全文获取类型
收费全文 | 6847篇 |
免费 | 216篇 |
国内免费 | 55篇 |
专业分类
化学 | 4283篇 |
晶体学 | 50篇 |
力学 | 107篇 |
数学 | 1311篇 |
物理学 | 1367篇 |
出版年
2024年 | 8篇 |
2023年 | 31篇 |
2022年 | 143篇 |
2021年 | 179篇 |
2020年 | 129篇 |
2019年 | 191篇 |
2018年 | 205篇 |
2017年 | 173篇 |
2016年 | 253篇 |
2015年 | 216篇 |
2014年 | 216篇 |
2013年 | 481篇 |
2012年 | 430篇 |
2011年 | 534篇 |
2010年 | 373篇 |
2009年 | 307篇 |
2008年 | 439篇 |
2007年 | 405篇 |
2006年 | 367篇 |
2005年 | 354篇 |
2004年 | 304篇 |
2003年 | 245篇 |
2002年 | 199篇 |
2001年 | 88篇 |
2000年 | 86篇 |
1999年 | 99篇 |
1998年 | 77篇 |
1997年 | 55篇 |
1996年 | 86篇 |
1995年 | 49篇 |
1994年 | 46篇 |
1993年 | 51篇 |
1992年 | 41篇 |
1991年 | 29篇 |
1990年 | 14篇 |
1989年 | 17篇 |
1988年 | 10篇 |
1987年 | 10篇 |
1986年 | 12篇 |
1985年 | 15篇 |
1984年 | 13篇 |
1983年 | 18篇 |
1982年 | 14篇 |
1981年 | 13篇 |
1979年 | 8篇 |
1978年 | 11篇 |
1977年 | 12篇 |
1976年 | 6篇 |
1975年 | 11篇 |
1973年 | 5篇 |
排序方式: 共有7118条查询结果,搜索用时 0 毫秒
81.
Ovcharenko VV Pihlaja K Stájer G 《Journal of the American Society for Mass Spectrometry》2003,14(9):1049-1056
The mass spectrometric behavior of stereo- and regioisomeric, partially saturated isoindoloquinazolines was studied by positive-ion electron ionization (EI) and fast-atom bombardment (FAB/LSIMS) mass spectrometry combined with collision-induced dissociation (CID). A highly stereospecific retro-Diels-Alder process was observed in the cyclohexene-fused isomers under the EI conditions, and a corresponding (although less specific) fragmentation was observed in their FAB spectra. In the absence of RDA fragmentations, regio- and stereoisomers of the cyclohexane-fused heterocycles could be distinguished based on their FAB/CID spectra. 相似文献
82.
Balakumar A Lysenko AB Carcel C Malinovskii VL Gryko DT Schweikart KH Loewe RS Yasseri AA Liu Z Bocian DF Lindsey JS 《The Journal of organic chemistry》2004,69(5):1435-1443
A molecular approach to information storage employs redox-active molecules tethered to an electroactive surface. Attachment of the molecules to electroactive surfaces requires control over the nature of the tether (linker and surface attachment group). We have synthesized a collection of redox-active molecules bearing different linkers and surface anchor groups in free or protected form (hydroxy, mercapto, S-acetylthio, and Se-acetylseleno) for attachment to surfaces such as silicon, germanium, and gold. The molecules exhibit a number of cationic oxidation states, including one (ferrocene), two [zinc(II)porphyrin], three [cobalt(II)porphyrin], or four (lanthanide triple-decker sandwich compound). Electrochemical studies of monolayers of a variety of the redox-active molecules attached to Si(100) electrodes indicate that molecules exhibit a regular mode of attachment (via a Si-X bond, X = O, S, or Se), relatively homogeneous surface organization, and robust reversible electrochemical behavior. The acetyl protecting group undergoes cleavage during the surface deposition process, enabling attachment to silicon via thio or seleno groups without handling free thiols or selenols. 相似文献
83.
Copolymer of divinyl ether and maleic anhydride (DIVEMA) is known to possess some anti-tumor and immune-stimulating activity and use as a drug carrier in anti-tumor drug delivery systems. Samples of DIVEMA of different degrees of polymerization were synthesized and characterized. Interaction of the hydrolyzed water-soluble DIVEMA polyanions with poly(N-ethyl-4-vinylpyridinium) cations (PEVP) has been studied. According to the potentiometry data, almost all carboxylic groups of the polyanions were able to form ion pairs with PEVP. In aqueous and water-salt solutions, formation of either soluble or insoluble polyelectrolyte complexes occurred depending on pH, ratio of the oppositely charged groups, and degree of polymerization of PEVP and/or DIVEMA. The phase separations followed general rules revealed by studying mixtures of PEVP and polycarboxylic acids. However in the case of DIVEMA, a significant broadening of the region for insoluble complexes at the expense of the region of soluble complexes was established. The data obtained demonstrate plausible advantages of the complex formation as the non-covalent modification of the polymeric carrier that endow DIVEMA with the ability for reversible soluble-insoluble transformation, in particular at physiological pH and ionic strength. 相似文献
84.
