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Synthesis and evaluation of structural requirements for antifungal activity of cyrmenin B1 analogues
Narayan S. Chakor Sabrina Dallavalle Loana Musso Paola Sardi 《Tetrahedron letters》2012,53(2):228-231
In a study aiming to define the structural elements essential to cyrmenin B1 antifungal activity, the synthesis of a series of analogues was carried out. The structural modification introduced stepwise in distinct areas of the parent molecule allowed a deeper insight to be gained into the most relevant structural features affecting the activity of the natural compound. The bioassay results clearly indicate the relevance of each portion of the parent molecule, only the modification of the conjugated double bond geometry being tolerated. 相似文献
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Antonello S Benassi R Gavioli G Taddei F Maran F 《Journal of the American Chemical Society》2002,124(25):7529-7538
The dissociative reduction of a series of symmetrical (RSSR, R = H, Me, t-Bu, Ph) and unsymmetrical disulfides (RSSR', R = H, R' = Me and R = Ph, R' = Me, t-Bu) was studied theoretically, by MO ab initio calculations and, for five of them, also experimentally, by convolution voltammetry in N,N-dimethylformamide. The reduction is dissociative but proceeds by a stepwise mechanism entailing the formation of the radical anion species. The electrochemical data led to estimated large intrinsic barriers, in agreement with an unusually large structural modification undergone by the disulfide molecules upon electron transfer. The theoretical results refer to MP2/3-21G*//MP2/3-21G*, MP2/3-21*G*//MP2/3-21G*, CBS-4M, and G2(MP2), the latter approach being used only for the molecules of small molecular complexity. A loose radical-anion intermediate was localized and the dissociation pattern for the relevant bonds analyzed. For all compounds, the best fragmentation pathway in solution is cleavage of the S-S bond. In addition, S-S bond elongation is the major structural modification undergone by the disulfide molecule on its way to the radical anion and eventually to the fragmentation products. The calculated energy of activation for the initial electron transfer was estimated from the crossing of the energy profiles of the neutral molecule and its radical anion (in the form of Morse-like potentials) as a function of the S-S bond length coordinate. The inner intrinsic barrier obtained in this way is in good agreement with that determined by convolution voltammetry, once the solvent effect is taken into account. 相似文献
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Marco Sangermano Wayne D. Cook Simone Papagna Sabrina Grassini 《European Polymer Journal》2012,48(10):1796-1804
Hybrid organic–inorganic UV-cured coatings based on interpenetrating polymer networks (IPN) were prepared starting by an equimolar methacrylate-epoxy UV-curable mixture (bisphenol-A-diglycidyl dimethacrylate/bisphenol-A-diglycidyl ether, abbreviated as BisGMA/BADGE), in the presence of tetrafunctional silane monomer tetrakis(methacryloyloxy-ethoxy)silane (TetMESi) as inorganic precursor. The photocuring kinetics of the BisGMA/BADGE IPN monomer mixture were strongly affected by the order of the cure of the individual components. Addition of TetMESi resulted in higher degrees of reaction. DMTA of the BisGMA/BADGE IPN suggest a two phase structure. The rubbery modulus of the hydrolysed BisGMA/BADGE/TetMESi systems increased as the level of TetMESi was raised in the formulation due primarily to the significant reinforcing effect of the nano-silica particles. TGA of the BisGMA/BADGE IPN showed three degradation stages with no residual char but the hydrolysed BisGMA/BADGE/TetMESi systems formed a carbonaceous silica char which increased in mass as the level of TetMESi was raised. The two phase morphology of the BisGMA/BADGE IPN was confirmed by FE-SEM analysis. For IPNs prepared with TetMESi, SiO2 particles are evident in the FE-SEM image and have diameters in the nanometric size range. 相似文献
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Aggarwal R Benedetti F Berti F Buchini S Colombatti A Dinon F Galasso V Norbedo S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(13):3132-3142
Amidase antibody 312d6, obtained against the sulfonamide hapten 4 a that mimics the transition state for hydrolysis of a distorted amide, accelerates the hydrolysis of the corresponding amides 1 a-3 a by a factor of 10(3) at pH 8. The mechanisms of both the uncatalyzed and antibody-catalyzed reactions were studied. Between pH 8 and 12 the uncatalyzed hydrolysis of N-toluoylindoles 1 a and 3 a shows a simple first-order dependence on [OH(-)], while hydrolysis of 3 a is zeroth-order in [OH(-)] below pH 8. The pH profile for hydrolysis of the corresponding tryptophan amide 2 a is more complex due to the dissociation of the zwitterion into an anion with pK(a) 9.74; hydrolysis of the zwitterionic and the anionic form of 2 a both show simple first-order dependence on [OH(-)]. Absence of (18)O exchange between H(2) (18)O/(18)OH(-) and the substrate, a normal SKIE for both 1 a (k(H)/k(D)=1.12) and 3 a (k(H)/k(D)=1.24) and the value of the Hammett constant rho for hydrolysis of p-substituted amides 3 a-e are consistent with an ester-like mechanism in which formation of the tetrahedral intermediate is rate-determining and the amine departs as anion. The 312d6-catalyzed hydrolysis of 3 a was studied between pH 7.5 and 9, and its independence of pH in this range indicates that water is the reacting nucleophile. Hydrolysis of 3 a is only partially inhibited by the sulfonamide hapten, and this indicates that non-specific catalysis by the protein accompanies the specific process. Only the nonspecific process is observed in the hydrolysis of amides 3 with para substituents other than methyl. Binding studies on the corresponding series of p-substituted sulfonamides 5 a-e confirm the high specificity of antibody 312d6 for p-methyl substituted substrates. 相似文献
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Gensberger S Mittelmaier S Glomb MA Pischetsrieder M 《Analytical and bioanalytical chemistry》2012,403(10):2923-2931
High-fructose corn syrup (HFCS) is a widely used liquid sweetener produced from corn starch by hydrolysis and partial isomerization of glucose to fructose. During these processing steps, sugars can be considerably degraded, leading, for example, to the formation of reactive α-dicarbonyl compounds (α-DCs). The present study performed targeted screening to identify the major α-DCs in HFCS. For this purpose, α-DCs were selectively converted with o-phenylendiamine to the corresponding quinoxaline derivatives, which were analyzed by liquid chromatography with hyphenated diode array-tandem mass spectrometry (LC-DAD-MS/MS) detection. 3-Deoxy-D-erythro-hexos-2-ulose (3-deoxyglucosone), D-lyxo-hexos-2-ulose (glucosone), 3-deoxy-D-threo-hexos-2-ulose (3-deoxygalactosone), 1-deoxy-D-erythro-hexos-2,3-diulose (1-deoxyglucosone), 3,4-dideoxyglucosone-3-ene, methylglyoxal, and glyoxal were identified by enhanced mass spectra as well as MS/MS product ion spectra using the synthesized standards as reference. Addition of diethylene triamine pentaacetic acid and adjustment of the derivatization conditions ensured complete derivatization without de novo formation for all identified α-DCs in HFCS matrix except for glyoxal. Subsequently, a ultra-high performance LC-DAD-MS/MS method was established to quantify 3-deoxyglucosone, glucosone, 3-deoxygalactosone, 1-deoxyglucosone, 3,4-dideoxyglucosone-3-ene, and methylglyoxal in HFCS. Depending on the α-DC compound and concentration, the recovery ranged between 89.2% and 105.8% with a relative standard deviation between 1.9% and 6.5%. Subsequently, the α-DC profiles of 14 commercial HFCS samples were recorded. 3-Deoxyglucosone was identified as the major α-DC with concentrations up to 730 μg/mL HFCS. The total α-DC content ranged from 293 μg/mL to 1,130 μg/mL HFCS. Significantly different α-DC levels were not detected between different HFCS specifications, but between samples of various manufacturers indicating that the α-DC load is influenced by the production procedures. 相似文献
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