全文获取类型
收费全文 | 4819篇 |
免费 | 284篇 |
国内免费 | 32篇 |
专业分类
化学 | 3327篇 |
晶体学 | 57篇 |
力学 | 169篇 |
数学 | 752篇 |
物理学 | 830篇 |
出版年
2023年 | 34篇 |
2022年 | 137篇 |
2021年 | 145篇 |
2020年 | 97篇 |
2019年 | 188篇 |
2018年 | 151篇 |
2017年 | 107篇 |
2016年 | 240篇 |
2015年 | 154篇 |
2014年 | 246篇 |
2013年 | 475篇 |
2012年 | 280篇 |
2011年 | 293篇 |
2010年 | 208篇 |
2009年 | 198篇 |
2008年 | 213篇 |
2007年 | 203篇 |
2006年 | 203篇 |
2005年 | 169篇 |
2004年 | 154篇 |
2003年 | 130篇 |
2002年 | 172篇 |
2001年 | 72篇 |
2000年 | 109篇 |
1999年 | 64篇 |
1998年 | 40篇 |
1997年 | 46篇 |
1996年 | 35篇 |
1995年 | 36篇 |
1994年 | 35篇 |
1993年 | 37篇 |
1992年 | 32篇 |
1991年 | 23篇 |
1990年 | 16篇 |
1989年 | 29篇 |
1988年 | 27篇 |
1987年 | 20篇 |
1986年 | 17篇 |
1985年 | 29篇 |
1984年 | 24篇 |
1983年 | 22篇 |
1982年 | 22篇 |
1981年 | 26篇 |
1980年 | 16篇 |
1979年 | 17篇 |
1978年 | 15篇 |
1977年 | 9篇 |
1976年 | 13篇 |
1975年 | 17篇 |
1959年 | 8篇 |
排序方式: 共有5135条查询结果,搜索用时 15 毫秒
91.
A fundamental study was made on the reduction of calcium phosphate by carbon. The mechanism of reduction was presented on applying different additions. Both silica and alumina increased the extent of reduction but with variable rates. The activation energies were calculated on the basis of first-order reactions. The phases formed during reduction were investigated by X-ray analysis. 相似文献
92.
E. Betranhandy Samir F. Matar Ch. El‐Kfoury R. Weihrich J. Etourneau 《无机化学与普通化学杂志》2004,630(15):2587-2598
The changes in electronic structure and hardness as inferred from the bulk modulus are investigated for model structures of ternary compounds XC3N3 (X = B, Al, P, As, Ga) within the framework of density functional theory (DFT). The optimisations of the proposed two‐ (2D) and three‐dimensional (3D) structures and the calculations of the bulk moduli are performed by a pseudo potential method. The electronic structures are calculated with the augmented sphere wave method (ASW). The obtained hardness for 2D BC3N3 system (B0 ~ 220 GPa) points to a magnitude close to that of graphitic C3N4. For heavier X atoms it decreases rapidly. This is equally observed for the 3D systems examined in the β‐C3N4 structure for which B0(β‐BC3N3) amounts to ~330 GPa. Within the magnitude of the well known hard material cubic BN, the BC3N3 phases can be predicted as candidates for ultra hard materials. The electronic effect induced by the chemical nature of the X substitutional was examined according to its position in the periodic table i.e. XIII or XV. Both, band structures and the electron localisation function (ELF) were used for this analysis. The ELF plots show a decreasing covalency with heavier X‐atoms. Potential applications of the devised systems are proposed such as dopings with atoms (Li, rare gas) and molecules (N2). 相似文献
93.
Abdelfetah Mounir Mohamed El Guendouzi Abderrahim Dinane 《Journal of solution chemistry》2002,31(10):793-799
Ternary aqueous solutions of MgSO4 and K2SO4 have been studied by the hygrometric method at 25°C. The relative humidity of this system is measured at total molalities from 0.35 mol-kg–1 to about saturation for three ionic-strength fractions (y = 0.25, 0.50, and 0.80 of MgSO4. The data allow calculation of water activities and osmotic coefficients. From these measurements, the Pitzer ionic mixing parameters are determined and used to predict the solute activity coefficients in the mixture. The results are used to calculate the excess Gibbs energy at total molalities for ionic-strength fraction y. 相似文献
94.
