全文获取类型
收费全文 | 28179篇 |
免费 | 1326篇 |
国内免费 | 5613篇 |
专业分类
化学 | 31889篇 |
晶体学 | 339篇 |
力学 | 163篇 |
综合类 | 262篇 |
数学 | 85篇 |
物理学 | 2380篇 |
出版年
2024年 | 50篇 |
2023年 | 321篇 |
2022年 | 917篇 |
2021年 | 869篇 |
2020年 | 890篇 |
2019年 | 877篇 |
2018年 | 779篇 |
2017年 | 930篇 |
2016年 | 1100篇 |
2015年 | 1012篇 |
2014年 | 1199篇 |
2013年 | 2484篇 |
2012年 | 1968篇 |
2011年 | 1650篇 |
2010年 | 1404篇 |
2009年 | 1640篇 |
2008年 | 1711篇 |
2007年 | 1895篇 |
2006年 | 1792篇 |
2005年 | 1659篇 |
2004年 | 1497篇 |
2003年 | 1210篇 |
2002年 | 1031篇 |
2001年 | 772篇 |
2000年 | 747篇 |
1999年 | 601篇 |
1998年 | 499篇 |
1997年 | 514篇 |
1996年 | 472篇 |
1995年 | 425篇 |
1994年 | 396篇 |
1993年 | 317篇 |
1992年 | 313篇 |
1991年 | 215篇 |
1990年 | 176篇 |
1989年 | 184篇 |
1988年 | 130篇 |
1987年 | 90篇 |
1986年 | 63篇 |
1985年 | 52篇 |
1984年 | 57篇 |
1983年 | 30篇 |
1982年 | 45篇 |
1981年 | 30篇 |
1980年 | 26篇 |
1979年 | 21篇 |
1978年 | 24篇 |
1977年 | 5篇 |
1973年 | 5篇 |
1968年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
A convenient and large-scale preparation of retinoic acid 1 from β-ionone in five steps with 38% overall yield is described.The key steps are the epoxidization of 2 with a new methylated agent and the condensation 4 with tetraethyl methylenediphophonate in one-pot procedure to prepare 6. 相似文献
22.
Z. J. Yu L. J. Liu R. X. Zhuo 《Journal of polymer science. Part A, Polymer chemistry》2003,41(1):13-21
The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by 1H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (Mw) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (Mw/Mn)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with Mw = 12,100 and Mw/Mn = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in Mw of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003 相似文献
23.
Erzs bet Ill s Etelka Tomb cz 《Colloids and surfaces. A, Physicochemical and engineering aspects》2003,230(1-3):99-109
The ionic strength dependence of humic acid (HA) adsorption on magnetite (Fe3O4) was investigated at pH 5, 8 and 9, where variable charged magnetite is positive, neutral and negative, respectively. The adsorption studies revealed that HA has high affinity to magnetite surface especially at lower pH, where interacting partners have opposite charges. However, in spite of electrostatic repulsion at pH 9 notable amounts of humate are adsorbed. Increasing ionic strength enhances HA adsorption at each pH due to charge screening. The dominant interaction is probably a ligand-exchange reaction, nevertheless the Coulombic contribution to the organic matter accumulation on oxide surface is also significant under acidic condition. The results from size exclusion chromatography demonstrate that the smaller size HA fractions enriched with functional groups are adsorbed preferentially on the surface of magnetite at pH 8 in dilute NaCl solution. 相似文献
24.
副品红共振光散射法测定脱氧核糖核酸 总被引:3,自引:0,他引:3
本文基于脱氧核糖核酸 (DNA)对有机染料副品红的共振光散射的增强效应 ,拟定了一种测定DNA的共振光散射法。在pH =0 5~ 1 5范围内 ,有机染料副品红于 35 5nm处的共振光散射强度被DNA强烈增强 ,且增强程度与DNA浓度呈线性关系 ,线性范围为 0 10~ 15 μg·mL- 1 ,检出限可达 36ng·mL- 1 。该方法简便、快速、具有较高的灵敏度和准确度 ,且线性范围较宽。将该方法用于混合样品中DNA的测定 ,结果令人满意。 相似文献
25.
