999 resultados para Corresponding aldehydes
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Mode of access: Internet.
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Mode of access: Internet.
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First American edition.
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Mode of access: Internet.
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MS. date: Jan. 1, 1847.
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Oxidative DNA damage is postulated to be involved in carcinogenesis, and as a consequence, dietary antioxidants have received much interest. A recent report indicates that vitamin C facilitates the decomposition of hydroperoxides in vitro, generating reactive aldehydes. We present evidence for the in vivo generation of glyoxal, an established product of lipid peroxidation, glucose/ascorbate autoxidation, or free radical attack of deoxyribose, following supplementation of volunteers with 400 mg/d vitamin C. Utilizing a monoclonal antibody to a deoxycytidine-glyoxal adduct (gdC), we measured DNA lesion levels in peripheral blood mononuclear cells. Supplementation resulted in significant (p = .001) increases in gdC levels at weeks 11, 16, and 21, with corresponding increases in plasma malondialdehyde levels and, coupled with previous findings, is strongly suggestive of a pro-oxidative effect. However, continued supplementation revealed a highly significant (p = .0001) reduction in gdC levels. Simultaneous analysis of cyclobutane thymine dimers revealed no increase upon supplementation but, as with gdC, levels decreased. Although no single mechanism is identified, our data demonstrate a pro-oxidant event in the generation of reactive aldehydes following vitamin C supplementation in vivo. These results are also consistent with our hypothesis for a role of vitamin C in an adaptive/repair response and indicate that nucleotide excision repair specifically may be affected. © 2003 Elsevier Science Inc.
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The Knoevenagel condensation of aromatic aldehydes with active methylene compounds proceeded efficiently in a reusable ionic liquid, ethylammonium nitrate, at room temperature in the absence of any catalyst with high yields.
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The Knoevenagel condensation of aromatic aldehydes with (2-thio)barbituric acid proceeded efficiently in reusable ionic liquids, EAN, BmimBF4, and BmimPF6 at room temperature in the absence of any catalyst with high yields.
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Mistuning a harmonic produces an exaggerated change in its pitch, a component-pitch shift. The origin of these pitch shifts was explored by manipulations intended to alter the grouping status of a mistuned target component in a periodic complex tone. In experiment 1, which used diotic presentation, reinstating the corresponding harmonic (in-tune counterpart) caused the pitch shifts on the mistuned target largely to disappear for components 3 and 4, although they remained for component 2. A computational model of component-pitch shifts, based on harmonic cancellation, was unable to explain the near-complete loss of pitch shifts when the counterpart was present; only small changes occurred. In experiment 2, the complex tone and mistuned component 4 were presented in the left ear and the in-tune counterpart was presented in the right. The in-tune counterpart again reduced component-pitch shifts, but they were restored when a captor complex into which the counterpart fitted as harmonic 3 was added in the right ear; presumably by providing an alternative grouping possibility for the counterpart. It is proposed that component-pitch shifts occur only if the mistuned component is selected to contribute to the complex-tone percept; these shifts are eliminated if it is displaced by a better candidate.
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The extremely surface sensitive technique of metastable de-excitation spectroscopy (MDS) has been utilized to probe the bonding and reactivity of crotyl alcohol over Pd(111) and provide insight into the selective oxidation pathway to crotonaldehyde. Auger de-excitation (AD) of metastable He (23S) atoms reveals distinct features associated with the molecular orbitals of the adsorbed alcohol, corresponding to emission from the hydrocarbon skeleton, the O n nonbonding, and C═C π states. The O n and C═C π states of the alcohol are reversed when compared to those of the aldehyde. Density functional theory (DFT) calculations of the alcohol show that an adsorption mode with both C═C and O bonds aligned somewhat parallel to the surface is energetically favored at a substrate temperature below 200 K. Density of states calculations for such configurations are in excellent agreement with experimental MDS measurements. MDS revealed oxidative dehydrogenation of crotyl alcohol to crotonaldehyde between 200 and 250 K, resulting in small peak shifts to higher binding energy. Intramolecular changes lead to the opposite assignment of the first two MOs in the alcohol versus the aldehyde, in accordance with DFT and UPS studies of the free molecules. Subsequent crotonaldehyde decarbonylation and associated propylidyne formation above 260 K could also be identified by MDS and complementary theoretical calculations as the origin of deactivation and selectivity loss. Combining MDS and DFT in this way represents a novel approach to elucidating surface catalyzed reaction pathways associated with a “real-world” practical chemical transformation, namely the selective oxidation of alcohols to aldehydes.
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2000 Mathematics Subject Classification: Primary 47A48, Secondary 60G12
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2000 Mathematics Subject Classification: Primary 47A48, 93B28, 47A65; Secondary 34C94.