Comparison of rigid and flexible simple point charge water models at supercritical conditions

This study investigates the differences between the predictions of various properties of rigid and flexible simple point charge water models at supercritical conditions. Molecular dynamics simulations were conducted for supercritical water in a temperature range of 773–1073 K and densities in the range 115–659 kg/m³. We present thermodynamic data, pair correlation functions, self-diffusivity, power spectra, dielectric constants, and variaous measures of hydrogen bonding at different state conditions. The flexible water model performs better in predicting the pressures along the supercritical isotherms simulated. Agreement between experimental and calculated dielectric constants is superior for the flexible water model, particularly at high densities. The flexible model exhibits a greater degree of hydrogen bonding and more persistent hydrogen bonds than does the rigid model. The structural features of supercritical water at high densities are identical for the two water models. At low densities, however, the flexible potential exhibits pair correlation functions with enhanced peaks. Inclusion of flexibility in the potential model does not result in a significant shift in the position of the rotational/librational peak in the power spectrum. The self-diffusivities obtained from the simulations are within the accuracy of the experimental values for both the rigid and flexible models. On balance the inclusion of flexibility improves agreement with the properties of real supercritical water while incurring little or no additional computational burden. © 1996 by John Wiley & Sons, Inc.     

Measurement of the hydrodynamic radii of PEE-G dendrons by diffusion spectroscopy on a benchtop NMR spectrometer

Benchtop nuclear magnetic resonance (NMR) spectroscopy is a useful tool for the rapid determination of the self-diffusion coefficient and the hydrodynamic radius of dendrons. The self-diffusion coefficients of the first four generations of poly ethoxy ethyl glycinamide (PEE-G) dendrons are measured by diffusion-ordered spectroscopy (DOSY) on a benchtop NMR equipped with diffusion gradient coils. The hydrodynamic radii of the dendrons are calculated via the Stokes–Einstein equation. The effects of solvent and pH are determined with the hydrodynamic radius increasing with generation and decreasing upon neutralization of an acidic solution. These measurements provide valuable information for biological and pharmaceutical applications of dendrons.     

Numerical studies on the anderson localization problem

Our study of Anderson's tight binding model for strongly disordered electronic systems is extended to a numerical treatment of thed c-conductivity atT=0. For 100 × 100 square lattices, 129 × 129 triangular lattices, and for diamond lattices with 27,000 sites, the behaviour of is studied as a function of the Fermi energy and the disorder. The calculations are based on the exact eigenfunction representation of the Kubo formula, which is evaluated by the systematic application of recursion algorithms. Our results are in favour of Mott's original suggestion of a minimum metallic conductivity _min, both in two and three dimensions. In two dimensions we find the universal value of _min=(0.11 ±0.02)e ²/. Based on the thesis of J. Stein, Regensburg 1979     

Numerical studies on the anderson localization problem

The electron localization is studied for Anderson's tight-binding model with diagonal and off-diagonal disorder for a very large square lattice (10,000 sites) and diamond lattice (27,000 sites). The numerical investigations are based on the Lanczos recursion method. The convergence of the recursion coefficientsa _n ,b _n is discussed with regard to the electron localization.From Anderson's criterion and an exact real space renormalization method the energy of the localization edge is found as a function of the degree of disorder. Also the dependence of the spatial decay rate of localized wave functions on the energy and the degree of disorder is evaluated. Near the Anderson transition, where all states become localized, we get two critical exponentsv _E andv _W , which lead us to the tentative suggestion of multicritical scaling laws for this transition.     

Application of multiple quench parameters for confirmation of radionuclide identity in radioanalytical quality control

Journal of Radioanalytical and Nuclear Chemistry - Robust and reliable radiochemical analysis is the key factor in the appropriate disposal and management of radioactive wastes arising from the...     

Progress toward the synthesis of piperazimycin A: exploration of the synthesis of γ-hydroxy and γ-chloropiperazic acids

Employing Hamada’s chemistry with MAOS optimization of several steps, an expedient route to key (3S,5S)- and (3R,5R)-γ-hydroxy and (3R,5S)-γ-chloropiperazic acids, was developed en route to a total synthesis of piperazimycin A.     

Precursors to [FeFe]-hydrogenase models: syntheses of Fe2(SR)2(CO)6 from CO-free iron sources

This report describes routes to iron dithiolato carbonyls that do not require preformed iron carbonyls. The reaction of FeCl 2, Zn, and Q 2S 2C n H 2 n (Q (+) = Na (+), Et 3NH (+)) under an atmosphere of CO affords Fe 2(S 2C n H 2 n )(CO) 6 ( n = 2, 3) in yields >70%. The method was employed to prepare Fe 2(S 2C 2H 4)( (13)CO) 6. Treatment of these carbonylated mixtures with tertiary phosphines, instead of Zn, gave the ferrous species Fe 3(S 2C 3H 6) 3(CO) 4(PR 3) 2, for R = Et, Bu, and Ph. Like the related complex Fe 3(SPh) 6(CO) 6, these compounds consist of a linear arrangement of three conjoined face-shared octahedral centers. Omitting the phosphine but with an excess of dithiolate, we obtained the related mixed-valence triiron species [Fe 3(S 2C n H 2 n ) 4(CO) 4] (-). The highly reducing all-ferrous species [Fe 3(S 2C n H 2 n ) 4(CO) 4] (2-) is implicated as an intermediate in this transformation. Reactive forms of iron, prepared by the method of Rieke, also combined with dithiols under a CO atmosphere to give Fe 2(S 2C n H 2 n )(CO) 6 in modest yields under mild conditions. Studies on the order of addition indicate that ferrous thiolates are formed prior to the onset of carbonylation. Crystallographic characterization demonstrated that the complexes Fe 3(S 2C 3H 6) 3(CO) 4(PEt 3) 2 and PBnPh 3[Fe 3(S 2C 3H 6) 4(CO) 4] feature high-spin ferrous and low-spin ferric as the central metal, respectively.     

Reactions of the Dirhenium(II) Complexes Re2 X 4(μ-dppm)2 (X=Cl, Br; dppm=Ph2PCH2PPh2) with Isocyanides. Part XV: A Fifth Structural Isomer of the [Re2Cl3(μ-dppm)2(CO)(CNXyl)2]+ Cation (Xyl = 2, 6-Dimethylphenyl)

The reaction of the unsymmetrical, coordinatively unsaturated dirhenium(II) complex [(XylNC)(OC)CIRe(μ-dppm)₂ReCl₂]O₃SCF₃ (dppm = Ph₂PCH₂PPh₂) with one equivalent of XylNC in CH₂Cl₂ affords a fifth structural isomer of the [Re₂Cl₃(μ-dppm)₂(CO)(CNXyl)₂] ⁺ cation; this is believed to have a CO-bridged structure of the type [(XylNC)ClRe(μ-Cl)(μ-CO)(μ-dppm)₂ReCl(CNXyl)]⁺. The latter complex reacts with a further equivalent of XylNC in the presence of Tl⁺ to form the [Re₂Cl₂(μ-dppm)₂(CO)(CNXyl)₃]²⁺ cation, which has been shown by IR spectroscopy, and by the X-ray crystallographic characterization of its neutral congener Re₂Cl₂(μ-dppm)₂(CO)(CNXyl)₃, to contain a very weak and unsymmetrical CO bridge.     

Fluoroalkyl and alkyl chains have similar hydrophobicities in binding to the "hydrophobic wall" of carbonic anhydrase

The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H(2)NSO(2)C(6)H(4)-CONHCH(2)(CX(2))(n)CX(3), n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and entropic contributions to the hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions).