The Analysis of Synthetic Organic, Neutral Polymers Using Nonaqueous Capillary Gel Electrophoresis (NACGE)

Li, Guodong; Zhou, Xiaojuan; Wang, Yonghui; Krull, Ira S.; Mistry, Kavita; Grinberg, Nelu; Cortes, Hernan J.

doi:10.1081/jlc-120030171

Cited by 12 publications

(8 citation statements)

References 32 publications

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“…, and zone electrophoresis of inorganic anions [7] and drugs (sometimes in a binary mixture with ,6% acetic acid) [8][9][10][11][12]. It has been used in chiral separations [13][14][15][16], in capillary electrochromatography of retinyl esters (in a mixture with 1% methanol) [17], in capillary size exclusion electrochromatography [18][19][20], in capillary gel electrophoresis of neutral polymers (mostly in mixtures with 1-6% water) [21], and in other applications [22][23][24][25][26]. Its influence on the electroosmotic flow (EOF) has been studied in both uncoated [7,[27][28][29][30] …”

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confidence: 99%

Capillary electrophoresis in N,N‐dimethylformamide

Porras

Kenndler

2005

Electrophoresis

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N,N-Dimethylformamide (DMF) is a dipolar protophilic solvent with physicochemical properties that makes it suitable as solvent for capillary electrophoresis (CE). It is prerequisite for the proper application of CE to adjust and to change the pH of the background electrolyte (BGE) in a defined manner. This was done in the present work using benzoic acid-benzoate by selecting different concentration ratios of acid and salt, and calculating the theoretical pH from the activity-corrected Henderson-Hasselbalch equation. The mobilities of the analytes (chloro- and nitro-substituted phenolates) were found to follow reasonably well the typical sigmoid mobility versus pH curve as predicted by theory. The actual mobilities and pK(a) values (at 25 degrees C) of the analytes were derived from these curves. pK(a) values were in the range of 11.1-11.7, being thus 3-4.4 units higher than in water. This pK(a) shift is caused by the destabilization of the analyte anion and the better stability (solubility) of the molecular analyte acid in DMF, which overcome the higher basicity of DMF compared to water. Absolute mobilities were calculated from the actual mobilities; they were between 32x10(-9) and 42x10(-9) m(2)/Vxs. Slight deviations of the measured mobilities from the theoretical mobility versus pH curve were discussed on the bases of ion pairing and heteroconjugation and homoconjugation of either buffer components or buffer components and analytes. Heteroconjugation was used as a mechanism for the electrically driven separation of neutral analyte molecules in a BGE where salicylate acted as complex forming ion. Rough estimation of the complexation constants for the phenolic analytes gave values in the range of 100-200 L/mol. Addition of water to the solvent decreased the effect of heteroconjugation, but it was still present up to the surprisingly high concentration of 20% water. Electrophoretically relevant parameters like ionic mobilities and pK(a) values, and conjugation and ion pairing are dependent on the water content of the solvent. The water uptake of DMF was measured when exposed to humidity of ambient air. The resulted behavior of the water uptake was found rather similar to that for acetonitrile and methanol.

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confidence: 99%

Capillary electrophoresis in N,N‐dimethylformamide

Porras

Kenndler

2005

Electrophoresis

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“…For water‐insoluble and neutral linear synthetic polymers such as PSs and polymethylmethacrylates (PMMAs), only a few papers reported their electrophoretic separation in NACE . In these papers, addition of ionic surfactants to the NA medium is required to provide a driving force for the electrophoretic migration of the neutral polymers, akin to SDS‐PAGE.…”

Section: Introductionmentioning

confidence: 99%

“…In 2004, Li et al. reported size‐based separation of PSs and PMMAs in dimethylformamide‐based solution with polyethylene oxide as the sieving material and stearyltributylphosphonium bromide as the source of electrophoretic mobility for the neutral polymer . They mainly investigated the separation of PSs with different molecular weights by nonaqueous capillary gel electrophoresis (NACGE).…”

