超高效液相色谱法检验复印纸中荧光增白剂及其在文件真实性鉴定中的应用研究  

Determination of Fluorescent Whitening Agent in Copy Paper by UHPLC and Its Application in Authentication of Documents

作　　者：李扬动 赵鹏程[1] 王宗兴 王逸飞 吕荫妮[1] 张泽恩 王千羽 于郁沛 何宇桓 LI Yang-dong;ZHAO Peng-cheng;WANG Zong-xing;WANG Yi-fei;LÜYin-ni;ZHANG Ze-en;WANG Qian-yu;YU Yu-pei;HE Yu-huan(College of Criminal Science and Technology,Criminal Investigation Police University of China,Shenyang 110854,China)

机构地区：[1]中国刑事警察学院刑事科学技术学院,辽宁沈阳110854

出　　处：《分析测试学报》2024年第9期1398-1408,共11页Journal of Instrumental Analysis

基　　金：公安部科技强警基础工作计划项目(2022JC03,2023JC05)。

摘　　要：利用超高效液相色谱法对144种A4复印纸中荧光增白剂进行鉴别并对其老化规律进行研究。采用40%乙腈水溶液作为提取剂,以含25 mmol/L四丁基溴化铵(TBA)的甲醇-水溶液(5∶95,体积比)和乙腈-甲醇混合溶液(2∶3,体积比)为流动相梯度洗脱。结果表明,复印纸中7种常见荧光增白剂在0.5~200μg/mL范围内线性关系良好,r^(2)均大于0.999,检出限为0.03~0.08μg·mL^(-1),定量下限为0.11~0.28μg·mL^(-1);3个不同加标水平下的平均回收率为92.1%~108%,相对标准偏差(RSD)为1.6%~5.9%。在144种A4复印纸中共检出3种荧光增白剂,分别为荧光增白剂BBU、VBL和MST,依据其组成和比例将纸张样品分为8个大类,45个小类,再结合白度测量值,又可分为53种类型。相同品牌型号的纸张,克重不同,所含染料配比与含量不一定相同。选取89号、29号和28号复印纸,在紫外仪中透射老化10天,2天测量一次,3种复印纸荧光增白剂的含量和白度值均发生明显下降,证明了利用荧光增白剂检验文件制成时间的可行性。该方法前处理简单,数据稳定可靠,可为文件的真实性鉴定提供一定的参考依据。In this paper,the fluorescent whitening agents in 144 types of A4 copy paper,along with their identification and aging patterns,were investigated using the ultra-high performance liquid chromatography method,laying a research foundation for further determination of the production time of the documents based on the aging patterns of the paper.A 40%aqueous acetonitrile solution was employed as the extractant,while a methanol-aqueous solution(5∶95,volume ratio)containing 25 mmol/L tetrabutylammonium bromide(TBA)and an acetonitrile-methanol mixed solution(2∶3,vol⁃ume ratio)were utilized as the mobile phase with gradient elution.The flow rate was 1 mL/min,the column temperature was 35℃,the detection wavelength of the ultraviolet detector was 350 nm,and the injection volume was 10μL.The results indicated that a good linear relationship was observed for the seven common fluorescent whitening agent standards in copy paper within the range of 0.5-200μg/mL,with all r^(2) values greater than 0.999.The detection limits of the method ranged from 0.03 to 0.08μg/mL,and the quantitation limits of the method were 0.11-0.28μg/mL.The average recov⁃eries at three spiked levels were 92.1%-108%,and the relative standard deviations(RSDs)were 1.6%-5.9%.Among the 144 types of A4 copy paper,a total of three fluorescent whitening agents,namely BBU,VBL and MST,were detected.Based on their composition and proportion,the paper samples could be classified into 8 major categories and 45 minor categories.Combined with the mea⁃sured whiteness values,53 types could be distinguished.It was discovered during the experiment that for the same brand and model of paper,if the grammage differed,the dye ratio and content con⁃tained might not be the same.Copy papers numbered 89,29,and 28 were selected and underwent transmission aging in an ultraviolet instrument for 10 days,with measurements taken once every two days.The contents of fluorescent whitening agents and the whiteness values of the three copy papers decreased significantly,demo

关 键 词：超高效液相色谱 荧光增白剂 法庭科学 纸张鉴别 纸张老化 

分 类 号：O657.7[理学—分析化学] D919.2[理学—化学]