全文获取类型
收费全文 | 2954篇 |
免费 | 72篇 |
国内免费 | 21篇 |
专业分类
化学 | 1929篇 |
晶体学 | 28篇 |
力学 | 86篇 |
数学 | 474篇 |
物理学 | 530篇 |
出版年
2021年 | 31篇 |
2020年 | 40篇 |
2019年 | 33篇 |
2018年 | 27篇 |
2017年 | 21篇 |
2016年 | 48篇 |
2015年 | 50篇 |
2014年 | 50篇 |
2013年 | 138篇 |
2012年 | 137篇 |
2011年 | 148篇 |
2010年 | 83篇 |
2009年 | 66篇 |
2008年 | 165篇 |
2007年 | 144篇 |
2006年 | 170篇 |
2005年 | 138篇 |
2004年 | 109篇 |
2003年 | 94篇 |
2002年 | 103篇 |
2001年 | 40篇 |
2000年 | 34篇 |
1999年 | 39篇 |
1998年 | 42篇 |
1997年 | 34篇 |
1996年 | 30篇 |
1995年 | 29篇 |
1994年 | 34篇 |
1993年 | 38篇 |
1992年 | 34篇 |
1991年 | 37篇 |
1990年 | 29篇 |
1989年 | 40篇 |
1988年 | 29篇 |
1987年 | 21篇 |
1986年 | 21篇 |
1985年 | 41篇 |
1984年 | 47篇 |
1983年 | 36篇 |
1982年 | 48篇 |
1981年 | 52篇 |
1980年 | 31篇 |
1979年 | 26篇 |
1978年 | 38篇 |
1977年 | 30篇 |
1976年 | 49篇 |
1975年 | 34篇 |
1974年 | 34篇 |
1973年 | 31篇 |
1969年 | 18篇 |
排序方式: 共有3047条查询结果,搜索用时 31 毫秒
991.
Jakub Olchowka Clément Falaise Dr. Christophe Volkringer Dr. Natacha Henry Dr. Thierry Loiseau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(6):2012-2022
The hydrothermal reactions of uranyl nitrate and metallic copper with aromatic polycarboxylic acids gave rise to the formation of five heterometallic UO22+? Cu2+ coordination polymers: (UO2)Cu(H2O)2(1,2‐bdc)2 ( 1 ; 1,2‐bdc=phthalate), (UO2)Cu(H2O)2(btec) ? 4 H2O ( 2 ) and (UO2)Cu(btec) ( 2′ ; btec=pyromellitate), (UO2)2Cu(H2O)4(mel) ( 3 ; mel=mellitate), and (UO2)2O(OH)2Cu(H2O)2(1,3‐bdc) ? H2O ( 4 ; 1,3‐bdc=isophthlalate). Single‐crystal X‐ray diffraction (XRD) analysis of compound 1 revealed 2D layers of chains of UO8 and CuO4(H2O)2 units that were connected through the phthalate ligands. In compound 2 , these sheets were connected to each other through the two additional carboxylate arms of the pyromellitate, thus resulting in a 3D open‐framework with 1D channels that trapped water molecules. Upon heating, free and bonded water species (from Cu? OH2) were evacuated from the structure. This thermal transition was followed by in situ XRD and IR spectroscopy. Heating induced a solid‐state topotactic transformation with the formation of a new set of Cu? O interactions in the crystalline anhydrous structure ( 2′ ), in order to keep the square‐planar environment around the copper centers. The structure of compound 3 was built up from trinuclear motifs, in which one copper center, CuO4(OH2)2, was linked to two uranium units, UO5(H2O)2. The assembly of this trimer, “U2Cu”, with the mellitate generated a 3D network. Complex 4 contained a tetranuclear uranyl core of UO5(OH)2 and UO6(OH) units that were linked to two copper centers, CuO(OH)2(H2O)2, which were then connected to each other through isophthalate ligands and U?O? Cu interactions to create a 3D structure. The common structural feature of these different compounds is a bridging oxo group of U?O? Cu type, which is reflected by apical Cu? O distances in the range 2.350(3)–2.745(5) Å. In the case of a shorter Cu? O distance, a slight lengthening of the uranyl bond (U?O) is observed (e.g., 1.805(3) Å in complex 4 ). 相似文献
992.
