Enthalpy of solution of phenoxyalcohols solubilized in aqueous sodium dodecylsulfate and hexadecyltrimethylammonium bromide solutions

The enthalpy of solution of phenoxy 2-ethanol, 1 phenoxy,-3 propanol and benzylalcohol was determined at 25 °C in aqueous sodium dodecylsulfate and hexadecyltrimethylammonium bromide solution, up to 0.2 mol/kg surfactant concentration. Using the pseudo-phase model, the standard enthalpy of transfer and the partition coefficient of the alcohols between micelle and water are calculated. The latter quantity is found to be systematically larger when derived from enthalpy than from free energy measurements. Using the so-called compensation plot, the solution thermodynamics of aromatic and aliphatic alcohols in aqueous sodium dodecylsulfate and in the octane+water systems are compared. Aromatic alcohols display an anomalous behavior in the octane+ water system but not in the micellar one.The standard enthalpy of solution of various alcohols presents, when plotted against hexadecyltrimethylammonium bromide concentration, a shoulder in the region around 0.05 mol/kg; a discussion is presented on the evidence for alleged micellar structural changes in aqueous micellar systems.     

An investigation of heparinase immobilization

A systematic investigation of the parameters that affect the efficiency of immobilizing heparinase onto cyanogen bromide activated crosslinked 8% agarose beads was conducted. Two experimental measures, the “fraction bound” and the “fraction retained,” were used to monitor the coupling efficiency. The fraction bound is the portion of the total initial enzyme that is bound to the agarose gel. The fraction retained is the fraction of bound enzyme that is active. The product of the two measures indicates the coupling efficiency. The activity of the immobilized heparinase was measured under conditions free of both internal and external mass transfer limitations, and thus, the fraction retained represents the true immobilized enzyme activity. Increasing the degree of activation of the beads results in an increase in the fraction bound, the fraction retained, and consequently, the coupling efficiency. As the ratio of enzyme solution to gel volume increases from 1.5 to 2.2, the fraction bound remains constant but the fraction retained decreases (heparinase concentration; 0.15 mg/mL and degree of activation; 9.5 μmol of cyanate esters/g of gel). At volume ratios greater than 2.2, both the fraction bound and the fraction retained decline continuously. Changing the heparinase concentration in the coupling solution changes the coupling efficiency in a manner similar to that of the volume ratio change. When heparin is added during the coupling process, the fraction bound declines as the heparin concentration increases, whereas the fraction retained increases up to a heparin concentration of 12 mg/mL and decreases thereafter. When arginine, lysine, and glycine are used to block the unreacted cyanate ester groups after the coupling process, the immobilized heparinase shows different pH optima of 6.5, 6.9, and 7.2, respectively. Based upon these findings, a protocol to optimize heparinase immobilization is developed.     

Solubility of copper (I) bromide in aqueous solutions of potassium bromide

The solubilities of cuprous bromide were measured at 24.8°C in aqueous KBr and in aqueous KBr-KNO₃ mixtures. The results have been analyzed to give equilibrium constanns from formation of neutral and negatively charged complexes of CuBr, and sets of virial parameters suitable for calculation of activity coefficients for the complexes.     

Micellization of Alkyltriphenylphosphonium Bromides in Ethylene Glycol and Diethylene Glycol + Water Mixtures: Thermodynamic and Kinetic Investigation

The thermodynamics of micellization and other micellar properties of alkyl- (C₁₀-, C₁₂-, C₁₄- and C₁₆-) triphenylphosphonium bromides in water + ethylene glycol (EG) (0 to 30% v/v) mixtures over a temperature range of 298 to 318 K and cetyltriphenylphosphonium bromide in water + diethylene glycol (DEG) mixtures (0 to 30% v/v) at 298 K have been studied conductometrically. In all cases, an increase in the percentage of co-solvent results in an increase in the cmc values. On the basis of these results, the thermodynamic parameters, the Gibbs energy (ΔG _m^o), enthalpy (ΔH _m^o) and entropy (ΔS _m^o) of micellization have been evaluated. In addition to the conductivity measurements, kinetic experiments have also been done to determine the dependence of observed rate constant for the nucleophilic substitution reaction of p-nitrophenyl acetate and benzohydroxamate ions in the presence of the surfactant cetyltriphenylphosphonium bromide with a varying concentration of EG and DEG ranging from 0 to 50% v/v at pH=7.9 and 300 K. All of the reactions followed pseudo-first-order kinetics. An increase in the surfactant concentration results in an increase in the reaction rate and for a given surfactant concentration, the rate constant decreases as the concentration of co-solvent in the mixture increases. The kinetic micellar effects have been explained by using the pseudophase model. The thermodynamic and structural changes originating from the presence of solvents control the micellar kinetic effects.     

