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排序方式: 共有4654条查询结果,搜索用时 15 毫秒
891.
《Journal of Coordination Chemistry》2012,65(1):78-86
The reaction of Brønsted acids with cis-[Ru(bpy)2(CO3)] (bpy?=?2,2′-bipyridine) under CO results in cleavage of the carbonato ligand and formation of cationic cis-[Ru(bpy)2(CO)L] n + complexes [L?=?ONO2 (1 +), OH2 (2 2+), Cl (3 +), OCOH (4 +), and OCOCH3 (5 +)]. The structures of 1 + and 2 2+ were confirmed by single-crystal X-ray diffraction. Crystal data for 1(PF6): monoclinic, P21/c, a?=?10.5242(3), b?=?15.4727(3), c?=?14.6571(3) Å, β?=?92.3219(9)°, V?=?2384.77(9) Å3, Z?=?4, D calcd?=?1.806?g cm?3, 5460 unique reflections (R int?=?0.032), R 1?=?0.0540 [I?>?2σ(I)], wR 2?=?0.1642 (all reflections); crystal data for 2(ClO4)2?·?H2O: monoclinic, C2/c, a?=?20.4247(7), b?=?10.0777(3), c?=?15.6039(5) Å, β?=?127.7569(8)°, V?=?2539.31(14) Å3, Z?=?4, D calcd?=?1.769?g cm?3, 2895 unique reflections (R int?=?0.036), R 1?=?0.0343 [I?>?2σ(I)], wR 2?=?0.0907 (all reflections). Except for 2(PF6)2 the complexes exhibit oxidation at 1.02–1.30?V versus Fc+/Fc in acetonitrile. Bipyridine-centered reductions are also observed; these redox potentials depend on the nature of L. This convenient synthesis will be useful for producing cis-[Ru(bpy)2(CO)L] n +-type complexes in high yield. 相似文献
892.
Hongmei Chai Hongyun Liu Xihong Guo Dong Zheng Yasemin Kutes Bryan D. Huey James F. Rusling Naifei Hu 《Electroanalysis》2012,24(5):1129-1140
Glutathione‐decorated 5 nm gold nanoparticles (AuNPs) and oppositely charged poly(allylamine hydrochloride) (PAH) were assembled into {PAH/AuNP}n films fabricated layer‐by‐layer (LbL) on pyrolytic graphite (PG) electrodes. These AuNP/polyion films utilized the AuNPs as electron hopping relays to achieve direct electron transfer between underlying electrodes and redox proteins on the outer film surface across unprecedented distances >100 nm for the first time. As film thickness increased, voltammetric peak currents for surface myoglobin (Mb) on these films decreased but the electron transfer rate was relatively constant, consistent with a AuNP‐mediated electron hopping mechanism. 相似文献
893.
Weiss VU Subirats X Pickl-Herk A Bilek G Winkler W Kumar M Allmaier G Blaas D Kenndler E 《Electrophoresis》2012,33(12):1833-1841
During infection, enteroviruses, such as human rhinoviruses (HRVs), convert from the native, infective form with a sedimentation coefficient of 150S to empty subviral particles sedimenting at 80S (B particles). B particles lack viral capsid protein 4 (VP4) and the single-stranded RNA genome. On the way to this end stage, a metastable intermediate particle is observed in the cell early after infection. This subviral A particle still contains the RNA but lacks VP4 and sediments at 135S. Native (150S) HRV serotype 2 (HRV2) as well as its empty (80S) capsid have been well characterized by capillary electrophoresis. In the present paper, we demonstrate separation of at least two forms of subviral A particles on the midway between native virions and empty 80S capsids by CE. For one of these intermediates, we established a reproducible way for its preparation and characterized this particle in terms of its electrophoretic mobility and its appearance in transmission electron microscopy (TEM). Furthermore, the conversion of this intermediate to 80S particles was investigated. Gas-phase electrophoretic mobility molecular analysis (GEMMA) yielded additional insights into sample composition. More data on particle characterization including its protein composition and RNA content (for unambiguous identification of the detected intermediate as subviral A particle) will be presented in the second part of the publication. 相似文献
894.
《Analytical letters》2012,45(8):1339-1357
Abstract An amperometric enzyme electrode for the determination of glucose (<16mmol?1) is constructed by incorporating electron mediators tetrathiafulvalene in Nafion and subsequently coating with immobilized glucose oxidase. The results obtained from measurements of glucose in fermentation samples containing biomass or molasses indicate the utility of the electrode for glucose assay in such media over at least 12 weeks. Digital simulation is employed to study the cyclic voltammetry (CV) of Tetrathiafulvalene-Glucose Oxidase-Modified Glassy Carbon Electrode (TTF-GOD-GCE); the digital model is built and the effects of kinetic parameters on CV-curves are discussed. The response process of the Tetrathiafulvalene-Glucose Oxidase-Modified Electrode is partly explained by the simulation results and further research is expected to guide the design of biosensors and improve the properties of the enzyme-mediator modified electrode. 相似文献
895.
