Characterization and application of molecular binary mixed molecular micelles of sodium 10-undecenyl sulfate and sodium N-undecenyl leucinate as pseudostationary phases in micellar electrokinetic chromatography.

Poly (sodium 10-undecenyl sulfate) (poly SUS), poly (sodium 10-undecenyl leucinate) (poly SUL), and their five molecular binary mixed micelles with varied SUS:SUL composition were prepared. The purity of these molecular micelles was confirmed by elemental analysis. Their partial specific volume, aggregation number, methylene selectivity, polarity, phase ratio, mobility, and elution window values were determined using a variety of analytical techniques. These molecular micelles were then evaluated as pseudostationary phases in micellar electrokinetic chromatography (MEKC) for separation of benzene derivatives with a wide range of chemical properties. Elemental analysis results reveal that the ratio of the two surfactants in the binary mixture does not change significantly during the polymerization process. Poly SUS was found to have the lowest partial specific volume and it increases gradually with an increase of SUL mole fraction. Poly SUL was found to provide the most hydrophobic environment for test solutes. Based on the retention results, the strength of interaction between the molecular micelles and the analytes was found to follow the following order: NHB>HBA>HBD. This order indicates that the hydrophobic interaction plays a major role in retention of benzene derivatives.

Study of chemical selectivity of molecular binary mixed micelles of sodium 10-undecenyl sulfate and sodium N-undecenyl leucinate using linear solvation energy relationships model.

Poly(sodium 10-undecenyl sulfate) (poly-SUS), poly(sodium N-undecenyl leucinate) (poly-SUL) and their five molecular binary mixed micelles with varied SUS:SUL composition were prepared and used as pseudostationary phases in micellar electrokinetic chromatography (MEKC). Linear solvation energy relationships (LSERs) model and free energy of transfer studies were used to characterize the retention behavior and the selectivity differences among the seven surfactant systems. System constant differences and regression models for varied benzene derivative compounds are used to establish the selectivity differences of the seven pseudostationary phases. The cavity formation and dispersion interaction (the v system constant) and the hydrogen-bonding acidity (the b system constant) of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention. The molecular micelle with sulfate head group, poly-SUS, was found to be more hydrogen-bond acidic than the molecular micelle with leucinate head group, poly-SUL. The other system constants (a, s and e) have modest effect on the retention and selectivity of the benzene derivatives. The model intercept coefficients (c system constants), which are negative for all surfactant systems have unusually large values. The free energy changes of transfer for the functional groups studied have all negative values except phenol and benzyl alcohol. Selectivity differences between pseudostationary phases were also compared by plotting the log k values against each other and were found to agree well with LSER results.

Cationic gemini surfactants as pseudostationary phases in micellar electrokinetic chromatography. Part I: effect of head group.

Two cationic gemini surfactants with pyrrolidinium or alkyl ammonium head groups with but-2-yne spacers, but with the same length hydrocarbon chain have been characterized with respect to their aggregation behaviors and separation power as pseudostationary phases (PSPs) for micellar electrokinetic chromatography (MEKC). They were compared with a commonly used PSP, sodium dodecylsulfate (SDS). The results suggest that the head groups of the surfactants have some effect on physicochemical properties such as critical micelle concentration (CMC), C(20), gamma(CMC), partial specific volume, methylene selectivity and mobilities of the surfactants. CMC values of G1, G2 and SDS in pure water were found to be 0.82, 0.71, and 8.08 mM, respectively; they were reduced to 0.21, 0.11, and 3.0 mM when measured in 10 mM phosphate buffer at pH 7.0. G1 (alphaCH2 = 2.74) and G2 (alphaCH2 = 2.48) provided the most and the least hydrophobic environment, respectively. According to their partial specific volumes, geminis were found to have more flexible structures as compared with sodium dodecylsulfate. The effects of the head group structure were also characterized with the linear solvation energy relationship (LSER) model, which was able to evaluate the role of solute size, polarity/polarizability, and hydrogen bonding on retention and selectivity. The cohesiveness, hydrogen bond acidic and basic character of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention of the gemini surfactants. It should be noted that with their large positive coefficient a values, G1 and G2 were found to be stronger HB acceptors than anionic and most of the cationic surfactants studied in the literature.

