全文获取类型
收费全文 | 2865篇 |
免费 | 90篇 |
国内免费 | 9篇 |
专业分类
化学 | 1907篇 |
晶体学 | 42篇 |
力学 | 56篇 |
数学 | 452篇 |
物理学 | 507篇 |
出版年
2023年 | 10篇 |
2022年 | 10篇 |
2021年 | 71篇 |
2020年 | 63篇 |
2019年 | 60篇 |
2018年 | 46篇 |
2017年 | 55篇 |
2016年 | 92篇 |
2015年 | 86篇 |
2014年 | 98篇 |
2013年 | 190篇 |
2012年 | 159篇 |
2011年 | 183篇 |
2010年 | 148篇 |
2009年 | 117篇 |
2008年 | 180篇 |
2007年 | 156篇 |
2006年 | 129篇 |
2005年 | 133篇 |
2004年 | 112篇 |
2003年 | 94篇 |
2002年 | 86篇 |
2001年 | 34篇 |
2000年 | 40篇 |
1999年 | 37篇 |
1998年 | 31篇 |
1997年 | 26篇 |
1996年 | 25篇 |
1995年 | 26篇 |
1994年 | 25篇 |
1993年 | 17篇 |
1992年 | 26篇 |
1991年 | 38篇 |
1990年 | 27篇 |
1989年 | 21篇 |
1988年 | 21篇 |
1987年 | 16篇 |
1986年 | 14篇 |
1985年 | 27篇 |
1984年 | 26篇 |
1983年 | 16篇 |
1982年 | 17篇 |
1981年 | 17篇 |
1980年 | 19篇 |
1979年 | 13篇 |
1978年 | 16篇 |
1977年 | 19篇 |
1976年 | 20篇 |
1974年 | 8篇 |
1969年 | 7篇 |
排序方式: 共有2964条查询结果,搜索用时 15 毫秒
71.
Trávníček Zdeněk Machala Viktor Szüčová Lucie Maloň Michal Marek Jaromír 《Transition Metal Chemistry》2004,29(4):352-357
A series of new [NiX(S2P{O-c-Hex}2)(PPh3)](X = Cl–, Br–, I– and NCS–)(1)–(4) and [Ni(NCS)(S2P{OR}2)(PPh3)][R =n-Pr (5), i-Pr (6)] complexes has been synthesized and characterized by elemental analyses, f.i.r., i.r., u.v.–vis., 1H-, 13C{1H}- and 31P{1H}-n.m.r. spectra, magnetochemical and conductivity measurements. A single crystal X-ray analysis of [Ni(NCS)(S2P{O-n-Pr}2)(PPh3)](5) reveals the molecular structure of the complex and confirms a square-planar geometry around the central atom of nickel with the NCS anion coordinated via the nitrogen atom. 相似文献
72.
V. Goliáš D. Pittauerová R. Procházka Z. Třískala 《Journal of Radioanalytical and Nuclear Chemistry》2005,266(3):461-470
Summary The activities of218Po,214Po and211Bi were determined in samples obtained of soil/gas. Sampling work was taken in Jáchymov (Czech Republic) at the outcrop of
the Geister-vein,by electrostatic precipitation from filtered soil gas on stainless steel disks.The samples were measured
in a field laboratory using a semi-conductor alpha-spectrometer.The activities of218Po,214Po and211Bi were calculated.Samples taken from active dump material (near-by radon source) exhibited a high211Bi/214Po ratio, while those of the vein outcrop (a relatively deeper source) had a low ratio.A mathematical model was employed to
determine the radon age calculated from the actinon/radon input ratio.This varied in a range of 5.6 to -7.7 seconds.Negative
age values are probably caused by the preference for actinon, which rapidly comes into equilibrium with the source of this
gas. 相似文献
73.
Erik Rakovský Ľudmila Žúrková Jaromír Marek 《Monatshefte für Chemie / Chemical Monthly》2002,133(3):277-283
Summary. Anhydrous 1,6-hexanediammonium dihydrogendecavanadate ((HdaH2)2H2V10O28, 1) was prepared by reaction of V2O5 with 1,6-hexanediamine in aqueous solution. The crystal structure of 1 was determined, and the proton positions in the H2V10O28
4− anion were calculated by the bond length/bond number method. The protons are bound to the centrosymmetrically oriented μ–OV3 groups of the decavanadate anion. Based on the analysis of IR spectra of 1 prepared from H2O and D2O, the absorption band at 871 cm−1 can be attributed to δ(V–Ob–H) vibrations.
Received August 3, 2001. Accepted (revised) October 8, 2001 相似文献
74.
Wagner-Czauderna Elżbieta Boroń-Cegiełkowska Agata Orłowska Elżbieta Kalinowski Marek K. 《Transition Metal Chemistry》2004,29(1):61-65
The visible absorption spectra of CoCl2 in binary mixtures of acetone, dmf, dma and dmso with H2O show the existence of configuration equilibria between tetrahedral (T) and octahedral (O) species. Linear correlations between the values of log K (K = [O]/[T]) and the mole fraction of H2O,
w, have been observed in all the systems under study; their slopes decrease linearly with an increase of the donor number, DN, of the organic component of the mixture. The formation of octahedral species is enthalpy favoured but entropy disfavoured. It was found that both H and S values change linearly with
w and the slopes of these relationships depend clearly on the DN values. 相似文献
75.