Ryabov AD Otto S Samuleev PV Polyakov VA Alexandrova L Kazankov GM Shova S Revenco M Lipkowski J Johansson MH 《Inorganic chemistry》2002,41(16):4286-4294
Structural and mechanistic aspects of orthoplatination of acetophenone and benzaldehyde oximes by the platinum(II) sulfoxide and sulfide complexes [PtCl(2)L(2)] (2, L = SOMe(2) (a), rac-SOMePh (b), R-SOMe(C(6)H(4)Me-4) (c), and SMe(2) (d)) to afford the corresponding platinacycles cis-(C,S)-[Pt(II)(C(6)H(3)-2-CR'=NOH-5-R)Cl(L)] (3, R, R' = H, Me) have been investigated. The reaction of acetophenone oxime with sulfoxide complex 2a in methanol solvent occurs noticeably faster than with sulfide complex 2d due to the fact that the sulfoxide is a much better platinum(II) leaving ligand than the sulfide. Evidence is presented that the orthoplatination is a multistep process. The formation of unreactive dichlorobis(N-oxime)platinum(II) cations accounts for the rate retardation by excess acetophenone oxime and suggests the importance of pseudocoordinatively unsaturated species for the C-H bond activation by Pt(II). A comparative X-ray structural study of dimethyl sulfoxide platinacycle 3b (R = R' = Me) and its sulfide analogue 3e (R = H, R' = Me), as well as of SOMePh complex 3c (R = H, R' = Me), indicated that they are structurally similar and a sulfur ligand is coordinated in the cis position with respect to the sigma-bound phenyl carbon. The differences concern the Pt-S bond distance, which is notably longer in the sulfide complex 3e (2.2677(11) A) as compared to that in sulfoxide complexes 3b (2.201(2)-2.215(2) A) and 3c (2.2196(12) A). Whereas the metal plane is practically a plane of symmetry in 3b due to the H-bonding between the sulfoxide oxygen and the proton at carbon ortho to the Pt-C bond, an S-bonded methyl of SOMePh and SMe(2) is basically in the platinum(II) plane in complexes 3c and 3e, respectively. There are intra- and intermolecular hydrogen bond networks in complex 3b. An interesting structural feature of complex 3c is that the two independent molecules in the asymmetric unit of the crystal reveal an extremely short Pt-Pt contact of 3.337 A. 相似文献
85.
Novel representatives of the important group of biologically active dibenzosuberone derivatives were prepared: 3,7-dibromo-5-(dimethylaminoethyl- oxyimino)-10,11-dihydro-5H-dibenzo[a,d]cyclohepta-1,4-diene (1), 3,7-dibromo-5-(3- dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2) and 1,7- dibromo-5-(3-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo-[a,d]-cycloheptene (3). These compounds are potential tricyclic antidepressants (TCAs), which are still the most frequently prescribed antidepressants in many countries. 相似文献
86.
87.
Darian E Hnizdo V Fedorowicz A Singh H Demchuk E 《Journal of computational chemistry》2005,26(7):651-660
A method of statistical estimation is applied to the problem of evaluating the absolute entropy of internal rotation in a molecule with two torsional degrees of freedom. The configurational part of the entropy is obtained as that of the joint probability density of an arbitrary form represented by a two-dimensional Fourier series, the coefficients of which are statistically estimated using a sample of the torsional angles of the molecule obtained by a stochastic simulation. The internal rotors in the molecule are assumed to be attached to a common frame, and their reduced moments of inertia are initially calculated as functions of the two torsional angles, but averaged over all the remaining internal degrees of freedom using the stochastic-simulation sample of the atomic configurations of the molecule. The torsional-angle dependence of the reduced moments of inertia can be also averaged out, and the absolute internal-rotation entropy of the molecule is obtained in a good approximation as the sum of the configurational entropy and a kinetic contribution fully determined by the averaged reduced moments of inertia. The method is illustrated using Monte Carlo simulations of isomers of stilbene and halogenated derivatives of propane. The two torsional angles in cis-stilbene are found to be much more strongly correlated than those in trans-stilbene, while the degree of the angular correlation in propane increases strongly on substitution of hydrogen atoms with chlorine. 相似文献
88.
Mono- or 1,1′-bis-acylation of ferrocene, its mono and 1,1′-dimethyl and phenyl derivatives and of [3]ferrocenophane with o-chlorobenzoyl chloride/AlCl3 affords the corresponding (isomeric) chlorobenzoyl ferrocenes in high yields which can be separated by column, layer or high pressure liquid chromatography and in the case of the monomethylferrocene monoketones also by crystallization. The cleavage of the (o-chlorobenzoyl)ferrocenes by potassium-t-butoxide (and traces of water) yields the corresponding ferrocene carboxylic acids except for the α-phenyl derivatives in almost quantitative yields, thus offering a very convenient access to these acids. In all cases the isomer distribution and thereby the relative site reactivities were determined. 相似文献
89.
Nataliya A. Mayorova Olga A. Khazova Vladimir S. Bagotzky 《Journal of Solid State Electrochemistry》1998,2(4):262-265
Methanol electrooxidation on smooth platinum electrodes bonded to solid polymer electrolytes was studied in water and acid
solution by voltammetric measurements with different scanning rates. An enhancement of the oxidation rates was observed in
these systems as compared to identical platinum electrodes in contact with liquid electrolytes. This electrocatalytic effect
strongly depends on the measuring conditions and on the electrode potential. The reasons for the catalytic effects at different
potentials are discussed.
Received: 8 January 1997 / Accepted: 1 December 1997 相似文献
90.
Alexander D. Dilman Dmitry E. Arkhipov Valentine P. Ananikov Vladimir A. Tartakovsky 《Journal of organometallic chemistry》2005,690(16):3680-3689
A general method for the synthesis of carbon-centered tris(pentafluorophenyl)silyl derivatives (RSi(C6F5)3) by reaction of trichlorosilanes (RSiCl3) with pentafluorophenylmagnesium bromide was described. The crystal structures of obtained compounds were studied by X-ray diffraction analysis (7 structures). The peculiarities of crystal packing were analyzed by means of DFT calculations. 相似文献