全文获取类型
收费全文 | 1471篇 |
免费 | 60篇 |
国内免费 | 11篇 |
专业分类
化学 | 1048篇 |
晶体学 | 7篇 |
力学 | 50篇 |
数学 | 215篇 |
物理学 | 222篇 |
出版年
2023年 | 14篇 |
2022年 | 10篇 |
2021年 | 25篇 |
2020年 | 24篇 |
2019年 | 37篇 |
2018年 | 23篇 |
2017年 | 12篇 |
2016年 | 50篇 |
2015年 | 38篇 |
2014年 | 30篇 |
2013年 | 51篇 |
2012年 | 80篇 |
2011年 | 101篇 |
2010年 | 42篇 |
2009年 | 43篇 |
2008年 | 74篇 |
2007年 | 92篇 |
2006年 | 77篇 |
2005年 | 80篇 |
2004年 | 71篇 |
2003年 | 57篇 |
2002年 | 52篇 |
2001年 | 22篇 |
2000年 | 45篇 |
1999年 | 31篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 11篇 |
1995年 | 15篇 |
1994年 | 10篇 |
1992年 | 14篇 |
1991年 | 22篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 7篇 |
1986年 | 9篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1983年 | 14篇 |
1982年 | 16篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 14篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 8篇 |
1975年 | 10篇 |
1974年 | 10篇 |
1973年 | 12篇 |
1969年 | 7篇 |
排序方式: 共有1542条查询结果,搜索用时 17 毫秒
31.
Alvarez-Bercedo P Bond AD Haigh R Hopkins AD Lawson GT McPartlin M Moncrieff D Mosquera ME Rawson JM Woods AD Wright DS 《Chemical communications (Cambridge, England)》2003,(11):1288-1289
The reaction of CyPHNa with Sn(NMe2)2 in the presence of PMDETA (= (Me2NCH2CH2)2NMe) gives the title compound [(Sn(mu-PCy))3(Na x PMDETA)2] (1), containing an electron-deficient [(Sn(mu-PCy))]3(2-) dianion with a novel two-electron, three centre (2e-3c) bonding arrangement. 相似文献
32.
33.
Functional-based screening of crude β-galactosidase activities from 42 yeast strains resulted in the selection of a single
enzyme of potential interest as a digestive supplement. β-Galactosidase produced by Kluyveromyces marxianus DSM5418 was purified to homogeneity by a combination of gel filtration, ion-exchange, and hydroxylapatite chromatographies.
The denatured (123 kDa) and native molecular masses (251 kDa) suggest that the enzyme is a homodimer. The optimum pH and temperature
of the purified enzyme were 6.8 and 37°C, respectively. The unpurified β-galactosidase in particular displayed a high level
of stability when exposed to simulated intestinal conditions in vitro for 4 h. Matrix-assisted laser desorption ionization
mass sectrometry analysis revealed that the enzyme's trypsin-generated peptide mass fingerprint shares several peptide fragment
hits with β-galactosidases from Kluyveromyces lactis. This confirms the enzyme's identity and indicates that significant sequence homology exists between these enzymes. 相似文献
34.
Brittain DE Gray BL Schreiber SL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):5086-5093
A crossover in the ability of two distinct ruthenium-based metathesis pre-catalysts to effect the synthesis of dialkenylboronic esters in solution and on the solid-phase was observed. Specifically, while the Grubbs 2nd generation pre-catalyst 3 affords a greater degree of conversion to product than the Hoveyda-Grubbs pre-catalyst 2 in a solution-phase enyne-metathesis reaction, this trend is reversed in the solid-phase variant. Systematic investigation showed this trend to be general, regardless of variations in the homoallylic alcohol and alkynylboronic ester components of the reaction, as well as in the type of solid support employed. Experiments to determine a mechanistic hypothesis for this trend highlighted the significance of the ruthenium remaining bound to the substrate after metathetic rearrangement and found the presence of phosphine ligand to be detrimental to the success of the solid-phase reaction. Therefore, these results suggest an expanded role for phosphine-free pre-catalysts, such as 2, in challenging solid-phase metathesis reactions. 相似文献
35.
Rios R Jimeno C Carroll PJ Walsh PJ 《Journal of the American Chemical Society》2002,124(35):10272-10273
We have demonstrated the feasibility of the kinetic resolution of atropisomeric amides using the commercially avaliable AD-mix. To our knowledge, this methodology represents the first catalytic kinetic resolution of such compounds. Relative rates of up to 32 have been found for the kinetic resolution processes. We have also determined the barriers to rotation and half-lives of some of these amides. The half-lives range from 7 to 135 h at room temperature. 相似文献
36.
