全文获取类型
收费全文 | 1044篇 |
免费 | 17篇 |
国内免费 | 6篇 |
专业分类
化学 | 738篇 |
晶体学 | 11篇 |
力学 | 13篇 |
数学 | 49篇 |
物理学 | 256篇 |
出版年
2022年 | 9篇 |
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 25篇 |
2018年 | 20篇 |
2017年 | 13篇 |
2016年 | 16篇 |
2015年 | 16篇 |
2014年 | 28篇 |
2013年 | 41篇 |
2012年 | 40篇 |
2011年 | 69篇 |
2010年 | 42篇 |
2009年 | 23篇 |
2008年 | 64篇 |
2007年 | 49篇 |
2006年 | 60篇 |
2005年 | 50篇 |
2004年 | 49篇 |
2003年 | 39篇 |
2002年 | 41篇 |
2001年 | 31篇 |
2000年 | 17篇 |
1999年 | 12篇 |
1998年 | 8篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 11篇 |
1994年 | 17篇 |
1993年 | 14篇 |
1992年 | 14篇 |
1991年 | 13篇 |
1990年 | 14篇 |
1989年 | 12篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 19篇 |
1985年 | 17篇 |
1984年 | 13篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 12篇 |
1980年 | 12篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 12篇 |
1976年 | 9篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1972年 | 4篇 |
排序方式: 共有1067条查询结果,搜索用时 595 毫秒
111.
112.
Akihiko Takagi Xiobin Peng Takuya Matsumoto Atsuhiro Osuka Tomoji Kawai 《Surface science》2007,601(10):2178-2181
Conformations of two dodecameric porphyrin wheels adsorbed on a Cu(1 0 0) were probed by using scanning tunneling microscopy (STM). Whereas a wheel consisting of six meso-meso linked diporphyrins was detected as uniform ring structure, several different images with three discrete molecular heights were detected for a wheel consisting of six meso-meso, β-β,β-β triply-linked planar diporphyrins. These results indicate that the former has a conformation similar to that in a free space, while the latter has various conformations with respect to orientation of planar diporphyrin units toward the metal surface. Several discrete STM images of the latter have been interpreted in terms of possible eight conformations, which vary as to relative orientation of neighboring diporphyrin units. 相似文献
113.
114.
Dr. Aya Yoshimura Yuki Takamachi Prof. Dr. Li‐Biao Han Prof. Dr. Akiya Ogawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):13930-13933
An efficient metal‐free diboration of terminal alkynes is reported. In the presence of a catalytic amount of organosulfides under light, the addition of bis(pinacolato)diboron (B2pin2) to terminal alkynes takes place efficiently to produce the corresponding double borylation products in good yields. Mechanistic studies indicate that this metal‐free sulfide‐catalyzed diboration of alkynes likely occurs by generation of a boryl‐centered radical with the aid of light and a sulfide, since such a radical was detected in the reaction mixture by electron spin resonance (ESR) spectroscopy. The present form of catalysis (sulfide/light) is thought to be unprecedented and provides a new means of preparation for organoboranes without heavy metal contamination in the products, which is highly desired in the preparation of drugs and electronic materials. 相似文献
115.
Aya Yoshimura Akihiro Nomoto Mari Uchida Hiroki Kusano Tomokazu Saeki Akiya Ogawa 《Research on Chemical Intermediates》2017,43(6):3433-3443
The functionalization of polysilanes is an important subject in materials science because functionalized polysilanes are expected to exhibit potentially innovative properties. This research aims at the addition of a water-shedding property to polysilanes by introducing perfluoroalkyl groups into their skeleton. The photoinduced iodoperfluoroalkylation of various vinylsilanes takes place successfully upon irradiation with a xenon lamp: vinylmonosilanes undergo iodoperfluoroalkylation with perfluoroalkyl iodides (RfI) regioselectively, and the corresponding perfluoroalkylated silanes are obtained in moderate to high yields. Detailed optimization of the photoinduced iodoperfluoroalkylation has been investigated to apply this method to the functionalization of polysilanes. Polysilanes having vinyl groups can be synthesized by the reductive coupling of dichlorovinylsilanes with samarium diiodide (SmI2) and samarium metal (Sm) upon irradiation with visible light. The synthesized vinylpolysilanes and RfI (about 1.0 mM CHCl3 solution) are coated on a glass plate sequentially, and then the following photoirradiation with light of a wavelength over 300 nm successfully adds an excellent water-shedding property to the glass plate. 相似文献
116.
