全文获取类型
收费全文 | 4002篇 |
免费 | 173篇 |
国内免费 | 14篇 |
专业分类
化学 | 3255篇 |
晶体学 | 54篇 |
力学 | 33篇 |
数学 | 76篇 |
物理学 | 771篇 |
出版年
2023年 | 24篇 |
2022年 | 39篇 |
2021年 | 62篇 |
2020年 | 55篇 |
2019年 | 88篇 |
2018年 | 66篇 |
2017年 | 47篇 |
2016年 | 90篇 |
2015年 | 97篇 |
2014年 | 105篇 |
2013年 | 190篇 |
2012年 | 278篇 |
2011年 | 311篇 |
2010年 | 147篇 |
2009年 | 130篇 |
2008年 | 234篇 |
2007年 | 229篇 |
2006年 | 192篇 |
2005年 | 207篇 |
2004年 | 179篇 |
2003年 | 153篇 |
2002年 | 122篇 |
2001年 | 108篇 |
2000年 | 82篇 |
1999年 | 72篇 |
1998年 | 38篇 |
1997年 | 42篇 |
1996年 | 34篇 |
1995年 | 34篇 |
1994年 | 29篇 |
1993年 | 28篇 |
1992年 | 42篇 |
1991年 | 31篇 |
1990年 | 39篇 |
1989年 | 27篇 |
1988年 | 21篇 |
1987年 | 35篇 |
1986年 | 20篇 |
1985年 | 36篇 |
1984年 | 36篇 |
1983年 | 20篇 |
1982年 | 34篇 |
1981年 | 33篇 |
1980年 | 24篇 |
1979年 | 47篇 |
1978年 | 27篇 |
1977年 | 23篇 |
1975年 | 23篇 |
1974年 | 22篇 |
1973年 | 15篇 |
排序方式: 共有4189条查询结果,搜索用时 0 毫秒
1.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
2.
3.
R. Bairava Ganesh Hitoshi Matsuo Takahiro Kawamura Yoshihiro Kangawa Koji Arafune Yoshio Ohshita Masafumi Yamaguchi Koichi Kakimoto 《Journal of Crystal Growth》2008,310(11):2697-2701
Multicrystalline silicon was grown by unidirectional solidification method using the accelerated crucible rotation technique. The application of the accelerated crucible rotation technique in unidirectional solidification method induced growth striations across the axial direction of the grown crystal. This striation pattern was observed from carbon concentration distribution, obtained by using Fourier transform infrared spectroscopy. The generated striation pattern was found to be weak and discontinuous. Some striations were absent, probably due to back melting, caused during each crucible rotation. From the growth striations and applied time period in crucible rotation, the growth rate was estimated by using Fourier transformation analysis. 相似文献
4.
Takashi Yoshitake Ryuji Iizuka Kaoru Fujino Osamu Inoue Kenji Yamagata Hitoshi Nohta Masatoshi Yamaguchi 《Analytical sciences》2004,20(12):1687-1690
An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification. 相似文献
5.
Norikazu Yamaguchi 《Mathematical Methods in the Applied Sciences》2005,28(13):1507-1526
In this paper we are concerned with the initial boundary value problem of the micropolar fluid system in a three dimensional bounded domain. We study the resolvent problem of the linearized equations and prove the generation of analytic semigroup and its time decay estimates. In particular, Lp–Lq type estimates are obtained. By use of the Lp–Lq estimates for the semigroup, we prove the existence theorem of global in time solution to the original nonlinear problem for small initial data. Furthermore, we study the magneto‐micropolar fluid system in the final section. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
6.
Longlan Cui Hong Xu Ping He Keiko Sumitomo Yoshinori Yamaguchi Hongchen Gu 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5285-5295
A hybrid emulsion polymerization was formulated for synthesizing Fe3O4/polystyrene composite latex. This system, containing binary droplets that are magnetic (Mag)‐droplets with a diameter of 100–200 nm and styrene (St)‐droplets with a diameter of 3–4 μm, was obtained by mixing Mag‐miniemulsion and St‐macroemulsion. With extremely low surfactants concentration (?critical micelle concentration, CMC), the nucleated loci are selectively controlled in the Mag‐droplets, as the result of smaller droplet size and larger surface ratio. Both water‐soluble potassium persulfate (KPS) and oil‐soluble 2,2′‐azobis(2‐isobutyronitrile) was adopted to initiate the polymerization. In the presence of KPS, magnetic polystyrene latices with particles size of 60–200 nm, narrow size distribution, and high magnetite content (86 wt % measured by TGA) were attained successfully. The synthesized magnetic Fe3O4/polystyrene latices assembled into well‐ordered hexagonal structure in the surface of a carbon supported copper grid. The influence of various parameters on various aspects of the as‐synthesized Fe3O4/polystyrene was investigated in detail: type of initiator on composite morphology, feed ratio of Mag‐miniemulsion and St‐macroemulsion on magnetite content, and hydrophobic agent or amount of surfactant on size and size distribution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5285–5295, 2007 相似文献
7.
8.
H. Yamaguchi K. Kanisawa S. Miyashita Y. Hirayama 《Physica E: Low-dimensional Systems and Nanostructures》2004,23(3-4):285
We studied the structural, electrical, and mechanical properties of an InAs thin film grown on GaAs (1 1 1)A substrates by molecular beam epitaxy. In contrast to conventionally used (0 0 1) surfaces, where Stranski–Krastanov growth dominates the highly mismatched heteroepitaxy, layer-by-layer growth of InAs can be established. One of the largest advantages of this unique heteroepitaxial system is that it provides a two-dimensional electron gas system in the near-surface region without the problem of electron depletion. We review the fundamental properties and applications of this unique heteroepitaxial system. 相似文献
9.
Endoscopic Observation of Tissue by Narrowband Illumination 总被引:6,自引:0,他引:6
Kazuhiro Gono Kenji Yamazaki Nobuyuki Doguchi Tetsuo Nonami Takashi Obi Masahiro Yamaguchi Nagaaki Ohyama Hirohisa Machida Yasushi Sano Shigeaki Yoshida Yasuo Hamamoto Takao Endo 《Optical Review》2003,10(4):211-215
We propose a new illumination method for a medical endoscope: narrow band imaging (NBI), in which the spectral bandwidth of the filtered light is narrowed. To confirm how the spectral specifications of the filtered light influence a reproduced image, an experiment was conducted observing the endoscopic images of the back mucosa of a human tongue. In addition, the effect of NBI on endoscopic images was investigated through preliminary clinical tests in colonoscopy and upper gastrointestinal endoscopy. It has been shown that NBI can enhance the capillary pattern and the crypt pattern on the mucosa. These patterns are useful features for diagnosing an early cancer. 相似文献
10.
Arata Yajima Ayumi Yamaguchi Fumihiro Saitou Tomoo Nukada Goro Yabuta 《Tetrahedron》2007,63(5):1080-1084
A convergent synthetic strategy for abietane diterpenoids via B-alkyl Suzuki-Miyaura coupling and Lewis acid-mediated cyclization reactions is established. Asymmetric total synthesis of 12-deoxyroyleanone, an antileishmanial diterpene, is described. 相似文献