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101.
The [MoCu] carbon monoxide dehydrogenase (CODH) is a Cu-containing molybdo-flavoprotein, the active site of which contains a pterin-dithiolene cofactor bound to a sulfido-bridged dinuclear Mo-Cu complex. In this paper, the synthesis and characterization of dinuclear Mo-Cu complexes relevant to the active site of [MoCu]-CODH are described. Reaction of [MoO2S2]2- with CuCN affords the dinuclear complex [O2MoS2Cu(CN)]2- (1), in which the CN- ligand can be replaced with various aryl thiolates to give rise to a series of dinuclear complexes [O2MoS2Cu(SAr)]2- (Ar = Ph (2), o-Tol (3), and p-Tol (4)). An alternative synthesis of complex 2 is the reaction of [MoO2S2]2- with [Cu(SPh)3]2-. Similarly, [O2MoS2Cu(PPh3)]- (5), [O2MoS2Cu(dppe)]- (dppe = 1,2-bis(diphenylphosphino)ethane) (6), and [O2MoS2Cu(triphos)]- (triphos = 1,1,1-tris[(diphenylphosphino)methyl]ethane) (7) were prepared from the reactions of [MoO2S2]2- with the Cu(I) phosphine complexes. Treatment of 1, 2, 4, or 5 with dithiols (1,2-(SH)2C6H4, 1,2-(SH)2C6H2-3,6-Cl2, and 1,2-(SH)2C2H4), in acetonitrile, leads to the replacement of a molybdenum-bound oxo ligand to yield [(dithiolate)Mo(O)S2CuL]2- (L = CN, SAr; dithiolate = 1,2-S2C6H4, 1,2-S2C6H2-3,6-Cl2, or 1,2-S2C2H4) (8-13) or [(1,2-S2C6H4)Mo(O)S2Cu(PPh3)]- (14) complexes. 相似文献
102.
Aggregation‐Induced Delayed Fluorescence Based on Donor/Acceptor‐Tethered Janus Carborane Triads: Unique Photophysical Properties of Nondoped OLEDs 下载免费PDF全文
In Seob Park Jiyoung Lee Prof. Dr. Takuma Yasuda 《Angewandte Chemie (International ed. in English)》2016,55(25):7171-7175
Luminescent materials consisting of boron clusters, such as carboranes, have attracted immense interest in recent years. In this study, luminescent organic–inorganic conjugated systems based on o‐carboranes directly bonded to electron‐donating and electron‐accepting π‐conjugated units were elaborated as novel optoelectronic materials. These o‐carborane derivatives simultaneously possessed aggregation‐induced emission (AIE) and thermally activated delayed fluorescence (TADF) capabilities, and showed strong yellow‐to‐red emissions with high photoluminescence quantum efficiencies of up to 97 % in their aggregated states or in solid neat films. Organic light‐emitting diodes utilizing these o‐carborane derivatives as a nondoped emission layer exhibited maximum external electroluminescence quantum efficiencies as high as 11 %, originating from TADF. 相似文献
103.
RhI‐Catalyzed Intramolecular Carbonylative C−H/C−I Coupling of 2‐Iodobiphenyls Using Furfural as a Carbonyl Source 下载免费PDF全文
Takuma Furusawa Prof. Dr. Tsumoru Morimoto Dr. Yasuhiro Nishiyama Dr. Hiroki Tanimoto Prof. Dr. Kiyomi Kakiuchi 《化学:亚洲杂志》2016,11(16):2312-2315
Synthesis of fluoren‐9‐ones by a Rh‐catalyzed intramolecular C?H/C?I carbonylative coupling of 2‐iodobiphenyls using furfural as a carbonyl source is presented. The findings indicate that the rate‐determining step is not a C?H bond cleavage but, rather, the oxidative addition of the C?I bond to a RhI center. 相似文献
104.
This paper examines the dynamic property of a macroeconomic model developed by Matsuyama [Am. Econ. Rev. 97(2007), pp. 503–516] in detail. It is shown that the model can be transformed into a version of the neuron model analysed by Hata [J. Math. Kyoto Univ. 22(1982), pp. 155–173, Chaos in Neural Network Models (in Japanese), Asakura, Tokyo 1998] and that the system can exhibit either periodic fluctuations or non-periodic (chaotic) fluctuations. 相似文献
105.
