The spin-S Blume-Capel RG flow diagram

Using the finite-size scaling renormalization group, we obtain the two-dimensional flow diagram of the Blume-Capel model forS=1 andS=3/2. In the first case our results are similar to those of mean-field theory, which predicts the existence of first- and second-order transitions with a tricritical point. In the second case, however, our results are different. While we obtain in theS=1 case a phase diagram presenting a multicritical point, the mean-field approach predicts only a second-order transition and a critical endpoint.     

Fluorimetric determination of the levels of urinary neopterin and serum thiobarbituric acid reactive substances in the nonagenarians

Twelve self-sustaining nonagenarians, 10 women and two men, aged 94+/-3 years, and eight institutionalised nonagenarians, eight women, aged 91+/-1 year as well as 11 control subjects, seven women and four men, aged 84+/-5 years entered the study. Urinary neopterin, an indicator of systemic immune activation, and serum thiobarbituric acid reactive substances (TBARS), a marker of lipoperoxidation, were determined initially, and collection of the blood and urine samples was repeated at 3-month interval. Neopterin was measured in the urine specimens by reversed-phase high performance liquid chromatography. A C(18) reversed-phase column 3.3x150 mm, 5 mum-diameter packing Separon SGX was used. Potassium phosphate buffer (15 mmol l(-1), pH 6.4) at flow rate of 0.8 ml min(-1) was used as mobile phase. After centrifugation (5 min, 1300xg) and diluting 100 mul of urine specimens with 1.0 ml of mobile phase containing 2 g of disodium-EDTA per litre, a 20 mul sample was injected on a column. Neopterin was identified by its native fluorescence (353 nm excitation, 438 nm emission). Creatinine was determined by Jaffé kinetic reaction after dilution of sample 1:50 (v/v). The concentration of neopterin in urine was expressed as neopterin/creatinine ratio (mumol mol(-1) creatinine). TBARS were determined spectrofluorometrically using LS-5 spectrofluorimeter (excitation wavelength 528 nm, emission wavelength 558 nm) after extraction with n-butanol treatment with thiobarbituric acid. The significance of differences between nonagenarians and control group was examined by ANOVA-Kruskal-Wallis tests, using statistical software NCSS 6.0.21 (Kaysville, UT, 1996). The decision on significance was based on P=0.05. Urinary neopterin was significantly higher in institutionalised compared to self-sustaining subjects and controls (625+/-565 vs. 203+/-63 mumol mol(-1) creatinine, and 198+/-128 mumol mol(-1) creatinine, respectively, P=0.006). The serum TBARS were higher in both groups of nonagenarians (3.23+/-1.16 mumol l(-1) and 2.69+/-0.39 vs. 2.12+/-0.83 mumol l(-1) for the self-sustaining, institutionalised and controls, respectively, P=0.023). We conclude that the fluorimetric determinations of urinary neopterin and serum TBARS can be useful for the monitoring health status in the elderly patients.     

Quantification of copper and zinc species fractions in legume seeds extracts by SEC/ICP-MS: validation and uncertainty estimation

Fractions of Cu and Zn species in legume samples (common white bean, pea, chick pea and lentil seeds and defatted soybean flour) were analysed by on-line hyphenation of size exclusion chromatography and inductively coupled plasma-mass spectrometry. Samples were extracted by 0.02 mol l⁻¹ Tris–HCl buffer solution, pH 7.5. The extraction efficiency lay in the region 60–90 and 60–80% for Cu and Zn, respectively. Quantification of elements in the individual chromatographic fractions was carried out by isotope dilution (ID) and external calibration (EC) techniques. For ID analysis the chromatographic effluent was mixed with the flow of ⁶⁵Cu and ⁶⁸Zn isotope enriched solution and the isotope ratio values ⁶³Cu/⁶⁵Cu and (⁶⁴Zn+⁶⁶Zn)/⁶⁸Zn were measured. In the case of EC technique calibration solutions of elements were injected to the flow of mobile phase by the second injector. Prior entering detector the effluent was mixed with the flow of internal standard solution (In, 50 μg l⁻¹). Both methods have similar precision, however the behaviour of both studied elements was not the same. The chromatographic analysis itself was the main source of variability in the case of Cu. For Zn species analysis, the extraction process and the manipulation with the extract, played the significant role too. It was probably caused by lower stability of the present zinc chelates. The total amounts of Zn found in all chromatographic fractions represented 85–95% of Zn in sampled extract whereas those of Cu approached 100%. In case of small peaks the results of ID and EC were not the same. The EC results were lower then ID results. The great deal of results uncertainty accounts for the precision.     

