全文获取类型
收费全文 | 4661篇 |
免费 | 720篇 |
国内免费 | 500篇 |
专业分类
化学 | 3468篇 |
晶体学 | 51篇 |
力学 | 257篇 |
综合类 | 36篇 |
数学 | 524篇 |
物理学 | 1545篇 |
出版年
2024年 | 17篇 |
2023年 | 73篇 |
2022年 | 128篇 |
2021年 | 164篇 |
2020年 | 152篇 |
2019年 | 171篇 |
2018年 | 153篇 |
2017年 | 132篇 |
2016年 | 222篇 |
2015年 | 190篇 |
2014年 | 239篇 |
2013年 | 338篇 |
2012年 | 335篇 |
2011年 | 375篇 |
2010年 | 270篇 |
2009年 | 265篇 |
2008年 | 298篇 |
2007年 | 267篇 |
2006年 | 276篇 |
2005年 | 182篇 |
2004年 | 181篇 |
2003年 | 160篇 |
2002年 | 187篇 |
2001年 | 131篇 |
2000年 | 104篇 |
1999年 | 115篇 |
1998年 | 101篇 |
1997年 | 84篇 |
1996年 | 53篇 |
1995年 | 74篇 |
1994年 | 63篇 |
1993年 | 51篇 |
1992年 | 51篇 |
1991年 | 31篇 |
1990年 | 36篇 |
1989年 | 15篇 |
1988年 | 18篇 |
1987年 | 12篇 |
1986年 | 26篇 |
1985年 | 24篇 |
1984年 | 17篇 |
1983年 | 15篇 |
1982年 | 12篇 |
1981年 | 12篇 |
1980年 | 6篇 |
1979年 | 10篇 |
1977年 | 4篇 |
1974年 | 7篇 |
1973年 | 7篇 |
1969年 | 4篇 |
排序方式: 共有5881条查询结果,搜索用时 15 毫秒
151.
The cob(I) alamin (1(I)) -catalyzed2 transformation of the aldehyde 2 has been studied (cf. Table 1). Kinetic examinations showed a rapid isomerization of 2 to 3 (cf. Fig. 1 and 2). From the transformations in glacial AcOH, the two cyclopropanols 5 and 7 were isolated as main products (cf. Tables 1–3 and Fig. 1 and 2). Using large amounts of 1(I) , the aldehyde 4 was very slowly transformed. Accepting the intermediate formation of 6 interconnected Co-complexes, i. e. A , B , C , D , E and F (cf. Scheme), the generation of all the products observed can be explained. 相似文献
152.
153.
[3-3H]-valine was efficiently synthesised from sodium α-ketoisovalerate. With a β-lactam negative mutant of C. acremonium, l-[1-14C-3-3H]-valine and dl-[1-14C-3-3H]-valine were independently incorporated into the Arnstein tripeptide dimer, i.e. Bis-δ-(l-α-aminodipyl)-l-cystinyl-bis-d-valine, with full retention of trieium at C-3 of the d-valine residue. This result strongly suggested retention of configuration at C-3 of valine when the tripeptide was biosynthesised, and further limited the number of possible mechanisms for the biosynthesis of penicillins. 相似文献
154.
15-甲基-双环[10,3,0]十五碳-1(12)-烯-13-酮的单晶属空间群P2_1/n,晶胞参数:a=0.4838(1)nm,b=1.3949(2)nm,c=2.1645(4)nm,β=92.07(1)°,Z=4.其中平面五员环呈刚性。另一个含烯十二员环的实际构象与分子力学计算的最稳定构象一致。 相似文献
155.
A new dihydrobenzodioxane derivative, origalignanol ( 10 ), together with nine polyphenolic compounds, salvianolic acid A ( 1 ), salvianolic acid C ( 2 ), lithospermic acid ( 3 ), apigenin 7‐O‐β‐D‐glucuronide ( 4 ), apigenin 7‐O‐β‐D‐(6″‐methyl)glucuronide ( 5 ), luteolin, ( 6 ), luteolin 7‐O‐β‐D‐glucopyranoside ( 7 ), luteolin 7‐O‐β‐D‐glucuronide ( 8 ), and luteolin 7‐O‐β‐D‐xylopyranoside ( 9 ), were isolated from the aqueous ethanolic extract of the aerial parts of Origanum vulgare for the first time. The structure of new compound 10 was determined on the basis of spectroscopic methods. Compound 5 is probably an artifact formed during the isolation. Compounds 1, 2 and 3 showed strong DPPH radical scavenging activity with an EC50 of 7.2 ± 0.4, 9.6 ± 0.9, and 9.5 ± 0.7 μM, respectively, and protected rat hepatocytes from CCl4‐damage at 100 μM. 相似文献
156.
