全文获取类型
收费全文 | 4639篇 |
免费 | 226篇 |
国内免费 | 20篇 |
专业分类
化学 | 3311篇 |
晶体学 | 44篇 |
力学 | 150篇 |
数学 | 353篇 |
物理学 | 1027篇 |
出版年
2024年 | 5篇 |
2023年 | 22篇 |
2022年 | 54篇 |
2021年 | 104篇 |
2020年 | 99篇 |
2019年 | 88篇 |
2018年 | 66篇 |
2017年 | 55篇 |
2016年 | 153篇 |
2015年 | 146篇 |
2014年 | 176篇 |
2013年 | 271篇 |
2012年 | 378篇 |
2011年 | 419篇 |
2010年 | 216篇 |
2009年 | 212篇 |
2008年 | 305篇 |
2007年 | 277篇 |
2006年 | 268篇 |
2005年 | 253篇 |
2004年 | 187篇 |
2003年 | 171篇 |
2002年 | 160篇 |
2001年 | 100篇 |
2000年 | 96篇 |
1999年 | 85篇 |
1998年 | 59篇 |
1997年 | 40篇 |
1996年 | 49篇 |
1995年 | 48篇 |
1994年 | 50篇 |
1993年 | 45篇 |
1992年 | 32篇 |
1991年 | 21篇 |
1990年 | 30篇 |
1989年 | 21篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 12篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 6篇 |
1974年 | 7篇 |
1973年 | 5篇 |
排序方式: 共有4885条查询结果,搜索用时 31 毫秒
71.
Jong Seung Kim Moon Hwan Cho Sang Chul Lee Kyung Bok Lee Wonbo Sim Jae Hyung Yoo 《Microchemical Journal》1998,60(3):282-289
The mole transport rate of alkaline earth metal ions through a bulk liquid membrane and a supported liquid membrane using a series of proton diionizable acyclic polyethers was measured. Among alkaline earth metal ions, the calcium ion was observed to be selectively transported in both single and competitive transport experiments. Potentiometric titration and solution calorimetric titration also gave calcium selectivity over other alkaline earth metal ions. Acyclic polyether bearing a diethylene glycol unit andn-tetradecyl lipophilic chain at the α position of carboxylic acid affords the best selectivity for the calcium ion in bulk and supported liquid membranes. 相似文献
72.
Sergey Y. Savinov Hwaung Lee Hyung Keun Song Byung-Ki Na 《Plasma Chemistry and Plasma Processing》2003,23(1):159-173
An experimental study of plasmachemical reaction involving CH4 and N2 molecules in rf discharge was studied in order to know the effect of vibrational excitation of N2 molecules. When the relative nitrogen concentration was greater than 0.8, the main product of CH4 decomposition was HCN, and the rate of methane decomposition at this condition was faster than that one in pure methane. These results could be confirmed through the mass spectroscopic method. The reason for these results is the vibrational energy of N2 excited by rf discharge. The chain reaction mechanisms of producing HCN by vibrational excitation of N2 were examined closely through numerical simulation. The rate-controlling step was the dissociation reaction of excited nitrogen molecule to the atomic nitrogen, so the process of HCN synthesis was limited by the value of reaction constant, kN. 相似文献
73.
[reaction: see text]. A novel synthetic methodology for 2,5-disubstituted tetrahydrofurans having an allenyl group at the 3-position via Prins-type cyclization was developed. The reaction led to excellent selectivity and moderate to high yields. 相似文献
74.
In this study, we developed an analytical method for the enantioseparation of ofloxacin, using capillary electrophoresis with fluorescence detection. The optimum background electrolyte was obtained to be 60 mM hydroxylpropyl‐β‐cyclodextrin (HP‐β‐CD) in 50 mM phosphate buffer at pH 2.30. Under these conditions, the (+) and (‐) ofloxacin were completely separated, with the detection limit of 10 nM when the sample was prepared in deionized water. The linear ranges of levofloxacin in deionized water and untreated urine were 10?7 to 5 × 10?3 M with R2 = 0.9989 and 5 × 10?6to 5 × 10?3 M with R2 = 0.9943, respectively. We also applied this method to investigate the purity of a commercial drug. The results revealed that the ratio between (+)‐ofloxacin and (‐)‐ofloxacin (levofloxacin) was 99.9:0.1, and there is about 93 mg levofloxacin per tablet (200 mg). The concentration of levofloxacin in patient's urine was founded to be 7.9 × 10?4M, and the ratio between the two optical isomers was 99.3:0.7. 相似文献
75.
Chan Sik Cho Tae Kyung Kim Bok Tae Kim Tae-Jeong Kim Sang Chul Shim 《Journal of organometallic chemistry》2002,650(1-2):65-68
Nitroarenes react with trialkylamines in the presence of a catalytic amount of a ruthenium catalyst together with tin(II) chloride dihydrate at 180 °C in an aqueous medium (toluene–H2O) to afford the corresponding quinolines in moderate to good yields. The catalytic pathway seems to be proceeded via a sequence involving initial reduction of nitroarenes to anilines, alkyl group transfer from alkylamines to anilines to form an imine, dimerization of imine, and heterocyclization. 相似文献
76.
