沉淀聚合制备荧光聚脲微球及Fe3+检测

doi:10.7503/cjcu20180788

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (6): 1317.doi: 10.7503/cjcu20180788

沉淀聚合制备荧光聚脲微球及Fe³⁺检测

宫明慧¹, 杨珊珊¹, 李树生¹(), 匡芮²(), 孔祥正¹

1. 济南大学化学化工学院, 济南250022
2. 山东交通学院交通土建工程学院, 济南 250357

收稿日期:2018-11-21 出版日期:2019-06-10 发布日期:2019-03-29
作者简介:
联系人简介: 李树生, 男, 博士, 讲师, 主要从事聚脲及有机硅材料研究. E-mail: chm_liss@ujn.edu.cn;匡芮, 女, 博士, 讲师, 主要从事金属有机复合材料研究. E-mail: kuangr1985@foxmail.com
基金资助:
国家自然科学基金(批准号: 21304038, 51473066)、山东省自然科学基金(批准号: ZR2018BB049, ZR2018MB021)和济南大学科技计划(批准号: XKY1824)资助.

Preparation of Fluorescence Polyurea Microspheres Through Precipitation Polymerization and Their Use for Fe³⁺ Determination^†

GONG Minghui¹, YANG Shanshan¹, LI Shusheng¹(), KUANG Rui²(), KONG Xiangzheng¹

1. College of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China
2. College of Traffic Civil Engineering, Shandong Jiaotong University, Jinan 250357, China

Received:2018-11-21 Online:2019-06-10 Published:2019-03-29
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21304038, 51473066), the Natural Science Foundation of Shandong Province, China(Nos. ZR2018BB049, ZR2018MB021) and the Science and Technology Project of Jinan University, China(No.XKY1824).

摘要/Abstract

摘要：

以异氟尔酮二异氰酸酯为单体, 以氨基功能化的1.8-萘二甲酰亚胺(AABD)为荧光基团, 在水/丙酮质量比为3/7的混合溶剂中, 通过沉淀聚合制备了表面洁净的高度单分散荧光聚脲微球(FPU). 通过FTIR及¹H NMR对AABD及FPU的化学结构进行了表征; 通过UV-Vis光谱确定FPU中嵌入的AABD荧光单元的含量; 通过荧光光谱研究了FPU固体粉末分散在水中及溶解在N-甲基吡咯烷酮中的荧光特性以及FPU分散在不同Fe³⁺浓度水溶液中的荧光变化. 结果表明, FPU的平均粒径(D_n)为5.24 μm, 粒径分布(D_w/D_n)为1.004, 具有强烈的绿色荧光(激发波长为420 nm, 最大发射波长为522 nm); FPU分散在水中不发生荧光自猝灭, 其荧光强度随着Fe³⁺浓度的增加(10^-4 ~10^-3 mol/L)呈线性降低.

关键词: 荧光聚脲微球, 沉淀聚合, Fe³⁺检测

Abstract:

Uniform and fluorescent polyurea microspheres(FPU) were synthesized via precipitation polymerization of isophorone diisocyanate in water/acetone mixture, bonding different amount amino-functionalized 1,8-naphthalimide(AABD) as fluorescent chromorephore. The chemical structure of AABD was confirmed by ¹H NMR and FTIR spectra. The AABD content in FPU was investigated by UV-Vis spectroscopy, and the enhanced properties of FPU was characterized by fluorescent spectroscopy. The results showed that, the uniform FPU microspheres of about 5 μm in diameter exhibited considerable green fluorescence emission at 522 nm when they were excited at 420 nm, and the fluorescence intensity was significant enhacced in comparsion with pure AABD in water or FPU dissolved in N-methyl pyrrolidone at the same concentration of AABD units. A linear decrease in fluorescence intensity of FPU was observed with increased Fe³⁺ concentration changed from 10^-4 mol/L to 10^-3 mol/L. This provides a potential application for AABD-containing FPU for Fe³⁺ determination in aqueous systems.

Key words: Fluorescence polyurea microsphere, Precipitation polymerization, Ferric ion detection

中图分类号:

O631

TrendMD:

宫明慧, 杨珊珊, 李树生, 匡芮, 孔祥正. 沉淀聚合制备荧光聚脲微球及Fe³⁺检测. 高等学校化学学报, 2019, 40(6): 1317.

GONG Minghui,YANG Shanshan,LI Shusheng,KUANG Rui,KONG Xiangzheng. Preparation of Fluorescence Polyurea Microspheres Through Precipitation Polymerization and Their Use for Fe³⁺ Determination^†. Chem. J. Chinese Universities, 2019, 40(6): 1317.

图/表 9

Scheme 1 Syntheses of AABD and fluorescence polyurea microspheres FPU

Fig.1 FTIR(A) and 1H NMR(B) spectra of BAD(a), AABD(b) and FPU(c)

Fig.2 LSCM(A) and SEM(B) images of FPU

Fig.3 UV-Vis spectra of AABD in NMP at different concentration, and relationship of the maximum absorbance peak with AABD(inset)(A) and FPU in NMP(0.1%, mass fraction)(B)

Table 1 FPU preparation through precipitation polymerization of IPDI in water in the presence of AABD and AABD content in FPU determined by UV-Vis spectra*

Sample	m(IPDI)/g	m(AABD)/g	Sphere yield(%)	c(AABD)/(10^-5 mol·g^-1)		Converted into FPU(%)
Sample	m(IPDI)/g	m(AABD)/g	Sphere yield(%)	Feed	UV-Vis	Converted into FPU(%)
FPU1	2	0.0103	79.32	1.472	1.723	93.33
FPU2	2	0.0275	81.30	3.867	4.606	96.84
FPU3	2	0.0447	80.68	6.799	7.504	89.05

Fig.4 Fluorescent excitation and emission spectra of dried FPU powder(A), fluorescent emission spectra of AABD in water(B), and those of FPU dissolved in NMP(C) or dispersed in water(D) at different AABD unit concentrations

Scheme 2 Possible formation of intermolecular exciplex for AABD mlecules

Fig.5 Fluorescence spectra of FPU(10-5 mol/L of AABD unit) dispersed in aqueous solutions of different ions(6×10-4 mol/L)(A) and those of PPU in water of different Fe3+ concentration, and relationship of the maximum fluorescence peak value versus Fe3+ concentration(inset)(B)

Scheme 3 Possible binding of Fe3+ with AABD in FPU

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沉淀聚合制备荧光聚脲微球及Fe³⁺检测

Preparation of Fluorescence Polyurea Microspheres Through Precipitation Polymerization and Their Use for Fe³⁺ Determination^†

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