruminal pH did not change compared with a single addition of starch. This trans-11 to trans-10 shift occurred progressively, after a decrease in the proportion of trans-11 FA in the rumen, suggesting that this shift could result from a dysbiosis in the rumen in favor of trans-10-producing bacteria at the expense of those producing trans-11 or a modification of bacterial activities. Copyright © 2013 American Dairy Science Association. Published by Elsevier

Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries.

Science.gov (United States)

Wang, Qin-Chao; Hu, Enyuan; Pan, Yang; Xiao, Na; Hong, Fan; Fu, Zheng-Wen; Wu, Xiao-Jing; Bak, Seong-Min; Yang, Xiao-Qing; Zhou, Yong-Ning

2017-11-01

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na + and vacancy ordering. An interesting structure change of Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g -1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g -1 can still be obtained, indicating a promising rate capability. The low valence Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 , effectively suppressing the Mn 3+ -induced Jahn-Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 during charge/discharge is contributed by Co 2.2+ /Co 3+ and Mn 3.3+ /Mn 4+ redox couples. This is the first time that the highly reversible Co 2+ /Co 3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

Silicate complexation of NpO2+ ion in perchlorate media

International Nuclear Information System (INIS)

Pathak, P.N.; Choppin, G.R.

2007-01-01

Complexation behavior of NpO 2 + with ortho-silicic acid (o-SA) has been studied using solvent extraction at ionic strengths varying from 0.10 to 1.00M (NaClO 4 ) at pcH 3.68±0.08 and 25 deg C with bis-(2-ethylhexyl) phosphoric acid (HDEHP) as the extractant. The stability constant value (log β 1 ) for the 1:1 complex, NpO 2 (OSi(OH) 3 ), was found to decrease with increase in ionic strength of the aqueous phase [6.83±0.01 at I = 0.10M to 6.51±0.02 at I = 1.00M]. These values have been fitted in the SIT model expression and compared with similar values of complexation of the metal ions Am 3+ , Eu 3+ , UO 2 2+ , PuO 2 2+ , Np 4+ , Ni 2+ and Co 2+ . The speciation of NpO 2 + -o-silicate/carbonate system has been calculated as a function of pcH under ground water conditions. (author)

'Homens trans': novos matizes na aquarela das masculinidades? 'Trans men': new colours in the masculinities picture?

Directory of Open Access Journals (Sweden)

Guilherme Almeida

2012-08-01

Full Text Available O artigo discute de forma exploratória a emergência de uma nova categoria identitária no Brasil, a de 'homem trans'. Essa se constrói diferenciando-se da identidade lésbica e, também, de expressões de gênero de outros grupos que tiveram seus corpos assignados como femininos ao nascimento, mas que contestam essa assignação sem, contudo, se afirmarem 'homens' de forma constante. Afirma-se que a emergência dos 'homens trans' tem sido potencializada pelo estabelecimento do processo transexualizador no SUS. Discutem-se o uso do termo "homem trans" e algumas características comuns a tais sujeitos. Problematizam-se a complexidade de seus processos de autorreconhecimento e construção de masculinidades, sua rápida capacidade de indiferenciação a partir de modificações corporais e, alguns dos efeitos políticos e subjetivos, da visibilidade e da indiferenciação.The article discusses in an exploratory form the emergence of a new identity category in Brazil, namely "transmen". This identity is constructed as a differentiation from the lesbian identity and also from gender expressions of other groups that had their bodies assigned as female upon birth, but that later refuted this assignment without, however, affirming themselves as "men" on a permanent way. The article claims that the emergence of "transmen" has been made possible by the establishment of the transexualization process in the Public Health Care System. Furthermore, the article discusses the use of the term "transman" and some common characteristics related to those persons. The author critiques their complex processes of self-knowledge and construction of masculinities, as well as their quick capacity for non-differentiation from the stand-point of bodily modifications. Finally, the author discusses the political and subjective consequences of their visibility and non-differentiation.

A novel submicron emulsion system loaded with vincristine–oleic acid ion-pair complex with improved anticancer effect: in vitro and in vivo studies

Directory of Open Access Journals (Sweden)

Zhang T

2013-03-01

Full Text Available Ting Zhang,1 Yong Zheng,2 iang Peng,3 Xi Cao,1 Tao Gong,1 Zhirong Zhang11Key Laboratory of Drug Targeting and Drug Delivery Systems, Sichuan University, Chengdu, People’s Republic of China; 2Second Affiliated Hospital, Chongqing Medical University, Chongqing, People’s Republic of China; 3State Key Laboratory of Oral Diseases, Sichuan University, Chengdu, People’s Republic of ChinaBackground: Vincristine (VCR, which is a widely used antineoplastic drug, was integrated with a submicron-emulsion drug-delivery system to enhance the anticancer effect.Methods: After the formation of a VCR–oleic acid ion-pair complex (VCR-OA, the VCR-OA-loaded submicron emulsion (VCR-OA-SME, prepared by classical high-pressure homogenization, was characterized and its in vitro anticancer effects were evaluated.Results: The submicron-emulsion formulation exhibited a homogeneous round shape. The mean particle size, zeta potential, and encapsulation efficiency were 157.6 ± 12.6 nm, −26.5 ± 5.0 mV and 78.64% ± 3.44%, respectively. An in vitro release study of the VCR-OA-SME revealed that 12.4% of the VCR was released within the first 2 hours (initial burst-release phase and the rest of the drug was detected in the subsequent sustained-release phase. Compared with VCR solution, the pharmacokinetic study of VCR-OA-SME showed relatively longer mean residence time (mean residence time [0–∞] increased from 187.19 to 227.56 minutes, higher maximum concentration (from 252.13 ng/mL to 533.34 ng/mL, and greater area under the curve (area under the curve [0–∞] from 11,417.77 µg/L/minute to 17,164.34 µg/L/minute. Moreover, the VCR-OA-SME exhibited higher cytotoxicity (P < 0.05 on tumor cells by inducing cell arrest in the G2/M phase or even apoptosis (P < 0.05.Conclusion: The VCR-OA-SME formulation in our study displayed great potential for an anticancer effect for VCR.Keywords: ion-pair complex, submicron emulsion, cytotoxicity, apoptosis, cell uptake

Ácidos graxos trans: implicações nutricionais e fontes na dieta Trans fatty acids: nutritional implications and sources in the diet

Directory of Open Access Journals (Sweden)

Clayton Antunes Martin

2004-09-01

Full Text Available Este artigo revisa as principais fontes de ácidos graxos trans na dieta e as implicações nutricionais da ingestão elevada destes isômeros. São apresentados resumidamente os métodos analíticos utilizados na identificação e quantificação dos ácidos graxos trans, sendo abordados as suas vantagens e desvantagens. Os alimentos que empregam gordura parcialmente hidrogenada na sua produção, são fontes importantes de isômeros trans na dieta da maior parte da população em países industrializados. Este estudo compara os níveis de ácidos graxos trans em gorduras hidrogenadas, margarinas e batatas frita, analisados em diversos países, incluindo o Brasil. Esta avaliação indica a presença de níveis elevados de isômeros trans em alimentos produzidos no Brasil.This article review the main sources of trans fatty acids in the diet and nutritional implications of the high intake of these isomers. Analytical methods for the identification and quantification of trans fatty acids are presented briefly with regard to advantages and drawbacks of each method. Foods make with partially hidrogenated fats are important sources of trans isomers in the diets of most people in industrialized countries. It is made a comparison between levels of trans fatty acids in shortenings, margarines and potato chips evaluated in Brazil and in other countries. High levels of trans isomers are noted in Brazilian foods.

The Mechanism of Redox Reaction between Palladium(II Complex Ions and Potassium Formate in Acidic Aqueous Solution

Directory of Open Access Journals (Sweden)

Wojnicki M.

2017-06-01

Full Text Available The kinetics studies of redox reaction between palladium(II chloride complex ions and potassium formate in acidic aqueous solutions was investigated. It was shown, that the reduction reaction of Pd(II is selective in respect to Pd(II complex structure. The kinetic of the process was monitored spectrophotometrically. The influence of chloride ions concentration, Pd(II initial concentration, reductant concentration, ionic strength as well as the temperature were investigated in respect to the process dynamics. Arrhenius equation parameters were determined and are equal to 65.8 kJ/mol, and A = 1.12×1011 s−1.

Preparation of the copolymer of acrylic acid and acrylamide grafted onto polyethylene and its complexation with samarium ion

International Nuclear Information System (INIS)

Kido, Junji; Akiba, Hideto; Nishide, Hiroyuki; Tsuchida, Eishun; Omichi, Hideki; Okamoto, Jiro.

1986-01-01

Acrylic acid (AA) and acrylamide (AAm) were graft-copolymerized onto polyethylene (PE) powder by the pre-irradiation method. Complex formation constants of Sm ion with the PE powder grafted with both AA and AAm (PE-g-(AA-co-AAm)) were larger than those with the PE powder grafted with AA (PE-g-AA). Sm ion was efficiently separated from the solution containing both Sm ion and a transition metal ion such as Cu ion. Even after the γ-ray irradiation on PE-g-(AA-co-AAm) and PE-g-AA, the adsorption did not decrease. (author)

Inhibition of cellulase-catalyzed lignocellulosic hydrolysis by iron and oxidative metal ions and complexes.

Science.gov (United States)

Tejirian, Ani; Xu, Feng

2010-12-01

Enzymatic lignocellulose hydrolysis plays a key role in microbially driven carbon cycling and energy conversion and holds promise for bio-based energy and chemical industries. Cellulases (key lignocellulose-active enzymes) are prone to interference from various noncellulosic substances (e.g., metal ions). During natural cellulolysis, these substances may arise from other microbial activities or abiotic events, and during industrial cellulolysis, they may be derived from biomass feedstocks or upstream treatments. Knowledge about cellulolysis-inhibiting reactions is of importance for the microbiology of natural biomass degradation and the development of biomass conversion technology. Different metal ions, including those native to microbial activity or employed for biomass pretreatments, are often tested for enzymatic cellulolysis. Only a few metal ions act as inhibitors of cellulases, which include ferrous and ferric ions as well as cupric ion. In this study, we showed inhibition by ferrous/ferric ions as part of a more general effect from oxidative (or redox-active) metal ions and their complexes. The correlation between inhibition and oxidation potential indicated the oxidative nature of the inhibition, and the dependence on air established the catalytic role that iron ions played in mediating the dioxygen inhibition of cellulolysis. Individual cellulases showed different susceptibilities to inhibition. It is likely that the inhibition exerted its effect more on cellulose than on cellulase. Strong iron ion chelators and polyethylene glycols could mitigate the inhibition. Potential microbiological and industrial implications of the observed effect of redox-active metal ions on enzymatic cellulolysis, as well as the prevention and mitigation of this effect in industrial biomass conversion, are discussed.

Trans-nationalisation Processes in the Ukrainian Economy

OpenAIRE

Bolharova Natalya K.; Panevnyk Tetyana M.

2013-01-01

The article considers main processes of trans-nationalisation of Ukrainian economy, identifies specific features of trans-national production and explains some theoretical aspects of these issues. It provides main stages of theoretical comprehension of activity of trans-national corporations (TNC), specific features of the theory of competitive advantages of TNC and specifies the basic ones of them. The article conducts analysis of flows of direct foreign investments into the Ukrainian econom...

Finding a Trans-Affirmative Provider: Challenges Faced by Trans and Gender Diverse Psychologists and Psychology Trainees.

Science.gov (United States)

Dickey, Lore M; Singh, Anneliese A

2017-08-01

This article explores some of the challenges faced by trans and gender diverse (TGD) individuals who not only are attempting to access trans-affirmative care, but who are also members of the very profession from which they are seeking services. The authors explore challenges related to finding supervision, accessing care for assessment services, and finding a provider for personal counseling. With each example, the authors unpack the challenges and also address the implications for training for all involved. Based on these challenges that TGD psychologists and trainees face in attempting to access care, the authors provide recommendations related to trans-affirmative training for psychologists. © 2017 Wiley Periodicals, Inc.

