全文获取类型
收费全文 | 703篇 |
免费 | 31篇 |
国内免费 | 3篇 |
专业分类
化学 | 514篇 |
晶体学 | 4篇 |
力学 | 3篇 |
数学 | 127篇 |
物理学 | 89篇 |
出版年
2023年 | 9篇 |
2022年 | 3篇 |
2021年 | 7篇 |
2020年 | 15篇 |
2019年 | 16篇 |
2018年 | 10篇 |
2017年 | 15篇 |
2016年 | 17篇 |
2015年 | 24篇 |
2014年 | 32篇 |
2013年 | 27篇 |
2012年 | 44篇 |
2011年 | 58篇 |
2010年 | 26篇 |
2009年 | 28篇 |
2008年 | 48篇 |
2007年 | 48篇 |
2006年 | 46篇 |
2005年 | 26篇 |
2004年 | 45篇 |
2003年 | 36篇 |
2002年 | 31篇 |
2001年 | 14篇 |
2000年 | 15篇 |
1999年 | 5篇 |
1998年 | 9篇 |
1996年 | 6篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1990年 | 8篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 4篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1938年 | 1篇 |
排序方式: 共有737条查询结果,搜索用时 15 毫秒
91.
Okram B Nagle A Adrián FJ Lee C Ren P Wang X Sim T Xie Y Wang X Xia G Spraggon G Warmuth M Liu Y Gray NS 《Chemistry & biology》2006,13(7):779-786
Kinase inhibitors that bind to the ATP cleft can be broadly classified into two groups: those that bind exclusively to the ATP site with the kinase assuming a conformation otherwise conducive to phosphotransfer (type I), and those that exploit a hydrophobic site immediately adjacent to the ATP pocket made accessible by a conformational rearrangement of the activation loop (type II). To date, all type II inhibitors were discovered by using structure-activity-guided optimization strategies. Here, we describe a general pharmacophore model of type II inhibition that enables a rational "hybrid-design" approach whereby a 3-trifluoromethylbenzamide functionality is appended to four distinct type I scaffolds in order to convert them into their corresponding type II counterparts. We demonstrate that the designed compounds function as type II inhibitors by using biochemical and cellular kinase assays and by cocrystallography with Abl. 相似文献
92.
The compounds Re(CO)3Br[CH2(S-tim)2] (1) and {Re(CO)3(CH3CN)[CH2(S-tim)2]}(PF6) (2), where tim is 1-methylthioimidazolyl, were prepared in high yields and characterized both in the solid state and in solution. The solid-state structures show that the ligand acts in a chelating binding mode where the eight-member chelate ring adopts twist-boat conformations in both compounds. A comparison of both solid-state IR data for CO stretching frequencies and the solution-phase voltammetric measurements for the Re(1+/2+) couples between 1, 2, and related N,N-chelates of the rhenium tricarbonyl moiety indicate that the CH2(S-tim)2 ligand is a stronger donor than even the ubiquitous dipyridyl ligands. A combination of NMR spectroscopic studies and voltammetric studies revealed that compound 1 undergoes spontaneous ionization to form {Re(CO)3(CH3CN)[CH2(S-tim)2]+}(Br-) in acetonitrile. Ionization does not occur in solvents such as CH2Cl2 or acetone that are less polar and Lewis basic (less coordinating). The equilibrium constant at 293 K for the ionization of 1 in CH3CN is 4.3 x 10(-3). The eight-member chelate rings in each 1 and 2 were found to be conformationally flexible in all solvents, and boat-chair conformers could be identified. Variable-temperature NMR spectroscopic studies were used to elucidate the various kinetic and thermodynamic parameters associated with the energetically accessible twist-boat to twist-boat and twist-boat to boat-chair interconversions. 相似文献
93.
Bernhardt PV Bozoglián F González G Martínez M Macpherson BP Sienra B 《Inorganic chemistry》2006,45(1):74-82
The preparation and characterization of a series of trinuclear mixed-valence cyano-bridged Co(III)-Fe(II)-Co(III) compounds derived from known dinuclear [[L(n)Co(III)(mu-NC)]Fe(II)(CN)(5)](-) complexes (L(n)() = N(5) or N(3)S(2) n-membered pendant amine macrocycle) are presented. All of the new trinuclear complexes were fully characterized spectroscopically (UV-vis, IR, and (13)C NMR). Complexes exhibiting a trans and cis arrangement of the Co-Fe-Co units around the [Fe(CN)(6)](4-) center are described (i.e., cis/trans-[{L(n)Co(III)(mu-NC)](2)Fe(II)(CN)(4)](2+)), and some of their structures are determined by X-ray crystallography. Electrochemical experiments revealed an expected anodic shift of the Fe(III/II) redox potential upon addition of a tripositively charged [Co(III)L(n)] moiety. The Co(III/II) redox potentials do not change greatly from the di- to the trinuclear complex, but rather behave in a fully independent and noncooperative way. In this respect, the energies and extinction coefficients of the MMCT bands agree with the formal existence of two mixed-valence Fe(II)-CN-Co(III) units per molecule. Solvatochromic experiments also indicated that the MMCT band of these compounds behaves as expected for a class II mixed-valence complex. Nevertheless, its extinction coefficient is dramatically increased upon increasing the solvent donor number. 相似文献
94.
Assembly of a supramolecular cube, [(Cp*WS3Cu3)8 Cl8(CN)12Li4] from a preformed incomplete cubane-like compound [PPh4][Cp*WS3(CuCN)3 总被引:2,自引:0,他引:2
Lang JP Xu QF Chen ZN Abrahams BF 《Journal of the American Chemical Society》2003,125(42):12682-12683
A supramolecular cube has been formed by linking WS3Cu3 clusters with bidentate ligands. Eight WS3Cu3 clusters, which have an incomplete cubane-like structure, serve as the three connecting nodes of the cube, while 12 bridging cyanide anions coordinated to copper centers lie along the edges of the cube. Eight chloride anions and four lithium cations are located inside the cube. 相似文献
95.
