全文获取类型
收费全文 | 1000篇 |
免费 | 15篇 |
国内免费 | 5篇 |
专业分类
化学 | 775篇 |
晶体学 | 18篇 |
力学 | 6篇 |
数学 | 52篇 |
物理学 | 169篇 |
出版年
2023年 | 2篇 |
2022年 | 4篇 |
2021年 | 5篇 |
2020年 | 4篇 |
2019年 | 10篇 |
2018年 | 7篇 |
2017年 | 7篇 |
2016年 | 14篇 |
2015年 | 12篇 |
2014年 | 24篇 |
2013年 | 54篇 |
2012年 | 52篇 |
2011年 | 41篇 |
2010年 | 25篇 |
2009年 | 51篇 |
2008年 | 72篇 |
2007年 | 69篇 |
2006年 | 81篇 |
2005年 | 79篇 |
2004年 | 73篇 |
2003年 | 49篇 |
2002年 | 40篇 |
2001年 | 12篇 |
2000年 | 21篇 |
1999年 | 16篇 |
1998年 | 9篇 |
1997年 | 9篇 |
1996年 | 17篇 |
1995年 | 10篇 |
1994年 | 8篇 |
1993年 | 7篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 9篇 |
1984年 | 9篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 12篇 |
1980年 | 12篇 |
1979年 | 13篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 9篇 |
1975年 | 8篇 |
1974年 | 6篇 |
1973年 | 2篇 |
排序方式: 共有1020条查询结果,搜索用时 15 毫秒
61.
The photosynthetic reaction center is an efficient molecular device for the conversion of light energy to chemical energy. In a previous study, we synthesized the hydrogenase/photosystem I (PSI) complex, in which Ralstonia hydrogenase was linked to the cytoplasmic side of Synechocystis PSI, to modify PSI so that it photoproduced molecular hydrogen (H2). In that study, hydrogenase was fused with a PSI subunit, PsaE, and the resulting hydrogenase-PsaE fusion protein was self-assembled with PsaE-free PSI to give the hydrogenase/PSI complex. Although the hydrogenase/PSI complex served as a direct light-to-H2 conversion system in vitro, the activity was totally suppressed by adding physiological PSI partners, ferredoxin (Fd) and ferredoxin-NADP+-reductase (FNR). In the present study, to establish an H2 photoproduction system in which the activity is not interrupted by Fd and FNR, position 40 of PsaE from Synechocystis sp. PCC6803, corresponding to the Fd-binding site on PSI, was selected and targeted for the cross-linking with cytochrome c3 (cytc3) from Desulfovibrio vulgaris. The covalent adduct of cytc3 and PsaE was stoichiometrically assembled with PsaE-free PSI to form the cytc3/PSI complex. The NADPH production by the cytc3/PSI complex coupled with Fd and FNR decreased to approximately 20% of the original activity, whereas the H2 production by the cytc3/PSI complex coupled with hydrogenase from Desulfovibrio vulgaris was enhanced 7-fold. Consequently, in the simultaneous presence of hydrogenase, Fd, and FNR, the light-driven H2 production by the hydrogenase/cytc3/PSI complex was observed (0.30 pmol Hz/mg chlorophyll/h). These results suggest that the cytc3/PSI complex may produce H2 in vivo. 相似文献
62.
Tsuchiya S Sunazuka T Hirose T Mori R Tanaka T Iwatsuki M Omura S 《Organic letters》2006,8(24):5577-5580
K01-0509 B is a novel natural product which contains a carbamoylated cyclic guanidine. Our asymmetric total synthesis features a Sharpless asymmetric epoxidation and a stereocontrolled construction of the cyclic guanidine via an asymmetric nitroaldol reaction, followed by intramolecular SN2 cyclization. These reactions allowed the cyclic guanidine and the adjacent hydroxy group to be assembled, facilitating the asymmetric total synthesis and determination of the absolute stereochemistry of K01-0509 B. [reaction: see text]. 相似文献
63.