Section: Introductionmentioning

confidence: 99%

Effect of surfactant species and electrophoretic medium composition on the electrophoretic behavior of neutral and water‐insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis

2017

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We have recently demonstrated the separation of neutral and water-insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis (NACZE) using a cationic surfactant of cetyltrimethylammonium chloride (CTAC). In this study, eight ionic surfactants were investigated for the separation of four synthetic polymers (polystyrene, polymethylmethacrylates, polybutadiene, and polycarbonate); only three surfactants (CTAC, dimethyldioctadecylammonium bromide, and sodium dodecylsulfate) caused their separation. The order of the interaction between the polymers and the surfactants depended on both the surfactant species and the composition of the electrophoretic medium. Their investigation revealed that the separation is majorly affected by the hydrophobic interactions between the polymers and the ionic surfactants. In addition, the electrophoretic behavior of polycarbonate suggested that electrostatic interaction also affects the selectivity of the polymers.

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“…Notably, many synthetic polymers, such as polystyrenes (PSs) and polymethylmethacrylates (PMMAs), are water-insoluble and neutral in solution. Therefore, only a few studies have focused on their CE separation, and the study of their electrophoretic behavior is insufficient [16][17][18].…”

Section: Introductionmentioning

confidence: 99%

“…In 2004, Li et al reported the size-based separation of PSs and PMMAs of different molecular weights in nonaqueous capillary gel electrophoresis (NACGE) with a dimethylformamide-based electrophoretic medium containing polyethylene oxide as the sieving matrix and stearyltributylphosphonium bromide as the source of electrophoretic mobility for the neutral polymer analyte [16]. Recently, we demonstrated the separation of four water-insoluble and neutral linear synthetic polymers (PS, PMMA, polybutadiene (PBD), and polycarbonate (PC)) in nonaqueous capillary zone electrophoresis (NACZE) using tetrahydrofuran (THF)-based electrophoretic medium containing cetyltrimethylammonium chloride (CTAC) [17].…”

Section: Introductionmentioning

confidence: 99%

Separation of Water-Insoluble and Neutral Linear Synthetic Polymers in Nonaqueous Capillary Zone Electrophoresis Using Phosphonium-Based Ionic Liquid

2017

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The separation of neutral and water-insoluble linear synthetic polymers in non-aqueous capillary zone electrophoresis using the hydrophobic phosphonium-based ionic liquid trihexyl(tetradecyl)phosphonium chloride (P 66614 Cl) were investigated using polystyrene, polymethylmethacrylates, polybutadiene, and polycarbonate as test analytes. The solubility of P 66614 Cl in tetrahydrofuran was above 500 mM, which was significantly higher than that of the general ionic surfactants used in our previous studies. The separation of the four polymers was achieved using a binary mixture of tetrahydrofuran/methanol or tetrahydrofuran/acetonitrile containing P 66614 Cl as the electrophoretic medium. It was confirmed that an increase in hydrophobicity or bulkiness of the cationic reagent improved the polymer separation. The interaction between polycarbonate with P 66614 Cl was reduced by the addition of acetonitrile, and enhanced by the methanol addition.

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The Analysis of Synthetic Organic, Neutral Polymers Using Nonaqueous Capillary Gel Electrophoresis (NACGE)

Cited by 12 publications

References 32 publications

Capillary electrophoresis in N,N‐dimethylformamide

Capillary electrophoresis in N,N‐dimethylformamide

Effect of surfactant species and electrophoretic medium composition on the electrophoretic behavior of neutral and water‐insoluble linear synthetic polymers in nonaqueous capillary zone electrophoresis

Separation of Water-Insoluble and Neutral Linear Synthetic Polymers in Nonaqueous Capillary Zone Electrophoresis Using Phosphonium-Based Ionic Liquid

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