Kang K Bae SJ Kim WM Lee DH Cho U Lee MH Lee MS Nam S Kuettner KE Schwartz DE 《Experimental & molecular medicine》2000,32(3):146-154
Nonsteroidal antiinflammatory drugs(NSAIDs) are known as clinically effective agents for treatment of inflammatory diseases. Inhibition of cyclooxygenase has been thought to be a major facet of the pharmacological mechanism of NSAIDs. However, it is difficult to ascribe the antiinflammatory effects of NSAIDs solely to the inhibition of prostaglandin synthesis. Human neutrophil elastase (HNElastase; HNE, EC 3.4.21.37) has been known as a causative factor in inflammatory diseases. To investigate the specific relationship between HNElastase inhibition and specificity of molecular structure of several NSAIDs, HNElastase was purified by Ultrogel AcA54 gel filtration, CM-Sephadex ion exchange, and HPLC (with TSK 250 column) chromatography. HNElastase was inhibited by aspirin and salicylate in a competitive manner and by naproxen, ketoprofen, phenylbutazone, and oxyphenbutazone in a partial competative manner, but not by ibuprofen and tolmetin. HNElastase-phenylbutazone-complex showed strong Raman shifts at 200, 440, 1124, 1194, 1384, 1506, and 1768 cm(-1). The Raman bands 1194, 1384, and 1768 cm(-1) may represent evidences of the conformational change at -N=N-phi radical, pyrazol ring, and -C=O radical of the elastase-drug complex, respectively. Phenylbutazone might be bound to HNElastase by ionic and hydrophobic interaction, and masked the active site. Inhibition of HNElastase could be another mechanism of action of NSAIDs besides cyclooxygenase inhibition in the treatment of inflammatory diseases. Different inhibition characteristics of HNE-lastase by NSAIDs such as aspirin, phenylbutazone-like drugs and ineffective drugs could be important points for drawing the criteria for appropriate drugs in clinical application. 相似文献
77.
78.
The morphology, crystallization behavior, and properties of an impact-modified polypropylene (PP) copolymer with or without
sodium benzoate were investigated. The contents of ethylene–propylene rubber (EPR) in the reactor-made PP copolymer is about
15 wt%. For comparison, blends of PP and EPR containing the same EPR composition were prepared by melt-mixing. Morphological
studies by scanning probe microscopy indicated that the impact-modified copolymer consists of three different phases, i.e.,
polyethylene, PP, and EPR phases, which is considerably different from the morphology of the conventional PP/EPR blend of
the corresponding composition. The impact-modified PP copolymer exhibited a higher crystallization rate in terms of the lower
crystallization half-time and thus higher thermal and mechanical properties, such as impact strength and hardness, than the
PP/EPR blend did. The addition of sodium benzoate as a nucleating agent to the copolymer increased the crystallization rate
and the mechanical properties.
Received: 4 June 2001 Accepted: 31 October 2001 相似文献
79.
Huffer DM Chang HF Cho BP Zhang LK Chiarelli MP 《Journal of the American Society for Mass Spectrometry》2001,12(4):376-380
The product ion formation characteristics of the four diastereomeric tetrahydroxy benzo[ghi]fluoranthene compounds formed by hydrolysis of the syn and anti diastereomers of trans-3,4-dihydroxy-5,5a-epoxy-3,4,5,5a-tetrahydrobenzo[ghi]fluoranthene are studied using matrix-assisted laser desorption/ionization and post-source decay (PSD) to determine a correlation between the fragmentation characteristics of these tetraols and the structures of the diol-epoxide diastereomers from which they are hydrolyzed. The tetraols formed by the trans ring opening of the diol epoxides during hydrolysis yield product ion spectra specific for the syn and anti configurations of their precursor diol epoxides. All four diastereomeric tetraols form product ions by the losses of one and/or two water molecules in varying proportions when lithium-cationized molecule ions (m/z 301) are selected for PSD product ion analysis. The differences in the PSD spectra of these four Li+-cationized molecules are rationalized in terms of a water loss mechanism that involves the 1,2 elimination of a hydrogen atom and hydroxyl group that are cis with respect to each other on adjacent carbons. 相似文献
80.
Lee Y. H. Chung J. W. Choi Y. R. Chung J. S. Cho M. H. Namkung W. 《Plasma Chemistry and Plasma Processing》2004,24(2):137-154
NOx removal characteristics and NO conversion trends were investigated for plasma process, catalytic process, and plasma catalytic hybrid process. In the experiments, we studied effects of the flow rate and the carrier gas on the NO conversion in the plasma process, and effects of ammonia concentration and temperature on the NOx removal in the catalytic process. We also investigated the synergetic effect of a plasma-catalytic hybrid process. Dielectric barrier discharge was combined with V2O5–WO3/TiO2 catalyst for removing nitrogen oxides. The maximum conversions of nitrogen oxides were approximately 52, 80, and 98% at the temperature of 100, 200, and 300°C, respectively. The optimal energy density, ammonia concentration, and ratio of nitrogen oxides exist for the highest removal of nitrogen oxides in the plasma catalytic hybrid process. 相似文献