Free radical reactions induced by the photolysis of the lignin model compound α-guaiacoxylacetoveratrone have been studied by conventional and time-resolved ESR spectroscopy. In the presence of efficient hydrogen donors such as aqueous and hydroxylic solvents the primary reaction involves photoreduction of the triplet phenacyl ether to form the ketyl radical followed by rapid cleavage to the phenacyl radical and guaiacol. Subsequent formation of polarized guaiacoxyl radicals is due to secondary photo-oxidation. The cleavage of the ketyl radical is retarded in basic media and accelerated in acetic acid. Minor reaction pathways involving excited singlets cannot be ruled out by the current CIDEP observations. 相似文献
157.
We present a comprehensive survey of different C-H activation pathways over various kinds of active sites of terminal oxygens [=O] and bridge oxygens [-O-] by using Mo3O9 model systems. This allows us to provide some insights into fundamental issues concerning C-H activation by metal oxo species involved in many heterogeneous, homogeneous, and enzymatic processes. We show that H abstraction is the most feasible reaction pathway for the activation of a C-H bond on molybdenum oxides; and that [=O] is more active than [-O-]. Our calculations also suggest that (2+2) can be an alternative if M=O bond possesses a high polarity, while (5+2) can provide another effective pathway if two M=O bonds are in close proximity. Implications for the related heterogeneous, homogeneous, and enzymatic processes are discussed. 相似文献
158.
Xu QM Wang D Han MJ Wan LJ Bai CL 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3006-3010
Scanning tunneling microscopy (STM) combined with cyclic voltammetry has been employed to investigate the adsorption of cinchonine on Cu(111). Similar to cinchonidine, cinchonine forms a long-range ordered adlayer with (4 x 4) symmetry on the substrate. The structural details on molecular adsorption were obtained by high-resolution STM images. On the basis of the previous results and obtained STM images, the quinoline ring is proposed to lie parallel to Cu(111) and serve as an anchoring group. The chiral quinuclidine moiety extends out of the surface to facilitate the interaction with the prochiral reactants. 相似文献
159.
Ning Fang Vincent Chan Kai-Tak Wan Hai-Quan Mao Kam W. Leong 《Colloids and surfaces. B, Biointerfaces》2002,25(4):347-362
High-resolution reflection interference contrast microscopy (HR-RICM) was developed for probing the deformation and adhesion of phospholipid vesicles induced by colloidal forces on solid surfaces. The new technique raised the upper limit of the measured membrane–substrate separation from 1 to 4.5 μm and improved the spatial resolution of the heterogeneous contact zones. It was applied to elucidate the effects of wall thickness, pH and osmotic stress on the non-specific adhesion of giant unilamellar vesicles (ULV) and multilamellar vesicles (MLV) on fused silica substrates. By simultaneous cross-polarization light microscopy and HR-RICM measurements, it was observed that ULV with the wall thickness of a single bilayer would be significantly deformed in its equilibrium state on the substrate as the dimension of its adhesive–cohesive zone was 29% higher than the theoretical value of a rigid sphere with the same diameter. Besides, electrostatic interaction was shown as a significant driving force for vesicle adhesions since the reduction in pH significantly increased the degree of deformation of adhering ULV and heterogeneity of the adhesion discs. The degree of MLV deformation on the solid surfaces was significantly less than that of ULV. When the wall thickness of vesicle increased, the dimension of contact zone was reduced dramatically due to the increase of membrane bending modulus. Most important, the adhesion strength of colloidal adhesion approached that of specific adhesion. Finally, the increase of osmotic stress led to the collapse of adhering vesicles on the non-deformable substrate and raised the area of adhesive contact zone. To interpret these results better, the equilibrium deformation of adhering vesicle was modeled as a truncated sphere and the adhesion energy was calculated with a new theory. 相似文献
160.
Taian Li Mong-Feng Chiou Yajun Li Changqing Ye Min Su Mengyu Xue Xiaobin Yuan Chuanchuan Wang Wen-Ming Wan Daliang Li Hongli Bao 《Chemical science》2022,13(19):5667
Pyrroles are among the most important heterocycles in pharmaceuticals and agrochemicals. Construction of pyrrole scaffolds with different substituents and a free NH group, however, is challenging. Herein, a metal-free method for the synthesis of unsymmetrically tetrasubstituted NH-pyrroles using a consecutive chemoselective double cyanation is reported. The desired pyrroles were obtained with yields up to 99% and good functional group tolerance. Mechanistic studies identified a reaction mechanism that features a subtle sequence of first cyano-addition and migration, followed by cyano-addition and aromatization to afford the pyrrole skeleton. Pyrrolo[1,2-a]pyrimidines are synthesized as the synthetic applications of NH-pyrroles, and these pyrrolo[1,2-a]pyrimidines exhibit unpredicted time-dependent aggregation-induced emission enhancement (AIEE) properties.A novel method for the challenging synthesis of unsymmetrically tetrasubstituted NH-pyrroles from chalcone derivatives is reported. The pyrrolo[1,2-a]pyrimidine derivatives that were synthesized from NH-pyrroles exhibit AIE and AIEE property. 相似文献