单分散键合型含铕聚苯乙烯微球的制备与荧光传感性能

doi:10.7503/cjcu20180383

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (1): 153.doi: 10.7503/cjcu20180383

单分散键合型含铕聚苯乙烯微球的制备与荧光传感性能

张春燕^1,², 罗建新²(), 李文军², 欧丽娟², 喻桂朋¹, 潘春跃¹()

1. 中南大学化学化工学院, 长沙 410083
2. 湖南工学院材料与化学工程学院, 衡阳 421002

收稿日期:2018-05-25 出版日期:2019-01-10 发布日期:2018-12-04
作者简介:
联系人简介: 罗建新, 男, 博士, 副教授, 主要从事荧光功能材料研究. E-mail: luojianxin392@163.com;潘春跃, 男, 博士, 教授, 主要从事多孔材料研究. E-mail: panchunyue@csu.edu.cn
基金资助:
国家自然科学基金(批准号: 21376272, 21674129)、国家级大学生创新创业训练计划项目(批准号: 教高司函〔2017〕40号)、湖南省大学生研究性学习和创新性实验计划项目(批准号: 湘教通[2017]205号、湘教通[2018]255号)和湖南省“十二五”重点建设学科(批准号: 湘教发[2011]76号)资助.

Preparation and Sensing Properties of Covalent-linked Europium Complex Monodisperse Polystyrene Microspheres^†

ZHANG Chunyan^1,², LUO Jianxin^2,^*(), LI Wenjun², OU Lijuan², YU Guipeng¹, PAN Chunyue^1,^*()

1. College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China
2. Department of Materials and Chemical Engineering, Hunan Institute of Technology, Hengyang 421002, China

Received:2018-05-25 Online:2019-01-10 Published:2018-12-04
Contact: LUO Jianxin,PAN Chunyue E-mail:luojianxin392@163.com;panchunyue@csu.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21376272, 21674129), the National College Students’ Innovation and Entrepreneurship Training Program Project, China(Jiao Gao Si No.[2017]40), Hunan Province College Students’ Research Learning and Innovative Experiment Project, China(Xiang Jiao Tong Nos.[2017]205, [2018]255), and the Construct Program of the Key Discipline in Hunan Province, China(Xiang Jiao Fa No.[2011]76).

摘要/Abstract

摘要：

制备了一种可定性定量检测水溶液中三价铁离子的含铕聚苯乙烯微球, 分别用固体核磁碳谱(¹³C CP/MAS NMR)、傅里叶变换红外光谱(FTIR)、 X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、元素分析、粒度分析和ζ电位分析等对其化学组成和结构形貌进行表征. 当铕配合物单体用量低于2.5%时, 可以得到稳定的单分散键合型含铕聚苯乙烯微球. 用紫外光激发时, 该含铕聚苯乙烯微球发射铕离子的特征红光. Fe³⁺能猝灭该微球的荧光, 酸根离子和其它金属离子对其干扰较少; 猝灭效率与Fe³⁺浓度在0~300 μmol/L浓度范围内均呈线性关系; 随着铕配合物单体用量的增加, 微球的荧光增强, 其在检测Fe³⁺的荧光时, 猝灭常数(K_SV)增加, 检测限(LOD)下降. 调节铕配合物单体的用量, 可获得热性能优异、红光发射强度高且稳定性好的单分散聚苯乙烯荧光微球, 对Fe³⁺荧光检测显示出较高的选择性, 在生物检测和环境保护等领域具有较高的应用价值.

关键词: 聚苯乙烯微球, 铕配合物, 荧光传感, 铁离子

Abstract:

