双功能聚合物基质阳离子交换固定相的制备及其在离子色谱中的应用

doi:10.3724/SP.J.1123.2019.07023

色谱 ›› 2020, Vol. 38 ›› Issue (4): 445-451.DOI: 10.3724/SP.J.1123.2019.07023

双功能聚合物基质阳离子交换固定相的制备及其在离子色谱中的应用

张恺¹^,^*(), 支明玉², 何艺², 朱岩³^,^*(), 曾秀琼³, 寿旦⁴

1. 宁波大学科学技术学院,浙江宁波 315212
2. 杭州职业技术学院,浙江杭州 310018
3. 浙江大学化学系,浙江杭州 310028
4. 浙江省中医药研究院,浙江杭州 310007

收稿日期:2019-07-24 出版日期:2020-04-08 发布日期:2020-12-10
通讯作者: 张恺,朱岩
基金资助:
浙江省自然科学基金项目(LY18C200001);浙江省自然科学基金项目(YB19B050002);浙江省中医药重点学科项目(2017-XK-A23)

Preparation of difunctional polymer-based cation exchangers and their application in ion chromatography

ZHANG Kai¹^,^*(), ZHI Mingyu², HE Yi², ZHU Yan³^,^*(), ZENG Xiuqiong³, SHOU Dan⁴

1. College of Science & Technology, Ningbo University, Ningbo 315212, China
2. Hangzhou Vocational and Technical College, Hangzhou 310018, China
3. Department of Chemistry, Zhejiang University, Hangzhou 310028, China
4. Zhejiang Academy of Traditional Chinese Medicine, Hangzhou 310007, China

Received:2019-07-24 Online:2020-04-08 Published:2020-12-10
Contact: ZHANG Kai, ZHU Yan
Supported by:
Zhejiang Provincial Natural Science Foundation of China(LY18C200001);Zhejiang Provincial Natural Science Foundation of China(YB19B050002);Zhejiang Provincial Key Subject of TCM(2017-XK-A23)

摘要/Abstract

摘要：

离子色谱是分离分析阳离子型化合物的重要手段之一。高效阳离子交换固定相的制备研究对离子色谱技术的发展具有重要的意义。该文以丙烯酸和顺丁烯二酸酐为单体,2-巯基乙基磺酸钠为巯基改性剂,提出了聚合物基质微球巯基改性自由基聚合修饰方法,用以制备新型双功能的阳离子交换固定相。该固定相以羧基和磺酸基为功能基,仅用简单的强酸淋洗液便可以实现常规阳离子的基线分离。利用色谱学模型,对金属离子和有机胺的保留行为进行了研究。采用梯度淋洗模式,可在24 min内实现10种阳离子的分离,表明固定相具有优异的色谱性能。“巯基-烯”修饰方法简单、高效。此外,通过调节巯基改性剂的比例能够实现对固定相交换能力的调控。

关键词: 巯基-烯, 聚合物基质, 阳离子交换剂, 固定相, 离子色谱

Abstract:

Ion chromatography (IC) is one of the most important means for the separation and analysis of cationic compounds. Research on high-performance cation exchangers is of great significance for the advancement of modern IC techniques. Herein we proposed a newly developed modification method for polymer-based particles, based on thiol-radical-mediated polymerization. Specifically, acrylic acid and maleic anhydride were used as monomers and sodium 2-mercaptoethanesulfonate was used as the thiol modifier to prepare novel difunctional cation exchangers, functionalized with both carboxylic and sulfonic groups. With simple strong acid eluents, typical cations were well separated with good resolution. The retention behaviors of metal cations and organic amines on the cation exchangers were investigated using multiple chromatographic models. The good performances of the cation exchangers were also demonstrated by the gradient separation of ten cations within 24 min. The new method was easy to perform with high efficiency. Additionally, the cation exchange capacities of the cation exchangers were easily modulated by adjusting the initial content of the thiol modifier.

Key words: thiol-ene, polymer-based, cation exchanger, stationary phase, ion chromatography (IC)

中图分类号:

O658

张恺, 支明玉, 何艺, 朱岩, 曾秀琼, 寿旦. 双功能聚合物基质阳离子交换固定相的制备及其在离子色谱中的应用[J]. 色谱, 2020, 38(4): 445-451.

ZHANG Kai, ZHI Mingyu, HE Yi, ZHU Yan, ZENG Xiuqiong, SHOU Dan. Preparation of difunctional polymer-based cation exchangers and their application in ion chromatography[J]. Chinese Journal of Chromatography, 2020, 38(4): 445-451.

图/表 8

图1 阳离子交换固定相的制备过程

Fig. 1 Scheme for the preparation of the cation exchangers AIBN: azobisisobutyronitrile.

表1 阳离子交换固定相的元素含量以及估算的交换容量

Table 1 Element contents of the cation exchangers and their estimated capacities

Stationary phase	Element contents/%					Capacities/ (μequiv/g)
Stationary phase	N	C	H	O	S	-COOH	-SO₃H
EVB-DVB	0.00	89.82	7.87	2.31	0.00	n. a.	n. a.
CE-R	0.87	83.63	7.88	7.62	0.00	1659	0
CE-1	0.06	78.19	7.52	13.90	0.34	3542	53
CE-2	0.06	77.61	7.52	13.44	0.37	3389	58
CE-3	0.05	77.94	7.46	14.13	0.42	3600	66

图2 固定相微球的扫描电镜图像

Fig. 2 Scanning electron microscopic images of the stationary phase particles a. EVB/DVB; b. cation exchanger (CE-3).

图3 阳离子交换固定相的色谱图对比

Fig. 3 Comparison of the chromatograms of the cation exchangers Eluent: 20 mmol/L methanesulfonic acid (MSA).

图4 7种无机阳离子的色谱图

Fig. 4 Chromatograms of the seven inorganic cations

图5 7种无机阳离子在固定相上的保留因子-淋洗液pH对数关系图以及色谱模型的拟合

Fig. 5 Plots of the log k and pH, and the fittings of chromatographic models of the seven inorganic cations on the cation exchangers

图6 铵根离子、脂肪胺以及烷醇胺在CE-3上的保留因子-正辛醇/水分配系数对数关系图

Fig. 6 plot of the log k and log P of N H 4 +, alkylamines, and alkanolamines on CE-3 n-PrNH2: n-propylamine; NHEt2: diethylamine; NMe3: trimethylamine; EtNH2: ethylamine; NHMe2: dimethylamine. Eluent: 30 mmol/L MSA.

图7 10种阳离子在CE-3上的梯度分离色谱图

Fig. 7 Chromatogram of the ten cations on CE-3 in a gradient mode

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双功能聚合物基质阳离子交换固定相的制备及其在离子色谱中的应用

Preparation of difunctional polymer-based cation exchangers and their application in ion chromatography

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