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Charge Density (charge + density)
Kinds of Charge Density Terms modified by Charge Density Selected AbstractsChemInform Abstract: Ab initio Calculations of Electronic Band Structure and Charge Densities of Zinc Blende-Type GaN, BN and Their Solid Solution B0.5Ga0.5N.CHEMINFORM, Issue 51 2008Rabah Riane Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Substituent Influences on the Stability of the Ring and Chain Tautomers in 1,3-O,N-Heterocyclic Systems: Characterization by 13C NMR Chemical Shifts, PM3 Charge Densities, and Isodesmic ReactionsCHEMINFORM, Issue 39 2001Kari Neuvonen Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] ChemInform Abstract: Comparative Studies on the Phase Stability, Electronic Structure, and Topology of the Charge Density in the Li3XO4 (X: P, As, V) Lithium Orthosalt PolymorphsCHEMINFORM, Issue 31 2009Christine Frayret Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Topological properties of hydrogen bonds and covalent bonds from charge densities obtained by the maximum entropy method (MEM)ACTA CRYSTALLOGRAPHICA SECTION B, Issue 5 2009Jeanette Netzel Charge densities have been determined by the Maximum Entropy Method (MEM) from the high-resolution, low-temperature (T, 20,K) X-ray diffraction data of six different crystals of amino acids and peptides. A comparison of dynamic deformation densities of the MEM with static and dynamic deformation densities of multipole models shows that the MEM may lead to a better description of the electron density in hydrogen bonds in cases where the multipole model has been restricted to isotropic displacement parameters and low-order multipoles (lmax = 1) for the H atoms. Topological properties at bond critical points (BCPs) are found to depend systematically on the bond length, but with different functions for covalent C,C, C,N and C,O bonds, and for hydrogen bonds together with covalent C,H and N,H bonds. Similar dependencies are known for AIM properties derived from static multipole densities. The ratio of potential and kinetic energy densities |V(BCP)|/G(BCP) is successfully used for a classification of hydrogen bonds according to their distance d(H...O) between the H atom and the acceptor atom. The classification based on MEM densities coincides with the usual classification of hydrogen bonds as strong, intermediate and weak [Jeffrey (1997). An Introduction to Hydrogen Bonding. Oxford University Press]. MEM and procrystal densities lead to similar values of the densities at the BCPs of hydrogen bonds, but differences are shown to prevail, such that it is found that only the true charge density, represented by MEM densities, the multipole model or some other method can lead to the correct characterization of chemical bonding. Our results do not confirm suggestions in the literature that the promolecule density might be sufficient for a characterization of hydrogen bonds. [source] Effects of shear and electrical properties on flow characteristics of pharmaceutical blendsAICHE JOURNAL, Issue 3 2010Kalyana C. Pingali Abstract This article examines the effects and interactions of shear rate, shear strain on electrical and flow properties of pharmaceutical blends. An unexpectedly strong relation between the flow and passive electrical properties of powders is observed to depend on the shear history of the powder bed. Charge density, impedance, dielectrophoresis, flow index, and dilation were measured for several pharmaceutical blends after they were subjected to a controlled shear environment. It was found that the increase in the shear strain intensified the electrical properties for blends that did not contain MgSt. The opposite effect was found in blends lubricated with MgSt. Different shear conditions resulted in different correlations between flow index and dilation. Flow properties of powders were found to improve with continuous exposure to shear strain. It was also found that flow properties correlated to charge acquisition and impedance for different shear treatments. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Charge density and electrostatic potential analyses in paracetamolACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2009Nouzha Bouhmaida The electron density of monoclinic paracetamol was derived from high-resolution X-ray diffraction at 100,K. The Hansen,Coppens multipole model was used to refine the experimental electron density. The topologies of the electron density and the electrostatic potential were carefully analyzed. Numerical and analytical procedures were used to derive the charges integrated over the atomic basins. The highest charge magnitude (,1.2,e) was found for the N atom of the paracetamol molecule, which is in agreement with the observed nucleophilic attack occurring in the biological