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91.
Rodica Cǎpriţǎ Adrian Cǎpriţǎ Ludovic Kurunczi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract The polyphosphates have the capacity of forming chelates with most of that metal cations[l]. Polyphosphatic complexes with trace- and macroelements art used as fodder additives for animals. In our experiments we studied the effect 01pyrophosphate (PP), tripolyphosphate (TPP) and hexametaphosphate (HMP), at different concentrations (0.909 mM, 1.8 I8 mM and 2.727 mM), on the enzymatic activity of carbonic anhydrase (CA), and the effect of polyphosphate chelates or the enzymatic activity of alkaline phosphatase (AP), both zincenzymes. The meta; ion, which can be dissociated in the presence of a chelating agent, is essential foi their catalytic activity 121. The presence of metal atoms as essential constituents of some enzymes, and the metal requirements of others for maximum activity, provide an obvious link between enzymatic reaction and coordination chemistry. 相似文献
92.
N. N. Medvedev V. P. Voloshin A. V. Kim A. V. Anikeenko A. Geiger 《Journal of Structural Chemistry》2013,54(2):271-288
This paper is a review of our recent computational studies of volumetric characteristics using computer models of dilute solutions. Partial molar volume (PMV) and its components are calculated for simple and complex molecules in water (methane, noble gases, surfactants, polypeptides). Advantages and disadvantages of various computational methods are discussed. It is proposed to use the Voronoi-Delaunay technique to determine the reasonable boundary between a solute molecule and solvent molecules and to identify the PMV components related to the molecule, the boundary layer, and the solvent. It is noted that the observed increase in PMV with temperature for large molecules is due to an increase in the volume of voids in the boundary layer, i.e., due to the “thermal volume.” In this case, the solvent gives a negative contribution to the PMV. In contrast, for simple molecules (methane), the contribution from the solvent is positive and is the main factor in the increase in the PMV, which is associated with a specific change in water structure around a spherical hydrophobic particle outside the boundary layer. For surfactant molecules, the contribution from the solvent changes sign (from negative to positive) with increasing temperature. 相似文献
93.
Adrian Adamski Andrzej Biadasz Krzysztof Domieracki Marek Andrzej Kojdecki Dominik Paukszta Dominika Uryzaj 《Liquid crystals》2013,40(4):456-462
Liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) forms characteristic dendritic or flower-like structures at room temperature when it is deposited on a hydrophilic glass substrate using the zone-casting technique. It was found that such unique structures were not possible to be created simply by recrystallisation of this dye from a liquid-crystalline columnar phase. On the basis of the observations using a confocal microscope and the study of wide angle X-ray scattering (WAXS) as well as the analysis of the absorption and fluorescence spectra, some conclusions, concerning the molecular organisation in the dendritic structure, are drawn. Based on the research, one can assume that the dendrites are formed by columnar molecular aggregates with the column axes parallel to the substrate. Such an organisation of the molecules can be interesting from the point of view of organic electronics. 相似文献
94.
Dr. Paul Smart Dr. Charles A. Mason Jason R. Loader Dr. Anthony J. H. M. Meijer Prof. Alastair J. Florence Dr. Kenneth Shankland Dr. Ashleigh J. Fletcher Dr. Stephen P. Thompson Dr. Michela Brunelli Dr. Adrian H. Hill Prof. Lee Brammer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3552-3557
95.
