全文获取类型
收费全文 | 55909篇 |
免费 | 8771篇 |
国内免费 | 1504篇 |
专业分类
化学 | 53863篇 |
晶体学 | 454篇 |
力学 | 914篇 |
数学 | 5101篇 |
物理学 | 5852篇 |
出版年
2023年 | 139篇 |
2022年 | 195篇 |
2021年 | 429篇 |
2020年 | 1593篇 |
2019年 | 2932篇 |
2018年 | 1234篇 |
2017年 | 874篇 |
2016年 | 3907篇 |
2015年 | 4001篇 |
2014年 | 3986篇 |
2013年 | 5023篇 |
2012年 | 4016篇 |
2011年 | 3363篇 |
2010年 | 3527篇 |
2009年 | 3404篇 |
2008年 | 3394篇 |
2007年 | 2763篇 |
2006年 | 2407篇 |
2005年 | 2506篇 |
2004年 | 2197篇 |
2003年 | 1952篇 |
2002年 | 2607篇 |
2001年 | 1649篇 |
2000年 | 1552篇 |
1999年 | 639篇 |
1998年 | 310篇 |
1997年 | 284篇 |
1996年 | 292篇 |
1995年 | 275篇 |
1994年 | 247篇 |
1993年 | 248篇 |
1992年 | 229篇 |
1991年 | 207篇 |
1990年 | 203篇 |
1989年 | 211篇 |
1988年 | 180篇 |
1987年 | 145篇 |
1986年 | 134篇 |
1985年 | 207篇 |
1984年 | 210篇 |
1983年 | 164篇 |
1982年 | 203篇 |
1981年 | 209篇 |
1980年 | 164篇 |
1979年 | 167篇 |
1978年 | 197篇 |
1977年 | 145篇 |
1976年 | 148篇 |
1975年 | 149篇 |
1974年 | 124篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Mercedes Cano JosV. Heras M.Luz Gallego Josefina Perles Caridad Ruiz‐Valero Elena Pinilla M.Rosario Torres 《Helvetica chimica acta》2003,86(9):3194-3203
Two new (η3‐allyl)palladium complexes containing the ligand 3,5‐dimethyl‐4‐nitro‐1H‐pyrazole (Hdmnpz) were synthesized and characterized as [Pd(η3‐C3H5)(Hdmnpz)2]BF4 ( 1 ) and [Pd(η3‐C3H5)(Hdmnpz)2]NO3 ( 2 ). The structures of these compounds were determined by single‐crystal X‐ray diffraction to evaluate the intermolecular assembly. Each complex exhibits similar coordination behavior consistent with cationic entities comprised of two pyrazole ligands coordinated with the [Pd(η3‐C3H5)]+ fragment in an almost square‐planar coordination geometry. In 1 , the cationic entities are propagated through strong intermolecular H‐bonds formed between the pyrazole NH groups and BF ions in one‐dimensional polymer chains along the a axis. These chains are extended into two‐dimensional sheet networks via bifurcated H‐bonds. New intermolecular interactions established between NO2 and Me substituents at the pyrazole ligand of neighboring sheets give rise to a three‐dimensional network. By contrast, compound 2 presents molecular cyclic dimers formed through N? H???O H‐bonds between two NO counterions and the pyrazole NH groups of two cationic entities. The dimers are also connected to each other through C? H???O H‐bonds between the remaining O‐atom of each NO ion and the allyl CH2 H‐atom. Those interactions expand in a layer which lies parallel to the face (101). 相似文献
992.
Studies on Hydroiodination and Deconjugation of 5—Aryloxy—(thiophenyl)—3—pentyn—2—one 总被引:1,自引:0,他引:1
One-pot hydroiodination and deconjugation of 5-aryloxy(or thiophenyl)-3-pentyn-2-one with a reagent system of sodium iodide/trimethylsilyl chloride/water in acetonitrile at 25℃ have been described.The plasuible mechanism was discussed.The reaction provided a simple and useful method for the preparation of (Z)-β-substituted β,γ-enones and (Z)-β-substituted α,β-unsaturated ketones. 相似文献
993.
