全文获取类型
收费全文 | 7015篇 |
免费 | 152篇 |
国内免费 | 38篇 |
专业分类
化学 | 5556篇 |
晶体学 | 71篇 |
力学 | 96篇 |
数学 | 345篇 |
物理学 | 1137篇 |
出版年
2022年 | 43篇 |
2021年 | 58篇 |
2020年 | 71篇 |
2019年 | 87篇 |
2018年 | 56篇 |
2017年 | 51篇 |
2016年 | 90篇 |
2015年 | 108篇 |
2014年 | 147篇 |
2013年 | 406篇 |
2012年 | 292篇 |
2011年 | 412篇 |
2010年 | 194篇 |
2009年 | 193篇 |
2008年 | 355篇 |
2007年 | 363篇 |
2006年 | 381篇 |
2005年 | 399篇 |
2004年 | 333篇 |
2003年 | 307篇 |
2002年 | 321篇 |
2001年 | 153篇 |
2000年 | 186篇 |
1999年 | 101篇 |
1998年 | 76篇 |
1997年 | 69篇 |
1996年 | 104篇 |
1995年 | 79篇 |
1994年 | 91篇 |
1993年 | 64篇 |
1992年 | 78篇 |
1991年 | 69篇 |
1990年 | 67篇 |
1989年 | 74篇 |
1988年 | 85篇 |
1987年 | 67篇 |
1986年 | 83篇 |
1985年 | 100篇 |
1984年 | 100篇 |
1983年 | 57篇 |
1982年 | 87篇 |
1981年 | 72篇 |
1980年 | 81篇 |
1979年 | 89篇 |
1978年 | 68篇 |
1977年 | 55篇 |
1976年 | 44篇 |
1975年 | 55篇 |
1974年 | 53篇 |
1973年 | 36篇 |
排序方式: 共有7205条查询结果,搜索用时 15 毫秒
51.
Akira Watanabe 《Tetrahedron letters》2004,45(33):6229-6233
Oxovanadium(V)(salen) complex 4 was found to catalyze Meerwein-Ponndorf-Verley cyanation of aliphatic aldehydes with good to high enantioselectivity. This cyanation showed a positive nonlinear effect. 相似文献
52.
Microgel-like poly(allyl methacrylate) (PAMA nanosphere) was prepared by the emulsion polymerization of AMA as the reactive crosslinked polymer nanosphere with abundant pendant allyl groups. The terpolymerization of PAMA nanosphere with allyl benzoate (ABz) and vinyl benzoate (VBz) was conducted in bulk using benzoyl peroxide as initiator at 80 °C. The gelation depended on the feed ABz/VBz molar ratio since the molecular weights of resulting poly(ABz-co-VBz)s that act as the bridges increased with an increase in the mole fraction of VBz in the feed monomer. Beyond the gel point, the sol was rapidly incorporated into the gel and the increasing tendency of the gel fraction became steeper from 70 to 95 mol% of VBz as a reflection of increased chain length of bridge between PAMA nanospheres. Moreover, the swelling ratio became lower with increasing the mole percentage of VBz in the feed monomer. These results would support the preferential incorporation of PAMA nanosphere into the gel and the longer bridge can capture more nanospheres to give a much shrunken gel. 相似文献
53.
Synthesis and photochemical properties of photoactivated antitumor prodrugs releasing 5-fluorouracil
A new family of antitumor prodrugs (1-3) of 5-fluorouracil (5-FU) possessing photolabile 2-nitrobenzyl chromophores have been designed and synthesized to investigate the efficiency and mechanism of photoactivated 5-FU release upon UV-irradiation at lambda(ex)= 365 nm. The photoactivated prodrug 3 derived from conjugation of 2 with a tumor-homing cyclic peptide Cys-Asn-Gly-Arg-Cys (CNGRC) was so designed as to manifest a tumor-targeting function. 相似文献
54.
Takeo Ito Hideki Shirakawa Sakuji Ikeda 《Journal of polymer science. Part A, Polymer chemistry》1974,12(1):11-20
A direct method of simultaneously polymerizing and forming acetylene monomer to produce uniformly thin films of polyacetylene was investigated in terms of catalyst system, catalyst concentration, and polymerization temperature. The best catalyst was a Ti(OC4H9)4–Al(C2H5)3 system (Al/Ti = 3–4) and the critical concentration was 3 mmole/l. of Ti(OC4H9)4. Below the critical concentration, only a solid or a powder was obtained. The configuration of the polymers obtained depends strongly upon the polymerization temperature. Thus an all-cis polymer was obtained at temperatures lower than ?78°C, whereas an all-trans polymer resulted at temperatures higher than 150°C. Observations either in an electron microscope by direct transmission or in a scanning electron microscope showed that the film is composed of an accumulation of fibrils about 200–300 Å in width and of indefinite length. 相似文献
55.