Conductive polyethylene-carbon black composites by elongational-flow injection molding Part 3. Study of the structure and morphology

The morphology and structure of high molecular weight linear polyethylene (M _w 450000) filled with carbon black and processed using molds that introduce an elongational flow component during injection molding has been examined using electron microscopy and x-ray diffraction techniques. The study of fracture surfaces reveals the display of shish-kebabs oriented along the injection direction with segregated longitudinal channels of carbon black particles. Molecular and lamellar changes in orientation are, furthermore, studied across the thickness of the moldings. It is shown that addition of carbon black particles to injection-molded polyethylene induces significant changes in lamellar orientation. Thus, while lamellar overgrowth proceeds perpendicular to the fiber axes within carbon free channels, lamellae grow randomly within carbon-enriched regions where flow is less pronounced.     

Micellar solutions of sulfobetaine surfactants in water-ethylene glycol mixtures: surface tension, fluorescence, spectroscopic, conductometric, and kinetic studies

Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model.     

Models of pesticides inside cavities of molecular dimensions. A role of the guest inclusion in the dechlorination process

The reduction mechanism of the pesticide vinclozoline (3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione) was studied in nonaqueous solvents in the confined environment of a cyclodextrin (CD) cavity. The effect of the cavity dimensions on the mechanism of the redox process was evaluated using glucose as a reference and using three cyclodextrin molecules of different cavity sizes, namely, alphaCD, betaCD, and gammaCD. In the absence of CD the main reduction product of vinclozoline in the first reduction step is dichloroaniline. An addition of glucose leads to a quantitative change of mechanism with 10 products in total. Addition of CD, however, leads exclusively to dechlorination of the phenyl ring. The degree of dechlorination depends strongly on the choice of cyclodextrin molecule. The importance of the complex formation equilibria in the change of the mechanism is supported by a series of semiempirical AM1 quantum-mechanical calculations. Very good correlation (correlation coefficient 0.995) was obtained between the complex stabilization energy of the inclusion complex and the degree of pesticide dechlorination. Additionally, we were able to show that the complexes are stabilized by the formation of intermolecular hydrogen bonds between the host and guest species. CD molecules do not simply act as proton donors in a nonaqueous environment, but also protect parts of the molecule included within the cavity and steer the degradation process toward fewer products.     

Separation and detection of oxidation products of fluorodeoxyglucose and glucose by high-performance liquid chromatography-electrospray ionisation mass spectrometry

2-Deoxy-2-[18F]fluoro-D-glucose ([18F] FDG), the most popular positron emitting radiopharmaceutical, may oxidise by autoradiolysis in aqueous solution. The aim of this work was to use LC-MS for determination of the oxidation products of fluorodeoxyglucose and glucose (Glc) obtained by oxidation with Fenton's reagent. Asahipak NH2P-50 polyamide silica column and acetonitrile-0.025% aqueous ammonium formate (80:20 (v/v)) eluent were utilised with an Agilent 1100 HPLC-MS instrument. Ten major oxidation products of FDG and Glc were separated and identified by mass spectrometry: 2-fluorogluconic acid, 2-fluoroglucuronic acid, 2-oxoerythronic acid, arabinose, arabonic acid, araburonic acid, erythrose, erythrulose, gluconic acid, and glucuronic acid. The most intensive electrospray ionisation signals were found in the negative ion spectra and were due to HCOO- adducts, the other acids being in their lactone forms.     

Simultaneous determination of two components by spectrofluorimetric techniques

A procedure is described for the resolution of two-component mixtures by use of data from variable-angle fluorescence spectrometry. The experimental data are treated by multilinear regression. The method is applied to the resolution of mixtures of fluorescein and dichlorofluorescein at the ng ml^?1 level; mean errors are < 4%.     

Supramolecular helical mesomorphic polymers. Chiral induction through H-bonding

The work described here concerns a challenge of general interest in supramolecular chemistry: the achievement of chiral helical organizations with controlled structures. This work provides a strategy to obtain supramolecular polymers in which a chiral helical conformation has been induced by a noncovalent association, that is, through hydrogen bonding. Polycatenar 2,4,6-triarylamino-1,3,5-triazines, which organize into columnar mesophases and are susceptible to H-bonding interactions, were chosen as a starting point to build up the chiral supramolecular structure. The stacking of these mesogens has been forced to wind in a helical way by means of H-bond association with (R)-3-methyladipic acid, within the mesophase. The optically active columnar organization has been studied in depth by optical microscopy, differential scanning calorimetry (DSC), X-ray diffraction, and circular dichroism. Formation of stable complexes between the triazine units and (R)-3-methyladipic acid has also been investigated by means of NMR diffusion-ordered spectroscopy (DOSY) experiments in chloroform.