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排序方式: 共有600条查询结果,搜索用时 31 毫秒
1.
A new hydrophilic copolymer having three kinds of hydroxyl groups, i.e. primary OH on -hydroxy allyl alcohol component, secondary OH on cyclic hemiacetal component and tertiary OH on -hydroxy acrylate component, was prepared by reducing a ‘polylactone’, poly(1-oxa-2-oxobutane-1,4:3,3-tetrayl), with NaBH4 in mixed solvents containing an alcohol. The structural analyses were performed by the solution 1H NMR and the solid state 13C NMR spectroscopies of the reduced samples. The composition of the three components turned out to be variable to the alcohol species used for the mixed solvent. 相似文献
2.
The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (1,3CH2), the additions of carbenes (1,3CH2 and1,3CF2) as well as amino radicals (2NH2 and2NF2) toward ethylene, and the hydrogen abstractions by methylenes (1,3CH2), nitrene (3NH), and hydroxyl radical (2OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions. 相似文献
3.
A. C. Bhasikuttan A. V. Sapre L. V. Shastri 《Journal of photochemistry and photobiology. A, Chemistry》1995,90(2-3):177-182
The reactions of two triphenyl methane (TPM) dyes—crystal violet (CV+) and malachite green (MG+)—with N3• and OH• radicals were studied by pulse radiolytic kinetic spectrophotometry. The rate constants for the reaction of the cationic dyes (D+) with N3• are (9.0±0.6)×109 and (3.0±0.2)×109 dm3 mol−1 s−1 respectively and those for the reaction with OH• are obtained as (8.0±0.6)×109 and (1.1±0.1)×109 dm3 mol−1 s−1 respectively. The transient spectra resulting from the oxidation of the dyes were characterized. The time-resolved spectra indicate that the reaction with OH• radicals initially generates an adduct which subsequently dissociates to form the radical dication D•2+. The D•2+ species decay by further reaction with the parent dye. 相似文献
4.
The adsorption of hydroxyl on Pt(1 1 1) single crystal electrodes from aqueous acidic solutions is carefully reinvestigated. The effect of small additions (10−8–10−5 M) of chloride and bisulphate anions on the OH adsorption region in perchloric acid solution has been studied. Two regions can be differentiated in the voltammetric profile, that behave differently after the addition of the foreign anion. The initial broad adsorption process is unaffected until the highest concentration is attained. However, the sharper peak at higher potentials is affected even at the lower anion concentration. Since mass transport limitations allow to discard the anion adsorption as the main process giving this peak, we propose that the two processes are due to the dissociative adsorption of two different kinds of water, that are affected by the anion in a different way. From this idea, a new model, based on the Frumkin adsorption isotherm, is proposed, which gives an excellent fit of the experimental results. 相似文献
5.
Xiao Zhen Liu Fei Wang Dong Dong Luo Xing Guo Guang Qing Lei 《中国化学快报》2007,18(11):1339-1341
The hydroxyl group of carbocyclic nucleosides was inversed when the compounds were treated with Me_3SiCl,KCN and a catalytic amount of NaI in DMF/CH_3CN. 相似文献
6.
A. G. Taranto J. W. de M. Carneiro F. G. de Oliveira M. T. de Araujo C. R. Correa 《Journal of Molecular Structure》2002,580(1-3):207-215
Artemisinin is a sesquiterpene lactone with an endoperoxide function that is essential for its antimalarial activity. Endoperoxides are supposed to act on heme leading to the reduction of the peroxide bond and production of radicals, which can be responsible for killing the parasite. The geometries of artemisinin, radical anions and neutral species generated by rearrangement after reduction of the peroxide bond were fully optimized with the AM1 and PM3 semi-empirical methods, in order to characterize the intermediates formed during the process. Among the radicals calculated along the pathway for reductive decomposition of artemisinin, the secondary radical centered on carbon C4 has the highest stability when compared to other radicals that can be achieved either by hydrogen migration to the original O-centered radical or by homolytic break of C–C bond. This suggests that the C4-centered radical may be the species responsible for killing the parasite, as has been indicated previously in experimental studies. 相似文献
7.
