全文获取类型
收费全文 | 2836篇 |
免费 | 56篇 |
国内免费 | 16篇 |
专业分类
化学 | 1745篇 |
晶体学 | 22篇 |
力学 | 85篇 |
数学 | 287篇 |
物理学 | 769篇 |
出版年
2022年 | 22篇 |
2021年 | 37篇 |
2020年 | 49篇 |
2019年 | 40篇 |
2018年 | 23篇 |
2017年 | 21篇 |
2016年 | 37篇 |
2015年 | 27篇 |
2014年 | 33篇 |
2013年 | 124篇 |
2012年 | 108篇 |
2011年 | 145篇 |
2010年 | 81篇 |
2009年 | 42篇 |
2008年 | 121篇 |
2007年 | 115篇 |
2006年 | 146篇 |
2005年 | 116篇 |
2004年 | 110篇 |
2003年 | 102篇 |
2002年 | 85篇 |
2001年 | 72篇 |
2000年 | 67篇 |
1999年 | 40篇 |
1998年 | 39篇 |
1997年 | 45篇 |
1996年 | 47篇 |
1995年 | 48篇 |
1994年 | 50篇 |
1993年 | 64篇 |
1992年 | 39篇 |
1991年 | 38篇 |
1990年 | 38篇 |
1989年 | 45篇 |
1988年 | 28篇 |
1987年 | 37篇 |
1986年 | 24篇 |
1985年 | 44篇 |
1984年 | 32篇 |
1983年 | 49篇 |
1982年 | 39篇 |
1981年 | 34篇 |
1980年 | 36篇 |
1979年 | 26篇 |
1978年 | 34篇 |
1977年 | 42篇 |
1975年 | 37篇 |
1974年 | 26篇 |
1973年 | 19篇 |
1972年 | 25篇 |
排序方式: 共有2908条查询结果,搜索用时 0 毫秒
61.
The FAKE method of approximate molecular-orbital calculations is presented and illustrated by application to a number of molecules. The method is of the extended Huckel type but uses accurately computed kinetic-energy matrix elements and avoids scale factors of the Wolfsberg—Helmholtz type. It also includes neighbor-atom charge effects and single-center off-diagonal matrix elements. These features permit FAKE occupied-orbital energies and charge distributions to come into close agreement with corresponding ab initio quantities. 相似文献
62.
Alan P. Marchand Anna Hazlewood Zilin Huang Satish Kumar Vadlakonda John-David R. Rocha Trevor D. Power Kata Mlinarić-Majerski Lada Klaić Goran Kragol Jeffrey C. Bryan 《Structural chemistry》2003,14(3):279-288
Bis-cage-annulated 18-crown-6 and 20-crown-6 macrocyclic ethers (i.e., 1 and 2, respectively) have been synthesized, and their alkali metal picrate extraction profiles have been determined. Host system 1 proved to be a significantly more avid alkali metal cation complexant than 2 and somewhat more avid than 18-crown-6. Both 1 and 18-crown-6 display modest selectivity toward K+ and Rb+. A stable host–guest complex was prepared by slow evaporation of a CH2Cl2–hexane solution of an equimolar mixture of 2 and potassium picrate. The X-ray crystal structure of this complex reveals that picrate anion functions as a bidentate ligand therein. The gas-phase interaction energy between the 2 K+ complex and picrate anion was calculated to be ca. –64.9 kcal mol–1, thereby indicating that participation of picrate anion as an additional bidentate ligand results in significant stabilization of complex 10. 相似文献
63.
