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11.
Oxyallyl cations generated in situ from dihaloketones have been found to undergo the Favorskii rearrangement in preference to an intramolecular Type-II 4 + 3 cycloaddition reaction in trifluoroethanol and hexafluoropropan-2-ol solvents, generating acrylate esters with high cis selectivity. A synthetic alternative to the intramolecular Type-II 4 + 3 cycloaddition has been developed on the basis of intramolecular enolate alkylation to close a 7-membered ring with an exocyclic double bond. 相似文献
12.
Roda A Simoni P Mirasoli M Baraldini M Violante FS 《Analytical and bioanalytical chemistry》2002,372(7-8):751-758
A chemiluminescent enzyme-immunoassay for urinary 1-hydroxypyrene has been developed and optimized. The enzymatic activity of horseradish peroxidase-labeled tracer was measured with an enhanced chemiluminescent system and the results were compared with those from conventional colorimetric detection. The method fulfilled all the requirements of accuracy and precision and the detection limit was 0.001 pmol/well, which enabled analysis in less than 1 microL urine. Subjects working in the center of Bologna who were exposed daily to vehicular exhaust gas were studied. Their urinary 1-hydroxypyrene concentrations were compared with the levels of benzo( a)pyrene in air particulate matter. Urinary 1-hydroxypyrene, which ranged from 0.5 to 10 nmol L(-1), correlated poorly with the concentration of benzo( a)pyrene in air particulate matter, which ranged from 5 to 140 ng m(-3). No significant effect of vehicle exhaust gas exposure was observed among the different groups of subjects working in different areas of the town. Thus, at a relatively low level of exposure 1-hydroxypyrene does not seem to be a sensitive biomarker of exposure to polycyclic aromatic hydrocarbons. 相似文献
13.
Barros N. Feijóo S. Simoni A. Critter S. A. M. Airoldi C. 《Journal of Thermal Analysis and Calorimetry》2000,63(2):577-588
The microcalorimetric method was used to calculate the metabolic enthalpy change per mol of glucose degraded by soil microorganisms,
ΔH
met. This parameter has been calculated by microcalorimetry for many organic, inorganic and biochemical reactions, but there
is only some information about its quantification for microbial growth reactions in soils. Values of ΔH
met were calculated for different soil samples collected in Galicia (Spain) and Campinas (Săo Paolo, Brazil). Exponential microbial
growth was stimulated in all soil samples by the addition of glucose and power-time curves were recorded. Results showed changes
in the values of ΔH
met calculated for all the soil samples, suggesting a dependence of this value with the microbial growth rate constant, with
the percentage of growth, with the initial number of microorganisms of soil samples, with the quantity of glucose added and
with the strain of bacteria growing in soil.
The interpretation of variations of ΔH
met provides important qualitative and quantitative information. It reports data that allow to interpret from a qualitative point
of view, the increase in biomass as a consequence of the degradation of the organic matter in soil, to understand changes
in the percentages of soil organic matter and to know if the microbial population growing in differential soil samples is
homogeneous. Therefore, to report that value would be very important in ecological studies, but beforehand, it is necessary
to solve some problems that can appear in the experiments done to make the quantification
.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
14.
The CD curves of a set of condensed γ-butyrolactones have been investigated. A simple correlation between the sign of the Cotton effect (CE) and the configuration of C can be deduced from the resulting data. 相似文献
15.
Calaminici P Jug K Köster AM Arbez-Gindre C Screttas CG 《Journal of computational chemistry》2002,23(2):291-297
This paper presents calculations of dipole moments (mu), static polarizabilities (alpha), and first hyperpolarizabilities (beta) of phosphonic acid stilbene derivatives calculated in the framework of density functional theory. These calculations were performed using a finite field approach implemented in the density functional program ALLCHEM and were of an all-electron type using local exchange-correlation functional and specially designed basis sets. The molecular structures have been fully optimized using the semiempirical program MSINDO. Some of the investigated stilbenes have been synthesized very recently while others are described for the first time. Donor and acceptor groups of these analogues have been modified and the influence of these changes on the first hyperpolarizabilities has been investigated. This work demonstrates that the nonlinear optical response beta of these compounds increases dramatically when the acceptor moiety is displaced by analogues containing alkali metal groups. A general mechanism for the design of novel nonlinear optical materials with large first hyperpolarizabilities is described. 相似文献
16.