Noboru Matsumura Atsushi Ito Masaaki Tomura Yasuyuki Okumura Kazuhiko Mizuno 《Journal of heterocyclic chemistry》2004,41(1):99-102
Tetraazathiapentalene derivative 1 reacts with heterocumulenes such as diphenylketene (2) and 2‐pyridylisothiocyanate (5) to give heterocycles 3, 6 and 7 with elimination of methylisothiocyanate. The reactions of thiadiazolopyrimidine derivatives 8a‐b with ethoxycarbonyl isothiocyanate (9) and carbon disulfide (11) gives heterocycles 10 and 12 via thermal decomposition of 1:1 cycloadducts C and D which have a hypervalent sulfur. The mechanistic and reactivity features of these reactions are described. 相似文献
56.
Mitsuru Ueda Akira Sato Yoshio Imai 《Journal of polymer science. Part A, Polymer chemistry》1979,17(3):783-787
Catalytic actions of various additives were studied in the polycondensation of di(4-nitrophenyl) isophthalate with bis(4-aminophenyl) ether in N-methyl-2-pyrrolidone, and 1-hydroxybenzotriazole (HOBt) was found to be a highly effective catalyst that yielded high-molecular-weight polyamide. In addition to the polycondensation of the 4-nitrophenyl ester, the polymerization of negatively substituted phenyl esters like di(2,4,5-trichlorophenyl) isophthalate was also accelerated by HOBt. For the HOBt-catalyzed aminolysis of esters a bifunctional concerted mechanism that involves an eight-membered transition state was proposed. 相似文献
57.
Shuntaro Mataka Akira Hosoki Kazufumi Takahashi Masashi Tashiro 《Journal of heterocyclic chemistry》1980,17(8):1681-1685
The reaction of tetrasulfur tetranitride ( 1 ) with various aryl and alkyl benzyl ketones ( 2a-o ), oxindole ( 11 ), benzyl α-pyridyl ketone ( 12 ) and α-phenacylpyridine ( 13 ) afforded the corresponding 1,2,5-thiadiazoles ( 3a-n, 11 and 14 ). The scope and limitations of the above reaction were investigated and the evidences suggesting the radical anion mechanism are presented. 相似文献
58.
The basic primary and scatter dose-spread kernels used for convolution methods are usually produced by Monte Carlo simulations with the interaction point forced to the center of a large water phantom. However, it is still not clear whether such Monte Carlo based kernels allow accurate dose calculations with a wide range of field sizes and depths, especially in thorax phantoms. Using the differential primary and scatter concept, this paper proposes another type of basic kernel, with which perfectly accurate primary and scatter absorbed dose calculations can be performed under conditions that the beam is parallel, the incident beam intensity is uniform within and zero outside the field, and the primary beam attenuation coefficient along raylines is not a function of depth and off-axis distance. 相似文献
59.
Yoshimasa Fukazawa Satoshi Harada Akira Inai Toshiya Okajima 《Tetrahedron letters》1993,34(52):8493-8496
The title compound (2) has been synthesized, the structure and the physical properties of which are investigated by X-ray, spectroscopic analyses, and MO calculations. There exists charge transfer (CT) interaction between the tropylium ion and the facing phenyl ring. From the pKR+ value of 2, it can be clear that the cation 2 is stabilized by the CT interaction. In spite of the presence of bond weakening σ-π orbital mixing, the cation 2 withstands retro[4+4]type bond cleavage, which is quite interesting when compared to a facile cleavage for the congener with anthracene photodimer type structure. 相似文献
60.
Yoshikatsu Ito Meng Ji-Ben Shin Suzuki Yoshitaka Kusunaga Teruo Matsuura Keiichi Fukuyama 《Tetrahedron letters》1985,26(17):2093-2096
In contrast to simple imidazoles, 1-methy1–2,4,5-triphenylimidazole () produced stable oxetane photoadducts - with good efficiency upon irradiation in the presence of benzophenone derivatives - in acetonitrile solution. Irradiation in the solid-phase was also studied. The oxetanes - readily underwent cycloreversion by acid catalysis or by heating. 相似文献