media. The electric field generated by the paracetamol molecule was used to calculate the atomic charges using the divergence theorem. This was simultaneously applied to estimate the total electrostatic force exerted on each atom of the molecule by using the Maxwell stress tensor. The interaction electrostatic energy of dimers of paracetamol in the crystal lattice was also estimated. [source] The ultrastructural distribution of prestin in outer hair cells: a post-embedding immunogold investigation of low-frequency and high-frequency regions of the rat cochleaEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 9 2010Shanthini Mahendrasingam Abstract Outer hair cells (OHCs) of the mammalian cochlea besides being sensory receptors also generate force to amplify sound-induced displacements of the basilar membrane thus enhancing auditory sensitivity and frequency selectivity. This force generation is attributable to the voltage-dependent contractility of the OHCs underpinned by the motile protein, prestin. Prestin is located in the basolateral wall of OHCs and is thought to alter its conformation in response to changes in membrane potential. The precise ultrastructural distribution of prestin was determined using post-embedding immunogold labelling and the density of the labelling was compared in low-frequency and high-frequency regions of the cochlea. The labelling was confined to the basolateral plasma membrane in hearing rats but declined towards the base of the cells below the nucleus. In pre-hearing animals, prestin labelling was lower in the membrane and also occurred in the cytoplasm, presumably reflecting its production during development. The densities of labelling in low-frequency and high-frequency regions of the cochlea were similar. Non-linear capacitance, thought to reflect charge movements during conformational changes in prestin, was measured in OHCs in isolated cochlear coils of hearing animals. The OHC non-linear capacitance in the same regions assayed in the immunolabelling was also similar in both the apex and base, with charge densities of 10 000/,m2 expressed relative to the lateral membrane area. The results suggest that prestin density, and by implication force production, is similar in low-frequency and high-frequency OHCs. [source] A detailed analysis of hotspots and insulation breakdown phenomena in power inductor windings at high frequency regimes: overcurrents and overvoltagesEUROPEAN TRANSACTIONS ON ELECTRICAL POWER, Issue 6 2008J. A. Brandão Faria Abstract This research paper is the last of a group of three papers dedicated to the analysis and computation of the high-frequency electromagnetic behaviour of inductor windings where a multiconductor transmission line approach is used. The present work is essentially concerned with application aspects linked up with the important engineering problem of windings insulation damage, which can occur either because of excessive temperature (winding hotspots) or because of excessive electric field strength (dielectric breakdown). For single and multilayer windings we present here a wealth of information in graphical and tabular form concerning the distribution of voltages, currents, electric charges, charge densities, electric field components and power losses along the inductor winding turns, operating at the critical resonance frequencies characteristic of the structure (which is the worst possible scenario). This information is analysed and processed in order to allow for a detection of the winding zones where breakdown phenomena and hotspots could most probably occur. Copyright © 2007 John Wiley & Sons, Ltd. [source] Gauge-independent quantum dynamics on phase-space of charged scalar particlesFORTSCHRITTE DER PHYSIK/PROGRESS OF PHYSICS, Issue 2-3 2003S. Varró On the basis of the Hamiltonian form of the Klein-Gordon equation of a charged scalar particle field introduced by Feshbach and Villars, the gauge-invariant 2×2 Wigner matrix has been constructed whose diagonal elements describe positive and negative charge densities and the off-diagonal elements correspond to cross-densities in phase-space. The system of coupled transport equations has been derived in case of interaction with an arbitrary external electromagnetic field. A gauge-independent generalization of the free particle representation due to Feshbach and Villars is given, and on the basis of it both the nonrelativistic and the classical limits of the general relativistic quantum Boltzmann-Vlasov equation(RQBVE) is discussed. In the non-relativistic limit (p/mc,0) the set of equations of motion decouple to two independent quantum transport equations describing the dynamics of oppositely charged positon and negaton densities separately. In the classical limit(,,0) two relativistic Boltzmann-Vlasov equations result for the diagonal