罗丹明荧光自组装膜制备及其对苯酚测定
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摘要
以石英片作为基底,利用吸附作用力将壳聚糖组装到硅烷化的石英表面,罗丹明B通过与壳聚糖的酯化反应间接组装到石英表面,构建壳聚糖-罗丹明B自组装膜。对该膜进行扫描电镜(SEM)表征、荧光显微镜表征,考察膜的组装条件、膜的性质、膜与苯酚的相互作用机理及抗干扰实验。结果表明苯酚与该膜在一定的范围内呈良好的线性关系,线性范围为0.00～20.00×10-10g/L,检出限(DL)为0.13×10-10g/L,该膜具有良好的稳定性和可再生性。并且将壳聚糖-罗丹明B自组装膜应用于芳名湖水和绶溪河水中的苯酚污染物含量的测定,发现二者水中的苯酚含量均达到了国家Ⅰ类水标准,样品加标回收率在91%～97%,该自组装膜适合于痕量样品的分析检测。
By using Quartz as the substrate, chitosan was assembled on the silanization layer of the quartz surface by the adsorption force. Then RhB was indirectly assembled onto the surface of quartz substrate through its esterification of chitosan, and hence the chitosan-RhB self-assembled monolayer was constructed. The chitosan-RhB self-assembled membrane was characterized by SEM and fluorescence microscope, so that the assembly conditions of the self-assembled film, the properties of the self-assembled membrane, the interaction with the phenol and the anti-interference test were investigated. Linear relationship between the phenol concentration and the RhB self-assembled membrane was found in the range of 0—20×10-10 g/L, and the detection limit(DL) was 0.13×10-10 g/L, and the membrane showed good stability and reproducibility. Furthermore, the chitosan-RhB self-assembled membrane was applied to detect phenol in the water of lake and stream. It was found that the phenol content in both water samples reached the national water standard of Class Ⅰ, and the sample recovery rate was between 91% and 97%, which suggests that the self-assembled membrane is suitable for the analysis and detection of trace samples.
By using Quartz as the substrate, chitosan was assembled on the silanization layer of the quartz surface by the adsorption force. Then RhB was indirectly assembled onto the surface of quartz substrate through its esterification of chitosan, and hence the chitosan-RhB self-assembled monolayer was constructed. The chitosan-RhB self-assembled membrane was characterized by SEM and fluorescence microscope, so that the assembly conditions of the self-assembled film, the properties of the self-assembled membrane, the interaction with the phenol and the anti-interference test were investigated. Linear relationship between the phenol concentration and the RhB self-assembled membrane was found in the range of 0—20×10-10 g/L, and the detection limit(DL) was 0.13×10-10 g/L, and the membrane showed good stability and reproducibility. Furthermore, the chitosan-RhB self-assembled membrane was applied to detect phenol in the water of lake and stream. It was found that the phenol content in both water samples reached the national water standard of Class Ⅰ, and the sample recovery rate was between 91% and 97%, which suggests that the self-assembled membrane is suitable for the analysis and detection of trace samples.
引文
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[18]杨广烈.荧光与荧光显微镜[J].光学仪器, 2011, 23(2):19-21.YANG Guanglie. Fluorescence and fluorescence microscope[J].Optical Instruments, 2011, 23(2):19-21.
[19]汪竹青,沈玉永,吴根华,等.双重印迹法制备汞离子印迹聚合物及其性能研究[J].分析化学(研究简报), 2009, 37(3):449-453.WANG Zhuqing, SHEN Yuyong, WU Genhua, et al. Synthesis and properties study of mercury ion imprinted polymer[J]. Chinese Journal of Analytical Chemistry, 2009, 37(3):449-453.
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[21]何菲,孙向英,刘斌.桑色素修饰金纳米粒子自组装膜的制备及其性能研究[J].光谱学与光谱分析, 2007, 27(10):2102-2106.HE Fei, SUN Xiangying, LIU bin. Preparation and characterization of morin-modified self-assembled multilayer films of gold nanoparticles[J]. Spectroscopy and Spectral Analysis, 2007, 27(10):2102-2106.
