Nitroxide Mediated Degradation of Anthocyanidins

The degradation of the six anthocyanidins (pelargonidin, cyanidin, delphinidin, peonidin, petunidin and malvidin) mediated by the nitroxides: 2,2,6,6-tetramethylpiperidine-1-oxyl (Tempo), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (Tempol) and 4-methoxy-2,2,6,6-tetramethylpiperidine1-oxyl (4-CH3O-Tempo) at 25 °C in aqueous acid solution was investigated spectrophotometrically and by EPR and HPLC measurements. The reaction kinetics were followed under pseudo-first order conditions using a large excess of nitroxide reactants. The spontaneous degradation of anthocyanidins under these conditions is several orders of magnitude slower, and it did not influence the measurements. However, it was found that the reaction rate increases with the age of acidified nitroxide solutions, reaching a maximum after 24 hours. This result indicates that in every case the oxoammonium cation, generated by disproportionation of nitroxyl radicals, is somewhat more reactive toward anthocyanidins than the nitroxyl itself. The products were identified by HPLC as ring substituted benzoic acids. The relative reactivities of the six anthocyanidins and the accelerating influence of the p-substituent of nitroxides on the reaction is discussed.</p

Kinetics and Mechanism of the Reaction between Mercury(II) and a Series of Macrocyclic Organochromium Cations

Kinetic data are presented for the reaction of alkylchromium complexes (H2O)([14]aneN4)CrR2+ ([14]aneN4 = 1,4,8,11-tetraazacyclo-tetradecane) with Hg2+ via electrophilic substitution. The rate constants decrease in the order CH3 (1.1 × 106 mol-1 dm3 s-1) > C2H5 (7.7 × 102) > C3H7 (59) > 2-C3H7 (0.12) > CH2C(CH3)3 (0.0086). A series of meta and para substituted benzyl complexes obey a Ham-mett relationship with the reaction constant &rho; = -1.66, consistent with electrophilic substitution at &alpha;-carbon

New experimental model of acute aqueductal blockage in cats: effects on cerebrospinal fluid pressure and the size of brain ventricles

It is generally assumed that cerebrospinal fluid (CSF) is secreted in the brain ventricles, and so after an acute blockage of the aqueduct of Sylvius an increase in the ventricular CSF pressure and dilation of isolated ventricles may be expected. We have tested this hypothesis in cats. After blocking the aqueduct, we measured the CSF pressure in both isolated ventricles and the cisterna magna, and performed radiographic monitoring of the cross-sectional area of the lateral ventricle. The complete aqueductal blockage was achieved by implanting a plastic cannula into the aqueduct of Sylvius through a small tunnel in the vermis of the cerebellum in the chloralose-anesthetized cats. After the reconstitution of the occipital bone, the CSF pressure was measured in the isolated ventricles via a plastic cannula implanted in the aqueduct of Sylvius and in the cisterna magna via a stainless steel cannula. During the following 2 h, the CSF pressures in the isolated ventricles and cisterna magna were identical to those in control conditions. We also monitored the ventricular cross-sectional area by means of radiography for 2 h after the aqueductal blockage and failed to observe any significant changes. When mock CSF was infused into isolated ventricles to imitate the CSF secretion, the gradient of pressure between the ventricle and cisterna magna developed, and disappeared as soon as the infusion was terminated. However, when mock CSF was infused into the cisterna magna at various rates, the resulting increased subarachnoid CSF pressure was accurately transmitted across the brain parenchyma into the CSF of isolated ventricles. The lack of the increase in the CSF pressure and ventricular dilation during 2 h of aqueductal blockage suggests that aqueductal obstruction by itself does not lead to development of hypertensive acute hydrocephalus in cats

Long-term Ozone Data Analysis

Various approaches to the analysis of 10-year continuous ozone mo-nitoring from the EUROTRAC-TOR network station Puntijarka near Zagreb are reported. The site has a rural character (45.90° N; 15.97° E, 980 m a.s.l.) and is representative of the lower troposphere of a wider region. Mean hourly ozone volume fractions measured from 1990-1999, autocorrelation plots for ali data and for data for summer periods (May-Sep.), box and whiskers representations of diurnal variations during winter (Nov.-March) and summer periods, mean monthly values and 12-month moving averages, and the Fourier transform of the complete set of 94,248 hourly mean ozone volume fractions are discussed. The data show no increase, or possibly a slight decrease, of the ozone volume fraction toward the end of the decade

Analiza podataka dugoročnog mjerenja ozona

Various approaches to the analysis of 10-year continuous ozone monitoring from the EUROTRAC-TOR network station Puntijarka near Zagreb are reported. The site has a rural character (45.90degrees N15.97degrees E, 980 m a.s.l.) and is representative of the lower troposphere of a wider region. Mean hourly ozone volume fractions measured from 1990-1999, autocorrelation plots for all data and for data for summer periods (May-Sep.), box and whiskers representations of diurnal variations during winter (Nov.-March) and summer periods, mean monthly values and 12-month moving averages, and the Fourier transform of the complete set of 94,248 hourly mean ozone volume fractions are discussed. The data show no increase, or possibly a slight decrease, of the ozone volume fraction toward the end of the decade