全文获取类型
收费全文 | 6669篇 |
免费 | 347篇 |
国内免费 | 34篇 |
专业分类
化学 | 5196篇 |
晶体学 | 32篇 |
力学 | 136篇 |
数学 | 714篇 |
物理学 | 972篇 |
出版年
2023年 | 62篇 |
2022年 | 73篇 |
2021年 | 119篇 |
2020年 | 144篇 |
2019年 | 162篇 |
2018年 | 133篇 |
2017年 | 110篇 |
2016年 | 262篇 |
2015年 | 201篇 |
2014年 | 205篇 |
2013年 | 337篇 |
2012年 | 554篇 |
2011年 | 653篇 |
2010年 | 298篇 |
2009年 | 224篇 |
2008年 | 483篇 |
2007年 | 478篇 |
2006年 | 483篇 |
2005年 | 448篇 |
2004年 | 323篇 |
2003年 | 281篇 |
2002年 | 232篇 |
2001年 | 74篇 |
2000年 | 45篇 |
1999年 | 35篇 |
1998年 | 37篇 |
1997年 | 42篇 |
1996年 | 37篇 |
1995年 | 30篇 |
1994年 | 27篇 |
1993年 | 36篇 |
1992年 | 30篇 |
1991年 | 25篇 |
1990年 | 19篇 |
1989年 | 16篇 |
1988年 | 20篇 |
1987年 | 19篇 |
1986年 | 14篇 |
1985年 | 26篇 |
1984年 | 24篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 16篇 |
1979年 | 24篇 |
1978年 | 20篇 |
1977年 | 16篇 |
1976年 | 15篇 |
1975年 | 11篇 |
1974年 | 17篇 |
1973年 | 16篇 |
排序方式: 共有7050条查询结果,搜索用时 31 毫秒
71.
Mueller JA Cowell A Chandler BD Sigman MS 《Journal of the American Chemical Society》2005,127(42):14817-14824
A kinetic investigation into the origin of enantioselectivity for the Pd[(-)-sparteine]Cl(2)-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(-)-sparteine]Cl(2) prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(-)-sparteine]Cl(2) to form cationic Pd(-)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) beta-hydride elimination of Pd-alkoxide to form ketone product and a Pd-hydride. Utilizing the addition of (-)-sparteine HCl to control the [Cl(-)] and [H(+)] and the resulting derived rate law, the key microscopic kinetic and thermodynamic constants were extracted for each enantiomer of sec-phenethyl alcohol. These constants allow for the successful simulation of the oxidation rate in the presence of exogenous (-)-sparteine HCl. A rate law for oxidation of the racemic alcohol was derived that allows for the successful prediction of the experimentally measured k(rel) values when using the extracted constants. Besides a factor of 10 difference between the relative rates of beta-hydride elimination for the enantiomers, the main enhancement in enantiodetermination results from a concentration effect of (-)-sparteine HCl and the relative rates of reprotonation of the diastereomeric Pd-alkoxides. 相似文献
72.
[reaction: see text]. Addition of the configurationally stable organolithium species produced by enantioselective deprotonation of N-Boc-N-(p-methoxyphenyl) allylamines to alpha,beta-unsaturated carbonyl compounds affords 1,4-addition products in good yields with high diastereomeric and enantiomeric ratios. Further transformations of these compounds provide [3.3.0]-, [4.3.0]-, [5.3.0]-, and [5.4.0]-carbocycles and heterocycles with high stereoselectivities. 相似文献
73.