[22]中国环境监测总站.环境监测方法标准实用手册[M].北京:中国环境科学出版社, 2013.China National Environmental Monitoring Center. Environmental monitoring methods standard practical manual[M]. Beijing:China Environmental Science Press, 2013.
[23]史鑫,冯晓军,赵子云.电位滴定法快速测定饲料级磷酸氢钙中钙的含量[J].理化检验(化学分册), 2017, 53(12):1450-1453.SHI Xin, FENG Xiaojun, ZHAO Ziyun. Rapid determination of calcium in feed grade calcium hydrogen phosphate by potentiometric titration[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis), 2017, 53(12):1450-1453.
[24]王金.合成双酚A型聚碳酸酯新工艺中苯酚的回收与测定[J].武汉大学学报, 2015, 61(2):188-190.WANG Jin. Recovery and determination of phenol in the new synthesis process of bisphenol a polycarbonate[J]. Journal of Wuhan University,2015, 61(2):188-190.
[2]潘如彬,张明德.水中苯酚的测定方法[J].污染防治技术, 2015, 22(6):1-2.PAN Rubin, ZHANG Mingde. Phenol determination in water[J].Pollution Control Technology, 2015, 22(6):1-2.
[3]国家环境保护总局.水和废水监测分析方法[M].北京:中国环境科学出版社, 2002:458-463.State Environmental Protection Administration. Water and wastewater monitoring and analysis methods[M]. Beijing:China Science Press,2002:458-463.
[4]刘亚苓,王玉娥,郝金枝.水中挥发酚的测定方法研究进展[J].理化检验(化学分册), 2013, 49(7):893-896.LIU Yaling, WANG Yu’e, HAO Jinzhi. On the progress of methods for determination of volatile phenols inwater[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis), 2013, 49(7):893-896.
[5] STEPHEM W. Examples of molecular self-assembly at surfaces[J].Surface Chemistry and Colloids, 2014, 66:1-7.
[6]杨绍明,黄爱花,魏志鹏,等.层层自组装法制备碳纳米管/酶多层膜电极及其检测酚类物质[J].化学学报, 2009, 67(24):2857-2861.YANG Shaoming, HUANG Aihua, WEI Zhipeng, et al. Cnt/enzyme multilayer electrode prepared by layer-by-layer self-assembly and its detection for phenols[J]. Acta Chimica Sinica. 2009, 67(24):2857-2861.
[7] KHATRI P K, JAIN S L. Multiple oxo-vanadium schiff base containing cyclotriphosphazene as a robust heterogeneous catalyst for regioselectiveoxidation of naphthols and phenols to quinones[J].Catalysis Letters, 2012, 142(8):1020-1025.
[8]孙向英,翁文婷.荧光性自组装双层膜的制备及其性能研究[J].高等学校化学学报, 2005, 26(6):1030-1034.SUN Xiangying, WENG Wenting. Preparation and properties of fluorescent self assembled bilayer membrane[J]. Chemical Journal of Chinese Universities, 2005, 26(6):1030-1034.
[9] YANG B, WU W H. Fabrication of a novel natural cellulose-based paper chemodosimeter via grafting-to of Rhodamine B moieties for detection of Hg2+[J]. Reactive&Functional Polymers, 2013, 73(11):1553-1558.
[10] XIE P H, XIAO Y, YAO D H, et al. A novel colorimetric and fluorescent“off-on”chemosensor for Cu2+based on a Rhodamine derivative bearing naphthyridine group[J]. Journal of Fluorescence,2013, 23(2):265-271.
[11]胡文英,傅丽君,黄建辉,等.荧光性纳米金CdTe自组装膜制备及其对汞离子识别[J].化工进展, 2017, 36(2):641-646.HU Wenying, FU Lijun, HUANG Jianhui, et al. Preparation of fluorescent gold nanoparticle CdTe self-assembled monolayers and recognition for mercury(Ⅱ)[J]. Chemical Industry and Engineering Progess, 2017, 36(2):641-646.
