Preparation of mew functional dehydrogenative polymer (DHP) from γ-substituted monolignol derivatives

γ-取代木质素单体衍生物制备新功能脱氢聚合物（DHP）

• 批准号: 18580162
• 负责人: TAKANO Toshiyuki
• 金额: $ 2.48万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18580162/
• 关键词: Lignin; Monolignol; Sinapyl alcohol; Toll-like receptor-ligand; Ferulic acid; Two dimensional polymerization; シナピルアルコール; キノメタイド; 自己組織化

Two type of γ-substituted monolignol derivatives were selected ; one was monolignol glycoside in which a hydrophilic group (D-glucose) was introduced, the another was ferulic alkyl ester in which a hydrophobic group (n-decanoyl group) was introduced., and their dehydrogenative polymerizations were investigated.The dehydrogenative polymerizations of monolignol glycoside proceeds homogeneously to afford water soluble DHP, whereas the polymerization of monolignol proceeds heterogeneously. It was found that the polymerization behaviors in the polymerizations of monolignol glycoside were reflected with those in the polymerizations of monolignol. And the in suit UV analysis of the polymerization of monolignol glycoside revealed that unexpected stability of the intermediate (quinine methide) is one of the reasons for the peculiar polymerization behaviors of sinapyl alcohol.The dehydrogenative polymerizations of ferulic alkyl ester by two dimensional method and by micelle method were carried out. The DHPs obtained are quietly different from DHP by normal dehydrogenative polymerization, suggesting that the hydrophobic group significantly influenced to the chemical structure of DHP.

选择了两种γ取代的单甘醇衍生物，一种是引入亲水基团(D-葡萄糖)的单甘醇糖苷，另一种是引入疏水基团(正癸酰基)的阿魏酸烷基酯，考察了它们的脱氢聚合反应。研究发现，单甘醇糖苷的聚合行为与单甘醇的聚合行为是一致的。单甘醇糖苷聚合的现场UV分析表明，中间体(甲基奎宁)的意外稳定性是芥子醇具有特殊聚合行为的原因之一。采用二维法和胶束法对阿魏酸酯进行了脱氢聚合。得到的DHP与常规脱氢聚合得到的DHP相差不大，说明疏水基团对DHP的化学结构有显著影响。

项目成果

"Studies on the dehydrogenative polymerization from monolignol β-glycosides. Part 3. Horseradish peroxidase catalyzed dehydrogenative polymerization of triandrin and isosyringin."

“单木质醇 β-糖苷脱氢聚合的研究。第 3 部分。辣根过氧化物酶催化三苯醌和异丁香苷的脱氢聚合。”

• 发表时间: 2008
• 期刊: Journal of Wood Chemistry and Technology (In press)
• 作者: Yuki Tobimatsu;et. al.
• 通讯作者: et. al.

"求核試薬存在下におけるシナピルアルコールの脱水素重合"

“在亲核试剂存在下芥子醇脱氢”

• 发表时间: 2008
• 作者: Yuki Tobimatsu;et. al.;飛松 裕基
• 通讯作者: 飛松 裕基

モノリグノール配糖体によるシリンギル型DHPの生成挙動解析

木质素单苷生成紫丁香基型 DHP 的行为分析

• 发表时间: 2007
• 作者: 飛松裕基;上高原浩;高野俊幸;中坪文明
• 通讯作者: 中坪文明

Azido ion as a quinone methide scavenger in the horseradish peroxidase-catalyzed polymerization of sinapyl alcohol

叠氮离子作为辣根过氧化物酶催化芥子醇聚合中醌甲基化物清除剂

• 发表时间: 2008
• 期刊: Journal of Wood Science 54
• 作者: Y. Tobimatsu;T. Takano;H;Kamitakahara;F. Nakatsubo
• 通讯作者: F. Nakatsubo

"Studies on the dehydrogenative polymerization from monolignol β-glycosides. Part 2. Horseradish peroxidase catalyzed dehydrogenative polymerization of isoconiferin."

“单木质醇 β-糖苷脱氢聚合的研究。第 2 部分。辣根过氧化物酶催化异松柏苷的脱氢聚合。”

• 发表时间: 2006
• 期刊: Holzforschung 60
• 作者: Yuki Tobimatsu;et. al.
• 通讯作者: et. al.