全文获取类型
收费全文 | 9701篇 |
免费 | 359篇 |
国内免费 | 9篇 |
专业分类
化学 | 6603篇 |
晶体学 | 65篇 |
力学 | 320篇 |
数学 | 1471篇 |
物理学 | 1610篇 |
出版年
2023年 | 61篇 |
2022年 | 85篇 |
2021年 | 116篇 |
2020年 | 170篇 |
2019年 | 165篇 |
2018年 | 198篇 |
2017年 | 168篇 |
2016年 | 340篇 |
2015年 | 308篇 |
2014年 | 302篇 |
2013年 | 628篇 |
2012年 | 641篇 |
2011年 | 704篇 |
2010年 | 394篇 |
2009年 | 352篇 |
2008年 | 611篇 |
2007年 | 651篇 |
2006年 | 570篇 |
2005年 | 554篇 |
2004年 | 413篇 |
2003年 | 383篇 |
2002年 | 321篇 |
2001年 | 149篇 |
2000年 | 125篇 |
1999年 | 104篇 |
1998年 | 96篇 |
1997年 | 71篇 |
1996年 | 116篇 |
1995年 | 80篇 |
1994年 | 82篇 |
1993年 | 71篇 |
1992年 | 64篇 |
1991年 | 56篇 |
1990年 | 42篇 |
1989年 | 41篇 |
1987年 | 44篇 |
1986年 | 25篇 |
1985年 | 68篇 |
1984年 | 51篇 |
1983年 | 26篇 |
1982年 | 72篇 |
1981年 | 55篇 |
1980年 | 64篇 |
1979年 | 52篇 |
1978年 | 33篇 |
1977年 | 36篇 |
1976年 | 47篇 |
1975年 | 41篇 |
1974年 | 36篇 |
1973年 | 33篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
92.
93.
94.
Jarroux N Keller P Mingotaud AF Mingotaud C Sykes C 《Journal of the American Chemical Society》2004,126(49):15958-15959
A new inisurf (acting as surfactant and initiator) molecule for ring-opening metathesis polymerization (ROMP) was synthesized and used in aqueous solution in order to control the size and shape of polymer nodules grown from liposomes. Nodules were observed to grow in size with conversion of monomer, and depending on the monomer used, they adopted either a spherical or comet-like shape. Here, we investigate polymer production from a liposome surface. We use a hydrophobic derivative of the Grubbs catalyst positioned at the liposome surface to allow for ROMP of monomers dissolved in the aqueous outer phase. We obtain nodules of polymer that can grow up to tens of micrometers, unveiling new efficient possibilities of polymerization from a membrane in an aqueous solution. 相似文献
95.
Lépine F Milot S Déziel E He J Rahme LG 《Journal of the American Society for Mass Spectrometry》2004,15(6):862-869
The opportunistic pathogen Pseudomonas aeruginosa produces a large array of 4-hydroxy-2-alkylquinolines (HAQs). These compounds were analyzed by LC/MS, using positive electrospray ionization, in the culture supernatant of strain PA14. Fifty-six HAQs and related compounds were detected and their [M + H](+) ions were further analyzed by collision induced dissociation (CID). These HAQs were grouped into five different series based on the presence of an hydrogen or hydroxyl group at the 3 position, an N-oxide group in place of the quinoline nitrogen, and an unsaturation on their alkyl side chain. Two new analogs of 3,4-dihydroxy-2 heptylquinoline, the Pseudomonas quinolone signal (PQS), were found with an alkyl chain longer by one and two methylene groups. Moreover, two additional series of compounds were identified in which a saturated or unsaturated alkyl side chain is located at the 3 position along with an hydroxyl group at the 3 position and a ketone at the 2 position. No HAQ N-oxides, nor any compounds from the latter two series, were detected in a pqsL mutant derivative of PA14, indicating that this gene is involved in the biosynthesis of these compounds. This work demonstrates the large repertoire of HAQ and HAQ-related compounds produced by P. aeruginosa, and provides insight into N-oxides biosynthesis and confirm the hypothesis that N-oxides are the precursors of compounds from Series 6 and 7. 相似文献
96.
