全文获取类型
收费全文 | 483篇 |
免费 | 23篇 |
专业分类
化学 | 414篇 |
晶体学 | 3篇 |
力学 | 7篇 |
数学 | 12篇 |
物理学 | 70篇 |
出版年
2023年 | 4篇 |
2022年 | 3篇 |
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 12篇 |
2018年 | 8篇 |
2017年 | 4篇 |
2016年 | 12篇 |
2015年 | 11篇 |
2014年 | 20篇 |
2013年 | 21篇 |
2012年 | 42篇 |
2011年 | 51篇 |
2010年 | 24篇 |
2009年 | 23篇 |
2008年 | 27篇 |
2007年 | 47篇 |
2006年 | 28篇 |
2005年 | 30篇 |
2004年 | 29篇 |
2003年 | 27篇 |
2002年 | 10篇 |
2001年 | 5篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1995年 | 1篇 |
1994年 | 4篇 |
1991年 | 1篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
排序方式: 共有506条查询结果,搜索用时 640 毫秒
31.
Prof. Nobutaka Fujieda Kyohei Umakoshi Yuta Ochi Dr. Yosuke Nishikawa Prof. Sachiko Yanagisawa Prof. Minoru Kubo Prof. Genji Kurisu Prof. Shinobu Itoh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13487-13492
The dinuclear copper enzyme, tyrosinase, activates O2 to form a (μ-η2:η2-peroxido)dicopper(II) species, which hydroxylates phenols to catechols. However, the exact mechanism of phenolase reaction in the catalytic site of tyrosinase is still under debate. We herein report the near atomic resolution X-ray crystal structures of the active tyrosinases with substrate l -tyrosine. At their catalytic sites, CuA moved toward l -tyrosine (CuA1 → CuA2), whose phenol oxygen directly coordinates to CuA2, involving the movement of CuB (CuB1 → CuB2). The crystal structures and spectroscopic analyses of the dioxygen-bound tyrosinases demonstrated that the peroxide ligand rotated, spontaneously weakening its O−O bond. Thus, the copper migration induced by the substrate-binding is accompanied by rearrangement of the bound peroxide species so as to provide one of the peroxide oxygen atoms with access to the phenol substrate's ϵ carbon atom. 相似文献
32.
Hayate Saito Keita Yamamoto Yosuke Sumiya Ling‐Jun Liu Keisuke Nogi Satoshi Maeda Hideki Yorimitsu 《化学:亚洲杂志》2020,15(16):2442-2446
C?H iodination of aromatic compounds has been accomplished with the aid of sulfinyl directing groups under palladium catalysis. The reaction proceeds selectively at the peri‐position of polycyclic aryl sulfoxides or at the ortho‐position of phenyl sulfoxides. The iodination products can be further converted via iterative catalytic cross‐coupling at the expense of the C?I and C?S bonds. Computational studies suggest that peri‐C?H palladation would proceed via a non‐directed pathway, wherein neither of the sulfur nor oxygen atom of the sulfinyl group coordinates to the palladium before and at the transition state. 相似文献
33.
Takashi Minoshima Yosuke Matsumoto Takanobu Amano 《Journal of computational physics》2011,230(17):6800-6823
We present a new numerical scheme for solving the advection equation and its application to Vlasov simulations. The scheme treats not only point values of a profile but also its zeroth to second order piecewise moments as dependent variables, for better conservation of the information entropy. We have developed one-and two-dimensional schemes and show that they provide quite accurate solutions within reasonable usage of computational resources compared to other existing schemes. The two-dimensional scheme can accurately solve the solid body rotation problem of a gaussian profile for more than hundred rotation periods with little numerical diffusion. This is crucially important for Vlasov simulations of magnetized plasmas. Applications of the one- and two-dimensional schemes to electrostatic and electromagnetic Vlasov simulations are presented with some benchmark tests. 相似文献
34.
Water‐ and Temperature‐Triggered Reversible Structural Transformation of Tetranuclear Cobalt(II) Cores Sandwiched by Polyoxometalates 下载免费PDF全文
Yosuke Kuriyama Dr. Yuji Kikukawa Dr. Kosuke Suzuki Dr. Kazuya Yamaguchi Prof. Dr. Noritaka Mizuno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):3962-3966
Although stimuli‐responsive structural transformations of inorganic materials have attracted considerable attention because of their potential use as functional switchable materials, multinuclear metal cores frequently suffer from unexpected dissociation of metal cations and/or irreversible transformations into infinite structures. In this study, we describe the successful demonstration of the water‐ and temperature‐triggered reversible structural transformation between cubane‐ and planar‐type tetranuclear CoII cores sandwiched by polyoxometalates. The arrangements and coordination geometries of the CoII cations were interconverted by simple hydration and dehydration, resulting in the manipulation of the magnetic and optical properties of these compounds. Moreover, this system showed unique thermochromism through temperature‐dependent reversible structural interconversion. 相似文献
35.
