全文获取类型
收费全文 | 97064篇 |
免费 | 20355篇 |
国内免费 | 8410篇 |
专业分类
化学 | 70630篇 |
晶体学 | 883篇 |
力学 | 2936篇 |
综合类 | 448篇 |
数学 | 6931篇 |
物理学 | 19534篇 |
无线电 | 24467篇 |
出版年
2024年 | 255篇 |
2023年 | 1479篇 |
2022年 | 2016篇 |
2021年 | 2535篇 |
2020年 | 3922篇 |
2019年 | 5105篇 |
2018年 | 3286篇 |
2017年 | 2872篇 |
2016年 | 6360篇 |
2015年 | 6672篇 |
2014年 | 7067篇 |
2013年 | 8460篇 |
2012年 | 8322篇 |
2011年 | 7563篇 |
2010年 | 6729篇 |
2009年 | 6732篇 |
2008年 | 6479篇 |
2007年 | 5581篇 |
2006年 | 4895篇 |
2005年 | 4621篇 |
2004年 | 3577篇 |
2003年 | 3146篇 |
2002年 | 3916篇 |
2001年 | 2840篇 |
2000年 | 2642篇 |
1999年 | 1712篇 |
1998年 | 1069篇 |
1997年 | 919篇 |
1996年 | 893篇 |
1995年 | 749篇 |
1994年 | 612篇 |
1993年 | 511篇 |
1992年 | 448篇 |
1991年 | 372篇 |
1990年 | 304篇 |
1989年 | 241篇 |
1988年 | 169篇 |
1987年 | 171篇 |
1986年 | 140篇 |
1985年 | 119篇 |
1984年 | 72篇 |
1983年 | 65篇 |
1982年 | 49篇 |
1981年 | 31篇 |
1980年 | 18篇 |
1979年 | 14篇 |
1976年 | 9篇 |
1975年 | 14篇 |
1973年 | 7篇 |
1957年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
921.
922.
冻干保护剂溶液低温退火特性的研究 总被引:3,自引:0,他引:3
利用差示扫描量热仪(DSC)研究了10%叔丁醇/10%蔗糖/水溶液的冻结特性, 退火温度及退火时间, 分析了溶液的退火行为. 实验结果表明, 溶液降温时, 蔗糖的存在阻碍了叔丁醇析出, 最大冻结浓缩溶液玻璃化转变温度Tg′由-32.5 ℃降低到-42.0 ℃, 升温时在-30 ℃叔丁醇发生反玻璃化. 在反玻璃化峰附近的温度进行退火可使叔丁醇充分析出, Tg′由-42.0 ℃上升到-34.9 ℃. 所需的退火时间与退火温度有关, 退火温度越接近Tg′, 所需的退火时间越长. 在-37 ℃时, 退火20 min可完全消除反玻璃化. 相似文献
923.
The mechanism of reductive etherification reactions between aromatic aldehydes and alcohols has been investigated with the DFT(B3LYP)/6-31G method. One or two BH(3) molecules have been used to simulate the role of the catalyst and reducing agent. The solvent effects of the title reactions have been studied by the PCM model. It is found that the reactions between aromatic aldehydes and primary, secondary, and tertiary alcohols can proceed more easily in a polar solvent such as acetonitrile. The results provide evidence in theory to broaden the applications of reductive etherification reactions for the optimization of the radiochemical synthesis process of (18)F-labeled ether radiotracers. 相似文献
924.
Probing the water coordination of protein-targeted MRI contrast agents by pulsed ENDOR spectroscopy.
Stephan G Zech Wei-Chuan Sun Vincent Jacques Peter Caravan Andrei V Astashkin Arnold M Raitsimring 《Chemphyschem》2005,6(12):2570-2577
A novel methodology based on electron-nuclear double resonance (ENDOR) spectroscopy is used for the direct determination of the water coordination number (q) of gadolinium-based magnetic resonance imaging (MRI) contrast agents. Proton ENDOR spectra can be obtained at approximately physiological concentrations for metal complexes in frozen aqueous solutions either in the presence or absence of protein targets. It is shown that, depending on the structure of the co-ligand, the water hydration number of a complex in aqueous solution can be significantly different to when the complex is noncovalently bound to a protein. From the ENDOR spectra of the exchangeable protons, precise information on the metal-proton distance can be derived as well. These essential parameters directly correlate with the efficacy of MRI contrast agents and should therefore aid the development of novel, highly efficient compounds targeted to various proteins. 相似文献
925.
