Glass capillary gas chromatography of amino acid enantiomers

Glass capillaries coated with Chirasil-Val, a chirally functionalised polysiloxane, are capable in principle of resolving all protein amino-acid enantiomers in a single run and within a short analysis time, thus allowing for example the quantitative amino acid determination by enantiomer labelling. The elution characteristics of the individual amino acids however are also dependent upon the chemical nature of the capillary wall surface, and a surface pretreatment is found to be necessary if all protein amino acids are to be analysed. Of the various methods of pretreatment tested, etching of borosilicate glass with gaseous HCl followed by deposition of colloidal silicic acid is considered to be the most suitable.     

Structure elucidation of triglycerides by chromatographic techniques. Part 1: Capillary GC of ozonized triglycerides

Structure determination of triglycerides according to their number of unsaturated fatty acids (N.U.F.A.) is more easily achieved after ozonolysis of their mixtures (fats and oils) than by capillary gas chromatographic analysis of the mixture as such. Analyses performed before and after ozonolysis of cocoa buttel, hazelnut oil, and a mixture of both fats illustrate the potential of this approach to the structure elucidation of triglycerides by chromatographic techniques.     

The Glass Transition of Water and Aqueous Systems

After a brief introduction of the terms supercooling, amorphous solid state, glass transition and devitrification, the known ways of production of amorphous solid water are discussed. DSC experiments with quench cooled aqueous solutions show the phenomenon of glass transition and devitrification.This revised version was published online in November 2005 with corrections to the Cover Date.     

Oxidation of dibenzothiophene catalyzed by heme-containing enzymes encapsulated in sol-gel glass

We have encapsulated several hemoproteins in the sol-gel glass to catalyze the oxidation reaction of dibenzothiophene (model for organic sulfur compounds in coal) with hydrogen peroxide. In addition to cytochrome c and myoglobin, which have previously been encapsulated in sol-gel glasses, two other hemoproteins, horseradish peroxidase and bovine blood hemoglobin, have now been successfully immobilized in sol-gel media with the retention of their spectroscopic properties. All four hemoproteins studied also demonstrate similar catalytic activities toward the oxidation of dibenzothiophene as compared with the results obtained with the proteins in solution. In the case of encapsulated cytochrome c, the more water-soluble S-oxide was obtained with much higher selectivity over the less water-soluble sulfone (S-oxide/sulfone = 7.1) as compared to what was obtained in the aqueous/organic medium (S-oxide/sulfone = 2.3). Because of the advantage of easy separation of the encapsulated proteins from the liquid reaction mixture, it is clear from these studies that the immobilization of active hemoproteins in the solid glass media could serve as more practical biocatalysts.     

On the correlation of the glass transition temperature of a copolymer with its comonomer sequences

The glass transition temperature of a copolymer depends not only on chemical composition but also on its comonomer sequences. This experimental fact is explained by Barton's and Johnston's equations. Their equations, though complicated, become simple, if a suitable parameter is used to describe the comonomer sequences. It is shown that with these new expressions, their equations can be used to understand glass transition temperatures of two additional types of copolymers, compatible multiblock copolymers and homopolymers with various tacticities treated as steric copolymers.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayWe wish to thank the reviewer for his/her kind linguistic improvement of this article.     

Hole Burning and Fluorescence Spectra of Sol-Gel Derived Sm2+-Doped Glasses

Sm2+-doped glasses in the system of Al2O3-SiO2 were prepared by sol-gel processing of metal alkoxides and reacting with H2 gas at 800°C. The hole burning properties of these glasses were investigated. The holes were burned in the 7F0 5D0 line of the Sm2+ ions using a DCM dye laser at 77 K. The hole depth increased with increasing the laser irradiation time, reaching up to 15% of the total intensity within a few hundred seconds. The hole width was 3 cm–1 full width at half maximum. Fluorescence line narrowing spectra of the 5D0 7 F1 transition were analyzed to study the local structure surrounding the Sm2+ ion. It is concluded that the Sm2+ ions are closely coordinated with nine oxygens of the AlO6 group in aluminosilicate glasses and that the addition of Al3+ ions into glass induces an increase in the coordination number of the Sm2+.     

Epoxy-based azo molecular glasses with four-arm architecture: Preparation,characterization and holographic recording

A series of epoxy-based azo molecular glasses with four-arm architecture was synthesized, characterized and applied to holographic recording.     

A DSC study of the effects of sugars on thermal properties of rice starch gels before and after aging

Thermal characterization of gelatinized binary rice starch-water and ternary starch-sugar-water gels before and after aging was carried out using differential scanning calorimetry. The glass transition temperature of the maximally freeze-concentrated solution (T_g) in both fresh and aged gels was observed to decrease progressively with increasing sugar concentration. Aging of the gels generally shiftedT_g to higher temperatures, but had little or no effect on the ice melting peak temperature (T _m). The presence of various sugars could either accelerate or retard starch (amylopectin) recrystallization, depending on the type and concentration of sugar, as well as on starch/water ratio. A hypothesis based on the dual antiplasticizing-plasticizing effects of sugars was postulated to explain the observed effects. Of the sugars studied, xylose and fructose appeared to display exceptional retardative and accelerative effects, respectively, on retrogradation.This study was funded by a Sixth Malaysia Plan R&D grant under the Intensification of Research Priority Areas (IRPA) Program of the Ministry of Science, Technology and Environment, Malaysia. We thank Dr. Harry Levine and Dr. Louise Slade for giving us the opportunity to contribute a paper to this special issue of JTA.     

一种非晶硅膜改性弹性玻璃毛细管交联中等极性固定相色谱柱的制备

研究了非晶硅膜改性的弹性玻璃毛细管交联ＯＶ－１７０１中等极性固定相色谱柱。在适当温度下，采用过氧化二异丙苯（ＤＣＵＰ）游离基引发交联ＯＶ－１７０１固定液，成功地制备了交联ＯＶ－１７０１柱，该柱具有柱效高、惰性好、耐溶剂、抗腐蚀和耐高温等性能，是一种新型高性能的中等极性交联柱。     

Glass capillary columns for separation of free organic acids

Glass capillary columns have been prepared without acidic additive in the stationary phase, from which free organic acids elute as sharp and symmetrical peaks. The required surface in the borosilicate glass capillary was generated by a combination of leaching with aqueous HCl and deposition of colloidal silica particles; it can be coated with stationary phases have a broad range of polarity. Aqueous samples containing free organic acids can also be analyzed in such columns in an isothermal mode.