新型水溶性咪唑基硅量子点制备及用于果蔬中痕量铜的荧光检测

引用本文: 王佳佳, 连曼, 熊杰, 李在均. 新型水溶性咪唑基硅量子点制备及用于果蔬中痕量铜的荧光检测[J]. 分析化学, 2016, 44(3): 367-376. doi: 10.11895/j.issn.0253-3820.150778 shu

Citation: WANG Jia-Jia, LIAN Man, XIONG Jie, LI Zai-Jun. Synthesis of Novel Water-Soluble Silicon Quantum Dots with Imidazole Groups and Its Application in Fluorescent Detection of Trace Copper in Fruits and Vegetables[J]. Chinese Journal of Analytical Chemistry, 2016, 44(3): 367-376. doi: 10.11895/j.issn.0253-3820.150778 shu

新型水溶性咪唑基硅量子点制备及用于果蔬中痕量铜的荧光检测

王佳佳 ^1, ,
连曼 ^1, ,
熊杰 ^1, ,
李在均 ^{1,2,
,}

1.
¹ 江南大学化学与材料工程学院;
2.
² 食品胶体与生物技术教育部重点实验室, 无锡 214122

通讯作者: 李在均

基金项目:
本文系国家自然科学基金资助项目(No.21176101) (No.21176101)

摘要: 硅量子点因其极佳的亲生物性和光学性能成为纳米材料新宠,但传统硅量子点水溶性差限制了它的广泛应用。本实验以三甲基硅咪唑为硅前驱体采用水热法制备水溶性咪唑基硅量子点。相对于硼氢化钠、抗坏血酸、牛血清蛋白、半胱氨酸和柠檬酸,柠檬酸钠作为还原剂和稳定剂制得的硅量子点荧光发射最强。合成反应于220℃下可在2 h内完成,所制备的硅量子点水溶性好,平均粒径为2.6 nm,红外分析证实其表面存在游离的咪唑基。研究表明,硅量子点能与铜离子相互作用导致荧光强度的明显下降。考察不同温度下Cu²⁺对硅量子点荧光的猝灭行为,发现荧光猝灭程度随温度升高而增大。这说明荧光下降属于静态猝灭,即Cu²⁺与硅量子点上的咪唑基作用形成稳定配合物。此外,共振光散射分析还揭示荧光猝灭过程伴随着粒子团聚。基于硅量子点的荧光猝灭行为,建立了痕量铜的荧光检测方法。当Cu²⁺浓度在0.04~2400 μmol/L之间,硅量子点的荧光强度随Cu²⁺浓度的增加而线性下降,检出限(S/N=3)达1.29×10^-8 mol/L。本方法具有高的灵敏度、选择性和重现性,已应用于果蔬中痕量铜的荧光检测。

关键词:

English

Synthesis of Novel Water-Soluble Silicon Quantum Dots with Imidazole Groups and Its Application in Fluorescent Detection of Trace Copper in Fruits and Vegetables

1.
¹ School of Chemical and Materials Engineering;
2.
² Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, Jiangnan University, Wuxi 214122, China

Corresponding author: 李在均

Received Date: 07 October 2015
Fund Project:
本文系国家自然科学基金资助项目(No.21176101)

Abstract: Silicon quantum dot has become an attractive nanomaterial due to their excellent biocompatibility and optical performance. However, poor water-solubility of the traditional silicon quantum dot limits its wide application. In this study, we reported the synthesis of water-soluble silicon quantum dots with imidazole groups by using hydrothermal method, in which N-trimethysilylimidazole was used as a precursor of silicon. Compared with sodium borohydride, ascorbic acid, bovine serum protein, cysteine and citric acid, the as-prepared silicon quantum dots offered the strongest fluorescence intensity when sodium citrate was used as the reducing agent and stabilizer for the synthesis. The reaction could complete within 2 h at 220℃. The obtained silicon quantum dots showed good water-solubility with an average particle size of 2.6 nm, and the result of infrared spectroscopic analysis verified the existence of free imidazole groups on the surface. By means of the investigation of the fluorescence quenching behavior of copper ions towards the silicon quantum dots at different temperatures, we found that the degree of fluorescence quenching increased with the increase of temperature. There results proved that the fluorescence decrease belongs to static quenching. Namely, the interaction of Cu²⁺ with imidazole groups on the surface of silicon quantum dots formed stable complex. In addition, the resonance light scattering analysis also showed that the fluorescence quenching process was accompanied by the agglomeration of particles. Based on the fluorescence quenching behavior of silicon quantum dots, we established a method for the fluorescent detection of Cu²⁺. When the concentration of Cu²⁺ was in the range of 0.04-2400 μmol/L, the fluorescence intensity would linearly decrease with the increase of Cu²⁺ concentration, and the detection limit (S/N=3) reached 1.29×10^-8 mol/L. The method provided high sensitivity, selectivity and reproducibility, and was successfully applied to the determination of trace copper in fruits and vegetables.

