A novel,efficient procedure for acylation of cellulose under homogeneous solution conditions

Commercially available cellulose (Avicel PH101) was successfully acylated under homogeneous solution conditions by the following novel procedure: 2.0 g of cellulose and 5.0 g of LiCl were introduced into a glass reactor, magnetic stirring was started, the pressure was reduced to 2 mmHg, the temperature was raised to 110°C in 30 min, and the reactor was kept under these conditions for another 30 min. N,N‐Dimethylacetamide, 60 mL, was introduced, atmospheric pressure was restored, and the temperature was raised to 150°C in 30 min. The system was kept under these conditions for 1 h, then the temperature was decreased to 40°C; in 2 h a clear cellulose solution was obtained. Acid anhydride was added, and the solution was stirred at 60°C for additional 18 h. Acetates, propionates, butyrates, and acetate/butyrate mixed ester were prepared with excellent reproducibility of the degree of substitution, from 1 to 3. The degree of polymerization of cellulose is negligibly affected by these reaction conditions. The distribution of the acetyl moiety among the three OH groups of the anhydroglucose unit follows the order C₆ > C₂ > C₃. Features relevant to the industrial application of this novel procedure are discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1355–1360, 1999     

二烷基酰亚胺萃取剂的合成与表征

以丙酰氯、正戊酰氯、正庚酰氯为酰化试剂,在温度≤10℃下分别与氨水反应生成丙酰胺、正戊酰胺和正庚酰胺. 以吡啶作缚酸剂,将生成的酰胺与含相同碳链长的酰氯在温度≤0℃下反应,得到3种具有对称结构的含直链烷基的二烷基酰亚胺(二丙酰亚胺、二正戊酰亚胺和二正庚酰亚胺),对终产物进行了表征. 结果表明,以乙醇为良溶剂、水为不良溶剂,经多次重结晶后其最终产率分别为30%, 35%, 33%,终产物的熔点分别为153.7~154.0, 91.5~91.7, 89.0~89.5℃,二烷基酰亚胺纯度大于99%.     

笃斯越橘酰化花青素稳定性分析

采用分光光度法,通过多梯度、多组合系列试验,对光照、温度、金属离子、氧化剂、还原剂等因素下的笃斯越橘酰化花青素和笃斯越橘花青素的稳定性进行比较分析。研究表明,与未酰化的花青素相比,酰化花青素耐光性提高,各种环境里的抗色素分解能力增加。Fe2+、Fe3+、Cu2+对无论酰化与否的花青素都会产生不同程度的不利影响,在色素应用过程中（加工、保存及运输）应避免与其接触。结果证明,笃斯越橘酰化花青素稳定性优于未经修饰的花青素,有较高的开发应用和研究价值。     

琥珀酰化改性花生蛋白研究

为考察琥珀酰化改性因素对花生蛋白改性效果及结构性质的影响,采用单因素试验、响应面试验分析花生蛋白质量浓度、琥珀酸酐添加量、反应温度对改性花生蛋白酰化度与产率的影响,确定最优琥珀酰化改性条件。通过红外光谱、电子显微镜、氮溶解指数评价琥珀酰化改性花生蛋白的结构性质。结果表明:花生蛋白质量浓度、琥珀酸酐添加量是显著影响因素;最佳改性条件为花生蛋白质量浓度58.5 g/L、琥珀酸酐添加量为花生蛋白质量的19.55%、反应温度49℃,在最佳条件下改性花生蛋白酰化度与产率分别为(82.82±0.59)%和(76.89±0.74)%;引入琥珀酰基改变了花生蛋白的分子结构,使蛋白质分子由折叠趋向伸展,蛋白质聚集体尺寸减小;改性花生蛋白的溶解性得到明显改善。     

酶催化的多糖酯化反应研究进展

酯化改性可以赋予多糖诸多新的优异性能,拓宽工业应用前景。作为生物催化剂的酶可以在有机溶剂中对多糖进行对映选择性、区域选择性的酯化,具有条件温和、步骤简单、无须基团保护、产物可生物降解等优点,符合绿色化学的理念。本文从酶催化多糖酯合成的影响因素、多糖酯的酶催化制备方法方面综述了酶催化多糖酯化反应的研究进展。     

Regioselective acylation of pyridoxine catalyzed by immobilized lipase in ionic liquid

The regioselective acylation of pyridoxine catalyzed by immobilized lipase (Candida Antarctica) in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF₆) has been investigated, and compared with that in acetonitrile (ACN). The acetylation of pyridoxine using acetic anhydride in [BMIM]PF₆ gave comparable conversion of pyridoxine to 5-monoacetyl pyridoxine with considerably higher regioselectivity (93%–95%) than that in ACN (70%–73%). Among the tested parameters, water activity (a _w) and temperature have profound effects on the reaction performances in either [BMIM]PF₆ or ACN. For the reaction in [BMIM] PF₆, higher temperature (50°C–55°C) and lower a _w (<0.01) are preferable conditions to obtain better conversion and regioselectivity. Mass transfer limitation and intrinsic kinetic from the ionic nature of ionic liquids (ILs) may account for a different rate-temperature profile and a lower velocity at lower temperature in [BMIM]PF₆-mediated reaction. Moreover, consecutive batch reactions for enzyme reuse also show that lipase exhibited a much higher thermal stability and better reusability in [BMIM]PF₆ than in ACN, which represents another advantage of ILs as an alternative to traditional solvents beyond green technology.     

聚氨酯用羟基化合物羟值的分析

综述了聚氨酯用羟基化合物羟值的分析方法,并对各种方法进行了分析比较。基于醇羟基和酚羟基化合物的特殊性,分析方法有类似又有区别,实际工作中要区别对待。     

Non‐Enzymatic Geometry‐Selective Acylation of Tri‐ and Tetrasubstituted α,α′‐Alkenediols

A highly geometry‐selective organocatalytic acylation of tri‐ and tetra‐substituted 2‐alkylidene‐1,3‐propanediols has been developed. The highly E‐selective acylation of various tetrasubstituted 2‐alkylidene‐1,3‐propanediols was achieved in 96 to >99% selectivity for the first time by a non‐enzymatic protocol.