Ethanolysis and base promoted elimination reaction of bridgehead α-amino sulfides : 3-thioethoxy-4-azahomoadamantanes

Solvolysis of N-methyl-3-thioethoxy-4-azahomoadamantane (4c) in ethanolic sodium ethoxide followed first order kinetics. Reaction presumably proceeds via an S_N1 mechanism with resonance stabilization of the bridgehead carbonium ion by the electrons on adjacent nitrogen. Addition of ethoxide to the bridgehead carbonium ion yields N-methyl-3-ethoxy-4-azahomoadamantane (4c). Solvolysis of N-protio compound (4b) under similar conditions was much more rapid, and followed first order kinetics for both substrate and base. The mechanism apparently involves an elimination-addition pathway in which ethoxide promoted elimination of ethyl mercaptan is followed by net addition of ethanol across the bridgehead imine to form ether 4d.     

Classification of certain pairs of operators (P, Q) satisfying [P, Q] = −i Id

In a separable Hilbert space a certain class of pairs of operators (P, Q) satisfying the Born-Heisenberg commutation relation [P, Q] = ?i Id on a dense domain Ω is investigated. This class is essentially defined by requiring Q bounded and self-adjoint, P symmetric and $\text{PΩ ? Ω, QΩ ? Ω}$. We show that Q is absolutely continuous and that P can be thought of as a first order differential operator. The class considered contains the pair “angle ?” and “angular momentum L_z.” It is expected that the methods of this paper can be applied to more general classes of operators (P, Q) including the Schrödinger case.     

Protein type effects on steady-state crossflow membrane ultrafiltration fluxes and protein transmission

The permeate fluxes and percent protein transmission were evaluated for steady-state crossflow ultrafiltration of two proteins of different composition: bovine serum albumin (BSA), containing fatty acid, and “fatty-acid-poor” BSA, from which most of the fatty acids had been removed (BSA/FAP). The influences of protein concentration up to 6.5 percent w/v, transmembrane pressure, ionic environment and membrane type (i.e. nominal molecular weight cut-off) were investigated. For both BSA and BSA/FAP, the fluxes and the protein transmission were dependent on the amount of salt present. The higher fatty acid content in the BSA apparently enhanced protein-protein interaction, resulting in a more cohesive and resistant fouling layer; permeate fluxes were lower with BSA/FAP than with BSA at otherwise corresponding operating conditions. A hysteresis behaviour of the flux (J)-transmembrane pressure (TMP) relationship was observed whenever the ultrafiltration unit was operated at a TMP less than some higher value to which the membrane previously had been exposed.     

Atomic concentration of hydrogen in tetra- and hexaamine heteroligand chromium(III) complexes with cyclic tetraamines

Based on the revealed dependence of the atomic concentration of hydrogen (N_H) on the composition and structure of tetra- and hexaamine heteroligand chromium(III) complexes with cyclic tetraamines, routes to new materials with high N_H for preparing effective composites for protection from neutron radiation were suggested.     

Exposure of Arctic Field Scientists to Ultraviolet Radiation Evaluated Using Personal Dosimeters

During July 2000 we used an electronic personal dosimeter (X-2000) and a biological dosimeter (Deutsches Zentrum für Luft- und Raumfahrt: Biofilm) to characterize the UV radiation exposure of arctic field scientists involved in biological and geological fieldwork. These personnel were working at the Haughton impact structure on Devon Island (75 degrees N) in the Canadian High Arctic under a 24 h photoperiod. During a typical day of field activities under a clear sky, the total daily erythemally weighted exposure, as measured by electronic dosimetry, was up to 5.8 standard erythemal dose (SED). Overcast skies (typically 7-8 okta of stratus) reduced exposures by a mean of 54%. We estimate that during a month of field activity in July a typical field scientist at this latitude could potentially receive approximately 80 SED to the face. Because of body movements the upper body was exposed to a UV regimen that often changed on second-to-second time-scales as assessed by electronic dosimetry. Over a typical 10 min period on vehicle traverse, we found that erythemal exposure could vary to up to 87% of the mean exposure. Time-integrated exposures showed that the type of outdoor field activities in the treeless expanse of the polar desert had little effect on the exposure received. Although absolute exposure changed in accordance with the time of day, the exposure ratio (dose received over horizontal dose) did not vary much over the day. Under clear skies the mean exposure ratio was 0.35 +/- 0.12 for individual activities at different times of the day assessed using electronic dosimetry. Biological dosimetry showed that the occupation was important in determining daily exposures. In our study, scientists in the field received an approximately two-fold higher dose than individuals, such as medics and computer scientists, who spent the majority of their time in tents.     