Henry Taube 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10-11):1173-1187
Electron transfer between metal complexes which can be in intimate contact has been the subject of systematic study for about four decades. A major conclusion of the vast amount of work which has been done with intermolecular reactions of ordinary metal complexes is that the reactions are adiabatic, or nearly so (i.e., the only barriers to the reactions are the work of bringing the reagents into contact and the work of exciting them to the isoergic state, which is the configuration reached after the nuclei have readjusted so that the energy of the system is independent of the alternate sites the electron occupies). In adiabatic transfer, the rate of chemical change does not depend on the frequency of electron transfer between the two sites in the isoergic state. The measurement of the rate of electron transfer over large distances, especially when the intervening matter is made up of protein, has been a matter of great interest. At present, it is a very active field of investigation and several different methods for making such measurements have been introduced. The results obtained with one such method, developed by S. S. Isied in 1973, are emphasized. A key feature of the method is that reactions are studied in the intramolecular mode. This is a great simplification because the work of assembling the precursor complex is no longer a factor, and the interesting effects which arise from nonadiabatic behavior are more directly exposed. The method was first applied to simple bridging groups such as 4,4′-bipyridine, which tie the metal-containing moieties (NH3)5Co(III) and (NH3)5 Ru(III) together. An external reducing agent reduces Ru(III) in preference to Co(III), and the subsequent chemical change, which involves reduction of Co(III) by Ru(II) by an intramolecular process, can be followed spectrophotometrically. The work with these simple bridging ligands showed that unless measures are taken to uncouple the two centers electronically, electron transfer in these systems is adiabatic, a conclusion confirmed by studies of the properties of mixed valence molecules with the same bridging groups. Isied has gone on to study electron transfer through polyprolines using the same general kind of technique. Even with the simplest bridging group of the series, the reactions are nonadiabatic. They become quite slow as the length of the polypeptide chain increases, and with longer chains a conformation change in which the metal centers are brought closer together precedes electron transfer. A similar technique has also been applied by Isied and others to studying the rate of electron transfer between the iron center of cytochrome C and a ruthenium complex attached to a histidine diametrically opposite the heme group. 相似文献
993.
Theresa Rosario-jansen Henry J. Pownall Joseph P. Noel Ming-Daw Tsai 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):601-604
Abstract Thiophospholipids and thiophosphate analogs of platelet activating factor were synthesized and used to compare the stereochemical properties in three different biological systems. Phospholipase A2 shows high stereo-specificity, and this has been substantiated by computer graphics. Lecithin-cholesterol acyl transferase shows no stereospecificity. Platelet aggregation shows, preliminarily, a small degree of stereospecificity. 相似文献
994.
Prof. Dr. Marcus L. Cole Prof. Dr. Glen B. Deacon Dr. Craig M. Forsyth Prof. Dr. Peter C. Junk Dr. Kristina Konstas Dr. Jun Wang Henry Bittig Daniel Werner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1410-1420
New reactive, divalent lanthanoid formamidinates [Yb(Form)2(thf)2] (Form=[RNCHNR]; R=o‐MeC6H4 (o‐TolForm; 1 ), 2,6‐Me2C6H3 (XylForm; 2 ), 2,4,6‐Me3C6H2 (MesForm; 3 ), 2,6‐Et2C6H3 (EtForm; 4 ), o‐PhC6H4 (o‐PhPhForm; 5 ), 2,6‐iPr2C6H3 (DippForm; 6 ), o‐HC6F4 (TFForm; 7 )) and [Eu(DippForm)2(thf)2] ( 8 ) have been prepared by redox transmetallation/protolysis reactions between an excess of a lanthanoid metal, Hg(C6F5)2 and the corresponding formamidine (HForm). X‐ray crystal structures of 2 – 6 and 8 show them to be monomeric with six‐coordinate lanthanoid atoms, chelating N,N′‐Form ligands and cis‐thf donors. However, [Yb(TFForm)2(thf)2] ( 7 ) crystallizes from THF as [Yb(TFForm)2(thf)3] ( 7 a ), in which ytterbium is seven coordinate and the thf ligands are “pseudo‐meridional”. Representative complexes undergo C? X (X=F, Cl, Br) activation reactions with perfluorodecalin, hexachloroethane or 1,2‐dichloroethane, and 1‐bromo‐2,3,4,5‐tetrafluorobenzene, giving [Yb(EtForm)2F]2 ( 9) , [Yb(o‐PhPhForm)2F]2 ( 10) , [Yb(o‐PhPhForm)2Cl(thf)2] ( 11) , [Yb(DippForm)2Cl(thf)] ( 12) and [Yb(DippForm)2Br(thf)] ( 16) . X‐ray crystallography has shown 9 to be a six‐coordinate, fluoride‐bridged dimer, 12 and 16 to be six‐coordinate monomers with the halide and thf ligands cis to each other, and 11 to have a seven‐coordinate Yb atom with “pseudo‐meridional” unidentate ligands and thf donors cis to each other. The analogous terbium compound [Tb(DippForm)2Cl(thf)2] ( 13 ), prepared by metathesis, has a similar structure to 11 . C? Br activation also accompanies the redox transmetallation/protolysis reactions between La, Nd or Yb metals, Hg(2‐BrC6F4)2, and HDippForm, yielding [Ln(DippForm)2Br(thf)] complexes (Ln=La ( 14 ), Nd ( 15 ), Yb ( 16 )). 相似文献
995.
