全文获取类型
收费全文 | 1022篇 |
免费 | 18篇 |
国内免费 | 2篇 |
专业分类
化学 | 807篇 |
晶体学 | 7篇 |
力学 | 9篇 |
数学 | 9篇 |
物理学 | 210篇 |
出版年
2023年 | 5篇 |
2021年 | 9篇 |
2020年 | 15篇 |
2019年 | 16篇 |
2017年 | 6篇 |
2016年 | 9篇 |
2015年 | 16篇 |
2014年 | 23篇 |
2013年 | 37篇 |
2012年 | 56篇 |
2011年 | 56篇 |
2010年 | 20篇 |
2009年 | 31篇 |
2008年 | 60篇 |
2007年 | 69篇 |
2006年 | 64篇 |
2005年 | 54篇 |
2004年 | 55篇 |
2003年 | 33篇 |
2002年 | 49篇 |
2001年 | 25篇 |
2000年 | 24篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1996年 | 11篇 |
1995年 | 9篇 |
1994年 | 10篇 |
1993年 | 11篇 |
1992年 | 13篇 |
1991年 | 14篇 |
1990年 | 12篇 |
1989年 | 10篇 |
1988年 | 15篇 |
1987年 | 20篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 13篇 |
1980年 | 7篇 |
1979年 | 11篇 |
1978年 | 14篇 |
1977年 | 9篇 |
1976年 | 11篇 |
1975年 | 4篇 |
1974年 | 9篇 |
1973年 | 11篇 |
1970年 | 4篇 |
1966年 | 4篇 |
排序方式: 共有1042条查询结果,搜索用时 15 毫秒
31.
Sulphoximides (Ia–Ie) were found to react with dimethyl diazomalonate (DDM) in the presence of a catalytic amount of Cu-salts affording the corresponding oxosulphonium ylides in moderate yields. The reaction did not proceed at all under irradiation of UV light. (?)-Methylphenyloxosulphonium bis(methoxycarbonyl)-methylide ((?)-IIb) was obtained from (+)-(S)-methylphenylsulphoximide ((+)-(S)-Ib) together with (?)-(S)-methyl phenyl sulphoxide ((?)-(S)-IIIb) by this reaction. Hydrolysis of (?)-IIb gave (+)-methylphenyloxosulphonium methoxycarbonylmethylide ((+)-IIf) which was converted to (?)-(S)-IIIb upon treatment with dibenzoylethylene. Stereochemical cycle starting from (+)-(S)-Ib to (?)-(S)-IIIb was established and the absolute configurations of both ylides, (?)-IIb and (+)-IIf were assigned as (R)-configuration. The stereochemical courses, namely from (+)-(S)-Ib or (?)-(S)-IIIb to (?)-(R)-IIb or (+)-(R)-IIf to (?)-(S)-IIIb were determined as retention processes. The optical purities of the oxosulphonium ylides obtained from both reactions, (+)-(S)-Ib→(?)-(R)-IIb and (?)-(S)-IIIb→(?)-(R)-IIb, were almost equal. These results indicate that the mechanism of the reaction of sulphoximides with carbenes (or carbenoids) involves the initial formation of the sulphoxides which react subsequently with carbenes to afford the final products. 相似文献
32.
Vibrational spectra reveal that ice VII′ transforms to low-density amorphous ice (LDA) at low temperature on release of pressure to ambient pressure and low temperature. The measurements were obtained using in situ Raman spectroscopy of samples of ice VII′ as a function of pressure at 135 K. The observation of this direct decompression-induced VII′-LDA transition complements the previously observed pressure-induced reversible transition between LDA and high-density amorphous ice (HDA) at 120–140 K and the temperature-induced amorphization of metastable ice VII and ice VIII at 0.1 MPa. 相似文献
33.
Angle-resolved photoelectron spectra were measured for a single-domain monolayer film of naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA) prepared on a cleaved GeS(0 0 1) surface using synchrotron radiation. The observed photoelectron angular distributions were analyzed by a calculation using the single-scattering approximation combined with molecular orbital calculation. With the help of the low-energy electron diffraction pattern, the structure of the NTCDA monolayer on GeS(0 0 1) was estimated quantitatively. 相似文献
34.