Tao Huang Seyyedmohsen Hosseinibarkooie Adam L. Borne Mitchell E. Granade Jeffrey W. Brulet Thurl E. Harris Heather A. Ferris Ku-Lung Hsu 《Chemical science》2021,12(9):3295
Sulfonyl-triazoles are a new class of electrophiles that mediate covalent reaction with tyrosine residues on proteins through sulfur-triazole exchange (SuTEx) chemistry. Recent studies demonstrate the broad utility and tunability of SuTEx chemistry for chemical proteomics and protein ligand discovery. Here, we present a strategy for mapping protein interaction networks of structurally complex binding elements using functionalized SuTEx probes. We show that the triazole leaving group (LG) can serve as a releasable linker for embedding hydrophobic fragments to direct molecular recognition while permitting efficient proteome-wide identification of binding sites in live cells. We synthesized a series of SuTEx probes functionalized with a lipid kinase fragment binder for discovery of ligandable tyrosines residing in catalytic and regulatory domains of protein and metabolic kinases in live cells. We performed competition studies with kinase inhibitors and substrates to demonstrate that probe binding is occurring in an activity-dependent manner. Our functional studies led to discovery of probe-modified sites within the C2 domain that were important for downregulation of protein kinase C-alpha in response to phorbol ester activation. Our proof of concept studies highlight the triazole LG of SuTEx probes as a traceless linker for locating protein binding sites targeted by complex recognition elements in live cells.Sulfonyl-triazole probes modified with a kinase recognition element are developed for live cell activity-based profiling to identify tyrosine sites located in catalytic and regulatory domains that are important for kinase function. 相似文献
64.
The Grignard reagents R3Si(CC)nMgBr (R = Me, n = 1; R = Et, n = 1,2) couple with cyclooctatetraene dibromide 1 in THF to give, as major products, the silyl-stabilised E, Z, Z, E-polyeneynes, Me3SiCC(CHCH)4CCSiMe33a, Et3SiCC(CHCH)4CCSiEt34a and Et3Si(CC)2(CHCH)4(CC)2SiEt36a together with minor proportions of configurational isomers Z, E, Z, Z 3c, all -E 3b, 4b, 6b and compounds in which a bicyclo-octadiene structure 2, 5 and 7 is retained. Irradiation converts the cis(Z)-rich isomers e.g. 3c into the all-trans(E) products. Treatment of the bissilyl compounds 3, 4 and 6 with aqueous base liberates the respective parent polyeneynes, H(CC)n(CHCH)4(CC)nH, in each case. 相似文献
65.
The complexing ability of a range of 19 symmetrical, unsymmetrical and bridged calix[4]arene derivatives having ester, ketone, amide, amine and thioether functionalities were determined by the picrate extraction method. On incorporating these calix[4]arene derivatives as neutral carrier ionophores in sodium-selective poly (vinyl chloride) membrane electrodes the performance was assessed on the basis of the sensitivity and selectivity over the alkali, alkaline earth metals and hydrogen and ammonium ions. The temperature dependence, response times and lifetimes were also determined. Four ionophores in particular gave excellent sensitivity and selectivity and lifetimes of > 200 days. These electrodes were then tested without additional lipophilic additives and one ionophore was incorporated into poly (vinyl chloride) membrane electrodes with plasticizing solvents of varying polarity. 相似文献
66.
Abdel-Magid AF Carson KG Harris BD Maryanoff CA Shah RD 《The Journal of organic chemistry》1996,61(11):3849-3862
Sodium triacetoxyborohydride is presented as a general reducing agent for the reductive amination of aldehydes and ketones. Procedures for using this mild and selective reagent have been developed for a wide variety of substrates. The scope of the reaction includes aliphatic acyclic and cyclic ketones, aliphatic and aromatic aldehydes, and primary and secondary amines including a variety of weakly basic and nonbasic amines. Limitations include reactions with aromatic and unsaturated ketones and some sterically hindered ketones and amines. 1,2-Dichloroethane (DCE) is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF) and occasionally in acetonitrile. Acetic acid may be used as catalyst with ketone reactions, but it is generally not needed with aldehydes. The procedure is carried out effectively in the presence of acid sensitive functional groups such as acetals and ketals; it can also be carried out in the presence of reducible functional groups such as C-C multiple bonds and cyano and nitro groups. Reactions are generally faster in DCE than in THF, and in both solvents, reactions are faster in the presence of AcOH. In comparison with other reductive amination procedures such as NaBH(3)CN/MeOH, borane-pyridine, and catalytic hydrogenation, NaBH(OAc)(3) gave consistently higher yields and fewer side products. In the reductive amination of some aldehydes with primary amines where dialkylation is a problem we adopted a stepwise procedure involving imine formation in MeOH followed by reduction with NaBH(4). 相似文献
67.
