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31.
Bian Y Li L Dou J Cheng DY Li R Ma C Ng DK Kobayashi N Jiang J 《Inorganic chemistry》2004,43(23):7539-7544
Three (1,8,15,22-tetrasubstituted phthalocyaninato)lead complexes Pb[Pc(alpha-OR)(4)] [H(2)Pc(alpha-OC(5)H(11))(4) = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine; H(2)Pc(alpha-OC(7)H(15))(4) = 1,8,15,22-tetrakis(2,4-dimethyl-3-pentyloxy)phthalocyanine; H(2)Pc(alpha-OC(10)H(7))(4) = 1,8,15,22-tetrakis(2-naphthyloxy)phthalocyanine] (1-3) have been prepared as racemic mixtures by treating the corresponding metal-free phthalocyanines H(2)Pc(alpha-OR)(4) (4-6) with Pb(OAc)(2).3H(2)O in refluxing n-pentanol. The molecular structure of Pb[Pc(alpha-OC(5)H(11))(4)] (1) in the solid state has been determined by single-crystal X-ray diffraction analysis. This compound, having a nonplanar structure, crystallizes in the monoclinic system with a P2(1)/c space group. Each unit cell contains two pairs of enantiomeric molecules, which are linked by weak coordination of the Pb atom of one molecule with an aza nitrogen atom and its neighboring oxygen atom from the alkoxy substituent of another molecule, forming a pseudo-double-decker supramolecular structure in the crystals with a short ring-to-ring separation, 2.726 A, and thus a strong ring-ring pi-pi interaction. The decreased molecular symmetry for these complexes has also been revealed by the NMR spectra of 1 and 2. The methyl protons of the 3-pentyloxy and 2,4-dimethyl-3-pentyloxy side chains of 1 and 2, respectively, are chemically inequivalent. In addition to the elemental analysis and various spectroscopic characterizations, these compounds have also been electrochemically studied. Two one-electron oxidations and up to five one-electron reductions have been revealed by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods. 相似文献
32.
Muranaka A Matsumoto Y Uchiyama M Jiang J Bian Y Ceulemans A Kobayashi N 《Inorganic chemistry》2005,44(11):3818-3826
A series of heteroleptic rare-earth sandwich complexes [M(Nc)(OEP)] (M = La, Nd, Eu, Dy, and Lu; Nc = 2,3-naphthalocyaninate; OEP = octaethylporphyrinate) have been investigated by electronic absorption and magnetic circular dichroism (MCD) spectroscopy. The electronic absorption spectra of the neutral forms showed two characteristic transitions (bands I and II) in the near-IR region, both of which were systematically shifted depending on the size of their central metal. In the MCD spectra, a relatively intense Faraday A term and a significantly weak Faraday B term have been observed corresponding to bands II and I, respectively. The spectral features were successfully interpreted using a simple MO model by considering the relevant interactions of Gouterman's four orbitals of the constituent chromophores. The model succeeded in assigning the MCD spectra of the related compounds, the oxidized and reduced forms of the dimer ([M(Nc)(OEP)]+ and [M(Nc)(OEP)]-), and neutral forms of the triple-decker compounds (M2(Nc)(OEP)2, M = Nd, Eu). DFT calculations of the dimers supported the validity of this model. 相似文献
33.
Xiaoqing Zeng Maofa Ge Zheng Sun Jiang Bian Dianxun Wang 《Journal of Molecular Structure》2007,840(1-3):59-65
Gaseous nitryl azide N4O2 is generated by the heterogeneous reaction of gaseous ClNO2 with freshly prepared AgN3 at −50 °C. The geometric and electronic structure of the molecule in the gas phase has been characterized by in situ photoelectron spectroscopy (PES) and quantum chemical calculations. The experimental first vertical ionization energy of N4O2 is 11.39 eV, corresponding to the ionization of an electron on the highest occupied molecular orbital (HOMO) {4a″(πnb(N4–N5–N6))}−1. An apparent vibrational spacing of 1600 ± 60 cm−1 (νasO1N2O3) on the second band at 12.52 eV (πnb(O1–N2–O3)) further confirms the preference of energetically stable chain structure in the gas phase. To complement the experimental results, the potential-energy surface of this structurally novel transient molecule is discussed. Both calculations and spectroscopic results suggest that the molecule adopts a trans-planar chain structure, and a five-membered ring decomposition pathway is more favorable. 相似文献
34.
Influences of permeation of vanadium ions through PVDF-g-PSSA membranes on performances of vanadium redox flow batteries 总被引:6,自引:0,他引:6
Luo X Lu Z Xi J Wu Z Zhu W Chen L Qiu X 《The journal of physical chemistry. B》2005,109(43):20310-20314
The preparation and physical characterization of a poly(vinylidene fluoride)-graft-poly(styrene sulfonic acid) (PVDF-g-PSSA) membrane prepared by a solution-grafting method were described. These membranes exhibited high conductivity with a value 3.22 x 10(-2) S/cm at 30 degrees C. ICP studies revealed that the PVDF-g-PSSA membrane showed dramatically lower vanadium ion permeability compared to Nafion 117. Trivalent vanadium ions had the highest permeability through all these membranes in contrast to pentavalent vanadium ions with the lowest. The VRB with the low-cost PVDF-g-PSSA membrane exhibited a higher performance than that with Nafion 117 under the same operating conditions, and its energy efficiency reached 75.8% at 30 mA/cm(2). The performance of VRB with the PVDF-g-PSSA membrane can be maintained after more than 200 cycles at a current density of 60 mA/cm(2). 相似文献
35.
