全文获取类型
收费全文 | 15568篇 |
免费 | 638篇 |
国内免费 | 145篇 |
专业分类
化学 | 10117篇 |
晶体学 | 50篇 |
力学 | 325篇 |
综合类 | 1篇 |
数学 | 2935篇 |
物理学 | 2923篇 |
出版年
2023年 | 141篇 |
2022年 | 290篇 |
2021年 | 349篇 |
2020年 | 422篇 |
2019年 | 495篇 |
2018年 | 379篇 |
2017年 | 291篇 |
2016年 | 603篇 |
2015年 | 569篇 |
2014年 | 551篇 |
2013年 | 919篇 |
2012年 | 1086篇 |
2011年 | 1282篇 |
2010年 | 680篇 |
2009年 | 567篇 |
2008年 | 920篇 |
2007年 | 834篇 |
2006年 | 842篇 |
2005年 | 775篇 |
2004年 | 611篇 |
2003年 | 472篇 |
2002年 | 438篇 |
2001年 | 241篇 |
2000年 | 172篇 |
1999年 | 181篇 |
1998年 | 157篇 |
1997年 | 164篇 |
1996年 | 168篇 |
1995年 | 147篇 |
1994年 | 113篇 |
1993年 | 102篇 |
1992年 | 89篇 |
1991年 | 79篇 |
1990年 | 64篇 |
1989年 | 41篇 |
1988年 | 44篇 |
1987年 | 50篇 |
1986年 | 45篇 |
1985年 | 71篇 |
1984年 | 57篇 |
1983年 | 34篇 |
1982年 | 59篇 |
1981年 | 49篇 |
1980年 | 45篇 |
1979年 | 40篇 |
1978年 | 44篇 |
1977年 | 42篇 |
1976年 | 48篇 |
1974年 | 35篇 |
1973年 | 30篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Alexander Kaiser Klaus K. Mayer Andreas Sellmer Wolfgang Wiegrebe 《Monatshefte für Chemie / Chemical Monthly》2003,43(11):343-354
The molecular ion 1 of N-(n-propoxy)benzaldimine I rearranges by an 1,5-H-shift to the δ-distonic ion 2 which subsequently cyclizes to the α-distonic ion 3. Homolytic cleavage of the N–O bond in 3 results in the δ-distonic ion 4 which expels CH2O leading to the β-distonic ion 5. Ion 5 is also formed from the molecular ions of tetrahydrooxazines II and III and from M+• of phenylazetidine IVa. In a subsequent step, ion 5 cyclizes to the N-protonated 3,4-dihydroisoquinolinium ion 6. The syntheses of II–IV and their derivatives are described. 相似文献
112.
Varughese M. Alexander 《Tetrahedron letters》2005,46(40):6957-6959
Bismuth(III) nitrate pentahydrate is found to be an efficient catalyst for the Pechmann condensation reaction of phenols and β-ketoesters under solvent-free conditions. The reaction protocol is simple and is followed by aqueous work-up leading to the formation of the corresponding coumarin derivatives in good yield and high purity. 相似文献
113.
Nanogel nanosecond photonic crystal optical switching 总被引:3,自引:0,他引:3
Reese CE Mikhonin AV Kamenjicki M Tikhonov A Asher SA 《Journal of the American Chemical Society》2004,126(5):1493-1496
We developed a robust nanosecond photonic crystal switching material by using poly(N-isopropylacrylamide) (PNIPAM) nanogel colloidal particles that self-assemble into crystalline colloidal arrays (CCAs). The CCA was polymerized into a loose-knit hydrogel which permits the individual embedded nanogel PNIPAM particles to coherently and synchronously undergo their thermally induced volume phase transitions. A laser T-jump from 30 to 35 degrees C actuates the nanogel particle shrinkage; the resulting increased diffraction decreases light transmission within 900 ns. Additional transmission decreases occur with characteristic times of 19 and 130 ns. Individual NIPAM sphere volume switching occurs in the approximately 100 ns time regime. These nanogel nanosecond phenomena may be useful in the design of fast photonic crystal switches and optical limiting materials. Smaller nanogels will show even faster volume phase transitions. 相似文献
114.
115.
A simple, accurate and reproducible reversed-phase high-performance liquid chromatography (HPLC) method was developed for the separation and characterisation of alkylphenols (APs) and alkylphenol polyethoxylates (APEOs), using a C18 octadecyl silica (ODS) column. APs and each APEO oligomer were separated successfully within a reasonable time without gradient elution. An excellent resolution was obtained, even for mixtures of APs and low EO number APEOs, which are otherwise difficult to separate using conventional normal-phase HPLC methods. This method, combined with solid-phase extraction, was highly applicable for the simultaneous determination of alkylphenols and alkylphenol ethoxylates in real samples. 相似文献
116.