Binary mixed micelles of chiral sodium undecenyl leucinate and achiral sodium undecenyl sulfate: I. Characterization and application as pseudostationary phases in micellar electrokinetic chromatography.

Sodium 10-undecenyl sulfate (SUS), sodium 10-undecenyl leucinate (SUL) and their five different mixed micelles at varied percent mole ratios were prepared. The critical micelle concentration (CMC), C(20), gamma(CMC), partial specific volume, methylene group selectivity, mobilities and elution window were determined using a variety of analytical techniques. These surfactant systems were then evaluated as novel pseudostationary phases in micellar electrokinetic chromatography (MEKC). As a commonly used pseudostationary phase in MEKC, sodium dodecyl sulfate (SDS) was also evaluated. The CMC values of SUS and SUL were found to be 26 and 16 mM, respectively, whereas the CMC of mixed surfactants was found to be very similar to that of SUL. The C(20) values decreased dramatically as the concentration of SUL is increased in the mixed micelle. An increase in SUL content gradually increased the methylene group selectivity making the binary mixed surfactants more hydrophobic. Linear solvation energy relationships (LSERs) and free energy of transfer studies were also applied to predict the selectivity differences between the surfactant systems. The cohesiveness and the hydrogen bond acidic character of the surfactant systems were found to have the most significant influence on selectivity and MEKC retention. The SUS and SDS showed the strongest while SUL showed the weakest hydrogen bond donating capacity. The basicity, interaction with n and pi-electrons of the solute and dipolarity/polarizability were the least significant factors in LSER model for the surfactant systems studied. Free energies of transfer of selected functional groups in each surfactant systems were also calculated and found to be in good agreement with the LSER data.

Antimicrobial activity of some thiourea derivatives and their nickel and copper complexes.

Five thiourea derivative ligands and their Ni(2+) and Cu(2+) complexes have been synthesized. The compounds were screened for their in vitro anti-bacterial activity using Gram-positive bacteria (two different standard strains of Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, Streptococcus pyogenes, Bacillus cereus) and Gram-negative bacteria (Esherichia coli, Pseudomonas aeruginosa, Enterobacter cloacae, Proteus vulgaris, Enterobacter aerogenes) and in vitro anti-yeast activity (Candida albicans, Candida krusei, Candida glabrata, Candida tropicalis, Candida parapsilosis). The minimum inhibitory concentration was determined for all ligands and their complexes. In vitro anti-yeast activity of both ligands and their metal complexes is greater than their in vitro anti-bacterial activity. The effect of the structure of the investigated compounds on the antimicrobial activity is discussed.

Thermodynamic studies of the interaction of molecular micelles and copolymerized molecular micelles with benzodiazepines and alkyl phenyl ketones using MEKC.

In this study, polymers of sodium 10-undecenoyl L-leucinate (SUL) and sodium undecenyl sulfate (SUS) as well as their copolymerized molecular micelles (CoPMMs) were applied in MEKC as pseudostationary phases to separate benzodiazepines and alkyl phenyl ketones. SDS, a common pseudostationary phase used in MEKC, was also used for comparison. The van't Hoff relationship was applied to compute the temperature dependence of the MEKC retention factors of the test solutes to estimate the enthalpy, entropy, and the Gibbs free energy. Nonlinear van't Hoff plots were obtained with the majority of benzodiazepines indicating that the thermodynamic parameters were temperature-dependent in all surfactant systems for these solutes. In contrast, all alkyl phenyl ketones resulted in linear van't Hoff plots.

Glycine-based polymeric surfactants with varied polar head group: II. chemical selectivity in micellar electrokinetic chromatography using linear solvation energy relationships.

