纤维素酶降解壳聚糖的研究

通过测定溶液的粘度和还原糖浓度 ,探讨了温度、 p H值、反应时间、底物浓度、金属离子及壳聚糖的脱乙酰度对酶反应的影响 .结果表明 ,纤维素酶能很容易地降解壳聚糖 ,在 2 h内壳聚糖溶液粘度下降了 93 %.其催化特点是 :最适宜温度为 3 0～ 40℃ ,最适宜 p H值为 5 .0～ 6.0 ,米氏常数 Km=9.4× 1 0 -2 g/L,金属离子 Na+ ,Fe2 +对酶活性无影响 ;而 Zn2 + ,Mg2 + ,Cu2 + ,Li+ ,K+抑制酶活性 .当酶量与底物量达到1 5 mg/g时可达到最大反应速度 ;壳聚糖的脱乙酰度在 80 %～ 90 %时酶催化反应速度较快 .     

Unzipping and scrambling reaction-induced sequence control of copolymer chains via temperature changes during cationic ring-opening copolymerization of cyclic acetals and cyclic esters

A temperature change-dependent sequence transformation of copolymer chains was demonstrated by a method based on tandem depolymerization and transacetalization reactions during the cationic ring-opening copolymerization of cyclic acetals and cyclic esters. In this study, the position of polymerization-depolymerization equilibrium was controlled by the reaction temperature rather than by the decrease in monomer concentration under vacuum conditions, as in our previous study. First, the conditions for efficient copolymerization were optimized, with a particular focus on the structures of cyclic acetals and cyclic esters. Subsequently, sequence transformation induced by temperature change was examined during the copolymerization of 2-methyl-1,3-dioxepane (generated in situ from 4-hydroxybutyl vinyl ether) and δ-valerolactone using EtSO₃H. The homosequence length of cyclic acetals decreased during depolymerization (unzipping) at the oxonium chain ends upon increasing the temperature from 30 to 90 °C, while transacetalization (scrambling) of the main chain transferred midchain cyclic acetal homosequences to the oxonium chain ends. As a result of the cycle of unzipping and scrambling reactions, an alternating-like copolymer was obtained. Interestingly, the possibility of reversible sequence transformation upon heating and cooling was also demonstrated.     

Kinetic Analysis of Mechanochemical Chain Scission of Linear Poly(phthalaldehyde)

The kinetics of mechanochemical chain scission of poly(phthalaldehyde) (PPA) are investigated. Ultrasound‐induced cavitation is capable of causing chain scission in the PPA backbone that ultimately leads to rapid depolymerization of each resulting polymer fragment when above the polymer's ceiling temperature (T_c). An interesting feature of the mechanochemical breakdown of PPA is that “half‐chain” daughter fragments are not observed, since the depolymerization is rapid following chain scission. These features facilitate the determination of rate constants of activation for multiple molecular weights from a single sonication experiment. Additionally, the degradation kinetics are modified with chain‐end trapping agents through variation of the nature and amount of small molecule nucleophile or electrophile.