弱碱性低共熔溶剂溶解角蛋白过程及氢键机制  

Process and hydrogen bonding mechanism of keratin dissolution in weakly alkaline eutectic solvent

作　　者：刘屹首 李瑞鹏 秦大恩 宋凯利 LIU Yishou;LI Ruipeng;QIN Daen;SONG Kaili(Key Laboratory of Advanced Textile Materials&Manufacturing Technology,Ministry of Education,Zhejiang Sci-Tech University,Hangzhou 310018,Zhejiang,China;Engineering Research Center for Eco-Dying and Finishing of Textiles,Ministry of Education,Zhejiang Sci-Tech University,Hangzhou 310018,Zhejiang,China;Zhejiang Sci-Tech University Tongxiang Research Institute Co.,Ltd.,Tongxiang 314500,Zhejiang,China)

机构地区：[1]浙江理工大学先进纺织材料与制备技术教育部重点实验室,浙江杭州310018 [2]浙江理工大学生态染整技术教育部工程研究中心,浙江杭州310018 [3]浙江理工大学桐乡研究院有限公司,浙江桐乡314500

出　　处：《精细化工》2024年第8期1780-1787,1839,共9页Fine Chemicals

基　　金：国家自然科学基金项目(52303067);桐乡研究院开放基金项目(TYY202210);中国国家博士后面上基金项目(2020M681918)。

摘　　要：利用低共熔溶剂(DES)较强的氢键拆解能力定向解构角蛋白分子间的次级键,结合还原剂和DES高效断裂二硫键的能力,建立了一种弱损溶解并提取鸡毛中角蛋白的方法。以氯化胆碱为氢键受体(HBA)、乙醇胺、乙二醇、乳酸等为氢键供体(HBD),设计合成了3类(碱性、中性和酸性)13种功能性的DES,考察了还原剂用量(以鸡毛质量为基准,下同)、温度、DES中水质量分数对角蛋白相对分子质量和提取率的影响,通过密度泛函(DFT)理论计算和溶剂显色参数分析了DES内部的氢键网络结构,研究了DES对鸡毛角蛋白的弱损溶解机制。结果表明,以乙醇胺为HBD,不添加还原剂,在n(乙醇胺)∶n(氯化胆碱)=2∶1、DES中不含水、温度65℃、0.5h的最优条件下,再生角蛋白提取率为31.8%,相对分子质量最高,为66000。以乙醇胺为HBD制备的DES具有还原性,作为碱性DES,其内部的氢键数量多,氢键作用小,氢键能低,可以打乱鸡毛内部的氢键网络,而不会对鸡毛二级结构造成太大破坏。A method for dissolving and extracting keratin with little damage from chicken feathers was established by using the strong hydrogen bond dissolving ability of low eutectic solvent(DES)and the efficient disulfide bond breaking ability of reducing agent and DES.13 DES in three types(basic,neutral and acidic)were designed and synthesized using choline chloride as hydrogen bond acceptor(HBA),ethanolamine,ethylene glycol,lactic acid and so on as hydrogen bond donors(HBD),and the influence of reducing agent content(based on the mass of chicken feathers,the same below),temperature,water mass fraction in DES on the relative molecular mass and extraction rate of keratin were investigated.The hydrogen bond network structure in DES was analyzed by density functional theory(DFT)and solvent polarity parameters,and the dissolution mechanism of DES on chicken feather keratin with weak loss was studied.The results showed that under the optimal extraction process of using ethanolamine as HBD without reducing agent added,n(ethanolamine)∶n(choline chloride)=2∶1,temperature 65℃,no water in DES and extraction time of 0.5 h,regenerated keratin exhibited an extraction yield of 31.8%and the highest relative molecular mass of up to 66000.The DES prepared with ethanolamine as HBD displayed reducibility,and as basic DES,it showed large internal hydrogen bond number,small hydrogen bond action and low hydrogen bond energy,which could disrupt the hydrogen bond network inside the chicken feathers without causing too much damage to the secondary structure of the chicken feathers.

关 键 词：低共熔溶剂 角蛋白 溶解机制 分子模拟 氢键 分离提纯技术 

分 类 号：O636.9[理学—高分子化学]