A series of four acyl and four alkenoxy glycinates (i.e., mono-, di-, tri-, and tetraderivatives of polysodium N-undecenoyl glycinate (poly-SUGs) as well as polysodium N-undecenoxy carbonyl glycinates (poly-SUCGs)) were compared for simultaneous separation of nonhydrogen bonding (NHB), hydrogen-bond acceptor (HBA), and hydrogen-bond donor (HBD) solutes. An increase in the number of glycine units in the polar head group of polymeric surfactant decreases both the retention and the migration window of all solutes with some changes in separation selectivity. The poly(sodium N-undecenoxy carbonyl-glycinate) (poly-SUCG1) with one glycine unit was the least polar surfactant and has the lowest phase ratio, but this monoglycinate surfactant provided the best simultaneous separation of 10-NHBs and 8-HBAs. On the other hand, 9-HBDs were well separated using any of the six mono-, di-, and triglycinate surfactants compared to the two tetraglycinates. Linear solvation energy relationships (LSERs) and separation of the geometrical isomers studies were also performed to further envisage the selectivity differences. From LSER studies, the phase ratio and hydrogen-bond-donating strength of the poly-SUG series of surfactant were found to increase with an increase in the size of the head group, but no clear trends were observed for poly-SUCG surfactants. The cohesiveness for all poly-SUG and poly-SUCG was positive, but the values were generally lower (with exception of the poly(sodium N-undecenoyl glycyl-glycyl-glycinate)) at a higher number of glycine units. Finally, the poly(sodium N-undecenoyl glycinate) and poly-SUCG1 were found to be the two best polymeric surfactants as they provided relatively higher shape selectivity for separation of two of the three sets of geometrical isomers.

Simultaneous enantioseparation and tandem UV-MS detection of eight beta-blockers in micellar electrokinetic chromatography using a chiral molecular micelle.

The feasibility of using a new and more versatile polymeric chiral surfactant, i.e., poly(sodium N-undecenoxy carbonyl-L-leucinate (poly-L-SUCL) is investigated for simultaneous enantioseparation and detection of eight structurally similar beta-blockers with tandem UV and MS detection. Three optimization approaches, i.e., direct infusion-MS, capillary zone electrophoresis-MS, and chiral micellar electrokinetic chromatography-mass spectrometry (CMEKC-MS), were investigated to optimize sheath liquid parameters, spray chamber parameters, and CMEKC separation parameters for maximum sensitivity and chiral resolution. Compared to unpolymerized micelle of L-SUCL, the use of micelle polymer (i.e., poly-L-SUCL) provided significantly higher separation efficiency, lower separation current, and higher detection sensitivity for CMEKC-ESI-MS of beta-blockers. It was also observed that, unlike monomeric L-SUCL, polymeric L-SUCL provided enantioseparation of all beta-blockers even at the lowest surfactant concentration (i.e., 5 mM poly-L-SUCL). Under optimum CMEKC and ESI-MS conditions (15 mM poly-L-SUCL, 25 mM each of NH4OAc and TEA (pH 8.0); 80% (v/v) methanol sheath liquid containing 40 mM NH4OAc (pH 8.0); sheath liquid flow rate, 5.0 microL/min; drying gas flow rate, 5 L/min; drying gas temperature, 200 degrees C; nebulizing pressure, 6 psi (0.414 bar); capillary voltage, +2.5 kV; fragmentor voltage, 85 V), baseline enantioseparation of eight beta-blockers was achieved by tandem UV (in approximately 30 min) and MS (in approximately 60 min) detection. Calibration curves for all beta-blockers were linear in the range of 0.01-0.6 mM for both CMEKC-UV and CMEKC-MS methods, but the later method provided better concentration limit of detection with similar RSD for migration time and peak areas. The CMEKC-ESI-MS method appears suitable for use as a routine procedure for high-throughput separation of beta-blockers with high sensitivity.

Monomeric and polymeric anionic gemini surfactants and mixed surfactant systems in micellar electrokinetic chromatography. Part I: characterization and application as novel pseudostationary phases.

