全文获取类型
收费全文 | 2678篇 |
免费 | 95篇 |
国内免费 | 11篇 |
专业分类
化学 | 1789篇 |
晶体学 | 8篇 |
力学 | 45篇 |
数学 | 493篇 |
物理学 | 449篇 |
出版年
2023年 | 14篇 |
2022年 | 19篇 |
2021年 | 34篇 |
2020年 | 43篇 |
2019年 | 54篇 |
2018年 | 28篇 |
2017年 | 18篇 |
2016年 | 69篇 |
2015年 | 70篇 |
2014年 | 62篇 |
2013年 | 73篇 |
2012年 | 141篇 |
2011年 | 167篇 |
2010年 | 91篇 |
2009年 | 79篇 |
2008年 | 102篇 |
2007年 | 114篇 |
2006年 | 143篇 |
2005年 | 136篇 |
2004年 | 93篇 |
2003年 | 82篇 |
2002年 | 71篇 |
2001年 | 69篇 |
2000年 | 55篇 |
1999年 | 57篇 |
1998年 | 56篇 |
1997年 | 49篇 |
1996年 | 47篇 |
1995年 | 39篇 |
1994年 | 45篇 |
1993年 | 36篇 |
1992年 | 50篇 |
1991年 | 42篇 |
1990年 | 27篇 |
1989年 | 25篇 |
1988年 | 19篇 |
1987年 | 13篇 |
1985年 | 15篇 |
1984年 | 17篇 |
1983年 | 27篇 |
1982年 | 21篇 |
1981年 | 20篇 |
1980年 | 15篇 |
1978年 | 11篇 |
1976年 | 13篇 |
1974年 | 14篇 |
1973年 | 12篇 |
1943年 | 12篇 |
1933年 | 11篇 |
1923年 | 11篇 |
排序方式: 共有2784条查询结果,搜索用时 15 毫秒
21.
W. Ketterle P. Graßhoff H. Figger H. Walther 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1988,9(4):325-329
The emission of the ND4 Schüler band was observed after neutralization of a mass-selected ND 4 + ion beam. Thus the assignment of this band to the ammonium radical was confirmed. The lifetime of the upper state (3p 2 F 2) was determined to be 4.2 ns, which is much shorter than ab initio values of the radiative lifetime, showing that this state decays predominantly by predissociation. The Schuster band was not observed, neither after neutralization of ND 4 + , nor of ND 3 + . 相似文献
22.
Duygu Avci Selim H. Kseflu Robert D. Thompson Lon J. Mathias 《Journal of polymer science. Part A, Polymer chemistry》1994,32(15):2937-2945
New ester derivatives of ethyl α-hydroxymethylacrylate were synthesized using acid chlorides (traditional solution reactions), sodium salts of acids (with phase transfer catalysis), and trifluoroacetic anhydride (trifluoroacetate). The interfacial process gave high yields of clean products under very mild conditions. Derivatives obtained include the formate, acetate, hexanoate, stearate, benzoate, trifluoroacetate, and adamantanoate. Bulk polymerizations with 2,2′-azobis (isobutyronitrile) gave high molecular weight polymers with intrinsic viscosities of over 2 dL/g and molecular weights of several million [based on size-exclusion chromatography (SEC) comparison to polystyrene standards]. These high molecular weights were the result of autoacceleration in the bulk as shown by monitoring molecular weight with respect to conversion. Solution polymerization in benzene gave more typical polymer, e.g., the acetate derivative showed an SEC molecular weight of 52,000. Glass transition temperatures for the n-alkyl esters decreased from the formate (77°C) to the hexanoate (15°C); the stearate showed a side-chain melting point of 40°C but no Tg. Glass transitions were observed for the trifluoroacetate, benzoate, and adamantanoate polymers at 69, 130, and 214°C, respectively. Solution 13C-NMR showed evidence of tacticity information for the formate and acetate derivatives with appaent preference for syndiotactic polymer formation similar to that of methyl methacrylate. FTIR and solid-state 13C-NMR analysis gave spectra with functional group peaks and chemical shift values expected based on composition. The stearate monomer and polymer gave solid-state 13C chemical shifts of 34 and 33 ppm, respectively, for the central CH2 units consistent with monoclinic and orthorhombic crystal packing. © 1994 John Wiley & Sons, Inc. 相似文献
23.
