Protein separation and surfactant control of electroosmotic flow in poly(dimethylsiloxane)-coated capillaries and microchips

A thermally pyrolyzed poly(dimethylsiloxane) (PDMS) coating intended to prevent surface adsorption during capillary electrophoretic (CE) [Science 222 (1983) 266] separation of proteins, and to provide a substrate for surfactant adsorption for electroosmotic mobility control was prepared and evaluated. Coating fused-silica capillaries or glass microchip CE devices with a 1% solution of 100 cSt silicone oil in CH2Cl2, followed by forced N2 drying and thermal curing at 400 degrees C for 30 min produced a cross-linked PDMS layer. Addition of 0.01 to 0.02% Brij 35 to a 0.020 M phosphate buffer gave separations of lysozyme, cytochrome c, RNase, and fluorescein-labeled goat anti-human IgG Fab fragment. Respective plates/m typically obtained at 20 kV (740 V cm(-1)) were 2, 1.5, 1.25, and 9.4-10(5). In 50 mM ionic strength phosphate, 0.01% Brij 35 running buffer, the electroosmotic flow observed was about 25% of that in a bare capillary, and showed no pH dependence between pH 6.3-8.2. Addition of sodium dodecylsulfate (SDS) or cetyltrimethylammonium bromide (CTAB) to this running buffer allowed ready control of electroosmotic mobility, mu(eo). Concentrations of SDS between 0.005 to 0.1% resulted in mu(eo) ranging from 3 to 5 x 10(-4) cm2 V(-1) s(-1). Addition of 1 to 2.3 x 10(-4)% (2.7-6.3 microM) CTAB caused flow reversal. CTAB concentrations between 3.5 x 10(-4) and 0.05% (0.0014-1.37 mM) allowed control of mu(eo) between -1 x 10(-4) and -5.0 x 10(-4) cm2 V(-1) s(-1). For both surfactants the added presence of 0.01% Brij 35 provided slowly varying changes in mu(eo) with charged surfactant concentration.     

Electrokinetic characterization of poly(dimethylsiloxane) microchannels

This paper characterizes the basic electrokinetic phenomena occurring within native poly(dimethylsiloxane) (PDMS) microchannels. Using simple buffers and current measurements, current density and electroosmosis data were determined in trapezoidal, reversibly sealed PDMS/PDMS and hybrid PDMS/glass channels with a cross-sectional area of 1035.5 microm(2) and about 6 cm length. This data was then compared to that obtained in an air-thermostated 50 microm inner diameter (1963.5 microm(2) cross-sectional area) fused-silica (FS) capillary of 70 cm length. Having a pH 7.8 buffer with an ionic strength (I) of 90 mM, Ohms's law was observed in the microchannels with electric field strengths of up to about 420 V/cm, which is about twice as high as for the FS capillary. The electroosmotic mobility (micro(EO)) in PDMS and FS is shown to exhibit the same general dependences on I and pH. For all configurations tested, the experimentally determined micro(EO) values were found to correlate well with the relationship micro(EO) = a + b log(I), where a and b are coefficients that are determined via nonlinear regression analysis. Electroosmotic fluid pumping in native PDMS also follows a pH dependence that can be estimated with a model based upon the ionization of silanol. Compared to FS, however, the magnitude of the electroosmotic flow in native PDMS is 50-70% smaller over the entire pH range and is difficult to maintain at acidic pH values. Thus, the origin of the negative charge at the inner wall of PDMS, glass, and FS appears to be similar but the density is lower for PDMS than for glass and FS.     

1,3-dialkylimidazolium-based room-temperature ionic liquids as background electrolyte and coating material in aqueous capillary electrophoresis

The 1-ethyl-3-methylimidazolium (EMIM) cation was found to have constant mobility of 4.5 x 10(-4) cm2 V(-1) s(-1) over the pH range of 3 to 11. The electroosmotic flow of bare silica capillary was reversed by the covalently bonded room-temperature ionic liquid (RTIL) coating. With run buffer of 5 mM EMIM (pH 8.5), NH4+ in human urine was separated from the K+ matrix and was detected to be 0.37 +/- 0.012%. K+, Na+, Li+, Ca2+, Mg2+ and Ba2+ were baseline separated in RTIL-coated capillary with run buffer of 10 mM EMIMOH-acetic acid at pH 5, and the concentration of the above ions in a red wine were detected to be 907, 27.9, 0, 71.0, 83.4 and 31.1 microg/ml, respectively. The RTIL-coated capillary showed stable electroosmotic flow for at least 80 h in the run buffer.     