The role of helium ion microscopy in the characterisation of complex three-dimensional nanostructures

International Nuclear Information System (INIS)

Rodenburg, C.; Liu, X.; Jepson, M.A.E.; Zhou, Z.; Rainforth, W.M.; Rodenburg, J.M.

2010-01-01

This work addresses two major issues relating to Helium Ion Microscopy (HeIM). First we show that HeIM is capable of solving the interpretation difficulties that arise when complex three-dimensional structures are imaged using traditional high lateral resolution techniques which are transmission based, such as scanning transmission electron microscopy (STEM). Secondly we use a nano-composite coating consisting of amorphous carbon embedded in chromium rich matrix to estimate the mean escape depth for amorphous carbon for secondary electrons generated by helium ion impact as a measure of HeIM depth resolution.

Study of the alkaline cations complexation by photo-isomerizable calixarenes; Etude de la complexation de cations alcalins par des calixarenes photoisomerisables

Energy Technology Data Exchange (ETDEWEB)

Reynier, N.

1996-04-25

The first step to reduce the volume and the toxicity of radioactive waste coming from the spent fuel reprocessing is to separate long life radioisotopes from others ones with a shorter period. The aim of this study is to show that the control of the two phenomenons, complexation of the cation by the calixarenes and its de-complexation, can be envisaged by the introduction on the molecule of a chromophore group, azo benzene, able to modify the complexing site structure of the calixarenes with an isomerization trans-cis induced by ultraviolet radiation, and isomerization cis-trans thermally induced by a visible radiation. (N.C.). 112 refs., 78 figs., 23 tabs.

Study the effect of ion-complex on the properties of composite gel polymer electrolyte based on Electrospun PVdF nanofibrous membrane

International Nuclear Information System (INIS)

Li, Weili; Xing, Yujin; Wu, Yuhui; Wang, Jiawei; Chen, Lizhuang; Yang, Gang; Tang, Benzhong

2015-01-01

In this paper, nanofibrous membranes based on poly(vinylidene fluoride) (PVdF) doped with ion-complex (SiO 2 -PAALi) were prepared by electrospinning technique and the corresponding composite gel-polymer electrolytes (CGPEs) were obtained after being activated in liquid electrolyte. The microstructure, physical and electrochemical performances of the nanofibrous membranes and the corresponding CGPEs were studied by various measurements such as Fourier Transform Infrared Spectroscopy(FTIR), Scanning Electron Microscope (SEM), Differential Scanning Calorimetry (DSC), Thermal Gravimetric Analysis (TGA), Stress-strain test, Linear Sweep Voltammetry (LSV), AC impedance measurement and Charge/discharge cycle test. As to the ion-complex doped nanofibrous membranes, PVdF can provide mechanical support with network structure composed of fully interconnection; while the ion-complexes are absorbed onto the surface of the PVdF nanofibers evenly instead of being aggregated. With the help of doped ion-complex, the prepared nanofibrous membranes present good liquid electrolyte absorbability, excellent mechanical performance, and high decomposition temperature. For the corresponding CGPEs, they possess high ionic conductivity, wide electrochemical window, and good charge/discharge cycle performance

Multiheteromacrocycles that complex metal ions. Fourth progress report, 1 May 1977--30 April 1978

International Nuclear Information System (INIS)

Cram, D.J.

1978-01-01

Results are reported in a program to design, synthesize, and evaluate polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions. Work during the reporting period was devoted to synthesis and study of cyclohexametaphenylenes and cyclic phosphine oxides

Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses

Energy Technology Data Exchange (ETDEWEB)

Poad, Berwyck L.; Zheng, Xueyun; Mitchell, Todd A.; Smith, Richard D.; Baker, Erin M.; Blanksby, Stephen J.

2017-12-21

One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.

Crystal structure of trans-dichloridobis[N-(5,5-dimethyl-4,5-dihydro-3H-pyrrol-2-yl-κNacetamide]palladium(II dihydrate

Directory of Open Access Journals (Sweden)

Jamal Lasri

2017-04-01

Full Text Available The title complex, [PdCl2(C8H14N2O2]·2H2O, was obtained by N–O bond cleavage of the oxadiazoline rings of the trans-[dichlorido-bis(2,5,5-trimethyl-5,6,7,7a-tetrahydropyrrolo[1,2-b][1,2,4]oxadiazole-N1]palladium(II complex. The palladium(II atom exhibits an almost square-planar coordination provided by two trans-arranged chloride anions and a nitrogen atom from each of the two neutral organic ligands. In the crystal, N—H...O, O—H...O and O—H...Cl hydrogen bonds link complex molecules into double layers parallel to the bc plane.

Analysis of supramolecular surface nanostructures using secondary ion mass spectrometry (poster)

International Nuclear Information System (INIS)

Halaszova, S.; Velic, D.

2013-01-01

Our system consists of host molecules β-cyclodextrin (C 42 H 70 O 35 ), of implemented Iron nanoparticles (guest). Whole supramolecular complex is placed on a gold substrate. In our project we work with monotiolated β-cyclodextrin (C 42 H 70 O 34 S), consisting of seven α-D-1-4 glucopyranose units. Cyclodextrins have been selected deliberately because of their ability to form inclusion complexes .They are also capable of forming structures similar to self-assembly monolayers. To study the formation of these supramolecular surface nanostructures mass secondary ion spectrometry is used. With this technique fragmentation of monotiolated β-cyclodextrin and the presence of the supramolecular complex on a gold surface can be examined. The observed fragments of monotiolated cyclodextrines films can be divided into three groups: Au X H Y S Z , fragments originating from cyclodextrin molecules associated with Au. Fragments as (C 42 H 70 O 34 S)Na + , (C 42 H 70 O 35 )Na + and (AuC 42 H 69 O 34 S)Na + were identified as well as fragments thereof in cationized form with K + . The main objective of the project is a detailed study and preparation of supramolecular nanostructures consisting of complex guest-host monotiolated β-cyclodextrin host-iron), and a gold substrate. (Authors)

Metabolism of trans, trans-muconaldehyde, a cytotoxic metabolite of benzene, in mouse liver by alcohol dehydrogenase Adh1 and aldehyde reductase AKR1A4

International Nuclear Information System (INIS)

Short, Duncan M.; Lyon, Robert; Watson, David G.; Barski, Oleg A.; McGarvie, Gail; Ellis, Elizabeth M.

2006-01-01

The reductive metabolism of trans, trans-muconaldehyde, a cytotoxic metabolite of benzene, was studied in mouse liver. Using an HPLC-based stopped assay, the primary reduced metabolite was identified as 6-hydroxy-trans, trans-2,4-hexadienal (OH/CHO) and the secondary metabolite as 1,6-dihydroxy-trans, trans-2,4-hexadiene (OH/OH). The main enzymes responsible for the highest levels of reductase activity towards trans, trans-muconaldehyde were purified from mouse liver soluble fraction first by Q-sepharose chromatography followed by either blue or red dye affinity chromatography. In mouse liver, trans, trans-muconaldehyde is predominantly reduced by an NADH-dependent enzyme, which was identified as alcohol dehydrogenase (Adh1). Kinetic constants obtained for trans, trans-muconaldehyde with the native Adh1 enzyme showed a V max of 2141 ± 500 nmol/min/mg and a K m of 11 ± 4 μM. This enzyme was inhibited by pyrazole with a K I of 3.1 ± 0.57 μM. Other fractions were found to contain muconaldehyde reductase activity independent of Adh1, and one enzyme was identified as the NADPH-dependent aldehyde reductase AKR1A4. This showed a V max of 115 nmol/min/mg and a K m of 15 ± 2 μM and was not inhibited by pyrazole

Trans issues in Liz Lochhead's 'Not Changed'

OpenAIRE

Kaličanin Milena M.

2017-01-01

The paper is divided into four sections. In the first section entitled 'Introducing and Defining Trans (Issues)', the basic terms of transgender, transvestite, and transsexual are defined by relying on Stryker's Transgender History (2008). The second part of the paper, 'Trans Studies: In-Between Feminist and Queer Theory?', places transgender studies into an academic context by referring to the theoretical framework provided by trans theorists Stryker, Stone, and Ranck who unanimously claim t...

Trans fats in New Zealand: time for labelling regulations?

Science.gov (United States)

Gladding, Patrick; Benatar, Jocelyne R

2007-11-09

Trans fats (trans fatty acids) are commonly used for deep frying in restaurants and in the fast food, snack food, fried food, and baked goods industries, often to extend the shelf life of foods. However they are widely considered to be harmful to health. Trans fats were banned in New York City restaurants from 1 July 2007, and there is growing vocal opposition to trans fats in the European Union. Denmark became the first country, in March 2003, to introduce laws regulating the content of trans fats in food (maximum of 2% of edible fats and oils). What are trans fats, what harm do they cause, and should New Zealand also consider imposing mandatory regulations on their use in food? This article explores the issues.

Physics of Trans-Planckian Gravity

CERN Document Server

Dvali, Gia; Germani, Cristiano

2011-01-01

We study aspects of the phenomenon of gravitational UV-self-completeness and its implications for deformations of Einstein gravity. In a ghost-free theory flowing to Einstein gravity in the IR trans-Planckian propagating quantum degrees of freedom cannot exist. The only physical meaning of a trans-Planckian pole is the one of a classical state (Black Hole) which is fully described by the light IR quantum degrees of freedom and gives exponentially-suppressed contributions to virtual processes. In this sense Einstein gravity is UV self-complete, although not Wilsonian. We show that this UV/IR correspondence puts a severe constraint on any attempt of conventional Wilsonian UV-completion of trans-Planckian gravity. In particular, there is no well-defined energy domain in which gravity could become asymptotically weak or safe.

Is there such a thing as Tech Trans?

DEFF Research Database (Denmark)

Helms, Niels Henrik

2009-01-01

This short paper is an attempt to start a discussion on some basic issues within the concept of Tech Trans especially the relationship between flow and structure within the concept. The background to this paper is first of all an academic interest in the relationship between flow and structure...... explores the concept of Tech Trans, show rooms and innovation systems, and it suggests that the notion of Tech Trans should be defined in the fix point of vertical and horizontal innovation. Finally this paper suggests a mathematical formula for evaluating Tech Trans....

Lutetium(III) aqua ion: On the dynamical structure of the heaviest lanthanoid hydration complex

Energy Technology Data Exchange (ETDEWEB)

Sessa, Francesco; D’Angelo, Paola, E-mail: p.dangelo@uniroma1.it [Dipartimento di Chimica, Università di Roma “La Sapienza,” P. le A. Moro 5, 00185 Roma (Italy); Spezia, Riccardo [CNRS, UMR 8587, Laboratoire Analyse et Modelisation Pour la Biologie et l’Environnement, Université d’Evry Val d’Essonne, Blvd. F. Mitterrand, 91025 Evry Cedex (France)

2016-05-28

The structure and dynamics of the lutetium(III) ion in aqueous solution have been investigated by means of a polarizable force field molecular dynamics (MD). An 8-fold square antiprism (SAP) geometry has been found to be the dominant configuration of the lutetium(III) aqua ion. Nevertheless, a low percentage of 9-fold complexes arranged in a tricapped trigonal prism (TTP) geometry has been also detected. Dynamic properties have been explored by carrying out six independent MD simulations for each of four different temperatures: 277 K, 298 K, 423 K, 632 K. The mean residence time of water molecules in the first hydration shell at room temperature has been found to increase as compared to the central elements of the lanthanoid series in agreement with previous experimental findings. Water exchange kinetic rate constants at each temperature and activation parameters of the process have been determined from the MD simulations. The obtained structural and dynamical results suggest that the water exchange process for the lutetium(III) aqua ion proceeds with an associative mechanism, in which the SAP hydration complex undergoes temporary structural changes passing through a 9-fold TTP intermediate. Such results are consistent with the water exchange mechanism proposed for heavy lanthanoid atoms.