positon and negaton densities. It is obtained that, though in the latter equations the Planck constant , is absent, the real part of the cross-density does not vanish. [source] Electrochemically Tuned Properties for Electrolyte-Free Carbon Nanotube SheetsADVANCED FUNCTIONAL MATERIALS, Issue 14 2009Alexander A. Zakhidov Abstract Injecting high electronic charge densities can profoundly change the optical, electrical, and magnetic properties of materials. Such charge injection in bulk materials has traditionally involved either dopant intercalation or the maintained use of a contacting electrolyte. Tunable electrochemical charge injection and charge retention, in which neither volumetric intercalation of ions nor maintained electrolyte contact is needed, are demonstrated for carbon nanotube sheets in the absence of an applied field. The tunability of electrical conductivity and electron field emission in the subsequent material is presented. Application of this material to supercapacitors may extend their charge-storage times because they can retain charge after the removal of the electrolyte. [source] Electrostatic BEM for MEMS with thin beamsINTERNATIONAL JOURNAL FOR NUMERICAL METHODS IN BIOMEDICAL ENGINEERING, Issue 6 2005Zhongping Bao Abstract Micro-electro-mechanical (MEM) and nano-electro-mechanical (NEM) systems sometimes use beam- or plate-shaped conductors that can be very thin,with h/L,,,(10,2,10,3) (in terms of the thickness h and length L of a beam or the side of a square pate). Conventional boundary element method (BEM) analysis of the electric field in a region exterior to such thin conductors can become difficult to carry out accurately and efficiently,especially since MEMS analysis requires computation of charge densities (and then surface tractions) separately on the top and bottom surfaces of such objects. A new boundary integral equation (BIE) is derived in this work that, when used together with the standard BIE with logarithmically singular kernels, results in a powerful technique for the BEM analysis of such problems with thin beams. This new approach, in fact, works best for very thin beams. This thin beam BEM is derived and discussed in this work. Copyright © 2005 John Wiley & Sons, Ltd. [source] Quantitative assessment of the effect of basis set superposition error on the electron density of molecular complexes by means of quantum molecular similarity measuresINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 11 2009Pedro Salvador Abstract The Chemical Hamiltonian Approach (CHA) method is applied to obtain Basis Set Superposition Error (BSSE)-free molecular orbitals at the Hartree,Fock (HF) and Density Functional Theory (DFT) levels of theory. To assess qualitatively the effect of the BSSE on the first-order electron density, we had previously applied Bader's analysis of the intermolecular critical points located on the electron density, as well as density difference maps for several hydrogen bonded complexes. In this work, Quantum Molecular Similarity Measures are probed as an alternative avenue to properly quantify the electronic relaxation due to the BSSE removal by means of distance indices between the uncorrected and corrected charge densities. It is shown that BSSE contamination is more important at the DFT level of theory, and in some cases, changes on the topology of the electron density are observed upon BSSE correction. Inclusion of diffuse functions have been found to dramatically decrease the BSSE effect in both geometry and electron density. The CHA method represents a good compromise to obtain accurate results with small basis sets. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Synthesis and alkylation of 5-(3-chlorobenzo[b]thien-2-yl)-4H -1,2,4-triazole-3-thiol under classical and microwave conditions.JOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 6 2006AM1 semiemperical calculations for investigating the regioselectivity of alkylation Under microwave irradiation (MWI), 5-(3-chlorobenzo[b]thien-2-yl)-4H -1,2,4-triazole-3-thiol (3) was synthesized in a good yield by intramolecular cyclization of the carbonyl thiosemicarbazide 2. A regioselective S-alkylation of 3 with benzyl chloride or allyl bromide has been achieved by using triethylamine as a base, while other different basic conditions led to a mixture of bis(alkylated) derivatives N4, S- and S, N2 -, under both of classical and MWI conditions. The relative stabilities, charge densities, dipole moments and electronic energies of reactants, transition states and intermediates were calculated by the AM1 method and used for investigating the regioselectivity. [source] pH-responsive ampholytic terpolymers of acrylamide, sodium 3-acrylamido-3-methylbutanoate, and (3-acrylamidopropyl)trimethylammonium chloride.