An ultra-performance liquid chromatographic (UPLC) electrospray ionisation tandem quadrupole mass spectrometric method has been developed for the determination of 52 pesticides in cereal-based baby foods, oranges and potatoes. The fast polarity switching capability of the mass spectrometer used enabled the determination of 44 of the compounds in the positive ionisation mode and 8 of the compounds in the negative ionisation mode in a single run. Prior to analysis, co-extractives were removed from acetonitrile extracts using dispersive solid-phase extraction with primary secondary amine (50 mg). The UPLC method separates all of the pesticides, resolves structural isomers (e.g. butocarboxim sulfoxide and aldicarb sulfoxide) and has a short (7 min) cycle time. Extracts spiked with pesticides at 0.10 and 0.01 mg kg(-1) yielded average recoveries in the range of 66-124% with relative standard deviations less than 19% for the majority of the analytes. 相似文献
96.
Kerwyn G. Alley Roland Bircher Hans U. Güdel Boujemaa Moubaraki Keith S. Murray Brendan F. Abrahams Colette Boskovic 《Polyhedron》2007
The reaction of Ni(OAc)2, NiX2 (X = Cl, Br) or CoCl2 with the proligand 2-amino-2-methyl-1,3-propanediol (ampdH2) affords a new family of tetranuclear complexes. The syntheses of [Ni4(OAc)4(ampdH)4] (1) and [M4X4(ampdH)4] (M = Ni, X = Cl, 2; M = Ni, X = Br, 3; M = Co, X = Cl, 4) are reported, together with the single crystal X-ray structures of 1, 2 and 4 and the magnetochemical characterization of 1, 3 and 4. Each member of this family of complexes displays a low symmetry structure that incorporates a {M4O4} core unit based on a distorted cubane. Magnetic measurements reveal ferromagnetic exchange interactions for 1, 3 and 4. These give rise to S = 4 ground state spins for the tetranuclear Ni complexes and an anisotropic effective S′ = 2 ground state for the Co complex. 相似文献
97.
Gao H Ye C Gupta OD Xiao JC Hiskey MA Twamley B Shreeve JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(14):3853-3860
2,4,5-Trinitroimidazolate (TNI) salts with "high-nitrogen" cations tend to be highly hydrogen bonded and have heats of formation ranging up to 616 kJ mol(-1). Density, oxygen balance, and thermostability are enhanced by the presence of TNI. Based on theoretical calculations, all of the new salts are potential propellants. 相似文献
98.
Vibrational corrections to the Verdet constants of nine molecules (H2, N2, CO, H2O, CH4, benzene, toluene, p-xylene, and o-xylene) were calculated with pure density functional theory (DFT), hybrid DFT, and an approximate coupled-cluster theory. Comparisons are made for the accuracy of the vibrational averages among different methods and with respect to experimental data where available. It is found that vibrational corrections to magneto-optical rotation can be as large as 10% of the equilibrium value. Hybrid DFT with the B3LYP hybrid functional offers reasonable accuracy at a relatively inexpensive computational cost for accurate calculations of vibrationally averaged Verdet constants. 相似文献
99.
Reactions of two preformed trinuclear W/Cu/S clusters, [A](2)[WS(4)(CuCN)(2)] (1: A = Et(4)N; 2: A = PPh(4)), with different concentrations of acetic acid in MeCN generate two interesting 2D polymeric clusters [Et(4)N](3)[(WS(4)Cu(2))(2)(mu-CN)(3)].2MeCN (3), and [PPh(4)][WS(4)Cu(3)(mu-CN)(2)].MeCN (4), respectively. Compound 4 can also be readily obtained in a high yield from the reaction of 2 with equimolar [Cu(MeCN)(4)]PF(6) in MeCN. These compounds have been characterized by elemental analysis, IR spectra, thermal analysis, and single-crystal X-ray diffraction. An X-ray analysis reveals that compound 3 retains the WS(4)Cu(2) cluster core, which serves as a 3-connecting node to link equivalent nodes via single cyanide bridges, forming an anionic 2D (6,3) net. Compound 4 consists of a T-shaped WS(4)Cu(3) core, which also acts as a 3-connecting node, with links to 3 equivalent clusters either through single or double cyanide bridges, affording a different anionic 2D (6,3) network. The acetic acid induced aggregation of 3 and 4 from the two cluster precursors 1 and 2 suggests that this simple synthetic strategy is likely to be applicable to many related systems. 相似文献
100.
Brendan J. Kennedy Paul J. Saines Qingdi Zhou 《Journal of solid state chemistry》2009,182(10):2858-2866
The crystal structures of the perovskite manganites SrxCa1−x−yNdyMnO3 with y=0.1 or 0.2 have been investigated using synchrotron X-ray powder diffraction. At room temperature the structures change from depending on the cation distribution, the different structures exhibiting different tilts of the MnO6 octahedra. High temperature diffraction measurements demonstrate the presence of, an apparently continuous, isosymmetric I4/mcm to I4/mcm phase transition associated with the removal of long range orbital ordering. Heating the manganites to still higher temperatures results in a continuous transition to the cubic structure. A feature of such transitions is the continuous evolution of the octahedral tilt angle through the I4/mcm to I4/mcm phase transition. The orthorhombic structures do not exhibit orbital ordering and although a first order transition to the tetragonal structure is observed in Sr0.4Ca0.5Nd0.1MnO3, this high temperature tetragonal structure does not exhibit orbital ordering. 相似文献