全文获取类型
收费全文 | 15453篇 |
免费 | 2158篇 |
国内免费 | 2338篇 |
专业分类
化学 | 15848篇 |
晶体学 | 471篇 |
力学 | 943篇 |
综合类 | 96篇 |
数学 | 133篇 |
物理学 | 2458篇 |
出版年
2024年 | 13篇 |
2023年 | 173篇 |
2022年 | 286篇 |
2021年 | 534篇 |
2020年 | 823篇 |
2019年 | 650篇 |
2018年 | 596篇 |
2017年 | 635篇 |
2016年 | 851篇 |
2015年 | 907篇 |
2014年 | 892篇 |
2013年 | 1501篇 |
2012年 | 992篇 |
2011年 | 869篇 |
2010年 | 757篇 |
2009年 | 871篇 |
2008年 | 878篇 |
2007年 | 1030篇 |
2006年 | 951篇 |
2005年 | 900篇 |
2004年 | 829篇 |
2003年 | 753篇 |
2002年 | 535篇 |
2001年 | 378篇 |
2000年 | 415篇 |
1999年 | 316篇 |
1998年 | 250篇 |
1997年 | 249篇 |
1996年 | 210篇 |
1995年 | 191篇 |
1994年 | 147篇 |
1993年 | 101篇 |
1992年 | 105篇 |
1991年 | 54篇 |
1990年 | 51篇 |
1989年 | 41篇 |
1988年 | 40篇 |
1987年 | 30篇 |
1986年 | 25篇 |
1985年 | 29篇 |
1984年 | 19篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1980年 | 9篇 |
1979年 | 3篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1973年 | 7篇 |
1971年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 421 毫秒
21.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(9):2399-2399
22.
A. V. Semykin I. A. Kazarinov E. A. Khomskaya 《Russian Journal of Electrochemistry》2006,42(6):643-648
The hydrogen ionization process is studied experimentally on an industrial sintered nickel oxide electrode in models of sealed nickel-metal hydride batteries. It is shown that the hydrogen ionization rates that are reached during overcharge by high current densities in conditions of forced gas delivery into the electrode pores (up to 40 mA cm?2) exceed the self-discharge rate of a nickel-hydrogen battery by two orders of magnitude. Up to 70% of hydrogen delivered into the compact assembly block undergoes ionization during forced charge of models of sealed nickel-metal hydride batteries with a closed hydrogen cycle. Two independent methods (potentiostatic and manometric) are used to determine the relationship between rates of hydrogen ionization with the degree of the electrode filling with gas and perform estimation of the process intensity at a unit reaction surface. It is established that, in conditions of forced gas delivery, practically all the hydrogen oxidation current is generated at the surface of the nickel oxide electrode beneath thin films of an electrolyte solution at the rate of 4–5 mA cm?2. It is shown that the hydrogen oxidation rate on a nickel oxide electrode filled in part by gas is independent of the electrode potential, probably because of a tangible contribution made by diffusion limitations to the overall hampering of the process. 相似文献
23.
Cosmic dust and our origins 总被引:1,自引:0,他引:1
J Mayo Greenberg 《Surface science》2002,500(1-3):793-822
The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized. 相似文献
24.
The coordination polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n (phth = phthalate, phen = 1,10-phenanthroline) with formula C22H20CoN2O6 (Mr = 467.33) was synthesized by the solvothermal method under low temperature, and its crystal structure was determined by singlecrystal X-ray diffraction. The complex belongs to monoclinic system, space group P21/n with a =12.7352(16), b = 8.8125(11), c = 18.677(2) (A), β = 102.633(2)°, V = 2045.3(4) (A)3, Z = 4, Dc =1.518 g/cm3,μ = 0.882 mm-1, F(000) = 964, S = 1.053, the final R = 0.0401 and wR = 0.0984 for 3135 observed reflections (I > 2σ(I)). Single-crystal X-ray analysis revealed that the Co(Ⅱ) ion is six-coordinated. The cobalt complex forms a one-dimensional chain structure via phthalate bridging ligand. In the cobalt complex, a 3D network structure is formed by π-π stacking interaction of 1,10-phenanthroline as well as intermolecular hydrogen bonding interactions. 相似文献
25.
Dimitar I. Pushkarov 《Central European Journal of Physics》2004,2(3):420-455
Basic ideas and results which characterize quantum diffusion of defects in quantum crystals like solid helium as a new phenomenon
are presented. Quantum effects in such media lead to a delocalization of point defects (vacancies, impurities etc.) and they
turn into quasiparticles of a new type—defectons, which are characterized not by their position in the crystal lattice but
by their quasimomentum and dispersion law. Defecton-defecton and defecton-phonon scattering are considered and an interpolation
formula for the diffusion coefficient valid in all interesting temperature and concentration regions is presented. A comparison
with the experimental data is made. Some alternative points of view are discussed in detail and the inconsistency of the Kisvarsanyi-Sullivan
theory is shown. 相似文献
26.
27.
Results of two urgent and practically important directions of research on the indirect oxidation of organic compounds by highly reactive intermediates generated electrochemically from oxygen (HO2
–, HO2
·, HO·) are considered and orderly arranged. The studies in question are the indirect synthesis and mineralization of organic toxicants in waste water. 相似文献
28.
The title compound (C2H7NO·C7H4N2O6) has been obtained by the reaction of etha- nolamine with 3,5-dinitrobenzoic acid in deionized water at room temperature. The crystal crystal- lizes in orthorhombic, space group P212121 with a = 6.048(2), b = 9.146(3), c = 21.955(7)(A), C9H11N3O7, Mr = 273.21, Z = 4, V = 1214.3(7)(A)3, Dc = 1.494 g/cm3, F(000) = 568, μ(MoKα) = 0.131 mm-1, R1 = 0.0338 and wR2 = 0.0497. The new organic adduct is composed of one ethanolamine and one 3,5-dinitrobenzoic acid, which are linked up by O-H…O and N-H…O types of hydrogen bonds to form a nine-membered ring and an eleven-membered ring, extending into a one-dimensional network structure. 相似文献
29.
《Magnetic resonance in chemistry : MRC》2003,41(1):37-41
The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D2O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu2+ cations, but not Fe3+ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
30.
NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl3 and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation. 相似文献