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181.
Enantioselective Self‐Assembly of Triangular Dy3 Clusters with Single‐Molecule Magnet Behavior 下载免费PDF全文
Three pairs of enantiopure chiral triangular Ln3 clusters, [Ln3LRRRRRR/SSSSSS(μ3‐OH)2(H2O)2(SCN)4]?xCH3OH?yH2O ( R ‐Dy3 , Ln=Dy, x=6, y=0; S ‐Dy3 , Ln=Dy, x=6, y=1; R ‐Ho3 , Ln=Ho, x=6, y=1; S ‐Ho3 , Ln=Ho, x=6, y=1; R ‐Er3 , Ln=Er, x=6, y=0; S ‐Er3 , Ln=Er, x=6, y=1), have been successfully synthesized by a rational enantioselective synthetic strategy. The core of triangular Ln3 is bound in the central N6O3 of the macrocyclic ligand, and the coordination spheres of Ln ions are completed by four SCN? anions and two H2O molecules in axial positions of the macrocycle. The circular dichroism (CD) and vibrational circular dichroism (VCD) spectra of the enantiomers demonstrate that the chirality is successfully transferred from the ligands to the resulting Ln3 clusters. Ac susceptibility measurements reveal that single‐molecule magnet behavior occurs for both enantiopure clusters of R ‐Dy3 and S ‐Dy3 . This work is one of the few examples of the successful design of a pair of triangular Dy3 clusters showing simultaneously slow magnetic relaxation and optical activity, and this might open up new opportunities to develop novel multifunctional materials. 相似文献
182.
Jinping Song Hui Li Jianbin Chao Chuan Dong Shaomin Shuang 《Journal of inclusion phenomena and macrocyclic chemistry》2012,72(3-4):389-395
The formation of the inclusion complex of p-sulfonatocalix[6]arene (SCX6) with different forms of vitamin B6 (VB6) was studied by using fluorescence spectroscopy. VB6 can exist in one of three forms (the acidic form, neutral zwitterionic form and basic form) depending on pH. The fluorescence intensities of acidic and basic forms of VB6 remarkably decreased in presence of SCX6. SCX6 preferred to form 1:1 inclusion complexes with acidic and basic forms of VB6 but hardly form inclusion complex with neutral zwitterionic form. According to the nonlinear curve fitting method, the inclusion constant (K) for the formation of inclusion complexes of acidic and basic forms of VB6 with SCX6 were evaluated to be 1.4?×?104 and 9?×?103 L/mol, respectively. The binding affinity of SCX6 towards acidic form is attributed to hydrogen bonds and hydrophobic interaction, furthermore, additional electrostatic interaction also plays a crucial role. The possible inclusion mode was given by 1H NMR technique. 相似文献
183.
184.
Yixuan Xie Chao Peng Yunyi Gao Xiaohong Liu Tianbo Liu Abraham Joy 《Journal of polymer science. Part A, Polymer chemistry》2017,55(23):3908-3917
Glycopolymers have been widely used to understand the interactions between carbohydrates and lectins, which facilitate the diagnosis and detection of disease and pathogens as well as the development of vaccines. While studies have been focused on the correlation of glycopolymer structure and their binding to lectins, graft‐type glycopolyesters are uncommon. Herein, we report the design and synthesis of mannose‐based graft polyesters by “grafting‐from” method and investigate their interactions with Concanavalin A (Con A). As confirmed by 1H NMR spectroscopy and sulfuric acid‐UV method, graft polyesters with different lengths of mannose graft were successfully synthesized. Our results from turbidimetry binding assay showed that graft polyesters with longer mannose graft exhibit higher initial binding rate (ki). Isothermal titration calorimetry measurements of these graft polyesters with Con A showed that polymers exhibit higher binding affinity (ka) with the number of side chain mannose. This study provides understanding of the interaction between Con A and mannose‐based graft polyesters, which can be employed for the development of glycopolymeric therapeutics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3908–3917 相似文献
185.
Chao Han 《Combustion Theory and Modelling》2017,21(4):603-629
Flamelet models for turbulent combustion modelling make use of presumed-shape probability density functions (PDFs) for integrating laminar flamelet solutions to obtain an integrated flamelet table that can readily be used for turbulent flame calculations. The existence of non-unique approaches for such an integration has rarely been investigated before. For the first time, this work studies systematically the non-uniqueness of the flamelet table integration approaches. A flamelet model called the flamelet/progress variable model is used in the study, although the issue exists generally in many other flamelet models. Two classes of table integration approaches are investigated, one preserving the laminar flamelet structures during integration and the other not. Three different table integration approaches are examined and compared in detail to provide a thorough understanding of the different approaches. A partially stirred reactor is used as a test case for examining the different approaches. A method based on the transported PDF method is also employed to provide a reference for the assessment of the different flamelet table integration approaches. It is found in general that the flamelet preserving integration approach yields a more reasonable joint PDF of the mixture fraction and the progress variable, and the prediction results are closer to the referenced transported PDF results. 相似文献
186.