Bowl‐shaped chiral homotriazacalixarenes were prepared by the cyclization reactions of chiral triamines with three equimolar amounts of bis(chloromethyl) phenols or bis(chloromethyl) phenol‐formaldehyde dimers in moderate yields. The corresponding acyclic phenol‐formaldehyde oligomers were also synthesized. The structural analysis of the macrocycles by nmr and circular dichroism spectra imply the existence of chiral transmission from the point chirality of the cysteine bridge to the cyclophane moiety. Their cyclic and acyclic compounds have a π‐base cavity large enough to include the ammonium ion. 相似文献
35.
The difference in the electron correlation between H- and other two-electron atoms is clarified by the introduction of the r12 term in the wave function. By using the expansion of r12, a certain modification of the usual electron correlation factor 1 + Cr12 is introduced and its effectiveness is examined. Calculations are carried out for the ground state and the three lowest excited states (23S, 23P and 21P). The peculiar electron correlation in the ground state of H? is shown by looking at the Coulomb hole for closed- and open-shelf models in comparison with those for other two-electron atoms. 相似文献
36.
Comparison of PAMAM-Au and PPI-Au nanocomposites and their catalytic activity for reduction of 4-nitrophenol 总被引:4,自引:0,他引:4
Dendrimer-Au nanocomposites are prepared in aqueous solutions using poly(amidoammine)dendrimers (PAMAM) (generation 2, 3, and 5) and poly(propyleneimine)dendrimers (PPI)(generation 2, 3, and 4) by wet chemical NaBH(4) method. The Au nanoparticles thus obtained are 2-4 nm in diameter for both dendrimers and no generation dependence on the particle size is observed, whereas the generations of the dendrimers are increased as stabilization of Au-nanoparticles is achieved with lower dendrimer concentrations. Studies of the reduction reaction of 4-nitrophenol using these nanocomposites show that the rate constants for the PAMAM dendrimers (generations 2 and 3) are higher than those for the PPI dendrimers (generations 2 and 3), while a distinct difference in the rate constants is not seen for the PAMAM dendrimer (generation 5) or the PPI dendrimer (generation 4). In addition, the rate constants for the reduction of 4-nitrophenol involving all the dendrimers decrease with increases in dendrimer concentrations. 相似文献
37.
38.
S Ikegawa N Hirabayashi T Yoshimura M Tohma M Maeda A Tsuji 《Journal of chromatography. A》1992,577(2):229-238
A qualitative and quantitative analysis of the conjugated 1 beta- and 6 alpha-hydroxy bile acids, including common bile acids, in human urine using high-performance liquid chromatography with chemiluminescence detection is described. After extraction of urine with C18 silica cartridges, the bile acids were separated into non-conjugated, glycine, taurine and sulphate fractions by ion-exchange chromatography on a lipophilic gel. Solvolysis of the sulphate was carried out by treatment with trifluoroethanol in acetone containing hydrochloric acid, and the liberated amino acid conjugates were fractionated again. The individual bile acids were separated on a reversed-phase C18 column (Bile Pak II), with detection by an immobilized 3 alpha-hydroxysteroid dehydrogenase enzyme reactor and chemiluminescence reaction of the generated NADH using 1-methoxy-5-methylphenazinium methylsulphate-isoluminol-microperoxidase system. The assay method showed the detection limits ranging from 8 to 250 pmol for the bile acids tested. Analysis of urine samples obtained from newborns, non-pregnant women and women in late pregnancy showed a large difference in bile acid composition and conjugation mode, suggesting that bile acid metabolism is different during fetal and neonatal periods. 相似文献
39.
Nakanishi I Miyazaki K Shimada T Iizuka Y Inami K Mochizuki M Urano S Okuda H Ozawa T Fukuzumi S Ikota N Fukuhara K 《Organic & biomolecular chemistry》2003,1(22):4085-4088
Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger. 相似文献
40.
Yuichi Yoshimura Tetsuya Kuze Fumiko Komiya Hiromichi Tanaka Kohei Yamada Nobuaki Kaneko 《Tetrahedron letters》2006,47(4):591-594
A practical synthesis of 4′-thioribonucleosides starting from inexpensive l-arabinose is described. 1,4-Anhydro-2,3-O-isopropylidene-4-thioribitol, which was prepared by using a novel reductive ring-contraction reaction, was converted to the 5-O-silylated sulfoxides. The Pummerer-type thioglycosylation of the sulfoxides gave the 4′-thioribonucleosides stereoselectively. 相似文献