全文获取类型
收费全文 | 843篇 |
免费 | 23篇 |
专业分类
化学 | 609篇 |
晶体学 | 8篇 |
力学 | 47篇 |
数学 | 21篇 |
物理学 | 181篇 |
出版年
2021年 | 12篇 |
2020年 | 17篇 |
2019年 | 13篇 |
2018年 | 7篇 |
2017年 | 7篇 |
2016年 | 19篇 |
2015年 | 10篇 |
2014年 | 24篇 |
2013年 | 33篇 |
2012年 | 52篇 |
2011年 | 36篇 |
2010年 | 15篇 |
2009年 | 27篇 |
2008年 | 42篇 |
2007年 | 55篇 |
2006年 | 62篇 |
2005年 | 56篇 |
2004年 | 45篇 |
2003年 | 29篇 |
2002年 | 38篇 |
2001年 | 17篇 |
2000年 | 18篇 |
1999年 | 7篇 |
1998年 | 8篇 |
1997年 | 6篇 |
1996年 | 7篇 |
1994年 | 10篇 |
1993年 | 7篇 |
1992年 | 12篇 |
1991年 | 10篇 |
1990年 | 8篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 13篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 9篇 |
1978年 | 9篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1972年 | 4篇 |
1967年 | 6篇 |
排序方式: 共有866条查询结果,搜索用时 31 毫秒
1.
The European Physical Journal H - The Japanese theoretical physicist Ryogo Kubo made remarkable contributions to statistical mechanics and condensed matter physics, amongst which his name is most... 相似文献
2.
3.
Dr. Christopher R. Opie Dr. Hidetoshi Noda Prof. Dr. Masakatsu Shibasaki Dr. Naoya Kumagai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4648-4653
The B3NO2 six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B3NO2 ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation. 相似文献
4.
Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献
5.
Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule 下载免费PDF全文
Hiroto Noda Dr. Ken Motokura Prof. Dr. Yusuke Wakabayashi Kaori Sasaki Dr. Hiroo Tajiri Dr. Akimitsu Miyaji Dr. Sho Yamaguchi Prof. Dr. Toshihide Baba 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(15):5113-5117
The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO2 surface is discussed based on the interaction between the functionalized SiO2 surface and a probe molecule, p‐formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT‐IR and solid‐state 13C and 11B MAS NMR. For the catalyst exhibiting high 1,4‐addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity. 相似文献
6.
Dr. Xinxin Tang Dr. Hidetoshi Noda Prof. Dr. Masakatsu Shibasaki 《Angewandte Chemie (International ed. in English)》2023,62(51):e202311027
The exponential proliferation of conformers makes it impossible to examine the entire population in most systems. Controlling conformational ensembles is thus pivotal in many areas of chemistry. Rh2(esp)2, a dicarboxylate-derived paddlewheel rhodium complex, is one of the most effective catalysts for nitrene chemistry. Its enormous success has led to preparing many analogous complexes. However, there has been little consideration for the conformational dynamics of the parent catalyst. Herein, we report a new ligand modification principle that prevents conformer interconversion. The resulting complex comprises two isolable conformers, whose structures have been determined by X-ray diffraction. Combined experimental and computational data has revealed similarities and dissimilarities between the conformationally confined and parent complexes. Three model cases have demonstrated the utility of conformational fixation in the development of stereoselective catalysts for nitrene transfer reactions. The design principle described in this study can be combined with other established modification strategies, serving as a springboard for further advancement of the chemistry of paddlewheel metal complexes. 相似文献
7.
Stereoselective catalytic synthesis of 3-trifluoromethyl indolines through the [4+1] cycloaddition of benzoxazinones and sulfur ylides in a transition-metal-free manner was developed. In the presence of a catalytic amount of sodium hydride, aza-ortho-quinone methide intermediates were formed from trifluoromethyl benzoxazinones through decarboxylation after the first nucleophilic attack of sulfur ylides, which progressed to a second nucleophilic attack of sulfur ylides, resulting in the [4+1] cycloaddition. The key for this catalytic transformation is the dual attack of sulfur ylides on substrates. This unique transition-metal-free protocol is applicable to the synthesis of non-fluorinated vinyl-, ethynyl- or methyl-substituted indolines. The synthesis of 3-trifluoromethyl indoles was also achieved described under stoichiometric conditions. 相似文献
8.
Ryo Nozawa Keitaro Yamamoto Prof. Dr. Ji‐Young Shin Prof. Dr. Satoru Hiroto Prof. Dr. Hiroshi Shinokubo 《Angewandte Chemie (International ed. in English)》2015,54(29):8454-8457
Treatment of antiaromatic nickel(II) norcorrole with potassium cyanide provided nickel(II) 3‐cyanonorcorrole with perfect regioselectivity without the help of a catalyst. The reaction of the nickel(II) norcorrole with phenol or thiophenol in the presence of a base also yielded substitution products. The antiaromatic 16π conjugation system in the norcorrole core was preserved in the functionalized products. Introduction of phenylthio groups significantly decreased the HOMO–LUMO gap and enhanced the near IR absorption property. 相似文献
9.
Variation of the stress intensity factor along the front of a 3-D rectangular crack subjected to mixed-mode load 总被引:3,自引:0,他引:3
Summary The singular integral equation method is applied to the calculation of the stress intensity factor at the front of a rectangular
crack subjected to mixed-mode load. The stress field induced by a body force doublet is used as a fundamental solution. The
problem is formulated as a system of integral equations with r
−3-singularities. In solving the integral equations, unknown functions of body-force densities are approximated by the product
of polynomial and fundamental densities. The fundamental densities are chosen to express two-dimensional cracks in an infinite
body for the limiting cases of the aspect ratio of the rectangle. The present method yields rapidly converging numerical results
and satisfies boundary conditions all over the crack boundary. A smooth distribution of the stress intensity factor along
the crack front is presented for various crack shapes and different Poisson's ratio.
Received 5 March 2002; accepted for publication 2 July 2002 相似文献
10.