Capillary zone electrophoresis of cationic and anionic drugs in methanol

The actual mobilities and dissociation constants of acidic and basic pharmaceuticals were determined in methanol. Actual mobilities were derived from the dependence of the effective mobilities of the analytes on the pH of the methanolic background electrolyte solution (pH(MeOH)). The pKa values of the pharmaceuticals in methanol (pK(a,MeOH)) were calculated by non-linear curve fitting to the measured mobility values. It was found that the shift in pKa value (when compounds were transferred from water to methanol) increased with the acidity of the analyte. The average pKa shift for compounds exhibiting acidic properties in water was ca. 5.5 units, and the shift for basic compounds about 2 units. As was shown for a mixture of beta-blockers, the calculated actual mobilities and pKa values can be utilised in the optimisation of pH conditions for separation. The practical value of the method was illustrated by the analysis of urine samples.     

Separation and determination of metals as complexes of 1-nitroso-2-naphthol-6-sulphonic and 2-nitroso-1-naphthol-6-sulphonic acids

A sensitive ion-pair liquid-liquid extraction-spectrophotometric method has been developed for the determination of copper, palladium, iron and cobalt, based on the formation of metal complexes with 1-nitroso-2-naphthol-6-sulphonic acid or 2-nitroso-1-naphthol-6-sulphonic acid as primary ligand, and zephiramine as counter-ion. The coloured metal complexes obtained over different pH ranges are easily and quantitatively extracted into dichloromethane. The method has been tested with samples containing known amounts of copper, palladium, iron and cobalt in ultrapure water. The reagents provide a sensitive spectrophotometric method for determining these metals.     

聚全氟丙醚油微观结构的研究

聚全氟丙醚油是一种新型的性能独特的润滑油。本实验采用~（１９）Ｆ－ＮＭＲ波谱法，结合~１Ｈ－ＮＭＲ和ＭＳ法，较详细地研究了油品微观结构。由谱线的化学位移和强度归纳出不同链节结构的分布，同时阐明了端基结构。     

A study of the electrocatalytic oxidation of aspirin on a nickel hydroxide-modified nickel electrode

The electrocatalytic oxidation of aspirin has been investigated on a nickel oxide-modified nickel electrode in alkaline solution. The process of oxidation and its kinetics have been investigated by using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy techniques and also steady-state polarization measurements. Voltammetric studies have indicated that in the presence of aspirin, the anodic peak current of low-valence nickel species increases, followed by a decrease in the corresponding cathodic current. This indicates that aspirin was oxidized on the redox mediator immobilized on the electrode surface via an electrocatalytic mechanism. The rate constant of the catalytic oxidation of aspirin and the electron transfer coefficient have been found to be 1.15×10⁵ cm³ mol⁻¹s⁻¹ and 0.49, respectively. Impedance measurements show that aspirin is diffused into the bulk of the modifier film, and the oxidation process of aspirin occurs in the bulk of nickel oxide film. It has been shown that by using this modified electrode, aspirin can be determined with a detection limit of 4.8×10⁻⁵ and successfully applied for determination of aspirin in tablet.     

Quantification of antimony depth profiles in Sb-doped tin dioxide thin films

Sb-doped SnO(2) thin films, deposited by atomic layer epitaxy (ALE) for gas sensor applications, have been characterized by secondary ion mass spectrometry (SIMS). Quantification of the depth profile data has been carried out by preparing a series of ion implanted standards. Average concentrations determined by SIMS have been compared with Sb/Sn ratios obtained by X-ray fluorescence (XRF) spectrometry and proton induced X-ray emission (PIXE) spectrometry and have been found to be in good agreement. However, a detection limit of 5x10(18) at cm(-3) could only be obtained because of mass interferences. SIMS data show that the ALE technique can be used to produce a controllable growth and doping of thin films.     

Isotachophoresis of beta-blockers in a capillary and on a poly(methyl methacrylate) chip

Analysis of the beta-blockers oxprenolol, atenolol, timolol, propranolol, metoprolol, and acebutolol in human urine by a combination of isotachophoresis (ITP) and zone electrophoresis (ZE) was investigated. Methods were developed with a conventional capillary electrophoresis (CE) apparatus and a poly(methyl methacrylate) (PMMA) microchip system. With CE the separation of oxprenolol, atenolol, timolol, and acebutolol from a standard solution containing 5 microg/mL of each compound was accomplished by performing ZE with transient ITP. The electrolyte system consisted of 10 mM sodium morpholinoethane sulfonate (pH 5.5) and 0.1% methylhydroxyethylcellulose as the leading electrolyte and 30 mM ortho-phosphoric acid (pH 2.0) as both the terminating and the ZE background electrolyte. With the microchip system the separation of oxprenolol and acebutolol from a standard solution containing 10 microg/mL of each compound was accomplished by a coupled-channel ITP-ZE device using the same leading electrolyte solution as the CE system but 5 mM glutamic acid (pH 3.4) as terminating and background electrolytes. The systems were used for analyses of patient urine samples. Water-soluble hydrophilic matrix compounds were removed from the urine samples by solid-phase extraction (SPE). Limits of quantification below 5 microg/mL could be achieved. The PMMA ITP-ZE chip has not earlier been used for analyses of any drugs from urine samples.     