The cover picture shows a model of the "progenitor-TADDOLs" in front of a panorama of the Fünffingersstocks and the Wenden Glacier in the Titlisgebiet (Switzerland). The model is flanked by a stylized view of the general mechanistic model for the preferred stereochemical pathway of the Ti-TADDOLate-catalyzed reaction of chelating substrates (left) and a blackboard (right) showing formulae of compounds that can be prepared with high enantioselectivity by nucleophilic addition in the presence of titanium TADDOLates. From TADDOL, introduced in 1982, a genuine auxiliary system for the "introduction of chirality" (not only by reaction) has been developed, which, in the final sprint against the competition has a good chance of securing a place on the winning podium. The photograph of the mountain landscape was taken by Dr. J. Frackenpohl, the cover picture was generated by one of the authors (A.H.) of the comprehensive review of TADDOLs in this issue (p. 92 ff.) with the help of the program Povray. Supporting information for this article is available on the WWW under http://www.angewandte.com or from the author. 相似文献
117.
Rudnev AV Aleksenko SS Semenova O Hartinger CG Timerbaev AR Keppler BK 《Journal of separation science》2005,28(2):121-127
A CE method has been developed to evidence and quantitatively characterize the interaction between platinum-based antitumor drugs and human serum proteins. This method is a variant of affinity CE modified regarding both experimental setup and data treatment so as to measure the peaks (or vacancies) that correspond to the bound drug when it slowly binds to the protein. Using the formalism of the Hummel-Dreyer method and cisplatin and oxaliplatin as test compounds, a protocol for determining albumin and transferrin binding constants and stoichiometries, including (and distinguished by) 48 hours of incubation of the reaction mixture, was elaborated. Relative affinities of drugs toward different proteins in aqueous solution at physiological pH, chloride concentration, and temperature were compared in terms of overall binding constants and numbers of drug molecules attached to the protein. The results indicate that both platinum drugs bind to albumin more strongly than to transferrin, supporting the concept that the albumin fraction is a major drug supply route for chemotherapeutical needs. From a comparison with the binding parameters measured previously for cisplatin by other methods, conclusions were drawn about the validity of CE as a simple and convenient method for assaying protein-drug reactions with slow kinetics. 相似文献
118.
Meerovich IG Jerdeva V Derkacheva VM Meerovich GA Lukyanets EA Kogan EA Savitsky AP 《Journal of photochemistry and photobiology. B, Biology》2005,80(1):57-64
The photodynamic activity of dibiotinylated aluminum sulfophthalocyanine was studied in vitro and in vivo. Dibiotinylated aluminum sulfophthalocyanine provided enhanced phototoxic action on OAT-75 cell monolayers as compared with the parent drug. Photodynamic therapy of mice with Ehrlich carcinoma using dibiotinylated aluminum sulfophthalocyanine (0.25 mg/kg) resulted in enhanced inhibition of tumor growth, pronounced vascular damage (thrombosis and destruction of vascular walls) and eventual tumor necrosis. 相似文献
119.
Alexander V. Stepakov Jörg Magull Galina L. Starova Rafael R. Kostikov 《Tetrahedron》2006,62(15):3610-3618
Treatment of substituted 1,3-dithiolanes and 1,3-oxathiolanes with methyl diazoacetate in the presence of Rh2(OAc)4 effects ring expansion to the corresponding substituted 1,4-dithiane-2-carboxylates and 1,4-oxathiane-3-carboxylates. The sulfur ylides initially generated in these reactions undergo Stevens rearrangement in competition with both [2,3]-C-C-sigmatropic rearrangement and intramolecular fragmentation. In the case of 2-styryl-substituted 1,3-oxathiolane and 1,3-dithiolane, ring expansion on one-, three- and four-carbons subsequently takes place. 相似文献
120.
Turan Ozturk Andrey S. Klymchenko Sule Oncul Sule Taskiran F. Betul Kaynak Alexander P. Demchenko 《Tetrahedron》2007,63(41):10290-10299
Nine new 3-hydroxyflavone derivatives as fluorescent molecular sensors having two well-separated emission bands were synthesized. These sensors can occupy well-determined locations and orientations in macromolecular ensembles, such as micelles due to their finely-tuned designs. These polarity-sensitive dyes can incorporate into the anhydrous hydrophobic core of aqueous micelles. 相似文献