Transition state localization by a density functional method. Applications to isomerization and symmetry-forbidden reactions

Summary A new transition state algorithm incorporated into the density functional code deMon, has been used to study thetrans cis-hydroxymethylene andtrans-hydroxymethylene formaldehyde isomerization processes and to localize the transition state for the decomposition of 1,3-diazacyclobutane to methyleneimine. Calculations have been performed using both local (LSD) and nonlocal spin density (NLSD) gradient-corrected approximations. Two different basis sets of small and large size have been used for the study in order to analyze the effect of the basis set dimension other than that of the nonlocal corrections on the activation energy barrier value. The results seem to confirm that density functional methods can be considered practical and reliable tools for the localization of transition states.     

The Dunford-Pettis Property for some Function Algebras in Several Complex Variables

The Dunford-Pettis property is shown to hold for the uniformalgebra A() and its dual for some standard domains , includingstrongly pseudoconvex bounded domains in Cⁿ, pseudoconvex boundeddomains of finite type in C², and bounded domains in C. Previouslythe result was known for the unit ball and unit polydisc inCⁿ. Techniques used involve Bourgain algebras, Hankel operators,properties of the Bergman kernel, quasi-metrics on the boundary,and -theory.     

Subthreshold pion production from nucleus-nucleus collisions around 100 MeV/nucleon

Several global variables were tested with the aim to determine the impact parameter in nucleus-nucleus collisions producing pions at incident energies around 100 MeV/nucleon. The experimental set-up includes the MEDEA multidetector, part of which is used as a ⁰ spectrometer, and an additional hodoscope of plastic scintillators to cover very forward angles. A statistical model was used to generate bothinclusive and pion-triggered events. Selection ofwell measured events was made through the measured total parallel momentum. Among the different global variables which were tested, the average parallel velocity was seen to give the best correlation with the impact parameter.     

Conformational behavior of nonfused biheterocycles: Part XVI. Isomeric phenyl-tetrazines and bitetrazines

We present here an ab-initio STO-3G and advanced semiempirical AM1 calculation for the structure and the conformational behavior of phenyltetrazine and bitetrazine molecules. Results for phenyltetrazine isomers show that in the absence of H-H interactions, the preferred conformation is the planar one. Instead, in the case of bitetrazines, the systems dominated by the lone pair-lone pair interactions are not planar. In the presence of direct H-H interaction as for 5-5-1,2,3,4 bitetrazine, the antiplanar conformation is the preferred one. Comparison with other systems (including one or more nitrogen lone pairs) shows that the compounds with the same ortho substituents have very similar conformational behavior irrespective of their composition. The AM1 results indicate that this method is able to give reliable conformational information for compounds in which H-H interactions are involved. A Fourier expansion of the torsional potential suggests that the first two terms fit the calculated torsional potentials well except in the case of two H-H interactions in the same molecule.     

Dehydroabietane from the oleoresin of Pinus pallasiana

Summary The known diterpene hydrocarbon dehydroabietane has been isolated from a natural source — the oleoresin of the Crimean pine — for the first time.Institute of Chemistry, Academy of Sciences of the Moldavian SSR. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 20–22, January, 1971.     

Hydrophobic-phase-modified fused-silica columns for capillary electrophoresis

Coated capillaries modified with a hydrophobic layer were developed. Linear hydrocarbons and ethylbenzene modified surfaces greatly improved the electrophoretic performance of the capillaries. The column efficiency for organic compounds reached as high as 327 000 theoretical plate numbers per meter on a 50 microm I.D. linear hydrocarbon (C6) surface treated fused-silica capillary column. This value did not change during 50 repeated analyses and the columns showed strong stability against 0.1 M NaOH and 0.1 M HCl. The relative standard deviation of the run-to-run, day-to-day, and capillary-to-capillary coating with hydrophobic layer showed values of < or =2.5%, and good reproducibility. The separations of four aromatic amines and six pharmacological amines at pH 2.5 is reported.     

OH radical oxidation of the sorbitylfurfural furanic ring to sugar derivatives induced by radiolysis in aerobic environment

Chemical radiolytic oxidation induced by OH addition on 1-(2-furan-2-yl-5-hydroxy-6-hydroxymethyl-[1,3]dioxan-4-yl)-ethan-1,2-diol (sorbitylfurfural, SF) leads, in the presence of controlled amounts of oxygen, to a permanent functional modification of the target molecule. The yield of conversion reaches 60% of the starting material. LC-MS analysis allowed the identification, as final products, of carboxylic acids, butenal and hydroxy-furan derivatives in which the sugar chain remains unbroken, while the furanic ring is attacked first by OH and then by oxygen, giving in succession an intra-/inter-molecular rearrangement of the allylperoxyl radicals thus formed. The proposed oxidation of the furanic ring envisages the peroxyl intermediates undergoing mono- and/or bi-molecular reactions; a reaction path has been outlined and is reported here. The presence of unsaturated bonds in the final products could provide a further site for radical scavenger activity. Therefore, the fast reaction with O₂ and the rearrangement of the produced peroxyl radicals to species, which are likely to be effective OH-capturers, reinforces the antioxidant ability of SF.