独立成分分析结合在线红外技术研究3,4-双(4'-氨基呋咱基-3')氧化呋咱的合成反应机理  

Independent Component Analysis Combined with On-line Infrared Spectroscopy for Researching the Synthesis Reaction Mechanism of 3,4-Bis( 4'-aminofurazano-3') furoxan

作　　者：孙昆仑[1] 吴楠[1] 杨欢[1] 杨小峰 李华[1] 

机构地区：[1]西北大学分析科学研究所 [2]化学与材料科学学院,西安710069

出　　处：《高等学校化学学报》2014年第2期244-249,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21175106);高等学校博士学科点专项科研基金(批准号:20126101110019,2010610111007)资助~~

摘　　要：利用在线红外技术监测3,4-双(4'-氨基呋咱基-3')氧化呋咱(DATF)的合成过程,并结合核独立成分分析算法对反应过程中获得的实时红外光谱数据进行解析,得到了反应物、中间体及产物各组分纯物质的红外光谱图.采用密度泛函理论B3LYP法,在6-31+G(d,p)基组水平上求得中间体的红外振动光谱,验证了所分离红外光谱图的正确性,从而推导出合理的合成反应机理.结果表明,核独立成分分析算法能合理地解析红外光谱在线数据,并有效捕捉合成反应的中间体,对合成反应机理的研究具有重要的指导意义.On-line infrared（IR） spectroscopy was used to monitor the synthesis process of 3,4-bis （4＇-aminofurazano-3＇） furoxan（DATF）. The IR spectra of components were determined by analyzing the IR data using principal component analysis （PCA） and independent component analysis （ICA）. The geometric configurations of intermediates were optimized using the density functional theory （DFT） at B3LYP/6-31 ＋ G （d,p） level. Their vibrational frequencies of IR spectra were obtained on the basis of vibrational analysis. The result obtained by the chemometric resolution methods agreed well with that of quantum chemical calculation method, which demonstrated the rehability of the proposed chemometric resolution methods. The unstable intermediate was confirmed via comparing the IR spectra that calculated using B3LYP/6-31 ＋G（ d ,p） and analyzed by ICA. Finally, the possible synthesis mechanism of DATF was deduced based on the analysis of the above IR spectra. The above mentioned work was expected to provide significant guidance to investigate the reaction mechanism in the future.

关 键 词：在线红外光谱 核独立成分分析 密度泛函理论 反应机理 氧化呋咱 

分 类 号：O657.33[理学—分析化学]