A fluorimetric assay for lecithin-cholesterol acyltransferase in human plasma (normal and pathological) is described. The lowered cholesterol concentration in the enzyme reaction is determined fluorimetrically by using the cholesterol oxidase—peroxidase —tyramine system. The assay requires only 10 μl of plasma. 相似文献
36.
[reaction: see text]. Novel photostable oxa[3.n](3,9)- and [3.3](3,10)phenanthrenophanes (n = 3, 4) bearing trimethylene-type linkage(s) were successfully synthesized by the intramolecular acid-catalyzed etherification of the corresponding precursor diols. syn-Oxa[3.3](3,10)phenanthrenophane afforded the most red-shifted excimer fluorescence (lambda(max) = 432 nm) among the phenanthrenophanes so far prepared. 相似文献
37.
Tavrov AV Kobayashi Y Tanaka Y Shioda T Otani Y Kurokawa T Takeda M 《Optics letters》2005,30(17):2224-2226
A three-dimensional common-path interferometer is proposed, which can achromatically null out an on-axis source while it maintains the detectability of an off-axis source. A geometric phase in the three-dimensional interferometer introduces an achromatic pi-phase shift to the light from the on-axis source, such that destructive interference nulls out the axial light at one of the ports of the interferometer. Light from the off-axis source, which is exempt from the pi-phase shift, comes out from both ports with equal intensity. The common-path scheme makes the system highly immune to environmental disturbances. 相似文献
38.
Recent experiments on the addition of alkene and alkyne molecules to H-terminated silicon surfaces have provided evidence for a surface chain reaction initiated at isolated Si dangling bonds and involving an intermediate carbon radical state, which, after abstraction of a hydrogen atom from a neighboring Si-H unit, transforms into a stable adsorbed species plus a new Si dangling bond. Using periodic density functional theory (DFT) calculations, together with an efficient method for determining reaction pathways, we have studied the initial steps of this chain reaction for a few different terminal alkynes and alkenes interacting with an isolated Si dangling bond on an otherwise H-saturated Si(111) surface. Calculated minimum energy pathways (MEPs) indicate that the chain mechanism is viable in the case of C(2)H(2), whereas for C(2)H(4) the stabilization of the intermediate state is so small and the barrier for H-abstraction so (relatively) large that the molecule is more likely to desorb than to form a stable adsorbed species. For phenylacetylene and styrene, stabilization of the intermediate state and decrease of the H-abstraction barrier take place. While a stable adsorbed species exists in both cases, the overall heat of adsorption is larger for the alkyne molecules. 相似文献
39.
A convergent total synthesis of leustroducsin B (1), which is known to exhibit a variety of biological activities, was successfully carried out. Notable features of our synthesis include construction of the C8 stereocenter by lipase-mediated desymmetrization of meso-diol 4 (90.2% ee) and preparation of the C9-C11 anti-diol moiety by the addition of alkynylzinc reagent 20 to the aldehyde 19. Furthermore, a new diol protecting group, p-silyloxybenzylidene, was developed for the deprotection from densely functionalized substrates under weakly acidic conditions. The protecting group was easily removed in a two-step procedure ((HF)3.Et3N; AcOH-THF-H2O). 相似文献
40.
Mitsuru Musha Yosuke Tamura Ken’ichi Nakagawa Ken-ichi Ueda 《Optics Communications》2007,272(1):211-216
We have developed a practical and precise frequency measurement system at 1.5 μm telecommunication band. An electro-optic-modulator based optical frequency comb is phase-locked to a dither-free acetylene-stabilized laser to realize an optical frequency comb with frequency uncertainty of 10 kHz (5 × 10−11) and the linewidth of 15 kHz. The present frequency comb can be also used as an optical frequency reference grid defined by ITU-T (International Telecommunication Union, Telecommunication Standardization Sector). Using the present frequency measurement system, we have demonstrated the first optical frequency measurement of 12C16O overtone absorption lines around 1.56 μm with the uncertainty of lower than 900 kHz. 相似文献