An efficient large-scale synthesis of gemcitabine employing a crystalline 2,2-difluoro-α-ribofuranosyl bromide

An efficient large-scale synthesis of gemcitabine was achieved without chromatography or fractional crystallization. The key steps include stereospecific conversion of a novel β-ribofuranosyl phosphate into a highly crystalline α-ribofuranosyl bromide and coupling of the α-ribofuranosyl bromide and trimethylsilyl cytosine to produce a β-nucleoside. p-Phenylbenzoyl group was introduced for the protection of one of hydroxy groups in order to enhance the crystallinity of intermediates. Continuous removal of trimethylsilyl bromide, generated during the coupling reaction, by distillation from the reaction medium substantially enhanced the β-selectivity of the crucial coupling reaction.     

DSC Investigations of DDAB,DTAB and DHAB Vesicle Aqueous Solutions in Presence of SDS

Interactions of anionic surfactant sodium dodecyl sulphate (SDS) with vesicles formed by synthetic dialkyldimethylammonium bromides i.e. didodecyldimethylammonium bromide (DDAB), ditetradecyldimethylammonium bromide (DTAB), dihexadecyldimethylammonium bromide (DHAB) have been examined by using differential scanning microcalorimetry and electron transmission microscopy. The temperatures and standard enthalpies characterising gel to liquid-crystal transitions increase significantly with increase of SDS concentration for all investigated systems. It means that incorporation of SDS monomers in these vesicular bilayers significantly stabilises their gel states. Moreover, in case of DDAB and DTAB vesicle systems added SDS limits kinetic features of recorded isobaric heat capacity dependencies on temperature observed earlier for the pure vesicular solutions. This revised version was published online in July 2006 with corrections to the Cover Date.     

硫酸铵-溴化钾-乙醇体系萃取分离金

研究了(NH4)2SO4存在下,KBr-乙醇体系萃取分离Au(Ⅲ）的行为。实验表明,Br^-与Au(Ⅲ）形成的AuBr4^-很容易被萃取到乙醇相中。当溶液中KBr、(NH4)2SO4和无水乙醇浓度分别为0．04g／mL、0．30g／mL、30％(V／V),pH=2—4时能使Au(Ⅲ）的萃取率达到100％,Al（Ⅲ）、Ni(Ⅱ)、Mn(Ⅱ)、Cr（Ⅲ）、Co(Ⅱ)、Fe（Ⅲ）、Zn(Ⅱ)、Cu(Ⅱ)、Mo（Ⅵ)、U(Ⅳ)基本不被萃取,实现了Au（Ⅲ）与上述离子的分离。     

Mixed micelles of tetradecyltrimethylammonium bromide and chlorhexidine digluconate in aqueous solutions of isopropyl alcohol

The influence of isopropyl alcohol (IPA) on the size and composition of the mixed micelles in mixtures of tetradecyltrimethylammonium bromide (TTAB) and chlorhexidine digluconate (CG) has been determined as a function of the composition of the systems. The addition of 0.5 M and 1.0 M IPA had little significant effect on the composition of the mixed micelles as determined both by analysis of critical micelle concentration (CMC) data using a theoretical treatment based on excess thermodynamic quantities and by an empirical treatment of conductivity data. Static and quasielastic light scattering measurements showed a progressive decrease of the aggregation number and hydrodynamic radius of TTAB micelles on addition of IPA, but minimal changes in the properties of the small CG aggregates. The results show that the micellar weight in the TTAB/CG/IPA solutions is determined by the ratio of the surfactants in the system and for each TTAB/CG ratio decreases on addition of IPA.     

The solubilization of alcohols in micellar solutions

The specific conductivities of dodecyldimethylbenzylammonium bromide (C12BBr) have been determined in aqueous butanol and aqueous benzyl alcohol solutions in the temperature range of 5-40°C. From these data the temperature dependent critical micelle concentration (cmc) was determined. The molar fraction of alcohol in the micelle was estimated using the theory suggested by Motomura et al. for surfactant binary mixtures. The thermal properties such as standard Gibbs free energy, enthalpy and entropy of solubilization of alcohols in the micelles were estimated for the phase separation model. The change in heat capacity upon solubilization of alcohol in the micelle has been estimated form the above properties. This revised version was published online in July 2006 with corrections to the Cover Date.