全文获取类型
收费全文 | 68200篇 |
免费 | 14572篇 |
国内免费 | 4939篇 |
专业分类
化学 | 63028篇 |
晶体学 | 657篇 |
力学 | 2602篇 |
综合类 | 246篇 |
数学 | 6025篇 |
物理学 | 15153篇 |
出版年
2024年 | 76篇 |
2023年 | 754篇 |
2022年 | 1037篇 |
2021年 | 1429篇 |
2020年 | 2516篇 |
2019年 | 3689篇 |
2018年 | 2038篇 |
2017年 | 1640篇 |
2016年 | 4730篇 |
2015年 | 4829篇 |
2014年 | 5161篇 |
2013年 | 6264篇 |
2012年 | 5896篇 |
2011年 | 5129篇 |
2010年 | 4818篇 |
2009年 | 4656篇 |
2008年 | 4328篇 |
2007年 | 3530篇 |
2006年 | 3112篇 |
2005年 | 2994篇 |
2004年 | 2574篇 |
2003年 | 2153篇 |
2002年 | 2752篇 |
2001年 | 2015篇 |
2000年 | 1902篇 |
1999年 | 1157篇 |
1998年 | 722篇 |
1997年 | 655篇 |
1996年 | 714篇 |
1995年 | 605篇 |
1994年 | 555篇 |
1993年 | 477篇 |
1992年 | 451篇 |
1991年 | 366篇 |
1990年 | 327篇 |
1989年 | 238篇 |
1988年 | 216篇 |
1987年 | 200篇 |
1986年 | 143篇 |
1985年 | 160篇 |
1984年 | 137篇 |
1983年 | 117篇 |
1982年 | 80篇 |
1981年 | 61篇 |
1980年 | 49篇 |
1979年 | 32篇 |
1978年 | 26篇 |
1976年 | 27篇 |
1975年 | 31篇 |
1974年 | 23篇 |
排序方式: 共有10000条查询结果,搜索用时 250 毫秒
991.
Wu K Bailey TC Willson CG Ekerdt JG 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11795-11801
Substrate hydration is demonstrated to be crucial to film quality during self-assembled (SA) film deposition of tridecafluoro-1,1,2,2,-tetrahydrooctyltrichlorosilane (FOTS) from the vapor phase. The surface hydration was studied by thermogravimetric analysis, and a model was developed to predict the conditions necessary to desorb all of the water adsorbed on a fused silica surface without significantly altering the concentration of the surface hydroxyl groups. The nature of the SA film was investigated as a function of the degree of rehydration of the dehydrated silica surface. The wettability and microstructure of the SA films were examined by water contact angle, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy. There is an optimum degree of substrate hydration, on the order of 1-1.2 monolayers of adsorbed water, required to produce a dense, durable and uniform FOTS film with high water repellency and a smooth surface. 相似文献
992.
The rates at which aluminum was removed from the N- and C-terminal monoaluminum ovotransferrins by pyrophosphate were evaluated by UV difference spectra in 0.01 mol/L Hepes, pH=7.4 and at 37℃. Pesudo first-order rate constants as a function of pyrophosphate concentration were measured. The results indicate that the pathways of aluminum removal are different. For the N-terminal binding site, aluminum removal follows simple saturation kinetics, while the removal of aluminum from the C-terminal binding site reverts to the combination of saturation and first-order kinetics. The saturation component is consistent with a rate-limiting conformational change in the protein as has been reported. We propose that the first-order kinetics mechanism is attributed to a pre-equilibrium process. The rate constants of saturation kinetics are accelerated from both terminals with the addition of 0.1 mol/L chloride to the monoaluminum ovotransferrin solutions, whereas the rates of the first-order kinetics are decreased for the C-terminal binding site. The effect of chloride ionic strength causes a continuing increase on kobs for the N- and C-terminal binding sites. Moreover, the kinetics behavior of the N-terminal is more easily affected by chloride than that of the C-terminal. In the experiment presumably the N-terminal site is apparently kinetically more labile than the C-terminal site. 相似文献
993.
The Brownian-type molecular dynamics simulation is revisited and applied to study the thermal and geometric properties of four mono- and two polyvalent metallic clusters. For the thermal property, we report the specific heat at constant volume CV and study the solid-liquid-like transition by scrutinizing its characteristic. For the geometric property, we calculate the root mean square relative bond-length fluctuation delta as a function of increasing temperature. The thermal change in delta reflects the movement of atoms and hence is a relevant parameter in understanding the phase transition in clusters. The simulated results for the CV of alkali and aluminum clusters whose ground state structures exhibit icosahedral symmetry generally show one phase transition. In contrast, the tetravalent lead is quite often seen to exhibit two phase transitions, a premelting process followed by a progressive melting. In connection with the premelting scenario, it is found here that those (magic number) clusters identified to be of lesser stability (among other stable ones) according to the second energy difference are clusters showing a greater possibility of undergoing premelting process. This energy criterion applies to aluminum clusters nAl=28 and 38. To delve further into the thermal behavior of clusters, we have analyzed also the thermal variation of deltaT and attempted to correlate it with CV(T). It turns out that the premelting (if exist) and melting temperatures of the smaller size clusters (n less, similar 50) extracted from CV do not always agree quantitatively with that deduced from delta. 相似文献
994.
