Characteristics of electroosmotic flow and migration of neutral solutes under stepwise gradient elution of capillary electrochromatography

A theoretical study on the velocity of electroosmotic flow (EOF) and the retention times of neutral solutes under multiple-step gradient of capillary electrochromatography (CEC) was carried out, focusing on that with three kinds of mobile phases. Through the model computations, the detaining time of the second kind of mobile phase in the column was proved to play an important role in affecting EOF. The variation speed of EOF was shown to be determined by the differences among dead times in different steps. In addition, the prediction of the retention times of 13 aromatic compounds under gradient mode was performed with the deduced equations. A relative error below 3.3% between the calculated and experimental values was obtained, which demonstrated the rationality of the theoretical deduction. Our study could not only improve the comprehension of stepwise gradient elution, but also be of significance for the further optimization of separation conditions in the analysis of complex samples.     

Evaluation of glycoalkaloids in tubers of genetically modified virus Y-resistant potato plants (var. Désirée) by non-aqueous capillary electrophoresis coupled with electrospray ionization mass spectrometry (NACE–ESI–MS)

The glycoalkaloid content of transgenic potatoes was evaluated by an optimised method based on non-aqueous capillary electrophoresis coupled on-line with electrospray ionization-mass spectrometry (NACE-ESI-MS). The potato material consisted of tubers from a conventional cv. Désirée and from three lines of modified plants resistant, intermediate and susceptible to infection by potato virus Y (PVY). The main glycoalkaloids were confirmed to be alpha-solanine and alpha-chaconine with parent ion masses m/z 852 and 868, respectively. In addition, an unknown minor peak at m/z 850.6 was found both in conventional (control) and susceptible line potato tubers. Such a compound exhibited an MS(2) spectrum with fragments ions at 704 and 396 m/z derived by loss of two ions, i.e. m/z 146 and 307, most likely corresponding to a rhamnose unit and a [glucose-(rhamnose)(2)] moiety, respectively. Up to 30-80-fold higher concentrations of total glycoalkaloids were found in the peel compared to flesh samples of all tubers examined. TGA content was nearly doubled in peel samples of resistant compared to control lines, and these levels were lower than the limit recommended for food safety, i.e. 20-60 mg of TGA per 100 g fresh weight. Moreover, it was established that tubers produced by virus-resistant clones are substantially equivalent in glycoalkaloid contents to those produced by conventional potato varieties.     

Prediction of soil organic carbon partition coefficients by soil column liquid chromatography

To avoid the limitation of the widely used prediction methods of soil organic carbon partition coefficients (KOC) from hydrophobic parameters, e.g., the n-octanol/water partition coefficients (KOW) and the reversed phase high performance liquid chromatographic (RP-HPLC) retention factors, the soil column liquid chromatographic (SCLC) method was developed for KOC prediction. The real soils were used as the packing materials of RP-HPLC columns, and the correlations between the retention factors of organic compounds on soil columns (ksoil) and KOC measured by batch equilibrium method were studied. Good correlations were achieved between ksoil and KOC for three types of soils with different properties. All the square of the correlation coefficients (R2) of the linear regression between log ksoil and log KOC were higher than 0.89 with standard deviations of less than 0.21. In addition, the prediction of KOC from KOW and the RP-HPLC retention factors on cyanopropyl (CN) stationary phase (kCN) was comparatively evaluated for the three types of soils. The results show that the prediction of KOC from kCN and KOW is only applicable to some specific types of soils. The results obtained in the present study proved that the SCLC method is appropriate for the KOC prediction for different types of soils, however the applicability of using hydrophobic parameters to predict KOC largely depends on the properties of soil concerned.     

Arylmercury(II) compounds involving intramolecular coordination via 2-Me2NCH2- and chiral (S)-2-Me2NCHMe-ring substituents

Arylmercury compounds of the type Ar₂Hg and ArHgX (X = Cl, OAc) have been synthesized and characterized by ¹H and ¹³C NMR spectroscopy; the Ar group was either 2-Me₂NCH₂C₆H₄ or (S)-2-Me₂NCH(Me)C₆H₄, both of which contain N-donor ligands. The observation of anisochronous NMe resonances in (S)-2-Me₂NCH(Me)C₆H₄HgX (X = Cl, OAc) at low temperature indicates that in solution the mercury centre is three-coordinate as a result of stable intramolecular HgN coordination     

Formation of Cyanohydrin Carbonates of Aromatic Aldehydes and Aryl Heteroaryl Ketones

Cyanohydrin derivatives cannot be made by direct addition to diaryl ketones due to the unfavourable equilibrium for the addition process.¹ We required a route to cyanohydrin carbonates of type (1, R¹=heteroaryl, R²=a1kyl), and approached their formation via the aromatic aldehyde analogues (2). Such derivatives (2) have been made using a single aqueous phase method,² and acyl analogues have been made using also a two-phase (water/ether) procedure.³ To obtain the carbonates (2) we have found the former method unreliable and that a satisfactory procedure is to stir an aqueous solution of KCN with the aldehyde and alkyl chloroformate in methylene chloride at 10°C (Table 1). Where necessary yields can be increased by the inclusion of a phase transfer catalyst,⁴ benzyltrimethylammonium chloride. A similar procedure, for addition to (heterocyclic) c=N, has recently been reported⁵ for the formation of certain Reissert compounds.     

