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961.
The mechanism of the A2 hydrolysis of acetamide has been investigated theoretically using MNDO Method. Fully optimized geometries of all species at the stationary points corresponding to energy minima and energy maxima along the reaction coordinate are determined for the two reaction paths: the rate-determining nucleophilic attack of water on the carbonyl carbon (i) of the O-protonated tautomer and (ii) of the N-protonated form. Results show that the latter provides a lower energy path by 7.5 Kcal/Mol compared to the former.Tetrahedral species' found were not at the energy minima but at or near the saddle points. Optimizied structures and formal charges on heavy atoms showed that the bond interchange with the concurrent proton interchange takes place at the rate-determining step. The negative charge on N atom was found to increase in the rate-determining step relative to that of the ground state, the O-protonated acetamide, and hence substitution of electron withdrowing group on N is predicted to depress the activation energy in agreement with the experimental results. 相似文献
962.
Sastri CV Park MJ Ohta T Jackson TA Stubna A Seo MS Lee J Kim J Kitagawa T Münck E Que L Nam W 《Journal of the American Chemical Society》2005,127(36):12494-12495
Axial ligand substitution of a mononuclear nonheme oxoiron(IV) complex, [FeIV(O)(TMC)(NCCH3)]2+ (1) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), leads to the formation of new FeIV=O species with relatively intense electronic absorption features in the near-UV region. The presence of these near-UV features allowed us to make the first observation of Fe=O vibrations of S = 1 mononuclear nonheme oxoiron(IV) complexes by resonance Raman spectroscopy. We have also demonstrated that the reactivity of nonheme oxoiron(IV) intermediates is markedly influenced by the axial ligands. 相似文献
963.
[reaction: see text] Electroreductive tandem cyclization of 4-allyl-4-(2-bromoprop-2-en-1-yl)cyclohex-2-en-1-one to tricyclo[6.2.1.0(1,6)]undecan-4-one has been demonstrated. This protocol represents an attractive alternative to conventional tandem radical cyclization. 相似文献
964.
The physical and electrolytic properties of difluorinated dimethyl carbonate (DFDMC) synthesized using F2 gas (direct fluorination) were examined. The dielectric constant and viscosity of DFDMC are higher than those of monofluorinated dimethyl carbonate (MFDMC) and dimethyl carbonate (DMC). The oxidative decomposition voltage of DFDMC is higher than those of DMC and MFDMC. The specific conductivity in DFDMC solution is considerably lower than those in MFDMC and DMC solutions. The ethylene carbonate (EC)-DFDMC equimolar binary solution containing 1 mol dm−3 LiPF6 shows a moderate conductivity of 6.91 mS cm−1 at 25 °C. The lithium electrode cycling efficiency (charge-discharge coulombic cycling efficiency of lithium electrode) in EC-DFDMC equimolar binary solution containing 1 mol dm−3 LiPF6 is higher than 80%. The EC-DFDMC solution is a good electrolyte for rechargeable lithium batteries. 相似文献
965.
966.
Bagasse, corn husk, and switchgrass were pretreated with ammonia water to enhance enzymatic hydrolysis. The sample (2 g) was
mixed with 1–6 mL ammonia water (25–28% ammonia) and autoclaved at 120°C for 20 min. After treatment, the product was vacuum-dried
to remove ammonia gas. The dried solid could be used immediately in the enzymatic hydrolysis without washing. The enzymatic
hydrolysis was effectively improved with more than 0.5 and 1 mL ammonia water/g for corn husk and bagasse, respectively. In
bagasse, glucose, xylose, and xylobiose were the main products. The adsorption of CMCase and xylanase was related to the initial
rate of enzymatic hydrolysis. In corn husks, arabinoxylan extracted by pretreatment was substantially unhydrolyzed because
of the high ratio of arabinose to xylose (0.6). The carbohydrate yields from cellulose and hemicellulose were 72.9% and 82.4%
in bagasse, and 86.2% and 91.9% in corn husk, respectively. The ammonia/water pretreatment also benefited from switchgrass
(Miscanthus sinensis and Solidago altissima L.) hydrolysis. 相似文献
967.
Masahiro Tsunooka Toshihiro Ueda Makoto Tanaka Hiroaki Egawa 《Journal of polymer science. Part A, Polymer chemistry》1984,22(9):2217-2225
Photocationic crosslinking of a poly(2,3-epithiopropyl methacrylate) (PETMA) film containing 4-N,N-diethylaminobenzene diazonium tetrafluoroborate (DAC) was investigated. Very rapid photocrosslinking of PETMA was observed and the rate was greater than that of poly(glycidyl methacrylate) with DAC. Post-heating of the irradiated PETMA film resulted in a decrease of the insoluble fraction. This decrease was explained by scission of crosslinking points by the BF3. In the present conditions, more than 0.3 wt % of DAC was required to insolubilize the PETMA film. Photopolymerizations of propylene sulfide (PS) and 2,3-epithiopropyl pivalate (ETPP) in the presence of DAC were investigated. The polymerization of PS proceeded smoothly but addition of ethyl acetate to PS depressed the rate and the degree of polymerization. ETPP could not be polymerized but copolymerized with PS by this method. Addition of ETPP to PS depressed both the rate of the polymerization and the degree of polymerization. From these results, it is deduced that the photocrosslinking of a PETMA film is caused by a cationic polymerization of episulfide groups but the chain length is not large. 相似文献
968.
Huh KM Cho YW Chung H Kwon IC Jeong SY Ooya T Lee WK Sasaki S Yui N 《Macromolecular bioscience》2004,4(2):92-99
Supramolecular hydrogels have been prepared on the basis of polymer inclusion complex (PIC) formation between poly(ethylene glycol) (PEG)-modified chitosans and alpha-cyclodextrin (alpha-CD). A series of PEG-modified chitosans were synthesized by coupling reactions between chitosan and monocarboxylated PEG using water-soluble carbodiimide (EDC) as coupling agent. With simple mixing, the resultant supramolecular assembly of the polymers and alpha-CD molecules led to hydrogel formation in aqueous media. The supramolecular structure of the PIC hydrogels was confirmed by differential scanning calorimetry (DSC), X-ray diffraction, and (13)C cross-polarized/magic-angle spinning (CP/MAS) NMR characterization. The PEG side-chains on the chitosan backbones were found to form inclusion complexes (ICs) with alpha-CD molecules, resulting in the formation of channel-type crystalline micro-domains. The IC domains play an important role in holding together hydrated chitosan chains as physical junctions. The gelation property was affected by several factors including the PEG content in the polymers, the solution concentration, the mixing ratio of host and guest molecules, temperature, pH, etc. All the hydrogels in acidic conditions exhibited thermo-reversible gel-sol transitions under appropriate conditions of mixing ratio and PEG content in the mixing process. The transitions were induced by supramolecular association and dissociation. These supramolecular hydrogels were found to have phase-separated structures that consist of hydrophobic crystalline PIC domains, which were formed by the host-guest interaction between alpha-CD and PEG, and hydrated chitosan matrices below the pK(a).The formation of inclusion complexes between alpha-cyclodextrin and PEG-modified chitosan leads to the formation of hydrogels that can undergo thermo-reversible supramolecular dissociation. 相似文献
969.
970.