The cationic ruthenium hydride complex [(PCy(3))(2)(CO)(CH(3)CN)(2)RuH](+)BF(4)(-) was found to be a highly effective catalyst for the C-H bond activation reaction of arylamines and terminal alkynes. The regioselective catalytic synthesis of substituted quinoline and quinoxaline derivatives was achieved from the ortho-C-H bond activation reaction of arylamines and terminal alkynes by using the catalyst Ru(3)(CO)(12)/HBF(4).OEt(2). The normal isotope effect (k(CH)/k(CD) = 2.5) was observed for the reaction of C(6)H(5)NH(2) and C(6)D(5)NH(2) with propyne. A highly negative Hammett value (rho = -4.4) was obtained from the correlation of the relative rates from a series of meta-substituted anilines, m-XC(6)H(4)NH(2), with sigma(p) in the presence of Ru(3)(CO)(12)/HBF(4).OEt(2) (3 mol % Ru, 1:3 molar ratio). The deuterium labeling studies from the reactions of both indoline and acyclic arylamines with DCCPh showed that the alkyne C-H bond activation step is reversible. The crossover experiment from the reaction of 1-(2-amino-1-phenyl)pyrrole with DCCPh and HCCC(6)H(4)-p-OMe led to preferential deuterium incorporation to the phenyl-substituted quinoline product. A mechanism involving rate-determining ortho-C-H bond activation and intramolecular C-N bond formation steps via an unsaturated cationic ruthenium acetylide complex has been proposed. 相似文献
926.
Ya‐Ching Shen Yun‐Sheng Lin Shaw‐Man Hsu Ashraf Taha Khalil Shih‐Sheng Wang Ching‐Te Chien Yao‐Haur Kuo Chang‐Hung Chou 《Helvetica chimica acta》2007,90(7):1319-1329
The phytochemical investigation of the more polar fractions from the leaves and twigs of Taxus sumatrana (Taxaceae) afforded five new taxane diterpene esters, tasumatrols P–T ( 1 – 5 ) possessing an 11(15→1),11(10→9)‐diabeotaxane skeleton. Compounds 1, 4 , and 5 contain an α‐hydroxy group at C(14), while 3 has no OH group at either C(13) or C(14). Compound 2 is a natural 4,5‐acetonide derivative, while 4 has an unusual spiro‐connected 2‐hydroxy‐2‐phenyl‐1,3‐dioxolane ring. Ten known taxoids, were also isolated in the course of the chromatographic fractionation. Five additional new O‐acetyl derivatives 3a, 4a, 4b, 5a , and 5b were prepared from the taxanes 3 – 5 . The structures of all new compounds were established on the basis of their spectroscopic analyses. Compound 1 showed mild cytotoxic activity against human Hela and Daoy tumor cells. 相似文献
927.
A new kind of multilayer of didodecyldimethylammonium bromide (DDAB) and 1:12 phosphomolybdic anions (PMo12) was achieved on the surface of a wax-impregnated graphite (WIG) electrode by ion exchange and electrostatic interaction.
The characterization and electrochemical behavior of the multilayer films of DDAB/PMo12 is described in detail. The chemically modified electrode was shown to exhibit an excellent electrocatalytic activity toward
the reduction of BrO3
– anion in 0.5 M H2SO4 and possesses several attractive features, such as simple preparation, fast response, good stability, etc.
Electronic Publication 相似文献
928.
煤中有机硫形态结构和热解过程硫变迁特性的研究 总被引:10,自引:1,他引:10
利用热解 质谱并结合固定床热解反应装置,对煤中有机硫的形态主其对加氢热解过程 变迁特性的影响,进行了较系统的研究。结果表明,煤中有机硫的形态结构在褐煤中主要以脂肪族、芳香族硫化物为主,而在 煤中则主要以各种不同芳构化程度的噻吩结构为主,初步表明煤中有机硫形态结构随煤变质程度的变迁呈较强的连续递变性。煤热解过程中硫在呼产物中的变迁和分布与煤中有机硫的形态结构特点密切相关。较高芳构化噻吩结构不完全的氧 相似文献
929.
The determination of lanthanides by Inductively Coupled Plasma Mass Spectrometry (ICP‐MS) is complicated by several spectral overlaps from M+, MO+ or MOH+ ions formed in the ICP. Especially, it is essential to avoid the spectral interferences from lighter lanthanide and Ba polyatomic ions on middle or heavier lanthanides. To tackle this problem, we have developed a mathematical correction method, which reduces all the spectral overlaps from oxide species of Pr, Nd, Ce and Sm over Gd, Tb, Dy and Ho, and Gd, Tb over Yb and Lu. It can also successfully correct the oxide and hydroxide interference of Ba over Eu. The effectiveness of the proposed the mathematical correction scheme is demonstrated for the USGS Standard Rock samples AGV‐1 and G‐2. The results show that the experimental data obtained by applying the mathematical correction scheme for lanthanides is in good agreement with the reported values, using pneumatic and ultrasonic nebulisation methods, for their ICP‐MS analysis. 相似文献
930.