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2004Abstract The solution properties of low-charge-density ampholytic terpolymers of acrylamide, sodium 3-acrylamido-3-methylbutanoate, and (3-acrylamidopropyl)trimethylammonium chloride were studied as functions of the solution pH, ionic strength, and polymer concentration. Terpolymers with low charge densities, large charge asymmetries, or both exhibited excellent solubility in deionized (DI) water, and higher charge density terpolymers were readily dispersible in DI water; however, the higher charge density terpolymer solutions separated into polymer-rich and polymer-poor phases upon standing over time. Charge-balanced terpolymers exhibited antipolyelectrolyte behavior at pH values greater than or equal to the ambient pH (6.5 ± 0.2); the same terpolymers behaved increasingly as cationic polyelectrolytes with decreasing solution pH because of the protonation of the 3-acrylamido-3-methylbutanoate (AMB) repeat units. Unbalanced terpolymers generally exhibited polyelectrolyte behavior, although the effects of intramolecular electrostatic attractions (i.e., polyampholyte effects) on the hydrodynamic volume of the unbalanced terpolymer coils were evident at certain values of the solution pH and salt concentration. The dilute-solution behavior of the terpolymers correlated well with the behavior predicted by several polyampholyte solution theories. In the semidilute regime, solution viscosities increased with increasing terpolymer charge density, and this indicated a significant enhancement of the solution viscosity by intermolecular electrostatic associations. Upon the addition of NaCl, semidilute-solution viscosities tended to decrease because of the disruption of the intermolecular electrostatic associations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3252,3270, 2004 [source] New Poly(sodium carboxylate)s Based on Saccharides, 1.MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 18 2002Characterization of Ionic Allyl Glycoside Polymers, Synthesis Abstract New poly(sodium carboxylate)s, containing monosaccharide side groups with ether linkages to the main chain, are presented as substitutes for water-soluble homo- and copolymers of acrylic acid. Neutral and ionic allyl glycoside monomers, namely allyl- , - D -galactopyranoside and allyl- , - D -glucofuranosidurono-6,3-lactone, were synthesized by Fischer glycosidation. These monomers were copolymerized with maleic anhydride and itaconic acid in aqueous and nonaqueous solution. The corresponding copolymers with different structures, degrees of functionalization, and charge densities were characterized by 13C NMR spectroscopy, molecular-weight measurements, and intrinsic viscosity [,] determination. From these, the monomer reactivity ratios and Mark,Houwink relations were established (see Figure). Copolymerization curves of maleic acid copolymers 6 and 10. M1: mole fraction of allyl monomer 2, and 5, in the feed; m1: mole fraction of allyl monomer in the copolymer. The dashed line shows the course of an ideal alternating copolymerization (excepted: M1,=,0 mol-%, M1,=,100 mol-%). [source] Existence of front solutions for a nonlocal transport problem describing gas ionizationMATHEMATICAL METHODS IN THE APPLIED SCIENCES, Issue 12 2010M. Günther Abstract We discuss a moving boundary problem arising from a model of gas ionization in the case of negligible electron diffusion and suitable initial data. It describes the time evolution of an ionization front. Mathematically, it can be considered as a system of transport equations with different characteristics for positive and negative charge densities. We show that only advancing fronts are possible and prove short-time well posedness of the problem in Hölder spaces of functions. Technically, the proof is based on a fixed-point argument for a Volterra-type system of integral equations involving potential operators. It crucially relies on estimates of such operators with respect to variable domains in weighted Hölder spaces and related calculus estimates. Copyright © 2010 John Wiley & Sons, Ltd. [source] First-principles calculations of the structural, electronic and optical properties of IIA,IV antifluorite compoundsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 10 2005O. Benhelal Abstract The structural, electronic and optical properties of the antifluorite semiconductors Mg2X (X = Si, Ge, Sn) have been studied using the full potential linearized augmented plane wave (FPLAPW) method. For treating the exchange-correlation term, the local density approximation (LDA) has been chosen. The total energy approach is used to determine the equilibrium volume. The energy gap is found to be indirect for all the compounds. Results for electronic properties such as band structures, density of states and electronic charge densities are presented. The optical properties are derived and interpreted. