非质子聚醚诱导的聚羟基烷酸酯分子量的降低为链转移剂的作用机制提供了新的见解

IF 7.4 2区 化学 Q1 POLYMER SCIENCE
Seiya Tanaka , Hiroshi Kikukawa , Hirotsugu Nakai , Shuzo Arai , Ayaka Kajikawa , Shin-ichi Hachisuka , Ken’ichiro Matsumoto
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引用次数: 0

摘要

一些醇类,如二甘醇(DEG),在聚羟基烷酸酯(PHA)生物合成过程中与聚合物链末端结合,被称为链转移(CT)剂。此外,CT制剂在PHA生物合成中的存在降低了PHA的分子量。本研究考察了与DEG结构相似的非质子聚醚、二甘醇二甲醚(DGDM)和三甘醇二甲醚(TGDM)是否能降低PHA的分子量。聚(3-羟基丁酸酯)[P(3HB)]是用表达PHA合成酶PhaCAR (I类)或PhaC1PsSTQK (II类)的工程大肠杆菌和在含有3HB、DEG、DGDM或TGDM的培养基上生长的提供单体的酶合成的。DGDM和TGDM降低了PhaCAR合成的P(3HB)的分子量。从聚合物中未检测到非质子聚醚,表明它们不作为CT剂。免疫印迹分析显示,非质子聚醚和DEG的加入没有改变PhaCAR的表达。此外,体外实验显示PhaCAR对聚合活性没有明显影响。然而,对于PhaC1PsSTQK,未观察到非质子聚醚对分子量的降低,这表明非质子聚醚的作用取决于PhaC类。综上所述,尽管非质子聚醚降低了PHA的分子量,但仍有必要进一步研究其不同于典型CT反应的潜在机制。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Aprotic polyether-induced decrease in the molecular weight of polyhydroxyalkanoate provides insights into the mechanism of action of chain-transfer agents
Some alcohols, such as diethylene glycol (DEG), bound to the polymer chain ends during polyhydroxyalkanoate (PHA) biosynthesis, are called chain-transfer (CT) agents. Moreover, the presence of CT agents in PHA biosynthesis decreases molecular weight of PHA. This study investigated whether the aprotic polyethers, diethylene glycol dimethyl ether (DGDM) and triethylene glycol dimethyl ether (TGDM), which are structurally similar to DEG, can decrease the molecular weight of PHA. Poly(3-hydroxybutyrate) [P(3HB)] was synthesized using engineered Escherichia coli expressing PHA synthase PhaCAR (class I) or PhaC1PsSTQK (class II) and a monomer-supplying enzyme grown on medium containing 3HB, and DEG, DGDM, or TGDM. DGDM and TGDM decreased the molecular weight of P(3HB) synthesized using PhaCAR. The aprotic polyethers were not detected from the polymers, indicating that they did not act as CT agents. Immunoblotting analysis revealed that the addition of the aprotic polyethers and DEG did not alter PhaCAR expression. Moreover, the in vitro assay exhibited no apparent effect of PhaCAR on polymerization activity. However, the decrease in the molecular weight by aprotic polyethers was not observed for PhaC1PsSTQK, indicating that the effect of aprotic polyethers depends on PhaC class. In conclusion, although the aprotic polyethers decrease the molecular weight of PHA, further studies are necessary to understand the underlying mechanisms different from typical CT reaction.
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来源期刊
Polymer Degradation and Stability
Polymer Degradation and Stability 化学-高分子科学
CiteScore
10.10
自引率
10.20%
发文量
325
审稿时长
23 days
期刊介绍: Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology. Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal. However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.
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