Solar irradiation including ultraviolet (UV) light causes tissue damage by generating reactive free radicals that can be electrophilic or nucleophilic due to unpaired electrons. Little is known about how free radicals induced by natural sunlight are rapidly detected and avoided by animals. We discover that Drosophila Transient Receptor Potential Ankyrin 1 (TRPA1), previously known only as an el...

A Bamberger rearrangement of N-phenylhydroxylamine, Ph-N(OH)H, to p-aminophenol was investigated by DFT calculations for the first time. The nitrenium ion, C6H5-NH(+), suggested and seemingly established as an intermediate was calculated to be absent owing to the high nucleophilicity of the water cluster around it. First, a reaction of the monoprotonated system, Ph-N(OH)H + H3O(+)(H2O) n (n = 4...

In regard to the worldwide interest in synthesis and application of stable carbenes, DFT calculations (B3LYP/6-311++G**//B3LYP/6-31+G* levels) are employed to reach at a series of phenyl carbenes. The singlet-triplet energy separations (ΔES-T), HOMO–LUMO energy gaps (ΔEHOMO-LUMO), as well as philicity indices (N and ω) and basicity of these carbenes are compared and contrasted with the synthesi...

Gas-phase activation data were obtained for model sulfoxide elimination reactions. The activation enthalpy for methyl 3-phenylpropyl sulfoxide is 32.9 +/- 0.9 kcal/mol. Elimination by methyl vinyl sulfoxide to form acetylene has an enthalpic barrier of 41.6 +/- 0.8 kcal/mol and that of 3-phenylpropyl methanesulfinate to form hydrocinnamaldehyde is 34.6 +/- 0.6 kcal/mol. Calculations at the MP2/...

The kinetics of the reactions of benzhydryl cations with eight diazo compounds 1 a-g were investigated photometrically in dichloromethane. The nucleophilicity parameters N and slope parameters s of these diazo compounds were derived from the equation log k (20 degrees C)=s (E+N) and compared with the nucleophilicities of other pi systems (alkenes, arenes, silyl enol ethers, silyl ketene acetals...

Additional specific rates of solvolysis have been determined, mainly in fluoroalcohol containing solvents, for benzenesulfonyl chloride (1) and p-nitrobenzene-sulfonyl chloride (2). For trans-beta-styrenesulfonyl chloride (3), a study has been carried out in 43 pure and binary solvents, covering a wide range of hyroxylic solvent systems. For the specific rates of solvolyses of each of the three...

Density functional theory (DFT) was used to study the regioselectivity of copolymerization propylene and bis-styrenic molecules (DVB BVPE) using a zirconocene catalyst. This reveals following: when hydrogen is introduced reactivate catalyst on vinyl bonds containing DVB or BVPE, second bond inserted into polymer in regio-irregular 1,2-way. (I) The 1,2-insertion mode forms more thermodynamically...

Lowering the regeneration temperature for solid CO2-capture materials is one of critical tasks economizing CO2-capturing processes. Based on reported pKa values and nucleophilicity, we compared two different polyethylenimines (PEIs): branched PEI (BPEI) linear (LPEI). LPEI outperformed BPEI in terms adsorption desorption properties. Because a below 73–75 °C, even high loading amount can effecti...

We herein report on the usefulness of the reactivity indices profiles along a reaction coordinate. The model is tested to fully describe the reaction mechanism of the title reactions. Group nucleophilicity and electrophilicity profiles help describe the bond-breaking/bond-formation processes and the intramolecular electron density reorganization. The reactivity indices' profile analysis is cons...

Aromatic cation activation is a useful strategy to promote deoxyfunctionalization; however, the deoxyfluorination of alcohols with cyclopropenium cation remains an unsolved problem due to the weak nucleophilicity of fluoride ion. Here we report the use of 3,3-difluoro-1,2-diarylcyclopropenes (CpFluors) as easily accessible and reactivity-tunable deoxyfluorination reagents. The electronic nature...