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] The topologies of the charge densities in Zr and RuACTA CRYSTALLOGRAPHICA SECTION A, Issue 2 2009Travis E. Jones We report on the atomic scale phenomena responsible for the variation of oxygen solubility in Zr and Ru. First-principles calculations reveal that the topologies of the charge densities in these hexagonal close-packed metals are distinct. Neither element was found to possess the topology of the prototype, Mg. There are 12 bond paths terminating at each Ru atom. These are the bonds between nearest neighbors. Only five bond paths terminate at each Zr atom and the Zr atoms are not bound to one another. Instead, they are bonded through non-nuclear maxima. As a result, channels of low charge density that can accommodate oxygen anions are present in Zr. [source] Form factors for core electrons useful for the application of quantum crystallography (QCr) to organic moleculesACTA CRYSTALLOGRAPHICA SECTION A, Issue 4 2002Lulu Huang Form factors are calculated for the core electrons of the first-row atoms B, C, N, O and F. The form factors are presented in an analytical form, as appears in International Tables for X-ray Crystallography [Ibers & Hamilton (1974), Vol. IV, pp. 103,145. Birmingham: Kynoch Press; present distributor Kluwer Academic Publishers, Dordrecht]. Having such form factors for the core electrons reduces the number of parameters to be determined by the methods of quantum crystallography (QCr). It is shown that the form factors obtained are quite accurate. Thus, when they are used in QCr, they are expected to be consistent with accurate charge densities. [source] On the origin of topological differences between experimental and theoretical crystal charge densitiesACTA CRYSTALLOGRAPHICA SECTION A, Issue 4 2000Anatoliy Volkov Topological analysis of experimental and theoretical (molecular and crystal) electron densities of p -nitroaniline and p -amino- p,-nitrobiphenyl reveals considerable discrepancies between experiment and theory for the bond critical points properties. Particularly large differences occur for the positive curvature along the bond path (,3). The differences become somewhat smaller when more extended basis sets and correlation effects are introduced in the theoretical calculations. The effect of the crystal matrix on the properties of bond critical points is evaluated for the p -nitroaniline molecule using the 6-21G** and 6-31G** basis sets. The differences between the isolated molecule and the molecule in the crystal are too small to explain the quantitative disagreement between the theoretical and experimental topologies reported in the literature and found in the current study. For most bonds, the observed changes in the properties of the electron density agree well for both basis sets but some discrepancies are found for changes in ,3 for N,H and aromatic C,C bonds. When the theoretical densities are projected into the multipole density functions through refinement of the theoretical structure factors, the topological properties change and differences between theory and experiment are reduced. The main origin of the observed discrepancies is attributed to the nature of the radial functions in the experimental multipole model. [source] Validation of experimental charge densities: refinement of the macrolide antibiotic roxithromycinACTA CRYSTALLOGRAPHICA SECTION B, Issue 5 2010J. J. Holstein Multipole refinements of larger organic molecules have so far been limited to a few exceptional cases. We report an investigation of the detailed experimental electron-density distribution (EDD) of roxithromycin, a macrolide antibiotic consisting of 134 atoms. Although the experimental multipole refinement on high-resolution synchrotron data converged smoothly, validation of the electron density by calculation of an `experiment minus invariom' difference density revealed conformational disorder of the H atoms. Hydrogen disorder is shown to affect the EDD, the electrostatic potential and atomic properties as defined by Bader's quantum theory of atoms in molecules. A procedure to obtain the electron density distribution in the presence of disorder is proposed. [source] Topological properties of hydrogen bonds and covalent bonds from charge densities obtained by the maximum entropy method (MEM)ACTA CRYSTALLOGRAPHICA SECTION B, Issue 5 2009Jeanette Netzel Charge densities have been determined by the Maximum Entropy Method (MEM) from the high-resolution, low-temperature (T, 20,K) X-ray diffraction data of six different crystals of amino acids and peptides. A comparison of dynamic deformation densities of the MEM with static and dynamic deformation densities of multipole models shows that the MEM may lead to a better description of the