全文获取类型
收费全文 | 9766篇 |
免费 | 186篇 |
国内免费 | 38篇 |
专业分类
化学 | 6099篇 |
晶体学 | 134篇 |
力学 | 295篇 |
数学 | 1095篇 |
物理学 | 2367篇 |
出版年
2022年 | 58篇 |
2021年 | 62篇 |
2020年 | 93篇 |
2019年 | 103篇 |
2017年 | 64篇 |
2016年 | 127篇 |
2015年 | 116篇 |
2014年 | 166篇 |
2013年 | 463篇 |
2012年 | 371篇 |
2011年 | 438篇 |
2010年 | 234篇 |
2009年 | 252篇 |
2008年 | 420篇 |
2007年 | 430篇 |
2006年 | 441篇 |
2005年 | 397篇 |
2004年 | 352篇 |
2003年 | 307篇 |
2002年 | 292篇 |
2001年 | 205篇 |
2000年 | 213篇 |
1999年 | 112篇 |
1998年 | 104篇 |
1997年 | 109篇 |
1996年 | 155篇 |
1995年 | 129篇 |
1994年 | 172篇 |
1993年 | 187篇 |
1992年 | 168篇 |
1991年 | 123篇 |
1990年 | 119篇 |
1989年 | 130篇 |
1988年 | 100篇 |
1987年 | 122篇 |
1986年 | 114篇 |
1985年 | 191篇 |
1984年 | 160篇 |
1983年 | 102篇 |
1982年 | 128篇 |
1981年 | 127篇 |
1980年 | 139篇 |
1979年 | 135篇 |
1978年 | 132篇 |
1977年 | 117篇 |
1976年 | 131篇 |
1975年 | 116篇 |
1974年 | 133篇 |
1973年 | 129篇 |
1971年 | 65篇 |
排序方式: 共有9990条查询结果,搜索用时 0 毫秒
141.
To determine the free concentration of a drug (propranolol) in the interstitial space in humans in vivo, seven male students were investigated by microdialysis of the periumbilical subcutaneous tissue. The microdialysis catheters were calibrated in vivo and the propranolol concentration was determined by high-performance liquid chromatography. Ten hours after intake of 80 mg of propranolol, the total plasma and free interstitial propranolol concentrations were 80 +/- 43 and 7 +/- 2 nM, respectively. After a second dose, maximum concentration was reached after 80 +/- 10 min and 98 +/- 12 min, in plasma, and the concentrations in the interstitial water were 594 +/- 138 and 27 +/- 7 nM, respectively. In a second study, microdialysis was performed on the left ventricular wall in six pigs receiving an intravenous injection of 5 mg of propranolol followed by a constant propranolol infusion for 40 min (5 mg propranolol per h). The maximum concentrations of propranolol were 97 +/- 29 and 6 +/- 2 nM in plasma and in interstitial water, respectively. The data suggest that microdialysis is a useful tool for recording the free concentrations of a drug in the interstitial space. 相似文献
142.
The electron impact (EI) and chemical ionization (CI) spectra of 2,2-diphenyl-3-aryl cyclobutanone oximes (1–5) are reported. Formation of diphenylmethyl cation at m/z 167 is a major fragmentation process in both EI and CI spectra. Labelling studies established that the hydrogen involved in this rearrangement transfers from the NOH group and not from cyclobutane ring positions. The [M + 3]+ ions are formed under CI conditions as a result of C?N double bond reduction. An interesting secondary kinetic isotope effect is observed in the formation of ion e at m/z 183 in both EI and CI spectra. Other characteristic fragmentation pathways occurring in the EI and CI spectra of these compounds are outlined. 相似文献
143.
THE CONTROL BY PHYTOCHROME OF NITRATE REDUCTASE IN THE CURD OF LIGHT-GROWN CAULIFLOWER 总被引:4,自引:0,他引:4
Abstract— The activity of nitrate reductase from the curd of light-grown cauliflower ( Brassica oleracea (L) var botrytis (DC) 'St. Hilary') is modulated by nitrate and by light. Using broad-band sources of equal photosynthetically active radiation but with different proportions of red and far-red light, a linear relationship between nitrate reductase activity and ψ(Estimated phytochrome photoequilibrium) was obtained. This relationship, apparent after 8 h incubation, was maintained and little altered after 48 h incubation. The linearity was apparent between ψE 0.26 and ψE 0.69; ψE 0.26 being no more effective than a dark control. Far-red reversibility confirmed the involvement of phytochrome. Brief pulses of red light were also used to establish a range of phytochrome photoequilibria within the tissue. Again a linear relationship between ψ and nitrate reductase activity was obtained with a threshold for the response at ψ 0.3. With both monochromatic and broad-band sources it was seen that neither photon fluence rate nor duration of exposure affected the final activity of the enzyme and that phytochrome was acting solely through ψ (or [Pfr] since phytochrome is stable in this tissue) to bring about these responses. 相似文献
144.
