全文获取类型
收费全文 | 6929篇 |
免费 | 299篇 |
国内免费 | 32篇 |
专业分类
化学 | 4791篇 |
晶体学 | 58篇 |
力学 | 133篇 |
数学 | 1178篇 |
物理学 | 1100篇 |
出版年
2024年 | 11篇 |
2023年 | 51篇 |
2022年 | 142篇 |
2021年 | 177篇 |
2020年 | 136篇 |
2019年 | 155篇 |
2018年 | 132篇 |
2017年 | 118篇 |
2016年 | 288篇 |
2015年 | 229篇 |
2014年 | 233篇 |
2013年 | 545篇 |
2012年 | 532篇 |
2011年 | 585篇 |
2010年 | 335篇 |
2009年 | 268篇 |
2008年 | 427篇 |
2007年 | 378篇 |
2006年 | 337篇 |
2005年 | 353篇 |
2004年 | 264篇 |
2003年 | 236篇 |
2002年 | 202篇 |
2001年 | 104篇 |
2000年 | 88篇 |
1999年 | 48篇 |
1998年 | 60篇 |
1997年 | 54篇 |
1996年 | 93篇 |
1995年 | 44篇 |
1994年 | 44篇 |
1993年 | 56篇 |
1992年 | 41篇 |
1991年 | 38篇 |
1990年 | 45篇 |
1989年 | 36篇 |
1988年 | 34篇 |
1987年 | 38篇 |
1986年 | 22篇 |
1985年 | 41篇 |
1984年 | 31篇 |
1983年 | 21篇 |
1982年 | 26篇 |
1981年 | 26篇 |
1980年 | 18篇 |
1979年 | 15篇 |
1978年 | 8篇 |
1977年 | 15篇 |
1976年 | 11篇 |
1974年 | 9篇 |
排序方式: 共有7260条查询结果,搜索用时 15 毫秒
101.
A molecular mechanics force field for studying some beta-lactams was developed from ab initio and experimental data. The optimized parameters allowed accurate calculation of the geometries of both the compounds on which the parametrization was based and others on which the validity of the predictions was checked. © 1994 by John Wiley & Sons, Inc. 相似文献
102.
The open circuit dissolution of ionic metal oxides in mineral acids is modelled assuming that the rate is controlled by the transfer of metal ions in hydrolytic equilibrium with bulk metal ions, from the metal oxide surface to the Stern plane. The site-binding model of the double layer metal oxide/electrolyte solution is used to obtain the pH dependence of surface and Stern potentials. The nature of the active sites is discussed and their surface concentration is assumed to be proportional to suface charge σ0. Again, the site-binding model is used to detemine the pH dependence of σ0. It is thus shown that the rate order in cH+ is essentially defined by the potential dependence of the charge transfer process, for oxides with points of zero charge near neutrality that dissolve in mildly or strongly acidic solutions. The role of surface complexation is also discussed in terms of the site-binding model and the difficulties in interpreting dissolution experiments under constant external applied potential are discussed in terms of the complexity of the semiconductor oxide/electrolyte solution interfacial region in magnetite.An experimental study of the open circuit dissolution of magnetite in sulfuric acid is presented and interpreted according to the proposed model.The reductive dissolution of magnetite is modelled by extension of the Valverde-Wagner model of oxide dissolution. Experimental results are presented to demonstrate that the reductive dissolution rate of magnetite in ferrous containing solutions is controlled by the rate of electron transfer from adsorbed Fe(II) to Fe(III) surface states of magnetite. 相似文献
103.