Selective Decontamination Effect of Metal Ions in Soil Using Supercritical CO{sub 2} and TBP Complex

Energy Technology Data Exchange (ETDEWEB)

Park, Jihye; Park, Kwangheon; Jung, Wonyoung [Kyunghee Univ., Yongin (Korea, Republic of)

2014-10-15

Decontamination of soil pollution is difficult because the type of contamination largely depends on the characteristics of the pollutant and the area. Also, existing soil decontamination methods generate large quantities of secondary waste and additional process costs. For this reason, new decontamination methods are always under active investigation. A method involving the use of supercritical carbon dioxide with excellent permeability in place of chemical solvents is currently being studied. Unlike other heavy metals in fission products, uranium is used as fuel, and must be handled carefully. Therefore, in this paper, we studied a supercritical carbon dioxide method for decontaminating heavy metal ions in soil using tri-n-butyl phosphate(TBP), which is well known as a ligand for the extraction of metal ions of actinium. We investigated the decontamination effect of heavy metal ions in the soil using TBP-HNO{sub 3} Complex and supercritical carbon dioxide. The study results showed that when heavy metals in soil are extracted using supercritical carbon dioxide, the extraction efficiency is different according to the type of pollutant metal ions in the soil. When TBP-HNO{sub 3} Complex is used with an extractant, uranium extraction is very effective, but lithium, strontium, and cesium extraction is not effective. Therefore, in the case of a mixture of uranium and other metals such as lithium, strontium, cesium, and so on in soil contaminated by fission product leaks from nuclear power plants, we can selectively decontaminate uranium with supercritical carbon dioxide and TBP-HNO{sub 3} Complex.

Mass-spectrometry-directed analysis and purification of pyrrolizidine alkaloid cis/trans isomers in Gynura japonica.

Science.gov (United States)

Fang, Lianxiang; Xiong, Aizhen; Yang, Xiao; Cheng, Wenzhi; Yang, Li; Wang, Zhengtao

2014-08-01

Pyrrolizidine alkaloids are highly hepatotoxic natural chemicals that produce irreversible chronic and acute hepatotoxic effects on human beings. Purification of large amounts of pyrrolizidine alkaloids is necessary for toxicity studies. In this study, an efficient method for targeted analysis and purification of pyrrolizidine alkaloid cis/trans isomers from herbal materials was developed for the first time. Targeted analysis of the hepatotoxic pyrrolizidine alkaloids was performed by liquid chromatography with tandem mass spectrometry (precursor ion scan and daughter ion scan), and the purification of pyrrolizidine alkaloids was achieved with a mass-directed auto purification system. The extraction and preparative liquid chromatography conditions were optimized. The developed method was applied to analysis of Gynura japonica (Thunb.) Juel., a herbal medicine traditionally used for detumescence and relieving pain but is potentially hepatotoxic as it contains pyrrolizidine alkaloids. Twelve pyrrolizidine alkaloids (six cis/trans isomer pairs) were identified with reference compounds or characterized by liquid chromatography with tandem mass spectrometry, and five individual pyrrolizidine alkaloids, including (E)-seneciphylline, seneciphylline, integerrimine, senecionine, and seneciphyllinine, were prepared from G. japonica roots with high efficiency. The results of this work provide a new technique for the preparation of large amounts of pyrrolizidine alkaloid reference substances, which will also benefit toxicological studies of pyrrolizidine alkaloids and treatments for pyrrolizidine alkaloid-induced toxicity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

(E-3-(4-Bromophenyl-1-(3,4-dichlorophenylprop-2-en-1-one

Directory of Open Access Journals (Sweden)

Rajni Kant

2009-04-01

Full Text Available The molecule of the title compound, C15H9BrCl2O, is shown to be the E isomer, with the 3,4-dichlorobenzoyl and p-bromophenyl substituents in trans positions with respect to the chalcone olefin bond. The molecule is non-planar, the two aromatic rings forming a dihedral angle of 49.58 (1°.

Fabrication of Chitosan-complexed Electrode and Evaluation of Its Efficiency in Removal of Copper Ion from Aqueous Solution

Directory of Open Access Journals (Sweden)

Yoon Young-Chan

2016-01-01

Full Text Available In this study, we fabricated chitosan/PVA/activated carbon complexed electrode to remove copper ion from aqueous solution. The prepared composite electrode was analyzed by BET and SEM to investigate its physicochemical properties. Electrochemical properties of prepared composite electrodes were analyzed via cyclic voltammetry. Adsorption performance of copper ion on chitosan composite complexed electrodes was evaluated. Almost similar pore size distribution results were observed in the series of ACP not included electrodes while observed differences in pore size distribution for the ACP included one. Cyclic voltammetry results exhibited that oxidation-reduction reaction does not occur in a potential range of -1.0 ~ 1.0 V. The amount of copper ion during adsroption reaction is increase according to increase of adsorption potential to 1.0 V.

Trans issues in Liz Lochhead's 'Not Changed'

Directory of Open Access Journals (Sweden)

Kaličanin Milena M.

2017-01-01

Full Text Available The paper is divided into four sections. In the first section entitled 'Introducing and Defining Trans (Issues', the basic terms of transgender, transvestite, and transsexual are defined by relying on Stryker's Transgender History (2008. The second part of the paper, 'Trans Studies: In-Between Feminist and Queer Theory?', places transgender studies into an academic context by referring to the theoretical framework provided by trans theorists Stryker, Stone, and Ranck who unanimously claim that transgender studies should have a place of its own within the academia and that trans theory should solely be written by transsexuals. These ideas are applied in the interpretation of Lochhead's story 'Not Changed' in the third segment of the paper. The critical insights of Butler (Gender Trouble, 1990; Undoing Gender, 2004 are found to be most helpful in the interpretation of Lochhead's story about Michael who has willingly undergone Hormone Replacement Therapy to become transsexual Michele. Finally, in the concluding remarks, Lochhead's story is viewed as a trans woman manifesto, urging both non-transsexual and transsexual persons to embrace new beginnings in their relationship.

Trans-nationalisation Processes in the Ukrainian Economy

Directory of Open Access Journals (Sweden)

Bolharova Natalya K.

2013-12-01

Full Text Available The article considers main processes of trans-nationalisation of Ukrainian economy, identifies specific features of trans-national production and explains some theoretical aspects of these issues. It provides main stages of theoretical comprehension of activity of trans-national corporations (TNC, specific features of the theory of competitive advantages of TNC and specifies the basic ones of them. The article conducts analysis of flows of direct foreign investments into the Ukrainian economy. It shows distribution of direct foreign investments into Ukraine by main countries-investors, regions-recipients and types of economic activity. It conducts review and analysis of the modern state of trans-national corporations of foreign origin in the Ukrainian market. It considers functioning of domestic TNC in Ukraine and main tendencies of entering of Ukrainian companies into the world environment and also identifies directions of further development of these phenomena. Prospects of further studies in this direction are identification of the degree of trans-nationalisation processes in the Ukrainian economy and identification of the positive effect, in particular, synergy from integration and globalisation.

Ligational, analytical and biological applications on oxalyl bis(3,4-dihydroxybenzylidene) hydrazone

Science.gov (United States)

El-Asmy, Ahmed A.; El-Gammal, O. A.; Radwan, H. A.; Ghazy, S. E.

2010-09-01

The molecular modeling and parameters have been calculated to confirm the geometry of oxalyl bis(3,4-dihydroxybenzylidene) hydrazone, H 6L. The metal complexes of Cr 3+, VO 2+, ZrO 2+, HfO 2+, UO 22+ and MoO 22+ with H 6L have been prepared and characterized by partial elemental analysis, spectral studies (electronic; IR), thermal analysis and magnetic measurements. The data suggest the formation of polymer complexes with a unit [Cr(H 4L)(H 2O) 3Cl]·H 2O, [VO(H 4L)(H 2O) 2], [Hf(H 4L)(H 2O)]·H 2O [UO 2(H 4L)(H 2O) 2]·2H 2O [MoO 2(H 4L)] and [(ZrO) 2(H 2L)-(C 2H 5OH) 2]. The ligand behaves as a dibasic bidentate in all complexes except ZrO 2+ which acts as a tetrabasic tetradentate with the two ZrO 2+ ions. An octahedral geometry was proposed for the Cr 3+, HfO 2+, MoO 22+and UO 22+ complexes and square pyramid for VO 2+. The Cr 3+ is necessary to degrade the DNA of eukaryotic subject completely; the other complexes have little effect. H 6L was found suitable as a new reagent for the separation and preconcentration of ZrO 2+ ions from different water samples using flotation technique with satisfactory results.

Selectivity in inter polymer complexation involving phenolic copolymer, poly electrolytes, non-ionic polymers and transition metal ions

International Nuclear Information System (INIS)

Vasheghani Farahani, B.; Hosseinpour Rajabi, F.

2006-01-01

Selectivity in inter polymer complex formation involving a typical four-component phenolic copolymer (ρ-chloro phenol-ρ-aminophenol-ρ-toluidine-ρ-cresol- HCHO copolymer), poly electrolytes such as polyethylene imine and polyacrylic acid, a non-ionic homopolymer polyvinyl pyrrolidone, and some transition metal ions (e.g., Cu (II), Ni (11)) have been studied in dimethylformamide-methanol solvents mixture. The coordinating groups of phenolic copolymer form complexes through hydrogen bonding and ion-dipole interactions. The different stages of interactions have been studied by several experimental techniques, e.g., viscometry, potentiometry and conductometry. Some schemes have been suggested to explain the mode of interaction between these components

Both cis and trans Activities of Foot-and-Mouth Disease Virus 3D Polymerase Are Essential for Viral RNA Replication.

Science.gov (United States)

Herod, Morgan R; Ferrer-Orta, Cristina; Loundras, Eleni-Anna; Ward, Joseph C; Verdaguer, Nuria; Rowlands, David J; Stonehouse, Nicola J

2016-08-01

The Picornaviridae is a large family of positive-sense RNA viruses that contains numerous human and animal pathogens, including foot-and-mouth disease virus (FMDV). The picornavirus replication complex comprises a coordinated network of protein-protein and protein-RNA interactions involving multiple viral and host-cellular factors. Many of the proteins within the complex possess multiple roles in viral RNA replication, some of which can be provided in trans (i.e., via expression from a separate RNA molecule), while others are required in cis (i.e., expressed from the template RNA molecule). In vitro studies have suggested that multiple copies of the RNA-dependent RNA polymerase (RdRp) 3D are involved in the viral replication complex. However, it is not clear whether all these molecules are catalytically active or what other function(s) they provide. In this study, we aimed to distinguish between catalytically active 3D molecules and those that build a replication complex. We report a novel nonenzymatic cis-acting function of 3D that is essential for viral-genome replication. Using an FMDV replicon in complementation experiments, our data demonstrate that this cis-acting role of 3D is distinct from the catalytic activity, which is predominantly trans acting. Immunofluorescence studies suggest that both cis- and trans-acting 3D molecules localize to the same cellular compartment. However, our genetic and structural data suggest that 3D interacts in cis with RNA stem-loops that are essential for viral RNA replication. This study identifies a previously undescribed aspect of picornavirus replication complex structure-function and an important methodology for probing such interactions further. Foot-and-mouth disease virus (FMDV) is an important animal pathogen responsible for foot-and-mouth disease. The disease is endemic in many parts of the world with outbreaks within livestock resulting in major economic losses. Propagation of the viral genome occurs within

Formation of trans fats during food preparation.