生物小分子与铜锌超氧化物歧化酶相互作用的波谱学研究及其应用 总被引:1,自引:0,他引:1
本工作以ESR和NMR为主要手段,并结合其它生化方法,考察了氨基酸、核酸碱基、糖等生命基本物质,和抗坏血酸等生命必需物质与钢锌超氧化物歧化酶的相互作用,实验观测到氨基酸、核酸碱基和抗坏血酸在水溶液中可以与酶中的Cu2+作用而使其脱离活性部位,以小分子络合物形式游离在溶液中,同时使酶失活,脱离活性部位的Cu2+的比例和酶的失活程度取决于小分子配体的加入量及其与Cu2+的络合能力。此外,首次尝试使用ESR方法,并借助氨基酸与酶的作用,考察了铜锌超氧化物歧化酶在盐酸胍变性和热变性过程中的构象变化行为,结果表明这一方法是直观而有效的。 相似文献
26.
巴旦杏中脂肪酸的测定 总被引:5,自引:1,他引:4
采用气相色谱仪进行定量分析,气-联质联用仪进行定性分析,巴旦杏中脂肪酸进行了测定,并探讨了样品处理方法和气-质联用仪的分析条件,得到了较为满意的分析结果。 相似文献
27.
Hisatoyo Morinaga Bungo Ochiai Hideharu Mori Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(5):736-744
Natural human hair was successfully modified by the graft polymerization of trimethylene carbonate, β‐propiolactone, ε‐caprolactone, glycidol, ε‐caprolactam, and 5,5‐dimethyl‐1,3‐dioxane‐2‐thione. In contrast, we could not modify natural human hair by the graft polymerization of oxetane under similar conditions. The model reaction suggested that the main initiating species in these polymerizations were the amino, thiol, and hydroxyl groups in hair, which could induce ring‐opening polymerization. Among the tested monomers, β‐propiolactone was most effective for hair modification with its graft polymer, whose concentration was as high as 0.5 g/g of hair though polymerization under mild conditions. The effects of the hair pretreatment and polymerization temperature on the weight ratio of the grafted polymers were also investigated. Hair modified by grafted polymers was characterized with scanning electron microscopy and Fourier transform infrared measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 736–744, 2007 相似文献
28.
N. S. Oliveira J. Dorgan J. A. P. Coutinho A. Ferreira J. L. Daridon I. M. Marrucho 《Journal of Polymer Science.Polymer Physics》2007,45(5):616-625
The sorption of carbon dioxide in glassy Poly(lactic acid) (PLA) films was studied by quartz crystal microbalance (QCM) at high pressures. Two thermal treatments, melted and quenched, were performed in PLA with two different L:D contents, 80:20 and 98:2, films and compared with a third thermal protocol, annealed, and used in a previous work. The results obtained show that for pressures higher than 2 MPa, the carbon dioxide solubility is larger in PLA 80:20 than in PLA 98:2, indicating that the L:D plays a dominant role on this property. The thermal treatments only affect the gas solubility in PLA 98:2. Sorption isotherms at temperatures 303, 313, and 323 K, below the glass transition temperature of the polymer, and pressures up to 5 MPa were measured and analyzed with three different models, the dual‐mode sorption model, the Flory–Huggins equation, and a modified dual‐mode sorption model where the Henry's law term was substituted by the Flory–Huggins equation. This last model performs especially well for CO2 in PLA 80:20, due to the convex upward curvature of the solubility isotherms for that system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 616–625, 2007 相似文献
29.
The present paper covers a salt of 2:18 heteropoly complex of tungstotitanophosphate prepared with the method of improved sequence preparation. The title compound was characterized by elemental analysis, 31P NMR spectra, polarography, cyclic voltammetry, IR, UV, X-ray powder diffraction , X-ray photoelectron spectra and TG-DTA analysis. The results show that the complex with the formula K8[TiP2W17O62]·12H2O has Dawson structure. Its properties such as spectra, redox behavior and thermal stability are discussed. 相似文献
30.
François Loiseau Jean-Mary Simone David Carcache Pavel Bobal Reinhard Neier 《Monatshefte für Chemie / Chemical Monthly》2007,138(2):121-129
Summary. Free radical couplings from furan, as cheap starting material, were studied in view of developing a rapid strategy en route to the synthesis of derivatives of nonactin. The chain containing the alcohol function was introduced in one or two steps
in 86% yield. For the introduction of the second chain with the ester function two different coupling methods were tested.
Starting from the advanced intermediates obtained nonactin derivatives can be prepared by catalytic hydrogenation of the furan
ring. 相似文献