electron density in hydrogen bonds in cases where the multipole model has been restricted to isotropic displacement parameters and low-order multipoles (lmax = 1) for the H atoms. Topological properties at bond critical points (BCPs) are found to depend systematically on the bond length, but with different functions for covalent C,C, C,N and C,O bonds, and for hydrogen bonds together with covalent C,H and N,H bonds. Similar dependencies are known for AIM properties derived from static multipole densities. The ratio of potential and kinetic energy densities |V(BCP)|/G(BCP) is successfully used for a classification of hydrogen bonds according to their distance d(H...O) between the H atom and the acceptor atom. The classification based on MEM densities coincides with the usual classification of hydrogen bonds as strong, intermediate and weak [Jeffrey (1997). An Introduction to Hydrogen Bonding. Oxford University Press]. MEM and procrystal densities lead to similar values of the densities at the BCPs of hydrogen bonds, but differences are shown to prevail, such that it is found that only the true charge density, represented by MEM densities, the multipole model or some other method can lead to the correct characterization of chemical bonding. Our results do not confirm suggestions in the literature that the promolecule density might be sufficient for a characterization of hydrogen bonds. [source] Combining crystallographic information and an aspherical-atom data bank in the evaluation of the electrostatic interaction energy in an enzyme,substrate complex: influenza neuraminidase inhibitionACTA CRYSTALLOGRAPHICA SECTION D, Issue 5 2009Paulina M. Dominiak Although electrostatic interactions contribute only a part of the interaction energies between macromolecules, unlike dispersion forces they are highly directional and therefore dominate the nature of molecular packing in crystals and in biological complexes and contribute significantly to differences in inhibition strength among related enzyme inhibitors. In the reported study, a wide range of complexes of influenza neuraminidases with inhibitor molecules (sialic acid derivatives and others) have been analyzed using charge densities from a transferable aspherical-atom data bank. The strongest interactions of the residues are with the acidic group at the C2 position of the inhibitor (,,300,kJ,mol,1 for ,COO, in non-aromatic inhibitors, ,,120,210,kJ,mol,1 for ,COO, in aromatic inhibitors and ,,450,kJ,mol,1 for ,PO32,) and with the amino and guanidine groups at C4 (,,250,kJ,mol,1). Other groups contribute less than ,100,kJ,mol,1. Residues Glu119, Asp151, Glu227, Glu276 and Arg371 show the largest variation in electrostatic energies of interaction with different groups of inhibitors, which points to their important role in the inhibitor recognition. The Arg292,Lys mutation reduces the electrostatic interactions of the enzyme with the acidic group at C2 for all inhibitors that have been studied (SIA, DAN, 4AM, ZMR, G20, G28, G39 and BCZ), but enhances the interactions with the glycerol group at C6 for inhibitors that contain it. This is in agreement with the lower level of resistance of the mutated virus to glycerol-containing inhibitors compared with the more hydrophobic derivatives. [source] Application of maximum-entropy maps in the accurate refinement of a putative acylphosphatase using 1.3,Å X-ray diffraction dataACTA CRYSTALLOGRAPHICA SECTION D, Issue 3 2008Eiji Nishibori Accurate structural refinement of a putative acylphosphatase using 1.3,Å X-ray diffraction data was carried out using charge densities determined by the maximum-entropy method (MEM). The MEM charge density clearly revealed detailed features of the solvent region of the putative acylphosphatase crystalline structure, some of which had never been observed in conventional Fourier maps. The structural model in the solvent region was constructed as distributions of anisotropic water atoms. The omit-difference MEM maps and the difference MEM maps were effective in revealing details of the protein structure, such as multiple conformations of the side chains of amino-acid residues, anisotropy of atoms and H atoms. By model building using the MEM charge densities, the reliability factors R1 and Rfree in the SHELX refinement were dramatically improved from 17.9% and 18.3% to 9.6% and 10.0%, respectively. The present results prove the usefulness of MEM in improving the accuracy of refinement of protein crystal structures. [source] Unexpected Structural Diversity in Alkali Metal Azide-Crown Ether Complexes: Syntheses, X-ray Structures, and Quantum-Chemical CalculationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 9 2006Michael D. Brown Abstract A series of alkali metal azide-crown ether