开管离子色谱柱的制备与表征

doi:10.3724/SP.J.1123.2019.08020

摘要/Abstract

摘要：

近年来,开管离子色谱(OTIC)的研究已取得重大进展,尤其是兼容OH^-淋洗液的OTIC柱的成功研制使OTIC梯度洗脱得以实现。该文介绍了各种OTIC柱的制备和表征方法,涵盖早期的二氧化硅开管柱和新近出现的有机聚合物基质开管柱,对静电乳胶附聚的OTIC柱的一系列表征方法进行了系统阐述,包括开管柱柱容量的实验测定和理论计算方法、固定相相同时填充柱与开管柱之间的联系、柱效改善方法以及开管柱均一性表征等。

关键词: 开管, 柱制备, 毛细管柱, 乳胶附聚, 离子色谱, 综述

Abstract:

In recent years, significant progress has been made in the area of open tubular ion chromatography (OTIC). In particular, gradient OTIC has been realized through the development of hydroxide eluent-compatible OTIC columns. This review covers the preparation and characterization of different OTIC columns, ranging from the historic silica-based columns to the newly emerging polymer-based open tubular (OT) columns. The preparation of various OTIC stationary phases, from grafted to latex agglomerated and monolayer to multilayer phases, has been briefly introduced. The characterization of electrostatic latex agglomerated OTIC columns has been extensively discussed, e. g. fluorescent ion displacement chromatography, frontal displacement chromatography, and frontal reaction chromatography have been used to measure the capacities of OT columns, and the results are compared with the theoretical calculation values. The variable α_iex, defined as the number of ion-exchange equivalents per unit surface area, is used as an indicator of the capacity of OT columns, to enable a straightforward comparison between OT columns having different inner diameters (i.d.). The newly introduced column capacity parameter, γ_iex, defined as the stationary phase capacity per unit liquid volume present, is used to investigate the relationship between packed and OT columns when using the same stationary phase. Methods for improving the column efficiency, such as decreasing the column diameter and/or increasing the column temperature, are presented. In addition, determination of the functionalization uniformity along an OT column by (a) separately measuring the capacities of two halves of the column, (b) measuring the retention factors for several ions in successive 10 cm segments of the column in multiple injections, and (c) measuring the retention variance of a single ion in different segments of the column from a single injection, is discussed.

Key words: open tubular, column preparation, capillary column, latex agglomeration, ion chromatography (IC), review

中图分类号:

O658

黄维雄. 开管离子色谱柱的制备与表征[J]. 色谱, 2020, 38(4): 399-408.

HUANG Weixiong. Preparation and characterization of open tubular ion chromatographic columns[J]. Chinese Journal of Chromatography, 2020, 38(4): 399-408.

图/表 7

图1 聚合物结构[18]

Fig. 1 Polymer structure[18] The monomers are shown in the inset. BDDE: 1,4-butanediol diglycidyl ether.

图2 双层乳胶附聚二氧化硅开管柱结构示意图[50]

Fig. 2 Schematic representation of a dual-layer latex agglomerated silica open tubular column[50]

图3 AS18乳胶附聚COP开管柱梯度色谱图[27]

Fig. 3 Gradient chromatogram on AS18 latex agglomerated open tubular cycloolefin polymer (COP) column[27] Column: 28 μm inner diameter (i.d.), 370 μm outer diameter (o.d.), 744 mm in length. Exit capillary: silica, 25 μm i.d., 370 μm o.d., with an Analytical Foundry detector (operated at 1.2 kHz) located 33 mm from the center of the suppressor. Linear gradient expressed as t (min) and LiOH concentration (mmol/L): 0, 8.0; 3, 40.0; 7, 40.0; 7.5, 8.0. Flow rate: 168 nL/min. Suppressor active length: 0.65 mm. Current: 15 μA; 6.7 nL injection; each analyte has a concentration of 100 μmol/L, except for phosphate (200 μmol/L).

图4 乳胶附聚前后的COP开管柱的(a)阴离子交换和(b)阳离子交换容量测定(虚线代表一阶求导数据)[31]

Fig. 4 (a) Anion-exchange and (b) cation-exchange capacity determination of open tubular COP column before and after latex agglomeration (dash lines represent differential data)[31] The cation-exchange capacity measurement experiment starts with a lightly sulfonated 28.0±0.5 mm i.d. COP column with an effective length of 700±1 mm. It is then coated with AS18 latex for anion-exchange capacity measurement.

图5 相同固定相的填充柱和开管柱的log10k/γiex-log10[E]图[9]

Fig. 5 log10 k/γiex vs. log10[E] for packed and open tubular columns with the same stationary phase[9] Open and filled symbols are used for open tubular and packed columns, respectively. Packed column: 4 mm×250 mm, AS18, 1 mL/min, 30 ℃, linear velocity 0.178 cm/s. OT column: sulfonated cyclic olefin polymer, AS18 latex coated 19 μm i.d., 951 mm long, 39 nL/min, 22 ℃, linear velocity 0.23 cm/s. [E]: eluent concentration.