Covalent-linked Eu-complex monodisperse polystyrene microspheres were prepared by a simple environment-friendly one-step soap-free emulsion polymerization. Styrene(St), Eu-complex monomer[Eu(AA)₃Phen] and methacrylic acid(MAA) were separately selected as matric monomer, fluorescent monomer, and water-soluble monomer. Meanwhile, Eu-complex monomer was also acted as cross-linked monomer. The chemical composition and morphology of the copolymer microspheres were characterized by ¹³C CP/MAS NMR, Fourier transform infrared spectrophotometer(FTIR), X-ray photoelectron spectroscopy(XPS), scanning electron microscope(SEM), transmission electron microscope(TEM), particle size analysis and zeta potential analysis. With the increase of Eu-complex content, the stability of the emulsion decreased, and the particle size and its distribution of the polystyrene microspheres increased; meanwhile, the thermal stability of the polystyrene microspheres was also decreased. Through regulating Eu-complex monomer content(0.25%—2.5%, mass fraction), the polystyrene microspheres feature a stable spherical morphology with a narrow size distribution. Excited by ultraviolet light, the polystyrene microspheres can emit the characteristic red light of europium ion. The luminescence of the polystyrene microspheres originates mainly from the sensitization of ligands to europium ions, that is, the energy transfer from ligands to europium ions. Due to the strong binding ability of Fe³⁺ to N and O atoms, the coordination structure of Eu-complex has changed after adding iron ions. As a result, the luminescence of the polystyrene microspheres can be quenched by Fe³⁺, and the common anions and other metal ions have little interference. The quenching efficiency are linearly related to the concentration of Fe³⁺ ranged from 0 to 300 μmol/L. With the increase of the content of the europium complex monomer, the fluorescence intensity of the polystyrene microspheres is enhanced, and the fluorescence detection K_SV of Fe³⁺ is increased, while limit of determent(LOD) is decreased. Regulating the content of the europium complex, the monodisperse copolymer fluorescent microspheres exhibit excellent thermal stability, strong red light emission, and high selectivity for Fe³⁺ fluorescence detection, which have high application value in biological detection and environmental protection.

Key words: Polymer microsphere, Europium complexe, Fluorescence sensor, Iron ion

中图分类号:

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张春燕, 罗建新, 李文军, 欧丽娟, 喻桂朋, 潘春跃. 单分散键合型含铕聚苯乙烯微球的制备与荧光传感性能. 高等学校化学学报, 2019, 40(1): 153.

ZHANG Chunyan,LUO Jianxin,LI Wenjun,OU Lijuan,YU Guipeng,PAN Chunyue. Preparation and Sensing Properties of Covalent-linked Europium Complex Monodisperse Polystyrene Microspheres^†. Chem. J. Chinese Universities, 2019, 40(1): 153.

图/表 8

Scheme 6 Preparation of the Eu-containing polystyrene microspheres

Table 1 Composition, yield, stability and particle size of the Eu-containing polystyrene microspheres

Microsphere	Mass fraction of Eu-complex(%)		$C COOH c$ (%)	Stability	Yeild(%)	d^d/nm	PDI^d	ζ^d/mV
Microsphere	Theoretical^a	Actual^b	$C COOH c$ (%)	Stability	Yeild(%)	d^d/nm	PDI^d	ζ^d/mV
n-PSEu-0	0	0	37	Stable	91	208	0.055	-26.9
n-PSEu-1	0.25	0.24	35	Stable	86	287	0.057	-26.5
n-PSEu-2	0.63	0.60	33	Stable	84	342	0.064	-25.8
n-PSEu-3	1.25	1.19	32	Stable	81	384	0.069	-25.7
n-PSEu-4	2.50	2.38	31	Stable	78	451	0.081	-23.9
n-PSEu-5	3.75	3.59	24	Unstable	69	526	0.232	-17.6

Table 1 Composition, yield, stability and particle size of the Eu-containing polystyrene microspheres

Microsphere	Mass fraction of Eu-complex(%)		$C COOH c$ (%)	Stability	Yeild(%)	d^d/nm	PDI^d	ζ^d/mV
Microsphere	Theoretical^a	Actual^b	$C COOH c$ (%)	Stability	Yeild(%)	d^d/nm	PDI^d	ζ^d/mV
n-PSEu-0	0	0	37	Stable	91	208	0.055	-26.9
n-PSEu-1	0.25	0.24	35	Stable	86	287	0.057	-26.5
n-PSEu-2	0.63	0.60	33	Stable	84	342	0.064	-25.8
n-PSEu-3	1.25	1.19	32	Stable	81	384	0.069	-25.7
n-PSEu-4	2.50	2.38	31	Stable	78	451	0.081	-23.9
n-PSEu-5	3.75	3.59	24	Unstable	69	526	0.232	-17.6

Fig.1 SEM(A, B) and TEM(C, D) images of n-PSEu-0(A, C) and n-PSEu-4(B, D)

Fig.2 13C CP/MAS NMR spectra(A), FTIR spectra(B), XPS scan survey(C), Eu3d(D) and N1s(E) XPS spectra of the Eu-containing polystyrene microspheres Inset: chemical structural formula of the Eu-containing polystyrene microspheres. a. n-PSEu-0; b. n-PSEu-4; c. Eu(AA)3Phen.

