全文获取类型
收费全文 | 2252篇 |
免费 | 76篇 |
国内免费 | 6篇 |
专业分类
化学 | 1709篇 |
晶体学 | 52篇 |
力学 | 74篇 |
数学 | 126篇 |
物理学 | 373篇 |
出版年
2023年 | 9篇 |
2022年 | 16篇 |
2021年 | 43篇 |
2020年 | 49篇 |
2019年 | 63篇 |
2018年 | 63篇 |
2017年 | 47篇 |
2016年 | 56篇 |
2015年 | 72篇 |
2014年 | 72篇 |
2013年 | 161篇 |
2012年 | 160篇 |
2011年 | 161篇 |
2010年 | 88篇 |
2009年 | 84篇 |
2008年 | 144篇 |
2007年 | 116篇 |
2006年 | 126篇 |
2005年 | 103篇 |
2004年 | 72篇 |
2003年 | 58篇 |
2002年 | 72篇 |
2001年 | 38篇 |
2000年 | 32篇 |
1999年 | 22篇 |
1998年 | 22篇 |
1997年 | 18篇 |
1996年 | 19篇 |
1995年 | 18篇 |
1994年 | 16篇 |
1993年 | 15篇 |
1992年 | 28篇 |
1991年 | 20篇 |
1990年 | 14篇 |
1989年 | 13篇 |
1988年 | 7篇 |
1987年 | 14篇 |
1986年 | 16篇 |
1985年 | 13篇 |
1984年 | 23篇 |
1983年 | 24篇 |
1982年 | 16篇 |
1981年 | 8篇 |
1980年 | 10篇 |
1979年 | 14篇 |
1978年 | 11篇 |
1977年 | 17篇 |
1976年 | 9篇 |
1975年 | 8篇 |
1974年 | 10篇 |
排序方式: 共有2334条查询结果,搜索用时 93 毫秒
21.
From analysis by gas chromatography/mass spectrometry (GC/MS), the presence of either 2,4,5-tribromo-1H-imidazole (1) or 3,4,5-tribromo-1H-pyrazole (2) was tentatively identified in lipophilic extracts from the egg masses of three muricid molluscs. Synthesis of these compounds, followed by comparison of the GC retention times and fragmentation patterns from electron impact MS, with those of the natural products, indicated that it was 2,4,5-tribromo-1H-imidazole rather than the pyrazole. This imidazole is likely to be responsible for some of the antimicrobial activity observed in the egg extracts. This is the first report of this compound from a natural source. 相似文献
22.
Basic salts of Co(II) crystallize in the rhombohedral structure. Two different polytypes, 3R1 and 3R2, with distinct stacking sequences of the metal hydroxide slabs, are possible within the rhombohedral structure. These polytypes are generated by simple translation of successive layers by (2/3, 1/3, z) or (1/3, 2/3, z). The symmetry of the anion and the mode of coordination influences polytype selection. Cobalt hydroxynitrate crystallizes in the structure of the 3R2 polytype while the hydroxytartarate, hydroxychloride and α-cobalt hydroxide crystallize in the structure of the 3R1 polytype. Cobalt hydroxysulfate is turbostratically disordered. The turbostratic disorder is a direct consequence of the mismatch between the crystallographically defined interlayer sites generated within the crystal and the tetrahedral symmetry of the SO42− ions. 相似文献
23.
Recent research has demonstrated that in a simulated flue gas stream containing NO(2) and SO(2) elemental mercury is initially captured on a carbon or manganese oxide sorbent. After approximately an hour, however, mercury breaks through relatively rapidly, and the volatile form of mercury emitted is an oxidized species. The volatile mercury species emitted from a granular MnO(2) sorbent was trapped in an impinger containing cold acetonitrile. Subsequent evaporation of 95% of the acetonitrile in a Kuderna-Danish apparatus and gas chromatography (GC) of the concentrate resulted in a single mercury-containing GC peak at 5.5 min; the retention time and mass spectrum of this compound matched exactly those of a standard mercury(II) nitrate hydrate, Hg(NO(3))(2).H(2)O dissolved in acetonitrile. The volatile mercury component analyzed from injection of this standard solution was shown to be a form of methylmercury that is produced in the GC column by reaction of the highly reactive mercury nitrate with the methylsiloxane GC phase. Because the on-column derivatization reaction seems to be unique to mercury nitrate, the GC-MS (gas chromatography-mass spectroscopic) analysis provides strong evidence for identification of the trapped oxidized mercury species as mercury nitrate although, because the nitrate becomes detached from the mercury atom in the on-column reaction, the identity is not proven. 相似文献
24.
A new series of N-substituted bis-(tetrahydropapaverine) ring systems have been synthesised in expectation of better antispasmodic activity in comparison with papaverine. The synthesis of the targeted heterocycles is described along with a discussion of their structure activity relationship. The general synthetic methods of bis-(tetrahydropapaverine) analogues involve tetrahydropapaverine, various piperazines, diisocyanates and diisothiocyanates as starting materials. Pharmacological evaluation involves the in vitro antispasmodic activity on a freshly removed guinea pig ileum using a force displacement transducer amplifier connected to a physiograph. Among the analogues synthesized in the present study, N,N'-bis-[2-carbamoyl-1-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolinyl]piperazine (22), was found to be the most potent muscle relaxant (IC(50): 0.31 microM). 相似文献
25.