Sodium di(undecenyl) tartarate monomer (SDUT), a vesicle-forming amphiphilic compound possessing two hydrophilic carboxylate head groups and two hydrophobic undecenyl chains gemini surfactant, was prepared and polymerized to form a polymeric gemini surfactant (i.e., poly-SDUT). These anionic surfactant systems with carboxylate (SDUT and poly-SDUT) and sulfate (sodium dodecyl sulfate, SDS) head groups as well as mixed surfactant systems (SDS/SDUT, SDS/poly-SDUT, and SDUT/poly-SDUT) were then applied as novel pseudostationary phases in micellar electrokinetic chromatography (MEKC). The SDUT and poly-SDUT were characterized using various analytical techniques. Retention factors of 36 benzene derivatives were calculated in 20 mM phosphate buffer of each surfactant system. The retention factor values of the test solutes show that there are distinctive selectivity differences between the surfactant systems. Solute-pseudostationary phase interactions in MEKC were also examined by determining the free energy of transfer of the substituted functional groups from the aqueous buffer phase into the pseudostationary phase.

Monomeric and polymeric anionic gemini surfactants and mixed surfactant systems in micellar electrokinetic chromatography. Part II: characterization of chemical selectivity using two linear solvation energy relationship models.

Sodium di(undecenyl) tartarate monomer (SDUT), a vesicle-forming amphiphilic compound possessing two hydrophilic carboxylate headgroups and two hydrophobic undecenyl chains, was prepared and polymerized to form a polymeric vesicle (i.e., poly-SDUT). The anionic surfactants of SDUT and poly-SDUT (carboxylate head group) and sodium dodecyl sulfate, SDS (sulfate head groups) as well as mixed surfactant systems (SDS/SDUT, SDS/poly-SDUT, and SDUT/poly-SDUT) were applied as pseudostationary phases in micellar electrokinetic chromatography (MEKC). Two linear solvation energy relationship (LSER) models, i.e., solvatochromic and solvation parameter models, were successfully applied to investigate the effect of the type and composition of pseudostationary phases on the retention mechanism and selectivity in MEKC. The solvatochromic and solvation parameter models were used to help understand the fundamental nature of the solute-pseudostationary phase interactions and to characterize the properties of the pseudostationary phases (e.g., solute size and hydrogen bond-accepting ability for all pseudostationary phases). The solute types were found to have a significant effect on the LSER system coefficients and on the predicted retention factors. Although both LSER models provide the same information, the solvation parameter model is found to provide much better results both statistically and chemically than the solvatochromic model.

Chiral separations in microemulsion electrokinetic chromatography. Use of micelle polymers and microemulsion polymers.

In this study, microemulsions of the chiral surfactant polysodium N-undecenoyl-D-valinate (poly-D-SUV) was utilized for enantiomeric separation by investigating two approaches using polymeric chiral surfactant in microemulsion electrokinetic chromatography (MEEKC). In the first approach, poly-D-SUV was used as an emulsifier surfactant along with 1-butanol and n-heptane. Enantioseparation of anionic or partially anionic binaphthyl derivatives, anionic barbiturates, and cationic paveroline derivatives were achieved by varying the mass fraction of 1-butanol, n-heptane and poly-D-SUV. For anionic or partially anionic analytes, relatively lower mass fractions of n-heptane, and poly-D-SUV were found to give optimum chiral separations as compared to that for cationic solutes. In the second approach, the chiral microemulsion polymer was prepared by polymerizing mixtures of 3.50% (w/w) of sodium N-undecenoyl-D-valinate (D-SUV) and 0.82% (w/w) of n-heptane (core phase) at varying concentration of 1-butanol. After polymerization, the n-heptane and 1-butanol were removed to yield solvent free microemulsion polymers (MPs) which were then utilized for the separation of anionic binaphthyl derivatives and anionic barbiturates. When MPs of D-SUV were utilized for chiral separation, 1.00% (w/w) 1-butanol and 3.50% (w/w) 1-butanol was optimum for enantioseparation of (+/-)-BNP and (+/-)-BOH, respectively. On the other hand, for anionic (+/-)-barbiturates very low concentration of butanol (0.25%, w/w) provided optimum resolution. Compared with micellar electrokinetic chromatography (MEKC), the use of micelle polymers or microemulsion polymers in MEEKC showed dramatic enhancement for resolution of (+/-)-BNP, while this enhancement was less dramatic for other binaphthyls [(+/-)-BOH, (+/-)-BNA] as well as for (+/-)-barbiturates and (+/-)-paveroline derivatives. However, higher separation efficiency of the enantiomers was always observed with MEEKC than in MEKC.