In present telecommunication networks, information transfer relies on the interplay of optical and electrical signals. Data are communicated optically but processed electronically. Methods to maintain the propagating signals solely at the optical level must be developed to overcome the transmission capacities and speed limits imposed by the electronic components. We have demonstrated that molecular switches can be used to gate optical signals in response to optical signals. We have realized a simple optical network consisting of three light sources, one cell containing a solution of three fluorescent molecules, one cell containing a solution of a three-state molecular switch and a detector. The light emitted by the three fluorophores is absorbed by the three states of the molecular switch. Using this simple operating principle, we have shown that multichannel digital transmission can be implemented on an ensemble of communicating molecules relying exclusively on the interplay of optical inputs and optical outputs. 相似文献
97.
Pavan FA Lucho AM Gonçalves RS Costa TM Benvenutti EV 《Journal of colloid and interface science》2003,263(2):688-691
The metal ion adsorption properties of the microporous hybrid anilinepropylsilica xerogel were studied using divalent copper, zinc, and cadmium ions in aqueous solutions in concentrations ranging from 10(-4) up to 5x10(-3) moll(-1). At low concentrations the surface of the solid phase presents selectivity for Cu (II), even in competitive conditions. This preferential sorption ability for copper in relation to zinc and cadmium ions was interpreted by considering the xerogel morphology. 相似文献
98.
Meng M Stievano L Lambert JF 《Langmuir : the ACS journal of surfaces and colloids》2004,20(3):914-923
Glycine was adsorbed on the surface of a well-defined silica from aqueous solutions of variable concentrations and pHs. The adsorbed molecules were characterized using middle-IR and UV-vis-NIR spectroscopies. Except at the lowest pH (2.0), they were predominantly present on the surface as zwitterions. Two successive deposition mechanisms were evidenced with increasing glycine concentration. At low concentrations, glycine is specifically adsorbed on silica surface sites, probably through its NH3+ moiety. The pH dependence suggests that these sites may be silanolate groups (approximately equal to Si-O-). At higher concentrations, specific adsorption sites are saturated and surface-induced precipitation of beta-glycine is observed. The thermal reactivity of adsorbed/deposited glycine was then investigated by thermogravimetric analysis, in situ diffuse reflectance IR spectroscopy, and thermoprogrammed desorption coupled with mass spectrometry. Adsorbed glycine molecules react to form peptide bonds at a temperature considerably lower than that for bulk crystalline alpha-glycine. The main reaction product is the cyclic dimer diketopiperazine, with no evidence of the linear dimer. The activation mechanism is not diffusionally limited; the formation of "surface acyls", previously proposed for related systems, has not been evidenced here. These findings are of relevance for the evaluation of prebiotic peptide synthesis scenarios. 相似文献
99.
Mathieu D Frapart YM Bartoli JF Boucher JL Battioni P Mansuy D 《Chemical communications (Cambridge, England)》2004,(1):54-55
Electron transfer from tetrahydropterins to iron porphyrins, with formation of intermediate tetrahydropterin cation radicals, is a very general reaction that was shown to occur not only with tetrahydrobiopterin, as originally found in NO-synthases, but also with another important biological cofactor, tetrahydrofolate, and various iron porphyrins, either in their ferric state, or in the Fe(II)O(2) state, as in the first model of the corresponding NO-synthase reaction described in this paper. 相似文献
100.
Workman JA Garrido NP Sançon J Roberts E Wessel HP Sweeney JB 《Journal of the American Chemical Society》2005,127(4):1066-1067
The first examples of highly enantioselective [2,3]-sigmatropic rearrangements of acyclic allylic ammonium ylids are reported. Thus, a range of N-{2'-[(N'-allyl-N',N'-dialkyl)ammonium]}acetyl camphor sultams undergo rearrangement at 0 degrees C in DME solution with high diastereofacial control (up to 99:1 dr) to give allylglycines in generally high yield. The power of the method has been demonstrated in a rapid and efficient synthesis of (R)-allyl glycine. 相似文献