全文获取类型
收费全文 | 1744篇 |
免费 | 30篇 |
国内免费 | 4篇 |
专业分类
化学 | 920篇 |
晶体学 | 9篇 |
力学 | 45篇 |
数学 | 198篇 |
物理学 | 606篇 |
出版年
2021年 | 13篇 |
2020年 | 12篇 |
2019年 | 17篇 |
2017年 | 13篇 |
2016年 | 27篇 |
2015年 | 15篇 |
2014年 | 27篇 |
2013年 | 87篇 |
2012年 | 57篇 |
2011年 | 82篇 |
2010年 | 58篇 |
2009年 | 29篇 |
2008年 | 78篇 |
2007年 | 98篇 |
2006年 | 67篇 |
2005年 | 58篇 |
2004年 | 60篇 |
2003年 | 29篇 |
2002年 | 57篇 |
2001年 | 45篇 |
2000年 | 38篇 |
1999年 | 17篇 |
1998年 | 22篇 |
1997年 | 19篇 |
1996年 | 18篇 |
1995年 | 30篇 |
1994年 | 36篇 |
1993年 | 39篇 |
1992年 | 32篇 |
1991年 | 26篇 |
1990年 | 21篇 |
1989年 | 16篇 |
1988年 | 28篇 |
1987年 | 14篇 |
1986年 | 19篇 |
1985年 | 32篇 |
1984年 | 17篇 |
1983年 | 17篇 |
1982年 | 24篇 |
1981年 | 20篇 |
1980年 | 27篇 |
1979年 | 24篇 |
1978年 | 31篇 |
1977年 | 21篇 |
1976年 | 32篇 |
1975年 | 34篇 |
1974年 | 20篇 |
1973年 | 33篇 |
1972年 | 14篇 |
1971年 | 15篇 |
排序方式: 共有1778条查询结果,搜索用时 15 毫秒
61.
Catalytic hydrogenation of dihydroindolizidinone occurred preferentially from the endo-face giving rapid entry to (8R,8aS)-8-methylhexahydroindolizin-5-one, a key intermediate in the synthesis of 5,8-disubstituted indolizidines and deoxypumiliotoxin 251H. The selectivity could be improved further by diimide reduction though this also resulted in some oxidation of the alkene to the diene. The basis of the unusual stereoselectivity in the diimide reduction is believed to be stereoelectronic in origin. 相似文献
62.
The synthesis of tetracyclo[5.4.1.04,12.09.12]dodecan-6-one via an intramolelecular photocycloaddition, its reduction to the hydrocarbon and its ring-contraction to tetracyclo-[4.4.1.03,11.09,11]undecane derivative is described. 相似文献
63.
J. M. Bayona J. Grimalt J. Albaigs W. Walker B. W. de Lappe R. W. Risebrough 《Journal of separation science》1983,6(11):605-611
Analyses of hydrocarbon fractions from different areas of the marine environment are described to illustrate the possibilities and limitations of high resolution gas chromatography (HRGC) in the analysis of environmental samples. Examples are given of dissolved, particulate, and sedimentary hydrocarbons and organochlorine compounds; the importance of an adequate sampling of the marine environment is stressed. HR chromatographic profiles obtained in two columns of low and high polarity (SE-52 and PEG 20M) permit the sources and transport pathways of both natural and anthropogenic hydrocarbons to be traced. Analysis of tissues of marine mammals, which metabolize or excrete many of the biogenic and petrogenic hydrocarbons present in other areas of the marine environment, may provide an opportunity to obtain relatively clean profiles of many anthropogenic compounds of interest. The plotting of mass chromatograms from data compiled by COM-GC-MS remains the most appropriate method for the conclusive indentification of these compounds. 相似文献
64.
65.
F. Christopher Bi Gary E. Aspnes Angel Guzman-Perez Daniel P. Walker 《Tetrahedron letters》2008,49(11):1832-1835
In this Letter, we report a novel approach to the preparation of 3-anilino-pyrazin-2(1H)-ones and 3-anilino-quinoxalin-2(1H)-ones from the corresponding 3-halo pyrazin-2-amines and 3-haloquinoxalin-2-amines, using a microwave-mediated Smiles rearrangement. 相似文献
66.
S. Dimitrov R. Breton† D. MacDonald† J.D. Walker O. Mekenyan 《SAR and QSAR in environmental research》2013,24(3-4):445-455
An evaluation of the capability of organic chemicals to mineralize is an important factor to consider when assessing their fate in the environment. Microbial degradation can convert a toxic chemical into an innocuous one, and vice versa , or alter the toxicity of a chemical. Moreover, primary biodegradation can convert chemicals into stable products that can be difficult to mineralize. In this paper, we present some new results obtained on the basis of a recently developed probabilistic approach to modeling biodegradation based on microbial transformation pathways. The metabolic transformations and their hierarchy were calibrated by making use of the ready biodegradability data from the MITI-I test and expert knowledge for the most probable transformation pathways. A model was developed and integrated into an expert software system named CATABOL that is able to predict the probability of biodegradation of organic chemicals directly from their structure. CATABOL simulates the effects of microbial enzyme systems, generates the most plausible transformation pathways, and quantitatively predicts the persistence and toxicity of the biodegradation products. A subset of 300 organic chemicals were selected from Canada's Domestic Substances List and subjected to CATABOL to compare predicted properties of the parent chemicals with their respective first stable metabolite. The results show that most of the stable metabolites have a lower acute toxicity to fish and a lower bioaccumulation potential compared to the parent chemicals. In contrast, the metabolites appear to be generally more estrogenic than the parent chemicals. 相似文献
67.