Hydrous amorphous Al (HAO), Fe (HFO), and Mn (HMO) oxides are ubiquitous in the subsurface as both discrete particles and coatings and exhibit a high affinity for heavy metal contaminants. To assess risks associated with heavy metals, such as Pb, to the surrounding environment and manage remedial activities requires accurate mechanistic models with well-defined transport parameters that represent sorption processes. Experiments were conducted to evaluate Pb sorption to microporous Al, Fe, and Mn oxides, as well as to montmorillonite and HAO-coated montmorillonite. Intraparticle diffusion, a natural attenuating process, was observed to be the rate-limiting mechanism in the sorption process, where best-fit surface diffusivities ranged from 10(-18) to 10(-15) cm(2) s(-1). Specifically, diffusivities of Pb sorption to discrete aluminum oxide, aluminum oxide-coated montmorillonite, and montmorillonite indicated substrate surface characteristics influence metal mobility where diffusivity increased as affinity decreased. Furthermore, the diffusivity for aluminum oxide-coated montmorillonite was consistent with the concentrations of the individual minerals present and their associated particle size distributions. These results suggest that diffusivities for other coated systems can be predicted, and that oxide coatings and montmorillonite are effective sinks for heavy metal ions. 相似文献
68.
Marcia I. Dawson Rebecca L.-S. Chan Ian S. Cloudsdale Wesley R. Harris 《Tetrahedron letters》1981,22(29):2739-2742
Tris(catecholcarboxamide) ligands were covalently linked to poly(vinyl amine—vinyl sulfonate sodium salt), and the iron binding capacity of the resultant polymers was found to exceed that of transferrin. 相似文献
69.
Whitten AE Dittrich B Spackman MA Turner P Brown TC 《Dalton transactions (Cambridge, England : 2003)》2004,(1):23-29
High-resolution X-ray diffraction data have been collected on the cubic polymorph of antimony(III) oxide (senarmontite) to determine the charge distribution in the crystal. The results are in quantitative agreement with crystal Hartree-Fock calculations for this polymorph, and have been compared with theoretical calculations on the orthorhombic polymorph (valentinite). Information about the nature of bonding and relative bond strengths in the two polymorphs has been extracted in a straightforward manner via topological analysis of the electron density. All the close contacts in both polymorphs are found to be similar in nature based on the value of the Laplacian, the magnitude of the electron density and the local energy density at the bond critical points, and these characterise the observed interactions as substantially polar covalent, similar to molecular calculation results on Si-O and Ge-O. Electrostatic potential isosurfaces reveal the octopolar nature of this function for senarmontite, and shed light on the observed packing arrangement of Sb4O6 molecules in the crystal. 相似文献
70.
Surface-enhanced resonance Raman scattering (SERRS) from the alpha-diimine complexes [Ru(bpm)(3)](2+) and [Ru(bpz)(3)](2+) is reported for the first time at a roughened silver electrode. In both cases, a possible adsorbate orientation has been proposed involving binding through nitrogen lone pair electrons to the silver surface, based on changes in band positions upon adsorption. The SERRS spectra of [Ru(bpm)(3)](2+) were found to change slightly with a change in applied potential. The relative intensity of the nu(C6C6') band was found to be dependent on both excitation wavelength and applied potential. This was ascribed to an active charge transfer (CT) mechanism operating synergistically with the electromagnetic mechanism. No such CT activity was observed in [Ru(bpz)(3)](2+). It is tentatively suggested that this behavior may arise from the different modes of adsorption of the two complexes. 相似文献