Electrochemistry of Organic Cations. VI. Investigations about the Cathodic Cleavage of Some Pyridinium and Triazolium Ions

The electrochemical reduction of some N-acylamino-, N-amino-, N-benzyl- and N-phenacyl-substituted pyridinium and triazolium ions is investigated in acetonitrile by voltammetric methods and potentiostatic electrolyses. The acylaminopyridinium ions 1 and the arylaminopyridinium ions 3 are cathodically cleaved into the pyridine derivative and the carboxylic amide or the aromatic amine. In the case of the 1-benzyl-4-acylaminotriazolium ions 5 the reductive formation of hydrogen from the acidic N-acylamino group is preferred and the corresponding ylide is formed, which reacts at more negative potential by splitting off the benzyl group. The reduction of the N-phenacylpyridinium ion 7d occurs with splitting off the phenacyl radical, which dimerizes to 1,2-dibenzoylethane in a good yield. In the case of N-benzyl- and N-p-cyanobenzylpyridinium ions the cathodic dimerization to the corresponding bisdihydropyridines was found, whereas the electrolysis of the N-nitrobenzylpyridinium ions occurs with cleavage of the N-substituent-bond, which is initiated by the primary formation of the nitrophenyl anion radical. It follows from electrogenerated chemiluminescence experiments that the cleavage of the cations 1 and 5 occurs with the uptake of one electron.     

On the reassessment of doses in TL-dosimetry by measuring the residual dose

Second readouts and the photo-transferred thermoluminscence (PTTL) method are sometimes used to reassess high doses. When using the common LiF:Mg,Ti, if the second readout is performed by a regular readout cycle of 13.3 s, its efficiency is low and the estimations cannot be obtained with acceptable accuracy for low doses in the 10-100 mSv range. By applying the PTTL method, the efficiency is much higher, but a high background is also present, deteriorating the quality of the reassessment. A simple and efficient method was studied, which consists of expanding the heating time to 30 s. Although the efficiency relative to a standard readout is improved by only a factor of 3, the low background enables to obtain results with the same uncertainty as the more complicated PTTL method. By applying region of integration discrimination, the errors can be further diminished.     

On the reassessment of thermal neutron doses in TLD-100 by measuring the residual dose

By employing second readouts and the Phototransferred thermoluminescence (PTTL) method, high doses may be reassessed on the basis of residual dose information. It was shown in the past that for TLD-100, gamma doses can be reassessed by using a simple and efficient method, which consists of expanding the heating time to 30 s. In the present study, the 'extended time' method and the PTTL residual dose evaluations are used for reassessing thermal neutron doses when using TLD-100 crystals. Reassessment characteristics are presented for relatively low thermal neutron doses, in the range between approximately 1 and 18 mSv gamma dose equivalent.     

Life events, relationship quality, and depression: An investigation of judgment discontinuity in vivo.

Relationships among stressful life events, negative affect, and judged quality of intimate relationships were explored. Three studies and a mini-meta-analysis revealed that as negative life events increased, judgments of close relationships gradually became less favorable, jumped back toward positivity, and then, again, gradually became less favorable. The same methods of analysis revealed a relationship between negative life events and negative affect with no evidence of significant discontinuities. Moreover, the correlation between relationship satisfaction and negative affect (with negative events held constant), was maximized at the point of relationship-judgment discontinuity. Although the findings are complex, they are consistent with the authors' theoretical account and represent an initial attempt to conceptualize the effect of negative life events in light of the recent social judgment literature. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Effect of specific dietary fatty acids on lipogenesis in the livers and mammary glands of lactating mice