Amide,urea and thiourea‐containing triphenylene derivatives: influence of H‐bonding on mesomorphic properties

The synthesis and thermotropic properties are reported for a series of hexaalkoxytriphenylenes that contain an amide, urea or thiourea group in one of their alkoxy tails. The intermolecular hydrogen bonding abilities of these molecules have a disturbing influence on the formation and stability of the columnar liquid crystalline phases. The stronger the hydrogen bonding the more the liquid crystallinity is suppressed, probably due to disturbance of the π–π stacking of the triphenylene discs. As a direct result, urea‐ and amide‐containing triphenylene derivatives are not liquid crystalline, but several thiourea derivatives show hexagonal columnar mesophases.     

Non‐symmetric bent‐core mesogens with one terminal vinyl group

Two series of non‐symmetric banana‐shaped compounds, both with one alkyl and one alkenyl terminal tail, have been synthesized and studied. Both series were compared with the corresponding series with two saturated terminal alkyl tails. All the compounds have a bent central 1,3‐phenylene bis(4‐benzoyloxy)benzoate core; their mesophases were characterized by polarizing optical microscopy, differential scanning calorimetry, X‐ray diffraction and switching current response experiments. In all four series one of the terminal tails is varied from OC₈H₁₇ to OC₁₆H₃₃. The other terminal tails are OC₁₁H₂₃, O(CH₂)₉CH?=?CH₂, OC₁₀H₂₁ and O(CH₂)₈CH?=?CH₂. The short‐tailed compounds show monotropic or enantiotropic B₁ phases and the long‐tailed compounds the B₂ phase. The introduction of one terminal vinyl group slightly lowers the transition temperatures. The introduction of a second terminal vinyl group further suppresses the liquid crystalline properties. All compounds with B₂ phases have layer spacings that suggest a tilt of ～45° of the bent molecules in the layers, and their switching behaviour is antiferroelectric.     

Visible-light detoxification and charge generation by transition metal chloride modified titania

Amorphous microporous metal oxides of titanium (AMM-Ti) modified with chlorides of PtIV, IrIV, RhIII, AuIII, PdII, CoII, and NiII have been prepared by the sol-gel method and characterized by various surface analytical methods. These hybrid AMM-Ti powders are catalysts for the photodegradation of 4-chlorophenol (4-CP) in aqueous solution when illuminated with visible (lambda > or = 400 or 455 nm) or UV (lambda > or = 335 nm) light. The initial rate depends on the dopant level and is highest at 3.0% Pt in the case of PtIV/AMM-Ti. When employed in a photoelectrochemical cell, the activity spectrum of the photocurrent extends downward to about 600 nm, as does the photodegradation of 4-CP. It is suggested that the metal salt acts as a redox-active chromophore, transmitting the photogenerated charges to the amorphous matrix.     

Optimisation of extraction procedures for metallothionein-isoforms and superoxide dismutase from liver samples using spiking experiments

The speciation of trace element species in solid matrices like liver samples is still problematic due to two reasons. On the one hand direct methods with sufficient selectivity and sensitivity are currently not available. Therefore extraction procedures have to be applied which are often problematic in respect to species stability. On the other hand there are no reference materials with known amounts of metal proteins like metallothionein-isoforms (MT) and superoxide dismutase (SOD) for quality control. So the aim of this study was to develop and optimise procedures for the species-preserving extraction of the model compounds MT and SOD from liver samples. Spiking experiments were performed to overcome the lack of appropriate reference materials. In a first step the stability of the model species without liver matrix was investigated by the variation of several extraction parameters. The extractant and exposure to ultrasonic energy especially had a great influence on the recovery of the species while temperature, buffer concentration and atmospheric conditions were less critical. In a second step spiked liver samples were extracted with a selection of procedures taken from the literature. Most of these methods provided recoveries between 70% and 100%. Additionally the buffer concentration and the extractant-to-liver ratio were varied for optimisation. The metal balance of an extraction showed recoveries of 81% for Cd, 94% for Cu and 87% for Zn.