高性能量子点编码磁性微球的制备

doi:10.7503/cjcu20160788

摘要/Abstract

摘要：

基于改进的层层组装法, 以氯仿/正丁醇混合溶液作为反应溶剂, 将油溶性CdSSe/ZnS量子点装载到表面氨基修饰的磁性聚苯乙烯微球(MS)表面, 通过调节量子点浓度, 制备出高性能CdSSe/ZnS量子点编码磁性微球(CdSSe/ZnS-MBs). 研究了氯仿和氯仿/正丁醇混合溶液对CdSSe/ZnS-MBs制备效果的影响. 结果表明, 氯仿/正丁醇混合溶液不仅能避免氯仿等量子点良溶剂对聚合物微球的形貌破坏, 同时能促进CdSSe/ZnS量子点高效地装载到磁性微球表面. 所制备的CdSSe/ZnS-MBs在水相具有较好的分散性, 荧光强度变异系数(CV)小, 形貌均一. 该方法为简单、精确可控地制备高编码容量的量子点编码微球提供了新思路.

关键词: 量子点, 荧光, 编码微球, 层层组装, 硒硫化镉, 硫化锌, 磁性聚苯乙烯

Abstract:

The key element of the suspension array based multiplexed assays lies in the preparation of barcodes. Quantum dots(QDs) are ideal candidate fluorophores for optical encoding because of their outstanding fluorescent properties. By using chloroform/butanol mixed solution as CdSSe/ZnS QD reaction solvent, hydrophobic CdSSe/ZnS QDs were loaded onto the surface of magnetic polystyrene spheres via the modified layer-by-layer assembly proposed here. By the adjustment of QD concentration, high-performance CdSSe/ZnS QD encoded magnetic barcodes with different fluorescence intensity levels were successfully prepared. By comparing the CdSSe/ZnS QD encoded magnetic barcodes respectively prepared by using chloroform and chloroform/butanol mixed solution as reaction solvent, it was testified that the mixed solution helped to avoid the good QD solvent’s damage to the morphology of polymer spheres and facilitated the assembly of CdSSe/ZnS QDs. The prepared CdSSe/ZnS QD encoded magnetic barcodes demonstrated good dispersity in water, narrow distribution of fluorescence intensity and uniform morphology. This method paves a new way for simple, accurate and controllable preparation of QD-encoded barcodes with high encoding capacity.

Key words: Quantum dots, Fluorescence, Barcode, Layer-by-layer assembly, CdSSe, ZnS, Magnetic polystyrene

中图分类号:

O614

TrendMD:

鲁思, 张鼎晟子, 刘冰, 徐宏, 古宏晨. 高性能量子点编码磁性微球的制备. 高等学校化学学报, 2017, 38(4): 509.

LU Si, ZHANG Dingshengzi, LIU Bing, XU Hong, GU Hongchen. Preparation of High-Performance QD-encoded Magnetic Barcodes^†. Chem. J. Chinese Universities, 2017, 38(4): 509.

图/表 9

Scheme 1 Fabrication of CdSSe/ZnS QD encoded magnetic barcodes

Fig.1 Zeta-potential of the microspheres at corresponding assembly stages(A), kinetics curve of CdSSe/ZnS QD loading process during the preparation of M-CdSSe/ZnS-MBs(B) and confocal image of M-CdSSe/ZnS-MBs(C)

Fig.2 SEM images of C-CdSSe/ZnS-MBs(A) and M-CdSSe/ZnS-MBs(B)Insets: confocal images of (A) and (B).

Fig.3 Scatter plots(A, C) and histogram(B, D) of C-CdSSe/ZnS-MBs(A, B) and M-CdSSe/ZnS-MBs(C, D) via flow cytometry

Fig.4 SEM images(A—E) and fluorescence intensity(F) of M-CdSSe/ZnS-MBs prepared by using CHCl3/C4H9OH in different volume ratios VCHCl3)/VC4H9OH): (A) 2∶1; (B) 1∶1; (C) 1∶2; (D) 1∶5; (E) 1∶10.

Fig.5 Relationship between the fluorescence intensity of M-CdSSe/ZnS-MBs and the concentration of the first layer PEI(A) and the concentration of the second layer PEI(B)

Fig.6 Emission spectra of M-CdSSe/ZnS-MBs with fluorescence intensity levels of L1—L6Inset: Enlarge emission spectra of L1—L3.

Fig.7 Scatter plots and confocal images(insets) of L1(A), L2(B), L3(C), L4(D), L5(E), L6(F), respectively

Fig.8 Flow cytometry analysis(A—C) of L1—L6 mixed together: scatter plot of FSC and SSC signal(A), histogram of L1—L6 distinguished by fluorescence intensity(B), scatter plot of L1—L6 distinguished by fluorescence intensity(C)