Shin-ichi Matsuoka Shintaro ShimakawaKoji Takagi Masato Suzuki 《Tetrahedron letters》2011,52(50):6835-6838
The head-to-tail dimerization of methacrolein via the conjugate addition of methanol is catalyzed by various organic bases, such as an amine, phosphine, and N-heterocyclic carbene, to give 2,4-dimethyl-2-methoxymethylpentane-1,5-dial in moderate yields. Based on the interpretation of the key intermediates by electrospray ionization mass spectrometry, we propose a reaction mechanism involving the initial conjugate addition of the organic bases to methacrolein to generate a zwitterionic base followed by the activation of methanol. 相似文献
117.
Liu B Nakata K Sakai M Saito H Ochiai T Murakami T Takagi K Fujishima A 《Langmuir : the ACS journal of surfaces and colloids》2011,27(13):8500-8508
A facile new method that combines electrospray and hydrothermal treatment is used to prepare mesoporous core-shell TiO(2) spheres with high specific surface areas and high pore volumes. Interestingly, the resulting TiO(2) spheres are composed of anatase TiO(2) nanocrystals with exposed step-like {001} and smooth {010} facets. The percentage of exposed {001} facets can be adjusted by changing the experimental parameters used in the electrospray and hydrothermal treatment processes, such as the contents of poly(N-vinyl-2-pyrrolidone) and acetic acid. The combination of high specific surface area (>100 m(2) g(-1)), high pore volume (>0.30 cm(3) g(-1)), useful pore size (10-15 nm), spherical core-shell structure, and exposed high energy facets makes these TiO(2) spheres an important candidate for use in many photoelectrochemical applications. The formation mechanism of the mesoporous TiO(2) spheres is also studied. The great advantage of this method is that interesting and complicated mesoporous superstructures can be prepared using electrospray technology. 相似文献
118.
Doi T Shibata K Yoshida M Takagi M Tera M Nagasawa K Shin-ya K Takahashi T 《Organic & biomolecular chemistry》2011,9(2):387-393
Total synthesis of the (S)-stereoisomer of telomestatin (1) was accomplished. (S)-Telomestatin exhibited potency four times that of the natural product, (R)-telomestatin, which was the most potent telomerase inhibitor previously reported. In the circular dichroism spectral analysis of the complexes possessing randomly structured single-stranded d[TTAGGG](4) oligonucleotide, (S)-telomestatin, like (R)-telomestatin, induced an antiparallel G-quadruplex structure. The melting temperature (T(m)) value of the (S)-isomer complex was greater than that of the (R)-telomestatin complex. Therefore, it is concluded that the stereochemistry of the thiazoline of telomestatin is important to the binding ability of a G-quadruplex binder, and (S)-telomestatin as a G-quadruplex binder is more potent than the natural product. 相似文献
119.
Benzynes were generated from o-(trimethylsilyl)phenols using nonafluorobutanesulfonyl fluoride (NfF) by a domino process, i.e., the nonaflation of the phenolic hydroxyl group of o-(trimethylsilyl)phenols by NfF followed by the attack of the produced fluoride ion on the trimethylsilyl group. The generated benzyne immediately underwent various reactions to give polysubstituted benzenes. 相似文献
120.
Ishida Y Shimada T Masui D Tachibana H Inoue H Takagi S 《Journal of the American Chemical Society》2011,133(36):14280-14286
The quantitative excited energy transfer reaction between cationic porphyrins on an anionic clay surface was successfully achieved. The efficiency reached up to ca. 100% owing to the "Size-Matching Rule" as described in the text. It was revealed that the important factors for the efficient energy transfer reaction are (i) suppression of the self-quenching between adjacent dyes, and (ii) suppression of the segregated adsorption structure of two kinds of dyes on the clay surface. By examining many different kinds of porphyrins, we found that tetrakis(1-methylpyridinium-3-yl) porphyrin (m-TMPyP) and tetrakis(1-methylpyridinium-4-yl) porphyrin (p-TMPyP) are the suitable porphyrins to accomplish a quantitative energy transfer reaction. These findings indicate that the clay/porphyrin complexes are promising and prospective candidates to be used for construction of an efficient artificial light-harvesting system. 相似文献