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141.
Favaro DC Ducati LC dos Santos FP Contreras RH Tormena CF 《The journal of physical chemistry. A》2011,115(50):14539-14545
Theoretical and experimental studies on (3)J(C2H6eq) NMR spin-spin coupling constants in both the 2-X-4-t-butyl-cyclohexanone (X = H, CH(3), F, Cl, and Br) and in their alcohol derivatives series are reported. Results thus found are rationalized in terms of the transmission of the Fermi contact contribution to such couplings. To this end, dependencies of (3)J(C2H6eq) couplings versus the C(2)-C(1)-C(6) angle are compared in both series for equatorial and axial X orientations. The main trend is described in terms of the rear lobes interaction. Besides, for X = halogen atom in equatorial orientation a rather strong interaction between oxygen and halogen lone pairs is observed, and its influence on (3)J(C2H6eq) couplings is discussed and rationalized in terms of different Fermi contact transmission pathways. 相似文献
142.
143.
Carina R. Martins Lucas C. Ducati Cludio F. Tormena Roberto Rittner 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2009,72(5):1089-1096
The conformational isomerism of 2-chlorocyclopentanone and 2-bromocyclopentanone has been determined through the solvent dependence of the 1H NMR 3JHH coupling constants, theoretical calculations and infrared data, using the solvation theory for the treatment of NMR data. In 2-chlorocyclopentanone, the energy difference (EΨ-e − EΨ-a), in the isolated molecule at B3LYP level of theory, between the pseudo-equatorial (Ψ-e) and pseudo-axial (Ψ-a) conformers is 0.42 kcal mol−1, which decreases in CCl4 and in acetonitrile solutions, in good agreement with infrared data (νCO), despite the uncertainties of the latter method. The conformational equilibrium for 2-bromocyclopentanone is also between the Ψ-e and Ψ-a conformations, with an energy difference (EΨ-e − EΨ-a), in the isolated molecule at B3LYP level of theory, is 0.85 kcal mol−1 which decreases in CCl4 and in acetonitrile solutions, also in good agreement with infrared data. 相似文献
144.
Production of Cellulolytic Enzymes by <Emphasis Type="Italic">Aspergillus phoenicis</Emphasis> in Grape Waste using Response Surface Methodology 总被引:1,自引:0,他引:1
Dedavid e Silva LA Lopes FC Silveira ST Brandelli A 《Applied biochemistry and biotechnology》2009,152(2):295-305
The production of cellulolytic enzymes by the fungus Aspergillus phoenicis was investigated. Grape waste from the winemaking industry was chosen as the growth substrate among several agro-industrial
byproducts. A 2 × 2 central composite design was performed, utilizing the amount of grape waste and peptone as independent
variables. The fungus was cultivated in submerged fermentation at 30 °C and 120 rpm for 120 h, and the activities of total
cellulases, endoglucanases, and β-glucosidases were measured. Total cellulases were positively influenced by the linear increase
of peptone concentration and decrease at axial concentrations of grape waste and peptone. Maximum activity of endoglucanase
was observed by a linear increase of both grape waste and peptone concentrations. Concentrations of grape waste between 5
and 15 g/L had a positive effect on the production of β-glucosidase; peptone had no significant effects. The optimum production
of the three cellulolytic activities was observed at values near the central point. A. phoenicis has the potential for the production of cellulases utilizing grape waste as the growth substrate. 相似文献
145.
利用高里德堡态氢原子飞行时间探测技术, 在224~248 nm激发波长研究了间-吡啶基紫外光化学中的氢原子解离通道的动力学过程.氢原子光解碎片产率谱显示在234 nm附近有较宽的吸收.产物的平动能释放较小;在224~248 nm激发波长区间平均〈 fT〉是0.12~0.19.产物的平动能分布显示产物是H+HC≡C-CH=CH-C≡N,H 3,4-吡啶和H 2,3-吡啶,以H HC≡C-CH=CH-C≡N为主要的氢原子生成通道.氢原子碎片具有各向同性的角度分布.研究结果表明,在紫外电子态激发以后,间-吡啶基经过内转换到电子基态,再经由单分子解离到H HC≡C-CH=CH-C≡N,H 3,4-吡啶和H 2,3-吡啶产物.间-吡啶基的紫外光解机理和以前报道过的邻-吡啶基的紫外光解机理相似. 相似文献
146.
