全文获取类型
收费全文 | 1220篇 |
免费 | 75篇 |
国内免费 | 4篇 |
专业分类
化学 | 1044篇 |
晶体学 | 13篇 |
力学 | 20篇 |
数学 | 55篇 |
物理学 | 167篇 |
出版年
2023年 | 16篇 |
2022年 | 20篇 |
2021年 | 27篇 |
2020年 | 30篇 |
2019年 | 26篇 |
2018年 | 38篇 |
2017年 | 19篇 |
2016年 | 55篇 |
2015年 | 41篇 |
2014年 | 66篇 |
2013年 | 71篇 |
2012年 | 106篇 |
2011年 | 149篇 |
2010年 | 70篇 |
2009年 | 64篇 |
2008年 | 94篇 |
2007年 | 73篇 |
2006年 | 66篇 |
2005年 | 53篇 |
2004年 | 54篇 |
2003年 | 49篇 |
2002年 | 30篇 |
2001年 | 16篇 |
2000年 | 10篇 |
1999年 | 6篇 |
1998年 | 8篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 4篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1299条查询结果,搜索用时 15 毫秒
91.
Dr. Chaolu Eerdun Thi Hien Thuy Nguyen Takuya Okayama Satoshi Hisanaga Prof. Dr. Jun-ichiro Setsune 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(22):5777-5786
The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with CuII, NiII, and PdII to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2′-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2′-bipyrrole subunit and an open form with a trans-2,2′-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3′-substituent of the central 2,2′-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C2-symmetric form or a heterohelical open Ci-symmetric form in solution. A theoretical study suggested that the closed form of 1 a Pd was stabilized by the Pd–Pd interaction. Compound 1 a Pd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc+) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm. 相似文献
92.
Dr. Masanori Shigeno Takuya Okawa Masaya Imamatsu Kanako Nozawa-Kumada Yoshinori Kondo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(44):10294-10297
We herein demonstrate that the amide base generated in situ from CsF and N(TMS)3 catalyzes the deprotonative coupling reactions of terminal alkynes with polyfluoroarenes, wherein mono- and dialkynylations occur efficiently for penta- and hexafluorobenzenes, respectively. Tetraalkynylated products could also be synthesized from dialkynylated compounds. 相似文献
93.
Rei Tomifuji Prof. Takuya Kurahashi Prof. Seijiro Matsubara 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(38):8987-8991
The development and use of a multiple-activation catalyst with ion-paired Lewis acid and Brønsted acid in an asymmetric aza-Diels–Alder reaction of simple dienes (non-Danishefsky-type electron-rich dienes) was achieved by utilizing the [FeBr2]+[FeBr4]− combination prepared in situ from FeBr3 and chiral phosphoric acid. Synergistic effects of the highly active ion-paired Lewis acid [FeBr2]+[FeBr4]− and a chiral Brønsted acid are important for promoting the reaction with high turnover frequency and high enantioselectivity. The multiple-activation catalyst system was confirmed using synchrotron-based X-ray absorption fine structure measurements, and theoretical studies. This study reveals that the developed catalyst promoted the reaction not only by the interaction offered by the ion-paired Lewis acid and the Brønsted acid but also noncovalent interactions. 相似文献
94.
Dr. Kevin Pappert Dr. Kateryna Loza Dr. Meital Shviro Dr. Ulrich Hagemann Dr. Marc Heggen Prof. Dr. Rafal E. Dunin-Borkowski Dr. Roland Schierholz Dr. Takuya Maeda Prof. Dr. Kenji Kaneko Prof. Dr. Matthias Epple 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(47):11048-11057
Porous particle superstructures of about 15 nm diameter, consisting of ultrasmall nanoparticles of iridium and iridium dioxide, are prepared through the reduction of sodium hexachloridoiridate(+IV) with sodium citrate/sodium borohydride in water. The water-dispersible porous particles contain about 20 wt % poly(N-vinylpyrrolidone) (PVP), which was added for colloidal stabilization. High-resolution transmission electron microscopy confirms the presence of both iridium and iridium dioxide primary particles (1–2 nm) in each porous superstructure. The internal porosity (≈58 vol%) is demonstrated by electron tomography. In situ transmission electron microscopy up to 1000 °C under oxygen, nitrogen, argon/hydrogen (all at 1 bar), and vacuum shows that the porous particles undergo sintering and subsequent compaction upon heating, a process that starts at around 250 °C and is completed at around 800 °C. Finally, well-crystalline iridium dioxide is obtained under all four environments. The catalytic activity of the as-prepared porous superstructures in electrochemical water splitting (oxygen evolution reaction; OER) is reduced considerably upon heating owing to sintering of the pores and loss of internal surface area. 相似文献
95.
