碳-单体同位素分析(C-CSIA)技术用于葡萄糖液化机理研究  

Research on Liquefaction Mechanism of Glucose by Carbon-Compound Specific Isotope Analysis

作　　者：郭康 沈娟章[1] 蒋剑春[1] 徐俊明[1] 谭卫红[1] GUO Kang;SHEN Juan-zhang;JIANG Jian-chun;XU Jun-ming;TAN Wei-hong(National Engineering Lab for Biomass Chemical Utilization,Key and Open Lab of Forest Chemical Engineering,SAF,Key Lab of Biomass Energy and Material,Institute of Chemical Industry of Forest Products,Chinese Academy of Forestry,Nanjing 210042,China;Co-innovation Center of Efficient Processing and Utilization of Forest Resources,Nanjing Forestry University,Nanjing 210037,China)

机构地区：[1]中国林业科学研究院林产化学工业研究所,生物质化学利用国家工程实验室,国家林业局林产化学工程重点开放性实验室,江苏省生物质能源与材料重点实验室,江苏南京210042 [2]南京林业大学,江苏省林业资源高效加工利用协同创新中心,江苏南京210037

出　　处：《质谱学报》2020年第6期604-613,I0005,共11页Journal of Chinese Mass Spectrometry Society

基　　金：国家自然科学基金重点项目(31530010)资助。

摘　　要：建立了碳-单体同位素分析(C-CSIA)技术测定葡萄糖液化产物中特定目标化合物的碳稳定同位素比值分析方法,分析得到的单体化合物δ13 C值误差小于0.3‰,低于仪器测试允许的偏差(0.5‰)。当葡萄糖在不同温度下液化时,对比了中间产物1,4;3,6-二脱水-α-d-吡喃葡萄糖(DGP)的碳稳定同位素变化及分馏特征。发现温度较低时,DGP发生显著的碳稳定同位素贫化效应,温度越高,DGP分子的碳稳定同位素富集因子越大。此外,在葡萄糖脱水生成DGP过程中仅发生C—O、C—H键的断裂及形成,而在DGP生成乙酰丙酸乙酯过程中,因脱羧、重排异构化反应等,不仅发生了C—O、C—H键断裂及形成,还有C—C键参与反应,导致后者具有更显著的碳稳定同位素动力学效应。该方法适用于葡萄糖催化液化等复杂体系的反应路径研究,可为液化机理研究提供信息。In recent years,the compound specific isotope analysis(CSIA)technology can be directly used to determine the stable isotope ratio of the element to be measured in a specific compound in the reaction system,and the analysis results are not affected by the reaction environment and have high accuracy.Therefore,this technology is not only applied to the transformation of environmental organic pollutants,but also gradually applied to the study of specific chemical reaction mechanism.In this paper,the carbon isotope ratio analysis method of specific target compounds in the liquefied products of glucose was established by C-CSIA,and the standard deviation ofδ13 C test value of the specific compounds was less than 0.3‰.Theδ13 C value and fractionation characteristics of intermediate products 1,4;3,6-dianhydro-alpha-d-glucopyranose(DGP)were compared with different liquefaction temperatures.At low temperature,the stable isotope ratio of the DGP has significant carbon isotope dilution effect,and the DGP gradually has carbon isotope enrichment effect when the temperature increases.At 140℃,theδ13 C value of the DGP decreases from(-15.89±0.08)‰to(-17.79±0.09)‰,and at this point,the carbon stable isotope ratio of DGP shows dilution effect during the liquefaction process,and the dilution value is-1.90‰.When the liquefaction temperature is 160℃,theδ13 C value of DGP increases from(-15.66±0.17)‰to(-11.95±0.09)‰,while theδ13 C of DGP increases from(-18.09±0.16)‰to(-9.26±0.06)‰at 180℃,the carbon stable isotope enrichment values are 3.71‰and 8.83‰,respectively.Meanwhile,the enrichment factor at 140,160 and 180℃are(-0.44±0.05)‰(R 2 is 0.9532),(0.17±0.01)‰(R 2 is 0.9816),(0.32±0.03)‰(R 2 is 0.9592),respectively.And combining with the variation tendency of the DGP’s yield,all of the above results show that,C—O,C—H bonds just participate in reacting in the process of glucose to generate DGP by dehydration.But during the generation of ethyl levulinate from DGP by decarboxylation and re

关 键 词：单体同位素分析(CSIA) 葡萄糖液化 液化机理 同位素分馏 动力学同位素效应 

分 类 号：O657.63[理学—分析化学] O656.9[理学—化学]