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用于离子色谱的共价键合超支化聚(苯乙烯-二乙烯基苯)基阴离子交换剂。

Covalently-bonded hyperbranched poly(styrene-divinylbenzene)-based anion exchangers for ion chromatography.

作者信息

Uzhel A S, Zatirakha A V, Shchukina O I, Smolenkov A D, Shpigun O A

机构信息

Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, 1/3, GSP-1, Moscow 119991, Russia.

Department of Chemistry, Lomonosov Moscow State University, Leninskie Gory, 1/3, GSP-1, Moscow 119991, Russia.

出版信息

J Chromatogr A. 2016 Oct 28;1470:97-103. doi: 10.1016/j.chroma.2016.10.009. Epub 2016 Oct 7.

Abstract

A number of covalently-bonded hyperbranched poly(styrene-divinylbenzene)-based (PS-DVB) anion exchangers having functional ion exchange layers of different branching degrees are prepared and investigated. The attachment of the hyperbranched functional layers to the substrate surface is realized via anchor secondary amino groups inserted into the polymeric backbone by means of acylation with acetic anhydride followed by reductive amination with methylamine. Further modification of the obtained secondary amino groups is provided by repeating the steps of alkylation with 1,4-butanediol diglycidyl ether (1,4-BDDGE) and amination of the terminal epoxide rings with methylamine (MA). The variation of the number of cycles including modification with 1,4-BDDGE and MA results in selectivity alterations for the obtained anion exchangers. Chromatographic parameters of the obtained stationary phases are evaluated using the model mixtures of anions (F, HCOO, Cl, EtCOO, BrO, NO, Br, NO, SO, PO) with hydroxide and carbonate/bicarbonate eluents. The anion exchangers show the increase of NO/EtCOO and NO/BrO selectivity and the decrease of EtCOO/Cl selectivity with increasing the number of modification cycles. In case of anion exchanger obtained after three modification cycles, the calculated values of column efficiencies for polarizable NO and Br are up to 18,000 and 16,000N/m, respectively.

摘要

制备并研究了多种具有不同支化度功能离子交换层的共价键合超支化聚(苯乙烯 - 二乙烯基苯)基(PS - DVB)阴离子交换剂。超支化功能层通过以下方式连接到基底表面:先通过乙酸酐酰化将锚定仲氨基插入聚合物主链,随后用甲胺进行还原胺化。通过重复用1,4 - 丁二醇二缩水甘油醚(1,4 - BDDGE)进行烷基化以及用甲胺(MA)使末端环氧环胺化的步骤,对所得仲氨基进行进一步修饰。包括用1,4 - BDDGE和MA进行修饰的循环次数的变化导致所得阴离子交换剂的选择性改变。使用阴离子(F、HCOO、Cl、EtCOO、BrO、NO、Br、NO、SO、PO)与氢氧化物和碳酸盐/碳酸氢盐洗脱剂的模型混合物评估所得固定相的色谱参数。随着修饰循环次数的增加,阴离子交换剂的NO/EtCOO和NO/BrO选择性增加,而EtCOO/Cl选择性降低。对于经过三次修饰循环后获得的阴离子交换剂,可极化的NO和Br的柱效计算值分别高达18,000和16,000N/m。

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