Ichimura AS Dye JL Camblor MA Villaescusa LA 《Journal of the American Chemical Society》2002,124(7):1170-1171
Electrides are materials in which alkali metals (Li through Cs) ionize to form bound alkali cations and "excess" electrons. The electrons reside in large cavities or channels or both in the host lattice. We report here the first synthesis of thermally stable inorganic electrides with cation-to-electron ratios of 1:1 as in organic electrides. Although alkali metal adducts to alumino-silicate zeolites are well known, the cation-to-electron ratio is generally 3:1 or greater because these zeolites contain alkali cations prior to incorporation of the alkali metal. In this work, two pure silica zeolites, ITQ-4and ITQ-7, with pore diameters of approximately 7 A, absorb up to 40 wt % cesium from the vapor phase (even at room temperature). The other alkali metals (except Li) can also be introduced at elevated temperatures. The optical and magnetic properties of the cesium-loaded samples suggest ionization to form Cs+ and e- with substantial electron-spin pairing. The metal-loaded samples are stable to at least 100 degrees C and are able to reduce small aromatic molecules such as benzene and naphthalene to the radical anions within the pores of the zeolite. 相似文献
104.
I. M. Miranda Salvado F. M. A. Margaça J. Teixeira 《Journal of Sol-Gel Science and Technology》1994,2(1-3):289-294
Silica-titania gels, prepared in acidic conditions, with contents of TiO2 up to 6 mol%, have been studied by small angle neutron scattering (SANS) as wet gel with increasing aging times. In all samples, small primary particles have been found with a diameter of about 3 nm. At the gel point, cylindrical clusters, ca. 10 nm long, were observed as well. These grow with aging time, becoming branched. The cluster-cluster diffusion limited aggregation model is found to be consistent with the SANS results. The growth process is independent of the TiO2 content. It is mainly influenced by the ratio of the aging time to the gelation time. 相似文献
105.
Cabeza A Ouyang X Sharma CV Aranda MA Bruque S Clearfield A 《Inorganic chemistry》2002,41(9):2325-2333
Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation. 相似文献
106.
Miguel Gascón-LópezMajid Motevalli George PaloumbisPeter Bladon Peter B Wyatt 《Tetrahedron》2003,59(47):9349-9360
Stabilised tributylphosphonium ylids Bu3PCHCH(EWG), where EWG is CO2Me, CO2tBu or CN, react with protected sugar lactones under mild conditions to give high yields of glycosylidene derivatives (4 and 5) with good Z/E selectivity. X-Ray crystallography shows that in the solid state the tetra-O-benzyl protected (Z)-glucosylideneacetonitrile (Z)-4c adopts a conformation intermediate between a boat and a twist-boat, whereas the isomeric galactose derivative (Z)-5c exists as a distorted chair. NMR data suggest that in solution chair-like conformations are again more favoured for galactosylidene derivatives than for their glucosylidene analogues. Solution phase NMR studies and molecular modelling show that the (E)-double bond geometry disfavours the chair-like geometry of the ring, even in the galactose series; this is consistent with the avoidance of allylic 1,3-strain. Reduction of the glycosylidene double bond to give stereoselective formation of β-C-glycoside derivatives may be achieved by using Et3SiH-CF3CO2H or Et3SiH-BF3·Et2O. 相似文献
107.
Castro C Karney WL Valencia MA Vu CM Pemberton RP 《Journal of the American Chemical Society》2005,127(27):9704-9705
Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes. 相似文献
108.
We have investigated the transitions between disordered phases in supercooled liquid silicon using computer simulations. The thermodynamic properties were directly obtained from the free energy, which was computed using the recently proposed reversible scaling method. The calculated free energies of the crystalline and liquid phases of silicon at zero pressure, obtained using the environment dependent interatomic potential, are in excellent agreement with the available experimental data. The results show that, at zero pressure, a weak first-order liquid-liquid transition occurs at 1135 K and a continuous liquid-amorphous transition takes place at 843 K. These results are consistent with the existence of a second critical point for the liquid-liquid transition at a negative pressure. 相似文献
109.
The Ramanujan Journal - This paper provides elementary proofs for several types of congruences involving multipartitions and self-convolutions of the divisor function. Our computations use... 相似文献
110.
Nazarov Anatoly Sztrik János Kvach Anna Tóth Ádám 《Methodology and Computing in Applied Probability》2022,24(3):1503-1518
Methodology and Computing in Applied Probability - This paper deals with a retrial queuing system with a finite number of sources and collision of the customers, where the server is subject to... 相似文献