全文获取类型
收费全文 | 189篇 |
免费 | 64篇 |
国内免费 | 23篇 |
专业分类
化学 | 265篇 |
综合类 | 4篇 |
数学 | 3篇 |
物理学 | 4篇 |
出版年
2023年 | 5篇 |
2022年 | 4篇 |
2021年 | 13篇 |
2020年 | 17篇 |
2019年 | 10篇 |
2018年 | 16篇 |
2017年 | 11篇 |
2016年 | 13篇 |
2015年 | 16篇 |
2014年 | 22篇 |
2013年 | 18篇 |
2012年 | 16篇 |
2011年 | 10篇 |
2010年 | 3篇 |
2009年 | 5篇 |
2008年 | 13篇 |
2007年 | 11篇 |
2006年 | 7篇 |
2005年 | 8篇 |
2004年 | 4篇 |
2003年 | 6篇 |
2002年 | 3篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1997年 | 16篇 |
1996年 | 6篇 |
1995年 | 10篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1989年 | 1篇 |
1985年 | 1篇 |
1982年 | 2篇 |
排序方式: 共有276条查询结果,搜索用时 375 毫秒
1.
In this research article, we describe the synthesis and characterization of mononuclear and dinuclear Cu complexes bound by a family of tridentate redox-active ligands with tunable H-bonding donors. The mononuclear Cu-anion complexes were oxidized to the corresponding “high-valent” intermediates by oxidation of the redox-active ligand. These species were capable of oxidizing phenols with weak O−H bonds via H-atom abstraction. Thermodynamic analysis of the H-atom abstractions, which included reduction potential measurements, pKa determination and kinetic studies, revealed that modification of the anion coordinated to the Cu and changes in the H-bonding donor did not lead to major differences in the reactivity of the “high-valent” CuY complexes (Y: hydroxide, phenolate and acetate), which indicated that the tridentate ligand scaffold acts as the H+ and e− acceptor. 相似文献
2.
3.
4.
Uncoupled metabolism stimulated by chemical uncoupler and oxic-settling-anaerobic combined process to reduce excess sludge production 总被引:1,自引:0,他引:1
The effects of three uncoupled metabolic systems (conventional activated sludge process with the addition of 3,3′,4′,5-tetrachlorosalicylanilide
[TCS], oxic-settling-anaerobic [OSA] process modified by insertion of a sludge-holding tank in the sludge return line, and
TCS and OSA combined process) on reducing excess sludge production were studied. Compared with the control conventional activated
sludge process, the most effective system was the combined process, which could reduce excess sludge production by 46.90%.
The 180-d operation results confirmed that TCS is an effective chemical uncoupler in reducing the sludge yield but that it
had an adverse effect on substrate removal capability, effluent nitrogen concentration, and sludge settleability. The OSA
process decreased excess sludge production by only 26% but had less adverse effect on effluent quality and could improve sludge
settleability. The effluent total phosphorous concentration of the three systems was slightly lower than of the control unit.
Microbial populations were monitored by both microscopic and molecular biologic analysis method (polymerase chain reaction
[PCR]-denaturing gradient gel electrophoresis [DGGE]). The presence of TCS caused metazoans to disappear and decreased the
number and activity of protozoa. PCR amplification of 16S rRNA and sequent DGGE analysis found a shift in the diversity of
the predominant species. The results imply that OSA combined with the chemical uncoupler process may effectively reduce excess
sludge yield and not affect process performance significantly. 相似文献
5.
Starting from the natural neo-clerodane diterpenoid teubotrin (1) several neo-clerodane derivatives (3-7,9-11) have been obtained. The naturally occurring diterpenoid teuscordinon (12) has also been synthesized from teubotrin (1), showing thereby how some of these transformations can be useful for the synthesis of other natural neo-clerodane diterpenes. The latter are of interest due to their activity as insect antifeedants and other important biological properties. 相似文献
6.
Jack H. Lunsford 《Angewandte Chemie (International ed. in English)》1995,34(9):970-980
One of the great challenges in the field of heterogeneous catalysis is the conversion of methane to more useful chemicals and fuels. A chemical of particular importance is ethene, which can be obtained by the oxidative coupling of methane. In this reaction CH4 is first oxidatively converted into C2H6, and then into C2H4. The fundamental aspects of the problem involve both a heterogeneous component, which includes the activation of CH4 on a metal oxide surface, and a homogeneous gas-phase component, which includes free-radical chemistry. Ethane is produced mainly by the coupling of the surface-generated CH radicals in the gas phase. The yield of C2H4 and C2H6 is limited by secondary reactions of CH radicals with the surface and by the further oxidation of C2H4, both on the catalyst surface and in the gas phase. Currently, the best catalysts provide 20% CH4 conversion with 80% combined C2H4 and C2H6 selectivity in a single pass through the reactor. Less is known about the nature of the active centers than about the reaction mechanism; however, reactive oxygen ions are apparently required for the activation of CH4 on certain catalysts. There is spectroscopic evidence for surface O? or O ions. In addition to the oxidative coupling of CH4, cross-coupling reactions, such as between methane and toluene to produce styrene, have been investigated. Many of the same catalysts are effective, and the cross-coupling reaction also appears to involve surface-generated radicals. Although a technological process has not been developed, extensive research has resulted in a reasonable understanding of the elementary reactions that occur during the oxidative coupling of methane. 相似文献
7.