Simone Gallarati Raimon Fabregat Rubn Laplaza Sinjini Bhattacharjee Matthew D. Wodrich Clemence Corminboeuf 《Chemical science》2021,12(20):6879
Hundreds of catalytic methods are developed each year to meet the demand for high-purity chiral compounds. The computational design of enantioselective organocatalysts remains a significant challenge, as catalysts are typically discovered through experimental screening. Recent advances in combining quantum chemical computations and machine learning (ML) hold great potential to propel the next leap forward in asymmetric catalysis. Within the context of quantum chemical machine learning (QML, or atomistic ML), the ML representations used to encode the three-dimensional structure of molecules and evaluate their similarity cannot easily capture the subtle energy differences that govern enantioselectivity. Here, we present a general strategy for improving molecular representations within an atomistic machine learning model to predict the DFT-computed enantiomeric excess of asymmetric propargylation organocatalysts solely from the structure of catalytic cycle intermediates. Mean absolute errors as low as 0.25 kcal mol−1 were achieved in predictions of the activation energy with respect to DFT computations. By virtue of its design, this strategy is generalisable to other ML models, to experimental data and to any catalytic asymmetric reaction, enabling the rapid screening of structurally diverse organocatalysts from available structural information.A machine learning model for enantioselectivity prediction using reaction-based molecular representations. 相似文献
74.
Matthew Ball 《Tetrahedron letters》2004,45(47):8737-8740
A synthesis of the C(1)-C(16) fragment of the brysostatins has been developed. Key steps are the stereoselective copper(I) catalysed addition of allylmagnesium bromide to an alkynyl ester, a condensation of a βγ-unsaturated aldehyde with a ketophosphonate, and the formation of the B-ring under mild conditions by stereoselective intramolecular conjugate addition. 相似文献
75.
Chen W Wu H Bernard D Metcalf MD Deschamps JR Flippen-Anderson JL MacKerell AD Coop A 《The Journal of organic chemistry》2003,68(5):1929-1932
Treatment of 5-trimethylsilylthebaine with L-Selectride gave rise to a rearrangement to 10-trimethylsilylbractazonine through migration of the phenyl group, whereas treatment of thebaine with strong Lewis acids is known to lead to a similar rearrangement through migration of the alkyl bridge to give, after reduction, (+)-neodihydrothebaine. It is suggested that the rearrangement of the alkyl group of thebaine is favored due to the formation of a tertiary benzylic cation. However, for 5-trimethylsilylthebaine, the lithium ion of L-Selectride acts as the Lewis acid and the beta-silyl effect dominates in the stabilization of any positive charge. This rearrangement provides a clear example of the greater relative migratory aptitude of phenyl groups over alkyl groups, and provides an efficient synthesis of (+)-bractazonine from thebaine. 相似文献
76.
Wipf P Coleman CM Janjic JM Iyer PS Fodor MD Shafer YA Stephenson CR Kendall C Day BW 《Journal of combinatorial chemistry》2005,7(2):322-330
Cascade reactions of internal and terminal alkynes, zirconocene hydrochloride, dimethylzinc, and phosphinoyl imines (prepared in one step from aldehydes and diphenylphosphinoyl amide) lead to allylic phosphinoyl amides after aqueous workup. Microwave acceleration allows the completion of this one-pot reaction sequence in 10 min. These allylic amides can be converted into a variety of derivatives, including carbamates and sulfonamides, or reacted prior to workup with diiodomethane to give novel C-cyclopropylalkylamides. A solution-phase "libraries from libraries" approach was used to generate an intermediate 20-member library which was subsequently expanded to a 100-member library by a series of N-functionalizations. The biological activity was evaluated in an assay for competitive binding to the estrogen receptor (ERalpha), revealing three potent lead compounds of a new structural type. 相似文献
77.
Khlobystov AN Brett MT Blake AJ Champness NR Gill PM O'Neill DP Teat SJ Wilson C Schröder M 《Journal of the American Chemical Society》2003,125(22):6753-6761
A series of structurally related binuclear metallacycles [Cd(NO(3))(2)L](2), where L is an angular exo-bidentate ligand, have been synthesized. Each metallacycle contains two coordinatively unsaturated, chiral metal centers within a single molecule, and the assembly of these metallacycles into polymeric framework structures has been studied systematically for the first time. Stereoselective homochiral association of [Cd(NO(3))(2)L](2) leads to the formation of helical coordination polymers, whereas meso type association results in nonhelical chain structures. The type of stereoselective aggregation depends on the conditions of self-assembly as well as on ligand functionality. Both helical and nonhelical polymeric complexes have been isolated for the metallacycle [Cd(NO(3))(2)(2,4'-pyacph)](2) (2,4'-pyacph = 2,4'-(4-ethynylphenyl)bipyridyl). Homochiral association results in the formation of helical [Cd(NO(3))]( infinity ) chains which link the binuclear [Cd(NO(3))(2)(2,4'-pyacph)](2) metallacycles into racemic two-dimensional sheets which contain both P and M [Cd(NO(3))]( infinity ) helices. In contrast, meso-association leads to the formation of nonhelical one-dimensional chains. It is shown that the product of homochiral association is predominately formed at room temperature and that of meso-association is generated at elevated temperatures. Thus, it may be concluded that the homochiral association appears to be energetically less favorable than the meso-association, a conclusion that has been confirmed by theoretical calculations of the crystal lattice energy. Several high-yield syntheses of bipyridyl-type ligands used for metallacyclic assembly are also reported. 相似文献
78.