Andrzejak M Sterzel M Pawlikowski MT 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(9):2029-2032
The absorption spectra of the N-(2,5-di-tert-butylphenyl) phthalimide (1-), N-(2,5-di-tert-butylphenyl)-1,8-naphthalimide (2-) and N-(2,5-di-tert-butylphenyl)-perylene-3,4-dicarboximide (3-) anion radicals are studied in terms of time dependent density functional theory (TDDFT). For these anion radicals a large number electronic states (from 30 to 60) was found in the visible and near-IR regions (5000-45,000 cm(-1)). In these regions the TD/B3LYP treatment at the 6-1+G* level is shown to reproduce satisfactorily the empirical absorption spectra of all three anion radicals studied. The most apparent discrepancies between purely electronic theory and the experiment could be found in the excitation region corresponding to D0-->D1 transitions in the 2- and 3- molecules. For these species we argue that the structures seen in the lowest energy part of the absorptions of the 2- and 3- species are very likely due to Franck-Condon (FC) activity of the totally symmetric vibrations not studied in this Letter. 相似文献
76.
Jakub Čížek Ivan Procházka Radomír Kužel Rinat K. Islamgaliev 《Monatshefte für Chemie / Chemical Monthly》2002,133(6):873-887
Summary. Ultra-fine grained (UFG) Cu (grain size 80 nm) containing 0.5 wt.% Al2O3 nanoparticles (size 20 nm) was prepared by high pressure torsion (HPT). Positron lifetime spectroscopy was employed to characterize
the microstructure of this material, especially with respect to types and concentration of lattice defects. The evolution
of microstructure with increasing temperature was studied by positron lifetime spectroscopy and X-ray diffraction measurements.
The thermal stability of the Cu + 0.5 wt.% Al2O3 nanocomposite was compared with that of pure UFG Cu prepared by the same technique. The processes taking place during thermal
recovery of the initial nanoscale structure in both studied materials are described.
Received October 5, 2001. Accepted (revised) December 20, 2001 相似文献
77.
Kopel Pavel Trávníček Zdeněk Kvítek Libor Biler Martin Pavlíček Marek Šindelář Zdeněk Marek Jaromír 《Transition Metal Chemistry》2001,26(3):282-286
NiII mixed-ligand complexes of compositions [Ni(pmdien)(ttcH)] (1), [Ni(baphen)2(ttcH)] · 4H2O (2), [Ni-(dpa)(ttcH)(H2O)] (3), [Ni(cyclam)(ttcH)] · 2H2O (4), [Ni(hexaa)](ttcH) (5) and [Ni(hexab)(ttcH)] · 2H2O (6), (baphen = 4,7-diphenyl-1,10-phenanthroline, dpa = 2,2-dipyridylamine, cyclam = 1,4,8,11-tetraazacyclotetradecane, hexaa = 1,3,6,9,11,14-hexaazatricyclo[12.2.1.16,9]-octadecane, hexab = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane) have been prepared and characterized by means of i.r., u.v.–vis. spectroscopies and magnetochemical measurements. The redox properties of the complexes were studied by cyclic voltammetry. The crystal and molecular structure of [Ni(pmdien)(ttcH)] was determined. The nickel atom is penta-coordinated by three N atoms of pmdien, and by S and N atoms of trithiocyanurate(2–) anion. 相似文献
78.
79.
80.
Klara Markova Klaudia Chmelova Srgio M. Marques Philippe Carpentier David Bednar Jiri Damborsky Martin Marek 《Chemical science》2020,11(41):11162
Computational design of protein catalysts with enhanced stabilities for use in research and enzyme technologies is a challenging task. Using force-field calculations and phylogenetic analysis, we previously designed the haloalkane dehalogenase DhaA115 which contains 11 mutations that confer upon it outstanding thermostability (Tm = 73.5 °C; ΔTm > 23 °C). An understanding of the structural basis of this hyperstabilization is required in order to develop computer algorithms and predictive tools. Here, we report X-ray structures of DhaA115 at 1.55 Å and 1.6 Å resolutions and their molecular dynamics trajectories, which unravel the intricate network of interactions that reinforce the αβα-sandwich architecture. Unexpectedly, mutations toward bulky aromatic amino acids at the protein surface triggered long-distance (∼27 Å) backbone changes due to cooperative effects. These cooperative interactions produced an unprecedented double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates to the active site, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. Despite these spatial restrictions, experimental tracing of the access tunnels using krypton derivative crystals demonstrates that transport of ligands is still effective. Our findings highlight key thermostabilization effects and provide a structural basis for designing new thermostable protein catalysts.Illustration of cooperative thermostabilization effects of the double-lock system that: (i) induced backbone changes, (ii) closed the molecular gates, (iii) reduced the volumes of the main and slot access tunnels, and (iv) occluded the active site. 相似文献