Heteroconjugation-based capillary electrophoretic separation of phenolic compounds in acetonitrile and propylene carbonate

A mixture of methyl- and hydroxy-substituted phenols was separated by capillary electrophoresis in pure acetonitrile and propylene carbonate. Interactions between undissociated phenolic compounds and the background electrolytes were investigated. In the present work, benzyltriethylammonium chloride, tetrabutylammonium acetate, and two room temperature-molten salts, 1-butyl-3-methyl imidazolium trifluoroacetate and 1-butyl-3-methyl imidazolium heptafluorobutanoate, were used as background electrolytes. The formation of a negative complex between background electrolyte anion and neutral phenolic compound was observed and the formation constant calculated. The formation constants for anion-analyte complexes were approximately the same in propylene carbonate and in acetonitrile. In both solvents the formation constants were the highest for acetate and the lowest for trifluoroacetate. The separation of analytes was slightly influenced by the nature of the solvent: in acetonitrile the resolution between peaks was higher for 1,3-dihydroxyphenol and 1,3,5-trihydroxyphenol, in propylene carbonate 3-methylphenol and phenol were better separated. It was demonstrated that traces of water influence the mobilities of anion-phenol complexes in propylene carbonate.     

On-line monitoring of enzymatic conversion of adenosine triphosphate to adenosine diphosphate by micellar electrokinetic chromatography

Capillary electrophoresis can be a valuable tool for the on-line monitoring of bioprocesses. The enzymatic conversion of nucleotide adenosine triphosphate (ATP) to adenosine diphosphate (ADP) by hexokinase (HK) was monitored in the bioreactor interfaced by a laboratory-built microsampler to a capillary electrophoresis unit. The use of this specially designed sampling device enabled rapid consecutive injections to be performed without high-voltage (HV) interruptions. No additional sample preparation was required. The method of micellar electrokinetic chromatography, employing reversed electroosmotic flow (EOF) by cationic surfactant and reversed polarity mode provided a good resolution and short analysis time of less than 5 min. The samples were injected electrokinetically, using -25 kV voltage for 3 s and detected by their UV absorbance at 254 nm. The analytes were detected at a microg/ml level with a reproducibility of about 7%. To demonstrate the potential of CE in understanding the processes of biological interest, such as nucleotide degradation and metabolism, the investigation of the efficiency and the time course of the enzymatic transformation was carried out.     

Separation of polyphenolic compounds extracted from plant matrices using capillary electrophoresis

Phenolic compounds constitute a large group of secondary plant products whose chemical structure may range from quite simple compounds to highly polymerized substances. The polyphenols content have been investigated in the alcoholic extract of the fruits of three different plants: sweet gale, sea buckthorn, hiprose. The trans-resveratrol content we have studied in roots, stems, leaves and flowers of Japanese knotweed grown in Estonia. Plant material was pre-treated in two different ways: by infusing with methanol and by supercritical fluid extraction with carbon dioxide modified with different alcohols. The relationship between variables (pressure, temperature, modifier amount) and yields are examined. The capillary zone electrophoresis methods were developed for the separation of polyphenolic anti-oxidative compounds. Using both water based borate buffer and acetonitrile based non-aqueous media it was possible to get reliable separation of several polyphenolic compounds. Based on that there has been identified such as flavone, trans-resveratrol, catechin, chlorogenic acid, quercetin and myricetin in plant extracts. Changes in the relative concentrations of trans-resveratrol in different parts of the knotweed have been established.     

Polycrystalline silicon films prepared by metal-induced crystallisation using pre- and post-deposited aluminium on amorphous silicon

We report on the successful fabrication of polycrystalline silicon films by aluminium-induced crystallisation (AIC) of Radio frequency (rf) plasma-enhanced chemical vapour deposited (PECVD) a-Si films. The effects of annealing at different temperatures (300 and 400°C), below the eutectic temperature of the Si–Al binary system, on the crystallisation process have been studied. This work emphasises the important role of the position of the Al layer with respect to the Si layer on the crystallisation process. The properties of the crystallised films were characterised using X-ray diffraction, Raman spectroscopy, ellipsometry, field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). With an increase in the annealing temperature, it was found that the degree of crystallisation of annealed a-Si/Al and Al/a-Si films increased. The results showed that the arrangement where the Al was on top of the a-Si had a more prominent effect on crystallisation enhancement than when Al was below the a-Si. The interfacial layer between the Al and a-Si film is crucial because it influences the layer-exchange process during annealing. The oxide layer formed between the Al and the a-Si layers greatly retards the crystallisation process in the case of the Al/Si arrangement. Our investigations suggest that polycrystalline Si films formed by AIC can be used as a seed layer in solar cell fabrication.     