参考文献 29

[1]	Cheng M. M. C., Cuda G., Bunimovich Y. L., Gaspari M., Heath J. R., Hill H. D., Mirkin C. A., Nijdam A. J., Terracciano R., Thundat T., Ferrari M., Curr. Opin. Chem. Biol., 2006, 10, 11—19
[2]	Liu N., Su P., Gao Z. X., Zhu M. X., Yang Z. H., Pan X. X., Chao F. H., Chinese Journal of Analytical Chemistry,2009, 37（7), 960—964
	(刘楠, 苏璞, 高志贤, 朱茂祥, 杨陟华, 潘秀颉, 晁福寰. 分析化学, 2009,37(7), 960—964)
[3]	Jun B. H., Kang H., Lee Y. S., Jeon D. H., Molecules,2012, 17, 2474—2490
[4]	Zhu Y., Xu H., Chen K., Fu J., Gu H., Chem. Commun., 2014, 50, 14041—14044
[5]	Liu M., Wang X. L., Liu Y. J., Chen Y. B., Fu Y. F., Zhou X., Chem. J. Chinese Universities,2015, 36（5), 850—855
	(刘敏, 王秀玲, 刘勇健, 陈勇兵, 甫亚锋, 周翔. 高等学校化学学报, 2015, 36(5), 850—855)
[6]	Dejneka M. J., Streltsov A., Pal S., Frutos A. G., Powell C. L., Yost K., Yuen P. K., Müller U., Lahiri J., Proc. Natl. Acad. Sci. USA,2003, 100（2), 389—393
[7]	Xiao X., Parandoosh Z., Nova M. P., J. Org. Chem., 1997, 62（17), 6029—6033
[8]	Oh B. K., Nam J. M., Lee S. W., Mirkin C. A., Small,2006, 2（1), 103—108
[9]	Evans M., Sewter C., Hill E., ASSAY and Drug Development Technologies ,2003, 1（1/2), 199—207
[10]	Han M., Gao X., Su J. Z., Nie S., Nat. Biotechnol., 2001, 19, 631—635
[11]	Gao X., Chan W. C. W., Nie S., J. Biomed. Opt., 2002, 7（4), 532—537
[12]	Gao X., Nie S., J. Phys. Chem. B,2003, 107（42), 11575—11578
[13]	Ma Q., Serrano I. C., Palomares E., Chem. Commun., 2011, 47, 7071—7073
[14]	Li Y., Liu E. C. Y., Pickett N., Skabara P. J., Cummins S. S., Ryley S., Sutherland A. J., O’Brien P., J. Mater. Chem., 2005, 15, 1238—1243
[15]	Vaidya S. V., Gilchrist M. L., Maldarelli C., Couzis A., Anal. Chem., 2007, 79（22), 8520—8530
[16]	Xie M., Hu J., Wen C. Y., Zhang Z. L., Xie H. Y., Pang D. W., Nanotechnology,2012, 23, 035602
[17]	Wilson R., Spiller D. G., Prior I. A., Veltkamp K. J., Hutchinson A., ACS Nano,2007, 1（5), 487—493
[18]	Hong X., Li J., Wang M., Xu J., Guo W., Li J., Bai Y., Li T., Chem. Mater., 2004, 16（21), 4022—4027
[19]	Wilson R., Spiller D. G., Prior I. A., Bhatt R., Hutchinson A., J. Mater. Chem., 2007, 17, 4400
[20]	Wang D., Rogach A. L., Caruso F., Nano Lett., 2002, 2（8), 857—861
[21]	Wen C. Y., Xie H. Y., Zhang Z. L., Wu L. L., Hu J., Tang M., Wu M., Pang D. W., Nanoscale,2016, 8, 12406—12429
[22]	Wang Y. L., Huang W., Wang R. F., Zhou L. Y., Chem. J. Chinese Universities,2011, 32（12), 2727—2732
	(王益林, 黄武, 王荣芳, 周立亚.高等学校化学学报, 2011, 32（12), 2727—2732)
[23]	Wang Y. L., Yang K., Pan H. Q., Liu S. Y., Xu X. M., Zhou L. Y., Chem. J. Chinese Universities,2012, 33（12), 2604—2608
	(王益林, 杨昆, 潘华桥, 刘声燕, 许献美, 周立亚.高等学校化学学报, 2012, 33（12), 2604—2608)
[24]	Wang X. D., Yin P. F., Gong H. P., Li P. P., Liu Z. Q., He Y. Q., Chem. J. Chinese Universities,2012, 33（6), 1182—1187
	(王晓丹, 殷鹏飞, 龚会平, 李萍萍, 刘正清, 何佑秋. 高等学校化学学报, 2012, 33（6), 1182—1187)
[25]	Wang H. Q., Liu T. C., Cao Y. C., Huang Z. L., Wang J. H., Li X. Q., Zhao Y. D., Anal. Chim. Acta,2006, 580, 18—23
[26]	Gao X., Nie S., Anal. Chem., 2004, 76（8), 2406—2410
[27]	Wang X., Wang G., Li W., Zhao B., Xing B., Leng Y., Dou H., Sun K., Shen L., Yuan X., Li J., Sun K., Han J., Xiao H., Li Y., Huang P., Chen X., ACS Nano,2013, 7（1), 471—481
[28]	Wang X., Wang G., Li W., Zhao B., Xing B., Leng Y., Dou H., Sun K., Shen L., Yuan X., Small,2013, 9（19), 3327—3335
[29]	Vignali D. A A., J. Immunol. Methods, 2000, 243, 243—255