Capillaries modified by noncovalent anionic polymer adsorption for capillary zone electrophoresis, micellar electrokinetic capillary chromatography and capillary electrophoresis mass spectrometry

A simple coating procedure for generation of a high and pH-independent electroosmotic flow in capillary zone electrophoresis (CZE) and micellar electrokinetic capillary chromatography (MEKC) is described. The bilayer coating was formed by noncovalent adsorption of the ionic polymers Polybrene and poly(vinylsulfonate) (PVS). A stable dynamic coating was formed when PVS was added to the background electrolyte. Thus, when the PVS concentration in the background electrolyte was optimized for CZE (0.01%), the EOF differed less than 0.3% after 54 runs. The electroosmotic mobility in the coated capillaries was (4.9+/-0.1) x 10(-4) cm2V(-1)s(-1) in a pH-range of 2-10 (ionic strength = 30 mM). When alkaline compounds were used as test substances intracapillary and intercapillary migration time variations (n = 6) were less than 1% relative standard deviation (RSD) and 2% RSD, respectively in the entire pH range. The coating was fairly stable in the presence of sodium dodecyl sulfate, and this made it possible to perform fast MEKC separations at low pH. When neutral compounds were used as test substances, the intracapillary migration time variations (n = 6) were less than 2% RSD in a pH range of 2-9. In addition to fast CZE and MEKC separations at low pH, analysis of the alkaline compounds by CE-MS was also possible.     

高效毛细管电泳分析羊栖菜多糖对肿瘤机体红细胞合淌度的影响

为了分析羊栖菜多糖（SFPS）对肿瘤机体红细胞合淌度的影响,建立了肿瘤动物模型,分高、中、低剂量腹腔给予羊栖菜多糖7 d,采集并制备红细胞悬液,应用高效毛细管电泳法检测红细胞的合淌度。实验条件:毛细管为75 μm×50 cm,电泳缓冲液为含2 g/L羟丙基甲基纤维素的磷酸盐溶液(0.1 mol/L,pH 7.4),压力进样为3.448 kPa×10 s,分离电压为20 kV,柱温为25 ℃,电渗淌度为2.16×10-4 cm2·V-1·s-1。实验结果表明：羊栖菜多糖能降低肿瘤机体红细胞的电泳迁移时间(阴性对照组为15.76 min,SFPS低剂量组为13.96 min,SFPS中剂量组为12.90 min,SFPS高剂量组为13.51 min,正常对照组为11.51 min),增加红细胞的合淌度(阴性对照组为1.06×10-4 cm2·V-1·s-1,SFPS低剂量组为1.19×10-4 cm2·V-1·s-1,SFPS中剂量组为1.29×10-4 cm2·V-1·s-1,SFPS高剂量组为1.23×10-4 cm2·V-1·s-1,正常对照组为1.45×10-4 cm2·V-1·s-1),SFPS 3个剂量组红细胞的合淌度与阴性对照组比较均有非常显著的差异(P＜0.01)。羊栖菜多糖能够改变肿瘤机体红细胞的合淌度,并使之趋向于正常机体水平,这可能与其改变红细胞表面的电荷密度有关。高效毛细管电泳法可以作为检测红细胞生理状态和功能的一种辅助工具。     

一种直接测定微流控芯片电渗流速度的新方法

随着微芯片技术的成熟,越来越迫切地需要有一个准确而简洁的电渗流速度的检测方法。根据荧光物质罗丹明123（Rh123）在不同pH缓冲溶液中迁移时间的变化,推导出Rh123在pH 9和10条件下分别有中性分子存在,而中性分子的移动速度等于电渗流速度,因此建立了直接以Rh123中性分子为标记物测定电渗流速度的方法。通过直接检测Rh123中性分子的迁移时间,计算得出所用玻璃微流控芯片在pH 9.3和pH 10.1的电渗流速度为3.9×10-4 cm2/(s·V)和4.1×10-4 cm2/(s·V),与经典方法对照无明显差异。     

