全文获取类型
收费全文 | 8190篇 |
免费 | 335篇 |
国内免费 | 33篇 |
专业分类
化学 | 5719篇 |
晶体学 | 49篇 |
力学 | 151篇 |
数学 | 1329篇 |
物理学 | 1310篇 |
出版年
2023年 | 43篇 |
2022年 | 136篇 |
2021年 | 179篇 |
2020年 | 140篇 |
2019年 | 162篇 |
2018年 | 124篇 |
2017年 | 100篇 |
2016年 | 238篇 |
2015年 | 217篇 |
2014年 | 247篇 |
2013年 | 433篇 |
2012年 | 495篇 |
2011年 | 1131篇 |
2010年 | 393篇 |
2009年 | 385篇 |
2008年 | 432篇 |
2007年 | 479篇 |
2006年 | 375篇 |
2005年 | 368篇 |
2004年 | 347篇 |
2003年 | 266篇 |
2002年 | 247篇 |
2001年 | 202篇 |
2000年 | 190篇 |
1999年 | 122篇 |
1998年 | 103篇 |
1997年 | 53篇 |
1996年 | 95篇 |
1995年 | 70篇 |
1994年 | 63篇 |
1993年 | 70篇 |
1992年 | 63篇 |
1991年 | 59篇 |
1990年 | 64篇 |
1989年 | 40篇 |
1988年 | 51篇 |
1987年 | 31篇 |
1986年 | 32篇 |
1985年 | 46篇 |
1984年 | 44篇 |
1983年 | 32篇 |
1982年 | 34篇 |
1981年 | 29篇 |
1980年 | 15篇 |
1979年 | 8篇 |
1978年 | 11篇 |
1977年 | 19篇 |
1976年 | 12篇 |
1975年 | 9篇 |
1974年 | 9篇 |
排序方式: 共有8558条查询结果,搜索用时 203 毫秒
91.
Coldham I Crapnell KM Fernàndez JC Moseley JD Rabot R 《The Journal of organic chemistry》2002,67(17):6181-6187
A synthesis of the core ABC ring system of the manzamine alkaloids is described, starting from arecoline. The key steps involve a Claisen rearrangement to set up a 4-substituted-3-methylenepiperidine and a stereoselective azomethine ylide dipolar cycloaddition reaction. Condensation of the aldehyde 6 and sarcosine ethyl ester hydrochloride salt gives an intermediate azomethine ylide, which undergoes an intramolecular cycloaddition reaction to set up two new rings and three new chiral centers stereoselectively. The aldehyde 6 was not a suitable substrate for related azomethine ylide cycloaddition reactions with other amines. However, the related dimethyl acetal 26 could be condensed with a variety of amines to give the desired tricyclic products. The cycloaddition reaction with N-methyl or N-allyl glycine ethyl ester gave almost exclusively the exo adduct, whereas cycloaddition with glycine ethyl ester gave the endo adduct. 相似文献
92.
David T. Connor Patricia A. Young Maximillian Von Strandtmann 《Journal of heterocyclic chemistry》1977,14(1):139-141
The reaction of 2-picoline N-Oxide anion with o-substituted henzoates and isatoic anhydrides to give synthetically useful l-(2-methoxyphenyl)-2-(2-pyridinyl)ethanone N-oxides, I-(2-hydroxy-phenyJ)-2-(2-pyridinyl)ethanone N-oxides and I -(2-arninopheny])-2-(2-pyridinyl)ethanone N-oxides is described. 相似文献
93.
Ana M. Reverdito Liliana Orelli Mnica Dalmaso Isabel Perillo Beatriz M. Fernndez 《Journal of heterocyclic chemistry》1991,28(2):273-281
Reaction of 1,2-diaryl-3-methyl-1,4,5,6-tetrahydropyrimidinium iodides 1a-i with alkaline solutions afforded N-aroyl-N-aryl-N'-methyltrimethylenediamines 2a-i . Compounds 2 are stable under acid conditions but in neutral or alkaline media spontaneously rearrange giving N-aroyl-N'-aryl-N-methyltrimethylenediamines 3a-i . Treating compounds 3 with concentrated acids reverse reaction takes place. Kinetic studies were performed on this intramolecular N → N' aroyl transfer over the Ho-pH range -0.9 to 2.30. Compounds 3 undergo acyl transfer to give 2 by a mechanism which involves a change in the rate determining step from formation to acid-catalysed decomposition of a six-membered heterocyclic intermediate on going from Ho to pH values. The existence of maxima in the pH rate profile allow to determine apparent pKa values of the hexahydropyrimidine intermediates which gave good correlation with the Swain F substituent constants. Stability of these heterocycles was also predicted by determination of thermodinamic parameters. Comparisons are made with the behaviour of five-membered heterocyclic intermediates (imidazolidine derivatives) which were studied in an earlier paper. 相似文献
94.