Binuclear Nickel(0) Complexes with “Snake Ligands” of 1-Azadiene Type: Model Systems of the Oxidative Coupling of 1-Azadienes and 1.3-Dienes at Nickel(0) Synthesis, properties, and reactions of dimeric nickel(0) complexes with special 1-azadiene typ ligands (“snake ligands”) are described. The X-ray analysis of a typical compound (Bis-(bis-cinnamaldehyde-N,N'-propylendiimine)-dinickel(0)) shows that both central atoms have the coordination number 3. The four 1-azadiene groups are coordinated in a different way: unidendate coordination by N-Ni(1) bond and bidendate coordination by N-Ni(1) and olefine-Ni(2) bond. The compound is a good model system for the oxidative coupling reaction of 1-azadienes with 1.3-dienes at 2 nickel(0) centres. IR and electronic spectra show other complexes with this type of ligands to have an analogous coordination sphere. 相似文献
24.
A method is described for the gas-chromatographic determination of the diastereomers of vitamin K1 (phylloquinone) in the form of their dihydro dimethyl ethers. The reported method of derivatization and chromatographic analysis in conjunction with optical rotation measurements are useful approaches for characterization of vitamin K1 samples with respect to their origin. 相似文献
25.
Protein-protein interactions play crucial roles in various biological pathways and functions. Therefore, the characterization of protein levels and also the network of interactions within an organism would contribute considerably to the understanding of life. The availability of the human genome sequence has created a range of new possibilities for biomedical research. A crucial challenge is to utilize the genetic information for better understanding of protein distribution and function in normal as well as in pathological biological processes. In this review, we have focused on different platforms used for systematic genome-based proteome analyses. These technologies are in many ways complementary and should be seen as various ways to elucidate different functions of the proteome. 相似文献
26.
Reactions of π-Organonickel Complexes with Tertiary Phosphanes In a hexane solution Ni(C5H5)2 reacts with PBu3 or Ph2PBu forming the nickel(O) complexes Ni(PBu3)4 or Ni(Ph2PBu)4 (A). Under the same conditions only one cyclopentadienyl ligand is substituted by PhPBu2 and the nickel(I) compound (C5H5)Ni (PhPBu2)2 (B) is obtained. Products of the reactions between B and α,α′-dipyridyl, hydrogen chlorid in ether, or Ni(PhPBu2),Cl2 are Ni(dipy)2, [PhPHBu2]2[NiCl4], or (C5H5) Ni(PhPBu2)2Cl. By the reaction with HgCl2 a cyclopentadienyl compound of an unknown structur is formed. The compound Ni(PhPBu2)4 which is analogous to A is synthesized by the reduction of bis(acety1acetonato)-nickel with Et2AlOEt in the presence of PhPBu2 or by the reaction of bis (cyclooctadiene-1,5)-nickel with PhPBu2. 相似文献
27.
Chiral salicylidenphenethylamines (R)‐HA or (S)‐HA , 2‐salicylidenfurfuryl‐imines HB , and 2‐salicylidenaminoethanol HC react with sodium hydride or sodium hexamethyldisilylamide to form the sodium complexes [Na(R)‐A] 4 · 0,5 Et 2 , [Na(S)‐A] 4 · 0,5 Et 2 O (1) , [NaB] 4 · 0,5 Ph‐Me (2) and [(dme)NaC] 4 (3) . In the presence of 18‐crown‐6 the complex [Na(18‐crown‐6)(thf) 2 ] 2 [Na 2 (C)] 4 · THF (4) can also be isolated. The crystal structure analyses of both 1 and 2 show that heterocubane structures with a Na4O4 frame work are formed. Additionally, the imine nitrogen atom is bonded at the Na atom which has the coordination number 4 in 1 . Additional coordination of the furfuryl oxygen atom results in the coordination number five for the sodium atom in 2 . In 3 which is also a tetramer, two Na2O2 units are connected via two imino‐ethanol bridges Na(1)‐N(=CH‐phenolat)‐CH2CH2‐OH‐Na(2A). The crystal structure analysis displays that 4 is an ionic compound consisting of two [(thf)2Na(18‐crown‐6)]+ cations and the dinuclear dianion [Na 2 (C) 4 ] 2? . Both 1 and 2 are carboxylation reagents which transfer CO2 to 2‐fluoropropiophenone. 1 is more active than 2 , but 3 and 4 are inactive. 相似文献
28.
29.
Mathias JM 《OR manager》1995,11(11):1, 6-1, 8
Hernia surgery, a bread and butter operation for many hospitals, seems a likely candidate for streamlining, standardization, and package pricing. But there's no consensus on the best way to do hernia repairs. Surgeons differ vehemently on which approach is preferable. The mesh plug attracted attention this summer when its advocate, Ira Rutkow, MD, appeared on TV. But the patch, traditional open repair, and laparoscopy also have their advocates. Here's a look at the techniques and why you're unlikely to see consensus soon. 相似文献
30.