New micellar polymers as polyfunctional modifiers of electrophoretic systems

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Abstract

New modifiers of electrophoretic systems – cationic polyelectrolytes with micellar properties poly-11-acryloyloyloxyundecyl-N-methylpiperidinium bromide (pAUMP-Br), poly-11-acryloyloxyundecylpyridinium bromide, poly-11-acryloyloxyundecyl-1,4-diazobicyclo[2. 2.2.2.2]octan-1-ium bromide and a chiral copolymer based on acylated quinine and N-(11-acryloyloyloyloxyundecyl)-N-methylpiperidinium bromide (pAUMP-AQin). The electrophoretic capabilities of these polymers were studied in the separation of model mixtures of biologically active substances: steroid hormones, biogenic amines and amino acids in the modes of micellar electrokinetic chromatography and capillary electrochromatography. It was found that new polyelectrolytes are polyfunctional modifiers of quartz capillary walls and background electrolyte and allow to realize different modes of electrophoretic separation of biologically active substances, indirect detection in the presence of chromophoric group in the polymer composition, generate anodic electroosmotic flow, influence the efficiency and selectivity of analytes separation. Field-amplified sample stacking was performed on a quartz capillary modified with pAUMP-Br, providing a 15-fold concentration of biogenic amines and lowering the detection limits. The chiral labeled pAUMP-AQin copolymer was found to facilitate the separation of tryptophan enantiomers.

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About the authors

A. A. Adamova

Saint Petersburg State University

Author for correspondence.
Email: st117588@student.spbu.ru
Russian Federation, Saint-Petersburg

D. A. Potapenko

Saint Petersburg State University

Email: st117588@student.spbu.ru
Russian Federation, Saint-Petersburg

P. A. Fetin

Saint Petersburg State University

Email: st117588@student.spbu.ru
Russian Federation, Saint-Petersburg

L. A. Kartsova

Saint Petersburg State University

Email: st117588@student.spbu.ru
Russian Federation, Saint-Petersburg

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Supplementary files

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2. Fig. 1. Chemical structures of modifier homopolymers: pAUMP-Br – poly(11-acryloyloxyundecyl-N-methylpiperidinium bromide), pAUPy-Br – poly(11-acryloyloxyundecylpyridinium bromide), pAUDABCO-Br – poly(11-acryloyloxyundecyl-1,4-diazabicyclo[2.2.2]octanium bromide).

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3. Fig. 2. Chemical structure of the pAUMP-Br copolymer and modified quinine molecule (AQin).

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4. Fig. 3. SEM image of the inner surface of a quartz capillary coated with pAUPy-Br.

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5. Fig. 4. Analysis data of biogenic amine mixture in capillary electrochromatography mode. (a) uncoated capillary, (b) pAUMP-AQin. Conditions: 210 nm, 10 mM phosphate buffer at pH 4.2, sample injection 2 s at 30 mbar, –20 kV, 20°C. 1 – adrenaline, 2 – metanephrine, 3 – normetanephrine, 4 – noradrenaline, 5 – dopamine.

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6. Fig. 5. Analysis data of a steroid hormone mixture in capillary electrochromatography mode. Stationary phase: pAUDABCO-Br (a) without and (b) with addition of pAUDABCO-Br to the background electrolyte. Conditions: 242 nm, 10 mM phosphate buffer at pH 4.2 + 1 mM pAUDABCO-Br, sample injection 2 s at 30 mbar, –25 kV, 20°C. 1 – cortisone, 2 – cortisol, 3 – corticosterone, 4 – 11-deoxycorticosterone.

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7. Fig. 6. Indirect detection data, stationary phase pAUPy-Br. (a): analysis of amino acid mixture: 1 – aspartic acid, 2 – asparagine, 3 – alanine, 4 – lysine; (b): analysis of a mixture of compounds of different nature: 1* – succinic acid, 2* – alanine, 3* – cortisone, 4* – cortisol, 5* – corticosterone, 6* – adrenaline, 7* – noradrenaline, 8* – lysine, 9* – dopamine. Conditions: 220 nm, 10 mM borate buffer at pH 9.2 + 5 mM pAUPy-Br, sample injection 2 s at 30 mbar, –20 kV, 20°C.

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8. Fig. 7. Stacking of catecholamines at 2 µg/mL, stationary phase pAUMP-Br. (a): standard injection 2 s at 30 mbar; (b): stacking injection 40 s at 30 mbar. Conditions: 210 nm, 10 mM phosphate buffer at pH 4.2, –20 kV, 20°C. 1 – adrenaline, 2 – normetanephrine, 3 – noradrenaline, 4 – dopamine.

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9. Fig. 8. Separation of tryptophan enantiomers, stationary phase pAUMP-AQin, addition of 9 mM β-cyclodextrin to the background electrolyte. Conditions: 280 nm, 10 mM phosphate buffer at pH 4.2, sample injection 2 s at 30 mbar, –20 kV, 20°C.

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