Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Aspects of alpha-particle scattering and structure of the nuclear surface

The interaction of α particles above 5 MeV with a 2s-1d target is dominated by resonances. It cannot be described only in terms of a mean-field one-body potential. An analysis of the elastic α-particle scattering by ²⁸Si encourages the comprehension of the resonance states to be mainly fragments of a mixed-parity band. In the present article, the angular distributions of particles scattered by ³²S are analyzed in terms of such bands. The analysis of new data from an experiment made at Florida State University reveals the existence of states that do not belong to the above bands. This follows from a coupled-channel analysis of the elastic and inelastic (2⁺) cross sections. An α-particle structure at the nuclear surface is suggested.     

Pentopyranosyl Oligonucleotide Systems. 9th Communication

Pyranosyl‐RNA (‘p‐RNA’ ) is an oligonucleotide system isomeric to natural RNA and composed of the very same building blocks as RNA. Its generational, chemical, and informational properties are deemed to be those of an alternative nucleic acid system that could have been a candidate in Nature's evolutionary choice of the molecular basis of genetic function. We consider the study of the chemistry of p‐RNA as etiologically relevant in the sense that knowledge of its structural, chemical, and informational properties on the chemical level offers both a perspective and reference points for the recognition of specific structural assets of the RNA structure that made it the (supposedly) superior system among possible alternatives and, therefore, the system that became part of biology as we know it today. The paper describes the chemical synthesis of β‐d‐ (and L )‐ribopyranosyl‐(4′→2′)‐oligonucleotide sequences, presents a resume of their structural and chemical properties, and cautiously discusses what we may and may not have learned from the pyranosyl isomer of RNA with respect to the conundrum of RNA's origin.     

Studies on pre-hump and main fractions of cellulose-2,5-acetate in acetone

Technical cellulose-2.5-acetates (CA 2.5) were characterized regarding their carbohydrate composition in comparison to the raw material. The association of the CA 2.5 samples in acetone was studied by size exclusion chromatography (SEC) using various acetone grades and styrene divinylbenzene copolymer columns. In HPLC grade acetone with and without addition of 1% water up to three different pre-humps eluted in front of the main fraction of the polymer. The evaluation of the main peak by light scattering measurements resulted in high molar masses indicating that for these technical CA 2.5 samples even the main fraction is not dissolved without association. No pre-humps or association phenomena were observed after addition of 1 ppm LiBr to HPLC grade acetone or with p.a. grade acetone. In addition pre-hump enriched and pre-hump free fractions were isolated by fractionated precipitation. The carbohydrate composition of these fractions was determined and correlated with their association pattern in SEC investigations.     

The use of sulfide cluster-derived catalysts to understand the promotional effect in hydrotreatment catalysis

Sulfide cluster-derived ensembles are promising models of the active sites in commercial hydrotreatment catalysts. A series of sulfide clusters were adsorbed intact onto high-surface-area γ-alumina, magnesium oxide and activated carbon supports, then pretreated to produce highly dispersed catalytic ensembles with sizes similar to those of their precursor clusters. The activities of the bimetallic cluster-derived catalysts were significantly higher than those of the monometallic catalysts. We took this as evidence that direct interactions between molybdenum and the promoter element cause the promotional effect observed in commercial hydrotreatment catalysts. The hydrodesulfurization and hydrodenitrogenation activities correlated with the extent of molybdenum reduction. Our results suggested that the active sites in promoted hydrotreatment catalysts are centered on molecular-scale ensembles containing molybdenum, sulfur and the promoter element.