Square-planar copper(II) and nickel(II) derivatives of the cis-dithiolate N(2)S(2) ligand bis(N,N'-2-mercapto-2-methylpropyl)-1,5-diazocyclooctane, (bme*daco)M, nucleate four Cu(I)Cl moieties, forming M(II)(2)Cu(I)(4)S(4) clusters with unusual triply bridging thiolates, mu(3)-SR, in the topological form of adamantane. As determined by X-ray crystallography, the (bme*daco)M (M = Cu or Ni) metallothiolate serves as a bidentate ligand that bridges four Cu(I) ions, utilizing all lone pairs on sulfurs. Further characterization by electrochemical and electronic spectral measurements suggests greater electron delocalization in the all-copper complex as compared to the NiCu heterometallic complex. Mass spectral data imply that the mixed-metal Ni(II)(2)Cu(I)(4)S(4) is more stable toward CuCl loss than Cu(II)(2)Cu(I)(4)S(4), a result that is corroborated by extraction of Cu(I) by 1,2-bis(diphenylphosphino)ethane in the latter but not the former. 相似文献
79.
Tingmin Wang Jerald S. Bradshaw Janet C. Curtis Peter Huszthy Reed M. Izatt 《Journal of inclusion phenomena and macrocyclic chemistry》1993,16(2):113-122
Significant - interaction is found in the complexes of (S, S)-dimethylpyridino-18-crown-6 with (R)- and (S)-[-(1-naphthyl)ethyl]ammonium perchlorate. This finding is supported by the1H NOESY NMR spectral technique, greater chemical shift changes of aromatic protons in both host and guest molecules upon complexation, and by molecular mechanics calculations. Because of the flexibility of the ligand, the tripod hydrogen bonding causes13C relaxation times of all periphery carbons to decrease without significant selectivity. Rotational energy barrier calculations of the methyl groups of the complexed ligand also show that the (S, S)-host-(R)-guest is the more stable complex. 相似文献
80.
Proshlyakov DA Henshaw TF Monterosso GR Ryle MJ Hausinger RP 《Journal of the American Chemical Society》2004,126(4):1022-1023
The reaction of substrate-bound taurine/alpha-ketoglutarate dioxygenase with O2 has been studied using cryogenic continuous-flow spectroscopy. Transient absorption spectra acquired at -38 degrees C show an exponential decay of a 318-nm chromophore with an apparent rate of 1.3 s-1. The observed optical changes and their kinetics are consistent with the profile of an Fe(IV) species detected recently by M?ssbauer spectroscopy (Price et al., Biochemistry 2003, 42, 7497-7508). Resonance Raman measurement upon excitation at 363.7 nm reveal at least two oxygen isotope-sensitive vibrations at 821/787 cm-1 and 583/555 cm-1 for 16O and 18O derivatives, respectively. An additional mode is likely to be obscured by an ethylene glycol vibration at 865 cm-1 and/or 1089 cm-1. The 821 cm-1 vibration is assigned to the stretching mode of Fe(IV)=O species on the basis of its frequency and isotopic shift amplitude. The 583 cm-1 band is likely to originate from an Fe-O2 precursor of the Fe(IV)=O species, although its structural details are unclear at present. 相似文献