Noriyuki Asakura Toshiaki Kamachi Ichiro Okura 《Research on Chemical Intermediates》2006,32(3-4):341-355
The behavior of redox molecules in solution that was not detected by electrochemical techniques was measured by a highly-sensitive electrochemical quartz crystal microbalance (EQCM) technique that has been improved in this study to obtain a high sensitivity of EQCM measurement in solution. The improved EQCM technique allowed to monitor the motion of a redox molecule, that is an access of the molecule to an electrode surface and repulsion from the surface during redox. An EQCM technique currently in use has measured adsorption of redox molecules on an electrode surface or polymerization on the surface caused by a chemical reaction following redox, which exhibits an enough large mass change response to detect with an EQCM measurement. However, access and repulsion of redox molecule, which is a slight motion of the molecule near on electrode surface, has not been detected and investigated by an EQCM technique, because the mass change response seems to be very small. In this study, the redox behavior of methyl viologen on a bare gold surface, pyridinethiol surface and methylpyridinethiol surface was investigated. Although the three electrodes give the same cyclic voltammogram of methyl viologen, the three are different in QCM response recorded at the same time as the voltammetry. Access/repulsion of methyl viologen within an electrical double layer was monitored by the highly-sensitive EQCM technique. 相似文献
64.
Yoshio Kobayashi Tsukasa Shirochi Takafumi Maeda Yusuke Yasuda Toshiaki Morita 《Surface and interface analysis : SIA》2013,45(9):1424-1428
This paper describes a metal–metal bonding technique using metallic Cu nanoparticles prepared in aqueous solution. A colloid solution of metallic Cu particles with a size of 54 ± 15 nm was prepared by reducing Cu2+ (0.01 M (CH3COO)2Cu) with hydrazine (0.6 M) in the presence of stabilizers (5 × 10?4 M citric acid and 5 × 10?3 M cetyltrimethylammonium bromide) in water at room temperature in air. Discs made of metallic materials (Cu, Ni/Cu, or Ag/Ni/Cu) were successfully bonded under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H2 gas with help of the metallic Cu particle powder. Shear strength required for separating the bonded discs was 27.9 ± 3.9 for Cu discs, 28.1 ± 4.1 for Ni/Cu discs, and 13.8 ± 2.6 MPa for Ag/Ni/Cu discs. Epitaxial crystal growth promotes on the discs with a good matching for the lattice constants between metallic nanoparticles and metallic disc surfaces, which leads to strong bonding. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
65.
Copper‐Catalyzed CH Bond Direct Chalcogenation of Aromatic Compounds Leading to Diaryl Sulfides,Selenides, and Diselenides by Using Elemental Sulfur and Selenium as Chalcogen Sources Under Oxidative Conditions 下载免费PDF全文
Prof. Fumitoshi Shibahara Takafumi Kanai Eiji Yamaguchi Akika Kamei Takayuki Yamauchi Prof. Toshiaki Murai 《化学:亚洲杂志》2014,9(1):237-244
The reactions of aromatic compounds and elemental chalcogens catalyzed by a copper salt with molecular oxygen as an oxidant were carried out. The reaction of 3‐substituted imidazo[1,5‐a]pyridines and elemental sulfur in the presence of CuTC (copper(I) thiophenecarboxylate) gave the corresponding bisimidazopyridyl sulfides in good to quantitative yields. The reaction proceeded even under aerobic oxidation conditions. The use of a polar solvent was crucial for the reaction, and DMSO (dimethyl sulfoxide) in particular stimulated the reaction. The reaction could be applied to common aromatic compounds, such as N‐methyl indole and dialkyl anilines. The reaction of indole proceeded at the nucleophilic C3 position rather than at the acidic C2 position. In addition, the reaction of dialkyl anilines proceeded with an ortho, para orientation. The reactions of imidazopyridines and elemental selenium under similar conditions gave the corresponding bisimidazopyridyl diselenides along with bisimidazopyridyl monoselenides. The resulting diselenides were readily converted to the corresponding monoselenides with unreacted imidazopyridines under the same conditions. The reaction could be applied to the copolymerization of bifunctional bisimidazopyridines and elemental sulfur to give oligomeric copolymers in quantitative yield. 相似文献
66.
