全文获取类型
收费全文 | 1773篇 |
免费 | 172篇 |
国内免费 | 5篇 |
专业分类
化学 | 1559篇 |
晶体学 | 21篇 |
力学 | 15篇 |
数学 | 68篇 |
物理学 | 287篇 |
出版年
2024年 | 2篇 |
2023年 | 21篇 |
2022年 | 15篇 |
2021年 | 38篇 |
2020年 | 64篇 |
2019年 | 75篇 |
2018年 | 43篇 |
2017年 | 27篇 |
2016年 | 102篇 |
2015年 | 86篇 |
2014年 | 88篇 |
2013年 | 98篇 |
2012年 | 191篇 |
2011年 | 214篇 |
2010年 | 76篇 |
2009年 | 64篇 |
2008年 | 131篇 |
2007年 | 112篇 |
2006年 | 103篇 |
2005年 | 81篇 |
2004年 | 81篇 |
2003年 | 51篇 |
2002年 | 41篇 |
2001年 | 18篇 |
2000年 | 12篇 |
1999年 | 7篇 |
1998年 | 8篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 6篇 |
1994年 | 7篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1986年 | 6篇 |
1985年 | 9篇 |
1984年 | 7篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1978年 | 5篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1971年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有1950条查询结果,搜索用时 15 毫秒
1.
Watanabe Sou Senzaki Tatsuya Shibata Atsuhiro Nomura Kazunori Takeuchi Masayuki Nakatani Kiyoharu Matsuura Haruaki Horiuchi Yusuke Arai Tsuyoshi 《Journal of Radioanalytical and Nuclear Chemistry》2019,322(3):1273-1277
Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate... 相似文献
2.
Recently, we developed a convenient microfluidic droplet generation device based on vacuum‐driven fluid manipulation with a piezoelectric diaphragm micropump. In the present study built on our previous work, we investigate the influence of settings applied to the piezoelectric pump, such as peak‐to‐peak drive voltage (Vp‐p) and wave frequency, on droplet generation characteristics. Stepwise adjustments to the drive voltage in ±10‐Vp‐p increments over the range of 200?250 Vp‐p during droplet creation revealed that the droplet generation rate could be reproducibly controlled at a specific drive voltage. The droplet generation rate switched within <0.5 s after the input of a new voltage. Although the droplet generation rate depended on the drive voltage, this setting had almost no influence on droplet size. The frequency over the selected range (50?60 Hz) did not markedly influence the droplet generation rate or droplet size. We show that the current fluid manipulation system can be conveniently used for both droplet generation and for rapid droplet reading, which is required in many microfluidic‐based applications. 相似文献
3.
Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis
Yuya Nakatsuji Yusuke Kobayashi Yoshiji Takemoto 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(40):14253-14257
The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity. 相似文献
4.
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
5.
Guangrui Chen Yuxing Yan Dr. Jie Wang Prof. Yong Sik Ok Guiyuan Zhong Prof. Bu Yuan Guan Prof. Yusuke Yamauchi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19831-19836
Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition. 相似文献
6.
7.
Noboru Nakatani 《Optical Review》2003,10(4):206-210
This paper describes a compulsorily phase locked differential interferometer using an orthogonally polarized light source of a modulated LD with high extinction ratio to reduce non-linearity of the interferometer caused by polarization cross-talk. The current modulated LD is used as a light source to make the interferometer compact and for the scanning phase of the interferometer. The interferometer is operated compulsorily at the maximum inclination point of the fringe intensity curve by fringe scanning and an electric system. A Wollaston prism of high extinction ratio (50 dB) is used to combine the polarizing beams and to make the polarization cross-talk very small. In one light source the polarized output beams are on the same propagation axis; in the other they have a small crossing angle (2.5 mrad ∼ 10 mrad) to completely exclude non-linearity of the interferometer causded by polarization cross-talk. Using jets of a gas mixture of nitrogen and ethylene, this interferometer was demonstrated to be useful in detecting the photothermal effect of a photothermal velocimeter under phase fluctuation in a turbulent flow. 相似文献
8.
The potential of an N-Troc-protected sialic acid donor, equipped with phenylsulfenyl functionality as a leaving group, has been explored. As a result, the entitled donor was proven to be highly reactive and to have broad applicability toward the synthesis of variant sialo-glycans, which have N-glycolyl, de-N-acetyl, 1,5-lactam and 8-O-sulfo sialic acid analogs. 相似文献
9.
The paper presents the first report on χ(2) polarization induced in molecular glass of conjugated compound by all-optical poling. Transparent thin film of molecular glass of 1,4-bis[2-[4-[N,N-di(p-tolyl)amino]phenyl]vinyl]benzene (BTAPVB) was prepared using a spin-cast technique. Dipolar as well as octupolar components in BTAPVB contributed to the formation of photoinduced χ(2) polarization. Growth rate of χ(2) polarization has good linear relation with Eω4E2ω, which suggested that the simultaneous processes of two-photon (ω + 2ω) and three-photon (ω + ω + ω) excitation on the same electronic level contributed to the formation of photoinduced χ(2) polarization. 相似文献
10.
(Triisopropylsilyl)acetaldehyde dimethyl acetal (TIPS-ADMA) was synthesized from chlorotriisopropylsilane in three steps. Cyclic and acyclic 1,2-diols can be transformed to (triisopropylsilyl)ethylidene acetals (TIPS-AA). Removal of the acetal by LiBF4 regenerates the starting diol in excellent yield even in the presence of an acetonide of 1,2-diol. The TIPS-AA group can survive under the deprotection conditions of the acetonide in acetic acid at 80 °C. Selective protection of 2,3- and 4,6-diols for O-methyl d-mannoside with TIPS-ADMA and selective deprotection of the acetals have been achieved. 相似文献