[12] TUTOV M V, SERGEE A A, ZADOROZHNY P A. et al. Dendrimeric Rhodamine based fluorescent probe for selective detection of Au[J].Sensors&Actuators B:Chemical, 2018, 273:916-920.
[13] QIANG LC, FANG H, LI D L. Controllable metal-enhanced fluorescence in organized films and colloidal system[J]. Advances in Colloid and Interface Science, 2014, 207:164-177.
[14] ZHU X, WANG X, HE F, et al. Self-assembled nanocomposite film with tunable enhanced fluorescence for the detection of DNA[J]. ACS Applied Materials&Interfaces, 2015, 7(2):1334-1339.
[15]张莺,孙向英,刘斌.罗丹明B自组装膜对单双链脱氧核糖核酸的荧光识别[J].分析化学, 2009, 37(5):665-670.ZHANG Ying, SUN Xiangying, LIU Bin. Fluorescent recognition of single-and double-stranded oligonucleotides based on Rhodamine Bmodified self-assembled bilayers[J]. Chinese Journal of Analytical Chemistry, 2009, 37(5):665-670.
[16]沈家骢.超分子层状结构-组装与功能[J].北京:科学出版社, 2004:5-6.SHEN Jiacong. Supramolecular layered structures-assemblyand function alization[J]. Beijing:Science Press, 2004:5-6.
[17]李芳,孙向英,吴凯.以异硫氰酸荧光素为指示剂的pH荧光自组装传感膜[J].分析化学, 2013, 41(7):1097-1100.LI Fang, SUN Xiangying, WU Kai. A pH sensitive self-assembled monolayer film based on fluoresce in isothiocyanate[J]. Chinese Journal of Analytical Chemistry, 2013, 41(7):1097-1100.
[18]杨广烈.荧光与荧光显微镜[J].光学仪器, 2011, 23(2):19-21.YANG Guanglie. Fluorescence and fluorescence microscope[J].Optical Instruments, 2011, 23(2):19-21.
[19]汪竹青,沈玉永,吴根华,等.双重印迹法制备汞离子印迹聚合物及其性能研究[J].分析化学(研究简报), 2009, 37(3):449-453.WANG Zhuqing, SHEN Yuyong, WU Genhua, et al. Synthesis and properties study of mercury ion imprinted polymer[J]. Chinese Journal of Analytical Chemistry, 2009, 37(3):449-453.
[20]宋春霞,羊小海,王柯敏,等.聚合物在荧光检测领域的应用[J].高等学校化学学报, 2016, 37(2):201-212.SONG Chunxia, YANG Xiaohai, WANG Kemin. et al. Application of polymers in fluorescence analysis[J]. Chemical Journal of Chinese Universities, 2016, 37(2):201-212.
[21]何菲,孙向英,刘斌.桑色素修饰金纳米粒子自组装膜的制备及其性能研究[J].光谱学与光谱分析, 2007, 27(10):2102-2106.HE Fei, SUN Xiangying, LIU bin. Preparation and characterization of morin-modified self-assembled multilayer films of gold nanoparticles[J]. Spectroscopy and Spectral Analysis, 2007, 27(10):2102-2106.
[22]中国环境监测总站.环境监测方法标准实用手册[M].北京:中国环境科学出版社, 2013.China National Environmental Monitoring Center. Environmental monitoring methods standard practical manual[M]. Beijing:China Environmental Science Press, 2013.
[23]史鑫,冯晓军,赵子云.电位滴定法快速测定饲料级磷酸氢钙中钙的含量[J].理化检验(化学分册), 2017, 53(12):1450-1453.SHI Xin, FENG Xiaojun, ZHAO Ziyun. Rapid determination of calcium in feed grade calcium hydrogen phosphate by potentiometric titration[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis), 2017, 53(12):1450-1453.
[24]王金.合成双酚A型聚碳酸酯新工艺中苯酚的回收与测定[J].武汉大学学报, 2015, 61(2):188-190.WANG Jin. Recovery and determination of phenol in the new synthesis process of bisphenol a polycarbonate[J]. Journal of Wuhan University,2015, 61(2):188-190.