The effects of linoleic, linolenic and columbinic acids fed as 4% of a high carbohydrate (50% glucose) diet on the activities and the amounts of several enzymes associated with fatty acid synthesis in livers and mammary glands of lactating mice were compared with those for stearic and oleic acids. Fatty acid synthesis, measured in vivo, was significantly lower in livers of mice ingesting all 3 polyunsaturated fatty acids (PUFA), whereas in mammary glands synthesis was lower only in mice receiving columbinic acid. The activities of fatty acid synthetase (FAS) and acetyl CoA carboxylase were significantly reduced in liver by all 3 PUFA, as were activities of glucose-6-phosphate dehydrogenase, malic enzyme (ME) and citrate cleavage enzyme (CCE), also associated with lipogenesis. In mammary gland, on the other hand, the activities of these enzymes were unaffected by dietary PUFA. The tissue contents of FAS, ME and CCE, measured by rocket immunoelectrophoresis, were found to be significantly reduced in liver by linoleate, linolenate and columbinate but were not significantly altered in mammary gland. The decrease in hepatic lipogenesis observed was principally due to a decrease in the amounts of these enzymes induced by the dietary PUFA but the inhibition in mammary gland caused by columbinate could not be accounted for by a reduction in enzyme contents and therefore may be due to allosteric effects which occur when fatty acid synthesis is measured with³H₂O. The fatty acid composition in liver and mammary gland of dams and in liver and kidney of pups completely reflected dietary fatty acids. Columbinate made up ca. 20% of the total fatty acids in both tissues of the columbinic acid-fed mice and ca. 15% in the pup tissues. This suggests that columbinate is incorporated into milk lipids of dams and is easily absorbed by pups. The elevated ratios of 16/16∶1 and 18/18∶1 in liver and mammary gland of dams and liver and kidney of the pups from dams fed linoleate, linolenate and columbinate suggest that each of these polyunsaturated fatty acids in the diet can inhibit the activity of Δ9 desaturase.     

Graft polymerization of propylene sulfide on crosslinked polystyrene

Sulfur containing graft polymers that may be of interest as polymeric transfer agents were synthesized. Graft polymerization of propylene sulfide on crosslinked polystyrene beads was investigated; both crosslinked polystyrene and its chloromethylated derivative were grafted. Crosslinked polystyrene was metallated by BuLi–TMEDA and was used to initiate anionic graft polymerization of propylene sulfide. Graft polymers of high polypropylene sulfide content corresponding to 10 mmol s/g were obtained. The grafted polypropylene sulfide was evenly distributed across the bead cross section. No change in bead surface characteristics was observed. Grafting on chloromethylated polystyrene beads was achieved by reaction between the chloromethylene groups with sulfide groups of performed polypropylene sulfide, and with terminal sodium thiolate groups of living polypropylene sulfide.     

The crystal state binding of dithionite to deoxy-hemoglobin

The crystal state binding of sodium ditbionite to deoxyhemoglobinis reported. Dithionite has been used extensively to deoxygenatehemoglobin and myoglobin and there has been considerable interestamong users of dithionite about its effect on protein structureand binding site(s). We have determined that dithionite bindsto deoxygenated hemoglobin crystals at the interface of twomolecules in the crystal lattice. Specific residues involvedin hydrogen bonds or salt interactions with dithionite includeHisll6 and Hisll7 of the ft subunit and Lysl6 of the ß₂subunit of the adjacent hemoglobin molecule. No binding wasobserved at the symmetry related Hisll6 and 117 ß1 residues.We have shown that dithionite does not affect the native hemoglobinstructure or the binding of several allosteric inhibitors tohemoglobin and can be used to mount T state crystals in theair     

Polysaccharide Biomaterials

An entire new genus of “polymer therapeutics” has emerged with wide applicability, including as mechanical supports, mechanical barriers, artificial tissue/organs, and pro-drug preparations with pharmacological effects. Polysaccharides are a class of biopolymers formed from many monosaccharide units joined together by glycosidic linkages. The physical properties of carbohydrates, such as solubility, gelation, and surface properties, are dictated by the monosaccharide composition, chain shapes, and molecular weight. These macromolecules exhibit good hemocompatibility, are non-toxic, and show unique biological functions, ranging from cell signaling to immune recognition. With few exceptions, they are more economical in comparison with others biopolymers. Polysaccharide-based polymers have been widely proposed as scaffold materials in tissue engineering applications as well as carriers for drug delivery.     

Tetraalkynylated and Tetraalkenylated Benzenes and Pyridines: Synthesis and Photophysical Properties

Tetra(arylalkynyl)pyridines and tetra(arylalkenyl)pyridines and their benzene analogues were prepared by palladium‐catalyzed cross‐coupling reactions from the commercially available chlorinated substrates in good to excellent yields. The photophysical properties of selected compounds were investigated and compared to each other. Very good fluorescence quantum yields were observed, especially for the pyridine derivatives.