Peter Hald Martin Bremholm Jacques Chevallier Bo B. Iversen 《Journal of solid state chemistry》2006,179(8):2674-2680
Highly crystalline anatase TiO2 nanoparticles have been synthesised in less than 1 min in a supercritical propanol-water mixture using a continuous flow reactor. The synthesis parameter space (T, P, concentration) has been explored and the average particle size can be accurately controlled within 10-18 nm with narrow size distributions (2-3 nm). At subcritical conditions amorphous products are obtained, whereas a broad range of T and P in the supercritical regime gives 11-14 nm particles. At high temperature and pressure, the particles size increase to 18 nm. The nanoparticles have been extensively characterised with powder X-ray diffraction (PXRD), transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) with excellent agreement on size and size distribution parameters. The SAXS analysis suggests disk-shaped particles with diameters that are approximately double the height. For comparison, a series of conventional autoclave sol-gel syntheses have been carried out. These also produce phase-pure anatase nanoparticles, but with much broader size distributions and at much longer synthesis times (hours). The study demonstrates that synthesis in supercritical fluids is a very promising method for manipulating the size and size distribution of nanoparticles, thus removing one of the key limitations in many applications of nanomaterials. 相似文献
994.
F. Halzen A. D. Martin D. M. Scott M. P. Tuite 《Zeitschrift fur Physik C Particles and Fields》1982,14(4):351-355
We study the hadronic transverse energy (E T ) accompanyingZ 0 events in \(p\bar p\) interactions and compare our result with the observedE T distribution in minimum bias events. We expect excess transverse energy to accompanyZ 0's. This effect can also be probed experimentally using Drell-Yan lepton pairs and represents an interesting way to probe the multi-gluon structure of QCD. 相似文献
995.
X-ray diffraction analysis reveals the thiogermanic acid H(4)Ge(4)S(10) possesses discrete adamantane-like Ge(4)S(10)(4)(-) complex anions. Each thioanion is composed of four corner shared GeS(2.5)(-) tetrahedral units. Crystals were grown from anhydrous liquid hydrogen sulfide reactions with glassy germanium sulfide at room temperature. The crystal structure was solved and refined from single crystal diffractometer data (Mo Kalpha radiation) obtained at 173 K. H(4)Ge(4)S(10) is triclinic, centrosymmetric space group Ponemacr;, with a = 8.621(4) A, b = 9.899(4) A, c = 10.009(4) A, alpha = 85.963(7) degrees, beta = 64.714(7) degrees, gamma = 89.501(8) degrees, and Z = 2. Average bridging and terminal d(Ge-S) distances are 2.229 and 2.206 A, respectively. Vibrational mode assignments are reported from Raman scattering and IR absorption spectra of polycrystalline samples. The nu(s)(Ge-S-Ge) and nu(s)(Ge-S(-)) stretching modes are observed at 354 and 405 cm(-)(1), respectively. 相似文献
996.
The role of tunneling for two proton-transfer steps in the reactions catalyzed by triosephosphate isomerase (TIM) has been studied. One step is the rate-limiting proton transfer from Calpha in the substrate to Glu 165, and the other is an intrasubstrate proton transfer proposed for the isomerization of the enediolate intermediate. The latter, which is not important in the wild-type enzyme but is a useful model system because of its simplicity, has also been examined in the gas phase and in solution. Variational transition-state theory with semiclassical ground-state tunneling was used for the calculation with potential energy surface determined by an AM1 method specifically parametrized for the TIM system. The effect of tunneling on the reaction rate was found to be less than a factor of 10 at room temperature; the tunneling becomes more important at lower temperature, as expected. The imaginary frequency (barrier) mode and modes that have large contributions to the reaction path curvature are localized on the atoms in the active site, within 4 A of the substrate. This suggests that only a small number of atoms that are close to the substrate and their motions (e.g., donor-acceptor vibration) directly determine the magnitude of tunneling. Atoms that are farther away influence the effect of tunneling indirectly by modulating the energetics of the proton transfer. For the intramolecular proton transfer, tunneling was found to be most important in the gas phase, to be similar in the enzyme, and to be the smallest in water. The major reason for this trend is that the barrier frequency is substantially lower in solution than in the gas phase and enzyme; the broader solution barrier is caused by the strong electrostatic interaction between the highly charged solute and the polar solvent molecules. Analysis of isotope effects showed that the conventional Arrenhius parameters are more useful as experimental criteria for determining the magnitude of tunneling than the widely used Swain-Schaad exponent (SSE). For the primary SSE, although values larger than the transition-state theory limit (3.3) occur when tunneling is included, there is no clear relationship between the calculated magnitudes of tunneling and the SSE. Also, the temperature dependence of the primary SSE is rather complex; the value of SSE tends to decrease as the temperature is lowered (i.e., when tunneling becomes more significant). For the secondary SSE, the results suggest that it is more relevant for evaluating the "coupled motion" between the secondary hydrogen and the reaction coordinate than the magnitude of tunneling. Although tunneling makes a significant contribution to the rate of proton transfer, it appears not to be a major aspect of the catalysis by TIM at room temperature; i.e., the tunneling factor of 10 is "small" relative to the overall rate acceleration by 10(9). For the intramolecular proton transfer, the tunneling in the enzyme is larger by a factor of 5 than in solution. 相似文献
997.
