Application of sulphonated styrene and divinylbenzene copolymers with various degree of crosslinking for ion exclusion chromatography

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Abstract

The chromatographic retention of neutral polar compounds (alcohols, ketones, carboxylic acids, carbohydrates, and sweeteners) and compounds in ionized form (mono- and dibasic organic acids) on cation exchange columns filled with sulfonated poly(styrene-divinylbenzene) with a crosslinking degree of 8 % (Nautilus-IE) and 10 % (Sevko AA) is studied in a variant of ion exclusion chromatography. Using 5 mM sulfuric acid, the retention parameters of the compounds are determined and new patterns are obtained that clarify the mechanism of retention of organic acids in the ion-exclusion chromatography variant. It is found that the retention of all the studied compounds (logk’) is directly proportional to the hydrophobicity values logPexp). In this case, the electrostatic repulsion of organic acids from the sulfo groups of the cation exchanger shifts the logk’–logPexp dependences by a fixed value proportional to the number of carboxyl groups. The possibility of using the Sevko AA column not only for amino acid analysis, but also for ion exclusion chromatographic determination of organic acids and alcohols in complex samples with simultaneous spectrophotometric and refractometric detection is shown.

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About the authors

A. Yu. Laptev

Lomonosov Moscow State University

Author for correspondence.
Email: p.nesterenko@phys.chem.msu.ru
Russian Federation, 1, Leninskie Gory, Moscow, 119991

N. B. Rozhmanova

Lomonosov Moscow State University

Email: p.nesterenko@phys.chem.msu.ru
Russian Federation, 1, Leninskie Gory, Moscow, 119991

A. V. Sevko

Lomonosov Moscow State University

Email: p.nesterenko@phys.chem.msu.ru
Russian Federation, 1, Leninskie Gory, Moscow, 119991

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Supplementary files

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2. Fig. 1. Microphotographs of Nautilus IE cation exchanger particles.

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3. Fig. 2. Dependence of retention of homologues of n-alkanols (1, 2), diols (3, 5) and n-alkano acids (4, 6) on the number of carbon atoms on Nautilus IE (1, 3, 4) and Sevco AA (2, 5, 6) columns.

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4. Fig. 3. Dependence of retention (logk') of polar organic compounds on the Nautilus IE column on hydrophobicity (logPexp). 1 - neutral compounds ((●) - monoatomic alcohols, (■) - ketones, (◆) - polyatomic alcohols, (▽) - glucose), 2 - mono-basic acids (⬢), and 3 - poly-basic acids (△).

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5. Fig. 4. Chromatogram of separation of a model mixture of one-atomic alcohols with a concentration of 0.5 mg/ml: 1 - methanol, 2 - ethanol, 3 - isopropanol, 4 - tert-butanol, 5 - n-propanol, 6 - tert-butanol, 7 - isobutanol, 8 - n-butanol, 9 - isopentanol, 10 - n-pentanol. Refractometric detector. Columns: 200 × 4.6 mm.

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6. Fig. 5. Chromatogram of the separation of a model mixture of polyatomic alcohols with a concentration of 1.2 mg/ml. 1 - glycerol, 2 - ethylene glycol, 3 - propanediol-1,3, 4 - butanediol-1,3, 5 - butanediol-1,4. Refractometric detector. Columns: 200 × 4.6 mm.

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7. Fig. 6. Chromatogram of separation of a model mixture of ketones with a concentration of 0.5 mg/ml. 1 - acetone, 2 - methyl ethyl ketone, 3 - diethyl ketone, 4 - methylisobutyl ketone, 5 - methyl butyl ketone. Refractometric detector. Columns: 200 × 4.6 mm.

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8. Fig. 7. Chromatogram of the separation of a model mixture of acids with a concentration of 0.1 mg/ml: 1 - oxalic acid, 2 - citric acid, 3 - tartaric acid, 4 - glyoxylic acid, 5 - glycolic acid, 6 - lactic acid, 7 - formic acid, 8 - acetic acid, 9 - propionic acid, 10 - butyric acid. Spectrophotometric detector, 210 nm.

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9. Fig. 8. Chromatogram of separation of a model mixture of organic acids, carbohydrates and alcohols with a concentration of 0.46 mg/ml. 1 - oxalic acid, 2 - citric acid, 3 - tartaric acid, 4 - glucose, 5 - fructose, 6 - arabinose, 7 - succinic acid, 8 - lactic acid, 9 - glycerol, 10 - acetic acid, 11 - propionic acid, 12 - methanol, 13 - ethanol, 14 - isopropanol, 15 - n-propanol, 16 - butanol, 17 - n-butanol, 18 - isopentanol, 19 - n-pentanol. Refractometric detector. 150 × 4.6 and 200 × 4.6 mm Nautilus IE columns connected in series.

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10. Fig. 9. Chromatograms of low alcoholic beverages. a - UV detection (210 nm), b - refractometric detection. Identified components: 1 - oxalic acid, 2 - citric acid, 3 - malic acid, 4 - succinic acid, 5 - lactic acid, 6 - fumaric acid, 7 - acetic acid, 8 - propionic acid, 9 - glycerol, 10 - ethanol. Sequentially connected Nautilus IE columns of 150 × 4.6 and 200 × 4.6 mm.

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