Toshiaki Ohtsuka Masahide Iida Mikito Ueda 《Journal of Solid State Electrochemistry》2006,10(9):714-720
The polypyrrole coating was prepared from phosphoric acid aqueous solution containing the hetero-polyanion and pyrrole monomer to make new coating for corrosion prevention of carbon steels. The coating thus formed in the phosphate acid solution was doped by and by . The coating was flexible enough to cover the steel homogeneously without cracks, although many cracks were observed on the coating formed in a neutral aqueous solution of Na2MoO2. The 5.1-μm-thick polypyrrole coating makes the steel maintain the passive state for 48 h in neutral 3.5 wt% NaCl solution at pH 5.3 and for 80 h in acidic 3.5 wt% NaCl solution at pH 1.9. The coating decreased the corrosion rate of the steel by 1/200 in the neutral NaCl solution and by 1/340 in the acidic NaCl solution, if compared with the rate of the bare steel. The dissolution current of the steel during the immersion remained at the level of the typical passive current in the respective solutions. 相似文献
67.
Takashi Kosone Chikahide Kanadani Toshiaki Saito Takafumi Kitazawa 《Polyhedron》2009,28(9-10):1930-1934
68.
Vu Quoc Thang Toshiaki Taniike Masaki Umemori Mitsuhiro Ikeya Yuichi Hiraoka Nguyen Duc Nghia Minoru Terano 《大分子反应工程》2009,3(8):467-472
Preservation of initial polymer/catalyst particle morphology under air, was examined using stopped‐flow Ziegler–Natta polymerization with various quenching conditions and post‐chemical treatments. The exposure of the initial particles to air caused the fast formation of cracks on the surface, finally leading to significant reformation of the particle shape, when polymerizing particles were washed with heptane at ?65 °C under N2 or under CO2. On the other hand, when the particles were washed with heptane containing an appropriate amount of tetrahydrofuran under CO2, the particle morphology under air was almost completely maintained even after 1 h exposure. The present results are useful for various ex situ characterizations of unstable initial polymer/catalyst particles.
69.
Blends of polypropylene (PP) and ethylene-octene copolymers (EOC) were investigated by transmission electron microscopy (TEM) and by differential scanning calorimetry (DSC). The EOC contained 28, 37, 40 or 52 wt% of octene. Only the 50/50 PP/EOC ratio was used for all blends. None of the blends was fully miscible, there was always two-phase morphology. TEM observation followed by image analysis by ImageJ software revealed that the largest particles were in blend containing EOC-28 and the smallest were in blend with EOC-52. The coarsening rate at 200 °C was evaluated by TEM. The glass transition temperature (Tg) shift indicated partial miscibility. Partial miscibility was then confirmed by direct observation of bright PP lamellae in EOC dark phase. 相似文献
70.
Zhongqi Xu Toshiaki EsumiNatsuki Ikuta Takeshi Hirokawa 《Journal of chromatography. A》2009,1216(17):3602-3605
In this report aimed on further development of a high-sensitivity capillary gel electrophoresis (CGE) method for analysis of DNA fragments, we firstly explored online transient isotachophoresis (tITP) preconcentration combined with fluorescence detection (FD). The fluorescence signal (excitation: 488 nm; emission: 590 nm) was generated using the intercalating dye of ethidium bromide (EB). It was found when the leading electrolyte (LE) was injected behind the sample zone, such a special tITP mode has significant advantages to solve the bubble formation issue and to improve the analytical performance stability. Two standard DNA samples, a 50 bp DNA step ladder and the φX174/HaeIII digest, were used to evaluate the qualitative and quantitative abilities of the tITP-FD approach. A highly diluted sample (10,000-fold in the water, e.g. the φX174/HaeIII digest diluted from 500 μg/ml to the 50 ng/ml level) was enriched and detected; the LOD was down to 0.09 ng/ml for the 72 bp fragment, apparently improved more than 1000-fold in comparison with UV detection. Although the RSD of peak areas (n = 3) was around 15.5% for the sample was electrokinetically injected, good linearity of peak area response showed that the proposed method is suitable for quantitative analysis. 相似文献