Kyung‐Youl Baek Masami Kamigaito Mitsuo Sawamoto 《Journal of polymer science. Part A, Polymer chemistry》2002,40(12):1937-1944
A series of functionalized 2‐bromoisobutyrates and 2‐chloro‐2‐phenylacetates led to α‐end‐functionalized poly(methyl methacrylate)s in Ru(II)‐catalyzed living radical polymerization; the terminal functions included amine, hydroxyl, and amide. These initiators were effective in the presence of additives such as Al(Oi‐Pr)3 and n‐Bu3N. The chlorophenylacetate initiators especially coupled with the amine additive gave polymers with well‐controlled molecular weights (Mw/Mn = 1.2–1.3) and high end functionality (Fn ~ 1.0). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1937–1944, 2002 相似文献
998.
Michael Chariss Andrea Zickgraf Heike Stenger Elmar Bru Cristelle Desmarquet Martin Drger Silke Gerstmann Dainis Dakternieks James Hook 《Polyhedron》1998,17(25-26)
44 members of thecompound series Ph4−nMRn (M=Si, Ge, Sn, Pb; R=o-, m-, p-Tol; n=0–4) were synthesized (15 newcompounds). The crystal structures of Ph3Sn (o-Tol) and PhSn (o-Tol)3 were determined and compared to 16 known structures. Subject to the distanced (M–C), an interplay between through-space π–π repulsion and π–σ attraction leads to either elongated or compressed tetrahedral geometry. 29 Si-, 119 Sn- and 207 Pb-NMR chemical shifts were determined in solution and in the solid state. 73 Ge chemical shifts were measured only in solution. Anupfield or downfield sagging of the chemical shifts along each series is rationalized in terms of a π–σcharge transfer which is constrained by torsion of the aromatic groups. 相似文献
999.
van Leeuwen PW Zuideveld MA Swennenhuis BH Freixa Z Kamer PC Goubitz K Fraanje J Lutz M Spek AL 《Journal of the American Chemical Society》2003,125(18):5523-5539
The mechanism and kinetics of the solvolysis of complexes of the type [(L-L)Pd(C(O)CH(3))(S)](+)[CF(3)SO(3)](-) (L-L = diphosphine ligand, S = solvent, CO, or donor atom in the ligand backbone) was studied by NMR and UV-vis spectroscopy with the use of the ligands a-j: SPANphos (a), dtbpf (b), Xantphos (c), dippf (d), DPEphos (e), dtbpx (f), dppf (g), dppp (h), calix-6-diphosphite (j). Acetyl palladium complexes containing trans-coordinating ligands that resist cis coordination (SPANphos, dtbpf) showed no methanolysis. Trans complexes that can undergo isomerization to the cis analogue (Xantphos, dippf, DPEphos) showed methanolyis of the acyl group at a moderate rate. The reaction of [trans-(DPEphos)Pd(C(O)CH(3))](+)[CF(3)SO(3)](-) (2e) with methanol shows a large negative entropy of activation. Cis complexes underwent competing decarbonylation and methanolysis with the exception of 2j, [cis-(calix-diphosphite)Pd(C(O)CH(3))(CD(3)OD)](+)[CF(3)SO(3)](-). The calix-6-diphosphite complex showed a large positive entropy of activation. It is concluded that ester elimination from acylpalladium complexes with alcohols requires cis geometry of the acyl group and coordinating alcohol. The reductive elimination of methyl acetate is described as a migratory elimination or a 1,2-shift of the alkoxy group from palladium to the acyl carbon atom. Cis complexes with bulky ligands such as dtbpx undergo an extremely fast methanolysis. An increasing steric bulk of the ligand favors the formation of methyl propanoate relative to the insertion of ethene leading to formation of oligomers or polymers in the catalytic reaction of ethene, carbon monoxide, and methanol. 相似文献
1000.
Zheng‐Yu Yue Shu‐Hui Li Po Gao Jin‐Hui Zhang Peng‐Fei Yan 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(5):o281-o282
The title compound, C30H46O9, prepared from a mixture of α‐ and β‐dihydroartemisinin, has α‐ and β‐arteether moieties linked via an –O– bridge, so that the molecule is asymmetric about the bridge. The endoperoxide bridges of the parent compounds have been retained in each half of the ether‐bridged dimer. The rings exhibit chair and twist–boat conformations. 相似文献