Sensitive determination of sertraline by capillary electrophoresis with dispersive liquid-liquid microextraction and field-amplified sample stacking.

A novel method for the determination of sertraline using dispersive liquid-liquid microextraction (DLLME) coupled with capillary electrophoresis (CE) was developed. Acetone and dichloromethane were used as the disperser solvent and extraction solvent, respectively. A mixture of the extraction and disperser solvents was rapidly injected into a 1.0 mL aqueous sample to form a cloudy solution. After the extraction, sertraline was analyzed using CE that was equipped with UV detection. A 74-fold improvement in the sensitivity was observed when DLLME was used to extract sertraline. Since the DLLME extract residue was redissolved with 5 µL of water that contained 20% methanol, the detection sensitivity was further enhanced through the use of field-amplified sample stacking (FASS). A 11-fold improvement in the sensitivity was obtained when FASS was used to on-line concentrate sertraline. Under optimal extraction and stacking conditions, the calibration curve, which ranged from 0.01 to 1 µM was observed to be linear. The limit of detection (LOD) at a signal-to-noise ratio of 3 was 2.5 nM for sertraline. An approximately 814-fold improvement in the sensitivity was observed for sertraline compare with injection of standard solution without the DLLME and FASS procedures. This developed method was successfully applied to the determination of sertraline in human urine samples.

On-line concentration and separation of cationic and anionic neurochemicals by capillary electrophoresis with UV absorption detection.

This paper presents on-line simultaneous concentration and separation of cationic and anionic neurochemicals by capillary electrophoresis (CE) with UV absorbance spectroscopy. Neurochemical stacking exploits differences in local electric field and viscosity between the sample zone and the background electrolyte (BGE). To achieve these discontinuous conditions for CE, neurochemicals were prepared in a solution containing 1mM formic acid and 20% (v/v) acetonitrile (ACN). The capillary was filled with a solution of 500 mM Tris-borate (TB) and 10% (v/v) glycerol. The buffer vial contained 500 mM TB and 0.5% (v/v) polyethylene oxide (PEO). After injecting a large sample volume, PEO enters the capillary by electro-osmotic flow (EOF). Anionic neurochemicals stacked at the sample zone and PEO-containing BGE boundary. Simultaneously, cationic neurochemicals were concentrated at the boundary between the sample zone and the glycerol-containing BGE. The concentrated cationic neurochemicals were baseline separated in the presence of glycerol, mainly due to hydrogen bonding interactions between glycerol hydroxyl groups and the neurochemical's hydroxyl and amino groups. Under optimal stacking conditions, we observed the following: (a) the maximum sample injection volume was 720 nL; (b) the limit of detection for signal-to-noise ratio of 3 ranged from 14.7 to 313.4 nM; and (c) sensitivity enhancements compared to normal injection (15 nL) ranged from 116 to 281-fold. We evaluated the proposed method by the determination of neurochemicals in urine samples.

Highly sensitive detection of chiral amino acids by CE based on on-line stacking techniques.

We report a novel means for chiral separation and stacking of amino acids by MEKC with LED-induced fluorescence detection. Naphthalene-2,3-dicarboxaldehyde, hydroxypropyl-beta-cyclodextrin (Hp-beta-CD), SDS, and poly(ethylene oxide) (PEO) serve as a derivatized agent, chiral selector, pseudostationary phase, and concentrated medium, in sequence. To improve speed, resolution, and stacking efficiency, the analysis of chiral amino acids was performed under discontinuous conditions--the capillary was filled with a solution of 100 mM Tris-borate, 150 mM SDS, and 50 mM Hp-beta-CD, whereas buffer vials contain 20 mM Tris-borate, 150 mM SDS, 50 mM Hp-beta-CD, and 0.5% w/v PEO. A solution of nonionic PEO enters the capillary with the help of EOF during the separation. Through interaction of SDS micelles/Hp-beta-CD and chiral amino acid, the negatively charged complexes migrated into the PEO solution and stacked at the boundary between the sample zone and the PEO solution. Compared with normal sample injection (10 nL sample volume), a several hundred-fold sensitivity improvement for chiral amino acids was obtained under the injection of 270 nL sample volume (30% of the capillary volume). Meanwhile, the LOD at S/N of three for DL-amino acids were in the range of 0.18-0.22 nM. The proposed method has been applied for the determination of DL-leucine in urine and plasma samples.