Key words:

1. [1]
  1 Li J, Hong X, Li D, Zhao K, Wang L, Wang H, Du Z, Li J, Bai Y, Li T. Chem. Commun., 2004, 4(15): 1740-17411 Li J, Hong X, Li D, Zhao K, Wang L, Wang H, Du Z, Li J, Bai Y, Li T. Chem. Commun., 2004, 4(15): 1740-1741
2. [2]
  2 Hong X, Li J, Wang M, Xu J, Guo W, Li J, Bai Y, Li T. Chem. Mater., 2004, 16(21): 4022-40272 Hong X, Li J, Wang M, Xu J, Guo W, Li J, Bai Y, Li T. Chem. Mater., 2004, 16(21): 4022-4027
3. [3]
  3 WANG Zong-Hua, GAO Yan-Li, ZHANG Fei-Fei, XIA Yan-Zhi, LI Yan-Hui. Journal of Analytical Science, 2012, 28(1): 119-125王宗花, 高艳丽, 张菲菲, 夏延致, 李延辉. 分析科学学报, 2012, 28(1): 119-1253 WANG Zong-Hua, GAO Yan-Li, ZHANG Fei-Fei, XIA Yan-Zhi, LI Yan-Hui. Journal of Analytical Science, 2012, 28(1): 119-125王宗花, 高艳丽, 张菲菲, 夏延致, 李延辉. 分析科学学报, 2012, 28(1): 119-125
4. [4]
  4 Peng X G, Manna L, Yang W D, Wickham J, Scher E, Kadavanich A, Alivisatos A P. Nature, 2000, 404(6773): 59-614 Peng X G, Manna L, Yang W D, Wickham J, Scher E, Kadavanich A, Alivisatos A P. Nature, 2000, 404(6773): 59-61
5. [5]
  5 LIN Zhang-Bi, SU Xing-Guang, ZHANG Hao, MOU Ying, SUN Ye, HU Hai, YANG Bai, YAN GANG-Lin, LUO Gui-min, JIN Qin-Han. Chem. J. Chinese Universities, 2003, 24(2): 216-220林章碧, 苏星光, 张皓, 牟颖, 孙晔, 胡海, 杨柏, 闫岗林, 罗贵民, 金钦汉. 高等学校化学学报, 2003, 24(2): 216-2205 LIN Zhang-Bi, SU Xing-Guang, ZHANG Hao, MOU Ying, SUN Ye, HU Hai, YANG Bai, YAN GANG-Lin, LUO Gui-min, JIN Qin-Han. Chem. J. Chinese Universities, 2003, 24(2): 216-220林章碧, 苏星光, 张皓, 牟颖, 孙晔, 胡海, 杨柏, 闫岗林, 罗贵民, 金钦汉. 高等学校化学学报, 2003, 24(2): 216-220
6. [6]
  6 Yu W W, Qu L H, Guo W Z, Peng X G. Chem. Mater., 2003, 16(3): 2854-28606 Yu W W, Qu L H, Guo W Z, Peng X G. Chem. Mater., 2003, 16(3): 2854-2860
7. [7]
  7 Liu W Y, Lee J S, Talapin D V. J. Am. Chem. Soc., 2013, 135(4): 1349-13577 Liu W Y, Lee J S, Talapin D V. J. Am. Chem. Soc., 2013, 135(4): 1349-1357
8. [8]
  8 Liu Z P, Kumbhar A, Xu D, Zhang J, Sun Z Y, Fang J Y. Angew. Chem. Int. Ed., 2008, 47(19): 3540-35428 Liu Z P, Kumbhar A, Xu D, Zhang J, Sun Z Y, Fang J Y. Angew. Chem. Int. Ed., 2008, 47(19): 3540-3542
9. [9]
  9 Talapin D V, Rogach A L, Shevchenko E V, Kornowski A, Haase M, Weller H. J. Am. Chem. Soc., 2002, 124(20): 5782-57909 Talapin D V, Rogach A L, Shevchenko E V, Kornowski A, Haase M, Weller H. J. Am. Chem. Soc., 2002, 124(20): 5782-5790
10. [10]