Zhida Chen Yuqing Deng Jiang Bian Lemin Li Guangxian Xu 《Journal of Molecular Structure》1998,434(1-3)
A nonlocal density functional theory (DFT) method has been applied to the calculations on optimized geometry, Mulliken atomic net charges and interatomic Mulliken bond orders as well as total bonding energies (E) in the binary transition metal carbonyl anions with different reduced states [M(CO)n]z− (M=Cr, n=5, 4, 3, z=2, 4, 6; M=Mn, n=5, 4, 3, z=1, 3, 5; M=Fe, n=4, 3, 2, z=2, 4, 6; M=Co, n=4, 3, 2, z=1, 3, 5). For comparison of relative stability, a relative stabilization energy D is defined as D=E([M(CO)n]z−)−nE(CO). The calculated C–O distances are lengthened monotonously with the increase of the anionic charge, but the M–C distances are significantly lengthened only in the higher reduced states. The relative stabilization energy calculated is a considerable negative value in the lower reduced states, but a larger positive value in the higher reduced states. The DFT calculations show that with the increase of the anionic charge, the Mulliken net charges on the M, C, and O atoms all increase, however, an excess of the anionic charge is mainly located at the central metal atom. The calculated C–O Mulliken bond orders decrease consistently with the increase of the anionic charge, but the M–C bond orders exhibit an irregular behavior. However, the total bond orders calculated clearly explain the higher reduced states to be considerably unstable. From analysis of the calculated results, it is deduced that the stability of the binary transition metal carbonyl anions [M(CO)n]z− studied are associated with the coordination number n and the anionic charge z, further, it is possible for the anions studied to be stable if n≥z, conversely, it is impossible when n<z. 相似文献
36.
溴酸钾氧化亮绿SF催化光度法测定痕量亚硝酸根 总被引:27,自引:3,他引:27
本文基于亚硝酸根对溴酸钾氧化亮绿SF而使其褪色所起的催化作用,建立了高灵敏度催化吸光光度法测定痕量亚硝酸根的新方法,测定范围为0.05-20ng/ml,用于不同水样中亚硝酸根的测定,获得了满意结果。 相似文献
37.
聚N,N-二乙基丙烯酰胺溶液粘度的温度依赖性 总被引:2,自引:0,他引:2
通过自由基聚合,合成了线型聚N,N-二乙基丙烯酰胺(PDEA),用乌氏粘度计测定并考察了该聚合物在四氢呋喃(THF)、H2O以及THF-H2O混合溶剂中粘度的温度依赖性.实验结果表明,PDEA 在上述三种溶剂中粘度的温度依赖性不同,PDEA-THF体系的相对粘度随温度升高而增大;PDEA-H2O体系以及PDEA-THF-H2O体系的相对粘度随温度升高而减小,且THF体积分数φTHF < 0.7时具有透明-白浊转变现象;对PDEA-THF-H2O体系,φTHF增加,透明-白浊转变温度升高,而当φTHF=0.7时,则观察不到透明-白浊转变现象. 相似文献
38.
Bian Y Wang R Jiang J Lee CH Wang J Ng DK 《Chemical communications (Cambridge, England)》2003,(10):1194-1195
Treatment of MIII(Pc)(acac) (M = Sm, Eu, Gd; Pc = phthalocyaninate; acac = acetylacetonate), generated in situ, with 3-(3-pentyloxy)phthalonitrile in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol affords racemic mixtures of the chiral double-deckers MIII(Pc)[Pc(OC5H11)4] [Pc(OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate], which have been spectroscopically and structurally characterised. 相似文献
39.
Thermodynamics and dynamics of metallic glass formers: their correlation for the investigation on potential energy landscape 总被引:3,自引:0,他引:3
Great progress has been made in basic features of the potential energy landscape (PEL) theoretically. The present work, however, attempts to cast new light on it from experimental aspects. By a survey of experimental data related to thermodynamics or dynamics of metallic glass-forming liquids, it is found that the increased rate of excitation of vibrational entropy at glass transition tends to increase the rate of generation of configurational part. Although for the type of metallic materials a generally positive relationship exists between the density of the energy minima at glass transition and the liquid fragility strength, just as expected, our main attention is paid to the phenomenon of the scattering of the slopes. Analysis shows that the phenomenon results from the different average height of energy barriers between minima near glass transition. Investigation on the PdNiP metallic system indicates that the mismatch entropy is a dominant factor in the barrier height: a large value of it results in low energy barriers. Our previous work on the AlNiCe system gives the support to this finding. 相似文献
40.
加入适当的碳纤维和铝粉对双马来酰亚胺(BMI)树脂进行复合增韧,可以有效改善其力学性能,通常只能通过多次试验结果的优劣比较来评价BMI树脂的力学性能,而不能判断其力学性能是否达最优值。为此,基于数据包络分析理论,给出BMI树脂力学性能的评价模型和计算方法,利用试验数据可以有效测算其最优值,控制碳纤维和铝粉的加入量,使BMI树脂的力学性能达到最优。 相似文献