Hery Mitsutake Eloiza Guimares Helieder C. Freitas Lucas C. Gontijo Douglas Q. Santos Waldomiro Borges Neto 《Journal of Chemometrics》2015,29(7):411-419
In this work, mid‐infrared spectroscopy and multivariate control charts based on net analyte signal were applied for quality control of B5 blends of biodiesel/diesel (5% biodiesel/95% diesel). Control charts were constructed using instrumental signal decomposition, generating three charts: the net analyte signal chart for monitoring the analyte of interest (methyl soybean biodiesel); the interference chart, which corresponds to the contribution of all other compounds in the diesel sample (diesel); and the residual chart, which corresponds to non‐systematic variations. Statistical limits were established for each developed chart, using samples inside quality specifications (normal operation conditions). To validate multivariate control charts, new samples were analyzed. The new samples represented samples in‐control and samples out‐of‐control in relation to the content of biodiesel, adulterated biodiesel with severe vegetable oils and adulterated diesel with residual automotive lubricant oil, kerosene, and gasoline. The results obtained show an excellent distinction between the samples inside and out of the quality specifications, with 91% and 100% correctly classified, respectively, which demonstrates that the methodology developed is a viable alternative for quality monitoring of this type of fuel. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
147.
Gram‐Scale Enantioselective Formal Synthesis of Morphine through an ortho–para Oxidative Phenolic Coupling Strategy 下载免费PDF全文
Dr. Matthieu Tissot Dr. Robert J. Phipps Dr. Catherine Lucas Dr. Rafael M. Leon Dr. Robert D. M. Pace Dr. Tifelle Ngouansavanh Prof. Matthew J. Gaunt 《Angewandte Chemie (International ed. in English)》2014,53(49):13498-13501
A gram‐scale catalytic enantioselective formal synthesis of morphine is described. The key steps of the synthesis involve an ortho–para oxidative phenolic coupling and a highly diastereoselective “desymmetrization” of the resulting cyclohexadienone that generates three of the four morphinan ring junction stereocenters in one step. The stereochemistry is controlled from a single carbinol center installed through catalytic enantioselective hydrogenation. These transformations enabled the preparation of large quantities of key intermediates and could support a practical and scalable synthesis of morphine and related derivatives. 相似文献
148.
Michael T. Crimmins Prof. J. Michael Ellis Dr. Kyle A. Emmitte Dr. Pamela A. Haile Dr. Patrick J. McDougall Dr. Jonathan D. Parrish Dr. J. Lucas Zuccarello Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(36):9223-9234
Brevetoxin A is a decacyclic ladder toxin that possesses 5‐, 6‐, 7‐, 8‐, and 9‐membered oxacycles, as well as 22 tetrahedral stereocenters. Herein, we describe a unified approach to the B, E, G, and J rings based upon a ring‐closing metathesis strategy from the corresponding dienes. The enolate technologies developed in our laboratory allowed access to the precursor acyclic dienes for the B, E, and G medium‐ring ethers. The strategies developed for the syntheses of these four monocycles ultimately provided multigram quantities of each of the rings, supporting our efforts toward the completion of a convergent synthesis of brevetoxin A. 相似文献
149.
Jeferson G. da Silva Lucas S. Azzolini Solange M.S.V. Wardell James L. Wardell Heloisa Beraldo 《Polyhedron》2009
Reaction of N(4)-phenyl-2-formylpyridine thiosemicarbazone (H2Fo4Ph), N(4)-phenyl-2-acetylpyridine thiosemicarbazone (H2Ac4Ph) and N(4)-phenyl-2-benzoylpyridine thiosemicarbazone (H2Bz4Ph) with gallium nitrate gave [Ga(H2Fo4Ph)2](NO3)3 (1), [Ga(2Ac4Ph)2]NO3 (2) and [Ga(2Bz4Ph)2]NO3 (3). In all complexes coordination of the thiosemicarbazone via the Npy–N–S chelating system occurs. In 1 the thiosemicarbazone acts as a neutral ligand while in 2 and 3 the ligand is anionic. Upon slow diffusion of 2 in DMSO [Ga(2Ac4Ph)2]NO3·DMSO (2a) was formed. The crystal structure of 2a was determined. Upon coordination the antibacterial activity of both gallium and thiosemicarbazones against Pseudomonas aeruginosa significantly increases. 相似文献