全文获取类型
收费全文 | 860篇 |
免费 | 47篇 |
国内免费 | 4篇 |
专业分类
化学 | 652篇 |
晶体学 | 3篇 |
力学 | 32篇 |
数学 | 137篇 |
物理学 | 87篇 |
出版年
2023年 | 6篇 |
2022年 | 13篇 |
2021年 | 32篇 |
2020年 | 19篇 |
2019年 | 30篇 |
2018年 | 36篇 |
2017年 | 10篇 |
2016年 | 32篇 |
2015年 | 37篇 |
2014年 | 30篇 |
2013年 | 67篇 |
2012年 | 66篇 |
2011年 | 60篇 |
2010年 | 42篇 |
2009年 | 28篇 |
2008年 | 49篇 |
2007年 | 63篇 |
2006年 | 49篇 |
2005年 | 44篇 |
2004年 | 33篇 |
2003年 | 31篇 |
2002年 | 30篇 |
2001年 | 7篇 |
2000年 | 6篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1991年 | 2篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1977年 | 6篇 |
1975年 | 2篇 |
1973年 | 5篇 |
1972年 | 3篇 |
1966年 | 2篇 |
1965年 | 1篇 |
1964年 | 1篇 |
1963年 | 1篇 |
1961年 | 1篇 |
1955年 | 1篇 |
排序方式: 共有911条查询结果,搜索用时 31 毫秒
31.
Charbonnière LJ Schurhammer R Mameri S Wipff G Ziessel RF 《Inorganic chemistry》2005,44(20):7151-7160
A new ligand, LC, bis-[(6'-carboxy-2,2'-bipyridine-6-yl)]phenylphosphine oxide, in which the tridentate 6-carboxy-2,2'-bipyridyl arms are directly linked to a phenylphosphine oxide fragment, has been synthesized. The corresponding [Ln.LC]Cl.xH2O complexes (Ln = Eu, x = 4, and Tb, x = 3) were isolated from solutions containing equimolar amounts of LC and hydrated LnCl3 salts and characterized by elemental analysis, mass spectrometry, and infrared spectroscopy. The interactions of the Eu complex with various anions (AMP(2-), ADP3-, ATP,4- HPO4(2-), and NO3-) were studied by titration experiments, using UV-vis, luminescence spectroscopy, and excited-state lifetime measurements. The results are in keeping with strong interactions with the ADP3-, ATP4-, and phosphate anions in TRIS/HCl buffer (0.01 M, pH = 7.0), as revealed by the determination of the conditional stepwise association constants. These values are higher than the one determined for ligand LB, bis[(6'-carboxy-2,2'-bipyridine-6-methyl-yl)]-n-butylamine (Delta log K approximately 1-2). The interaction of complexes [Ln.LB]+ and [Ln.LC]+ with nitrate, monohydrogenophosphate, methyl phosphate (MeP2-), methyldiphosphate (MeDP3-), and methyltriphosphate (MeTP4-) anions was investigated by means of quantum mechanical (QM) calculations. The results, combined with data on the photophysical impact of the sequential competitive binding of anions to the Eu complexes in water, suggest that LB is too flexible to ensure a good coordination pocket, while the molecular structure of ligand LC stabilizes both the formation of the lanthanide complexes and its adducts with ATP. 相似文献
32.
Allylic nitro compounds undergo relatively clean [2,3] sigmatropic rearrangement upon heating in refluxing 1,2-dichlorobenzene in the presence of DABCO to give the corresponding allylic alcohols via the intermediate allylic nitrite. [reaction: see text] 相似文献
33.
Jnanadeva Maharana Samir K. Paul Gautam Sengupta 《Communications in Mathematical Physics》1991,139(3):527-549
The Neveu-Schwarz-Ramond type II closed superstring is considered to evolve in a curved space-time manifold. The Krichever-Novikov global operator formalism is used to construct the generators of a super-conformal algebra on a Riemann surface . The computation for the quantum algebra of these generators is explicitly presented. It is shown that the theory is free from super-conformal anomalies if the target manifold is ten dimensional and satisfies the Ricci flatness condition. 相似文献
34.
Samir B. Hanna Rita Hessley William H. Webb William R. Carroll 《Fresenius' Journal of Analytical Chemistry》1971,255(1):30-32
Summary The rates of oxidation of four chelating agents, NTA, EDTA, CDTA, and DTPA with Ce(IV), in sulfuric acid media, were determined spectrophotometrically by a stopped-flow technique. The reductive ability is in the order CDTA > EDTA > DTPA > NTA. The influence of varying the acidity of the medium was studied, and in each case a maximum in the rate constant vs. [H+] plot was observed. A possible interpretation of the reactivities and the influence of acidity is advanced.
