Capillary electrochromatographic analysis of barbiturates in serum
ABSTRACT A capillary electrochromatographic method was developed for the separation of barbiturates. The separation was optimized in a 75 microm ID capillary, packed with 3-(1,8-naphthalimido)propyl-modified silyl silica gel (NAIP), studying the effect of buffer pH, buffer concentration, and mobile phase composition. Using an applied voltage of 20 kV and the short-end injection method (9 cm capillary effective length), the mobile phase of 1.0 mM citrate buffer (pH 5.0) containing 40% methanol provided the baseline separation of barbital, phenobarbital, secobarbital, and thiopental (internal standard) in less than 4.5 min. The method was successfully applied to the analysis of barbiturates in human serum. Under the optimal conditions, good repeatability and linearity were obtained in the range of 2.90-43.29 microg/mL for barbital, phenobarbital, and secobarbital.
SourceAvailable from: Jean-Luc Veuthey[Show abstract] [Hide abstract]
ABSTRACT: A capillary isoelectric focusing (cIEF) method was developed for the determination of the ionization constants (pKa) of small molecules. Two approaches used to decrease the electroosmotic flow (EOF) were compared: (i) a hydroxypropylcellulose (HPC) coated capillary in aqueous medium and (ii) the addition of glycerol to act as a viscosifying agent. The cIEF method with the glycerol medium was selected, and the ionization constants of 22 basic and 21 acidic compounds, including 15 pharmaceutical drugs, were determined, resulting in pKa values from 3.5-7.4 and 6.4-9.3, respectively. cIEF offers an interesting alternative to other techniques for pKa determination with low sample consumption, high throughput and low cost.European journal of pharmaceutical sciences: official journal of the European Federation for Pharmaceutical Sciences 07/2014; 63. DOI:10.1016/j.ejps.2014.06.016 · 3.01 Impact Factor
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ABSTRACT: Three barbiturate drugs, barbital, phenobarbital, and secobarbital were separated and analyzed by electrokinetic supercharging. The influence of different parameters on electrokinetic supercharging performance was evaluated using both univariated and multivariated optimization processes. The parameters studied were sample pH, concentration, and length of the leading and terminating electrolytes, electrokinetic injection of the sample and composition and hydrodynamic injection of the solvent plug. The leading electrolyte (50 mM NaCl) was hydrodynamically injected (50 mbar × 120 s) prior to the sample that was adjusted to pH 9.6 and electrokinetically injected at -8.5 kV for 300 s. The terminating electrolyte (100 mM of 2-(cyclohexylamino) ethanesulphonic acid) was then hydrodynamically injected (50 mbar × 140 s). The results showed that this strategy enhanced detection sensitivity around 1050-fold compared with normal hydrodynamic injection, providing detection limits ranging between 1.5 and 2.1 ng/mL for standard samples with good repeatability in terms of peak area (values of relative standard deviation, %RSD < 3). The applicability of the optimized method was demonstrated by the analysis of human urine samples spiked with the studied compounds at different concentration levels and further liquid-liquid extraction step. The estimated detection limits obtained in the urine samples extract ranged between 8 and 15 ng/mL.Journal of Separation Science 02/2013; 36(3). DOI:10.1002/jssc.201200690 · 2.59 Impact Factor
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ABSTRACT: We discuss theoretically the concept of spatial resolution in near-field scanning optical microscopy (NSOM) in light of a recent work [Opt. Express 17 (2009) 19969] which reported on the achievement of active tips made of a single ultrasmall fluorescent nanodiamond grafted onto the apex of a substrate tip and on their validation in NSOM imaging. Since fluorescent nanodiamonds tend to decrease steadily in size, we assimilate a nanodiamond-based tip to a point-like single photon source and compare its ultimate resolution with that offered by standard metal-coated aperture NSOM tips. We demonstrate both classically and quantum mechanically that NSOM based on a point-like tip has a resolving power that is only limited by the scan height over the imaged system whereas the aperture-tip resolution depends critically on both the scan height and aperture diameter. This is a consequence of the complex distribution of the electromagnetic field around the aperture that tends to artificially duplicate the imaged objects. We show that the point-like tip does not suffer from this “squint” and that it rapidly approaches its ultimate resolution in the near-field as soon as its scan height falls below the distance between the two nano-objects to be resolved.Optics Communications 03/2011; 284(5):1444-1450. DOI:10.1016/j.optcom.2010.10.097 · 1.54 Impact Factor