Polymeric alkenoxy amino acid surfactants: II. Chiral separations of beta-blockers with multiple stereogenic centers.

Two amino acid-based (leucine and isoleucine) alkenoxy micelle polymers were employed in this study for the separation of multichiral center-bearing beta-blockers, nadolol and labetalol. These polymers include polysodium N-undecenoxy carbonyl-L-leucinate (poly-L-SUCL) and polysodium N-undecenoxy carbonyl-L-isoleucinate (poly-L-SUCIL). Detailed synthesis and characterization were reported in our previous paper [26]. It was found that poly-L-SUCIL gives better chiral separation than poly-L-SUCL for both nadolol and labetalol isomers. The use of 50-100 mM poly-L-SUCIL as a single chiral selector provided separation of four and three isomers of labetalol and nadolol, respectively. Further optimization in separation of both enantiomeric pairs of nadolol and labetalol was achieved by evaluation of type and concentration of organic solvents, capillary temperature as well type and concentration of cyclodextrins. A synergistic approach, using a combination of poly-L-SUCIL and sulfated beta-CD (S-beta-CD) was evaluated and it showed dramatic separation for enantiomeric pairs of nadolol. On the other hand for labetalol enantiomers, separation was slightly decreased or remain unaffected using the dual chiral selector system. Finally, simultaneous separation of both nadolol and labetalol enantiomers was achieved in a single run using 25 mM poly-L-SUCIL and 5% w/v of S-beta-CD in less then 35 min highlighting the importance of high-throughput chiral analysis.

Polymeric sulfated surfactants with varied hydrocarbon tail: II. Chemical selectivity in micellar electrokinetic chromatography using linear solvation energy relationships study.

The effect of hydrocarbon chain length on chemical selectivity in micellar electrokinetic chromatography (MEKC) was investigated using polymeric sulfated surfactants: poly-(sodium 7-octenyl sulfate), poly(sodium 8-nonenyl sulfate), poly(sodium 9-decenyl sulfate), and poly(sodium 10-undecenyl sulfate). Linear solvation energy relationships (LSERs) and free energy of transfer studies were conducted to predict the selectivity differences between the four polymeric surfactants. The overall nature of the solute/ polymeric micelle interactions was found to be different despite the fact that all polymeric surfactants have the same head group. The polar character and acidic strength of the polymeric surfactant are found to decrease as the hydrocarbon chain length of the surfactant is increased. On the other hand, the polarizability of the polymeric sulfated surfactants increases (upon interacting with solute lone-pair electrons) with increasing hydrocarbon chain length. The LSER results show that the solute size and hydrogen bond accepting ability play the key roles in MEKC retention.

Polymeric sulfated surfactants with varied hydrocarbon tail: I. Synthesis, characterization, and application in micellar electrokinetic chromatography.