K L Madhok 《Journal of Chemical Sciences》1982,91(2):165-171
Nicke(II) chloride reacts with N,N′-diarylformamidino-N′-arylcarbamides thiocarbamides and N-benzoylformamidino-N′-arylcarbamides,
thiocarbamides forming complexes of the general formula [Ni (Ar.NH.C (NH) NH.C.X. NH.R)2] Cl2 (R=phenyl, orthotolyl and paratolyl; Ar=benzoyl; X=S,O) and [Ni (R.NH.C.X.NH.C (N.Ph.).NH.Ph.)2] Cl2 (R=phenyl, orthotolyl, paratolyl; Ph=phenyl; X=S, O). The ligands when oxidized with iodine undergo ring closure to related
3,5-diarylamino 1,2,4-thiadiazolidines and 3,5-diarylamino-1,2,4-diazolidines, while the complexes are not susceptible to
oxidation. This confirms the binding in complexes is through sulphur and oxygen of the ligands. 相似文献
8.
This work describes the preparation of a new modified electrode containing a ruthenium complex (cis-aquadimethylbipyridyltriphenylphosphineruthenium II), bonded to a stable polyphenol film. This modified electrode promotes the fast electrocatalytic oxidation of safrol (5-allyl-benzo[1,3]dioxole) and isosafrol (5-propenyl-benzo[1,3]dioxole), giving two interesting products benzo[1,3]dioxole-5-carbaldehyde (piperonal) and 3-benzo[1,3]dioxol-5-yl-propenal respectively, with good yields. The electrode preparation can be carried out at a potential range which does not interfere on the anchored electroactive ruthenium complex, but it allows for the phenol oxidation to occur and therefore polymerize forming the polyphenol film. The catalytic character of this modified electrode is showed by its high turnover numbers. The procedure to isolate the products is very simple. 相似文献
9.
Iodinations of the ortho, meta, and para fluorous arenes (R(f8)CH(2)CH(2)CH(2))(2)C(6)H(4) (R(f8)=(CF(2))(7)CF(3)) with I(2)/H(5)IO(6) in AcOH/H(2)SO(4)/H(2)O give 3,4-(R(f8)CH(2)CH(2)CH(2))(2)C(6)H(3)I (5) and the analogous 2,4- (6) and 2,5- (7) isomers, respectively. Spectroscopic yields are >90 %, but 5 and 7 must be separated by chromatography from by-products (yields isolated: 70 %, 97 %, 61 %). Reaction of 1,3,5-(R(f8)CH(2)CH(2)CH(2))(3)C(6)H(3) with PhI(OAc)(2)/I(2) gives 2,4,6-(R(f8)CH(2)CH(2)CH(2))(3)C(6)H(2)I (8) on multigram scales in 97 % yield. The CF(3)C(6)F(11)/toluene partition coefficients of 5-8 (24 degrees C: 69.5:30.5 (5), 74.7:25.3 (6), 73.9:26.1 (7), 98.0:2.0 (8)) are lower than those of the precursors, but CF(3)C(6)F(11)/MeOH gives higher values (97.0:3.0 (5), 98.6:1.4 (6), 98.0:2.0 (7), >99.3:<0.3 (8)). Reactions of 5-8 with excess NaBO(3) in AcOH yield the corresponding ArI(OAc)(2) species 9-12 (9, 85 % as a 90:10 9/5 mixture; 10, 97 %; 11, 95 %; 12, 93 % as a 95:5 12/8 mixture). These rapidly oxidize 1,4-hydroquinones in MeOH. Subsequent additions of CF(3)C(6)F(11) give liquid biphase systems. Solvent removal from the CF(3)C(6)F(11) phases gives 5-8 in >99-98 % yields, and solvent removal from the MeOH phases gives the quinone products, normally in >99-95 % yields. The recovered compounds 5-8 are easily reoxidized to 9-12 and used again. 相似文献
10.
Isabel W. C. E. Arends Roger A. Sheldon Martin Wallau Ulf Schuchardt 《Angewandte Chemie (International ed. in English)》1997,36(11):1144-1163
Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O2, H2O2, and RO2H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted. 相似文献