全文获取类型
收费全文 | 4017篇 |
免费 | 112篇 |
国内免费 | 23篇 |
专业分类
化学 | 2728篇 |
晶体学 | 33篇 |
力学 | 77篇 |
数学 | 647篇 |
物理学 | 667篇 |
出版年
2023年 | 22篇 |
2021年 | 26篇 |
2020年 | 44篇 |
2019年 | 53篇 |
2018年 | 44篇 |
2017年 | 33篇 |
2016年 | 77篇 |
2015年 | 63篇 |
2014年 | 103篇 |
2013年 | 209篇 |
2012年 | 167篇 |
2011年 | 205篇 |
2010年 | 136篇 |
2009年 | 124篇 |
2008年 | 182篇 |
2007年 | 169篇 |
2006年 | 162篇 |
2005年 | 162篇 |
2004年 | 131篇 |
2003年 | 124篇 |
2002年 | 127篇 |
2001年 | 71篇 |
2000年 | 85篇 |
1999年 | 53篇 |
1998年 | 59篇 |
1997年 | 59篇 |
1996年 | 68篇 |
1995年 | 66篇 |
1994年 | 56篇 |
1993年 | 61篇 |
1992年 | 60篇 |
1991年 | 73篇 |
1990年 | 43篇 |
1989年 | 57篇 |
1988年 | 58篇 |
1987年 | 49篇 |
1986年 | 59篇 |
1985年 | 60篇 |
1984年 | 65篇 |
1983年 | 49篇 |
1982年 | 47篇 |
1981年 | 51篇 |
1980年 | 66篇 |
1979年 | 48篇 |
1978年 | 47篇 |
1977年 | 45篇 |
1976年 | 37篇 |
1975年 | 38篇 |
1974年 | 32篇 |
1973年 | 23篇 |
排序方式: 共有4152条查询结果,搜索用时 187 毫秒
41.
Brunner H Cattey H Meier W Mugnier Y Stückl AC Wachter J Wanninger R Zabel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3796-3802
The reaction of the cluster salts [Cp(2*) Nb(CO)(2)](n)[Co(11)Te(7)(CO)(10)] (Cp*=C(5)Me(5); n=1, 2) with excess PMe(2)Ph gave the neutral, dark brown clusters [Co(11)Te(7)(CO)(6)(PMe(2)Ph)(4)] (5) and [Co(11)Te(7)(CO)(5)(PMe(2)Ph)(5)] (6) with 147 metal valence electrons. The new compounds were characterized by IR spectroscopy, elemental analyses, and mass spectrometry. The molecular structure of 6 was determined by X-ray crystallography. Like its precursor anion, it consists of a pentagonal-prismatic [Co(11)Te(7)] core, but with a ligand sphere composed of five CO and five PMe(2)Ph ligands. Detailed electrochemical studies of both reactions reveal that a stepwise substitution of CO ligands in the initial cluster anions takes place leading to intermediate [Co(11)Te(7)(CO)(10-m)(PMe(2)Ph)(m)](n-) ions (m=1-5; n=1, 2). Each of these intermediates is distinguished by at least one oxidation and two reduction waves, giving rise to a total of 21 redox couples and 27 electroactive species. The electron sponge character of the new compounds is particularly pronounced in 5, which exhibits charges n between +1 and -4 corresponding to metal valence electron counts of between 146 and 151. 相似文献
42.
Quantitative measurement of both bulk and localized oxygen concentrations is of importance in the study of oxidation kinetics.
We describe the combined application of two nuclear techniques, fast neutron activation analysis and (d, p) nuclear microprobe,
to the determination of oxygen concentrations and surface profiles for steam-oxidized Zircaloy-4 cladding specimens. Results
of measurements using these techniques are presented.
Work partially supported by Electric Power Research Institute Contract T.S.A. No. 20. 相似文献
43.
Conditions influencing the extent of P-C(aryl) vs P-C(alkyl) bond cleavage in the reaction of Ph(2)P(CH(2))(2)PPh(2) with lithium in THF have been investigated. The results complement and elucidate earlier work; they indicate that the mechanism of P-C bond cleavage in tertiary phosphines of this type involves a thermodynamic equilibrium between P-C(aryl) and P-C(alkyl) cleaved radicals and anions, followed by reaction and stabilization of these as lithium salts. The addition of water to the reaction mixture causes a reestablishment of the cleavage equilibrium prior to the formation of the secondary phosphines. A mechanism involving competitive release of leaving groups as the thermodynamically most stable anion or radical has been proposed. The preparation of (R, R)-(+/-)/(R, S)-PhP(H)(CH(2))(2)P(H)Ph by this route has been optimized. 相似文献
44.
Wadysaw Charmas Wawrzyniec Podkocielny Joachim Brunn 《Journal of polymer science. Part A, Polymer chemistry》1989,27(7):2397-2415
The process of oxirane ring opening of thioether glycidyl resins under various temperatures has been described. Reaction rate constants (k) and the activaton parameters (Eα, ΔH*, ΔS*) for epoxy group loss of 1,2-epoxy-3-(phenylthio)propane, 1,2-epoxy-3-(p-tolythio)propane, and 1,2-epoxy-3-(p-chloro-phenylthio)propane using classical kinetic methods were determined. The reaction products were separated and analyzed by means of chromatography and the structure of the compounds was determined by means of the spectral analyses: IR, 1H-NMR, and 13C-NMR 相似文献
45.