Part I: Z. Anal. Chem. 246, 231 (1969). 相似文献
Oxydative Decarboxylierung von PolyaminocarbonsäurenII. Vergleichende kinetische Untersuchung der Oxydation von NTA, ÄDTA, CDTA und DTPA mit Ce(IV) in saurer Lösung
Zusammenfassung Die Oxydationsgeschwindigkeiten von 4 Chelaten (NTA, ÄDTA, CDTA und DTPA) mit Ce(IV) in saurer Lösung wurden spektrophotometrisch mit Hilfe der stopped-flow-Technik bestimmt. Die Reduzierfähigkeit nimmt in der Reihenfolge CDTA > ÄDTA > DTPA > NTA ab. Der Einfluß verschiedener Säuregehalte in der Lösung wurde untersucht, und in jedem Fall wurde ein Maximum in der graphischen Darstellung der Geschwindigkeitskonstante gegen [H+] beobachtet. Eine mögliche Erklärung des Reaktionsvermögens und des Säureeinflusses wird gegeben.
Part I: Z. Anal. Chem. 246, 231 (1969). 相似文献
35.
Bernard Loubinoux Jean-Luc Colin Samir Tabbache 《Journal of heterocyclic chemistry》1984,21(6):1669-1672
The preparation of 1-aryloxymethyl-1,2,3-triazoles, potential biologically active compounds particularly in the pesticide field, is described. The action of sodium azide on aryloxymethyl halides gave aryloxymethyl azides. The cycloaddition reactions of azides with acetylenic compounds provided the expected triazoles in good yields. 相似文献
36.
37.
Begaa Samir Messaoudi Mohammed Ouanezar Abdelkader Hamidatou Lylia Malki Abderrahim 《Journal of Radioanalytical and Nuclear Chemistry》2018,317(2):1107-1112
Journal of Radioanalytical and Nuclear Chemistry - The objectives of this research were to study the elemental concentrations of Mentha spicata L., using a sensitive nuclear analytical technique... 相似文献
38.
Shahaji Gaikwad Satej Deshmukh Samir H. Chikkali 《Journal of polymer science. Part A, Polymer chemistry》2014,52(1):1-6
This overview provides insights into the current state‐of‐the‐art solutions to insertion copolymerization of functional olefinic monomers. The challenges in insertion copolymerization of functional olefinic monomers, with a special emphasis on vinyl halides, are highlighted. The crucial design of the Pd–phosphinesulfonate [Pd(PO)] enables up to 3.6 mol % incorporation of vinyl fluoride (VF) in an ethylene–VF copolymerization reaction. In a significant development, insertion copolymerization of industrially relevant functional olefin, that is, vinyl chloride (VC), was unambiguously ascertained, and a detectable amount of VC (0.4 mol %) was incorporated (at the chain end). In a detailed investigation, the in situ existence of (PO)Pd? H species during the polymerization was revealed, and it was demonstrated that these are indeed responsible for VC incorporation. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1–6 相似文献
39.
Samir Z. Zard 《Helvetica chimica acta》2019,102(8)
The present account discusses in detail various mechanistic features of the degenerative radical addition‐transfer of xanthates and related thiocarbonylthio congeners and makes a comparison with the more classical Kharasch reactions to which it is similar in certain aspects. The xanthate group reacts reversibly with the ‘active’ radicals in the medium and is able to store them in a somewhat inactive form. This increases their effective lifetime in the medium and, at the same time, lowers their absolute concentration while regulating their relative concentration. These properties translate into a powerful carbon–carbon bond forming process, especially as regards intermolecular additions to electronically unbiased (‘unactivated’) alkenes. Most functional groups are tolerated, in particular polar functions that often require protection with other chemistries. This broad versatility is illustrated by examples where the xanthate addition to the alkene is combined with other, more classical reactions to provide a convergent, rapid access to a wide range of useful structures. Emphasis has been placed on the synthesis of open chain and more complex carbocycles, as well as on the transfer of chirality. These ‘radical alliances’ include organosilicon chemistry, the Diels–Alder cycloaddition and cheletropic extrusion of sulfur dioxide, the Claisen sigmatropic rearrangement, and the Horner–Wadsworth–Emmons (HWE) condensation. 相似文献
40.
Using tools from set-valued and variational analysis, we propose a mathematical formulation for a power DC-DC Buck converter.
We prove the existence of trajectories for the model. A stability and asymptotic stability results are established. The theoretical
results are supported by some numerical simulations with a discussion about explicit and implicit schemes. 相似文献