Table 2 Thermal, luminescence and sensing properties of the Eu-containing polystyrene microspheres

Microsphere	$T g a$ /℃	$T d b$ /℃	$T p c$ /℃	I^d/a.u.	10^-3 $K SV e$ /(mol·L^-1)	LOD^f(μmol·L^-1)
n-PSEu-0	103	351	446	——	——	——
n-PSEu-1	106	360	442	14	5.93	5.1
n-PSEu-2	110	352	439	45	6.21	3.9
n-PSEu-3	114	351	436	85	7.45	3.2
n-PSEu-4	117	333	424	115	8.37	2.6
n-PSEu-5	——	249	416	119	8.71	2.7

Table 2 Thermal, luminescence and sensing properties of the Eu-containing polystyrene microspheres

Microsphere	$T g a$ /℃	$T d b$ /℃	$T p c$ /℃	I^d/a.u.	10^-3 $K SV e$ /(mol·L^-1)	LOD^f(μmol·L^-1)
n-PSEu-0	103	351	446	——	——	——
n-PSEu-1	106	360	442	14	5.93	5.1
n-PSEu-2	110	352	439	45	6.21	3.9
n-PSEu-3	114	351	436	85	7.45	3.2
n-PSEu-4	117	333	424	115	8.37	2.6
n-PSEu-5	——	249	416	119	8.71	2.7

Fig.3 PL excitation(A) and emission(B) spectra of the water-dispersed Eu-containing polystyrene microspheres λem=616 nm; λex=300 nm. Inset of(B): the fluorescence photographs of the water-dispersed Eu-containing polystyrene microspheres(0.5 mg/mL) under UV-light irradiation. (A) a. n-PSEu-0; b. n-PSEu-1; c. n-PSEu-2; d. n-PSEu-3; e. n-PSEu-4; f. n-PSEu-5. (B) a. n-PSEu-1; b. n-PSEu-2; c. n-PSEu-3; d. n-PSEu-4; e. n-PSEu-5.

Fig.4 Fluorescence response profiles of n-PSEu-4 in aqueous solutions(0.5 mg/mL) upon addition of different metal ions(A), ferric salts(B) and the mixture of Fe3+ and different other metal ions(C)All of the added ion concentrations are 1500 μmol/L. (A)a. K(Ⅰ); b. Ca(Ⅱ); c. Mg(Ⅱ); d. Fe(Ⅲ); e. Co(Ⅱ); f. Ni(Ⅱ); g. Cu(Ⅱ); h. Sn(Ⅱ); i. Hg(Ⅱ); j. Pb(Ⅱ); k. Mn(Ⅱ); l. Ag(Ⅰ). (B) a. Cl-; b. SO42-; c. NO3-; d. CH3COO-. (C) a. None; b. K(Ⅰ); c. Ca(Ⅱ); d. Mg(Ⅱ); e. Co(Ⅱ); f. Ni(Ⅱ); g. Cu(Ⅱ); h. Sn(Ⅱ); i. Hg(Ⅱ); j. Pb(Ⅱ); k. Mn(Ⅱ); l. Ag(Ⅰ).

Fig.5 Fluorescence response of n-PSEu-4 in aqueous solutions(0.5 mg/mL) upon addition of Fe3+Inset of the graph illustrates Stern-Volmer graph of n-PSEu-4.

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单分散键合型含铕聚苯乙烯微球的制备与荧光传感性能

Preparation and Sensing Properties of Covalent-linked Europium Complex Monodisperse Polystyrene Microspheres^†

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单分散键合型含铕聚苯乙烯微球的制备与荧光传感性能

Preparation and Sensing Properties of Covalent-linked Europium Complex Monodisperse Polystyrene Microspheres†

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Preparation and Sensing Properties of Covalent-linked Europium Complex Monodisperse Polystyrene Microspheres^†