Surface composition and property of film prepared with aqueous dispersion of polyurethaneurea-acrylate including fluorinated block copolymer 总被引:1,自引:0,他引:1
The aqueous dispersion of polyurethaneurea-acrylate (PUA) including small amount of fluorinated block copolymers containing carboxyl groups (PATF), which can be dissolved in water, was used to make films and the surface properties of these films were examined. The experimental data show that the modified PUA film exhibits a hydrophobic surface property, although the original surface of PUA film is hydrophilic. The surface composition of the modified PUA film was measured by ATR and XPS. The results indicate that there is a concentration gradient of the fluorine groups along the lines of thickness of the modified film and towards the outmost surface layer, resulting from the migration of fluorinated blocks to the air side surface of the modified PUA film during the film formation process. However, the PUA film can not be modified effectively by adding the sodium salt of PATF, since the urethane groups in the system are easy to occupy on the surface of the film. 相似文献
995.
Yan Wu LI Liang HUANG* Institute of Materia Medica Chinese Academy of Medical Sciences & Peking Union Medical College Beijing 《中国化学快报》2002,13(10)
The natural product, hainanolide 1, also under the name harringtonolide2 demonstrated antitumor and antiviral activities in preliminary test. Its structure was determined by X-ray diffraction. The total synthesis of 1 was reported recently by Mander3. A different scheme of its synthesis has been studied in our laboratory4. Here the determination of the stereochemical structure of the key intermediate 2 in the synthesis was reported. HMBC and HMQC spectra identified the skeleton and H,… 相似文献
996.
997.
Jin-Ming Lin Tatsuro Nakagama Hitoshi Okazawa Xing-Zheng Wu Toshiyuki Hobo 《Fresenius' Journal of Analytical Chemistry》1996,354(4):451-454
Capillary gel electrophoresis (CGE) was successfully applied to the separation of optically active isomers and position isomers by incorporating a suitable cyclodextrin chiral selector in polyacrylamide gel. A commercially available ß-cyclodextrin (ß-CD) was used for enantioselectivity towards o-, m- and p-nitrobenzoic acid, o-, m- and p-hydroxybenzoic acid, o-, m- and p-toluic acid and the optical isomers of dansyl-D,L-leucine and R,S-1,1-binaphthyl-2,2-dihydrogenphosphate. Especially the effect of organic solvents, such as acetonitrile, methanol, dimethylsulphoxide and others were examined in detail. The resolution varied to some extent with the addition of the organic solvent to the polyacrylamide gel and the running buffer solution. The possible mechanism has also been discussed. In addition, quantitative aspects of the separation of stereoisomers using CGE have been studied, showing that both the resolution and accuracy of the determinations were affected by the ratio of the enantiomers. 相似文献
998.
在氩气氛中,合成子SrMgF4:xEu,yTb复合氟化物磷光体,该体系中Eu^3+和Eu^2+共存,随共掺入Tb浓度的增加,Eu^3+的荧光发射强度降低,Eu^3+的发光增强,并且Eu^2+的ESR信号增强,认为Eu^3+和Tb3+之间存在的电荷迁移,即Eu^3+Tb^3+→Eu^2++Tb^4+,通过半量手段研究了这一电荷迁移反应的平衡常数。 相似文献
999.
痕量Au Bi和Cd的萃取浮选及原子吸收光谱法测定 总被引:1,自引:0,他引:1
浮选法分离痕量金属离子,由于灵敏度高、选择性强已得到广泛应用。本文利用浮选法使Au~(3 )、Bi~(3 )和Cd~(2 )同KBr反应生成的络合阴离子与碱性染料罗丹明B(RB)生成既疏水又疏有机溶剂的三元离子缔合物,后者经甲苯浮选分出,用二甲基甲酰胺(DMF)溶解后,可用原子吸收法测定Au、Bi和Cd的含量。本方法用于海水,锌片和矿样中上述三种元素的微量测定,可提高检测灵敏度,而且K、Na、Ca、Mg等共存离子不生干扰。具体实验方法如下: 相似文献
1000.