complexes, [Li([12]crown-4)(N3)], [Na([15]crown-5)(N3)], [Na([15]crown-5)(H2O)2]N3, [K([18]crown-6)(N3)(H2O)], [Rb([18]crown-6)(N3)(H2O)], [Cs([18]crown-6)(N3)]2, and [Cs([18]crown-6)(N3)(H2O)(MeOH)], has been synthesised. In most cases, single crystals were obtained, which allowed X-ray crystal structures to be derived. The structures obtained have been compared with molecular structures computed by density functional theory (DFT) calculations. This has allowed the effects of the crystal lattice on the structures to be investigated. Also, a study of the MNterminal metal,azide bond length and charge densities on the metal (M) and terminal nitrogen centre (Nterminal) in these complexes has allowed the nature of the metal,azide bond to be probed in each case. The bonding in these complexes is believed to be predominantly ionic or ion-dipole in character, with the differences in geometries reflecting the balance between maximising the coordination number of the metal centre and minimising ligand-ligand repulsions. The structures of the crown ether complexes determined in this work show the subtle interplay of such factors. The significant role of hydrogen bonding is also demonstrated, most clearly in the structures of the K and Rb dimers, but also in the chain structure of the hydrated Cs complex. [source] Microstructure of microemulsion in MEEKCELECTROPHORESIS, Issue 4 2010Yuhua Cao Abstract The influences of the composition of microemulsion on the microstructure including dimensions and , potentials of microdroplets were measured in details. The average dynamic dimension of microdroplets was measured by dynamic laser light scattering, and , potential was determined to characterize average surface charge density of microdroplets. The experiment results showed that increase of the amount of surfactant resulted in decrease of microdroplet size but almost invariant , potential, which would enlarge migration time of the microdroplet in MEEKC. With increment of cosurfactant concentration, the microdroplet size had an increasing trend, whereas the , potential decreased. Thus, observed migration velocity of microdroplets increased, which made the separation window in MEEKC shortened. Neither dimension nor , potential of microdroplets changed by varying both the type and the amount of the oil phase. Adding organic solvent as modifier to microemulsion did not change the microdroplet size, but lowered , potential. The migration time of microdroplet still became larger, since EOF slowed down owing to organic solvent in capillary. So, besides increment of surfactant concentration, organic additive could also enlarge the separation window. Increase of cosurfactant concentration was beneficial for separation efficiency thanks to the looser structure of swollen microdroplet, and the peak sharpening might compensate for the resolution and peak capacity owing to a narrow separation window. Except the oil phase, tuning the composition of microemulsion would change the microstructure, eventually could be exploited to optimize the resolution and save analysis time in MEEKC. [source] Analysis of effect of electrolyte types on electrokinetic energy conversion in nanoscale capillariesELECTROPHORESIS, Issue 3 2010Reiyu Chein Abstract An analytical study on the effect of electrolyte types on the electrokinetic energy conversion is presented using nanoscale cylindrical capillary, which is either positively or negatively charged. The sign of surface charge determines the role and concentration magnitude of ions in the capillary and the energy conversion performance. Our study shows that the electrokinetic energy conversion performance (maximum efficiency, pressure rise and streaming potential) are approximately identical for 1:1 (KCl), 2:1 (CaCl2) and 3:1 (LaCl3) electrolytes when capillary is positively charged. For negatively charged capillary, energy conversion performance degrades significantly with the increase of counter-ion valence. For both positively and negatively charged capillaries, higher maximum efficiency can be resulted in low bulk concentration and surface charge density regimes. However, high maximum pressure rise generation for the pumping is found in the low bulk concentration and high surface charge density regimes. For the electric power generation, higher maximum streaming potential is found when both bulk concentration and surface charge density are low. [source] Computer-assisted 2-D agarose electrophoresis of Haemophilus influenzae type B meningitis vaccines and analysis of polydisperse particle populations in the size range of viruses: A reviewELECTROPHORESIS, Issue 4 2007Dietmar Tietz Dr. Abstract When protein,polysaccharide conjugated vaccines were first developed for the immunization of small children against meningitis caused by infection with Haemophilus influenzae type b (Hib), the vaccine preparations varied in immunogenicity. Testing for immunogenicity was time-consuming and alternative analytical procedures for determining vaccine quality were unsatisfactory. For example, due to the very high molecular weight of the vaccine particles, immunogens could only be physically characterized as a fraction in the void volume of Sepharose gel filtration. In search of better analytical methods, a computer-assisted electrophoretic technique for analyzing such vaccines was developed in the period from 1983 to 1995. This new approach made it possible to analyze highly negatively charged particles as large as or larger than intact viruses. 