Monitoring of the metal displacement from the recombinant mouse liver metallothionein Zn(7)-complex by capillary zone electrophoresis with electrospray MS detection

A solution of a Zn-complex of recombinant mouse MT-1 isoform (Zn(7)-MT-1) was prepared and titrated with Cd(2+) ions. A method based on the coupling of capillary zone electrophoresis (CZE) with electrospray MS detection was developed for the analysis of the stoichiometry of the species formed during the titration. The method offered the possibility of the on-line removal of up to 100 mM Tris or phosphate buffer solutions that would otherwise suppress the electrospray signal. By allowing the determination of the metal stoichiometry of the complex species present in solution the method was shown to be complementary to circular dichroism and UV-VIS spectrophotometry conventionally used for similar studies. The titration of the Zn(7)-MT complex with Cd(II) showed the sequential displacement of the Zn by Cd. The unusually high stability of the Cd(6)Zn(1)-MT species was observed which suggests a structural role of the remaining Zn(II) ion.     

An efficient reagent for the phosphorylation of deoxyribonucleosides, DNA oligonucleotides, and their thermolytic analogues

[reaction: see text] The phosphoramidite 11 was prepared in three steps from methyl 2-mercaptoacetate and demonstrated efficiency in the synthesis of conventional 5'-/3'-phosphate/thiophosphate monoester derivatives of 2'-deoxyribonucleosides and DNA oligonucleotides. Moreover, the use of 11 has enabled the preparation of the dinucleoside phosphorothioate analogue 26 in high yields (>95%) with minimal cleavage (<2%) of the thermolytic thiophosphate protecting group.     

Highly stereoselective synthesis, structure, and application of (E)-9-[2-(silyl)ethenyl]-9H-carbazoles

(E)-N-(Silyl)vinylcarbazole has been easily prepared via a new catalytic route, silylative coupling (SC) of vinylcarbazole with vinyltrisubstituted silanes catalyzed by [RuH(Cl)(CO)(PCy3)2]. X-ray structures of two silylvinylcarbazoles as first N-vinylcarbazole derivatives have been resolved. The Pd-catalyzed Hiyama coupling reaction (also as the tandem reaction with SC) of synthesized (E)-N-(triethoxysilyl)vinylcarbazole with iodobenzene has been performed to afford (E)-N-(phenylvinyl)carbazole with high yield and stereoselectivity.     

1,4-dioxane as a solvent in spectroscopy and photochemistry

Commercially available 1,4-dioxane, even of spectroscopic grade, contains various impurities that arise mostly from reaction of the solvent with oxygen. Aspects relevant to the spectroscopy and photochemistry of the dioxane/oxygen system are discussed. Methods of purification and storage of the solvent are presented.     

Controlled Rate Thermal Analysis of Hydrated Borates

Quasi-isothermal-isobaric analysis was applied as a main method for investigation of thermal decomposition of borates. The structural mechanism of the dehydration and dehydroxylation of selected borates is considered. It has been found that they consist of two independent stages: formation of gaseous water molecules localized into the structural framework and their release. The internal pressure of gaseous water molecules is the factor influencing the course of these processes. The strengths of the chemical bonds of the components and the freedom of their displacement also determine thermal stability of hydrated borates. This revised version was published online in July 2006 with corrections to the Cover Date.     

Micropatterning chemical oscillations: waves, autofocusing, and symmetry breaking

Arrays of chemical oscillators are micropatterned by Wet Stamping. The technique is used to demonstrate that chemical waves can be initiated and controlled in oscillatory systems and that such waves can give rise to phenomena not observed in excitable media. Interoscillator coupling and synchronization, kinetic autofocusing, and twist-symmetry breaking are a consequence of the dependence of the oscillation phase on the local concentrations of reagents and on systems' geometry. Conditions under which a generic oscillatory system would exhibit such behaviors are determined.     

Do proficiency tests always verify laboratories’ performance? The case of FAPAS PT 0270

In this paper, the case of FAPAS PT 0270 “Doramectin and Oxfendazole in Sheep Liver” is discussed. During evaluation of the data received from participants (determination of total, oxidised oxfendazole residue and calculation of the sum of oxfendazole and oxfendazole sulfone residues), significant differences were observed between the results obtained by use of two analytical approaches. This phenomenon can be explained by the route of oxfendazole metabolism, which results in the presence of fenbendazole in the sample. This was not predicted by the provider; consequently, not all the necessary tests on the material were conducted. Due to the high uncertainty of the z-scores in this test, the results of the PT cannot be used for purposes of evaluation, and the benefits of participation in PT 0270 are questionable.     

Pyrolysis-gas chromatography-mass spectrometry of cured phenolic resins

A previously described pyrolysis device with a movable reaction zone was used in the present work for thermal degradation of cured novolac and resol resins. After the pyrolysis the usual major components were identified, as well as relatively low-volatile aromatic compounds which were revealed after their separation in a capillary chromatographic column. Among the latter components, for both types of cured resins, xanthene and its methyl derivatives were found. The isomers of bis(hydroxyphenyl)methane were found in considerable quantities only in the case of partially cured novolac resins which contained any linear sequences in their structure.     

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.