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)     

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.     

Particle Adhesion to Drops

The adhesion of spheroidal particles to spherical drops is calculated and discussed in terms of an equilibrium-penetration index. The present study emphasizes the case of particles that are sufficiently large to affect the drop volume upon penetration. It is shown that the more elongated the particles, the steeper the dependence of the penetration index on the contact angle. The effect of line tension on nanoscale particles is considered. Positive line tensions increase the steepness of the dependence of penetration index on contact angle whereas negative line tensions decrease this dependence. In addition, the energy barrier caused by positive line tensions is presented and discussed.     

Biodegradable polymers: An update

The use of polymeric materials for the administration of pharmaceuticals, and as biomedical devices has increased dramatically. This review focuses on synthetic biodegradable polymers of current interest for medical use, based on ester and anhydride bonds. Special attention is given to factors affecting biodegradation, including: polymer structure, morphology, molecular weight, radiation, and chemical treatment, as well as the effects of drugs and plasticizers added to the polymer mass. The toxicity and biocompatibility of the polymers and their current and future applications in medicine are also briefly reviewed.     

Aging characteristics of high-power lithium-ion cells with LiNi0.8Co0.15Al0.05O2 and Li4/3Ti5/3O4 electrodes

The impedance rise that results from the accelerated aging of high-power lithium-ion cells containing LiNi_0.8Co_0.15Al_0.05O₂-based positive and graphite-based negative electrodes is dominated by contributions from the positive electrode. Data from various diagnostic experiments have indicated that a general degradation of the ionic pathway, apparently caused by surface film formation on the oxide particles, produces the positive electrode interface rise. One mechanistic hypothesis postulates that these surface films are components of the negative electrode solid electrolyte interphase (SEI) layer that migrate through the electrolyte and separator and subsequently coat the positive electrode. This hypothesis is examined in this article by subjecting cells with LiNi_0.8Co_0.15Al_0.05O₂-based positive and Li_4/3Ti_5/3O₄-based negative electrodes to accelerated aging. The impedance rise in these cells was observed to be almost entirely from the positive electrode. Because reduction products are not expected on the 1.55 V Li_4/3Ti_5/3O₄ electrode, the positive electrode impedance cannot be attributed to the migration of SEI-type fragments from the negative electrode. It follows then that the impedance rise results from mechanisms that are “intrinsic” to the positive electrode.