Generalized evaluation subgroups of product spaces relative to a factor

For any -complexes and , we show that . We use this fact to compute generalized evaluation subgroups of generalized tori relative to a sphere.

     

Sample preparation of human serum for the analysis of tumor markers. Comparison of different approaches for albumin and gamma-globulin depletion

LC-MS is a powerful method for the sensitive detection of proteins and peptides in biological fluids. However, the presence of highly abundant proteins often masks those of lower abundance and thus generally prevents their detection and identification in proteomic studies. In human serum the most abundant proteins are albumin and gamma-globulins. We tested several approaches to specifically reduce the level of these proteins based on either specific antibodies, dye ligands (for albumin) and protein A or G (for gamma-globulins). The resulting, depleted serum was analyzed by sodium dodecylsulfate-polyacrylamide gel electrophoresis and LC-MS for the residual presence of these abundant proteins as well as for other serum proteins that should remain after depletion. To test the applicability of this method to real-life samples, depleted serum of a cervical cancer patient was analyzed for the presence of a specific tumor marker protein SCCA1 (squamous cell carcinoma antigen 1; P29508), which is present at ng/ml concentrations. The results demonstrate that SCCA1 can be detected by LC-MS in patient serum following depletion of albumin and gamma-globulins thus opening the possibility of screening patient sera for other, so far unknown, tumor markers.     

New hydrolysis method for extremely small amount of lipids and capillary gas chromatographic analysis as n(O)-tert.-butyldimethylsilyl fatty acid derivatives compared with methyl ester derivatives

The organic basic solution, 1 M tetramethylammonium hydroxide (TMAH) in methanol, was employed for the hydrolysis of extremely small amounts of lipids compared to the classical inorganic basic solution, 1 M KOH in ethanol. The hydrolysed fatty acids were derivatized as N(O)-tert.-butyldimethylsilyl (tBDMSi) esters with N-methyl-N-(tert.-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) and compared with the classical derivatives, the methyl esters, made by the BF3-methanol method. Recoveries of fatty acids determined on the standard fatty acids and soybean oil hydrolysed with TMAH were high: about 1.1-2.1- and 2.0-5.4-times, respectively, in all fatty acids compared with the hydrolysis by KOH regardless of derivatization method. The relative standard deviations (RSDs) on the recoveries of standard fatty acids were less than 5% when hydrolysed with TMAH, regardless of derivatives, but when hydrolysed with KOH, RSDs were more than 5% for most fatty acids, especially for long-chain fatty acids. The RSDs on the recoveries of fatty acids on the soybean oil were also very high in the KOH hydrolysis. Fatty acid compositions of soybean oil were similar in the main fatty acids regardless of hydrolysis methods, but showed slightly different values, depending on the methods of derivatization. RSDs were also very high in the KOH hydrolysis. In view of these results, precision of analysis by KOH hydrolysis was very poor, so we could not rely on the data. On the other hand, the reliability of data by TMAH hydrolysis method was very high, so it is a useful new hydrolysis method for extremely small amounts of lipid samples. Both derivatives of 35 standard fatty acids were successfully separated on a HP-1 nonpolar capillary column. tBDMSi derivatives were completely resolved in 70 min by 295 degrees C. In the methyl ester derivatives it took about 80 min to get satisfying resolution, but these derivatives were completely resolved by 250 degrees C. The sensitivity of tBDMSi derivatives was about 1.5-6.3-times higher than that with methyl ester derivatives. The stability of tBDMSi derivatives was constant for about 144 h except arachidic, docosahexanoic, behenic and heneicosanoic acids, which were stable for only 86 h.     

Resolution optimisation in micellar electrokinetic chromatography using empirical models

Theoretical and empirical models can be used to model the migration or separation characteristics in micellar electrokinetic chromatography in order to optimise the resolution. In this paper only empirical models were used, because it is easier and more straightforward to obtain these models. Several empirical approaches for the optimisation of the resolution were compared in order to determine which response should be modelled preferably. The use of models of the effective mobility in combination with average plate numbers proved to be the most suitable approach to optimisation of the resolution, because the relative prediction errors of the models of the effective mobility were a factor of 2-4 smaller than the relative prediction errors of the models of the apparent mobility. Moreover for the least separated peak pair the resolutions based on the models of the apparent and effective mobility showed relative prediction errors that were approximately a factor of 2 smaller than the relative prediction errors of the resolutions based on the models of the resolution and separation factor. The predictions of the separation factor based on the different models generally showed lower prediction errors than the predictions of the corresponding resolutions. Although the relative prediction errors were large, particularly for closely migrating compounds, the empirical approach will probably lead to the optimum separation buffer composition.     

Gas chromatographic study of the urinary codeine-to-morphine ratios in controlled codeine consumption and in mass screening for opiate drugs

The urinary codeine-to-morphine ratios in fifteen volunteers administered codeine tablets at intervals were studied by gas chromatography (GC) and compared with one month's GC results for enzyme multiplied immunoassay technique (EMIT)-screened urine specimens in a mass-screening programme for abuse of opiate drugs, particularly heroin. It appears that when M less than 2 and C/M greater than 0 or when M greater than 2 and C/M greater than 0.5, where C and M are codeine and morphine concentrations in micrograms per 10 ml of urine, codeine consumption has to be presumed.     

Computational study of conformational preferences of thioamide-containing azaglycine peptides

The effect of thioamide substitution on the conformational stability of an azaglycine-containing peptide, For-AzaGly-NH2 (1), was investigated for the sake of finding possible applications by using ab initio and DFT methods. As model compounds, For-[psiCSNH]-AzaGly-NH2 (2), For-AzaGly-[psiCSNH]-NH2 (3), and For-[psiCSNH]-AzaGly-[psiCSNH]-NH2 (4) were used. Two-dimensional phi-psi potential energy surfaces (PESs) for 2-4 were calculated at the B3LYP/6-31G*//HF/6-31G* level in gas (epsilon = 1.0) and in water (epsilon = 78.4) by applying the isodensity polarizable continuum model (IPCM) method. On the basis of these PESs, the minimum energy conformations for 2-4 were characterized at the B3LYP level with 6-31G*, 6-311G**, and 6-31+G** basis sets. The remarkable structural effect of thioamide substitution for 2-4 is that beta-strand structure is observed as a global or local minimum. The minima of 2-4 are also compared with those for glycine and thioamide-containing glycine peptides. Our theoretical results demonstrate that compounds 2-4 would be used to design controllable secondary structures.     

Calix[4]crown in dual sensing functions with FRET

A new calix[4]crown chemosensor based on dual sensing probes reveals Pb²⁺ ion selectivity over other metal ions, which arises from a hypsochromic shift of azo units in UV spectrum as well as a fluorescence enhancement of pyrenyl parts in fluorescence spectrum via a suppressed FRET.     

Study of hydantoin. III . Mass spectrometric behaviour in the electron impact of 2-imino-4-thiazolidinone derivatives

The mass spectral decomposition modes of a series of 2-imino-4-thiazolidinone derivatives are reported and discussed. The fragmentation patterns and mechanisms postulated have been confirmed by the analysis of the MIKE spectra and using DADI technique and the effects of heteroatoms and substituents on the MIKE spectrum of these compounds are compared with that of 3-substituted hydantoins.