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The mechanism of nicotine toxicity is not completely delineated. Considerable evidence points to involvement of oxidative stress (OS), reactive oxygen species, lipid peroxidation, DNA damage, and beneficial effect of antioxidants. Previously, a suggestion was advanced for participation of iminium metabolites which might operate, via electron transfer (ET)(More)
Water is demonstrated to be an effective medium for the Wittig reaction over a wide range of stabilized ylides and aldehydes. Despite sometimes poor solubility of the reactants, good chemical yields normally ranging from 80 to 98% and high E-selectivities (up to 99%) are achieved, and the rate of the reactions in water is unexpectedly accelerated. The(More)
Abused drugs are of grave concern throughout the world for a variety of reasons. Although impressive advances have been made, there are many unknown mechanistic aspects. This report presents a novel hypothesis based on a unifying theme for action of the major classes of abused drugs, in addition to commonly abused therapeutic drugs. The approach is based on(More)
There are many gaps in our knowledge of the molecular basis of alcohol toxicity and addiction. Metabolism affords mainly acetic acid via acetaldehyde. A minor metabolite, diacetyl (an α-dicarbonyl), arises from the aldehyde. We propose that this C4 entity and/or its iminium derivatives from condensation with protein amino groups plays important roles in(More)
Detailed molecular orbital calculations were directed to the cyclopropylcarbinyl radical (1), the cyclopropoxy radical (2), and the cyclopropylaminium radical cation (3) as well as their ring-opened products. Since a considerable amount of data are published about cyclopropylcarbinyl radicals, calculations were made for this species and related ring-opened(More)
Experiment and theory have been used to study reactive alkyne pi complexes, intermediates in anti-Markovnikov alkyne hydration by CpRu bis(phosphine) catalysts with heterocyclic substituents. Each heterocycle accepts a hydrogen bond from an acetylene C-H, as revealed by NMR coupling constants between alkyne 13C and 1H nuclei as well as between alkyne 13C(More)
The voltammetry of 2,3,5,6-tetramethyl-p-phenylenediamine, H2PD, has been studied and compared to that of its isomer N,N,N'N'-tetramethyl-p-phenylenediamine, Me2PD. Both undergo two reversible electron transfer processes in acetonitrile that nominally correspond to 1e- oxidation to the radical cations, Me2PD(+) and H2PD(+), and a second 1e- oxidation at(More)
A novel palladium-based metallacage was self-assembled. This nanocage displayed two complementary effects that operate in synergy for guest encapsulation. Indeed, a metal complex, [Pt(NO2)4](2-), was hosted inside the cavity, as demonstrated by solution NMR studies. Single-crystal X-ray diffraction shows that the guest adopts two different orientations,(More)
A computational protocol has been developed to solve the bounded vibrational Schrödinger equation for up to three coupled coordinates on any given effective potential energy surface (PES). The dynamic Wilson G-matrix is evaluated from the discrete PES calculations, allowing the PES to be parametrized in terms of any complete, minimal set of coordinates,(More)