全文获取类型
收费全文 | 1569篇 |
免费 | 45篇 |
国内免费 | 3篇 |
专业分类
化学 | 1153篇 |
晶体学 | 25篇 |
力学 | 62篇 |
数学 | 92篇 |
物理学 | 285篇 |
出版年
2023年 | 7篇 |
2022年 | 22篇 |
2021年 | 30篇 |
2020年 | 44篇 |
2019年 | 50篇 |
2018年 | 40篇 |
2017年 | 36篇 |
2016年 | 44篇 |
2015年 | 48篇 |
2014年 | 56篇 |
2013年 | 112篇 |
2012年 | 120篇 |
2011年 | 124篇 |
2010年 | 68篇 |
2009年 | 60篇 |
2008年 | 111篇 |
2007年 | 69篇 |
2006年 | 89篇 |
2005年 | 67篇 |
2004年 | 48篇 |
2003年 | 36篇 |
2002年 | 37篇 |
2001年 | 23篇 |
2000年 | 18篇 |
1999年 | 15篇 |
1998年 | 12篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 13篇 |
1994年 | 9篇 |
1993年 | 9篇 |
1992年 | 12篇 |
1991年 | 9篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 10篇 |
1986年 | 9篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 7篇 |
1980年 | 9篇 |
1979年 | 13篇 |
1978年 | 11篇 |
1977年 | 16篇 |
1976年 | 5篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1964年 | 3篇 |
排序方式: 共有1617条查询结果,搜索用时 15 毫秒
11.
Summary The iron(III) compound, FeCl(OH)(MeCO2) · MeCO2H · 0.5 H2O, (1), interacts with the sample bidentate ligand, 2,2-bipyridyl (bipy), to form an aduct, Fe2Cl2(OH)2(MeCO2)2 · (bipy). By the loss of protons, anthranilic (anthH) and salicylic (salH2) acids behave as uninegative charged ligands to give FeCl(anth)2 · H2O and FcCl(salH)2 · H2O, respectively. The former decomposes on heatingin vacuo to form Fe2O(anth)4 while the latter yields Fe2O(sal)2. Acetylacetone (acacH) and 8-hydroxyquinoline (quinH) give FeCl(acac)2 and FeCl(quin)2 · (quinH). The latter desolvates at 140°/10–4 torr to form FeCl(quin)2. l.r. spectra, thermal decomposition, molar conductance and magnetic susceptibility studies at room temperature have been used to characterize these compounds. 相似文献
12.
Summary Reactions of titanium(IV) isopropoxide with ethyl 1-hydroxycyclohexylacetate, ethyl 2-hydroxy-2-arylpropionate, ethyl 2-hydroxy-2-arylbutyrate and ethyl 2-hydroxy-2-arylhydrocinnamate have been studied in dry benzene in different molar ratios under strictly anhydrous conditions. The Ti(OPr-i)4-nLn type compounds, where L = hydroxy ester and n = 1 to 4, have been isolated and characterised by elemental analysis, molecular weight, i.r. and n.m.r. spectral studies. These products may be distilled unchanged under reduced pressure.Reprints of this are not available. 相似文献
13.
Pramesh N. Kapoor Ajay K. Bhagi Ramesh N. Kapoor 《Journal of organometallic chemistry》1991,420(3):321-325
The first organotin(IV), aluminium(III)-μ-oxoisoprovides of the type [R3SnOA](OiPr)2] (R = Me or Ph) have been made by heating of trimethyl- or triphenyl-tin acetate with aluminium isopropoxide. The reactions of these μ-oxoisopropoxides with benzoylacetone in 1:1 and 1:2 molar ratios yielded the compounds of the type [R3SnOAl(OiPr)(bzac)] and [R3SnOAl(bzac)2] (where R = Me or Ph and BZAC = deprotonated benzoylacetone), respectively. 相似文献
14.
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
15.
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
16.
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
17.
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
18.
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
19.
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
20.
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