Xu Shan Chun-kai Xu Xiao-feng Yin Li-xia Zhou Ke-zun Xu Xiang-jun Chen 《化学物理学报(中文版)》2009,22(6):642-648
Electron momentum distributions for 4a1 orbitals of serial freon molecules CFaC1, CF2Cl2, and CFCl3 (CFxC14-x, x=1-3) have been reanalyzed due to the severe discrepancies between theory and experiment in low momentum region. The tentative calculations using equilibrium geometries of molecular ions have exhibited a great improvement in agreement with the experimental data, which suggests that the molecular geometry distortion may be responsible for the observed high intensities at p〈0.5 a.u.. Further analyses show that the severe discrepancies at low momentum region mainly arise from the influence of molecular geometry distortion on C-Cl bonding electron density distributions. 相似文献
896.
Electron paramagnetic resonance and electron-nuclear double resonance methods were used to study the polycyclic aromatic radical cations produced in a Friedel-Crafts alkylating sys- tem, with m-xylene, or p-xylene and alkyl chloride. The results indicate that the observed electron paramagnetic resonance spectra are due to polycyclic aromatic radicals formed from the parent hydrocarbons. It is suggested that benzyl halides produced in the Friedel-Crafts alkylation reactions undergo Scholl self-condensation to give polycyclic aromatic hydrocar- bons, which are converted into corresponding polycyclic aromatic radical cations in the presence of AlCl3. The identification of observed two radicals 2,6-dimethylanthracene and 1,4,5,8-tetramethylanthraeene were supported by density functional theory calculations using the B3LYP/6-31G(d,p)//B3LYP/6-31G(d) approach. The theoretical coupling constants support the experimental assignment of the observed radicals. 相似文献
897.
This study investigated the inductively coupled plasma etching reactor and RF coils developed by North Microelectronic Corporation. Full three dimensional simulations were made at different discharge conditions. The simulations examined and compared the distribution and non-uniformity of several plasma parameters at a fixed position upon the wafer at different pressures and coil currents. These parameters included electron density, electron temperature and power deposition. The results demonstrate that the electron density, power deposition and uniformity increase with either higher pressure or stronger coil currents, while the electron temperature decreases at this condition. Coil number increase can reduce the non-uniformity of parameters in the spatial distribution. The linear relationship between power deposition and electron density does not always exist. The comparison between simulation results and experiment results is also presented in the paper. 相似文献
898.
Calvin J. Gardner Brent L. AdamsJohn Basinger David T. Fullwood 《International Journal of Plasticity》2010
Recent advances in high-resolution electron backscatter diffraction (EBSD)-based microscopy are applied to the characterization of elastic fields and incompatibility structures near the grain boundaries (GBs) in polycrystals. Two main recoveries are reported here: surface geometrically necessary dislocation (density) tensors, as described by Kröner, and the elastic fields near cracks (unconsolidated portions of interface) in loaded samples. Context for the application of these recoveries is described, using Green’s function solutions for combined heterogeneity and dislocation. Featured recoveries required the cross-correlation based determination of the elastic distortion tensor, aided by application of the simulated pattern method, and determination of the absolute pattern center utilizing the expected pattern properties in a spherical Kikuchi reference frame. High-resolution data obtained along an ultrasonically consolidated nickel boundary of varying amalgamation indicates that the imposed traction free boundary condition at free surfaces is well observed in the data structure. Further, high-resolution data acquired near a single grain boundary in well-annealed, low content steel suggests that it may be possible to measure the intrinsic elastic properties of GBs. 相似文献
899.
用KMR模型研究了等离子体中多光子非线性Compton散射下电子相轨道的演化,发现电子与光子进行能量交换后,只有未被俘获电子的相轨道才能从周期性向非周期性、随机型演化,其演化剧烈程度随电子吸收光子数的增大而加剧,随电子与光子碰撞非弹性成分和碰撞前初始速度的增大而迅速减弱,但低于强激光场中的剧烈程度。当电子被光场俘获时,这种演化过程结束并做稳定的运动,光子不再为电子提供能量。 相似文献
900.
X. Wu A.K. Ray 《The European Physical Journal B - Condensed Matter and Complex Systems》2001,19(3):345-351
The electronic and geometric structures of bulk PuO2 and its (110) surface have been studied using a periodic model within the generalized gradient approximation (GGA) of density
functional theory (DFT). The sixty core electrons of the Pu atom have been represented by a relativistic effective core potential
and scalar relativistic effects have been incorporated on the valence orbitals. For bulk PuO2, we predict an equilibrium lattice constant of 10.10 a.u. and a cohesive energy of 17.28 eV, in good agreement with experimental
data. For the (110) surface, upon relaxation, the distance between the top layer and the next layer is found to decrease by
0.12 ?, i.e. 5.3% of the corresponding interlayer distance in the bulk. The distance between the two oxygen atoms on the top layer is
found to increase by 0.15 ?, i.e. 5.6% of the corresponding bulk value. The small surface relaxation energy of 0.268 eV per unit cell indicates the fair stability
of this surface. The effective charges on Pu and O atoms show that the chemical bonding in this system is not purely ionic.
Together with the metallic feature of the density of states (DOS) on the surface, the effective charge distribution provides
some basis for understanding surface reactivity and corresponding support for catalysis.
Received 16 June 2000 相似文献