The thermal degradation of styrene-4-nitrostyrene copolymers (SNS) has been studied using differential thermal analysis (DTA) and thermogravimetry (TGA) under isothermal and dynamic conditions in dynamic nitrogen. The apparent activation energy of the degradative process was determined following several methods of thermogravimetric analysis. The stability decreases as the nitrostyrene content in the copolymer increases. Fourier-transform infra-red spectroscopy has been used to analyze the degradation products at various degrees of conversion. 相似文献
95.
Kujawa P Moraille P Sanchez J Badia A Winnik FM 《Journal of the American Chemical Society》2005,127(25):9224-9234
The layer-by-layer growth of multilayer assemblies of two polysaccharides, the polyanion hyaluronan (HA) and the polycation chitosan (CH), was investigated using atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy, with primary emphasis on the effect of the polysaccharide molecular weights on the film thickness and surface morphology. The HA/CH multilayers exhibit an exponential increase of the optical film thickness with the number of deposited bilayers. We show that the multilayer thickness at a given stage depends on the size of both CH, the diffusing polyelectrolyte, and HA, the non-diffusing species. Assemblies (12 bilayers) of high molecular weight polysaccharides (HA, 360,000; CH, 160,000) were twice as thick (approximately 900 nm vs approximately 450 nm) as those obtained with low molecular weight polymers (HA, 30,000; CH, 31,000), as assessed by AFM scratch tests. The exponential growth rate is the same for the high and low molecular weight pairs; the larger film thicknesses observed by SPR and by AFM arising from an earlier onset of the steep exponential growth phase in the case of the high molecular weight pair. In all cases, isolated islets form during the deposition of the first CH layer onto the underlying HA. Upon further film growth, individual islets coalesce into larger vermiculate features. The transition from distinct islands to vermiculate structures depends on the molecular weights of the polysaccharides and the lower molecular weight construct presents larger worm-like surface domains than the high molecular weight pair. 相似文献
96.
José M. Bartoloméa Jesús AlcázarJ.Ignacio Andrés Marcel De BruynJavier Fernández Encarna MatesanzKristof Van Emelen 《Tetrahedron letters》2003,44(47):8545-8548
The synthesis of a series of novel analogues of the 3-substituted-2,3-dihydro-1,4-dioxino[2,3-b]pyridine core, modified in the non-aromatic ring, is described. Due to the presence of a versatile hydroxymethyl group in their structure, these novel scaffolds are attractive intermediates for the preparation of potential new therapeutic agents. 相似文献
97.
The solubilization of benzo[a]pyrene by organic solvents (dioxane, toluene and dichloromethane) and a surfactant (Triton X-100) was investigated. These media were successfully used for the determination of benzo[a]pyrene using fluorescence detection, with excellent limits of detection and large linear analytical ranges. Benzo[a]pyrene was detected in coal washing waters using liquid chromatography with fluorescence detection. The stability of this compound in dioxane was also examined. 相似文献
98.
Sanches-Silva A Rodríguez-Bernaldo de Quirós A López-Hernández J Paseiro-Losada P 《Journal of chromatography. A》2004,1032(1-2):7-15
A reversed-phase high performance liquid chromatographic (RP-HLPC) method was compared with a gas chromatography-flame ionization detection (GC-FID) method for determining fatty acids in potato crisps. Different extraction procedures were used. Fatty acids were quantified by linear regression. Both methods presented good precision (R.S.D. < or = 5.88%) and recovery (> or = 82.31%). The precision using HPLC method was slightly better than for GC-FID method. There was good agreement between the fatty acid composition of potato crisps analysed by both methods. For most purposes the HPLC method would be better. However, when more fatty acids need to be analysed, GC is a more suitable method. 相似文献
99.
The Hill determinant method is shown to be suitable for constructing potential energy curves of diatomic molecules. Both the Dunham and the perturbed Morse oscillator potentials are used to fit spectroscopic data. Results are shown for ionic and covalent molecules. 相似文献
100.
We present a theoretical study of dissociative photoionization of H2 via the 1Πu symmetry in the photon energy range 30–43 eV. Our results explain the various peaks observed in the experiments below 40 eV and illustrate, in particular, the important role of the 2Πu(2pπu) ionization threshold. At higher photon energies, they suggest the existence of new resonance structures that may be associated with doubly excited states of H2 lying above the third and fourth ionization thresholds (the Q3 and Q4 resonance series). From the calculated resonance parameters, we conclude that the dominant mechanism at high photon energies should involve the Q4 (and probably higher) doubly excited states of H2. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2002 相似文献