全文获取类型
收费全文 | 32388篇 |
免费 | 1936篇 |
国内免费 | 4910篇 |
专业分类
化学 | 32174篇 |
晶体学 | 598篇 |
力学 | 176篇 |
综合类 | 162篇 |
数学 | 1176篇 |
物理学 | 4948篇 |
出版年
2024年 | 36篇 |
2023年 | 305篇 |
2022年 | 411篇 |
2021年 | 674篇 |
2020年 | 805篇 |
2019年 | 1705篇 |
2018年 | 848篇 |
2017年 | 1701篇 |
2016年 | 1111篇 |
2015年 | 994篇 |
2014年 | 1308篇 |
2013年 | 2994篇 |
2012年 | 1925篇 |
2011年 | 2001篇 |
2010年 | 1480篇 |
2009年 | 1773篇 |
2008年 | 2039篇 |
2007年 | 2081篇 |
2006年 | 1948篇 |
2005年 | 1776篇 |
2004年 | 1721篇 |
2003年 | 1437篇 |
2002年 | 1282篇 |
2001年 | 996篇 |
2000年 | 955篇 |
1999年 | 738篇 |
1998年 | 679篇 |
1997年 | 525篇 |
1996年 | 449篇 |
1995年 | 453篇 |
1994年 | 362篇 |
1993年 | 313篇 |
1992年 | 301篇 |
1991年 | 222篇 |
1990年 | 132篇 |
1989年 | 124篇 |
1988年 | 100篇 |
1987年 | 61篇 |
1986年 | 53篇 |
1985年 | 63篇 |
1984年 | 51篇 |
1983年 | 23篇 |
1982年 | 53篇 |
1981年 | 52篇 |
1980年 | 27篇 |
1979年 | 56篇 |
1978年 | 20篇 |
1977年 | 18篇 |
1976年 | 15篇 |
1973年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
《Electroanalysis》2003,15(3):225-229
The interaction between avidin and biotin was evaluated electrochemically by monitoring the change in the electrode response of redox markers. Biotin was immobilized on the electrode surface by means of the electrochemical polymerization of biotinylated pyrrole and pyrrole. When avidin was introduced onto the biotinylated polypyrrole electrode surface, the large change in the electrode response of the redox marker was detected. The fact that the change in the electrode response of a marker ion could be attributed to the electrostatic interaction between avidin on the electrode surface and the redox marker ion present in a solution was verified by replacing avidin with NutrAvidin. At a pH lower than the isoelectric point of avidin, the electrode response of ferrocyanide as an anionic marker ion increased linearly within the range of 5.0×10?9 ?3.0×10?8 M avidin. The relative standard deviation at 1.5×10?8 M avidin was about 5.4% (n=5). The detection of biotin was also performed using a competitive reaction between biotin in solution and biotin that had been immobilized on the electrode surface in the form of the biotinylated polypyrrole. 相似文献
992.
表皮生长因子受体和抑制剂之间分子对接的研究 总被引:3,自引:0,他引:3
研究了表皮生长因子受体(EGFR)和4-苯胺喹唑啉类抑制剂之间的相互作用模式,表皮生长因子受体的三维结构通过同源蛋白模建的方法得到,而抑制剂和靶酶结合复合物结构则通过分子力学和分子动力学结合的方法计算得到。从模拟结果得到的抑制剂和靶酶之间的相互作用模式表明范德华相互作用、疏水相互作用以及氢键相互作用对抑制剂的活性都有重要的影响,抑制剂的苯胺部分位于活性口袋的底部,能够与受体残基的非极性侧链产生很强的范德华和疏水相互作用,抑制剂双环上的取代基团也能和活性口袋外部的部分残基形成一定的范德华和疏水性相互作用,而抑制剂喹唑啉环上的氮原子能和周围的残基形成较强的氢键相互作用,对抑制剂的活性有较大的影响,计算得到抑制剂和靶酶之间的非键相互作用能以及抑制剂和靶酶之间的相互作用信息能够很好地解释抑制剂活性和结构的关系,为全新抑制剂的设计提供了重要的结构信息。 相似文献
993.
Yoichiro Iwase Koichi Kondo Kenji Kamada Koji Ohta 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3534-3541
1,4‐Bis(4‐benzylpyridinium)butadiyne triflate was aggregated in dimethylformamide and spontaneously converted into the 1,4‐addition type of polydiacetylene. The polymerization took place in a dipolar aprotic solvent with a large dielectric constant that could enhance the aggregation of the ionic diacetylene salt through the electrostatic interaction. The molecular weight of the diacetylene was leveled off after 30 h at 80 °C to reach 1.5 × 104 (number‐average molecular weight) that consisted of the 1,4‐addition type of polydiacetylene similar to polydiacetylenes obtained in the conventional solid‐state polymerization. Electron spin resonance spectra revealed that diradicals were generated at the earlier state aggregation to give rise to a solution polymerization. The UV spectra also suggested the presence of the activated aggregation associated with the polymerization as well as the eximer emission spectra. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3534–3541, 2002 相似文献
994.