2-D gel patterns were generated that varied depending on the conditions of the particular vaccine preparation and were therefore characteristic of each vaccine sample. Thus, vaccine particle populations with a continuous size variation over a wide range (polydisperse) could be characterized according to size and free mobility (related to particle surface net charge density). These advances are reviewed in this article, since the developed methods are still a promising tool for vaccine quality control and for predicting immunogen effectiveness in the production of vaccines. The technique is potentially beneficial for Hib immunogens and other high-molecular-mass vaccines. Additional biomedical applications for this nondenaturing electrophoretic technique are briefly discussed and detailed information about computational and mathematical procedures and theoretical aspects is provided in the Appendices. [source] Use of poly(vinyl alcohol)-coated capillaries for separation of amino-terminated polyamidoamine dendrimersELECTROPHORESIS, Issue 3 2007Britton Carter Abstract Characterization of amino-terminated polyamidoamine dendrimers by CE suffers from a lack of resolution for higher generations and poor between-day reproducibility of retention times. Under optimal conditions of temperature, voltage, and sample amount, 0,5,generations of dendrimers could be resolved with a bare fused-silica capillary. However, reproducibility was poor due to potential interactions of the polycationic dendrimers with the uncoated quartz capillary wall. Use of a poly(vinyl alcohol)-coated capillary significantly decreased the migration times of the nanomolecules without compromising resolution. Dendrimer mixtures containing generations,0,5 are separated as discrete, nonoverlapping peaks in about 15,min. In addition, the between-day precision of retention times was dramatically improved without the need for internal standards or data normalization. Dendrimers of various generations and cores run on different days showed an RSD of retention times of less than 4%. The poly(vinyl alcohol) coating was very stable as shown by the excellent precision of migration times obtained on a capillary used for a month with more than 100,injections. Similar to PAGE, separation of polyamidoamine dendrimers on a bare fused-silica and poly(vinyl alcohol)-coated capillary showed an exponential relationship between migration times and calculated charge density of the nanomolecules. [source] Controlled Assembly of [Nb6,xWxO19](8,x), (x = 0,4) Lindqvist Ions with (Amine)copper ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2008Travis M. Anderson Abstract The mixed addenda isopolyanion, [N(CH3)4]2Na2[cis -Nb2W4O19]·18H2O, reacts with Cu(NO3)2 in water and in the presence of NH2CH2CH2NH2 (en) or NH4OH at 60 °C to yield a phase that is decorated {[Cu(en)2(H2O)]2[Nb2W4O19]·2H2O (1)} or charge-balanced {[Cu(NH3)4(H2O)]2[Nb2W4O19]·8H2O (2)}, respectively, by (amine)copper complexes. The prolonged heating at 95 °C of [N(CH3)4]6[Nb10O28]·6H2O, [N(CH3)4]2Na2[cis -Nb2W4O19]·18H2O, or Na4K2[cis -Nb4W2O19]·12H2O and Cu(NO3)2 in a mixed water/amine [en or NH2CH2CH2CH2NH2 (dap)] solution results in the formation of two-dimensional materials with alternate layers of (amine)copper complexes linking Lindqvist [Nb6,xWxO19](8,x), (x = 0,4) clusters. These phasesinclude: [Cu(dap)2]3[Nb4W2O19]·7H2O (3), [Cu(dap)2]3[H2Nb6O19]·6H2O (4), [Cu(dap)2]3[Nb3W3O19]·Cl·6H2O (5), and [Cu(en)2]3[Nb4W2O19]·6H2O (6). Complexes 4 and 5 result from the decomposition of [Nb10O28]6, and [cis -Nb2W4O19]4, to [H2Nb6O19]6, and [fac -Nb3W3O19]5,, respectively, in alkaline solution. Complex 5 contains an extra-framework site that is occupied by Cl,, but this site is occupied by a water molecule in 3 and is vacant in structures 4 and 6. The results of this study suggest that charge density, cluster charge and symmetry, and cluster-cation pairing are all important parameters in the incorporation of d-electron metals onto the surfaces of [Nb6,xWxO19](8,x), (x = 0,4) clusters or into the frameworks of Lindqvist-based complex materials.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] | |||||||||||||||||||||||||||||||||||||||||||