J. Wayne Mullinax David S. Hollman Prof. Henry F. Schaefer III 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7487-7495
Germanium has been a central feature in the renaissance of main‐group inorganic chemistry. Herein, we present the stationary‐point geometries of tetragermacyclobutadiene and its related isomers on the singlet potential energy surface at the CCSD(T)/cc‐pVTZ level of theory. Three of these 12 structures are reported for the first time and one of them is predicted to lie only 0.4 kcal mol?1 above the previously reported global minimum. Focal‐point analyses has provided electronic energies at the CCSD(T) level of theory, which are extrapolated to the complete basis‐set limit and demonstrate the convergence behavior of the electronic energies with improving levels of theory and increasing basis‐set size. The lowest‐energy structure is the bicyclic structure, which lies 35 kcal mol?1 below the “all‐Ge” cyclobutadiene structure. The reaction energies for the association of known Ge hydrides (e.g., digermene) to form Ge4H4 indicate that Ge4H4 could be observed experimentally. We investigate the bonding patterns by examining the frontier molecular orbitals. Our results demonstrate that: 1) the cyclic isomers of (GeH)4 distort to maximize the mixing of the p orbitals that are involved in the π system of tetragermacyclobutadiene and 2) the lowest‐energy isomers exhibit unusual bonding arrangements (e.g., bridging H bonds) that maximize the nonbonding electron density at the Ge centers. 相似文献
996.
997.
Henry ME Lauriat TL Shanahan M Renshaw PF Jensen JE 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,208(2):210-218
Proton magnetic resonance spectroscopy has the potential to provide valuable information about alterations in gamma-aminobutyric acid (GABA), glutamate (Glu), and glutamine (Gln) in psychiatric and neurological disorders. In order to use this technique effectively, it is important to establish the accuracy and reproducibility of the methodology. In this study, phantoms with known metabolite concentrations were used to compare the accuracy of 2D J-resolved MRS, single-echo 30 ms PRESS, and GABA-edited MEGA-PRESS for measuring all three aforementioned neurochemicals simultaneously. The phantoms included metabolite concentrations above and below the physiological range and scans were performed at baseline, 1 week, and 1 month time-points. For GABA measurement, MEGA-PRESS proved optimal with a measured-to-target correlation of R(2)=0.999, with J-resolved providing R(2)=0.973 for GABA. All three methods proved effective in measuring Glu with R(2)=0.987 (30 ms PRESS), R(2)=0.996 (J-resolved) and R(2)=0.910 (MEGA-PRESS). J-resolved and MEGA-PRESS yielded good results for Gln measures with respective R(2)=0.855 (J-resolved) and R(2)=0.815 (MEGA-PRESS). The 30 ms PRESS method proved ineffective in measuring GABA and Gln. When measurement stability at in vivo concentration was assessed as a function of varying spectral quality, J-resolved proved the most stable and immune to signal-to-noise and linewidth fluctuation compared to MEGA-PRESS and 30 ms PRESS. 相似文献
998.
The answers to data assimilation questions can be expressed as path integrals over all possible state and parameter histories. We show how these path integrals can be evaluated numerically using a Markov Chain Monte Carlo method designed to run in parallel on a graphics processing unit (GPU). We demonstrate the application of the method to an example with a transmembrane voltage time series of a simulated neuron as an input, and using a Hodgkin–Huxley neuron model. By taking advantage of GPU computing, we gain a parallel speedup factor of up to about 300, compared to an equivalent serial computation on a CPU, with performance increasing as the length of the observation time used for data assimilation increases. 相似文献
999.
The multiwavelength anomalous diffraction (MAD) method is used to determine phase information in x-ray crystallography by employing anomalous scattering from heavy atoms. X-ray free-electron lasers (FELs) show promise for revealing the structure of single molecules or nanocrystals, but the phase problem remains largely unsolved. Because of the ultrabrightness of x-ray FEL, samples experience severe electronic radiation damage, especially to heavy atoms, which hinders direct implementation of MAD with x-ray FELs. Here, we propose a generalized version of MAD phasing at high x-ray intensity. We demonstrate the existence of a Karle-Hendrickson-type equation in the high-intensity regime and calculate relevant coefficients with detailed electronic damage dynamics of heavy atoms. The present method offers a potential for ab initio structural determination in femtosecond x-ray nanocrystallography. 相似文献
1000.
Andriukaitis G Balčiūnas T Ališauskas S Pugžlys A Baltuška A Popmintchev T Chen MC Murnane MM Kapteyn HC 《Optics letters》2011,36(15):2755-2757
We demonstrate a compact 20 Hz repetition-rate mid-IR OPCPA system operating at a central wavelength of 3900 nm with the tail-to-tail spectrum extending over 600 nm and delivering 8 mJ pulses that are compressed to 83 fs (<7 optical cycles). Because of the long optical period (~13 fs) and a high peak power, the system opens a range of unprecedented opportunities for tabletop ultrafast science and is particularly attractive as a driver for a highly efficient generation of ultrafast coherent x-ray continua for biomolecular and element specific imaging. 相似文献