Solid-Phase Substitution of Ammonia in Hexaamine Heteroligand Complexes of Chromium(III) with Cyclic Tetraamines

The solid-phase substitution of ammonia in heteroligand hexaamine complexes of chromium(III) with cyclic tetraamines was studied. The kinetic stability of these compounds, determined from the value of the activation energy, is lower than for other hexaamine compounds of chromium(III). This is due to the weakening of the Cr—NH₃ bonds and to the less close packing of the ions in the crystal lattice. For complexes with the trans structure the thermal stability increases in the series of tetraazamacrocyclic ligands teta < cyclam < TMC.     

Conversion of nitrogen(I,II) oxides on nanodispersed [Pt(Pd)-Au]/HY zeolite catalysts

We have shown that conversion of nitrogen(I,II) oxides in reduction by carbon monoxide and light C₁, C₃–C₄ alkanes in the presence of nanodispersed [Pt(Pd)-Au]/HY catalysts is determined by the reagent activation routes in an oxidizing/reducing atmosphere. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 3, pp. 156–161, May–June, 2006.     

Bestimmung von Aziden durch F?llungstitration mit Adsorptionsindikatoren

Zusammenfassung Azid-Ionen können in entsprechender Weise wie Halogen-Ionen durch Fällungstitration mit Silbernitrat unter Verwendung von Adsorptions-Indikatoren einwandfrei und leicht analytisch bestimmt werden.Die Titrationen sind sowohl im Tageslicht als auch durch Beobachtung der Fluorescenzänderung im ultravioletten Licht möglich.Die Ursachen für gewisse Abweichungen bei der Titration von Azid-Ionen gegenüber dem Verhalten der Halogenide werden theoretisch erörtert.Dem Direktor des Kaiser-Wilhelm-Instituts, Herrn Professor Dr. P. A. Thiessen, danken wir aufrichtig für das fördernde Interesse, der Deutschen Forschungs-Gemeinschaft für die Bereitstellung von Mitteln.     

Influence of ice and snow covers on the UV exposure of terrestrial microbial communities: dosimetric studies

Bacillus subtilis spore biological dosimeters and electronic dosimeters were used to investigate the exposure of terrestrial microbial communities in micro-habitats covered by snow and ice in Antarctica. The melting of snow covers of between 5- and 15-cm thickness, depending on age and heterogeneity, could increase B. subtilis spore inactivation by up to an order of magnitude, a relative increase twice that caused by a 50% ozone depletion. Within the snow-pack at depths of less than approximately 3 cm snow algae could receive two to three times the DNA-weighted irradiance they would receive on bare ground. At the edge of the snow-pack, warming of low albedo soils resulted in the formation of overhangs that provided transient UV protection to thawed and growing microbial communities on the soils underneath. In shallow aquatic habitats, thin layers of heterogeneous ice of a few millimetres thickness were found to reduce DNA-weighted irradiances by up to 55% compared to full-sky values with equivalent DNA-weighted diffuse attenuation coefficients (K(DNA)) of >200 m(-1). A 2-mm snow-encrusted ice cover on a pond was equivalent to 10 cm of ice on a perennially ice covered lake. Ice covers also had the effect of stabilizing the UV exposure, which was often subject to rapid variations of up to 33% of the mean value caused by wind-rippling of the water surface. These data show that changing ice and snow covers cause relative changes in microbial UV exposure at least as great as those caused by changing ozone column abundance.