Oxidation State Specific Generation of Arsines from Methylated Arsenicals Based on L- Cysteine Treatment in Buffered Media for Speciation Analysis by Hydride Generation - Automated Cryotrapping - Gas Chromatography-Atomic Absorption Spectrometry with the Multiatomizer

An automated system for hydride generation - cryotrapping- gas chromatography - atomic absorption spectrometry with the multiatomizer is described. Arsines are preconcentrated and separated in a Chromosorb filled U-tube. An automated cryotrapping unit, employing nitrogen gas formed upon heating in the detection phase for the displacement of the cooling liquid nitrogen, has been developed. The conditions for separation of arsines in a Chromosorb filled U-tube have been optimized. A complete separation of signals from arsine, methylarsine, dimethylarsine, and trimethylarsine has been achieved within a 60 s reading window. The limits of detection for methylated arsenicals tested were 4 ng l(-1). Selective hydride generation is applied for the oxidation state specific speciation analysis of inorganic and methylated arsenicals. The arsines are generated either exclusively from trivalent or from both tri- and pentavalent inorganic and methylated arsenicals depending on the presence of L-cysteine as a prereductant and/or reaction modifier. A TRIS buffer reaction medium is proposed to overcome narrow optimum concentration range observed for the L-cysteine modified reaction in HCl medium. The system provides uniform peak area sensitivity for all As species. Consequently, the calibration with a single form of As is possible. This method permits a high-throughput speciation analysis of metabolites of inorganic arsenic in relatively complex biological matrices such as cell culture systems without sample pretreatment, thus preserving the distribution of tri- and pentavalent species.     

Methacrylate monolithic columns of 320 microm I.D. for capillary liquid chromatography

Monolithic capillary columns (320 microm I.D.) were prepared for capillary liquid chromatography (CLC) by radical polymerization of butylmethacrylate (BMA) and ethylenedimethacrylate (EDMA) in the presence of a porogen solvent containing propan-1-ol, butane-1,4-diol and water. The influence of the contents of the porogen solvent and EDMA in the polymerization mixture on the monolith porosity and column efficiency was investigated. The composition of the polymerization mixture was optimized to attain a minimum HETP of the order of tens of microm for test compounds with various polarities. The separation performance and selectivity of the most efficient monolithic column prepared was characterized by van Deemter curves, peak asymmetry factors and Walters hydrophobicity and silanol indices. It was demonstrated that the 320-microm I.D. monolithic column exhibited CLC separation performance similar to that observed for 100- and 150-microm I.D. monolithic columns reported in the literature; moreover, the 320-microm I.D. column was easier to operate in CLC and exhibited a higher sample loadability.     

Solubility of naphthalene in aqueous solutions of poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) triblock copolymers and (2-hydroxypropyl)cyclodextrins

The solubility of naphthalene was investigated in aqueous solutions of triblock copolymers poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) (PEG–PPG–PEG) and (2-hydroxypropyl)cyclodextrins. The results with solutions of the individual solubilizers were as expected: the solubility enhancement was much higher with a micelle-forming copolymer than with the non-micellizing one and with (2-hydroxypropyl)--cyclodextrin (HPBCD) than with (2-hydroxypropyl)--cyclodextrin (HPACD). Although the formation of inclusion complexes between HPACD and PEG and between HPBCD and PPG is well established, the naphthalene solubility in mixed solutions does not significantly deviate from that predicted for a mixture of independent solubilizers. Thus the interactions between HPCD and PEG–PPG–PEG copolymers are not strong enough to disrupt micelles and aggregates formed by those copolymers. In fact, slight synergetic deviations were observed with the micellizing copolymer, indicating the existence of ternary naphthalene/HPCD/copolymer interactions. For pharmaceutical applications, it is important that the solubilization efficacy of PEG–PPG–PEG copolymers and that of cyclodextrins modified by the 2-hydroxypropyl group would not be compromised if these two types of solubilizers were co-administered.     