The influence of surfactant hydrocarbon tail on the solute/pseudostationary phase interactions was examined. Four anionic sulfated surfactants with 8-, 9-, 10-, and 11-carbon chains having a polymerizable double bond at the end of the hydrocarbon chain were synthesized and characterized before and after polymerization. The critical micelle concentration (CMC), polarity, and aggregation number of the four sodium alkenyl sulfate (SAIS) surfactants were determined using fluorescence spectroscopy. The partial specific volume of the polymeric SAIS (poly-SAIS) surfactants was estimated by density measurements and capillary electrophoresis (CE) was employed for determination of methylene selectivity as well as for elution window. The CMC of the monomers of SAIS surfactants decrease with increase in chain length and correlated well when fluorescence method was compared to CE. The physicochemical properties (partial specific volume, methylene selectivity, electrophoretic mobility, and elution window) increased with an increase in chain length. However, no direct relationship was found between the aggregation number and the length of hydrophobic tail of poly-SAIS surfactants. These polymeric surfactants were then used as pseudostationary phases in micellar electrokinetic chromatography (MEKC) to study the retention behavior and selectivity factor of 36 benzene derivatives with different chemical characteristics. Although variation in chain length of the polymeric surfactants significantly affects the retention of nonhydrogen bonding (NHB) benzene derivatives, these effects were less pronounced for hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD) benzene derivatives. Therefore, hydrophobicity of poly-SAIS surfactants was found to be a major driving force for retention of NHB derivatives. However, for several benzene derivatives (NHB, HBA, and HBD) significantly higher selectivity factor was observed with longest chain polymeric surfactant (e.g., poly(sodium 10-undecenyl sulfate), poly-SUS) compared to shorter chain polymeric surfactant (e.g., poly(sodium 7-octenyl sulfate), poly-SOcS). In addition, the effect of the surfactant hydrophobic chain was also found to have some impact on migration order of NHB, HBA, and HBD benzene derivatives.

Novel anionic copolymerized surfactants of mixed achiral and chiral surfactants as pseudostationary phases for micellar electrokinetic chromatography.

One disadvantage of amino acid-based chiral selectors for micellar electrokinetic chromatography (MEKC) is that either they have very low solubility or are insoluble at acidic pHs. In order to increase solubilities at lower pHs, we have synthesized a highly water-soluble achiral surfactant and copolymerized it with an amino acid-based chiral surfactant. These two surfactants were polymerized either separately or at various molar rations of binary solutions, yielding pure molecular or copolymerized surfactant (CoPS), respectively. All surfactants were characterized by use of several analytical techniques prior to using them as novel pseudostationary phases in MEKC. The chromatographic performance of the CoPS in MEKC was tested with chiral and achiral analytes. The highly soluble sulfate head group significantly increased the solubility of amino acid-based CoPS over a wide range of pH. Three chiral binaphthyl derivatives were tested and each surfactant system was found to have different selectivity.

Characterization and application of sodium di(2-ethylhexyl) sulfosuccinate and sodium di(2-ethylhexyl) phosphate surfactants as pseudostationary phases in micellar electrokinetic chromatography.

Sodium di(2-ethylhexyl) sulfosuccinate (DOSS) and sodium di(2-ethylhexyl) phosphate (NaDEHP) surfactants, with double alkyl chains and negatively charged headgroups, were characterized using fluorescence quenching, densitometry, and tensiometry techniques to determine their aggregation number, partial specific volume, and critical aggregation concentration. These two surfactants were then applied as pseudostationary phases in micellar electrokinetic chromatography (MEKC) for separations of alkyl phenyl ketones. The aggregation number of NaDEHP was found to be more than two-fold higher than that of DOSS. The partial specific volumes of NaDEHP and DOSS were found to be 0.9003 and 0.8371 mL/g, respectively. The critical aggregation concentrations are 5.12 and 1.80 mM for NaDEHP and DOSS, respectively. The DOSS surfactant provided a wider separation window and had a greater hydrophobic environment than the NaDEHP surfactant under the MEKC experimental conditions studied.

Copolymerized polymeric surfactants: characterization and application in micellar electrokinetic chromatography.

An achiral monomeric surfactant (sodium 10-undecenyl sulfate, SUS) and a chiral surfactant (sodium 10-undecenoyl L-leucinate, SUL) were synthesized and polymerized individually to form poly-SUS and poly-SUL. These surfactants were then copolymerized at various molar ratios to produce a variety of copolymerized surfactants (CoPSs), possessing both achiral (sulfate) and chiral (leucinate) head groups. The CoPSs, poly-SUS, poly-SUL, and sodium dodecyl sulfate were characterized using several analytical techniques. The aggregation numbers of the polymeric surfactants and the partial specific volumes were determined by the use of fluorescence quenching and density measurements, respectively. These polymeric surfactants were investigated as novel pseudostationary phases in micellar electrokinetic chromatography (MEKC) for the separation of chiral and achiral solutes. Solute hydrophobicity was found to have major influence on the MEKC retention of alkyl phenyl ketones. In contrast, hydrogen-bonding ability of benzodiazepines is the major factor that governs their retention, but hydrophobicity has an insignificant effect on MEKC retention of benzodiazepines.

