全文获取类型
收费全文 | 325篇 |
免费 | 12篇 |
国内免费 | 1篇 |
专业分类
化学 | 236篇 |
晶体学 | 11篇 |
力学 | 4篇 |
数学 | 19篇 |
物理学 | 68篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 4篇 |
2020年 | 5篇 |
2019年 | 2篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 10篇 |
2015年 | 5篇 |
2014年 | 9篇 |
2013年 | 18篇 |
2012年 | 26篇 |
2011年 | 28篇 |
2010年 | 14篇 |
2009年 | 11篇 |
2008年 | 21篇 |
2007年 | 18篇 |
2006年 | 17篇 |
2005年 | 20篇 |
2004年 | 19篇 |
2003年 | 14篇 |
2002年 | 14篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 9篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1994年 | 5篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1988年 | 3篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有338条查询结果,搜索用时 31 毫秒
101.
102.
Takafumi Mori Tungalag Dong Kouji Yazawa Yoshio Inoue 《Macromolecular rapid communications》2007,28(21):2095-2099
Films of an α‐cyclodextrin/poly(ε‐caprolactone) inclusion complex have been successfully prepared and show high transparency and heat resistance in comparison to the pure polymer film. The physical properties, such as transparency, mechanical properties, and thermal stability, of the α‐CD‐PCL‐IC films are found to depend on the α‐cyclodextrin‐to‐polymer stoichiometry.
103.
Pressure‐based unified solver for gas‐liquid two‐phase flows where compressible and incompressible flows coexist 下载免费PDF全文
We propose a pressure‐based unified solver for gas‐liquid two‐phase flows where compressible and incompressible flows coexist. Unlike the original thermo–Cubic Interpolated Propagation Combined Unified Procedure (CIP‐CUP) method proposed by Himeno et al (Transactions of the Japan Society of Mechanical Engineers, Series B, 2003), we split the advection term of the governing equations into a conservation part and into the rest. The splitting of advection term has two advantages. One is the high degree of freedom in choosing discretization schemes such as central‐difference schemes, upwind schemes, and Total Variation Diminishing (TVD) schemes. The other is the ease of implementation on unstructured grids. The advantages enable the analyses of various flows such as turbulent and supersonic ones in actual complicated boundaries. Therefore, the solver is useful for practical analyses. The solver was validated on the following test cases: subsonic single‐phase flows, incompressible single‐phase turbulent flows, and incompressible gas‐liquid two‐phase flows. With unstructured grids, we obtained the equivalent results as the ones with structured grids. After the validations, subsonic jet impinging on a water pool was calculated and compared with experimental results. It was confirmed that the calculated results were consistent with the experimental ones. 相似文献
104.
Coupling Reaction of Enol Derivatives with Silyl Ketene Acetals Catalyzed by Gallium Trihalides 下载免费PDF全文
Dr. Yoshihiro Nishimoto Yuji Kita Hiroki Ueda Hiroto Imaoka Kouji Chiba Prof. Dr. Makoto Yasuda Prof. Dr. Akio Baba 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(33):11837-11845
A cross‐coupling reaction between enol derivatives and silyl ketene acetals catalyzed by GaBr3 took place to give the corresponding α‐alkenyl esters. GaBr3 showed the most effective catalytic ability, whereas other metal salts such as BF3?OEt2, AlCl3, PdCl2, and lanthanide triflates were not effective. Various types of enol ethers and vinyl carboxylates as enol derivatives are amenable to this coupling. The scope of the reaction with silyl ketene acetals was also broad. We successfully observed an alkylgallium intermediate by using NMR spectroscopy, suggesting a mechanism involving anti‐carbogallation among GaBr3, an enol derivative, and a silyl ketene acetal, followed by syn‐β‐alkoxy elimination from the alkylgallium. Based on kinetic studies, the turnover‐limiting step of the reaction using a vinyl ether and a vinyl carboxylate involved syn‐β‐alkoxy elimination and anti‐carbogallation, respectively. Therefore, the leaving group had a significant effect on the progress of the reaction. Theoretical calculations analysis suggest that the moderate Lewis acidity of gallium would contribute to a flexible conformational change of the alkylgallium intermediate and to the cleavage of the carbon?oxygen bond in the β‐alkoxy elimination process, which is the turnover‐limiting step in the reaction between a vinyl ether and a silyl ketene acetal. 相似文献
105.
Hiroyuki Kamata Anatoly Zinchenko Shizuaki Murata 《Colloid and polymer science》2011,289(12):1329-1335
The effects of anionic and cationic nanoparticles (15 and 100 nm in diameter) on the stability of the secondary structure
of DNA were studied in DNA denaturation and renaturation processes. The results showed that DNA denaturation is greatly inhibited
in the presence of cationic nanoparticles. In contrast, in the presence of even large amounts of anionic nanoparticles, the
DNA melting transition occurs at the original melting temperature. The effects of the size and concentration of nanoparticles
on DNA denaturation are discussed. 相似文献
106.