Reduced-size polarized basis sets for calculations of molecular electric properties. II. Simulation of the Raman spectra

The accuracies of the calculated vibrational frequencies and Raman intensities given by two new, highly compact Pol-type basis sets, Z2PolX and Z3PolX, have been determined and compared to the 6-31G(d), PolX, and aug-cc-pVTZ basis sets. Calculation of accurate Raman intensities has previously required large basis sets, but the ZmPolX basis sets are smaller even than PolX, which are the most compact basis sets able to calculate accurate Raman intensities. For the largest compound studied, C5H10O2, Z3PolX required more than an order of magnitude less CPU time than PolX, which has been shown to be 10 times faster than aug-cc-pVTZ. Two sets of test molecules were studied: one was a series of small molecules for which experimental values for absolute Raman activities were available; the second was a series of medium-sized molecules (mainly common organic solvents) where only relative Raman band intensities were available. The accuracies of the Raman intensities given by both of the ZmPolX basis sets were good compared to those of the PolX and aug-cc-pVTZ sets, and much better than the 6-31G(d) values. The errors in even unscaled frequency values <2000 cm(-1) were also acceptable and were slightly lower for Z3PolX than Z2PolX (30 cm(-1) vs. 48 cm(-1)). The combination of good intensity and frequency data meant that for the medium-sized organic molecules there was a close correspondence between the simulated Raman spectra and experimental data, and that the observed bands could easily be assigned on the basis of these calculations. Achieving this level of accuracy in the simulations at modest computational cost should now allow computational methods to be combined with experimental Raman studies much more widely than is currently the case.     

Interaction of oligopyrrole macrocycles with aromatic acids: spectroscopical, quantum chemical and chromatographic aspects

The study of the behavior of oligopyrrole macrocyclic compounds in solution and covalently bond on silica surface were carried out. For this purpose ultraviolet-visible titrations and chromatography measurements were employed. Interactions of porphyrin and sapphyrin with nitrobenzoic, aminobenzensulfonic, hydroxybenzoic and terephthalic acids were studied. The spectroscopic results were compared with quantum chemical calculations at semiempirical level and with the data obtained by HPLC measurements. Chromatographic data showed that interaction of the analytes with the metalled porphyrin and the sapphyrin core led to significant increase of retention factors of the aromatic acids and selectivity improvement of the separation.     

Preparation of inorganic crystalline compounds induced by ionizing,UV and laser radiations

Results on preparation of nickel, zinc, yttrium, aluminum and cobalt oxides, zinc peroxide and hydroxide, yttrium and lutetium aluminum garnets and cobalt(II) aluminate via irradiation of aqueous solutions containing soluble metal salts and radical scavengers (formate anion or propan-2-ol) are summarized in this paper. Various physico-chemical and structural properties of prepared compounds (e.g. crystallinity, specific surface area, particle size) are also reported.All used variants of radiation method are rather convenient and simple, and yield nano-scale powder materials with interesting characteristics. Prepared materials generally have high chemical purity, high specific surface area and narrow distribution of particle size (ranging in tens of nm).Generally, accelerated electrons, gamma, and UV radiation yield materials with comparable properties and structural characteristics, but UV-radiation seems to be the most convenient for preparation of intricate compounds such as synthetic garnets and spinels, while ionizing radiation is better for preparation of compounds doped with foreign ions.Among discussed compounds, only zinc oxide, peroxide and hydroxide were prepared directly via irradiation. For preparation of other crystalline oxidic compounds, mild heat treatment of amorphous or weakly crystalline solid phase was necessary.     

Anoxic granulated biomass and its storage

Laboratory experiments involving shutdown and repeated start-up of a denitrification USB reactor with granulated anoxic biomass were conducted in order to find suitable conditions for a safe storage period of the biomass. Anoxic granulated biomass stored under anaerobic conditions for a half year period at 6°C and for a half month period at 18–20°C retained its activity and granular morphology. Storage of anoxic granules under anaerobic conditions for a half year period at 18–20°C led to the loss of the biomass original activity and a significant portion of the granules disintegrated. Anoxic granulated biomass stored for a one and a half month period under endogenous anoxic conditions at 18–20°C retained its activity and granular morphology. A two month storage under endogenous anoxic conditions at 18–20°C was too long and the shutdown of the reactor had to be followed by repeated anoxic granulation. Minimum loading of the USB reactor with N-NO₃ to maintain endogenous anoxic conditions in the sludge bed was in the range of 0.06–0.1 kg of N-NO₃ per m³ per day. Restart of the USB reactor can be accelerated by an addition of anaerobic granulated biomass.