  10 Ellingson R J, Beard M C, Johnson J C, Yu P R, Micic O I, Nozik A J, Shabaev A, Efros A L. Nano Lett., 2005, 5(5): 865-87110 Ellingson R J, Beard M C, Johnson J C, Yu P R, Micic O I, Nozik A J, Shabaev A, Efros A L. Nano Lett., 2005, 5(5): 865-871
11. [11]
  11 Qin Jun-Jie, Cao Li-Xin, Liu Wei, Gao Rong-Jie, Su Ge, Qu Hua, Xia Cheng-Hui. Chin. J. Lumin., 2014, 35(7): 858-865秦俊杰, 曹立新, 柳伟, 高荣杰, 苏革, 曲华, 夏呈辉. 发光学报, 2014, 35(7): 858-86511 Qin Jun-Jie, Cao Li-Xin, Liu Wei, Gao Rong-Jie, Su Ge, Qu Hua, Xia Cheng-Hui. Chin. J. Lumin., 2014, 35(7): 858-865秦俊杰, 曹立新, 柳伟, 高荣杰, 苏革, 曲华, 夏呈辉. 发光学报, 2014, 35(7): 858-865
12. [12]
  12 Sun Lin, Zhang Qiu-Yan, Li Zhen-Zhen, Pan Yu-Jin, Wang Qing, Zhao Qiang. Chin. J. Lumin., 2015, 36(3): 339-347孙琳, 张秋艳, 李珍珍, 潘玉瑾, 王青, 赵强. 发光学报, 2015, 36(3): 339-34712 Sun Lin, Zhang Qiu-Yan, Li Zhen-Zhen, Pan Yu-Jin, Wang Qing, Zhao Qiang. Chin. J. Lumin., 2015, 36(3): 339-347孙琳, 张秋艳, 李珍珍, 潘玉瑾, 王青, 赵强. 发光学报, 2015, 36(3): 339-347
13. [13]
  13 Derfus A M, Chan W C W, Bhatia S N. Nano Lett., 2004, 4(1): 11-1813 Derfus A M, Chan W C W, Bhatia S N. Nano Lett., 2004, 4(1): 11-18
14. [14]
  14 Feng Y L, Liu Y F, Su C, Ji X H, He Z K. Sens. Actuators B, 2014, 203: 795-80114 Feng Y L, Liu Y F, Su C, Ji X H, He Z K. Sens. Actuators B, 2014, 203: 795-801
15. [15]
  15 Cao L, Wang X, Meziani M J, Lu F S, Wang H F, Luo P G, Lin Y, Harruff B A, Veca L M, Murray D, Xie S Y, Sun Y P. J. Lumin., 1998, 80(1): 159-16215 Cao L, Wang X, Meziani M J, Lu F S, Wang H F, Luo P G, Lin Y, Harruff B A, Veca L M, Murray D, Xie S Y, Sun Y P. J. Lumin., 1998, 80(1): 159-162
16. [16]
  16 Warner J H, Hoshino A, Yamamoto K, Tilley R D. Angewandte Chemie, 2005, 117(29): 4626-463016 Warner J H, Hoshino A, Yamamoto K, Tilley R D. Angewandte Chemie, 2005, 117(29): 4626-4630
17. [17]
  17 Warner J H, Rubinsztein-Dunlop H, Tilley R D. J. Phys. Chem. B, 2005, 109(41): 19064-1906717 Warner J H, Rubinsztein-Dunlop H, Tilley R D. J. Phys. Chem. B, 2005, 109(41): 19064-19067
18. [18]
  18 Heath J R. Science, 1992, 258(5085): 1131-113318 Heath J R. Science, 1992, 258(5085): 1131-1133
19. [19]
  19 Bley R A, Kauzlarich S M. J. Am. Chem. Soc., 1996, 118(49): 12461-1246219 Bley R A, Kauzlarich S M. J. Am. Chem. Soc., 1996, 118(49): 12461-12462
20. [20]
  20 Yang C S, Bley R A, Kauzlarich S M, Lee H W H, Delgado G R. J. Am. Chem. Soc., 1999, 121(22): 5191-519520 Yang C S, Bley R A, Kauzlarich S M, Lee H W H, Delgado G R. J. Am. Chem. Soc., 1999, 121(22): 5191-5195