106.
Journal of Visualization - An in situ visualization system based on the particle-based volume rendering offers a highly scalable and flexible visual analytics environment based on multivariate... 相似文献
107.
We consider the guaranteed a posteriori estimates for the inverse parabolic operators with homogeneous initial-boundary conditions. Our estimation technique uses a full-discrete numerical scheme, which is based on the Galerkin method with an interpolation in time by using the fundamental solution for semidiscretization in space. In our technique, the constructive a priori error estimates for a full discretization of solutions for the heat equation play an essential role. Combining these estimates with an argument for the discretized inverse operator and a contraction property of the Newton-type formulation, we derive an a posteriori estimate of the norm for the infinite-dimensional operator. In numerical examples, we show that the proposed method should be more efficient than the existing method. Moreover, as an application, we give some prototype results for numerical verification of solutions of nonlinear parabolic problems, which confirm the actual usefulness of our technique. 相似文献
108.
Columnar liquid‐crystalline (LC) truxene derivatives containing branched flexible alkyl chains have been designed and synthesized. The dicyanomethylene and dithiafulvene substituents have been introduced into the π‐conjugated truxene framework to tune their electronic and redox properties as well as the molecular assembled structures. The π‐conjugated cores of dicyanomethylene‐ and dithiafulvene‐appended truxenes adopt bowl‐shaped conformations, giving rise to a large intrinsic dipole moment perpendicular to the aromatic framework. These molecules form stable columnar LC structures through intermolecular dipole–dipole interactions. The redox properties of LC truxene derivatives have been examined by cyclic voltammetry. The dicyanomethylene‐appended truxene shows the reversible four‐step electrochemical reductions, whereas the dithiafulvene‐appended truxene undergoes three‐step oxidations. 相似文献
109.
This study focused on measurement of the autothermal reforming of biogas over a Ni based monolithic catalyst. The effects of the steam/CH4 (S/C) ratio, O2/CH4 (O2/C) ratio and temperature were investigated. The CH4 conversions were higher under all examined temperatures than the equilibrium conversion calculated using the blank outlet temperature, because the catalyst layer was heated by the exothermic catalytic partial oxidation reaction. The CH4 conversion increased with increasing O2/C ratio. Moreover, the CH4 conversion was higher than the equilibrium conversion calculated using the blank outlet temperature for O2/C>0.42 and reached about 100% at O2/C=0.55. However, the hydrogen concentration decreased for O2/C>0.45 because hydrogen was combusted to steam in the presence of excess oxygen. On the other hand, the hydrogen and CO2 concentrations increased and the CO concentration decreased with increasing S/C ratio. As a result, it was found that the highest hydrogen concentrations and CH4 conversions were attained at the O2/C ratios of 0.45-0.55 and the S/C ratios of 1.5-2.5. Moreover, the H2/CO ratio could also be controlled in the range from about 2 to 3.5 to give at least 90% CH4 conversion, by regulating the O2/C or S/C ratios. 相似文献
110.
To design a suitable periodontal disease formulation using basic fibroblast growth factor (bFGF), legally available thickeners were evaluated focusing on their viscosity, extrusive force from a syringe, flow property and inertness to bFGF. Thirteen candidate thickeners showed appropriate viscosity (about 1×10? mPa·s), and further evaluations were conducted on them. Flow property was evaluated by the tilting test tube method. As a result, most thickener solutions with the optimum viscosity showed appropriate flow time (about 100 s) and the flow time did not depend on thickener concentration, whereas the extrusive force from a syringe depended on thickener concentration despite the thickener type and grade. Thickener solutions of 2-3% showed ideal result (10-20 N) and thickener solutions prepared outside of the concentration range (2-3%) were found to show unsuitable extrusive force. Consequently, to obtain required properties for a dental drug formulation, thickener solutions needed to show adequate viscosity (about 1×10? mPa·s) at 2-3% thickener concentration. In addition, several types of cellulose derivatives showed inertness to the bFGF because of their structure, without strong ionic dissociable groups, and neutral pH. Overall, the present work demonstrates that some water-soluble cellulose derivatives, such as hydroxypropylcellulose (HPC) and hydroxyethylcellulose (HEC), were suggested to have required properties for a dental drug formulation including bFGF. 相似文献