图6 乳胶附聚PMMA开管柱的van Deemter曲线[37]

Fig. 6 van Deemter plots of latex agglomerated polymethylmethacrylate (PMMA) open tubular columns[37] Conditions: analyte, 500 μmol/L Cl-; injection volume, ~43 pL for 34 cm OT column, 90 pL for 67.5 cm OT column. Column radius: 9.8 μm; effective length: 58 cm. Eluent: 1 mmol/L sodium benzoate.

图7 (a)不同有效柱长的阴离子交换色谱图和(b)4种阴离子(Cl-, N O 2 -, Br-和N O 3 -)的保留因子[31]

Fig. 7 (a) Anion-exchange chromatograms at different effective lengths and (b) retention factors for four anions (Cl-, N O 2 -, Br-, and N O 3 -)[31]Flow direction: a. normal; b. both normal and reverse. AS18 latex coated COP column (28 μm i.d., ~750 mm in length; CAEX (31.2±0.1) peq/mm2). 2.5 nL injected; eluent: 5.0 mmol/L NaOH@18 psi (~0.31 cm/s). Peaks: 0. system peak; 1. F-; 2. Cl-; 3. N O 2 -; 4. Br-; 5. N O 3 -.

参考文献

[1]	Small H, Stevens T S, Bauman W C. Anal Chem, 1975, 47(11): 1801
[2]	Small H. J Chromatogr, 1991, 546: 3
[3]	Haddad P R, Jackon P E, Shaw M J. J Chromatogr A, 2003, 1000(1/2): 725
[4]	Lucy C A. J Chromatogr A, 2003, 1000(1/2): 711
[5]	Fritz J S, Gjerde D T. Ion Chromatography. 3rd ed. Berlin: Wiley-VCH, 2000
[6]	Mou S F, Zhu Y, Liu K N. Ion Chromatography and Its Application. 3rd ed. Beijing: Chemical Industry Press, 2018
[6]	牟世芬, 朱岩, 刘克纳. 离子色谱方法及应用. 3版. 北京: 化学工业出版社, 2018
[7]	Gjerde D T, Fritz J S, Schmuckler G. J Chromatogr, 1979, 186: 509
[8]	Huang Y, Mou S F. Chinese Journal of Chromatography, 2000, 18(5): 412
[8]	黄源, 牟世芬,. 色谱, 2000, 18(5): 412
[9]	Huang W, Pohl C A, Dasgupta P K. J Chromatogr A, 2018, 1550: 75
[10]	Guo D D, Zhu Y F, Zhu Y. Chinese Journal of Chromatography, 2018, 36(9): 835
[10]	郭丹丹, 朱越锋, 朱岩,. 色谱, 2018, 36(9): 835
[11]	Stillian J R, Pohl C A. J Chromatogr, 1990, 499: 249
[12]	Kuban P, Dasgupta P K. J Sep Sci, 2004, 27(17/18): 1441
[13]	Knox J H, Gilbert M T. J Chromatogr, 1979, 186: 405
[14]	Knox J H. J Chromatogr Sci, 1980, 18(9): 453
[15]	Ishii D, Takeuchi T. J Chromatogr, 1981, 218: 189
[16]	Muller S, Scheidegger D, Haber C, et al. J High Res Chromatogr, 1991, 14(3): 174
[17]	Pyo D J, Dasgupta P K, Yengoyan L S,. Anal Sci, 1997, 13(Suppl): 185
[18]	Kuban P, Dasgupta P K, Pohl C A. Anal Chem, 2007, 79(14): 5462
[19]	Zhang M, Yang B, Dasgupta P K. Anal Chem, 2013, 85(16): 7994
[20]	Huang W, Seetasang S, Azizi M, et al. Anal Chem, 2016, 88(24): 12013
[21]	Zemann A J, Schnell E, Volgger D, et al. Anal Chem, 1998, 70(3): 563
[22]	da Silva J A F, do Lago C L,. Anal Chem, 1998, 70(20): 4339
[23]	Zhang M, Stamos B N, Amornthammarong N, et al. Anal Chem, 2014, 86(23): 11538
[24]	Zhang M, Stamos B N, Dasgupta P K. Anal Chem, 2014, 86(23): 11547
[25]	Huang W, Chouhan B, Dasgupta P K. Anal Chem, 2018, 90(24): 14561
[26]	Huang X, Foss F W, Dasgupta P K. Anal Chim Acta, 2011, 707(1/2): 210
[27]	Huang W, Dasgupta P K. Anal Chem, 2016, 88(24): 12021
[28]	Ma J P, Ding M Y. Chinese Journal of Analytical Chemistry, 2006, 34(S1): 272