Science.gov (United States)

Przybylski, Oman; Aladedunye, Felix A

2012-01-01

An investigation was completed to determine how typical cooking procedures used in food preparation, such as baking and stir-frying, affect trans fats formation. Canola oil was used as the main fat ingredient. Zucchini cake and gingersnap cookies were baked at 180o C and 200o C, while stir-fried chicken was prepared at 200o C and 275o C. The lipids from the food were extracted following the Folch procedure, and analyzed for trans fatty acids according to ISO official method 15304. Minimal changes were observed in the amount of trans fats during baking. Application of extreme temperatures during baking, which caused carbonization of the outer layer of products, yielded an insignificant increase in the amount of trans isomers. As with baking, stir-frying did not result in significant isomerization of the fatty acids, even when the oil was heated to 275o C and smoking heavily before the food was placed in it. Irrespective of the cooking procedure, linolenic acid was the most prone to isomerization with the highest amount of trans isomers formation. Baking and stir-frying at normal and/or extreme temperatures do not significantly affect the amounts of trans fats. Likewise, heating oil to the smoking point during stir-frying may decrease the amount of polyunsaturated fatty acids because of oxidative degradation.

Binge-type behavior in rats consuming trans-fat-free shortening.

Science.gov (United States)

Wojnicki, F H E; Charny, G; Corwin, R L W

2008-07-05

Studies from this and another laboratory involving an animal model of binge-type behavior have used vegetable shortening containing trans-fats. Due to reformulations by vegetable shortening manufacturers to remove trans-fats from their products, only trans-fat-free shortenings are now available. The goal of the present study was to assess binge-type behavior in rats with trans-fat and trans-free vegetable shortening. Trans-fat-free shortening was provided to three different groups of non-food-deprived male Sprague Dawley rats on different schedules of access: continuous access (24 h/day-7 days/week), daily access (1 h every day), and intermittent access (1 h on Mondays, Wednesdays, Fridays). Trans-fat shortening was provided to a fourth group on the intermittent access schedule. A fifth group had no shortening access (chow only). Both intermittent groups (trans-fat-free and trans-fat) consumed significantly more shortening during the 1-h period of availability than did the daily group, and there was no difference in shortening intakes between the intermittent groups. These results are identical to previous reports of binge-type behavior in rats using this model. Thus, binge-type behavior in the present behavioral model depends upon the schedule of access, not the presence of trans-fats in the shortening.

Syntheses, crystal structures and spectroscopic properties of copper(II)-tetracyanometallate(II) complexes with nicotinamide and isonicotinamide ligands

Science.gov (United States)

Sayın, Elvan; Kürkçüoğlu, Güneş Süheyla; Yeşilel, Okan Zafer; Hökelek, Tuncer

2015-09-01

Four new one dimensional (1D) cyanide complexes, namely {[Cu(NH3)4(μ-na)][M‧(CN)4]}n and {[Cu(NH3)2(ina)2M‧(μ-CN)2(CN)2]}n (M‧(II) = Pd (1 and 3) or Pt (2 and 4), na:nicotinamide and ina:isonicotinamide) have been synthesized and characterized by elemental, spectral (FT-IR and Raman), and thermal (TG, DTG and DTA) analyses. The crystal structures of complexes 1-3 have been determined by single crystal X-ray diffraction technique. In complexes 1 and 2, na ligand is coordinated to the adjacent Cu(II) ions as a bridging ligand, giving rise to 1D linear cationic chain and the [M‧(CN)4]2- anionic complex acts as a counter ion. Complexes 3 and 4 are also 1D linear chain in which two cyanide ligands bridged neighboring M‧(II) and Cu(II) ions, while ina ligand is coordinated Cu(II) ion through nitrogen atom of pyridine ring. In the complexes, the Cu(II) ions adopt distorted octahedral geometries, while M‧(II) ions are four coordinated with four carbon atoms from cyanide ligands in square-planar geometries. The adjacent chains are further stacked through intermolecular hydrogen bond, Nsbnd Hṡṡṡπ, Csbnd H⋯M‧ and M‧⋯π interactions to form 3D supramolecular networks. Vibration assignments are given for all the observed bands. In addition, thermal stabilities of the compounds are also discussed.

Production of highly charged ion beams from electron cyclotron resonance ion sources (invited)

International Nuclear Information System (INIS)

Xie, Z.Q.

1998-01-01

Electron cyclotron resonance ion source (ECRIS) development has progressed with multiple-frequency plasma heating, higher mirror magnetic fields, and better technique to provide extra cold electrons. Such techniques greatly enhance the production of highly charged ions from ECRISs. So far at continuous wave (CW) mode operation, up to 300 eμA of O 7+ and 1.15 emA of O 6+ , more than 100 eμA of intermediate heavy ions for charge states up to Ar 13+ , Ca 13+ , Fe 13+ , Co 14+ , and Kr 18+ , and tens of eμA of heavy ions with charge states to Kr 26+ , Xe 28+ , Au 35+ , Bi 34+ , and U 34+ were produced from ECRISs. At an intensity of at least 1 eμA, the maximum charge state available for the heavy ions are Xe 36+ , Au 46+ , Bi 47+ , and U 48+ . An order of magnitude enhancement for fully stripped argon ions (I≥60enA) were also achieved. This article will review the ECR ion source progress and discuss key requirement for ECRISs to produce the highly charged ion beams. copyright 1998 American Institute of Physics

Cyanide ion complexation by a cationic borane.

Science.gov (United States)

Chiu, Ching-Wen; Gabbaï, François P

2008-02-14

While we have previously reported that [1-(Mes2B)-8-(Me3NCH2)-C10H6]+ ([2]+) complexes fluoride ions to form [1-(Mes2FB)-8-(Me3NCH2)-C10H6] (2-F), we now show that this cationic borane also complexes cyanide to form [1-(Mes2(NC)B)-8-(Me3NCH2)-C10H6] (2-CN). This reaction also occurs under biphasic conditions (H2O-CHCl3) and may serve to transport cyanide in organic phases. The zwitterionic cyanoborate 2-CN has been fully characterized and its crystal structure determined. UV-vis titration experiments carried out in THF indicate that [2]+ has a higher affinity for fluoride (K > 10(8) M(-1)) than cyanide (K = 8.0 (+/-0.5) x 10(5) M(-1)). Steric effects which impede cyanide binding to the sterically congested boron center of [2]+ are most likely at the origin of this selectivity. Finally, electrochemical studies indicate that [2]+ is significantly more electrophilic than its neutral precursor 1-(Mes2B)-8-(Me2NCH2)-(C10H6) (1). These studies also show that reduction of [2]+ is irreversible, possibly because of elimination of the NMe3 moiety under reductive conditions. In fact, [2]OTf reacts with NaBH4 to afford 1-(Mes2B)-8-(CH3)-(C10H6) (4) which has also been fully characterized.

Cis-trans photoisomerization of abscisic acid

International Nuclear Information System (INIS)

Brabham, D.E.; Biggs, R.H.

1981-01-01

An important regulator of numerous physiological processes in higher plants is abscisic acid (ABA), which is photoisomerized from the more biologically active cis isomer to the nearly inactive trans isomer by natural sunlight. It is possible that this photoisomerization is a UV control mechanism in functions regulated by ABA. The quantum yields of both the cis to trans and trans to cis photoisomerizations were measured under various conditions of pH and oxygen concentration at room temperature. The yield for photoisomerization of cis-ABA ranged from 0.25 at pH 3.0 to 0.11 at pH 7.0. Oxygen partially quenched the process. The quantum yield varied only slightly with wavelength. The quantum yield of photolysis of cis-ABA was reported for pH 3.0 as 0.06. This yield also varied slightly with wavelength and was relatively insensitive to oxygen. This relatively high yield explains the loss of potency of ABA during UV irradiation. Phosphorescence of cis- and trans-ABA was observed in methanol at 77 K. Onset of the emission was at 350 nm. The emission spectra were the same for both isomers. From these results a mechanism of UV action on plants based on the photoisomerization of the inactive trans-ABA to the biologically active cis isomer is proposed. (author)

Pulse radiolysis of solutions of trans-stilbene

International Nuclear Information System (INIS)

Langan, J.R.; Salmon, G.A.

1982-01-01

On pulse radiolysis of solutions of trans-stilbene (t-St) in THF the radical-anion of t-St is formed by reaction of e - sub(s) with t-St. The transient absorption spectrum observed with lambdasub(max) at 500 and 720 nm is attributed to the unassociated St - . The subsequent decay of the radical-anion is accounted for by reaction with the counter-cation of THF formed on radiolysis and with radiolytically generated radicals; rate constants for these processes are estimated. Addition of sodium tetrahydridoaluminate (NAH) results in the radical-anion being associated with Na + as a contact ion-pair and a shift of lambdasub(max) to 490 nm. In the presence of the lithium salt the absorption spectrum of the radical-anion reverts to 500 nm. On pulse radiolysis of solutions containing NAH the main reaction forming St - is that of (Na + , e - sub(s))ion pairs with t-St. In addition there is a delayed formation of St - over a period of microseconds. The presence of tetrahydridoaluminate salts also greatly enhances the stability of St - and at high doses per pulse little decay was observed over 700 μs. The variation of G(St - ) with [NAH] was studied and was found to attain a plateau value of 2.0 at the higher concentrations. (author)

High spin spectroscopy of 34Cl

International Nuclear Information System (INIS)

Bisoi, Abhijit; Ray, S.; Kshetri, R.; Goswami, A.; Saha Sarkar, M.; Pramanik, D.; Sarkar, S.; Nag, S.; Selva Kumar, K.; Singh, P.; Saha, S.; Sethi, J.; Trivedi, T.; Naidu, B.S.; Donthi, R.; Nanal, V.; Palit, R.

2011-01-01

Spectroscopic information for 34 Cl is of interest for understanding the large 33 S abundance observed in nova. This nucleus has been extensively studied using proton, light ions and alpha beams but there are few experiments where heavy ions were used. In the present work, heavy ion beams are used to extract spectroscopic data for high spin states above ∼ 5 MeV, important for astrophysical scenario. Spherical shell model calculations have been done to interpret the experimental data. Several options of truncation adopted have provided useful insight into the sd - fp cross-shell calculations

Cyanide bridged hetero-metallic polymeric complexes: Syntheses, vibrational spectra, thermal analyses and crystal structures of complexes [M(1,2-dmi)2Ni(μ-CN)4]n (M = Zn(II) and Cd(II))

Science.gov (United States)

Kürkçüoğlu, Güneş Süheyla; Sayın, Elvan; Şahin, Onur

2015-12-01

Two cyanide bridged hetero-metallic complexes of general formula, [M(1,2-dmi)2Ni(μ-CN)4]n (1,2-dmi = 1,2-dimethylimidazole and M = Zn(II) or Cd(II)) have been synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, single crystal X-ray diffraction, thermal analyses and elemental analyses. The crystallographic analyses reveal that the complexes, [Zn(1,2-dmi)2Ni(μ-CN)4] (1) and [Cd(1,2-dmi)2Ni(μ-CN)4] (2), have polymeric 2D networks. In the complexes, four cyanide groups of [Ni(CN)4]2- coordinated to the adjacent M(II) ions and distorted octahedral geometries of complexes are completed by two nitrogen atoms of trans 1,2-dmi ligands. The structures of 1 and 2 are similar and linked via intermolecular hydrogen bonding, C-H⋯Ni interactions to give rise to 3D networks. Vibration assignments are given for all the observed bands and the spectral features also supported to the crystal structures of heteronuclear complexes. The FT-IR and Raman spectra of the complexes are very much consistent with the structural data presented.

[CONTENT OF TRANS FATTY ACIDS IN FOOD PRODUCTS IN SPAIN].