Electroosmotic flow in poly(dimethylsiloxane) microchannels

This paper reports on the study of electroosmotic flow (EOF) in poly(dimethylsiloxane) (PDMS) microchannels on the basis of indirect amperometric detection method. Gradual increase of EOF rate in freshly prepared PDMS microchannels was observed with the running buffer of phosphate buffer solution (PBS). With the same concentration (10 mM) of PBS containing different cations and the same pH value (7.0) and, the time of the stable EOF in PDMS microchannels under the applied separation voltage of 1000 V was 49.8 s (Li+ -PBS), 57.1 s (Na+ -PBS), 91 s (K+ -PBS), respectively. Meanwhile, the different adsorption of cations (Li+, Na+ and K+) on hydrophobic PDMS wall was observed through their separation in PDMS microchannels. Such experimental results demonstrated that the EOF in PDMS microchannels came from the cations and anions adsorbed on PDMS wall. This study would not only help us understand the surface state of PDMS, but also provide a useful guidance for establishing the effective surface modification methods in PDMS microchip CE.     

Microfluidic flow control on charged phospholipid polymer interface

A type of charged phospholipid polymer biointerface was constructed on a quartz microfluidic chip to control the electroosmotic flow (EOF) and to suppress non-specific protein adsorption through one-step modification. A negatively charged phospholipid copolymer containing 2-methacryloyloxyethyl phosphorylcholine (MPC), n-butyl methacrylate (BMA), potassium 3-methacryloyloxypropyl sulfonate (PMPS) and 3-methacryloxypropyl trimethoxysilane (MPTMSi) moieties (referred to as PMBSSi) was synthesized to introduce such phosphorylcholine segments as well as surface charges onto the silica-based microchannels via chemical bonding. At neutral pH, the homogenous microchannel surface modified with 0.3 wt% PMBSSi in alcoholic solution, retained a significant cathodic EOF ((1.0 +/- 0.1) x 10(-4) cm(2) V(-1) s(-1)) with approximately one-half of the EOF of the unmodified microchannel ((1.9 +/- 0.1) x 10(-4) cm(2) V(-1) s(-1)). Along with another non-charged copolymer (poly(MPC-co-MPTMSi), PMSi), the regulation of the surface charge density can be realized by adjusting the concentration of PMBSSi or PMSi initial solutions for modification. Coincidently, the zeta-potential and the EOF mobility at neutral pH showed a monotonically descending trend with the decrease in the charge densities on the surfaces. This provides a simple but feasible approach to controlling the EOF, especially with regard to satisfying the requisites of miniaturized systems for biological applications requiring neutral buffer conditions. In addition, the EOF in microchannels modified with PMBSSi and PMSi could maintain stability for a long time at neutral pH. In contrast to the EOF in the unmodified microchannel, the EOF in the modified microchannel was only slightly affected by the change in pH (from 1 to 10). Most importantly, although PMBSSi possesses negative charges, the non-specific adsorptions of both anionic and cationic proteins (considering albumin and cytochrome c, respectively, as examples) were effectively suppressed to a level of 0.15 microg cm(-2) and lesser in the case of the 0.3 wt% PMBSSi modification. Consequently, the variation in the EOF mobility resulting from the protein adsorption was also suppressed simultaneously. To facilitate easy EOF control with compatibility to biomolecules delivered in the microfluidic devices, the charged interface described could provide a promising option.     

Measurement of electroosmotic flow in plastic imprinted microfluid devices and the effect of protein adsorption on flow rate.

