Sedimentation equilibrium of suspensions of colloidal particles at finite concentrations

Equilibrium concentration profiles of non-dilute colloidal suspensions are calculated by means of the Carnahan-Starling expression for the osmotic compressibility of hard sphere liquids. The profiles depend on the average volume fraction of the suspension, , and on the field interaction parameter, ₀ (reciprocal of the Péclet number at infinite dilution). Profiles are computed for values of and ₀ typical of those encountered in sedimentation field-flow fractionation experiments. It is found that, in most cases, the volume fraction at the depletion wall is negligibly small and that the volume fraction at the accumulation wall ₀, depends on the ratio <>₀/₀ only. An inflexion point is found in the concentration profile if ₀ is larger than 0.13 whatever the value of ₀.     

Synthesis and structure of the incomplete cuboidal clusters [W3Se4H3(dmpe)3]+, [W3Se4H(3-x)(OH)x(dmpe)3]+ and [W3Se4(OH)3(dmpe)3]+, and the mechanism of the acid-assisted substitution of the coordinated hydrides

The novel incomplete cuboidal cluster [W3Se4H3(dmpe)3](PF6), [1](PF6), has been prepared by reduction of [W3Se4Br3(dmpe)3](PF6) with LiBH4 in THF solution. The trihydroxo complex [W3Se4(OH)3(dmpe)3](PF6), [2](PF6), was obtained by reacting [W3Se4Br3(dmpe)3](PF6) with NaOH in MeCN-H2O solution. The complexes [1](PF6) and [2](PF6) were converted to their BPh4- salts by treatment with NaBPh4. Recrystallisation of [1](BPh4) in the presence of traces of water affords the mixed dihydride hydroxo complex [W3Se4H2(OH)(dmpe)3](BPh4). The crystal structures of [1](BPh4), [2](BPh4) and [W3Se4H2(OH)(dmpe)3](BPh4) have been resolved. Although the [1]+ trihydride does not react with an excess of halide salts, reaction with HX leads to [W3Se4X3(dmpe)3]+ (X = Cl, Br). The kinetics of this reaction has been studied at 25 degrees C in MeCN-H2O solution (1:1, v/v) and found to occur with two consecutive kinetic steps. The first step is independent of the nature and concentration of the X(-) anion but shows a first order dependence on the concentration of acid (k1 = 12.0 mol(-1) dm(3) s(-1)), whereas the second one is independent of the nature and concentration of both the acid and added salts (k2 = 0.024 s(-1)). In contrast, the reaction of [2]+ with acids occurs in a single step with kobs = 0.63 s(-1)(HCl) and 0.17 s(-1)(HBr). These kinetic results are discussed on the basis of the mechanism previously proposed for the reactions of the analogous [W3S4H3(dmpe)3]+ cluster, with special emphasis on the effects caused by the change of S by Se on the rate constants for the different processes involved.     

Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Enantioselective reduction and deracemisation using the non-conventional yeast Pichia glucozyma in water/organic solvent biphasic systems: preparation of (S)-1,2-diaryl-2-hydroxyethanones (benzoins)

Water/organic solvent two-liquid-phase systems have been successfully applied in the synthesis of enantiomerically pure (S)-benzoin through two different methodologies catalysed by whole cells from the non-conventional yeast Pichia glucozyma: the stereoselective monoreduction of benzil and the deracemisation of benzoin. The presence of the organic solvent influences the redox systems implied in the reactions, avoiding the formation of the corresponding diols, increasing the enantioselectivity and allowing the easy isolation of the products in high yields and excellent enantiomeric excesses. The use of both strategies has been extended to the preparation of different chiral benzoin derivatives.     

Binary mixed micelles of chiral sodium undecenyl leucinate and achiral sodium undecenyl sulfate: I. Characterization and application as pseudostationary phases in micellar electrokinetic chromatography

Sodium 10-undecenyl sulfate (SUS), sodium 10-undecenyl leucinate (SUL) and their five different mixed micelles at varied percent mole ratios were prepared. The critical micelle concentration (CMC), C₂₀, γ_CMC, partial specific volume, methylene group selectivity, mobilities and elution window were determined using a variety of analytical techniques. These surfactant systems were then evaluated as novel pseudostationary phases in micellar electrokinetic chromatography (MEKC). As a commonly used pseudostationary phase in MEKC, sodium dodecyl sulfate (SDS) was also evaluated. The CMC values of SUS and SUL were found to be 26 and 16 mM, respectively, whereas the CMC of mixed surfactants was found to be very similar to that of SUL. The C₂₀ values decreased dramatically as the concentration of SUL is increased in the mixed micelle. An increase in SUL content gradually increased the methylene group selectivity making the binary mixed surfactants more hydrophobic. Linear solvation energy relationships (LSERs) and free energy of transfer studies were also applied to predict the selectivity differences between the surfactant systems. The cohesiveness and the hydrogen bond acidic character of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention. The SUS and SDS showed the strongest while SUL showed the weakest hydrogen bond donating capacity. The basicity, interaction with n and π-electrons of the solute and dipolarity/polarizability were the least significant factors in LSER model for the surfactant systems studied. Free energies of transfer of selected functional groups in each surfactant systems were also calculated and found to be in good agreement with the LSER data.     

Safety neighbournoods for the invariants of the matrix similarity

We give safety neighbourhoods for the necessary conditions in the change of the Jordan canonical form of a matrix under small perturbations. We also obtain the minimum distance from an n × n complex matrix which has less than k nonconstant invariant factors (2≤ k≤ n) to the set of matrices which have more or equal to k. When k= 2, we get in particular the distance from a nonderogatory matrix to the set of derogatory matrices.     

Stereochemistry of organic sulphur compounds: 12—Configurational assignment of 2-methylsulphinyl-1-phenylethanol and some O-derivatives

The conformational analysis of the diastereomeric 2-methylsulphinyl-1-phenylethanol and its O-methyl and O-acetyl derivatives has been performed by ¹H NMR spectroscopy. The study of the influence of dilution and solvent polarity changes on the coupling constants has permitted the configurational assignment of each diastereoisomer. The role played by hydrogen bonding in the hydroxysulphoxides has also been studied by IR spectroscopy.