Science.gov (United States)

Robledo de Dios, Teresa; Dal Re Saavedra, M Ángeles; Villar Villalba, Carmen; Pérez-Farinós, Napoleón

2015-09-01

trans fatty acids are associated to several health disorders, as ischemic heart disease or diabetes mellitus. to assess the content of trans fatty acids in products in Spain, and the percentage of trans fatty acids respecting total fatty acids. 443 food products were acquired in Spain, and they were classified into groups. The content in fatty acids was analyzed using gas chromatography. Estimates of central tendency and variability of the content of trans fatty acids in each food group were computed (in g of trans fatty acids/100 g of product). The percentage of trans fatty acids respecting total fatty acids was calculated in each group. 443 products were grouped into 42 groups. Median of trans fatty acids was less than 0.55 g / 100 g of product in all groups except one. 83 % of groups had less than 2 % of trans fatty acids, and 71 % of groups had less than 1 %. the content of trans fatty acids in Spain is low, and it currently doesn't play a public health problem. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

Characterization of the TolB-Pal trans-envelope complex from Xylella fastidiosa reveals a dynamic and coordinated protein expression profile during the biofilm development process.

Science.gov (United States)

Santos, Clelton A; Janissen, Richard; Toledo, Marcelo A S; Beloti, Lilian L; Azzoni, Adriano R; Cotta, Monica A; Souza, Anete P

2015-10-01

The intriguing roles of the bacterial Tol-Pal trans-envelope protein complex range from maintenance of cell envelope integrity to potential participation in the process of cell division. In this study, we report the characterization of the XfTolB and XfPal proteins of the Tol-Pal complex of Xylella fastidiosa. X. fastidiosa is a major plant pathogen that forms biofilms inside xylem vessels, triggering the development of diseases in important cultivable plants around the word. Based on functional complementation experiments in Escherichia coli tolB and pal mutant strains, we confirmed the role of xftolB and xfpal in outer membrane integrity. In addition, we observed a dynamic and coordinated protein expression profile during the X. fastidiosa biofilm development process. Using small-angle X-ray scattering (SAXS), the low-resolution structure of the isolated XfTolB-XfPal complex in solution was solved for the first time. Finally, the localization of the XfTolB and XfPal polar ends was visualized via immunofluorescence labeling in vivo during bacterial cell growth. Our results highlight the major role of the components of the cell envelope, particularly the TolB-Pal complex, during the different phases of bacterial biofilm development. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis, characterization, density functional study and antimicrobial evaluation of a series of bischelated complexes with a dithiocarbazate Schiff base ligand

Directory of Open Access Journals (Sweden)

E. Zangrando

2017-02-01

Full Text Available A nitrogen-sulfur Schiff base HL (1 derived from S-hexyldithiocarbazate and 4-methylbenzaldehyde has been reacted with different divalent metal ions in 2:1 molar ratio, producing neutral complexes (2–7 of general formula MIIL2 (where M = Ni, Cu, Zn, Cd, Pd and Pb. All compounds were characterized using established physico-chemical and spectroscopic methods. The single crystal structures of CuII and ZnII complexes are compared and discussed with those of NiII and PdII already reported by us, underlining the geometrical variations occurring in the HL ligand upon coordination. The metal complexes, as revealed by the X-ray diffraction analyses, show a square planar or tetrahedral coordination geometry, and in the former case either a cisoid or transoid configuration of chelating ligands. Density functional theory (DFT and time-dependent density functional theory (TD-DFT calculations have been performed on the isolated cis/trans complexes of Ni and Pd complexes in order to evaluate the stability of the isomer isolated in solid state. The thermodynamic parameters for trans to cis isomerization of NiL2 complex [ΔH = −29.12 kJ/mol and ΔG = −43.97 kJ/mol] indicated that the trans isomer (observed in solid state is more stable than the cis one. On the other hand, relative enthalpy [ΔH = −4.37 kJ/mol] and Gibbs free energy [ΔG = −5.50 kJ/mol] of PdL2 complex disclosed a small difference between the energies of the two isomers. Experimental UV–vis and TD-DFT calculation confirmed that these complexes have distinctive LMCT bands with a broad shoulder at 400–550 nm. With the purpose of providing insight into the properties and behavior of the complexes in solution, photoluminescence and electrochemical experiments have been also performed. Finally, the anti-bacterial activity of these compounds was evaluated against three pathogenic Gram-negative organisms such as Escherichia coli, Salmonella typhi and Shigella flexneri, but

Photocontrol of Voltage-Gated Ion Channel Activity by Azobenzene Trimethylammonium Bromide in Neonatal Rat Cardiomyocytes.

Directory of Open Access Journals (Sweden)

Sheyda R Frolova

Full Text Available The ability of azobenzene trimethylammonium bromide (azoTAB to sensitize cardiac tissue excitability to light was recently reported. The dark, thermally relaxed trans- isomer of azoTAB suppressed spontaneous activity and excitation propagation speed, whereas the cis- isomer had no detectable effect on the electrical properties of cardiomyocyte monolayers. As the membrane potential of cardiac cells is mainly controlled by activity of voltage-gated ion channels, this study examined whether the sensitization effect of azoTAB was exerted primarily via the modulation of voltage-gated ion channel activity. The effects of trans- and cis- isomers of azoTAB on voltage-dependent sodium (INav, calcium (ICav, and potassium (IKv currents in isolated neonatal rat cardiomyocytes were investigated using the whole-cell patch-clamp technique. The experiments showed that azoTAB modulated ion currents, causing suppression of sodium (Na+ and calcium (Ca2+ currents and potentiation of net potassium (K+ currents. This finding confirms that azoTAB-effect on cardiac tissue excitability do indeed result from modulation of voltage-gated ion channels responsible for action potential.

Integrating genome-wide genetic variations and monocyte expression data reveals trans-regulated gene modules in humans.

Directory of Open Access Journals (Sweden)

Maxime Rotival

2011-12-01

Full Text Available One major expectation from the transcriptome in humans is to characterize the biological basis of associations identified by genome-wide association studies. So far, few cis expression quantitative trait loci (eQTLs have been reliably related to disease susceptibility. Trans-regulating mechanisms may play a more prominent role in disease susceptibility. We analyzed 12,808 genes detected in at least 5% of circulating monocyte samples from a population-based sample of 1,490 European unrelated subjects. We applied a method of extraction of expression patterns-independent component analysis-to identify sets of co-regulated genes. These patterns were then related to 675,350 SNPs to identify major trans-acting regulators. We detected three genomic regions significantly associated with co-regulated gene modules. Association of these loci with multiple expression traits was replicated in Cardiogenics, an independent study in which expression profiles of monocytes were available in 758 subjects. The locus 12q13 (lead SNP rs11171739, previously identified as a type 1 diabetes locus, was associated with a pattern including two cis eQTLs, RPS26 and SUOX, and 5 trans eQTLs, one of which (MADCAM1 is a potential candidate for mediating T1D susceptibility. The locus 12q24 (lead SNP rs653178, which has demonstrated extensive disease pleiotropy, including type 1 diabetes, hypertension, and celiac disease, was associated to a pattern strongly correlating to blood pressure level. The strongest trans eQTL in this pattern was CRIP1, a known marker of cellular proliferation in cancer. The locus 12q15 (lead SNP rs11177644 was associated with a pattern driven by two cis eQTLs, LYZ and YEATS4, and including 34 trans eQTLs, several of them tumor-related genes. This study shows that a method exploiting the structure of co-expressions among genes can help identify genomic regions involved in trans regulation of sets of genes and can provide clues for understanding the

Trans-nationalizing the African Public Sphere: What Role for Trans ...

African Journals Online (AJOL)

seriane.camara

2011-03-09

Mar 9, 2011 ... At a time when the notion of 'trans-national public spheres' is gaining .... ple refer specifically to the language and its speakers in Senegal and Mauri- .... of the Pulaar language and the improvement of the social and economic.

Asymmetric syntheses of 3,4-disubstituted tetrahydroquinoline derivatives using (+)- sparteine-mediated electrophilic substitution

International Nuclear Information System (INIS)

Choi, Yun Soo; Kang, Kyoung Hee; Park, Yong Sun

2015-01-01

Tetrahydroquinolines bearing substituents are frequently found as a substructure in a number of alkaloids and natural products. Since their individual stereoisomers displays different biological activities, it is desirable to develop a highly stereoselective synthetic method for tetrahydroquinolines. While some progress has recently been made toward the development of asymmetric synthetic methods for tetrahydroquinolines, it is still a challenging topic in organic synthesis. In order to investigate the source of diastereoselection attained in the substitution reaction with a racemic epoxide, we examined the substitution of 2 with an excess amount of racemic p-chlorophenyl-substituted oxirane. We have developed a novel method for the asymmetric synthesis of trans-3,4-diaryl-substituted tetrahy- droquinolines from ortho-substituted N-pivaloyl anilines. The enantioselective process includes (+)-sparteine-mediated stereoselective lithiati on, kinetic resolution of epoxides in substitution, and stereospecific Mitsu nobu cyclization as the key reactions. The simple protocol can provide highly functionalized tetrahydroqu inoline rings and would allow their further functionalization to access more complex target molecules

Asymmetric syntheses of 3,4-disubstituted tetrahydroquinoline derivatives using (+)- sparteine-mediated electrophilic substitution

Energy Technology Data Exchange (ETDEWEB)

Choi, Yun Soo; Kang, Kyoung Hee; Park, Yong Sun [Dept. of Chemistry, Konkuk University, Seoul (Korea, Republic of)

2015-05-15

Tetrahydroquinolines bearing substituents are frequently found as a substructure in a number of alkaloids and natural products. Since their individual stereoisomers displays different biological activities, it is desirable to develop a highly stereoselective synthetic method for tetrahydroquinolines. While some progress has recently been made toward the development of asymmetric synthetic methods for tetrahydroquinolines, it is still a challenging topic in organic synthesis. In order to investigate the source of diastereoselection attained in the substitution reaction with a racemic epoxide, we examined the substitution of 2 with an excess amount of racemic p-chlorophenyl-substituted oxirane. We have developed a novel method for the asymmetric synthesis of trans-3,4-diaryl-substituted tetrahy- droquinolines from ortho-substituted N-pivaloyl anilines. The enantioselective process includes (+)-sparteine-mediated stereoselective lithiati on, kinetic resolution of epoxides in substitution, and stereospecific Mitsu nobu cyclization as the key reactions. The simple protocol can provide highly functionalized tetrahydroqu inoline rings and would allow their further functionalization to access more complex target molecules.

Ca{sup 2+} ion sensing by a piperidin-4-one derivative and the effect of β-cyclodextrin complexation on the sensing

Energy Technology Data Exchange (ETDEWEB)

Sumithra, M.; Sivaraj, R.; Selvan, G. Tamil; Selvakumar, P. Mosae; Enoch, Israel V.M.V., E-mail: drisraelenoch@gmail.com

2017-05-15

In this paper, we report the turn-on fluorescence based Ca{sup 2+} ion sensing by an anthracene piperidin-4-one derivative. The compound is obtained using a simple two step synthesis. The compound is characterized using NMR and mass spectral methods. The host-guest complex formation of the compound with β-cyclodextrin is prepared and characterized using fluorescence and 2D ROESY spectroscopy. The compound forms the inclusion complex with a 1:1 stoichiometry. The structure of the host-guest complex is proposed. The Ca{sup 2+} ion selectivity of the compound in its free form and cyclodextrin-bound forms are studied. In both the forms, the piperidin-4-one derivative senses Ca{sup 2+} and in the case of the cyclodextrin encapsulated form it shows a better competitive binding of Ca{sup 2+} in the presence of other metal ions. - Highlights: •An anthracene iminoderivative of 3-methyl-2,6-diphenylpiperidin-4-one is synthesized. •The anthracene moiety of the compound is encapsulated by β-Cyclodextrin. •The compound senses Ca{sup 2+} ion both in water and β-CD media. •β-CD molecule does not interrupt the Ca{sup 2+} ion binding.

Bibliographies on radiation chemistry. 9. Metal ions and complexes. Part A: Cobalt, rhodium, iridium

Energy Technology Data Exchange (ETDEWEB)

Hoffman, M Z; Ross, A B

1986-01-01

The one-electron oxidation and reduction of metal ions and complexes can yield species in unusual oxidation states, and ligand-radicals coordinated to the central metal. These often unstable species can be mechanistically important intermediates in thermal, photochemical, and electrochemical reactions involving metal-containing substances. Their generation via radiolysis provides an alternate means of characterizing them using kinetic and spectroscopic techniques. We hope these bibliographies on the radiation chemistry of metal ions and complexes, presented according to periodic groups, will prove useful to researchers in metallo-redox chemistry. These bibliographies contain only primary literature sources; reviews are not included. However, a list of general review articles on the radiation chemistry of metal ions and complexes is presented here in the first section which covers cobalt, rhodium and iridium, Group 9 in the new IUPAC notation. Additional parts of the bibliography are planned, covering other periodic groups. Part A of the bibliography was prepared by a search of the Radiation Chemistry Data Center Bibliographic Data Base (RCDCbib) through January 1986 for papers on rhodium, iridium and cobalt compounds, and radiolysis (both continuous and pulsed). Papers in which the use of metal compounds was incidental to the primary objective of the study were excluded. Excluded also were publications in unrefereed and obscure sources such as meeting proceedings, internal reports, dissertations, and patents. The majority of the studies in the resultant compilation deal with experiments performed on solutions, mainly aqueous, although a substantial fraction is devoted to solid-state esr measurements. The references are listed in separate sections for each of the metals, and are presented in approximate chronological order.

Peel Region TransHelp's experience

Energy Technology Data Exchange (ETDEWEB)

NONE

2009-09-15

TransHelp was founded in the Peel Region of Ontario in 1981 to provide paratransit service to individuals unable to use conventional transit. The TransHelp vehicle fleet consists of 40 buses that make over 220,000 one way trips annually. Each vehicle has a typical life span of between 375,000 and 425,000 km. TransHelp vehicles spend much of their time idling in emissions-sensitive areas, such as outside hospitals. In order to reduce fuel costs, TransHelp adopted the use of propane to fuel its vehicles. However, difficulties were experienced with this technology, particularly on V-10 engines where increased maintenance was a problem. SFI Technologies Inc. provided a solution with their SEQUIN System which allows seamless transitioning between gasoline and propane under all conditions without any operator involvement in fuel selection. The technology favours propane as the fuel of choice and automatically switches between propane and gasoline based on the ideal conditions at the time of operation. The technology has received certification from the Environmental Protection Agency in the United States and the Canadian Standards Association. The use of the SEQUIN System has proven to successful for TransHelp. It has allowed the use of propane to be continued, meaning that vehicle emissions are greatly reduced relative to gasoline or diesel fuelled vehicles. TransHelp has realized a fuel savings of 15-20 per cent over gasoline and receives an additional federal transit rebate of 15 per cent for the conversion cost.

ION ACOUSTIC TURBULENCE, ANOMALOUS TRANSPORT, AND SYSTEM DYNAMICS IN HALL EFFECT THRUSTERS

Science.gov (United States)

2017-06-30

NUMBER (Include area code) 30 June 2017 Briefing Charts 26 May 2017 - 30 June 2017 ION ACOUSTIC TURBULENCE, ANOMALOUS TRANSPORT, AND SYSTEM DYNAMICS ...Robert Martin N/A ION ACOUSTIC TURBULENCE, ANOMALOUS TRANSPORT, AND SYSTEM DYNAMICS IN HALL EFFECT THRUSTERS Robert Martin1, Jonathan Tran2 1AIR FORCE...Approved for Public Release; Distribution is Unlimited. PA# 17394 1 / 13 OUTLINE 1 INTRODUCTION 2 TRANSPORT 3 DYNAMIC SYSTEM 4 SUMMARY AND CONCLUSION

Metal ion-assisted self-assembly of complexes for controlled and sustained release of minocycline for biomedical applications

International Nuclear Information System (INIS)

Zhang, Zhiling; Wang, Zhicheng; Nong, Jia; Nix, Camilla A; Zhong, Yinghui; Ji, Hai-Feng

2015-01-01

This study reports the development of novel drug delivery complexes self-assembled by divalent metal ion-assisted coacervation for controlled and sustained release of a hydrophilic small drug molecule minocycline hydrochloride (MH). MH is a multifaceted agent that has demonstrated therapeutic effects in infection, inflammation, tumor, as well as cardiovascular, renal, and neurological disorders due to its anti-microbial, anti-inflammatory, and cytoprotective properties. However, the inability to translate the high doses used in experimental animals to tolerable doses in human patients limits its clinical application. Localized delivery can potentially expose the diseased tissue to high concentrations of MH that systemic delivery cannot achieve, while minimizing the side effects from systemic exposure. The strong metal ion binding-assisted interaction enabled high drug entrapment and loading efficiency, and stable long term release for more than 71 d. Released MH demonstrated potent anti-biofilm, anti-inflammatory, and neuroprotective activities. Furthermore, MH release from the complexes is pH-sensitive as the chelation between minocycline and metal ions decreases with pH, allowing ‘smart’ drug release in response to the severity of pathology-induced tissue acidosis. This novel metal ion binding-mediated drug delivery mechanism can potentially be applied to other drugs that have high binding affinity for metal ions and may lead to the development of new delivery systems for a variety of drugs. (paper)

Trans Women Doing Sex in San Francisco.

Science.gov (United States)

Williams, Colin J; Weinberg, Martin S; Rosenberger, Joshua G

2016-10-01

This research investigates the sexuality of trans women (individuals who were assigned male status at birth who currently identify as women), by focusing on the "bodily techniques" (Crossley, 2006) they use in "doing" sexuality. The "doing sexuality" framework not only is modeled after the "doing gender" approach of West and Zimmerman (1987), but also utilizes the idea of "sexual embodiment" to emphasize the agency of trans women as they conceptualize and organize their sexuality in a socially recognized way. This is often difficult as they confront discrimination from medical and legal professionals as well as intimate partners who may find it difficult to adapt to the trans woman's atypical body and conception of gender. However, with a study group of 25 trans women from San Francisco, we found the study participants to be adept at overcoming such hurdles and developing techniques to "do" their sexuality. At the same time, we found trans women's agency constrained by the erotic habitus (Green, 2008) of the wider society. The interplay between innovation and cultural tradition provides an opportunity to fashion a more general model of "doing" sexuality.

Primary photochemical processes for Pt(iv) diazido complexes prospective in photodynamic therapy of tumors.

Science.gov (United States)

Shushakov, Anton A; Pozdnyakov, Ivan P; Grivin, Vjacheslav P; Plyusnin, Victor F; Vasilchenko, Danila B; Zadesenets, Andrei V; Melnikov, Alexei A; Chekalin, Sergey V; Glebov, Evgeni M

2017-07-25

Diazide diamino complexes of Pt(iv) are considered as prospective prodrugs in oxygen-free photodynamic therapy (PDT). Primary photophysical and photochemical processes for cis,trans,cis-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] and trans,trans,trans-[Pt(N 3 ) 2 (OH) 2 (NH 3 ) 2 ] complexes were studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The process of photolysis is multistage. The first stage is the photosubstitution of an azide ligand to a water molecule. This process was shown to be a chain reaction involving redox stages. Pt(iv) and Pt(iii) intermediates responsible for the chain propagation were recorded using ultrafast kinetic spectroscopy and nanosecond laser flash photolysis. The mechanism of photosubstitution is proposed.

Study of ruthenium complexation by 22' bipyridine in nitric aqueous solutions

International Nuclear Information System (INIS)

Alozy, J.P.

1982-01-01

Substitution of the NO 3- , NO + ions of RuNO(NO 3 )x.yH 2 Osup((3-x)+) complexes by 22'bipyridine (bipy) in nitric aqueous solution was studied by spectrophotometry. In the absence of reducing agent we observe the species RuNO(bipy)(NO3)sub(z)sup((3-z)+) and RuNO(bipy) 2 NO 3 2 + . Most reducing agents give rise to the RuNO(bipy) 2 NO 3 2 + + e → RuNO(bipy) 2 NO 3+ reaction. The oxydation potential of the reversible couple RuNO(bipy) 2 NO 3 2 + /RuNO(bipy) 2 NO 3+ was measured by cyclic voltamperometry at the platinum electrode. Its value is + 1.02 V/NHE. Substitution of NO + ions by a (bipy) molecule is only possible in the presence of reducing agents of apparent formal potential below + 0.5 V/NHE, and anti-nitrite agents are also needed; these two functions can be fulfilled by hydrazine and ascorbic acid. The presence of HSO 3 NH 2 was necessary to obtain the substitution of NO + and NO 3- by bipy during electrochemical reductions. The intermediate complexes RuNO(bipy) 2 NO 3 2 + and RuNO(bipy) 2 NO 3+ probably include two bipy molecules in the trans position whereas RuNO(bipy) 2 2 + complexes, where the sixth coordination position is occupied by π donors stronger than NO 3- , have two bipy molecules in the cis position [fr

Trans-Z-source Neutral Point Clamped inverter

DEFF Research Database (Denmark)

Mo, W.; Loh, P. C.; Li, D.

2012-01-01

Transformer based Z-source (trans-Z-source) inverters are recently proposed by extending the traditional Z-source inverter with higher buck-boost capability as well as reducing the passive components at the same time. Multi-Level Z-source inverters are single-stage topological solutions used...... for buck-boost energy conversion with all the favourable advantages of multi-level switching retained. This paper presents three-level trans-Z-source Neutral Point Clamped (NPC) inverter topology, which achieves both the advantages of trans-Z-source and three-level NPC inverter configuration. With proper...... modulation scheme, the three-level trans-Z-source inverter can function with minimum of six device commutations per half carrier cycle (same as the traditional buck NPC inverter), while maintaining to produce the designed volt-sec average and inductive voltage boosting at ac output terminals. The designed...

trans-Bis(methanol-κObis(quinoline-2-carboxylato-κ2N,Omanganese(II

Directory of Open Access Journals (Sweden)

Lucjan B. Jerzykiewicz

2008-11-01

Full Text Available The title compound, [Mn(C10H6NO22(CH4O2], was obtained unintentionally as the product of an attempt to synthesize a polynuclear carboxylate bridged manganese(III/IV complex, using methanol to reduce the permanganate ion. The molecule is centrosymmetric; the pairs of equivalent ligands coordinate trans to each other in a distorted octahedral geometry. Intramolecular C—H...O bonds lying in the equatorial plane stabilize the molecule. In the crystal, molecules are linked by O—H...O and C—H...O hydrogen bonds, creating a three-dimensional supramolecular structure. π–π and C—H...π interactions are also observed. The dihedral angle and centroid-to-centroid distance between the pyridine ring (A and the benzene ring (Bi of a symmetrically related molecule [symmetry code: (i −1 − x, −y, −z] are 1.27 (11° and 3.974 (2 Å, respectively. For the C—H...π interactions, the relevant distances and angles are: C...Cg[Aii] = 3.643 (2 Å, H...Cg[Aii] = 2.750 (2 Å and C—H...Cg[Aii] = 155 (1° [symmetry code: (ii x, −1 + y, z].

Repair Activity of trans-Resveratrol toward 2'-Deoxyguanosine Radicals.

Science.gov (United States)

Cheng, Xing; An, Ping; Li, Shujin; Zhou, Liping

2018-04-26

In the present study, the repair activity of trans-resveratrol toward 2'-deoxyguanosine (dGuo) radicals in polar and nonpolar solvents was studied using density functional theory. The hydrogen transfer/proton coupled electron transfer and single electron transfer (SET) mechanisms between trans-resveratrol and dGuo-radicals were considered. Taking into consideration the molar fraction of neutral trans-resveratrol (ROH) and anionic trans-resveratrol (RO - ), the overall rate constants for repairing dGuo-radicals by trans-resveratrol are 9.94 × 10 8 and 2.01 × 10 9 dm 3 mol -1 s -1 in polar and nonpolar solvents, respectively, and the overall rate constant of repairing cation radical (dGuo •+ ) by trans-resveratrol via an SET mechanism is 7.17 × 10 9 dm 3 mol -1 s -1 . The repair activity of RO - toward dGuo-radicals is better than that of ROH, but the repair activity of ROH toward dGuo •+ is better than that of RO - . Unfortunately, neither ROH nor RO - can repair the 2'-deoxyribose radicals of dGuo. It can therefore be concluded that trans-resveratrol is an effective antioxidant for repairing base radicals of dGuo and dGuo •+ . The study can help us understand the repair activity of trans-resveratrol toward dGuo radicals.