21. [21]
  21 Somogyi B, Zolyomi V, Gali A. Nanoscale, 2012, 4(24): 7720-772621 Somogyi B, Zolyomi V, Gali A. Nanoscale, 2012, 4(24): 7720-7726
22. [22]
  22 Choi J, Wang N S, Reipa V. Bioconjugate Chem., 2008, 19(3): 680-68522 Choi J, Wang N S, Reipa V. Bioconjugate Chem., 2008, 19(3): 680-685
23. [23]
  23 Sudeep P K, Page Z, Emrick T. Chem. Commun., 2008, 46: 6126-612723 Sudeep P K, Page Z, Emrick T. Chem. Commun., 2008, 46: 6126-6127
24. [24]
  24 Shiohara A, Hanada S, Prabakar S, Fujioka K, Lim T H, Yamamoto K, Northcote P T, Tilley R D. J. Am. Chem. Soc., 2010, 132(1): 248-25324 Shiohara A, Hanada S, Prabakar S, Fujioka K, Lim T H, Yamamoto K, Northcote P T, Tilley R D. J. Am. Chem. Soc., 2010, 132(1): 248-253
25. [25]
  25 Alsharif N H, Berger C E M, Varanasi S S, Chao Y, Horrocks B R, Datta H K. Small, 2009, 5(2): 221-22825 Alsharif N H, Berger C E M, Varanasi S S, Chao Y, Horrocks B R, Datta H K. Small, 2009, 5(2): 221-228
26. [26]
  26 Choi J K, Jang S, Sohn H, Jecong H D. J. Am. Chem. Soc., 2009, 131(49): 17894-1790026 Choi J K, Jang S, Sohn H, Jecong H D. J. Am. Chem. Soc., 2009, 131(49): 17894-17900
27. [27]
  27 Erogbogbo F, Yong K T, Roy I, Xu G X, Prasad P N. ACS Nano, 2008, 2(5): 873-87827 Erogbogbo F, Yong K T, Roy I, Xu G X, Prasad P N. ACS Nano, 2008, 2(5): 873-878
28. [28]
  28 Zhang J, Yu S H. Nanoscale, 2014, 6(8): 4096-409628 Zhang J, Yu S H. Nanoscale, 2014, 6(8): 4096-4096
29. [29]
  29 Feng Y L, Liu Y F, Su C, Ji X H, He Z K. Sens. Actuators B, 2014, 203: 795-80129 Feng Y L, Liu Y F, Su C, Ji X H, He Z K. Sens. Actuators B, 2014, 203: 795-801

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

新型水溶性咪唑基硅量子点制备及用于果蔬中痕量铜的荧光检测

通讯作者: 李在均

English

Synthesis of Novel Water-Soluble Silicon Quantum Dots with Imidazole Groups and Its Application in Fluorescent Detection of Trace Copper in Fruits and Vegetables

Corresponding author: 李在均

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

新型水溶性咪唑基硅量子点制备及用于果蔬中痕量铜的荧光检测

通讯作者: 李在均

English

Synthesis of Novel Water-Soluble Silicon Quantum Dots with Imidazole Groups and Its Application in Fluorescent Detection of Trace Copper in Fruits and Vegetables

Corresponding author: 李在均

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs