全文获取类型
收费全文 | 861篇 |
免费 | 37篇 |
国内免费 | 3篇 |
学科分类
数理化 | 901篇 |
出版年
2023年 | 8篇 |
2022年 | 11篇 |
2021年 | 44篇 |
2020年 | 31篇 |
2019年 | 32篇 |
2018年 | 34篇 |
2017年 | 21篇 |
2016年 | 44篇 |
2015年 | 34篇 |
2014年 | 32篇 |
2013年 | 68篇 |
2012年 | 57篇 |
2011年 | 60篇 |
2010年 | 42篇 |
2009年 | 36篇 |
2008年 | 61篇 |
2007年 | 32篇 |
2006年 | 27篇 |
2005年 | 27篇 |
2004年 | 18篇 |
2003年 | 19篇 |
2002年 | 26篇 |
2001年 | 3篇 |
2000年 | 15篇 |
1999年 | 12篇 |
1998年 | 14篇 |
1997年 | 7篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 8篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1977年 | 5篇 |
1976年 | 3篇 |
1975年 | 4篇 |
1972年 | 1篇 |
1969年 | 1篇 |
1965年 | 2篇 |
1963年 | 1篇 |
1960年 | 1篇 |
排序方式: 共有901条查询结果,搜索用时 453 毫秒
1.
Huang L Wojciechowski G Ortiz de Montellano PR 《Journal of the American Chemical Society》2005,127(15):5345-5353
Myeloperoxidase (MPO), eosinophil peroxidase (EPO), and chloroperoxidase can oxidize iodide, bromide, and chloride, but most peroxidases, including the prototypical horseradish peroxidase (HRP), reportedly only oxidize iodide and, in some cases, bromide. We report here that incubation of HRP with Br(-) and H(2)O(2) at acidic pH results in both bromination of monochlorodimedone and modification of the heme group. Mass spectrometry indicates that the heme 2- and 4-vinyl groups are modified by either replacement of a vinyl hydrogen by a bromide or addition of HOBr to give a bromohydrin. These reactions do not occur if protein-free heme and Br(-) are co-incubated with H(2)O(2) or if the HRP reaction is carried out at pH 7. Surprisingly, similar prosthetic heme modifications occur in incubations of HRP with H(2)O(2) and Cl(-). A mechanism is proposed involving oxidation of Br(-) or Cl(-) to give HOBr or HOCl, respectively, followed by addition to a vinyl group. In the reaction with Cl(-), a meso-chloro heme adduct is also formed. This first demonstration of Cl(-) oxidation by HRP, and the finding that prosthetic heme modification occurs when Br(-) or Cl(-) is oxidized in the absence of a cosubstrate, show that only modest tuning is required to achieve the unique chloride oxidation activity of MPO and EPO. The results raise the question of how the prosthetic hemes of MPO and EPO, whose function is to produce oxidized halide species, escape modification. 相似文献
2.
Rudovsky J Hermann P Botta M Aime S Lukes I 《Chemical communications (Cambridge, England)》2005,(18):2390-2392
A marked increase of relaxivity has been observed upon rigidifying the internal frame of Gd-containing PAMAM dendrimers: the effect has been attained by either protonation of the dendrimer or by forming supramolecular adducts with cationic polyaminoacids. 相似文献
3.
Grzegorz Wojciechowski Grzegorz Schroeder Vladimir Rybachenko Bogumil Brzezinski 《Journal of Molecular Structure》2002,610(1-3):81-84
The heats of reactions between various phenols and two strong N-bases of guanidine-like character in acetonitrile, are determined. The values can be used as a measure of self-assembly abilities of the phenol molecules in the interactions with strong N-bases, playing a very important role in biological systems. In the case of TBD complexes with corresponding nitrophenols, the protonated N-base is hydrogen-bonded to the nitro group excluding the self-assembly process of the phenols. In the case of other phenols, the self-assembly abilities are dependent on pKa values of phenols. With increasing acidity of phenols their ability to form the hydrogen-bonded chains decreases. The maximum of length of the chains is observed for 4-methylphenol, which has a similar pKa value to that in the tyrosine residue in biological systems. 相似文献
4.
Wojciechowski G Huang L Ortiz de Montellano PR 《Journal of the American Chemical Society》2005,127(45):15871-15879
The mammalian peroxidases eosinophil peroxidase, lactoperoxidase (LPO), and myeloperoxidase oxidize thiocyanate to the antimicrobial agents hypothiocyanous acid (HOSCN) and (SCN)2 and are part of a defense system that protects the host from infections. Horseradish peroxidase (HRP), a plant enzyme, also oxidizes thiocyanate. We report here that the prosthetic heme vinyl groups of HRP react with the catalytically generated HOSCN and (SCN)2 to form at least nine vinyl-modified heme adducts. Mass spectrometry combined with analysis of the equivalent reactions of HRP reconstituted with 2- or 4-cyclopropylheme, or mesoheme-d4, shows that all of the prosthetic heme modifications result from addition of oxidized thiocyanate to the heme vinyl groups. No delta-meso-substitution of the heme was observed, in contrast to what is observed with radical agents. Model studies show that incubation of either HRP with preformed HOSCN or a solution of heme with preformed (SCN)2 gives rise to the same products obtained in the HRP-catalyzed reaction. Model studies also demonstrate that the SCN* radical, if formed, should add to a meso-carbon. These findings implicate an electrophilic addition mechanism. In contrast, oxidation by LPO of thiocyanate, the normal substrate of this enzyme, does not result in heme modification. In view of the demonstrated intrinsic reactivity of the heme group, LPO must actively suppress heme modification. As the key difference between LPO (and other mammalian peroxidases) and HRP is the presence of two covalent ester links between the heme and the protein, we propose that these links contribute to steric protection of the adjacent heme vinyl groups. 相似文献
5.
Yan-Cong Chen Yan Meng Yan-Jie Dong Xiao-Wei Song Guo-Zhang Huang Chuan-Lei Zhang Zhao-Ping Ni Jakub Navaík Ondej Malina Radek Zboil Ming-Liang Tong 《Chemical science》2020,11(12):3281
Among responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here, in a 2D Hofmann-type coordination polymer, [Fe(isoq)2{Au(CN)2}2] (isoq = isoquinoline), a medium-temperature annealing process is introduced after light/temperature stimulation, which accesses the hidden multistability of the spin state. With the combined effort of magnetic, crystallographic and Mössbauer spectral investigation, these distinct spin states are identified and the light- and temperature-assisted transition pathways are clarified. Such excitation-relaxation and trapping-relaxation joint mechanisms, as ingenious interplays between the kinetic and thermodynamic effects, uncover hidden possibilities for the discovery of multistable materials and the development of multistate intelligent devices.Two new two-stage manipulation protocols, namely light- and temperature-assisted spin state annealing (LASSA/TASSA), are applied to a spin crossover coordination polymer, [Fe(isoq)2{Au(CN)2}2], revealing the hidden multistability of spin states. 相似文献
6.
Jakub Wojciechowski Henryk Krawczyk Marcin
liwiski Karolina Kafarska Wojciech M. Wolf 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(5):o280-o282
The title compound, C14H20O2, adopts a conformation in which the δ‐valerolactone and cyclohexane rings are almost coplanar with one another. The γ‐methyl substituent occupies an axial position with respect to the cyclohexane ring. The δ‐valerolactone moiety adopts an envelope arrangement, while the cyclohexane ring exists in a chair conformation. 相似文献
7.
T. Case K. M. Crowe K. Lou C. Petitjean W. H. Breunlich M. Jeitler P. Kammel B. Lauss J. Marton W. Prymas J. Zmeskal D. V. Balin V. N. Baturin Yu. S. Grigoriev A. I. Ilyin E. M. Maev G. E. Petrov G. G. Semenchuk Yu. V. Smirenin A. A. Vorobyov N. I. Voropaev P. Baumann H. Daniel F. J. Hartmann M. Mühlbauer W. Schott P. Wojciechowski 《Hyperfine Interactions》1993,82(1-4):295-302
Starting in 1989 an experiment was run at PSI to directly measure the final sticking probability in muon catalyzed dt fusion. This experiment was based on an active-target ionization chamber (IC) built at Gatchina, Russia, and an array of plastic neutron counters. In three runs approximately 5×106 isolated alpha signals were recorded with around one half of these occurring in the inner chamber region where we have more complete understanding of the systematic errors. Particularly from a long run in 1992 we were able to obtain a very clean sticking peak of some 5000 events. However, to reach an accurate value of sticking, all systematic effects and several major backgrounds had to be understood in detail. To this end a Monte Carlo code was written to simulate the full electrostatic environment of the IC and to recreate completely each signal type including the actual tritium decay noise from the live experiment. A slightly model dependent value of approx. 0.56±0.04% is obtained for final sticking. 相似文献
8.
W. Schott V. N. Baturin W. H. Breunlich T. Case H. Daniel F. J. Hartmann M. Jeitler P. Kammel K. Lou E. M. Maev J. Marton M. Mühlbauer C. Petitjean G. E. Petrov Yu. V. Petrov G. G. Semenchuk Yu. V. Smirenin A. A. Vorobyov P. Wojciechowski J. Zmeskal 《Hyperfine Interactions》1993,82(1-4):471-481
The triton energy of the muon capture reaction 3He t+v, where 3 He is the ground state of muonic3He, has been measured in order to investigate a possible heavy v admixture into the flavour with high sensitivity. 3 He has been formed via the pd fusion reaction by stopping – in an ionization chamber (IC) filled with an H/D gas mixture of 3% D concentration at a pressure of 161 bar. In a first short experiment 650 triton events were observed yielding an upper limit for the -heavy v mixing strength of 2.3×10–3 atE
0v=60 MeV. 相似文献
9.
P. Ackerbauer W. H. Breunlich M. Fuchs S. Fussy M. Jeitler P. Kammel B. Lauss J. Marton W. Prymas J. Werner J. Zmeskal K. Lou C. Petitjean P. Baumann H. Daniel F. J. Hartmann W. Schott T. von Egidy P. Wojciechowski D. Chatellard J. P. Egger E. Jeannet T. Case K. M. Crowe R. H. Sherman V. Markushin 《Hyperfine Interactions》1993,82(1-4):243-258
Complementary to the investigations of the most efficient dt cycle, also the other muon-induced fusion cycles in mixtures of hydrogen isotopes have been studied. The results of these dedicated experiments provide rich information about muon-induced few-body reactions and contribute significantly to a better overall understanding of CF. A summary of the recent progress will be presented. Special emphasis will be put on two characteristic examples, namely a new experimental approach to study the muonic cascade in H-D mixtures and the systematic study of hyperfine effects in muon-induced reactions. 相似文献
10.
Jakub Kołacz Henry G. Gotjen Robel Y. Bekele Jason D. Myers Jesse A. Frantz Michael Ziemkiewicz 《Liquid crystals》2020,47(4):531-539
ABSTRACTIn a planar dielectric waveguide, weak confinement of a propagating mode in a high index core leads to a measurable evanescent interaction with the cladding. In this work, we study the effect of a reorientable anisotropic cladding on the behaviour of Transverse Electric (TE) and Transverse Magnetic (TM) mode polarisations using a liquid crystal (LC)-clad waveguide architecture. The polarised evanescent field of a guided mode interacts with a voltage-tunable birefringent LC cladding to deflect an out-coupled beam. Experimental measurements are coupled with a theoretical framework and show good consistency with simulation results. We isolate the effect of mode confinement by changing the thickness of the high index core. Interactions between the LC index ellipsoid and the mode polarisation are probed by changing the initial alignment of the LC. Finally, we examine the difference in deflection between TE and TM modes, which incorporates both a change in mode confinement and a difference in LC index components. 相似文献