Adsorption and decomposition of cyclohexanone (C6H10O) on Pt(111) and the (2 × 2) and (√3 × √3)r30°-Sn/Pt(111) surface alloys

Adsorption and decomposition of cyclohexanone (C(6)H(10)O) on Pt(111) and on two ordered Pt-Sn surface alloys, (2 × 2)-Sn/Pt(111) and (√3 × √3)R30°-Sn/Pt(111), formed by vapor deposition of Sn on the Pt(111) single crystal surface were studied with TPD, HREELS, AES, LEED, and DFT calculations with vibrational analyses. Saturation coverage of C(6)H(10)O was found to be 0.25 ML, independent of the Sn surface concentration. The Pt(111) surface was reactive toward cyclohexanone, with the adsorption in the monolayer being about 70% irreversible. C(6)H(10)O decomposed to yield CO, H(2)O, H(2), and CH(4). Some C-O bond breaking occurred, yielding H(2)O and leaving some carbon on the surface after TPD. HREELS data showed that cyclohexanone decomposition in the monolayer began by 200 K. Intermediates from cyclohexanone decomposition were also relatively unstable on Pt(111), since coadsorbed CO and H were formed below 250 K. Surface Sn allowed for some cyclohexanone to adsorb reversibly. C(6)H(10)O dissociated on the (2 × 2) surface to form CO and H(2)O at low coverages, and methane and H(2) in smaller amounts than on Pt(111). Adsorption of cyclohexanone on (√3 × √3)R30°-Sn/Pt(111) at 90 K was mostly reversible. DFT calculations suggest that C(6)H(10)O adsorbs on Pt(111) in two configurations: by bonding weakly through oxygen to an atop Pt site and more strongly through simultaneously oxygen and carbon of the carbonyl to a bridged Pt-Pt site. In contrast, on alloy surfaces, C(6)H(10)O bonds preferentially to Sn. The presence of Sn, furthermore, is predicted to make the formation of the strongly bound C(6)H(10)O species bonding through O and C, which is a likely decomposition precursor, thermodynamically unfavorable. Alloying with Sn, thus, is shown to moderate adsorptive and reactive activity of Pt(111).     

Investigation of the surfactant type and concentration effect on the retention factors of glutathione and its analogues by micellar electrokinetic chromatography

In the present study, a micellar electrokinetic chromatographic method was used to determine the retention factors of hydrophilic monomeric and homodimeric forms of glutathione analogues. Ionic‐liquid‐based surfactant, 1‐tetradecyl‐3‐methylimidazolium chloride, as well as cetyltrimethylammonium bromide and phosphate buffer (pH 7.4) were employed in the experiments. Since the studied peptides possess a negative charge under physiological conditions, it is expected that the peptides interact with the oppositely charged 1‐tetradecyl‐3‐methylimidazolium chloride and cetyltrimethylammonium bromide micelles via hydrophobically assisted electrostatic forces. The dependence of the retention factor on the micellar concentration of 1‐tetradecyl‐3‐methylimidazolium chloride and cetyltrimethylammonium bromide is nonlinear and the obtained curves converge to a limiting value. The retention factor values of GSH analogues were in the range of 0.36–2.22 for glutathione analogues and –1.21 to 0.37 for glutathione when 1‐tetradecyl‐3‐methylimidazolium chloride was used. When cetyltrimethylammonium bromide was employed, the retention factor values were in the range of 0.27–2.17 for glutathione analogues and –1.22 to 0.06 for glutathione. If sodium dodecyl sulfate was used, the retention factor values of glutathione analogues with carnosine moiety were in the range of –1.54 to 0.38.     

Thermal marks as a signal processing aid for a portable capillary electropherograph

The interpretation of raw signals in capillary CE can be challenging if there are unknown peaks, or the signal is corrupt due to baseline fluctuations, EOF velocity drift, etc. Signal processing could be required before results can be interpreted. A suite of signal processing algorithms has been developed for CE data analysis, specifically for use in field experiments for the detection of nerve agents using portable CE instruments. Everything from baseline correction and electropherogram alignment to peak matching and identification is included in these programs. Baseline correction is achieved by interpolating a new baseline according to points found using all local extremes, by applying an appropriate outliers test. Irreproducible migration times are corrected by compensating for EOF drift, measured with the aid of thermal marks. Thermal marks are small disturbances in the capillary created by punctual heating that move with the velocity of EOF. Peaks in the sample electropherogram are identified using a fuzzy matching algorithm, by comparing peaks from the sample electropherogram to peaks from a reference electropherogram.     

Capillary electrophoretic analysis of neutral carbohydrates using ionic liquids as background electrolytes

In this study, ionic liquids (ILs) as BGE additives were applied for the analysis of neutral carbohydrates in CE. The ILs served primarily as chromophores for indirect UV detection. The influence of imidazolium-based ionic liquids on the separation, detection limits and mobility of underivatized neutral carbohydrates was investigated. BGEs consisting of 10-50 mM of ILs at pH 12.4 without other additives provided fast separation of neutral sugars. This method was used to determine sucrose, glucose and fructose in certain vegetable juices.     

Monitoring of the electroosmotic flow of ionic liquid solutions in non-aqueous media using thermal marks

The possibility of applying a new method employing thermal marks to measuring the rate of the electroosmotic flow (EOF) in non-aqueous capillary electrophoresis (NACE) was investigated. The thermal marks were monitored by using a contactless conductivity detection. During one experiment and in between the series of experiments the reproducibility of the method was excellent. The EOF rate was measured 4-7 times during one experiment, the precision of measurement being around 0.5%. In this study, the influence of 1-butyl-3-methyl-imidazolium salts in organic solvents on the rate of the EOF was investigated. Various organic solvents were mixed with an ionic liquid of various concentrations and the EOF rate was measured using thermal marks. The accuracy of the method was compared with that of the neutral marker one. Five benzoic acid derivatives were separated while the EOF was monitored. The relative standard deviations of the corrected effective mobilities of the above analytes were in the range of 1.0-6.1%.