Nataliya A. Samoylova Nikita M. Belov Victor A. Brotsman Dr. Ilya N. Ioffe Dr. Natalia S. Lukonina Dr. Vitaliy Yu. Markov Dr. Adrian Ruff Alexey V. Rybalchenko Paul Schuler Olesya O. Semivrazhskaya Prof. Dr. Bernd Speiser Prof. Dr. Sergey I. Troyanov Prof. Dr. Tatiana V. Magdesieva Dr. Alexey A. Goryunkov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(52):17969-17979
Novel difluoromethylenated [70]fullerene derivatives, C70(CF2)n (n=1–3), were obtained by the reaction of C70 with sodium difluorochloroacetate. Two major products, isomeric C70(CF2) mono‐adducts with [6,6]‐open and [6,6]‐closed configurations, were isolated and their homofullerene and methanofullerene structures were reliably determined by a variety of methods that included X‐ray analysis and high‐level spectroscopic techniques. The [6,6]‐open isomer of C70(CF2) constitutes the first homofullerene example of a non‐hetero [70]fullerene derivative in which functionalisation involves the most reactive bond in the polar region of the cage. Voltammetric estimation of the electron affinity of the C70(CF2) isomers showed that it is substantially higher for the [6,6]‐open isomer (the 70‐electron π‐conjugated system is retained) than the [6,6]‐closed form, the latter being similar to the electron affinity of pristine C70. In situ ESR spectroelectrochemical investigation of the C70(CF2) radical anions and DFT calculations of the hyperfine coupling constants provide evidence for the first example of an inter‐conversion between the [6,6]‐closed and [6,6]‐open forms of a cage‐modified fullerene driven by an electrochemical one‐electron transfer. Thus, [6,6]‐closed C70(CF2) constitutes an interesting example of a redox‐switchable fullerene derivative. 相似文献
96.
Andreia Alves Agnieszka Kucharska Claudio Erratico Fuchao Xu Elly Den Hond Gudrun Koppen Guido Vanermen Adrian Covaci Stefan Voorspoels 《Analytical and bioanalytical chemistry》2014,406(17):4063-4088
Human biomonitoring (HBM) is a scientific technique that allows us to assess whether and to what extent environmental pollutants enter humans. We review here the current HBM efforts for organophosphate esters, emerging flame retardants, perfluoroalkyl substances, and phthalate esters. Use of some of these chemicals has already been banned or restricted; they are regularly detected in the environment, wildlife, and human matrices. Traditionally, blood and urine collection have been widely used as sampling methods. New non-invasive approaches (e.g., saliva, hair, nails) are emerging as valid alternatives since they offer advantages with respect to sampling, handling, and ethical aspects, while ensuring similar reliability and sensitivity. Nevertheless, the identification of biomarkers of exposure is often difficult because chemicals may be metabolized in the human body. For many of the above-mentioned compounds, the mechanisms of the favorable metabolization pathways have not been unraveled, but research on important metabolites that could be used as biomarkers of exposure is growing. This review summarizes the state of the art regarding human exposure to, (non-invasive) HBM of, and metabolism of major organophosphate esters, emerging flame retardants, perfluoroalkyl substances, and phthalate esters currently detected in the environment. Figure
Human biomonitoring of emerging contaminants-non-invasive versus invasive matrices 相似文献
97.
Laura E. Muresan Adrian I. Cadis Ioana Perhaita Emil Indrea 《Central European Journal of Chemistry》2014,12(10):1023-1031
Yttrium silicate doped with cerium (Y2SiO5:Ce) was obtained from Y-Ce-Si based precursors prepared by the simultaneous addition of reagents (SimAdd) technique. The synthesis of the precursors was done in well controlled conditions using ammonium oxalate, ammonium carbonate or urea as precipitating agents. Results regarding the influence of precipitating agents on the morpho structural and photoluminescent characteristics of Y2SiO5:Ce are reported. The TG analysis in correlation with EGA, FT-IR and XRD investigations reveals the formation of oxalate, hydroxy-carbonate or hydroxy-nitrate based compounds, the same as the conversion of the precursors to well crystallized yttrium silicate. XRD patterns show that the precursors are amorphous except for the sample prepared with ammonium oxalate. Depending on the precipitation conditions, the phosphors phase composition varies from single phase (X2-Y2SiO5) to a mixture of phases (X2-Y2SiO5, X1-Y2SiO5, Y2O3). Under UV excitation, phosphors exhibit the specific blue emission of cerium with an intensity that varies from 175.8% (urea) to 96.0% (ammonium carbonate) and to 78.5% (ammonium oxalate). The emission intensity depends on the phase purity and order degree of the phosphors. PACS Classification codes:78.55 Hx, 81.20Fw 相似文献
98.