145.
[structure: see text] The design, synthesis, and biological evaluation of seven totally synthetic analogues of the antitumor agent (+)-discodermolide are reported. Saturation of the terminal diene system, alteration of the substituents on the lactone, and alkylation of the C7-hydroxyl group reveal significant structure-activity relationships. 相似文献
146.
[structure: see text]. The solution structure of (+)-discodermolide (1) has been determined via 1- and 2-D NMR techniques in conjunction with Monte Carlo conformational analysis. Taken together, the results demonstrate that in solution (+)-discodermolide occupies a helical conformation remarkably similar to the solid state conformation. 相似文献
147.
Rajarshi Roy D.S. Elliot D. Meschede F.M. Pipkin S.J. Smith 《Chemical physics letters》1982,93(6):603-607
We report the observation of collisional narrowing of the Q branch of the Raman spectrum for the (000) → (100) transition in CO2 at very low pressures. The minimum linewidth is reached at ≈250 Torr. An estimate for the difference in rotational constants of the (100) state and the ground state is obtained. The narrowing of the linewidth and the changes in line-shape are interpreted in terms of velocity changing collisions and rotationally inelastic collisions between the CO2 molecules. 相似文献
148.
Design, synthesis, and binding affinities of pyrrolinone-based somatostatin mimetics 总被引:1,自引:0,他引:1
Smith AB Charnley AK Mesaros EF Kikuchi O Wang W Benowitz A Chu CL Feng JJ Chen KH Lin A Cheng FC Taylor L Hirschmann R 《Organic letters》2005,7(3):399-402
[structure: see text] Tetrapyrrolinone somatostatin (SRIF) mimetics (cf. 1), based on a heterochiral (D,L-mixed) pyrrolinone scaffold, were designed, synthesized, and evaluated for biological activity. The iterative synthetic sequence, incorporating the requisite functionalized coded and noncoded amino acid side chains, comprised a longest linear synthetic sequence of 23 steps. Binding affinities at two somatostatin receptor subtypes (hsst 4 and 5) reveal micromolar activity, demonstrating that the d,l-mixed pyrrolinone scaffold can be employed to generate functional mimetics of peptide beta-turns. 相似文献
149.
Smith JC Siu KW Rafferty SP 《Journal of the American Society for Mass Spectrometry》2004,15(5):629-638
The investigation of protein quaternary structure, protein-cofactor, and protein-ligand interactions by mass spectrometry is often limited by the fragility of such interactions under experimental conditions. To develop more gentle conditions of perhaps general use, we used as a model for study the oxygenase domain of murine inducible nitric oxide synthase (iNOS), which is homodimeric, binds heme and tetrahydrobiopterin H(4)B cofactors, and the substrate L-arginine. The energetics of the collisions in q2 and in the lens region of the mass spectrometer were manipulated for varying the degree of solvation around the non-covalently bound ions. Furthermore, the number of low-energy collisions in the collision cell of the instrument was varied, focusing and dampening the ion beam. Under gentle source collision conditions, and using multiple low-energy collisions in the collision cell of the mass spectrometer, dimers of the iNOS oxygenase domain containing heme, H(4)B, and arginine were observed intact after electrospraying at pH values near neutrality; a mutant of this protein (Trp188 --> Phe) was monomeric and did not bind cofactors. The pH dependence of the iNOS oxygenase domain under acidic conditions was also studied; while heme remained bound to the protein between pH 2.5 and 4.0, the dimeric structure was disrupted. Our findings confirm that non-covalently bound macromolecular complexes are retained and observable using electrospray mass spectrometry under the appropriate experimental conditions. 相似文献
150.
Turney K Drake TJ Smith JE Tan W Harrison WW 《Rapid communications in mass spectrometry : RCM》2004,18(20):2367-2374
Nanoparticles for the extraction of peptides and subsequent analysis using atmospheric pressure matrix-assisted laser desorption/ionization (APMALDI) have been evaluated. The atmospheric pressure source allows for particles to be directly introduced in the liquid matrix, minimizing sample loss and analysis time. Described in this work are two sample preparation procedures for liquid APMALDI analysis: a C18 functionalized silica nanoparticle for hydrophobic extractions, and an aptamer functionalized magnetite core nanoparticle for rapid, affinity extractions. The C18 particles provide a non-selective support for rapid profiling applications, while the aptamer particles are directed towards reducing the complexity in biological samples. The aptamer functionalized particles provide a more selective analyte-nanoparticle interaction whereby the tertiary structure of the analyte becomes more critical to the extraction. In both cases, the liquid APMALDI matrix provides a support for ionization, and acts as the releasing agent for the analyte-particle interaction. Additionally, analyte enrichment was possible due to the large surface-to-volume ratio of the particles. The experiments conducted with functionalized nanoparticles, in an atmospheric pressure liquid matrix, present a basis for further methodologies and utilities of silica nanoparticles to be developed. 相似文献