Chiral separation of dansyl amino acids by capillary electrophoresis: Comparison of formamide andN-Methylformamide as background electrolytes

Summary Chiral separation of 12 dansyl amino acids has been achieved by capillary electrophoresis using -cyclodextrin dissolved inN-methylformamide or formamide. The viscosity and the dielectric constants of these two solvents are very different, giving them disimilar electrophoretic properties. Intense electroosmotic flow, high electrophoretic mobilities and high efficiency were achieved inN-methylformamide, but high chiral selector concentration was needed for sufficient resolution. In contrast, the separation of dansyl amino acids in formamide was characterized by longer analysis time and lower efficiency, but the resolution and selectivity of the separation were better and baseline separation could be achieved at lower -cyclodextrin concentrations.     

Migration behaviour and separation of tramadol metabolites and diastereomeric separation of tramadol glucuronides by capillary electrophoresis

Capillary electrophoresis with UV detection was used to separate tramadol (TR), a centrally acting analgesic, and its five phase I (M1, M2, M3, M4, M5) and three phase II metabolites (glucuronides of M1, M4 and M5). Several factors were evaluated in optimisation of the separation: pH and composition of the background electrolyte and the influence of a micellar modifier, sodium dodecyl sulfate. Baseline separation of TR and all the analytes was obtained with use of 65 mM tetraborate electrolyte solution at pH 10.65. The lowest concentrations of the analytes that could be detected were below 1 microM for the O-methylated, below 2 microM for the phenolic and ca. 7 microM for the glucuronide metabolites. The suitability of the method for screening of real samples was tested with an authentic urine sample collected after a single oral dose (50 mg) of TR. After purification and five-fold concentration of the sample (solid-phase extraction with Oasis MCX cartridges), the parent drug TR and its metabolites M1, M1G, M5 and M5G were easily detected, in comparison with standards, in an interference-free area of the electropherogram. Diastereomeric separation of TR glucuronides in in vitro samples was achieved with 10 mM ammonium acetate-100 mM formic acid electrolyte solution at pH 2.75 and with basic micellar 25 mM tetraborate-70 mM SDS electrolyte solution at pH 10.45. Both separations showed that glucuronidation in vitro produces glucuronide diastereomers in different amounts. The authentic TR urine sample was also analysed by micellar method, but unambiguous identification of the glucuronide diastereomers was not achieved owing to many interferences.     

Optimization of capillary electrophoretic-electrospray ionization-mass spectrometric analysis of catecholamines

The capillary electrophoretic-mass spectrometric analysis (CE-MS) of catecholamines was optimized with coaxial sheath flow interface and electrospray ionization (ESI). The parameters studied included the sheath liquid composition and its flow rate, separation conditions in ammonium acetate buffer together with the ESI and cone voltages as mass spectrometric parameters. In addition, the effect of ESI voltage on injection as well as the siphoning effect were considered. The optimized conditions were a sheath liquid composition of methanol-water (80:20 v/v) with 0.5% acetic acid, with a flow rate of 6 microL/min. The capillary electrophoretic separation parameters were optimized with 50 mM ammonium acetate buffer, pH 4.0, to +25 kV separation voltage together with a pressure of 0.1 psi. The most intensive signals were obtained with an ESI voltage of +4.0 kV and a cone voltage of +20 V. The nonactive ESI voltage during injection as well as avoidance of the siphoning effect increased the sensitivity of the MS detection considerably. The use of ammonium hydroxide as the CE capillary conditioning solution instead of sodium hydroxide did not affect the CE-MS performance, but allowed the conditioning of the capillary between analyses to be performed in the MS without contaminating the ion source.     

Characteristics and safety of nano-sized cellulose fibrils

A finely ground fibrillated cellulose was fractionated into separate size fractions. The characteristics of the smallest size fractions were studied, and the toxicity to humans was tested as part of a safety assessment. Morphological studies performed with state-of-the-art methods, such as scanning electron microscopy and atomic force microscopy, showed that the fraction obtained consisted of long thin fibrils but also larger fibril agglomerates, and spherical particles were present. The finest fraction did not show any sub-lethal effects as assessed by RNA inhibition test in vitro, nor were there any indications of genotoxicity as tested by the Ames test in vitro. Systemic effects tested in vivo with the nematode were also absent. No cytotoxic effects were seen in the highest tolerated dose test in vitro, but some indication of cytotoxicity was observed in the total protein content test in vitro at the highest sample concentration. The significance of this toxicity test result should be addressed in relation to the other toxicity tests, in which no toxicity was observed, with special emphasis on the in vivo test. Given this, the overall toxicity analyses support the conclusion that nano-scale cellulose fibrils can be considered to be safe towards humans. However, the reason for the positive cytotoxicity test result and, in addition, the effect of the biocide used in sample preservation on the toxicity tests need to be clarified before generalizing these results and declaring nanocellulose to be unambiguously safe.