David K. Geiger Dylan E. Parsons 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(7):681-688
The structures of 4‐nitrobenzene‐1,2‐diamine [C6H7N3O2, (I)], 2‐amino‐5‐nitroanilinium chloride [C6H8N3O2+·Cl−, (II)] and 2‐amino‐5‐nitroanilinium bromide monohydrate [C6H8N3O2+·Br−·H2O, (III)] are reported and their hydrogen‐bonded structures described. The amine group para to the nitro group in (I) adopts an approximately planar geometry, whereas the meta amine group is decidedly pyramidal. In the hydrogen halide salts (II) and (III), the amine group meta to the nitro group is protonated. Compound (I) displays a pleated‐sheet hydrogen‐bonded two‐dimensional structure with R22(14) and R44(20) rings. The sheets are joined by additional hydrogen bonds, resulting in a three‐dimensional extended structure. Hydrohalide salt (II) has two formula units in the asymmetric unit that are related by a pseudo‐inversion center. The dominant hydrogen‐bonding interactions involve the chloride ion and result in R42(8) rings linked to form a ladder‐chain structure. The chains are joined by N—H...Cl and N—H...O hydrogen bonds to form sheets parallel to (010). In hydrated hydrohalide salt (III), bromide ions are hydrogen bonded to amine and ammonium groups to form R42(8) rings. The water behaves as a double donor/single acceptor and, along with the bromide anions, forms hydrogen bonds involving the nitro, amine, and ammonium groups. The result is sheets parallel to (001) composed of alternating R55(15) and R64(24) rings. Ammonium N—H...Br interactions join the sheets to form a three‐dimensional extended structure. Energy‐minimized structures obtained using DFT and MP2 calculations are consistent with the solid‐state structures. Consistent with (II) and (III), calculations show that protonation of the amine group meta to the nitro group results in a structure that is about 1.5 kJ mol−1 more stable than that obtained by protonation of the para‐amine group. DFT calculations on single molecules and hydrogen‐bonded pairs of molecules based on structural results obtained for (I) and for 3‐nitrobenzene‐1,2‐diamine, (IV) [Betz & Gerber (2011). Acta Cryst. E 67 , o1359] were used to estimate the strength of the N—H...O(nitro) interactions for three observed motifs. The hydrogen‐bonding interaction between the pairs of molecules examined was found to correspond to 20–30 kJ mol−1. 相似文献
99.
In the context of ordinary differential equations, shooting techniques are a state-of-the-art solver component, whereas their application in the framework of partial differential equations (PDE) is still at an early stage. We present two multiple shooting approaches for optimal control problems (OCP) governed by parabolic PDE. Direct and indirect shooting for PDE optimal control stem from the same extended problem formulation. Our approach reveals that they are structurally similar but show major differences in their algorithmic realizations. In the presented numerical examples we cover a nonlinear parabolic optimal control problem with additional control constraints. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
100.
Terence Zhi Xiang Hong Liming You Madhavi Dahanayaka Adrian Wing-Keung Law Kun Zhou 《Molecules (Basel, Switzerland)》2021,26(11)
In this study, molecular dynamics simulation is used to investigate the effects of water-based substitutional defects in zeolitic imidazolate frameworks (ZIF)-8 membranes on their reverse osmosis (RO) desalination performance. ZIF-8 unit cells containing up to three defect sites are used to construct the membranes. These substitutional defects can either be Zn defects or linker defects. The RO desalination performance of the membranes is assessed in terms of the water flux and ion rejection rate. The effects of defects on the interactions between the ZIF-8 membranes and NaCl are investigated and explained with respect to the radial distribution function (RDF) and ion density distribution. The results show that ion adsorption on the membranes occurs at either the nitrogen atoms or the defect sites. Complete NaCl rejection can be achieved by introducing defects to change the size of the pores. It has also been discovered that the presence of linker defects increases membrane hydrophilicity. Overall, molecular dynamics simulations have been used in this study to show that water-based substitutional defects in a ZIF-8 structure reduce the water flux and influence its hydrophilicity and ion adsorption performance, which is useful in predicting the type and number of defect sites per unit cell required for RO applications. Of the seven ZIF-8 structures tested, pristine ZIF-8 exhibits the best RO desalination performance. 相似文献