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141.
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Torands Revisited: Metal Sequestration and Self‐Assembly of Cyclo‐2,9‐tris‐1,10‐phenanthroline Hexaaza Macrocycles 下载免费PDF全文
Dr. Matthias Georg Schwab Dr. Masayoshi Takase Dr. Alexey Mavrinsky Dr. Wojciech Pisula Prof. Dr. Xinliang Feng Dr. José A. Gámez Prof. Dr. Walter Thiel Dr. Kunal S. Mali Prof. Dr. Steven de Feyter Prof. Dr. Klaus Müllen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(23):8426-8434
A series of novel toroidal cyclo‐2,9‐tris‐1,10‐phenanthroline macrocycles with an unusual hexaaza cavity are reported. Nickel‐mediated Yamamoto aryl–aryl coupling was found to be a versatile tool for the cyclotrimerization of functionalized 1,10‐phenathroline precursors. Due to the now improved processability, both liquid‐crystalline behavior in the bulk phase and two‐dimensional self‐assembly at the molecular level could be studied, for the first time, for a torand system. The macrocycles exhibited a strong affinity for the complexation of different metal cations, as evidenced by MALDI‐TOF analysis and spectroscopic methods. Experimental results were correlated to an extensive computational study of the cyclo‐2,9‐tris‐1,10‐phenanthroline cavity and its binding mode for metal cations. Due to the combination of several interesting features, toroidal macrocycles may find future applications in the field of ion and charge transport through molecular channels, as well as for chemical sensing and molecular writing in surface‐confined monolayers under STM conditions. 相似文献
144.
Nowadays profitability and efficiency of practical and industrial applications and therefore of material design is becoming a more important issue. Due to different well-known and established approaches for analysis and simulation of complex heterogeneous materials on multiple scales based on numerical homogenisation techniques, development and production of high performance materials (using 3d printers for example) and as a consequence optimisation and design of materials is reality. The objective is to find optimal structures with optimal material distribution under given constraints related to posed problems and tailoring applications to their special requirements. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
145.
In the paper the 3-D model of a telescopic mobile crane is presented. In the model flexibilities and damping have been taken into account and also the number of degrees of freedom can be chosen according to the complexity of an approach. The algorithm of optimisation of drive functions for the slewing upper structure is given. The main goal of optimisation was to ensure load positioning at the end point of a work cycle in the case when oscillations are minimal. In order to achieve appropriate numerical effectiveness, the optimisation problem was solved for the simple, fully rigid model of a mobile crane. The method of compensating neglected flexibilities of the base structure of the crane and inner disturbances connected with the feedback control system via digital PID controller is presented. 相似文献
146.
Ma CQ Pisula W Weber C Feng XL Müllen K Bäuerle P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(5):1507-1518
Three-dimensional (3D) π-conjugated dendritic oligothiophenes up to a third generation have been functionalized with tris(decyloxy)phenylethynyl tails at the periphery. The first-generation compounds (3 T-p-Ph-C10 and 6 T-p-Ph-C10) were synthesized by palladium-catalyzed Sonogashira coupling reactions, whereas the higher generation products were synthesized by palladium-catalyzed Suzuki coupling reactions in a divergent approach. The optical and electrochemical properties were investigated by UV/Vis absorption, fluorescence spectroscopy, and cyclic voltammetry. The results revealed that the terminal tris(alkyloxy)phenylethynyl groups are conjugated to the branched oligothiophene core, yielding redshifted absorption and fluorescence spectra and reduced optical band gaps relative to the dendritic oligothiophene core. A structural study revealed a close relationship between the type of supramolecular organization and the size of the oligothiophene core. The first-generation compounds 3 T-p-Ph-C10 and 6 T-p-Ph-C10 displayed columnar phases in the bulk state, which was confirmed by two-dimensional wide-angle X-ray scattering (2D WAXS) measurements. The self-assembly into columnar stacks has mainly been attributed to phase separation between the rigid thiophene cores and the flexible side-chains assisted by minor π-stacking interactions between the conjugated dendritic oligothiophene units. The high-generation compounds, however, showed less ordered structures in the solid state. 相似文献
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148.