Several commercially available plastic materials were used as substrates in the fabrication of microfluid channels for biochemical analysis. Protocols for fabrication using the wire-imprinting method are reported for polystyrene, polymethylmethacrylate and a copolyester material. Channel sealing was accomplished by low-temperature bonding of a substrate of similar material; therefore, each channel was composed of a single material on all sides. The electroosmotic flow in 25-microm imprinted channels was evaluated for each substrate material. The copolyester material exhibited the highest electroosmotic flow mobility of 4.3 x 10(-4) cm2 V(-1) s(-1) which is similar to that previously reported for fused-silica capillaries. Polystyrene exhibited the lowest electroosmotic flow mobility of 1.8 x 10(-4) cm2 V(-1) s(-1). Plots of linear velocity versus applied electric field strength were linear from 100 V cm(-1) to 500 V cm(-1) indicating that heat dissipation is effective for all substrates in this range. Electroosmotic flow was reevaluated in the plastic channels following incubation in antibody solution to access the non-specific binding characteristics of a common biochemical reagent onto the substrate materials. All materials tested showed a high degree of non-specific adsorption of IgG as indicated by a decrease in the electroosmotic flow mobility in post-incubation testing.     

Using of S-(-)-2-hydroxymethyl-1,1-dimethylpyrrolidinium tetrafluoroborate as additive to the background electrolyte in capillary electrophoresis

We synthesised and used new type of quaternary ammonium salt [S-(-)-2-hydroxymethyl-1,1-dimethylpyrrolidinium tetrafluoroborate] as effective additive to acidic background electrolytes. We used this quaternary ammonium salt as effective agent for capillary zone electrophoresis separation of model mixture of five tricyclic antidepressants (amitriptyline, nortriptyline, imipramine, desipramine and clomipramine) as model analytes. We observed that addition of S-(-)-2-hydroxymethyl-1,1-dimethylpyrrolidinium tetrafluoroborate ([HMDP](+) [BF(4)](-)) to acidic background electrolytes leads to suppression of magnitude of electroosmotic flow (EOF) and gradually change the direction of the EOF. Baseline separation of five TAs was achieved by using of 91.1 mmol L(-1) (20 gL(-1)) of [HMDP](+) [BF(4)](-) in 25 mmol L(-1) sodium phosphate pH 2.5, where electroosmotic mobility was -11.3 x 10(-9) m(2) V(-1) s(-1). We achieved baseline separation of five TAs with using of [HMDP](+) [BF(4)](-) as water solution too. We observed that [HMDP](+) [BF(4)](-) can be used as buffer additive, which offers relatively smaller anodic electroosmotic flow instead of cationic surfactants that are mostly used for genarating of anodic electroosmotic flow in capillary electrophoresis.     

Glass/SU‐8 microchip for electrokinetic applications

In this communication, we describe the fabrication and electric characterization of a hybrid glass/SU‐8 microchannels for high‐performance electrokinetic applications. The bonding process employed SU‐8 film as intermediate layer with reduced baking times; all the procedure took less than 50 min (only about 10 min disregarding the cleaning and dehydration steps). Additionally, further steps to improve the adhesion of the substrate to the SU‐8 were not needed. The developed configuration aggregates the advantages of both substrates, including (i) simple fabrication techniques; (ii) high compatibility for integration of microelectromechanical, optical, and electrochemical components (SU‐8); (iii) high and stable electroosmotic mobility (μ_EO); and (iv) satisfactory heat dissipation capacity (glass). Electroosmotic mobilities were measured as a function of the pH using the current monitoring method, whereas the heat dissipation capacity was investigated through Ohm's law plots for both glass and glass/SU‐8 microchips. The measured μ_EO values were similar for both microdevices, with mobilities of the order of 4.0–4.5 × 10^?4 cm² V^?1 cm^?1 at 4–12 pH range using phosphate buffer (10 and 20 mmol/L). The heat dissipation assays were carried out in microchannels filled with 20 mmol/L phosphate buffer. A considerable Joule heating was observed only at electric field strengths greater than 580 V cm^?1 in hybrid glass/SU‐8 microdevices, representing a substantial increase of 48% when compared to all SU‐8 microdevices.     

Cyclodextrin-assisted capillary electrophoretic resolution of 1,1'-bi-2-naphthol atropisomers.