[28]	马继平, 丁明玉,. 分析化学, 2006, 34(S1): 272
[29]	Yang B C, Diao X F. Chinese Journal of Chromatography, 2012, 30(4): 333
[29]	杨丙成, 刁雪芳,. 色谱, 2012, 30(4): 333
[30]	Lam S C, Rodriguez E S, Haddad P R, et al. Analyst, 2019, 144(11): 3464
[31]	Huang W, Seetasang S, Dasgupta P K. Anal Chim Acta, 2018, 1036: 187
[32]	Zhou S S, Zhai R, Jiao F L, et al. Chinese Journal of Chromatography, 2016, 34(3): 226
[32]	周珊珊, 翟睿, 焦丰龙, 等. 色谱, 2016, 34(3): 226
[33]	Pan Y T, Ma C, Bai H H, et al. Chinese Journal of Chromatography, 2013, 31(10): 995
[33]	潘一廷, 马成, 白海红, 等. 色谱, 2013, 31(10): 995
[34]	Zhou S Y, Chen J Y, Tan J J, et al. Chinese Journal of Chromatography, 2015, 33(12): 1307
[34]	周孙英, 陈继涢, 谭静静, 等. 色谱, 2015, 33(12): 1307
[35]	Zhu P J, Tao Y, Zhang J H, et al. Chinese Journal of Chromatography, 2016, 34(12): 1219
[35]	朱鹏静, 陶勇, 章俊辉, 等. 色谱, 2016, 34(12): 1219
[36]	Diao X, Zhang F, Feng F, Yang B, et al. Talanta, 2012, 101: 91
[37]	Yang B, Zhang M, Kanyanee T, et al. Anal Chem, 2014, 86(23): 11554
[38]	Gorbounov V, Kuban P, Dasgupta P K, et al. Anal Chem, 2003, 75(15): 3919
[39]	Kuban P, Hauser P C. Electrophoresis, 2019, 40(1): 124
[40]	Kuban P, Hauser P C. Trends Anal Chem, 2018, 102: 311
[41]	Kuban P, Hauser P C. Electrophoresis, 2017, 38(1): 95
[42]	Kuban P, Hauser P C. Electrophoresis, 2015, 36(1): 195
[43]	Pfeffer W D, Takeuchi T, Yeung E S. Chromatographia, 1987, 24(1): 123
[44]	Manz A, Simon W J,. Chromatogr Sci, 1983, 21(7): 326
[45]	Muller S R, Simon W, Widmer H M, et al. Anal Chem, 1989, 61(24): 2747
[46]	Kuban P, Pelcova P, Kuban V, et al. J Sep Sci, 2008, 31(15): 2745
[47]	Stillian J R, Pohl C A. J Chromatogr, 1990, 499: 249
[48]	Slingsby R W, Pohl C A. J Chromatogr, 1988, 458: 241
[49]	Breadmore M C, Macka M, Avdalovic N, et al. Analyst, 2000, 125(7): 1235
[50]	Zhang S, Macka M, Haddad P R. Electrophoresis, 2006, 27(5/6): 1069
[51]	Hutchinson J P, Hilder E F, Macka M, et al. J chromatogr A, 2006, 1109: 10
[52]	Cremlyn R J W. Chlorosulfonic Acid: A Versatile Reagent. Cambridge: Royal Society of Chemistry, 2002
[53]	Ishii D, Takeuchi T. J Chromatogr Sci, 1980, 18(9): 462
[54]	Huang W, Pohl C A, Dasgupta P K. J Chromatogr A, 2018, 1550: 75
[55]	Sun Y A, Wang C W, Li Z X, et al. Chinese Journal of Chromatography, 2018, 36(12): 1206
[55]	孙雨安, 王超威, 李振兴, 等. 色谱, 2018, 36(12): 1206
[56]	Wang M H, Liu J W, Huang Z P, et al. Chinese Journal of Chromatography, 2015, 33(7): 678
[56]	王慕华, 刘军伟, 黄忠平, 等. 色谱, 2015, 33(7): 678
[57]	Walsh S, Diamond D. Talanta, 1995, 42: 561
[58]	Dasgupta P K. J Chromatogr A, 2008, 1213: 50
[59]	Caceci M S. Anal Chem, 1989, 61(20): 2324
[60]	Liu G, Djordjevic N M, Erni F. J Chromatogr, 1992, 592: 239
[61]	Pyo D, Kim H, Dasgupta P K. Bull Kor Chem Soc, 1999, 20(2): 223
[62]	Pyo D, Kim H,. Microchem J, 2001, 70(3): 159
[63]	Hatsis P, Lucy C A. J Chromatogr A, 2001, 920: 3
[64]	Stamos B N, Dasgupta P K, Ohira S-I. Anal Chem, 2017, 89(13): 7203