Reversible storage of molecular hydrogen by sorption into multilayered TiO2 nanotubes 总被引:4,自引:0,他引:4
Bavykin DV Lapkin AA Plucinski PK Friedrich JM Walsh FC 《The journal of physical chemistry. B》2005,109(41):19422-19427
The sorption of hydrogen between the layers of the multilayered wall of nanotubular TiO2 was studied in the temperature range of -195 to 200 degrees C and at pressures of 0 to 6 bar. Hydrogen can intercalate between layers in the walls of TiO2 nanotubes forming host-guest compounds TiO2 x xH2, where x < or = 1.5 and decreases at higher temperatures. The rate of hydrogen incorporation increases with temperature and the characteristic time for hydrogen sorption in TiO2 nanotubes is several hours at 100 degrees C. The rate of intercalate formation is limited by the diffusion of molecular hydrogen inside the multilayered walls of the TiO2 nanotube. 1H NMR-MAS and XRD data confirm the incorporation of hydrogen between the layers in the walls of TiO2 nanotubes. The nature and possible applications of the observed intercalates are considered. 相似文献
37.
Chow DC Lee WK Zauscher S Chilkoti A 《Journal of the American Chemical Society》2005,127(41):14122-14123
Nucleic acid nanostructures are useful as templates for bionanofabrication of composite molecular nanostructures in materials science, molecular electronics, and biosensing. Here, we demonstrate that terminal deoxynucleotidyl transferase, which repetitively adds mononucleotides to the 3' end of a short DNA initiator, can be used to rapidly fabricate DNA nanostructures up to 121 nm high with lateral dimensions from 0.1 to 4 mum in 2 h. These programmable scaffolds can potentially be employed to build more complex nanostructures consisting of natural or unnatural nucleotides with selective docking sites along the single-stranded DNA. 相似文献
38.
In this Communication, we outline a new one-pot, multicomponent coupling reaction that allows easy access to (Z)-trisubstituted allylic alcohols. Our strategy is based on E to Z isomerization of the 1-bromo-1-dialkylvinylborane upon reaction with dialkylzinc reagents, and subsequent transmetalation to give (Z)-trisubstituted vinylzinc species. In situ trapping of the reactive vinylzinc intermediates with aldehydes furnished a series of (Z)-trisubstituted allylic alcohols. This method represents a viable alternative to the Still-Gennari modification of the HWE olefination reaction, and it has the advantage that it allows coupling of larger fragments. 相似文献
39.
Liane M. Moreau Alexandre Herve Mark D. Straub Dominic R. Russo Rebecca J. Abergel Selim Alayoglu John Arnold Augustin Braun Gauthier J. P. Deblonde Yangdongling Liu Trevor D. Lohrey Daniel T. Olive Yusen Qiao Julian A. Rees David K. Shuh Simon J. Teat Corwin H. Booth Stefan G. Minasian 《Chemical science》2020,11(18):4648
We report the structural properties of ultra-small ThO2 and UO2 nanoparticles (NPs), which were synthesized without strong binding surface ligands by employing a covalent organic framework (COF-5) as an inert template. The resultant NPs were used to observe how structural properties are affected by decreasing grain size within bulk actinide oxides, which has implications for understanding the behavior of nuclear fuel materials. Through a comprehensive characterization strategy, we gain insight regarding how structure at the NP surface differs from the interior. Characterization using electron microscopy and small-angle X-ray scattering indicates that growth of the ThO2 and UO2 NPs was confined by the pores of the COF template, resulting in sub-3 nm particles. X-ray absorption fine structure spectroscopy results indicate that the NPs are best described as ThO2 and UO2 materials with unpassivated surfaces. The surface layers of these particles compensate for high surface energy by exhibiting a broader distribution of Th–O and U–O bond distances despite retaining average bond lengths that are characteristic of bulk ThO2 and UO2. The combined synthesis and physical characterization efforts provide a detailed picture of actinide oxide structure at the nanoscale, which remains highly underexplored compared to transition metal counterparts.ThO2 and UO2 nanoparticles synthesized using a COF-5 template exhibit unpassivated surfaces and provide insight into nanoscale properties of actinides. 相似文献
40.
Costa AM Jimeno C Gavenonis J Carroll PJ Walsh PJ 《Journal of the American Chemical Society》2002,124(24):6929-6941
The optimization of asymmetric catalysts for enantioselective synthesis has conventionally revolved around the synthesis and screening of enantiopure ligands. In contrast, we have optimized an asymmetric reaction by modification of a series of achiral ligands. Thus, employing (S)-3,3'-diphenyl BINOL [(S)-Ph(2)-BINOL] and a series of achiral diimine and diamine activators in the asymmetric addition of alkyl groups to benzaldehyde, we have observed enantiomeric excesses between 96% (R) and 75% (S) of 1-phenyl-1-propanol. Some of the ligands examined have low-energy chiral conformations that can contribute to the chiral environment of the catalyst. These include achiral diimine ligands with meso backbones that adopt chiral conformations, achiral diimine ligands with backbones that become axially chiral on coordination to metal centers, achiral diamine ligands that form stereocenters on coordination to metal centers, and achiral diamine ligands with pendant groups that have axially chiral conformations. Additionally, we have structurally characterized (Ph(2)-BINOLate)Zn(diimine) and (Ph(2)-BINOLate)Zn(diamine) complexes and studied their solution behavior. 相似文献