基于PLS/UV的二取代苯甲醛类化合物各自同分异构体的同时测定
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摘要
将偏最小二乘法(partial least squares method,PLS)用于紫外光谱(ultraviolet spectrophotometry,UV)数据的解析,建立了同时测定二取代苯甲醛类化合物3种同分异构体的模型。将其应用于取代基分别为甲基、甲氧基、羟基、硝基、醛基、苯氧基、羧基、氟、氯和溴的10种苯甲醛类化合物,发现在检测波长221～267nm范围内,10种化合物的同分异构体均呈现良好的加和性和线性关系,其相关系数在0.990 8～0.999 9之间,预测结果中除邻苯二甲醛外,其他化合物的平均回收率在90.67%～111.57%之间,预测均方根误差(RMSEP)≤0.95;而对于合成样品的分析,该方法的加标回收率均在80.01%～112.45%之间。实验结果表明:该方法可应用于二取代苯甲醛类化合物各自3种异构体的同时测定;化合物的吸光度及异构体间的相关程度对测定结果有一定的影响。
The calibration model was established for the simultaneous determination of isomers of disubstituted benzaldehyde compounds by partial least squares(PLS)and ultraviolet spectrophotometry.The other substituents of the 10 kinds of benzaldehyde compounds were—CH_3,—OCH_3,—OH,—NO_2,—CHO,—OPh,—COOH,—F,—Cl,—Br,respectively.These compounds were showing good additive property and linear relationship in 221～267 nm wavelength range.Their linear correlation coefficient was between 0.990 8 and 0.999 9.The prediction result of simultaneous determination of isomers of disubstituted benzaldehyde was good,except for o-phthalaldehyde.Their average recovery(AR)was 90.67～111.57% while the root mean square prediction error(RMSEP)was less than 0.95.The proposed method has been applied to simultaneous determination of isomers of disubstituted benzaldehyde compounds in simulating samples with satisfactory results.Some important conclusions were obtained by comparing these benzaldehyde compounds.Both absorption intensity and the correlation degree of the isomers had certain influence on determination results.
The calibration model was established for the simultaneous determination of isomers of disubstituted benzaldehyde compounds by partial least squares(PLS)and ultraviolet spectrophotometry.The other substituents of the 10 kinds of benzaldehyde compounds were—CH_3,—OCH_3,—OH,—NO_2,—CHO,—OPh,—COOH,—F,—Cl,—Br,respectively.These compounds were showing good additive property and linear relationship in 221～267 nm wavelength range.Their linear correlation coefficient was between 0.990 8 and 0.999 9.The prediction result of simultaneous determination of isomers of disubstituted benzaldehyde was good,except for o-phthalaldehyde.Their average recovery(AR)was 90.67～111.57% while the root mean square prediction error(RMSEP)was less than 0.95.The proposed method has been applied to simultaneous determination of isomers of disubstituted benzaldehyde compounds in simulating samples with satisfactory results.Some important conclusions were obtained by comparing these benzaldehyde compounds.Both absorption intensity and the correlation degree of the isomers had certain influence on determination results.
引文
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[2]项林敏,金煜彬.HPLC法同时测定糕点中7种食品添加剂[J].武汉工业学院学报,2015,34(3):16-19.XIANG L M,JIN Y B.Simultaneous determination of 7kinds of pastry food additives by HPLC[J].Journal of Wuhan Polytechnic University,2015,34(3):16-19.
[3]张海燕,费勇,杨晓红,等.微波萃取-全自动凝胶色谱净化-气相色谱法同时测定太湖沉积物中多氯联苯和有机氯[J].分析试验室,2010,29(10):75-80.ZHANG H Y,FEI Y,YANG X H,et al.Simultaneous determination of PCBs&OCPs in TAIHU lake sediments by MAE/GPC/GC[J].Chinese Journal of Analysis Laboratory,2010,29(10):75-80.
[4]唐晓萍,张磊,郑如兰,等.快速溶剂萃取-气质联用法同时测定纺织品中12种有机磷农药[J].分析试验室,2015,34(4):421-424.TANG X P,ZHANG L,ZHENG R L,et al.Simultaneous determination of twelve organophosphorus pesticides in textiles by accelerated solvent extraction-gas chromatography-mass spectrometry[J].Chinese Journal of Analysis Laboratory,2015,34(4):421-424.
[5]张礼春,曾凯,高舸,等.高效毛细管电泳法同时测定饮料中七种防腐剂[J].分析试验室,2015,34(1):77-80.ZHANG L C,ZENG K,GAO K,et al.Simultaneous determination of seven preservatives in drink by high-performance capillary electrophoresis[J].Chinese Journal of Analysis Laboratory,2015,34(1):77-80.
[6]李倩倩,吴丽君,刘玮,等.紫外光谱结合偏最小二乘法测定手性药物对映体的组成[J].光谱学与光谱分析,2012,32(2):500-504.LI Q Q,WU L J,LIU W,et al.UV spectroscopy coupled with partial least squares to determine the enantiomeric composition in chiral drugs[J].Spectroscopy and Spectral Analysis,2012,32(2):500-504.
[7]IOELE G,DE LUCA M,DINC E,et al.Artificial neural network combined with principal component analysis for resolution of complex pharmaceutical formulations[J].Chemical and Pharmaceutical Bulletin,2011,59(1):35-40.
[8]MAZINA J,ALEKSEIEV V,IVKINA T,et al.Qualitative detection of illegal drugs(cocaine,heroin and MDMA)in seized street samples based on SFS data and ANN:validation of method[J].Journal of Chemometrics,2012,26(8/9):442-455.
[9]李彦威,续健,方慧文,等.偏最小二乘紫外分光光度法同时测定甲基苯甲醛三种同分异构体[J].分析试验室,2010,29(8):9-12.LI Y W,XU J,FANG H W,et al.Simultaneous determination of three tolualdehyde isomers by partial least squares methodultraviolet spectrophotometry[J].Chinese Journal of Analysis Laboratory,2010,29(8):9-12.
[10]王彩红,张汇,刘强,等.基于化学计量学-紫外光谱法的甲氧基苯甲醛3种同分异构体的同时测定[J].化学试剂,2014,36(8):729-733.WANG C H,ZHANG H,LIU Q,et al.Simultaneous determination of three methoxybenzaldehyde isomers based on chemometrics-ultraviolet spectroscopy[J].Chemical Reagent,2014,36(8):729-733.
[11]张汇,李彦威,张照昱.基于PLS/ANN-RP-HPLC的甲基苯甲醛同分异构体的同时测定[J].太原理工大学学报,2014,45(1):97-101.ZHANG H,LI Y W,ZHANG Z Y.Simultaneous determination of tolualdehyde isomers based on PLS/ANN and reversed phase high performance liquid chromatography[J].Journal of Taiyuan University of Technology,2014,45(1):97-101.
[12]逸曾,汝勤.化学计量学[M].北京:高等教育出版社,2003:124-125.YI Z,RU Q.Chemometrics[M].Beijing:Higher Education Press,2003:124-125.
[13]盛骤,谢式千,潘承毅.概率论与数理统计[M].4版.北京:高等教育出版社,2008:106.SHENG Z,XIE S Q,PAN C Y.Probability and statistic[M].4th Edition.Beijing:Higher Education Press,2008:106.