(C6H16N2)Zn3(HPO3)4H2O: a new layered zinc phosphite templated by diprotonated trans-1,4-diaminocyclohexane

International Nuclear Information System (INIS)

Wang Yu; Yu Jihong; Li Yi; Du Yu; Xu Ruren; Ye Ling

2003-01-01

Employing trans-1,4-diaminocyclohexane (trans-1,4-DACH) as a template, a new two-dimensional layered zinc phosphite (C 6 H 16 N 2 )Zn 3 (HPO 3 ) 4 H 2 O (1) has been prepared hydrothermally. Single-crystal X-ray diffraction analysis shows that it crystallizes in the monoclinic space group P2 1 /n with a=10.458(2) A, b=14.720(3) A, c=13.079(3) A, β=97.93(3) deg. , V=1994.1(7) A 3 , Z=4, R 1 =0.0349 (I>2σ(I)) and wR 2 =0.0605 (all data). The inorganic layer is built up by alternation of ZnO 4 tetrahedra and HPO 3 pseudo pyramids forming a 4.6.8-net. The sheet is featured by a series of capped six-membered rings. The diprotonated trans-1,4-DACH molecules reside in the interlayer region and interact with the inorganic network through H-bonds

Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

KAUST Repository

Di Giovanni, Carlo; Poater, Albert; Benet-Buchholz, Jordi; Cavallo, Luigi; Solà , Miquel; Llobet, Antoni A.

2014-01-01

Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dinuclear ru-aqua complexes for selective epoxidation catalysis based on supramolecular substrate orientation effects

KAUST Repository

Di Giovanni, Carlo

2014-03-03

Ru-aqua complex {[RuII(trpy)(H2O)] 2(μ-pyr-dc)}+ is a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes. High turnover numbers (TNs), up to 17000, and turnover frequencies (TOF), up to 24120 h-1 (6.7 s -1), have been obtained using PhIO as oxidant. This species presents an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides. In addition, it shows different reactivity to cis and trans olefins due to a substrate orientation supramolecular effect transmitted by its ligand scaffold. This effect together with the impressive reaction rates are rationalized using electrochemical techniques and DFT calculations. A new Ru-aqua complex that behaves as a powerful epoxidation catalyst for a wide range of linear and cyclic alkenes is reported. High turnover numbers and frequencies are obtained by using PhIO as oxidant. The complex shows an outstanding stereospecificity for both cis and trans olefins towards the formation of their corresponding cis and trans epoxides (see figure). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

NMR spectroscopic studies of a TAT-derived model peptide in imidazolium-based ILs: influence on chemical shifts and the cis/trans equilibrium state.

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Wiedemann, Christoph; Ohlenschläger, Oliver; Mrestani-Klaus, Carmen; Bordusa, Frank

2017-09-13

NMR spectroscopy was used to study systematically the impact of imidazolium-based ionic liquid (IL) solutions on a TAT-derived model peptide containing Xaa-Pro peptide bonds. The selected IL anions cover a wide range of the Hofmeister series of ions. Based on highly resolved one- and two-dimensional NMR spectra individual 1 H and 13 C peptide chemical shift differences were analysed and a classification of IL anions according to the Hofmeister series was derived. The observed chemical shift changes indicate significant interactions between the peptide and the ILs. In addition, we examined the impact of different ILs towards the cis/trans equilibrium state of the Xaa-Pro peptide bonds. In this context, the IL cations appear to be of exceptional importance for inducing an alteration of the native cis/trans equilibrium state of Xaa-Pro bonds in favour of the trans-isomers.

Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

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Yedil Yergozhin

2013-05-01

Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

The importance of trans-generational effects in Lepidoptera.

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Woestmann, Luisa; Saastamoinen, Marjo

2016-10-01

The importance of trans-generational effects in shaping an individuals' phenotype and fitness, and consequently even impacting population dynamics is increasingly apparent. Most of the research on trans-generational effects still focuses on plants, mammals, and birds. In the past few years, however, increasing number of studies, especially on maternal effects, have highlighted their importance also in many insect systems. Lepidoptera, specifically butterflies, have been used as model systems for studying the role of phenotypic plasticity within generations. As ectotherms, they are highly sensitive to environmental variation, and indeed many butterflies show adaptive phenotypic plasticity in response to environmental conditions. Here, we synthesize what is known about trans-generational effects in Lepidoptera, compile evidence for different environmental cues that are important drivers of trans-generational effects, and point out which offspring traits are mainly impacted. Finally, we emphasize directions for future research that are needed for better understanding of the adaptive nature of trans-generational effects in Lepidoptera in particular, but potentially also in other organisms.

Determination and structural correlation of the pKa values of p-substituted trans-2,3-epoxy-4-oxo-4-phenylbutanoic acids

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I. JURANIC

2000-11-01

Full Text Available The pKa values for a series of eight p-substituted trans-2,3-epoxy-4-phenyl butanoic acids (p-substituted trans-b-aroylepoxyacrylic acids have been determined potentiometrically in aqueous media at 25°C at an ionic strength of 0.1 mol/dm3 (NaCl. The transmission of polar effects from the substituents on the phenyl nucleus to the carboxylic group through the side chain involving a carbonyl group and an epoxide ring was investigated. The pKa values were correlated with structure using the Hammett, Taft and Yukawa-Tsuno approaches. The Hammett r constant (0.34 was compared with analogue values for structurally similar acids.

The complete genome sequence of Cupriavidus metallidurans strain CH34, a master survivalist in harsh and anthropogenic environments.

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Paul J Janssen

Full Text Available Many bacteria in the environment have adapted to the presence of toxic heavy metals. Over the last 30 years, this heavy metal tolerance was the subject of extensive research. The bacterium Cupriavidus metallidurans strain CH34, originally isolated by us in 1976 from a metal processing factory, is considered a major model organism in this field because it withstands milli-molar range concentrations of over 20 different heavy metal ions. This tolerance is mostly achieved by rapid ion efflux but also by metal-complexation and -reduction. We present here the full genome sequence of strain CH34 and the manual annotation of all its genes. The genome of C. metallidurans CH34 is composed of two large circular chromosomes CHR1 and CHR2 of, respectively, 3,928,089 bp and 2,580,084 bp, and two megaplasmids pMOL28 and pMOL30 of, respectively, 171,459 bp and 233,720 bp in size. At least 25 loci for heavy-metal resistance (HMR are distributed over the four replicons. Approximately 67% of the 6,717 coding sequences (CDSs present in the CH34 genome could be assigned a putative function, and 9.1% (611 genes appear to be unique to this strain. One out of five proteins is associated with either transport or transcription while the relay of environmental stimuli is governed by more than 600 signal transduction systems. The CH34 genome is most similar to the genomes of other Cupriavidus strains by correspondence between the respective CHR1 replicons but also displays similarity to the genomes of more distantly related species as a result of gene transfer and through the presence of large genomic islands. The presence of at least 57 IS elements and 19 transposons and the ability to take in and express foreign genes indicates a very dynamic and complex genome shaped by evolutionary forces. The genome data show that C. metallidurans CH34 is particularly well equipped to live in extreme conditions and anthropogenic environments that are rich in metals.

Spectrophotometric Determination of Gemifloxacin Mesylate in Pharmaceutical Formulations Through Ion-Pair Complex Formation

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Marothu Vamsi Krishna

2008-01-01

Full Text Available Four simple and sensitive ion-pairing spectrophotometric methods have been described for the assay of gemifloxacin mesylate (GFX either in pure form or in pharmaceutical formulations. The developed methods involve formation of colored chloroform extractable ion-pair complexes of the drug with safranin O (SFN O and methylene blue (MB in basic medium; Napthol blue 12BR (NB 12BR and azocaramine G (AG in acidic medium. The extracted complexes showed absorbance maxima at 525, 650, 620 and 540 nm for SFN O, MB, NB 12BR and AG, respectively.Beer's law is obeyed in the concentration ranges 3-15, 4-20, 2-10 and 2-10 μg/mL with molar absorptivity of 2.81 × 104, 2.20 x 104, 4.02 × 104 and 4.15 × 104 L mole−1 cm−1 and relative standard deviation of 0.077, 0.104, 0.080 and 0.103% for SFN O, MB, NB 12BR and AG, respectively. These methods have been successfully applied for the assay of drug in pharmaceutical formulations. No interference was observed from common pharmaceutical adjuvants. Results of analysis were validated statistically and through recovery studies.

Fighting for Trans* Kids: Academic Parent Activism in the 21st Century

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Kimberley Manning

2015-12-01

Full Text Available In this article we explore some of the affective and ethical dimensions that we have faced as parent academic-activists seeking to understand and undo some of the structural transphobia that currently exists in Canadian society.  Informed by critical feminist, critical race and black feminist thought, trans* scholarship, queer theory, and anti-oppression analysis, we discuss how our academic-activism assumes complex configurations of privilege and vulnerability.

Sexualidade e experiências trans: do hospital à alcova Sexuality and trans experiences: from the hospital to the bedroom

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Berenice Bento

2012-10-01

Full Text Available Depois dos estudos das masculinidades, não é possível pensar a produção das identidades de gênero sem referenciá-las ao caráter relacional. Esta mudança deveu-se à incorporação da perspectiva relacional nesse campo de estudos e à crítica ao conceito de gênero assentado em uma suposta natureza feminina e masculina para construir as interpretações sobre o lugar dos corpos da ordem de gênero. Os objetivos desse artigo são: 1 apontar como um determinado conceito de gênero pode visibilizar múltiplas expressões de gênero, a exemplo das identidades trans (transexuais, travestis, cross dress, drag queen, drag king, transgêneros ou invisibilizá-las e contribuir para sua patologização. O segundo objetivo será apresentar narrativas de homens trans e de mulheres trans, que nos contarão suas vivências sexuais. Os saberes médicos-psi advogam a inexistência de sexualidade em seus corpos, sendo este um dos indicadores para produção do diagnóstico de transexua­lidade. Tentarei argumentar que a base teórica que sustenta a patologização das identidades trans e a afirmação que as pessoas trans são assexuadas tem como fundamento uma concepção que atrela e condiciona as identidades de gênero às estruturas biológicas.In the aftermath of studies on masculinity, it is impossible to consider the production of gender identities without linking them to the relationship aspect. This change was due to the incorporation of the relationship perspective in this field of study and criticism of the concept of gender founded upon an alleged concept of femininity and masculinity to create interpretations of the place of bodies in the gender order. The objectives of this paper are: 1 to show how a given concept of gender can render multiple expressions of gender visible, like the trans identities (transsexuals, transvestites, cross dressers, drag queens, drag kings, transgenders or sublimate them and contribute to their pathologization

Tunicate-Inspired Gallic Acid/Metal Ion Complex for Instant and Efficient Treatment of Dentin Hypersensitivity.