Klaus Rakus Sergej P. Verevkin Hans-Dieter Beckhaus Christoph Rüchardt 《欧洲无机化学杂志》1994,127(11):2225-2234
The thermolysis reactions of the tricyanomethyl compounds 10a-c were studied in solution. 2,2-Dicyano-3-methyl-3-phenylbutyronitrile ( 10a ) and 2,2-dicyano-3-methyl-3-(4-nitrophenyl)butyronitrile ( 10b ) decomposed heterolytically into carbenium ions and (CN)3C− anions, while 9-methyl-9-(tricyanomethyl)fluorene ( 10c ) underwent about 11% homolytic C-C bond cleavage into 9-methyl-9-fluorenyl- and tricyanomethyl radicals. The rates of the homolysis were determined by a radical scavenger procedure under conditions of pseudozero order kinetics. From the temperature effect on the rate constants the activation parameters were determined [ΔH ( 10c ) = 155· 2 kJ mol−1, ΔS ( 10c ) = 58· 5 J mol−1 K−1]. Standard enthalpies of formation ΔH (g) were determined for 2,2-dicyanopropionitrile ( 2 ) (422.45 kJ mol−1), 2,2-dicyanohexanenitrile ( 3 ) (349.74 kJ mol−1), 2,2-dicyano-3-phenylpropionitrile ( 4 ) (540.75 kJ mol−1), 2-butyl-2-methylhexanentrile ( 5 ) (-133.20 kJ mol−1), 2,2-dimethylpentanenitrile ( 6 ) (-45.78 kJ mol−1), and 2-methylbutyronitrile ( 7 ) (2.44 kJ mol−1) from the enthalpies of combustion and enthalpies of sublimation/vaporization. From these data and known Δ (g) values for alkanenitriles and -dinitriles, thermochemical increments for ΔH (g) were derived for alkyl groups with one, two, or three cyano groups attached. The comparison of these increments with those of alkanes reveals a strong geminal destabilization, which is interpreted by dipolar repulsions between the cyano groups. - From ΔH (g) of 10c and ΔH of its homolytic decomposition the radical stabilization enthalpy for the tricyanomethyl radical 1 RSE ( 1 ) = -18 kJ mol−1 was determined. Thus, 1 is destabilized, in comparison with the RSEs of tertiary α-cyanalkyl (23 kJ mol−1) and α,α-dicyanoalkyl (27 kJ mol−1) radicals, which were recalculated from bond homolysis measurements[4] and the new thermochemical data. This change of RSE on increasing the number of α-cyano groups is discussed as the result of the additive contributions by resonance stabilization and increasing destabilization by dipolar repulsion. The amount of the dipolar energies was estimated by molecular mechanics (MM2). 相似文献
8.
《中国化学快报》2021,32(9):2819-2822
Electrochemical oxidation of water to produce highly reactive hydroxyl radicals (OH) is the dominant factor that accounts for the organic compounds removal efficiency in water treatment. As an emerging carbon-based material, the investigation of electrocatalytic of water to produce OH on Graphdiyne (GDY) anode is firstly evaluated by using first-principles calculations. The theoretical calculation results demonstrated that the GDY anode owns a large oxygen evolution reaction (OER) overpotential (ηOER = 1.95 V) and a weak sorptive ability towards oxygen evolution intermediates (HO*, not OH). The high Gibbs energy change of HO* (3.18 eV) on GDY anode makes the selective production of OH (ΔG = 2.4 eV) thermodynamically favorable. The investigation comprises the understanding of the relationship between OER to electrochemical advanced oxidation process (EAOP), and give a proof-of-concept of finding the novel and robust environmental EAOP anode at quantum chemistry level. 相似文献
9.
CVD法不同条件下制备的多壁碳纳米管的Fenton氧化改性 总被引:2,自引:0,他引:2
碳纳米管经焙烧和稀硝酸纯化处理后,在相同的实验条件下,采用Fenton试剂产生的·OH分别对CVD法合成的两种制备条件不同的多壁碳纳米管进行氧化改性处理。红外光谱(FT IR)表明,改性后的两种碳管结构中都引入了羟基、羰基和羧基等含氧官能团。此外,由于制备条件不同,导致它们的石墨化程度、缺陷含量和抗氧化能力等性质也不同,因此CVD法制备条件能够对碳管Fenton氧化改性结果产生重要影响。机理分析表明,这些含氧官能团可以看作是具有强亲电性和强氧化性的·OH对碳管上缺陷位置和不饱和键进行攻击的结果。 相似文献
10.
The allomerization of chlorophyll b in methanol produced 132(S)-hydroxy-10-methoxychlorophyll b in a yield of ca. 8%. The formation of this allomer was totally unexpected, as 10-substituted chlorophylls have never been reported before. The structure of the new chlorophyll b derivative was determined on the basis of UV/Vis, FAB-MS, 1H NMR and 2D ROESY NMR spectra. This letter focuses on the NMR analysis. 相似文献