Joachim Heidberg Elisabeth Kampshoff Helmut Stein Helmut Weiss Michael Warskulat 《Mikrochimica acta》1988,94(1-6):105-108
Sample/spectrum relationships are investigated using both a low resolution rapid-scanning NIR monochromator and a Fourier transform instrument capable of high resolution and are evaluated in terms of whether or not the resolution of the instrument is sufficient for measuring the natural bandwidths corresponding to the sample. Based on the sample/spectrum relationship a criterion is developed which must be followed in order to apply either derivative spectroscopy or deconvolution to enhance the resolution of overlapped bands without generating spectral artifacts. 相似文献
46.
Extraction of proteins from plant tissues for two-dimensional electrophoresis analysis 总被引:17,自引:0,他引:17
To increase the number of proteins detectable by two-dimensional electrophoresis (2-DE) in plants, we present a new procedure for extracting total proteins from plant tissue. This method avoids any loss of proteins in the course of sample preparation and results in two different fractions, one comprising mainly the cytoplasmatic proteins, the other one containing predominantly structure bond proteins. 2-DE patterns obtained from these two fractions show that the total number of different protein spots detected exceeds the degree of resolution commonly reported for plant proteins threefold. 相似文献
47.
Eberhard Bothe Helmut Gorner Joachim Opitz Dietrich Schulte-Frohlinde Aslam Siddiqi Malgorzata Wala 《Photochemistry and photobiology》1990,52(5):949-959
Double-stranded (ds) calf thymus DNA (0.4 mM), excited by 20 ns laser pulses at 248 nm, was studied in deoxygenated aqueous solution at room temperature and pH 6.7 in the presence of a sodium salt (10 mM). The quantum yields for the formation of hydrated electrons (phi c-), single-strand breaks (phi ssb) and double-strand breaks (phi dsb) were determined for various laser pulse intensities (IL). phi c- and phi ssb increase linearly with increasing IL; however, phi ssb has a tendency to reach saturation at high IL (greater than 5 X 10(6) Wcm-2). The ratio phi ssb/phi c-, representing the number of ssb per radical cation, is about 0.08 at IL less than or equal to 5 X 10(6) Wcm-2. For comparison, the number of ssb per OH radical reacting with dsDNA is 0.22. On going from argon to N2O saturation, phi ssb and phi dsb become larger by factors of approximately 5 and 10-15, respectively. This enhancement is produced by attack on DNA bases by OH radicals generated by N2O-scavenging of the photoelectrons. While phi ssb is essentially independent of the dose (Etot), phi dsb depends linearly on Etot in both argon- and N2O-saturated solutions. The linear dependence of phi dsb implies a square dependence of the number of dsb on Etot. This portion of dsb formation is explained by the occurrence of two random ssb, generated within a critical distance (h) in opposite strands. For both argon- and N2O-saturated solutions h was found to be of the order of 40-70 phosphoric acid diester bonds. On addition of electron scavengers such as 2-chloroethanol (or N2O plus t-butanol), phi dsb is similar to that in neat, argon-saturated solutions. Thus, hydrated electrons are not involved in the chemical pathway leading to laser-pulse-induced dsb of DNA. 相似文献
48.
Dilatometrical indication can be employed to the neutralizing reactions of polybasic acids and is demonstrated by the following acid-base couples: H2SO4/NaOH, H3PO4/NaOH and H5JO6/NaOH. With amounts between 0.5 and 4 mMol several, frequently all, equivalence points can be determined with a deviation of less than 0.2%. The determination of the changes of molar volume of the reactions depending on the concentrations allow conclusions as to the course of the reactions. 相似文献
49.
Preparation of β-hydroxyesters from isoxazolines. A selective Nibpy-catalyzed electrochemical method
Viviane F. CaetanoF.W.Joachim Demnitz Flamarion B. DinizRonaldo M. Mariz Jr. Marcelo Navarro 《Tetrahedron letters》2003,44(45):8217-8220
An electrocatalytic method for the reductive N-O cleavage of isoxazolines is described. Ni0bpy, generated in situ, was used to promote selective ring opening of 3-methoxy-5-phenylisoxazoline (1a) and 3-methoxy-[4,5]cyclohexylisoxazoline (1b). DMF and NaI were used as solvent and supporting electrolyte, and β-hydroxyesters 2a and 2b were obtained in high yields respectively, after acid hydrolysis. β-Hydroxynitriles 3a and 3b were also identified as side products. 相似文献
50.
Friedrich J Dolg M Gansäuer A Geich-Gimbel D Lauterbach T 《Journal of the American Chemical Society》2005,127(19):7071-7077
The mechanism of titanocene mediated 3-exo cyclizations was investigated by a combined theoretical and experimental study. A gradient corrected density functional theory (DFT) method has been scaled against titanocene dichloride, the parent butenyl radical, and in bond dissociation energy (BDE) calculations. The BP86 method using density fitting, and a basis set of triple-zeta quality emerged as a highly reliable tool for studying titanocene mediated radical reactions. The computational results revealed important kinetic and thermodynamic features of cyclopropane formation. Surprisingly, the beta-titanoxy radicals, the first intermediates of our investigations, were demonstrated to possess essentially the same thermodynamic stabilization as the corresponding alkyl radicals by comparison of the calculated BDEs. In contrast to suggestions for samarium mediated reactions, the cyclization was shown to be thermodynamically favorable in agreement with earlier kinetic studies. It was established that stereoselectivity of the cyclization is governed by the stability of the intermediates and thus the trans disubstituted products are formed preferentially. The observed ratios of products are in good to excellent agreement with the DFT results. By a combination of computational and experimental results, it was also shown that for the completion of the overall cyclopropane formation the efficiency of the trapping of the cyclopropylcarbinyl radicals is decisive. 相似文献