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Prajatelistia, Ekavianty; Ju, Sung-Won; Sanandiya, Naresh D; Jun, Sang Ho; Ahn, Jin-Soo; Hwang, Dong Soo

2016-04-20

Dentin hypersensitivity is sharp and unpleasant pains caused by exposed dentinal tubules when enamel outside of the tooth wears away. The occlusion of dentinal tubules via in situ remineralization of hydroxyapatite is the best method to alleviate the symptoms caused by dentin hypersensitivity. Commercially available dental desensitizers are generally effective only on a specific area and are relatively toxic, and their performance usually depends on the skill of the clinician. Here, a facile and efficient dentin hypersensitivity treatment with remarkable aesthetic improvement inspired by the tunicate-self-healing process is reported. As pyrogallol groups in tunicate proteins conjugate with metal ions to heal the torn body armor of a tunicate, the ingenious mechanism by introducing gallic acid (GA) as a cheap, abundant, and edible alternative to the pyrogallol groups of the tunicate combined with a varied daily intake of metal ion sources is mimicked. In particular, the GA/Fe(3+) complex exhibits the most promising results, to the instant ≈52% blockage in tubules within 4 min and ≈87% after 7 d of immersion in artificial saliva. Overall, the GA/metal ion complex-mediated coating is facile, instant, and effective, and is suggested as an aesthetic solution for treating dentin hypersensitivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microwave synthesis, spectral, thermal, and antimicrobial activities of some transition metal complexes involving 5-bromosalicylaldehyde moiety

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Rajendra K. Jain

2012-07-01

Full Text Available The coordination complexes of Co(II, Ni(II and Cu(II derived from 5-bromosalicylidene-3,4-dimethylaniline (BSMA and 5-bromosalicylidene-3,4-dichloroaniline (BSCA have been synthesized by conventional as well as microwave methods. These compounds have been characterized by elemental analysis, FT-IR, molar conductance, electronic spectra, 1H-NMR, FAB-mass, ESR, magnetic susceptibility, electrical conductivity and thermal analysis. The complexes are coloured and stable in air. Analytical data revealed that all the complexes exhibited 1:2 (metal: ligand ratio with coordination number 4 or 6. IR data shows that the ligand coordinates with the metal ions in a bidentate manner through the phenolic oxygen and azomethine nitrogen. FAB-mass and thermal data show degradation pattern of the complexes. Solid state electrical conductivity studies reflect semiconducting nature of the complexes. The Schiff base and metal complexes show a good activity against the Gram-positive bacteria; Staphylococcus aureus and Gram-negative bacteria; Escherichia coli and fungi Aspergillus niger and Candida albicans.

Silver release and antimicrobial properties of PMMA films doped with silver ions, nano-particles and complexes

Energy Technology Data Exchange (ETDEWEB)

Lyutakov, O., E-mail: lyutakoo@vscht.cz [Department of Solid State Engineering, Institute of Chemical Technology, Prague (Czech Republic); Goncharova, I. [Department of Analytical Chemistry, Institute of Chemical Technology, Prague (Czech Republic); Rimpelova, S. [Department of Biochemistry and Microbiology, Institute of Chemical Technology, Prague (Czech Republic); Kolarova, K.; Svanda, J.; Svorcik, V. [Department of Solid State Engineering, Institute of Chemical Technology, Prague (Czech Republic)

2015-04-01

Materials prepared on the base of bioactive silver compounds have become more and more popular due to low microbial resistance to silver. In the present work, the efficiency of polymethylmethacrylate (PMMA) thin films doped with silver ions, nanoparticles and silver–imidazole polymer complex was studied by a combination of AAS, XPS and AFM techniques. The biological activities of the proposed materials were discussed in view of the rate of silver releasing from the polymer matrix. Concentrations of Ag active form were estimated by its ability to interact with L-cysteine using electronic circular dichroism spectroscopy. Rates of the released silver were compared with the biological activity in dependence on the form of embedded silver. Antimicrobial properties of doped polymer films were studied using two bacterial strains: Staphylococcus epidermidis and Escherichia coli. It was found that PMMA films doped with Ag{sup +} had greater activity than those doped with nanoparticles and silver–imidazole polymeric complexes. However, the antimicrobial efficiency of Ag{sup +} doped films was only short-term. Contrary, the antimicrobial activity of silver–imidazole/PMMA films increased in time of sample soaking. - Highlights: • PMMA thin films doped with silver ions, nanoparticles (AgNPs) and silver–imidazole helical complexes (AgIm) were studied. • Silver release from doped polymer films and its biological activity were estimated. • Antimicrobial properties of doped polymer films were also studied. • Ag ions doped films showed the strongest antimicrobial activity, which quickly disappeared. • AgIm and AgNPs doped films showed more stable antimicrobial properties. • AgIm complexes conserve their structure after addition into polymer and after leaching.

Silver release and antimicrobial properties of PMMA films doped with silver ions, nano-particles and complexes

International Nuclear Information System (INIS)

Lyutakov, O.; Goncharova, I.; Rimpelova, S.; Kolarova, K.; Svanda, J.; Svorcik, V.

2015-01-01

Materials prepared on the base of bioactive silver compounds have become more and more popular due to low microbial resistance to silver. In the present work, the efficiency of polymethylmethacrylate (PMMA) thin films doped with silver ions, nanoparticles and silver–imidazole polymer complex was studied by a combination of AAS, XPS and AFM techniques. The biological activities of the proposed materials were discussed in view of the rate of silver releasing from the polymer matrix. Concentrations of Ag active form were estimated by its ability to interact with L-cysteine using electronic circular dichroism spectroscopy. Rates of the released silver were compared with the biological activity in dependence on the form of embedded silver. Antimicrobial properties of doped polymer films were studied using two bacterial strains: Staphylococcus epidermidis and Escherichia coli. It was found that PMMA films doped with Ag + had greater activity than those doped with nanoparticles and silver–imidazole polymeric complexes. However, the antimicrobial efficiency of Ag + doped films was only short-term. Contrary, the antimicrobial activity of silver–imidazole/PMMA films increased in time of sample soaking. - Highlights: • PMMA thin films doped with silver ions, nanoparticles (AgNPs) and silver–imidazole helical complexes (AgIm) were studied. • Silver release from doped polymer films and its biological activity were estimated. • Antimicrobial properties of doped polymer films were also studied. • Ag ions doped films showed the strongest antimicrobial activity, which quickly disappeared. • AgIm and AgNPs doped films showed more stable antimicrobial properties. • AgIm complexes conserve their structure after addition into polymer and after leaching

Solvent extraction of anionic chelate complexes of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) with 2-thenoyltrifluoroacetone as ion-pairs with tetrabutylammonium ions

International Nuclear Information System (INIS)

Noro, Junji; Sekine, Tatsuya.

1992-01-01

The solvent extraction of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) in 0.1 mol dm -3 sodium nitrate solutions with 2-thenoyltrifluoroacetone (Htta) in the absence and presence of tetrabutylammonium ions (tba + ) into carbon tetrachloride was measured. The extraction of lanthanum(III), europium(III), and lutetium(III) was greatly enhanced by the addition of tba + ; this could be explained in terms of the extraction of a ternary complex, M(tta) 4 - tba + . However, the extractions of scandium(III) and indium(III) were nearly the same when tba + was added. The data were treated on the basis of the formation equilibrium of the ternary complex from the neutral chelate, M(tta) 3 , with the extracted ion-pairs of the reagents, tta - tba + , in the organic phase. It was concluded that the degree of association of M(tta) 3 with the ion-pair, tta - tba + , is greater in the order La(tta) 3 ≅ Eu(tta) 3 > Lu(tta) 3 , or that the stability of the ternary complex in the organic phase is higher in the order La(tta) 4 - tba + ≅ Eu(tta) 4 - tba + > Lu(tta) 4 - tba + . This is similar to those of adduct metal chelates of Htta with tributylphosphate (TBP) in synergistic extraction systems. (author)

Complex formation ions calcium with macromolecules pectin

International Nuclear Information System (INIS)

Khalikova, M.D.; Avloev, Kh.Kh.; Muhiddinov, Z.K.

2005-01-01

In clause the mechanism of sorption of ions of calcium by macromolecules of pectin is opened. Is shown, that the linkage of ions of calcium descends on acid bunches of pectin, and process carries cooperative character

Omega-6 and trans fatty acids in blood cell membranes: a risk factor for acute coronary syndromes?

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Block, Robert C; Harris, William S; Reid, Kimberly J; Spertus, John A

2008-12-01

Although fatty acid intake has been associated with risk of coronary disease events, the association between blood omega-6 and trans fatty acids (FAs) at the time of an acute coronary syndrome (ACS) is unknown. The relationship of blood FA composition to ACS was analyzed in 768 incident cases and 768 controls (matched on age, sex, and race). Compared to controls, ACS cases' blood cell membrane content of linoleic acid was 13% lower (P 3 times the odds for being a case (odds ratio [OR] 3.23, 95% confidence interval [CI] 2.63-4.17). The relationship of arachidonic acid to ACS was U shaped; compared to the first quartile of arachidonic acid, the ORs for case status in the second, third, and fourth quartiles were 0.73 (95% CI 0.47-1.13), 0.65 (95% CI 0.41-1.04), and 2.32 (95% CI 1.39-3.90), respectively. The OR for a 1-SD increase in trans oleic acid was 1.24 (95% CI 1.06-1.45), and for trans-trans linoleic acid, 1.1 (95% CI 0.93-1.30). All associations were independent of membrane omega-3 FA content. High blood levels of linoleic acid but low levels of trans oleic acid are inversely associated with ACS. The relationship of arachidonic acid to ACS appears more complex.

The peculiarity of animal complexes of chernozem

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O. V. Zhukov

2005-02-01

Full Text Available The genetic connection of animal complexes and soil cover is in the basis of diagnostic ability of animals to indicate and quantity assessment of soil processes. The ecoiGgical view and peculiarity of soil animal complexes has the most impotent value. The soil animal complexes of steppe and their trans-formation under artificial forest are discussed

trans-[Pt(BCat')Me(PCy3)2]: an experimental case study of reductive elimination processes in Pt-Boryls through associative mechanisms.

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Braunschweig, Holger; Bertermann, Rüdiger; Brenner, Peter; Burzler, Michael; Dewhurst, Rian D; Radacki, Krzysztof; Seeler, Fabian

2011-10-10

A stable trans-(alkyl)(boryl) platinum complex trans-[Pt(BCat')Me(PCy(3))(2)] (Cat'=Cat-4-tBu; Cy=cyclohexyl=C(6)H(11)) was synthesised by salt metathesis reaction of trans-[Pt(BCat')Br(PCy(3))(2)] with LiMe and was fully characterised. Investigation of the reactivity of the title compound showed complete reductive elimination of Cat'BMe at 80 °C within four weeks. This process may be accelerated by the addition of a variety of alkynes, thereby leading to the formation of the corresponding η(2) -alkyne platinum complexes, of which [Pt(η(2)-MeCCMe)(PCy(3))(2)] was characterised by X-ray crystallography. Conversion of the trans-configured title compound to a cis derivative remained unsuccessful due to an instantaneous reductive elimination process during the reaction with chelating phosphines. Treatment of trans-[Pt(BCat')Me(PCy(3))(2)] with Cat(2)B(2) led to the formation of CatBMe and Cat'BMe. In the course of further investigations into this reaction, indications for two indistinguishable reaction mechanisms were found: 1) associative formation of a six-coordinate platinum centre prior to reductive elimination and 2) σ-bond metathesis of B-B and C-Pt bonds. Mechanism 1 provides a straightforward explanation for the formation of both methylboranes. Scrambling of diboranes(4) Cat(2)B(2) and Cat'(2)B(2) in the presence of [Pt(PCy(3))(2)], fully reductive elimination of CatBMe or Cat'BMe from trans-[Pt(BCat')Me(PCy(3))(2)] in the presence of sub-stoichiometric amounts of Cat(2)B(2), and evidence for the reversibility of the oxidative addition of Cat(2)B(2) to [Pt(PCy(3))(2)] all support mechanism 2, which consists of sequential equilibria reactions. Furthermore, the solid-state molecular structure of cis-[Pt(BCat)(2)(PCy(3))(2)] and cis-[Pt(BCat')(2)(PCy(3))(2)] were investigated. The remarkably short B-B separations in both bis(boryl) complexes suggest that the two boryl ligands in each case are more loosely bound to the Pt(II) centre than in related bis

In-situ complex with by-product HCl and release chloride ions to dissolve aramid.