Alessandra LattanziLiliana R. Orelli Patrizia BaroneAntonio Massa Patrizia IanneceArrigo Scettri 《Tetrahedron letters》2003,44(7):1333-1337
A mild and practical procedure of Horner-Wadsworth-Emmons olefination promoted by lithium hydroxide and α-cyano phosphonates has been set up for the synthesis of α,β-unsaturated nitriles. The reaction conditions are tolerated by functionalized ketones and the exclusive formation of E-γ-hydroxy α,β-unsaturated nitriles has been observed. 相似文献
17.
Tarozzi A Marchesi A Hrelia S Angeloni C Andrisano V Fiori J Cantelli-Forti G Hrelia P 《Photochemistry and photobiology》2005,81(3):623-629
Ultraviolet-A (UVA) radiation causes significant oxidative stress because it leads to the generation of reactive oxygen species (ROS), leading to extensive cellular damage and eventual cell death either by apoptosis or necrosis. We evaluated the protective effects of cyanidin-3-O-beta-glucopyranoside (C-3-G) against UVA-induced apoptosis and DNA fragmentation in a human keratinocyte cell line (HaCaT). Treatment of HaCaT cells with C-3-G before UVA irradiation inhibited the formation of apoptotic cells (61%) and DNA fragmentation (54%). We also investigated antioxidant properties of C-3-G in HaCaT cells against ROS formation at apoptotic doses of UVA; C-3-G inhibited hydrogen peroxide (H2O2) release (an indicator of cellular ROS formation) after UVA irradiation. Further confirmation of the potential of C-3-G to counteract UVA-induced ROS formation comes from our demonstration of its ability to enhance the resistance of HaCaT cells to the apoptotic effects of both H2O2 and the superoxide anion (O2*-), two ROS involved in UVA-oxidative stress. Furthermore, in terms of Trolox Equivalent Antioxidant Activity, C-3-G treatment led to a greater increase in antioxidant activity in the membrane-enriched fraction than in the cytosol (55% vs 19%). The protective effects against UVA-induced ROS formation can be attributed to the higher membrane levels of C-3-G incorporation. These encouraging in vitro results support further research into C-3-G (and other anthocyanins) as novel agents for skin photoprotection. 相似文献
18.
Benincori T Brenna E Sannicolò F Trimarco L Antognazza P Cesarotti E Demartin F Pilati T 《The Journal of organic chemistry》1996,61(18):6244-6251
The synthesis and application of three examples of a new class of chiral (C(2)) atropisomeric diphosphines characterized by two interconnected five-membered heteroaromatic rings, with hindered rotation around the interanular bond, are described. Optically pure (+)- and (-)-2,2'-bis(diphenylphosphino)-4,4',6,6'-tetramethyl-3,3'-bibenzo[b]thiophene (tetraMe-bitianp) (1a) and the parent unsubstituted system (+)- and (-)-bitianp (1b) were synthesized. They were found to be optically stable at 100 degrees C and were successfully employed as ligands in the Ru(II)-catalyzed hydrogenation of alpha- and beta-oxo esters to the corresponding alpha- and beta-hydroxy esters and in the hydrogenation of olefinic substrates. The optical and chemical yields were comparable with those reported for the same Ru(II)-binap-catalyzed reactions carried out under the same experimental conditions. The 2,2'-bis(diphenylphosphino)-3,3'-bibenzo[b]furan (1c), the oxygenated analogue of bitianp, was found to be configurationally unstable at room temperature. Complete structural X-ray elucidation of the Pd complexes of 1a-c is reported. The advantages of these biheteroaromatic ligands over the classical biaryl systems are discussed. 相似文献
19.
Patrizia Calaminici Victor D. Domínguez-Soria Gerald Geudtner Elizabeth Hernández-Marín Andreas M. Köster 《Theoretical chemistry accounts》2006,115(4):221-226
The parallelization of the three-center electron repulsion integrals arising from the variational fitting of the Coulomb potential
is presented. A scheme for dynamical load balancing of the corresponding loop structure is discussed. The implementation in
the density functional theory program deMon using the message passing interface is described. The efficiency of the parallelization
is analyzed by selected benchmark calculations 相似文献
20.
Patrizia Ciminiello Carmela Dell'Aversano Martino Forino Federico Umberto Santelia Emmanuel N. Pitsinos 《Tetrahedron》2006,62(33):7738-7743
The analysis of a batch of toxic mussels (Mytilus galloprovincialis) from the Northern Adriatic Sea led to the isolation of a novel oxazinin, oxazinin-4. Its structure including the relative stereochemistry has been elucidated through extensive NMR analysis. A synthetic route to oxazinins has been crucial in establishing the absolute stereochemistry of oxazinin-4 and for reassigning the absolute C-2 configuration of oxazinin-1 and -2 previously isolated from toxic shellfish and stereostructurally characterized. 相似文献