Weiguo Zhang Junyu Xu Jing Cao Chao Fang Jindong Zhu Tao Lu Ding Du 《Tetrahedron》2017,73(23):3249-3254
An in situ activation of isatin-derived α,β-unsaturated acids 2 for the generation of isatin-derived α,β-unsaturated acyl azoliums II was described. The acyl azoliums II were successfully applied to undergo a formal [3 + 3] annulation with 1,3-dicarbonyl compounds to access functionalized 3,4′-spirooxindole δ-lactones 4. A scale-up synthesis and an enantioselective variant of this protocol were also investigated. The stable and easily prepared acids 2 may be further utilized as promising versatile electrophilic 1,3-synthons for divergent synthesis of spirooxindoles. 相似文献
187.
Chain-like systems have been studied by many researchers for their simple structure and wide range of application. Previously, the damage in a chain-like system was detected by the reduction of the mass-normalized stiffness coefficient for certain elements as reported by Nayeri et al. (2008 [16]). However, some shortcomings exist in that approach and for overcoming them; an improved approach is derived and presented in this paper. In our improved approach, the mass normalized stiffness coefficients under two states (baseline state and potentially damaged state) are first estimated by a least square method, then these mass-stiffness coupled coefficients are decoupled to derive stiffness and mass relative change ratios for individual elements. These ratios are assembled in a vector, which is defined as damage indication vector (DIV). Each component in DIV is normalized individually to one to get multiple solutions. These solutions are averaged for estimating relative system changes, while abnormal solutions are discarded. The work of judging a solution as normal or abnormal is done by a cluster analysis algorithm. The most intriguing merit of this improved approach is that the relative stiffness and mass changes, which are coupled in the previous approach, can be separately identified. By this approach, the damage (single or multiple) extent and location can be correctly detected under operational conditions, meanwhile the proposed damage index has a clear physical meaning and is directly related to the stiffness reduction of corresponding structural elements. For illustrating the effectiveness and robustness of the improved approach, numerical simulation of a four floor building was carried out and experimental data from a structure tested at the Los Alamos National Laboratory was employed. Identified structural changes with both simulation and experimental data properly indicated the location and extent of actual structural damage, which validated the proposed approach. 相似文献
188.
189.
Gold‐Catalyzed Tandem Cycloisomerization–Halogenation of Chiral Homopropargyl Sulfonamides 下载免费PDF全文
Chao Shu Long Li Cang‐Hai Shen Peng‐Peng Ruan Chao‐Yue Liu Prof. Dr. Long‐Wu Ye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(7):2282-2290
Two new gold‐catalyzed tandem cycloisomerization–halogenation reactions of chiral homopropargyl sulfonamides have been developed. Various enantioenriched 3,3‐diiodopyrrolidin‐2‐ols and 3‐fluoropyrrolidin‐2‐ols were obtained in moderate‐to‐good yields with excellent enantio‐ and diastereoselectivity. 相似文献
190.
A Luminescent Metal–Organic Framework Thermometer with Intrinsic Dual Emission from Organic Lumophores 下载免费PDF全文
Hao Zhang Dr. Chensheng Lin Prof. Tianlu Sheng Dr. Shengmin Hu Chao Zhuo Dr. Ruibiao Fu Dr. Yuehong Wen Haoran Li Shaodong Su Prof. Xintao Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4460-4468
A new mixed‐ligand metal–organic framework (MOF), ZnATZ‐BTB, has been constructed as a luminescent ratiometric thermometer by making use of the intrinsic dual emission at cryogenic temperatures. Its twofold interpenetrated network promotes the Dexter energy transfer (DET) between the mixed organic lumophores. The temperature‐dependent luminescent behavior arises from the thermal equilibrium between two separated excited states coupled by DET, which is confirmed by Boltzmann distribution fitting. The small excited‐state energy gap allows ZnATZ‐BTB to measure and visualize cryogenic temperatures (30–130 K) with significantly high relative sensitivity (up to 5.29 % K?1 at 30 K). Moreover, it is the first example of a ratiometric MOF thermometer the dual emitting sources of which are widely applicable mixed organic ligands, opening up new opportunities for designing such devices. 相似文献