Collision-induced dissociation (CID) of 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine was investigated using sequential tandem mass spectrometry. These adducts represent biomarkers of DNA damage linked to phenolic radicals and were investigated to gain insight into the effects of chemical structure of a C-8 modification on fragmentation pathways of modified 2'-deoxyguanosine (dG). CID in MS(2) of the deprotonated molecules of both the isomers generated the same product ion having the same m/z values. CID in MS(3) of the product ion at m/z 242 and CID in MS(4) experiments carried out on the selected product ions at m/z 225 and m/z 218 afford distinct fragmentation patterns. The conformational properties of isomeric product ions from CID showed that the ortho-isomers possess the unique ability to tautomerize through an intramolecular proton transfer between the phenolic OH group and the imine nitrogen (N7). Tautomerization of ortho-isomers to their keto-tautomers led to differences in their system of conjugated double bonds compared with either their enol-tautomer or the para-isomer. The charge redistribution through the N-7 site on the imidazole ring is a critical step in guanosine adduct fragmentation which is disrupted by the formation of the keto-tautomer. For this reason, different reaction pathways are observed for 8-(4'-hydroxyphenyl)-2'-deoxyguanosine and 8-(2'-hydroxyphenyl)-2'-deoxyguanosine. We present herein the dissociation and the gas-phase ion-molecule reactions for highly conjugated ions involved in the CID ion chemistry of the investigated adducts. These will be useful for those using tandem mass spectrometry for structural elucidation of C-8 modified dG adducts. This study demonstrates that the modification at the C-8 site of dG has the potential to significantly alter the reactivity of adducts. We also show the ability of tandem mass spectrometry to completely differentiate between the isomeric dG adducts investigated. 相似文献
149.
Fijalkowski KJ Genova RV Filinchuk Y Budzianowski A Derzsi M Jaroń T Leszczyński PJ Grochala W 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4407-4413
We describe the successful synthesis of the first mixed-cation (pseudoternary) amidoborane, Na[Li(NH(2)BH(3))(2)], with theoretical hydrogen capacity of 11.1 wt%. Na[Li(NH(2)BH(3))(2)] crystallizes triclinic (P1) with a = 5.0197(4) ?, b = 7.1203(7) ?, c = 8.9198(9) ?, α = 103.003(6)°, β = 102.200(5)°, γ = 103.575(5)°, and V = 289.98(5) ?(3) (Z = 2), as additionally confirmed by Density Functional Theory calculations. Its crystal structure is topologically different from those of its orthorhombic LiNH(2)BH(3) and NaNH(2)BH(3) constituents, with distinctly different coordination spheres of Li (3 N atoms and 1 hydride anion) and Na (6 hydride anions). Na[Li(NH(2)BH(3))(2)], which may be viewed as a product of a Lewis acid (LiNH(2)BH(3))/Lewis base (NaNH(2)BH(3)) reaction, is an important candidate for a novel lightweight hydrogen storage material. The title material decomposes at low temperature (with onset at 75 °C, 6.0% mass loss up to 110 °C, and an additional 3.0% up to 200 °C) while evolving hydrogen contaminated with ammonia. 相似文献
150.
Rowinska-Zyrek M Witkowska D Bielinska S Kamysz W Kozlowski H 《Dalton transactions (Cambridge, England : 2003)》2011,40(20):5604-5610
The Hpn and HspA proteins from H. pylori are significant for nickel homeostasis and protect the cells from higher concentrations of external metal ions. Both proteins have a unique histidine- and cysteine-rich domain at the C terminus. The interactions of Ni(2+), Bi(3+), Zn(2+) and Cd(2+) ions with C-terminal Ac-CCSTSDSHHQ-NH(2) and Ac-EEGCCHGHHE-NH(2) fragments from Hpn and the Ac-GSCCHTGNHD-NH(2) sequence from HspA were studied by potentiometry, mass spectrometry, circular dichroism and UV-Vis spectroscopy. Ac-CC-NH(2) was used as a reference peptide. The studies have shown that nickel ions form planar complexes with a {2S(-),N(-)} binding mode. The thiol sulfurs of the -Cys-Cys- motif are also the anchoring sites for Bi(3+), Zn(2+) and Cd(2+) ions. The studied protein fragments have the highest affinity for Bi(3+) ions. The thermodynamic stability of Ni(2+) is much higher then that of Zn(2+). 相似文献