Native beta- and gamma-cyclodextrin (CD), neutral beta-CD derivatives and ethylcarbonate derivatives of beta- and gamma-CD were used as stereoselective additives for CD-capillary zone electrophoresis (CZE) resolution of atropisomers of 1,1'-bi-(2-naphthol) (BN). CZE experiments at variable CD concentration allowed calculating binding constants from electrophoretic mobility data, corrected for electroosmotic flow (EOF) and running buffer viscosity variations. The CDs were chosen on the basis of geometric examination of molecular models of BN and CDs that suggested the possibility of inclusion complexes formation. Optimum concentrations, with aqueous 25 mM phosphate running buffer at pH 10.5, 36 cm x 50 microm capillary and 10 kV applied potential, were 3.6, 3.9, 2.1, 2.2, 1.9 mM for beta-CD, gamma-CD, ethylcarbonate-beta-CD, methyl-beta-CD and hydroxypropyl-beta-CD, respectively.     

Silanizing agent for semipermanent wall coating in micellar electrokinetic capillary chromatography

In this paper, the long-chained, silanizing agent chloro(dodecyl)dimethylsilane (CDDS) was investigated as a semipermanent coating in micellar electrokinetic capillary chromatography (MEKC). CDDS coating had great stability due to the formation of covalent bonding with the silanol groups on the surface of fused-silica capillary and remained stable for over 100 min after removal of the rinse step of CDDS solution. Anionic surfactant sodium dodecyl sulfate (SDS) could aggregate at this CDDS coating by the hydrophobic group and formed a SDS layer which could increase the electroosmotic flow (EOF). The separation was performed with the running buffer composed of 60mM sodium tetraborate, 12 mM SDS at pH 9.9, with the applied voltage of 20 kV and capillary temperature 25 degrees C. The effect of the coating agent was investigated by the analysis of amino acids. Compared with previous no-coating method, the EOF increases from 4.34 x 10(-4)cm(2)V(-1)s(-1) to 7.02 x 10(-4)cm(2)V(-1)s(-1). Migration time reproducibility was less than 0.97% R.S.D. from run to run and less than 1.56% R.S.D. from day to day.     

Multi-walled carbon nanotube composites with polyacrylate prepared for open-tubular capillary electrochromatography

A new phase containing immobilized carbon nanotubes (CNTs) was synthesized by in situ polymerization of acid-treated multi-walled CNTs using butylmethacrylate (BMA) as the monomer and ethylene dimethacrylate as the crosslinker on a silanized capillary, forming a porous-layered open-tubular column for CEC. Incorporation of CNT nanomaterials into a polymer matrix could increase the phase ratio and take advantage of the easy preparation of an OT-CEC column. The completed BMA-CNT column was characterized by SEM, ATR-IR, and EOF measurements, varying the pH and the added volume organic modifier. In the multi-walled CNTs structure, carboxylate groups were the major ionizable ligands on the phase surface exerting the EOF having electroosmotic mobility, 4.0 × 10(4) cm2 V(-1)1 S(-1)1, in the phosphate buffer at pH 2.8 and RSD values (n=5), 3.2, 4.1, and 4.3%, for three replicate capillaries at pH 7.6. Application of the BMA-CNT column in CEC separations of various samples, including nucleobases, nucleosides, flavonoids, and phenolic acids, proved satisfactory upon optimization of the running buffers. Their optima were found in the borate buffers at pH 9.0/50 mM, pH 9.5/10 mM/50% v/v ACN, and pH 9.5/30 mM/10% v/v methanol, respectively. The separations could also be used to assess the relative contributions of electrophoresis and chromatography to the CEC mechanism by calculating the corresponding velocity and retention factors. Discussions about interactions between the probe solutes and the bonded phase included the π-π interactions, electrostatic repulsion, and hydrogen bonding. Furthermore, a reversed-phase mode was discovered to be involved in the chromatographic retention.     