Use of poly(sodium oleyl-L-leucylvalinate) surfactant for the separation of chiral compounds in micellar electrokinetic chromatography.

A chiral amino acid-based monomeric and polymeric surfactant, sodium oleyl-L-leucylvalinate) (L-SOLV) and poly(sodium oleyl-L-leucylvalinate) (poly-L-SOLV) were synthesized and used for chiral separations in micellar electrokinetic chromatography (MEKC). Poly-L-SOLV was used successfully in the separation of various enantiomers of neutral, acidic, and basic analytes such as 1,1'-bi-2-napthol, 1,1'-binaphthyl-2,2'-diamine, benzoin, hydrobenzoin, benzoin methylether, warfarin, and coumachlor obtaining well-resolved peaks but with only partial separation of temazepam. In addition, the atropisomer 1,1'-binaphthyl-2, 2'-dihydrogen phosphate was chosen to study the applicability of the polymeric surfactant over a wide range of parameters such as concentration, temperature, voltage, and pH. The most striking characteristic of this new surfactant is its high hydrophobicity. It is favorable to interactions with hydrophobic chiral analytes, and thus may provide better chiral recognition for the compounds.

Open-tubular capillary electrochromatography using a polymeric surfactant coating.

A stable polyelectrolyte multilayer (PEM) coating was investigated for use in open-tubular capillary electrochromatography (o-CEC). In this approach, the PEM consisted of the cationic polymer of a quaternary ammonium salt, poly(diallyldimethylammonium chloride) and the anionic polymeric surfactant, poly(sodium undecylenic sulfate). Both the cationic and anionic polymers were physically adsorbed to the surface of a fused-silica capillary by use of a simple coating procedure. This procedure involved an alternate rinse of the positively and negatively charged polymers. The performance of the PEM coating as a dynamic stationary phase was evaluated by use of electrochromatographic experiments and showed good selectivity for both phenols and benzodiazepines. Reproducibility of the PEM coating was also evaluated by calculating the relative standard deviations (RSDs) of the electroosomotic flow (EOF). The run-to-run and capillary-to-capillary RSD values of the EOF were less than 1.5%. The endurance of the coating was more than 100 runs. The importance of the PEM coating was illustrated by comparing separations on a bare uncoated capillary with the coated capillary. In addition, the chromatographic performance using o-CEC and micellar electrokinetic chromatography (MEKC) was compared for the separation of benzodiazepines.

Analytical separations using molecular micelles in open-tubular capillary electrochromatography.

Open-tubular capillary electrochromatography (OT-CEC) is an alternative approach to conventional CEC. The primary advantage of OT-CEC is the elimination of problems associated with frits and silica particles in conventional CEC. This report is an investigation of the utility of using a polymeric surfactant (molecular micelle) for OT-CEC. In this approach, fused-silica capillaries coated with thin films of physically adsorbed charged polymers are developed by use of a polyelectrolyte multilayer (PEM) coating procedure. The PEM coating is constructed in situ by alternating rinses with positively and negatively charged polymers, where the negatively charged polymer is a molecular micelle. This can offer a number of advantages for separation of hydrophobic analytes. In this study, poly(diallyldimethylammonium chloride) was used as the cationic polymer and poly(sodium N-undecanoyl-L-glycinate) was used as the anionic polymer for PEM coating. The performance of the modified capillaries as a separation medium is evaluated by use of seven benzodiazepines as analytes. The run-to-run, day-to-day, week-to-week, and capillary-to-capillary reproducibilities of electroosmotic flow are very good with relative standard deviation values of less than 1% in all cases. In addition, the chromatographic performance of the monomeric form of the molecular micelle is compared for the separation of these analytes. The PEM-coated capillary was remarkably robust with more than 200 runs accomplished in this study. Strong stability against extreme pH values was also observed. The general utility of this approach is discussed in detail.