Hiroshi Maejima Yuji Kanetada Hitoshi Sunahori Azusa Murase Takuya Otani Nozomi Sakamoto Osamu Yoshimura Yoshiko Tobimatsu 《Physical Therapy Research》2008,11(1):7-13
The objective of this study was to assess the effect of comprehensive exercise program widely accepted as a community-based physical intervention for the prevention of falling in the elderly persons on their controlling standing balance. Twenty-six community-dwelling elderly persons (13 males and females; 69.8 ± 2.8 years old) participated in this study. Daily exercise was comprised of walking for more than 30 min, stretching, muscle strengthening and balance exercise without exercise equipments. The intervention was continued for three months. Indicators of standing balance related to static balance, dynamic balance and postural response were measured before and after the intervention. As an effect of the intervention on static balance, the sway of center of pressure (COP) in the static stance significantly increased. In the dynamic balance, significant improvements were observed in one leg standing time, the 10-m gait time, functional reach. Additionally, the maximal movable length of COP which subjects can move voluntarily to right and left significantly increased. In the postural response, the integrated electromyography (IEMG) induced by postural response for sudden postural perturbation significantly decreased in the lower leg muscles. Since less muscular activities were sufficient to maintain posture, it was suggested that postural response was elicited more efficiently following the intervention. This study suggested that the comprehensive exercise program, which has been widely introduced as community-based interventions for the prevention of falling, have extensive effects on the control of standing balance covering static balance, dynamic balance and postural response in the elderly persons. 相似文献
96.
Takuya Kawazu Kousuke Torii Hiroyuki Sakaki 《Physica E: Low-dimensional Systems and Nanostructures》2006,32(1-2):226
Landau levels have been theoretically investigated in a two-dimensional electron gas near a quantum dot (QD) layer. By a diagrammatical method, we have formulated the self-energy for the Landau level and deduced its relation to the AC conductivity σloc(ω) in the QD layer. As an example, we have examined the density of states in the case where σloc(ω) is described by AωS(S=0.8). It is found that the Landau levels are broadened due to the interaction with the localized electrons in the QDs. 相似文献
97.
Wen Piao Satoru Tsuda Dr. Yuji Tanaka Dr. Satoshi Maeda Dr. Fengyi Liu Shodai Takahashi Yu Kushida Dr. Toru Komatsu Dr. Tasuku Ueno Dr. Takuya Terai Prof. Toru Nakazawa Prof. Masanobu Uchiyama Prof. Keiji Morokuma Prof. Tetsuo Nagano Dr. Kenjiro Hanaoka 《Angewandte Chemie (International ed. in English)》2013,52(49):13028-13032
98.
Takuya Hashimoto 《Tetrahedron letters》2010,51(4):761-8145
FeCl3/AgOTf-catalyzed hydroarylation of propiolic acid with electron-rich arenes such as mesitylene, tetramethylbenzene, and pentamethylbenzene in trifluoroacetic acid proceeded to give 3-arylpropenoic acids in moderate to high yields. The same reactions with anisole and 1,4-dimethoxybenzene afforded double hydroarylation products, 3,3-diarylpropionic acids. 相似文献
99.
Lembehsterols A and B,novel sulfated sterols inhibiting thymidine phosphorylase,from the marine sponge Petrosia strongylata 总被引:1,自引:0,他引:1
Aoki S Naka Y Itoh T Furukawa T Rachmat R Akiyama S Kobayashi M 《Chemical & pharmaceutical bulletin》2002,50(6):827-830
Lembehsterols A (1) and B (2), two novel sulfated sterols, were isolated from the marine sponge Petrosia strongylata. Both sterols showed inhibitory activity against thymidine phosphorylase, which is an enzyme related to angiogenesis in solid tumors. The structures of these sulfated sterols were established on the basis of chemical and physicochemical evidence. 相似文献
100.
Matsumoto T Kominami T Ueda K Sugimoto T Tada T Noguchi S Yoshino H Murata K Shiro M Negishi E Toyota N Endo S Takahashi K 《Inorganic chemistry》2002,41(18):4763-4769
The 2:1 charge-transfer (CT) salts (1(2).FeBr(4) and 1(2).GaBr(4)) of ethylenedithiotetrathiafulvalenoquinone-1,3-dithiolemethide (1) with FeBr(4)(-) and GaBr(4)(-) counteranions were obtained as needle crystals, whose structures are almost the same as each other. The 1 molecules form a one dimensionally stacked column with alternation of their molecular axis direction, while the counteranions are aligned in parallel with the 1-stacked columns with the direction of their distorted-tetrahedral geometry maintained. The room-temperature electrical conductivities measured on the single crystals of 1(2).FeBr(4) and 1(2).GaBr(4) were 4.6 and 2.1 S cm(-1), respectively. From the temperature dependences of their electrical conductivities in both cases the electrical conducting properties were metallic between ca. 170 and 300 K, but below ca. 170 K converted to be semiconducting and continued till 5 K, although the activation energies are very small (4-10 meV). For 1(2).FeBr(4) very weak and antiferromagnetic interaction occurred between the d spins of FeBr(4)(-) ions in the temperature range of ca. 1-300 K. However, below ca. 15 K the ferromagnetic interaction was reversely preferential possibly by participation of the pi spin of 1. 相似文献