Control of electroosmotic flow in laser-ablated and chemically modified hot imprinted poly(ethylene terephthalate glycol) microchannels

The fabrication of microchannels in poly(ethylene terephthalate glycol) (PETG) by laser ablation and the hot imprinting method is described. In addition, hot imprinted microchannels were hydrolyzed to yield additional charged organic functional groups on the imprinted surface. The charged groups are carboxylate moieties that were also used as a means for the further reaction of different chemical species on the surface of the PETG microchannels. The microchannels were characterized by fluorescence mapping and electroosmotic flow (EOF) measurements. Experimental results demonstrated that different fabrication and channel treatment protocols resulted in different EOF rates. Laser-ablated channels had similar EOF rates (5.3+/-0.3 x 10(-4) cm(2)/Vs and 5.6+/-0.4 x 10(-4) cm(2)/Vs) to hydrolyzed imprinted channels (5.1+/-0.4 x 10(-4) cm(2)/Vs), which in turn demonstrated a somewhat higher flow rate than imprinted PETG channels that were not hydrolyzed (3.5+/-0.3 x 10(-4) cm(2)/Vs). Laser-ablated channels that had been chemically modified to yield amines displayed an EOF rate of 3.38+/- 0.1 x 10(-4) cm(2)/Vs and hydrolyzed imprinted channels that had been chemically derivatized to yield amines showed an EOF rate of 2.67+/-0.6 cm(2)/Vs. These data demonstrate that surface-bound carboxylate species can be used as a template for further chemical reactions in addition to changing the EOF mobility within microchannels.     

Bulk modification of polymeric microfluidic devices

The surface properties of microfluidic devices play an important role in their flow behavior. We report here on an effective control of the surface chemistry and performance of polymeric microchips through a bulk modification route during the fabrication process. The new protocol is based on modification of the bulk microchip material by tailored copolymerization of monomers during atmospheric-pressure molding. A judicious addition of a modifier to the primary monomer solution thus imparts attractive properties to the plastic microchip substrate, including significant enhancement and/or modulation of the EOF (with flow velocities comparable to those of glass), a strong pH sensitivity and high stability. Carboxy, sulfo, and amino moieties have thus been introduced (through the incorporation of methylacrylic acid, 2-sulfoethyl-methacrylate and 2-aminoethyl-methacrylate monomers, respectively). A strong increase in the electroosmotic pumping compared to the native poly(methylmethacrylate)(PMMA) microchip (ca. electroosmotic mobility increases from 2.12 to 4.30 x 10(-4) cm(2) V(-1) s(-1)) is observed using a 6% methylacrylate (MAA) modified PMMA microchip. A 3% aminoethyl modified PMMA microchip exhibits a reversal of the electroosmotic mobility (for example, -5.6 x 10(-4) cm(2) V(-1) s(-1) at pH 3.0). The effects of the modifier loading and the pH on the EOF have been investigated for the MAA-modified PMMA chips. The bulk-modified devices exhibit reproducible and stable EOF behavior. The one step fabrication/modification protocol should further facilitate the widespread production of high-performance plastic microchip devices.     

Optimization of separation and migration behavior of cephalosporins in capillary zone electrophoresis

The influences of buffer pH, buffer concentration and buffer electrolyte on the migration behavior and separation of 12 cephalosporin antibiotics in capillary zone electrophoresis using three different types of buffer electrolyte, including phosphate, citrate, and 2-(N-morpholino)ethanesulfonate (MES), were investigated. The results indicate that, although buffer pH is a crucial parameter, buffer concentration also plays an important role in the separation of cephalosporins, particularly when cefuroxime and cefazolin, cephalexin and cefaclor, or cefotaxime and cephapirin are present as analytes at the same time. The electrophoretic mobility of cephalosporins and electroosmotic mobility measured in citrate and MES buffers are remarkably different from those measured in phosphate buffer. With citrate buffer, optimum buffer concentration is confined to a small range (35-40 mM), whereas buffer concentrations up to 300 mM can be used with MES buffer. Complete separations of 12 cephalosporins could be satisfactorily achieved with these three buffers under various optimum conditions. However, the separability of 12 cephalosporins with citrate or MES buffer is better than that with phosphate buffer. As a consequence of a greater electrophoretic mobility of cephalosporins than the electroosmotic mobility with citrate buffer at pH below about 5, some cephalosporins are not detectable. The cloudiness of the peak identification and of the magnitudes of the electrophoretic mobility of cefotaxime and cefuroxime reported previously are clarified. In addition, the pKa values of cephradine, cephalexin, cefaclor, and cephapirin attributed to the deprotonation of either an amino group or a pyridinium group are reported, and the migration behavior of these cephalosporins in the pH range studied is quantitatively described.     

