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51.
We have used the oscillating peroxidase-oxidase (PO) reaction as a model system to study how oscillatory dynamics may affect the influence of toxic reaction intermediates on enzyme stability. In the peroxidase-oxidase reaction reactive intermediates, such as hydrogen peroxide, superoxide, and hydroxyl radical are formed. Such intermediates inactivate many cellular macromolecules such as proteins and nucleic acids. These reaction intermediates also react with peroxidase itself to form an inactive enzyme. The fact that the PO reaction shows bistability between an oscillatory and a steady state gives us a unique possibility to compare such inactivation when the system is in one of these two states. We show that inactivation of peroxidase is slower when the system is in an oscillatory state, and using numerical simulations we provide evidence that oscillatory dynamics lower the average concentration of the reactive intermediates. 相似文献
52.
The 1,4-elimination reaction of 1-amino-4-methoxy-(2Z)-alkenes is shown to proceed with high (1E,3E)-stereoselectivities to afford the corresponding 4-substituted-1-amino-1,3-dienes in good yield. The scope and stereochemical features of the synthetic method are described. 相似文献
53.
Kasai J Nakagawa Y Uchida S Yamaguchi K Mizuno N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(15):4176-4184
An organic-inorganic hybrid support has been synthesized by covalently anchoring an N-octyldihydroimidazolium cation fragment onto SiO2 (denoted as 1-SiO2). This modified support was characterized by solid-state 13C, 29Si, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis. The results showed that the structure of the dihydroimidazolium skeleton is preserved on the surface of SiO2. The modified support can act as a good anion exchanger, which allows the catalytically active polyoxometalate anion [gamma-1,2-H2SiV2W10O40]4- (I) to be immobilized onto the support by a stoichiometric anion exchange (denoted as I/1-SiO2). The structure of anion I is preserved after the anion exchange, as confirmed by IR and 51V NMR spectroscopy. The catalytic performance for the oxidation of olefins and sulfides, with hydrogen peroxide (only one equivalent with respect to substrate) as the sole oxidant, was investigated with I/1-SiO2. This supported catalyst shows a high stereospecificity, diastereoselectivity, regioselectivity, and a high efficiency of hydrogen peroxide utilization for the oxidation of various olefins and sulfides without any loss of the intrinsic catalytic nature of the corresponding homogeneous analogue of I (i.e., the tetra-n-butylammonium salt of I, TBA-I), although the rates decreased to about half that with TBA-I. The oxidation can be stopped immediately by removal of the solid catalyst, and vanadium and tungsten species can hardly be found in the filtrate after removal of the catalyst. These results rule out any contribution to the observed catalysis from vanadium and tungsten species that leach into the reaction solution, which means that the observed catalysis is truly heterogeneous in nature. In addition, the catalyst is reusable for both epoxidation and sulfoxidation without any loss of catalytic performance. 相似文献
54.
Kim YK Auchincloss P Blanis D Bodek A Budd H Eno S Fry CA Harada H Ho YH Kumita T Mori T Olsen SL Shaw NM Sill A Thorndike EH Ueno K Zheng HW Imlay R Kirk P Lim J McNeil RR Metcalf W Myung SS Cheng CP Gu P Li J Li YK Mao ZP Xu YT Zhu YC Abashian A Gotow K Hu KP Low EH Mattson ME Piilonen L Sterner KL Lusin S Rosenfeld C Wang AT Wilson S Frautschi M Kagan H Kass R Trahern CG Breedon RE Kim GN Ko W Lander RL Maeshima K Malchow RL Smith JR Stuart D Williams MC Abe K Fujii Y Higashi Y Kim SK 《Physical review letters》1989,63(17):1772-1775
55.
Eno S Auchincloss P Blanis D Bodek A Budd H Fry CA Harada H Ho YH Kim YK Kumita T Mori T Olsen SL Shaw NM Sill A Thorndike EH Ueno K Zheng HW Imlay R Kirk P Lim J McNeil RR Metcalf W Myung SS Cheng CP Gu P Li J Li YK Mao ZP Xu YT Zhu YC Abashian A Gotow K Hu KP Low EH Mattson ME Piilonen L Sterner KL Lusin S Rosenfeld C Wang AT Wilson S Frautschi M Kagan H Kass R Trahern CG Breedon RE Kim GN Ko W Lander RL Maeshima K Malchow RL Smith JR Stuart D Williams MC Abe K Fujii Y Higashi Y Kim SK 《Physical review letters》1989,63(18):1910-1913
56.
Shaw NM Blanis D Bodek A Budd H Coombes R Eno S Fry CA Harada H Ho YH Kim YK Kumita T Mori T Olsen SL Sill A Thorndike EH Ueno K Zheng HW Imlay R Kirk P Lim J McNeil RR Metcalf W Myung SS Cheng CP Gu P Li J Li YK Mao ZP Xu YT Zhu YC Abashian A Gotow K Hu K Low EH Mattson ME Naito F Piilonen L Sterner KL Lusin S Rosenfeld C Wang AT Wilson S Frautschi M Kagan H Kass R Trahern CG Breedon RE Kim GN Ko W Lander RL Maeshima K Malchow RL Smith JR Sparks K Williams MC Abe K Fujii Y Higashi Y Kim SK 《Physical review letters》1989,63(13):1342-1345
57.
Peroxotungstate immobilized on ionic liquid-modified silica as a heterogeneous epoxidation catalyst with hydrogen peroxide 总被引:6,自引:0,他引:6
Yamaguchi K Yoshida C Uchida S Mizuno N 《Journal of the American Chemical Society》2005,127(2):530-531
Peroxotungstate immobilized on ionic liquid-modified SiO2 is capable of heterogeneously epoxidizing a wide range of olefins with the maintenance of the catalytic activity of homogeneous analogue. The epoxidation was immediately stopped by the removal of the catalyst, and no tungsten species could be found in the filtrate after the removal of the catalyst. These results can rule out any contribution to the observed catalysis from the tungsten species that leached into the reaction solution, and the observed catalysis is truly heterogeneous in nature. Furthermore, the catalyst was reusable without the loss of the catalytic performance. 相似文献
58.
We present a robust linear-scaling algorithm to compute the symmetric square-root or Lowdin decomposition of the atomic-orbital overlap matrix. The method is based on Newton-Schulz iterations with a new approach to starting matrices. Calculations on 12 chemically and structurally diverse molecules demonstrate the efficiency and reliability of the method. Furthermore, the calculations show that linear scaling is achieved. 相似文献
59.
60.
Foderà V Groenning M Vetri V Librizzi F Spagnolo S Cornett C Olsen L van de Weert M Leone M 《The journal of physical chemistry. B》2008,112(47):15174-15181
The fluorescent dye thioflavin T (ThT) is commonly used for in situ amyloid fibril detection. In this work, we focused on the spectroscopic properties and chemical stability of ThT in aqueous solution as a function of pH, temperature, and dye concentration. A reversible hydroxylation process occurs in alkaline solutions, which was characterized using a combination of UV-vis absorption spectroscopy, proton NMR, and density functional theory (DFT). On the basis of these studies, we propose a chemical structure for the hydroxylated form. Finally, by means of fluorescence spectroscopy, ThT hydroxylation effects on in situ amyloid detection have been investigated, providing new insights on the efficiency of the ThT assay for quantitative fibril evaluation at basic pH. 相似文献