The First Titanate with ?Stuffed Pyrgoms”?: RbNa3Li12[TiO4]4 = RbNa3Li8{Li[TiO4]}4 By heating a well grounded mixture of the binary oxides Rb2O, Na2O, Li2O, and TiO2 [Rb:Na:Li:Ti = 1.1:3.1:12.5:4.0; 780°C, 41 d] we obtained RbNa3Li8{Li[TiO4]}4 as colourless platelike crystals. This first titanate with ?stuffed pyrgoms”? is isostructural with RbNa3Li8{Li[SiO4]}4, CsKNa2Li8{Li[SiO4]}4 and CsKNaLi9{Li[SiO4]}4 [2]. The compound crystallizes tetragonal I4/m with a = 1 125.8(1) pm and c = 652.4(1) pm (Guinier-Simon-Data, Z = 2). The structure was determined by four-cyrcle-data (Siemens AED2, MoK) and leds to the residual values R = 3.7% and Rw = 3.1% (additional data see text). The Madelung Part of Lattice Energy (MAPLE), Effective Coordination Numbers (ECoN), Mean Fictive Ionic Raddii (MEFIR) and the Charge Distribution in Solids (CHARDI) are calculated and discussed. 相似文献
995.
4,4-Difluoro-5-trifluoromethyl-2-(2,2,2-trifluoro-1-trifluoromethylethyl)-4H-1,3-dioxine andcis/trans-3-dimethylamino-2-trifluoromethacryloyl fluoride were obtained by reaction ofN-(3,3,3-trifluoro-2-trifluoromethylprop-1-enyl)dimethylamine with MgSO4·7H2O.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1069–1071, May, 1997. 相似文献
996.
Treatment of 4-nitrophenyl chloroformate with alkylammonium hydrochloride salts and solid anhydrous Na2CO3 in either CH2Cl2 or CH3CN gave 4-nitrophenyl N-methylcarbamate and other N-alkylcarbamate analogues in excellent yields. Of particular interest is the observation that 4-nitrophenyl N-methylcarbamate, a safer alternative to the highly toxic methyl isocyanate, is obtained in quantitative yield (?95% pure as determined by 1H NMR) after simple filtration and solvent evaporation. 相似文献
997.
t-Butyldimethylsilyl (TBDMS) ethers have been efficiently and selectively deprotected using silica supported sodium hydrogen sulfate (NaHSO4·SiO2) as a heterogeneous catalyst at room temperature to regenerate the parent alcohols in high yields. 相似文献
998.
L. G. Voskressensky T. N. Borisova T. A. Vorob’eva A. I. Chernyshev A. V. Varlamov 《Russian Chemical Bulletin》2005,54(11):2594-2601
Reactions of substituted tetrahydropyrrolo[3,2-c]pyridines with dimethyl acetylenedicarboxylate in protic and aprotic solvents were studied. A novel single-step method for
the synthesis of pyrrolo[2,3-d]azocine derivatives was developed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2513–2519, November, 2005. 相似文献
999.
H. N. Altshuler L. P. Abramova N. V. Malyshenko G. Yu. Shkurenko E. V. Ostapova 《Russian Chemical Bulletin》2005,54(8):1978-1981
The ion-exchange equilibrium in network polymers obtained from cis-2,8,14,20-tetraphenyl-4,6,10,12,16,18,22,24-octahydroxycalix[4]arene by template synthesis on cations Na+, K+, and Ba2+ as matrices was studied. The selectivity coefficients of ion exchanges Ba2+-H+, Na+-H+, K+-H+, Na+-K+, and Na+-NH4
+ were determined. The template synthesis enhanced the affinity of the polymers to matrix-forming cations by 6–8 kJ mol−1.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1919–1922, August, 2005. 相似文献
1000.
Mecheril V. Nandakumar 《Tetrahedron》2005,61(41):9775-9782
A Pd2dba3/P(i-BuNCH2CH2)3N catalyzed one-pot synthesis of unsymmetrically substituted trans-4-N,N-diarylaminostilbenes and both symmetrically and unsymmetrically substituted N,N-diarylaminostyrene derivatives is reported. The procedure involves two or more palladium catalyzed sequential coupling reactions (an amination and an inter-molecular Heck reaction) in one-pot using the same catalyst system with two different aryl halides, including aryl chlorides and hetero aryl halides as the coupling partners. 相似文献