Simultaneous determination of 2-nitrophenol and 4-nitrophenol based on the multi-wall carbon nanotubes Nafion-modified electrode

In this work, multi-wall carbon nanotubes (MWNT) were conveniently dispersed into Nafion-ethanol solution, and the MWNT-Nafion-modified glassy carbon electrode (GCE) was described for the simultaneous determination of 2-nitrophenol and 4-nitrophenol. At pH 4.0 phosphate buffer, the reduction peak currents of 2-nitrophenol (at -0.8 V) and 4-nitrophenol (at -1.0 V) increase significantly at the MWNT-Nafion-modified GCE, in comparison with that at the Nafion-modified GCE and the bare GCE. The experimental parameters, such as solution pH of phosphate buffer, accumulation potential and time, and the amounts of MWNT-Nafion onto the GCE surface, were optimized. The reduction peak currents are linear with the concentration of 2-nitrophenol from 5 x 10(-8) to 1 x 10(-5) mol L(-1) and with that of 4-nitrophenol from 1 x 10(-7) to 1 x 10(-5) mol L(-1). The detection limits after 3-min accumulation are 1 x 10(-8) mol L(-1) for 2-nitrophenol and for 4 x 10(-8) mol L(-1) for 4-nitrophenol. This modified electrode was applied to direct determination of 2-nitrophenol and 4-nitrophenol in lake water samples.     

Comparison of capillary zone electrophoresis performance of powder-blasted and hydrogen fluoride-etched microchannels in glass

The applicability of glass chips with powder-blasted microchannels for electrophoretic separations was examined, and the performance was compared to microchannels etched with hydrogen fluoride (HF), using bicarbonate buffer and rhodamine B and fluorescein as model compounds. The measured electroosmotic mobilities in all chips were comparable, with values of ca. 7 x 10(-4) cm(2) V(-1)s(-1). The effect of electrical field strength and detection length on the separation efficiency was monitored. It was found that the main source of dispersion is of the Taylor-Aris type, which was discussed in relation to channel roughness differences. Although in powder-blasted channels with a separation length of 8.20 cm, 7-9 times lower plate numbers were obtained than in a HF-etched channel with similar dimensions, successful separation of five fluorescein isothiocyanate (FITC)-labeled amino acids was obtained on a powder-blasted chip within 80 s. Efficiencies of up to 360 000 plates/m were demonstrated on this chip, when a higher buffer concentration was used at a field strength of 664 V/cm. It can be concluded that powder-blasted microchannel chips, although they have a lower separation efficiency compared to HF-etched chips, perform well enough for many applications. Powder blasting can therefore be considered a low-cost and efficient alternative to HF etching, in particular because of the possibility to fabricate access holes through the glass with the same process.     

Capillary electrophoresis with amperometric detection of curcumin in Chinese herbal medicine pretreated by solid-phase extraction

In the present study, curcumin from Chinese herbal medicine turmeric was determined by capillary electrophoresis with amperometric detection (CE-AD) pretreated by a self-designed, simple, inexpensive solid-phase extraction (SPE) cartridge based on the material of tributyl phosphate resin. An average concentration factor of 9 with the recovery of > 80% was achieved when applied to the analysis of curcumin in extracts of tumeric. Under the optimized CE-AD conditions: a running buffer composed of 15 mM phosphate buffer at a pH 9.7, separation voltage at 16 kV, injection for 6 s at 9 kV and detection at 1.20 V, CE-AD with SPE exhibited low detection limit as 3 x 10(-8) mol/l (S/N = 3), high efficiency of 1.0 x 10(5) N, linear range of 7 x 10(-4) -3 x 10(-6) mol/l (r = 0.9986) for curcumin extracted from light petroleum. The method developed resulted in enhancement of the detection sensitivity and reduction of interference from sample matrix in complicated samples and exhibited the potential application for routine analysis, especially in food, because a relatively complete process of sample treatment and analysis was described.