Busch BB Paz MM Shea KJ Staiger CL Stoddard JM Walker JR Zhou XZ Zhu H 《Journal of the American Chemical Society》2002,124(14):3636-3646
Trialkyl and aryl organoboranes catalyze the polymerization of dimethylsulfoxonium methylide (1). The product of the polymerization is a tris-polymethylene organoborane. Oxidation affords linear telechelic alpha-hydroxy polymethylene. The polymer molecular weight was found to be directly proportional to the stoichiometric ratio of ylide/borane, and polydispersities as low as 1.01-1.03 have been realized. Although oligomeric polymethylene has been the most frequent synthetic target of this method, polymeric star organoboranes with molecular weights of 1.5 million have been produced. The average turnover frequency at 120 degrees C in 1,2,4,5-tetrachlorobenzene/toluene is estimated at >6 x 10(6) g of polymethylene (mol boron)(-1) h(-1). The mechanism of the polyhomologation reaction involves initial formation of a zwitterionic organoborane.ylide complex which breaks down in a rate-limiting 1,2-alkyl group migration with concomitant expulsion of a molecule of DMSO. The reaction was found to be first order in the borane catalyst and zero order in ylide. DMSO does not interfere with the reaction. The temperature dependence of the reaction rate yielded the following activation energy parameters (toluene, DeltaH(++) = 23.2 kcal/mol, DeltaS(++) = 12.6 cal deg/mol, DeltaG(++) = 19.5 kcal/mol; THF, DeltaH(++) = 26.5 kcal/mol, DeltaS(++) = 21.5 cal deg/mol, DeltaG(++) = 20.1 kcal/mol). 相似文献
68.
Rivera M Caignan GA Astashkin AV Raitsimring AM Shokhireva TKh Walker FA 《Journal of the American Chemical Society》2002,124(21):6077-6089
The (13)C pulsed ENDOR and NMR study of [meso-(13)C-TPPFe(OCH(3))(OO(t)Bu)](-) performed in this work shows that although the unpaired electron in low-spin ferrihemes containing a ROO(-) ligand resides in a d(pi) orbital at 8 K, the d(xy) electron configuration is favored at physiological temperatures. The variable temperature NMR spectra indicate a dynamic situation in which a heme with a d(pi) electron configuration and planar porphyrinate ring is in equilibrium with a d(xy) electron configuration that has a ruffled porphyrin ring. Because of the similarity in the EPR spectra of the hydroperoxide complexes of heme oxygenase, cytochrome P450, and the model heme complex reported herein, it is possible that these two electron configurations and ring conformations may also exist in equilibrium in the enzymatic systems. The ruffled porphyrinate ring would aid the attack of the terminal oxygen of the hydroperoxide intermediate of heme oxygenase (HO) on the meso-carbon, and the large spin density at the meso-carbons of a d(xy) electron configuration heme suggests the possibility of a radical mechanism for HO. The dynamic equilibrium between the ruffled (d(xy)) and planar (d(pi)) conformers observed in the model complexes also suggests that a flexible heme binding cavity may be an important structural motif for heme oxygenase activity. 相似文献
69.
Walker EK Vanden Bout DA Stevenson KJ 《Langmuir : the ACS journal of surfaces and colloids》2012,28(2):1604-1610
This study investigates pyrolyzed photoresist film (PPF)-based carbon optically transparent electrodes (C-OTEs) for use in electrogenerated chemiluminescence (ECL) studies. Oxidative-reductive ECL is obtained with a well-characterized ECL system, C8S3 J-aggregates with 2-(dibutylamino)ethanol (DBAE) as coreactant. Simultaneous cyclic voltammograms (CVs) and ECL transients are obtained for three thicknesses of PPFs and compared to nontransparent glassy carbon (GC) and the conventional transparent electrode indium tin oxide (ITO) in both front face and transmission electrode cell geometries. Despite positive potential shifts in oxidation and ECL peaks, attributed to the internal resistance of the PPFs that result from their nanoscale thickness, the PPFs display similar ECL activity to GC, including the low oxidation potential (LOP) observed for amine coreactants on hydrophobic electrodes. Reductive-oxidative ECL was obtained using the well-studied ECL luminophore Ru(bpy)(3)(2+), where the C-OTEs outperformed ITO because of electrochemical instability of ITO at very negative potentials. The C-OTEs are promising electrodes for ECL applications because they yield higher ECL than ITO in both oxidative-reductive and reductive-oxidative ECL modes, are more stable in alkaline solutions, display a wide potential window of stability, and have tunable transparency for more efficient detection of ECL. 相似文献
70.