A high‐voltage rectangular pulse was applied to the electro‐spray deposition (ESD) to control the evaporation‐induced self‐assembly of poly(3‐hexylthiophene‐2,5‐diyl) (P3HT). Two groups of P3HT thin films were deposited by a series of high‐voltage rectangular pulses. Compared with the ESD driven by a constant voltage, the pulse‐driven ESD enables to probe the effect of solvent evaporation on the self‐assembly of P3HT molecules. The droplet size and the evaporation of residual solvent in the droplet determine the film morphology. Ultraviolet–visible absorption spectroscopy was used to identify the ordering of P3HT molecules in the films. The self‐assembly of P3HT molecules took place during the solvent evaporation which can be controlled by a combination of the pulse amplitude and the pulse interval. With an appropriate combination of the amplitude and the interval, the ESD produced a P3HT thin film with high chain ordering.
107.
A Basic Germanodecatungstate with a −7 Charge: Efficient Chemoselective Acylation of Primary Alcohols 下载免费PDF全文
Kosei Sugahara Naoto Satake Dr. Keigo Kamata Dr. Takahito Nakajima Prof. Dr. Noritaka Mizuno 《Angewandte Chemie (International ed. in English)》2014,53(48):13248-13252
The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ‐Keggin germanodecatungstate, [γ‐HGeW10O36]7? ( A ), having a ?7 charge was, for the first time, successfully synthesized by the reaction of [γ‐H2GeW10O36]6? with one equivalent of [(n‐C4H9)4N]OH under non‐aqueous conditions. The activities of germanodecatungstates for base‐catalyzed reactions dramatically increased with increase in the number negative charges from ?6 to ?7. In the presence of A , various combinations of acylating agents and primary alcohols including those with acid‐sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions. 相似文献
108.
Kouji Chiba Toshiyuki Hirano Fumitoshi Sato Masahiro Okamoto 《International journal of quantum chemistry》2013,113(21):2345-2354
This article reports the proton tautomerization effects of distal histidine residues in carbonmonoxy myoglobin according to the density functional calculations of the whole protein. The electron eigenstates and electrostatic potential (ESP) distributed around heme and its pocket vary significantly depending on the protonation positions of the distal histidine residues. To investigate the range over which the electronic structures are affected by the proton tautomerization, the quantum mechanics/molecular mechanics (QM/MM) method is applied to probe the QM size to reproduce the atomic partial charges and ESP around the active center. Consequently, we show that these properties converged for the 300 pm QM/MM system in this study. During the analysis, we also find that amino residues such as Phe43, Val68, and Phe138 interact strongly with heme through orbital mixing, indicating that the protein is a medium not only interacting with the reaction center, but also buffering on electrons. © 2013 Wiley Periodicals, Inc. 相似文献
109.
Jyunichi Koyanagi Katsumi Yamamoto Kouji Nakayama Akira Tanaka 《Journal of heterocyclic chemistry》1994,31(5):1303-1304
Phthalic anhydride in THF was added to 3-lithiofuran 2 in THF to give 3,3-di-(3-furyl)-1,3-dihy-droisobenzofuran-1-one 4 . On the other hand, 2 in THF was added to phthalic anhydride in THF to give 2-(3-furanoyl)benzoic acid 3 by the inverse addition method. Further, the parent naphtho[2,3-b]furan-4,9-dione 1 was obtained from the reaction of 3 with two equimolar amounts of LDA. 相似文献
110.
We present the result of our accurate measurements of the a- and b-axis resistivity (ρa and ρb), magnetoconductivity Δσ/σ, Hall coefficient RH, and the a-axis thermopower Sa in untwinned YBa2Cu3Oy single crystals in a wide range of doping (6.45≤y≤7.0). The systematics of our data reveals a number of novel 60-K-phase anomalies in the charge transport: (i) temperature dependences of ρa show anomalous overlap below ∼130 K for 6.65≤y≤6.80, (ii) Hall mobility μH shows an enhancement near y?6.65, which is reflected in an anomalous y dependence of σxy, (iii) with decreasing temperature RH shows a marked drop upon approaching Tc only in samples with 6.70≤y≤6.85, (iv) superconducting fluctuation magnetoconductivity is anomalously enhanced near y?6.7, and (v) Hc2 is anomalously reduced near y?6.70. We discuss that the fluctuating charge stripes might be responsible for these anomalies in the charge transport. 相似文献