The elucidation of structures of glutathione (GSH) complexes play an important role in the fundamental understanding of biochemical pathways of metal ion deactivation in plants. This article attempts to feature key studies for stoichiometry of metal complexes with glutathione and its constituent amino acids to obtain a better understanding of the different metal affinities of the complexation sites of glutathione. The SEC-ICP-MS experiments have indicated that oxidation process of glutathione was accelerated by metal ion presence in following order Cu+, Pb2+ and Cd2+. The redox activity of metal ions was confirmed by ESI-MS experiments, which allowed to observe formation of glutathione disulphide (GSSG) in time. The stoichiometry of Cd2+, Cu+ and Pb2+ complexes with GSH was defined by observing the isotope pattern of investigated metals and hydrogen loss or transfer during binding. The complexes with metal bound to sulphur of 1:1 and 1:2 stoichiometry were found in case of cadmium and lead. The number of hydrogen atoms lost during metal binding and the SEC-ESI-MS results allowed to elucidate that copper is bound by GSSG in ratio 1:1 and 1:2. Additionally, size exclusion chromatography coupled to electrospray MS allowed to differentiate more stable complexes from weak ones that could be created in the gas phase. 相似文献
95.
The paper presents a new method for the generation of acetaldehyde in the amounts that allow to calibrate the measuring system. The method is based on thermal decomposition of surface compounds at the range 130-190 °C, in which an acetaldehyde as the decomposition product is released. The synthetic pathway leading to the desired surface compounds is described. Investigations demonstrated that the synthesis of the compounds on the surface of the support material (silica gel) was carried out homogeneously. The technique proposed was used for the generation of gaseous standard mixtures containing acetaldehyde for the calibration of a thermal desorber-gas chromatograph-flame ionization detector system. 相似文献
96.
The new unsymmetrical N‐bridgehead, apo (zeromethine), mono‐methine, dimethine, meso substituted tetramethine and styryl cyanine dyes incorporating pyrazolo (4,5‐b) indolizine (benzoindolizine) nuclei were prepared. Structural confirmation was carried out by elemental analyses, IR, H‐NMR, mass spectra and 13C‐NMR with the aid of carbon DEPT spectral data. The visible absorption spectra for the newly synthesized cyanines were examined in 95% ethanol. 相似文献
97.
3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described. 相似文献
98.
Joy Chakraborty Brajagopal Samanta Andrei S. Batsanov Joan Ribas M. Salah El Fallah Samiran Mitra 《Structural chemistry》2006,17(4):401-407
A ligand–metal–ligand type co-ordination polymer [Ni (C6H12N4)(NCS)2(H2O)2]
n
has been synthesised under controlled hydrothermal conditions. Here 1,3,5,7-tetraazatricyclo[3.3.1]decane [or hexamethylenetetramine (hmt)] has been used as a μ-(N,N′) bidentate spacer molecule. The prepared polymeric complex has been characterised by elemental and spectral analyses. The structure has been confirmed by a single crystal X-ray diffraction study. Magneto-structural correlation has been drawn from cryomagnetic susceptibility measurements (2–300 K) which unequivocally reflects very weak magnetic spin interactions among the long distant octahedral Ni(II) metal centres mediated by hmt and weak hydrogen bonding interactions between the adjacent zigzag one-dimensional polymeric chains carrying into a two-dimensional infinite polymeric framework. 相似文献
99.
Emulsion liquid membranes (ELM) with di-2-ethylhexylphosphoric acid in n-alkane, and dipicrylamine and cobalt(III) dicarbollide in nitrobenzene stabilized in double emulsions by SPAN 80/85 surfactant were used for preconcentration of radioactive fission products (137Cs,90Sr,139Ce, and152Eu) from slightly acidic nitrate solutions. The efficiency of sulfuric, phosphotungstic and silicotungstic acids as stripping agents, and picric acid as the bulky anion additive was investigated. A group separation of the fission products is possible by the ELM technique and can be considered for their removal from waste water solutions. 相似文献
100.
van Hooft PA El Oualid F Overkleeft HS van der Marel GA van Boom JH Leeuwenburgh MA 《Organic & biomolecular chemistry》2004,2(9):1395-1403
The scope of a stereoselective three-step approach for the synthesis of sugar derived spiroketals is presented. The methodology consists of Grignard addition of vinyl- or allylmagnesium bromide to a carbohydrate lactone, followed by K-10 clay mediated glycosidation with a terminal alkenol and subsequent ring-closing metathesis of the resulting diene. The generality of this procedure is demonstrated by the synthesis of various pyranose- and furanose-derived spiroketals, as well as more advanced tricyclic spiroketal derivatives. It is shown that functionalisation of the double bond in the resulting spiroketals leads to fused polycyclic ethers. 相似文献