Formation of an amylose-polyester inclusion complex by means of phosphorylase-catalyzed enzymatic polymerization of α-D-glucose 1-phosphate monomer in the presence of poly(ε-caprolactone)
Formation of an amylose-polyester inclusion complex by means of phosphorylase-catalyzed enzymatic polymerization of α-D-glucose 1-phosphate monomer in the presence of poly(ε-caprolactone)
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DOI：
10.1021/ma010606n
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发表时间：
2001-09-11
期刊：
影响因子：
5.5
通讯作者：
Tagaya, H
中科院分区：
文献类型：
--
作者：
Kadokawa, J;Kaneko, Y;Tagaya, H
生物大分子如蛋白质、核酸和多糖调节与“生活”相关的重要体内功能。这些大分子的重要生物学功能似乎不仅由它们的一级结构控制，而且还由更高级的结构控制，例如DNA的双螺旋。1因此，从与生物学研究相联系的观点来看，对具有更高结构顺序的合成高分子的精确结构的研究领域，即“超分子化学”，最近已变得重要。特别是与聚合化学相联系的超分子化学的研究，被认为是阐明天然存在的大分子的生物学机制的重要研究课题。直链淀粉是一种天然螺旋多糖，是一种众所周知的分子，与单体有机客体分子形成更高结构的有序复合物。3.然而，直链淀粉与高分子客体分子之间形成复合物的研究却鲜有报道。4.最近，我们发现了一种通过直链淀粉形成聚合形成直链淀粉-聚合物包合物的新方法。5以聚四氢呋喃为客体聚合物，磷酸化酶催化R-D-葡萄糖1-磷酸单体（Glc-1-P）的酶促聚合，实现了这一新方法。6该通讯报道了通过该聚合技术使用具有羟基端基的遥爪聚（ε-己内酯）（PCL）作为新的客体聚合物形成直链淀粉-聚酯包合物（方案1）。7除了包合物的制备外，我们还描述了包合物在碱性条件下的独特性质。在遥爪PCL（DP）9.0，Mn）ca.的存在下，以麦芽七糖（Glc 7）为引物进行Glc-1-P的磷酸化酶催化酶促聚合。1000）8的柠檬酸盐缓冲液中。9，10沉淀的产物通过1H NMR和X射线衍射（XRD）测量表征。产物的1H NMR谱显示不仅由于直链淀粉而且由于PCL的信号。相同产品的XRD扫描显示在2θ）12.4和19.8处有两个强衍射峰，分别对应于d）0.71和0.45 nm（图1b）。XRD图谱完全不同于直链淀粉的图谱（图1a），而与直链淀粉与聚-β-环糊精包合物的图谱相似。
The biological macromolecules such as proteins, nucleic acids, and polysaccharides accommodate the important in vivo functions associated with “living”. The important biological functions of these macromolecules appear to be controlled by not only their first-order structures but also those of higher-order structures, eg, a double helix of DNA. 1 The research field on precision architecture of synthetic macromolecules with higher structural order, ie,“supramolecular chemistry”, therefore, has recently been of importance from the viewpoint of contact with study on biological works. 2 Specially, the study on the supramolecular chemistry connected with polymerization chemistry is conceived as a significant research topic to elucidate the biological mechanism of naturally occurring macromolecules. Amylose, a natural helical polysaccharide, is a wellknown molecule forming higher structural ordered complexes with monomeric organic guest molecules. 3 However, the chemical formation of the complexes between amylose and polymeric guest molecules had been scarcely reported. 4 Recently, we have found a new methodology for formation of an amylose-polymer inclusion complex by means of amylose-forming polymerization. 5 Such a new method was achieved by an enzymatic polymerization of R-D-glucose 1-phosphate monomer (Glc-1-P) catalyzed by phosphorylase in the presence of polyTHF as a guest polymer. 6 This communication reports formation of an amylose-polyester inclusion complex by means of this polymerization technique using telechelic poly (ϵ-caprolactone)(PCL) with hydroxy end groups as a new guest polymer (Scheme 1). 7 In addition to the preparation of the inclusion complex, we also describe the unique property of the included PCL under alkaline conditions. The phosphorylase-catalyzed enzymatic polymerization of Glc-1-P from maltoheptaose (Glc7) as a primer was carried out in the presence of a telechelic PCL (DP) 9.0, Mn) ca. 1000) 8 with hydroxy end groups in citrate buffer. 9, 10 The precipitated product was characterized by means of the 1H NMR and X-ray diffraction (XRD) measurements. The 1H NMR spectrum of the product shows the signals due not only to the amylose but also to the PCL. The XRD scan of the same product indicates two strong diffraction maxima at 2θ) 12.4 and 19.8, corresponding to d) 0.71 and 0.45 nm, respectively (Figure 1b). The XRD pattern is completely different from that of amylose (Figure 1a) and is similar to that of the inclusion complex of amylose with poly-