The photocyclization to benzocyclobutenols of o-alkyl aromatic aldehydes that are predestined for gamma-hydrogen abstraction is found to occur efficiently in the solid state; in contrast, solution-phase photolysis is known to afford a mixture of several products. It is shown that mesitaldehyde, which is a liquid, also undergoes efficient cyclization when subjected to photolysis as a solid inclusion complex. The marginal energy differences in the relative energies of the E-enols and the corresponding cyclobutenols in the case of cyano-substituted mesitaldehydes has permitted direct observation, for the first time, of the E-enols en route to benzocyclobutenols. The AM1 calculations suggest that the cyano-substitution causes intrinsic stabilization of the E-enols relative to the corresponding cyclobutenols, while the bromo groups do the opposite. The lack of observation of the red color in bromo- and formyl-substituted aldehydes is attributed to rapid cyclization of the E-enols to the their respective cyclobutenols even at low temperatures. 相似文献
26.
Crowe MC Kapoor RN Cervantes-Lee F Párkányí L Schulte L Pannell KH Brodbelt JS 《Inorganic chemistry》2005,44(18):6415-6424
Electrospray ionization (ESI) quadrupole ion trap mass spectrometry (QIT-MS) and collisionally activated dissociation (CAD) were used to evaluate the rare-earth binding properties of two hydrophobic carbamoylmethylphosphine oxide (CMPO) ligands, the normal bidentate variety, (t-BuC6H4)2P(O)CH2C(O)N(i-Bu)2 (A), a new potentially tridentate extractant, (t-BuC6H4)2P(O)CH[CH2C(O)N(i-Bu)2]C(O)N(i-Bu)2 (B), and tributyl phosphate. The mass spectral results obtained from analysis of 1% HNO3/methanol solution containing the ligands and dissolved lanthanide salts reveal that the favorable stoichiometries of the ligand/metal/nitrate complexes are 2:1:2 for the bidentate ligand A, 1:1:2 for the tridentate ligand B, and 3:1:2 for the monodentate tributyl phosphate. These observed stoichiometries correlate with the number of available binding sites on each ligand as well as with potential steric effects. Energy-variable collisionally activated dissociation experiments showed that for the 2:1:2 complexes involving ligand A or B, as the ionic radius of the bound metal decreased, the removal of nitric acid required less energy and resulted in less extensive spontaneous solvent coordination. This experimental trend suggests that, as the ionic radius of the lanthanide ion decreases, a pair of the carbamoylmethylphosphine ligands is able to more completely solvate the bound metal ion thereby weakening the nitrate-metal interaction. 相似文献
27.
A versatile synthesis has been developed to functionalize the 4-(2-aminoethyl)-6-dibenzofuran propionic acid residue (1a) at the 2 and 8 positions with a variety of different substructures. The unfunctionalized version of this peptidomimetic (1a) is known to facilitate beta-hairpin formation in a variety of small peptides and proteins in aqueous solution when incorporated in place of the i + 1 and i + 2 residues of a beta-turn. In this study, we append propionate substituents on 1a at the 2 and 8 positions to successfully overcome solubility problems encountered with the incorporation of 1a in place of the i + 1 and i + 2 residues of the beta-turn in loop 1 of the WW domain. The thermodynamic stability of several WW domain analogues incorporating residues 1a and 1b was compared to that of the wild-type sequence revealing comparable DeltaG(H(2)O) unfolding values at 4 degrees C ranging from 3 to 3.6 kcal/mol. WW domains incorporating residue 1b exhibit improved solubility (exceeding 100 microM) and resistance to aggregation without compromising thermodynamic stability. 相似文献
28.
Ramesh P Okazaki T Taniguchi R Kimura J Sugai T Sato K Ozeki Y Shinohara H 《The journal of physical chemistry. B》2005,109(3):1141-1147
Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes. 相似文献
29.
Methods for concentrating dilute fluids using adsorption followed by partial thermal regeneration were studied using the simulation package ADSIM. The systems studied were NaCl in liquid water on Amberlite XD-2 resin and benzene vapor in nitrogen on activated carbon. Cycles studied included counter-current regeneration with pure hot fluid, co-current regeneration with pure hot fluid, a new process called Hot Feed Addition (HFA) consisting of co-current regeneration with pure hot fluid followed by hot feed, and cycling zone adsorption (co-current alternating hot and cold feeds with no pure regeneration fluid). The optimum system depends upon the conditions of the system and the value function chosen to evaluate the systems. For example, for benzene in nitrogen with hot regeneration gas at 467.4 K, cycling zone adsorption used no carrier gas, had the most concentrated benzene stream and a very pure nitrogen product, but the energy use was greater than the other processes. For liquid systems counter-current operation could produce the purest product, but regenerant requirements were high. With slightly lower purity requirements HFA reduced solvent usage and increased the concentration of the concentrated waste stream. For the liquid system all processes used approximately 3% or less of the energy that would be required for evaporation. 相似文献
30.
Mariappan PeriasamyN. KishoreBabu Keela Natarajan Jayakumar 《Tetrahedron letters》2003,44(50):8939-8941
The reactions of arylacetic acid esters with tertiary arylamines in the presence of TiCl4 give α-arylated products in 65-90% yields, as well as 10-20% yields of the corresponding benzidines. 相似文献