邻苯二甲酸L-(+)-2,3-O-亚异丙基苏力糖酯的两种构象式的螺旋结构与旋光性

在晶 (固 )态下 ,化合物邻苯二甲酸 L-( +) -2 ,3 -O-亚异丙基苏力糖酯存在两种不同的构象形式 ,利用螺旋片段判定规则及ω值 ,结合 X射线衍射数据及扭转角数据 ,对这两种构象形式的所有螺旋片段进行了分析 ,尽管两种构象形式的净值螺旋性相反 ,但仍然得出总净值螺旋性与旋光方向一致的结论     

Titration calorimetric determination of the pairwise interaction parameters of glycerol,D-threitol,mannitol, and D-glucitol in dilute aqueous solutions

Enthalpic pairwise interaction parameters, h_jj, were determined by titration calorimetry at 25°C for dilute solutions of glycerol, D-threitol, manitol, and D-glucitol in water. The parameters for these and other polyols conform to the expression h_jj (J-kg^–1)=145+135n_OH–21.5n _OH ² –41.7 _dl ² -160.5n_dlld, where n_OH=n_C is the number of hydroxyl groups (carbon atoms), n_dl is the number of dl configuration of a vicinal pair of OH-groups, and n_dlld is the number of such configurations in the polyol molecules. A rationalization of this expression is given.     

甲基硼酸衍生法测定丁四醇中的碳同位素

对赤藻糖醇和苏阿糖醇进行甲基硼酸衍生化,并对反应物和生成的环状硼酸酯衍生产物进行稳定碳同位素测定.采用元素分析/同位素比质谱(EA/IRMS)对固体赤藻糖醇、苏阿糖醇、甲基硼酸的碳同位素的测定和气相色谱/燃烧/同位素比质谱(GC/C/IRM)对硼酸酯衍生产物的同位素测定的结果表明,当衍生化反应温度为60 ℃,反应时间为60 min,甲基硼酸和四醇化合物的摩尔比为10: 1时,通过反应物的同位素值及质量平衡关系计算而得的硼酸酯的δ13C数值和实际测定的产物的碳同位素之间的差异小于0.5‰,在该衍生化反应过程中不存在同位素分馏.此外,在GC/MS上,对赤藻糖醇、苏阿糖醇、2-甲基赤藻糖醇、2-甲基苏阿糖醇的甲基硼酸酯衍生产物进行确认,为进一步对天然源气溶胶中的2-甲基丁四醇进行稳定碳同位素分析提供实验基础.     

Linear polyurethanes derived from alditols and diisocyanates

A set of linear [m,n]‐type polyurethanes was synthesized by polycondensation in solution from hexamethylene diisocyanate and 4,4′‐methylene‐bis(phenyl isocyanate) with alditols. Threitol, arabinitol, and xylitol bearing the secondary hydroxy groups blocked as methyl ethers were used. Either regioregular or nonregioregular polymers (depending on the configuration of the alditol) were obtained in high yields and with number‐average molecular weights within the 20,000–30,000 range. All these polyurethanes were amorphous with T_g being highly dependent on the aliphatic or aromatic nature of the diisocyanate used, but scarcely depending on the chemical structure of the alditol moiety. They were found to be stable up to near 300 °C, decomposing at higher temperatures through a complex three‐stage mechanism. Polyurethanes obtained from threitol did not show significant enhancement of hydrolytic degradability as compared with polyurethanes obtained from 1,4‐butanediol. Conversely, polyurethane prepared from xylitol and hexamethylendiisocyanate was found to be almost fully hydrolyzed in 1 month when incubated in water either at 80 °C and pH 7.4 or at 37 °C and pH 10. It was concluded that the alditol size seems to be of prime importance in determining the hydrodegradability of these sugar containing polyurethanes. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4109–4117, 2007