全文获取类型
收费全文 | 1127篇 |
免费 | 35篇 |
国内免费 | 2篇 |
专业分类
化学 | 1004篇 |
晶体学 | 11篇 |
力学 | 9篇 |
数学 | 38篇 |
物理学 | 102篇 |
出版年
2022年 | 9篇 |
2021年 | 8篇 |
2020年 | 15篇 |
2019年 | 16篇 |
2018年 | 10篇 |
2017年 | 11篇 |
2016年 | 18篇 |
2015年 | 18篇 |
2014年 | 39篇 |
2013年 | 60篇 |
2012年 | 64篇 |
2011年 | 82篇 |
2010年 | 34篇 |
2009年 | 50篇 |
2008年 | 78篇 |
2007年 | 65篇 |
2006年 | 76篇 |
2005年 | 81篇 |
2004年 | 73篇 |
2003年 | 56篇 |
2002年 | 51篇 |
2001年 | 25篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 11篇 |
1997年 | 11篇 |
1996年 | 7篇 |
1995年 | 10篇 |
1994年 | 13篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 9篇 |
1986年 | 4篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 9篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 12篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1975年 | 9篇 |
1974年 | 6篇 |
1966年 | 2篇 |
排序方式: 共有1164条查询结果,搜索用时 31 毫秒
81.
Haino T Yamanaka Y Araki H Fukazawa Y 《Chemical communications (Cambridge, England)》2002,(5):402-403
The metal-induced regulation of fullerene complexation with double-calix[5]arene is described. The receptor shows strong binding to C70 only in the presence of Cu+. 相似文献
82.
[reaction: see text] D-Mannono-1,4-lactone was efficiently converted into L-ribose in eight steps. A key step of this synthesis is the cyclization of a gamma-hydroxyalkoxamate under Mitsunobu conditions. It is noteworthy that the O-alkylation product was obtained in 94% yield and that none of the N-alkylation product was detected in this cyclization. 相似文献
83.
84.
Masao Doi 《Journal of Polymer Science.Polymer Physics》1980,18(5):1005-1020
The primitive chain model of Doi and Edwards is generalized to include the short-time relaxation process. Stress relaxation after a sudden imposition of strain is studied in detail. It is shown that in the linear region (small strain) stress relaxation occurs in two steps, the relaxation of chain segments between the fixed entanglement points, and the relaxation of the entanglement points, in accordance with the conventional picture, whereas in the nonlinear region (large strain) there appears a new relaxation process between the above two. The characteristic time of this process is the Rouse relaxation time which the entire chain would have if there were no entanglements, and increases with the square of the molecular weight. This result is consistent with experimental observations. 相似文献
85.
Kaihara S Osanai Y Nishikawa K Toshima K Doi Y Matsumura S 《Macromolecular bioscience》2005,5(7):644-652
The enzymatic transformation into an oligomer was carried out with the objective of developing the chemical recycling of bacterial polyesters. Poly(R-3-hydroxyalkanoate)s (PHAs), such as poly[(R-3-hydroxybutyrate)-co-12%(R-3-hydroxyhexanoate)] and poly[(R-3-hydroxybutyrate)-co-12%(R-3-hydroxyvalerate)], were degraded by granulated Candida antarctica lipase B immobilized on hydrophilic silica (lipase GCA) in a diluted organic solvent at 70 degrees C. The degradation products were cyclic oligomers having a molecular weight of a few hundreds. The obtained cyclic oligomer was readily repolymerized by the same lipase (lipase GCA) to produce the corresponding polyester in a concentrated solution. The cyclic oligomer was copolymerized with epsilon-caprolactone using lipase to produce the corresponding terpolymers having an Mw of 21,000. This is the first example of the enzymatic chemical recycling of bacterial PHAs using lipase. Poly(R-3-hydroxybutyrate) [P(3HB)] was also degraded into the linear-type R-3HB monomer to trimer by P(3HB)-depolymerase (PHBDP) in phosphate buffer at 37 degrees C. The degradation using PHBDP required a longer reaction time compared with the lipase-catalyzed degradation in organic solvent. The monomer composition of the oligomer depended on the origin of the PHBDP. The R-3HB monomer was predominately produced by PHBDP from Pseudomonas stutzeri, while the R-3HB dimer was produced by PHBDP from Alcaligenes faecalis T1. Repolymerization of these oligomers by lipase in concentrated organic solvent produced a relatively low-molecular-weight P(3HB) (e.g., Mw=2,000). Degradation of P(3HB) by lipase in organic solvent into repolymerizable cyclic oligomer and degradation of P(3HB) by PHBDP in buffer into hydroxy acid type R-3HB dimer. 相似文献
86.
Nakano H Takahashi K Okuyama Y Senoo C Tsugawa N Suzuki Y Fujita R Sasaki K Kabuto C 《The Journal of organic chemistry》2004,69(21):7092-7100
Cationic palladium (Pd)- and platinum (Pt)-phosphinooxazolidine catalysts 13a-c, 15a-d, 17a-c, and 19a-c were prepared from phosphinooxazolidine ligands 1-3, MCl(2) (M = Pd and Pt), and counterions, and the activities of the catalysts in the asymmetric Diels-Alder (DA) reactions of cyclic or acyclic dienes with imide dienophiles were investigated. These catalysts demonstrated high levels of catalytic activity. The cationic Pd-POZ complex 13c provided particularly excellent enantioselectivity (98% ee) in the DA reactions of cyclopentadiene with acryloyl-, crotonyl-, and fumaroyl-1,3-oxazolidin-2-ones (20a-c). 相似文献
87.
Novel spirocyclic trichothecanes, spirotenuipesine A and B, isolated from entomopathogenic fungus, Paecilomyces tenuipes 总被引:8,自引:0,他引:8
Kikuchi H Miyagawa Y Sahashi Y Inatomi S Haganuma A Nakahata N Oshima Y 《The Journal of organic chemistry》2004,69(2):352-356
Entomopathogenic fungi forming fruiting bodies have been employed as tonics and antitussives from ancient times. Paecilomyces tenuipes, which is also called Isaria japonica, is a very popular entomopathogenic fungus and is often considered a health food in northeast Asian countries such as China, Korea, and Japan. We cultivated the fruiting bodies of Paecilomyces tenuipes. Among the large-scale cultivations, fruiting body grown in barley grain contained two novel spirocyclic trichothecane derivatives, spirotenuipesine A (1) and B (2), and known trichothecane mycotoxins. Compounds 1 and 2 showed potent activity in neurotrophic factor biosynthesis in glial cells. The isolation of these compounds indicated that P. tenuipes is a promising source for producing various biologically active substances including trichothecanes. It is noteworthy that trichothecane mycotoxins are present in Paecilomyces tenuipes, which is typically used in medicinal health food. 相似文献
88.
In order to examine the reason why the magnitude of the synergistic effect observed in the extraction of lanthanoids(III) with a β-diketone and a monodentate Lewis base generally decreases along with increasing atomic number, the hydration number of the extracted species when lanthanoids(III) are extracted with TTA (2-thenoyltrifluoroacetone, HA) and benzoic acid (HB) into chloroform by Karl Fischer titration and the enthalpy change in complexation between LnA3 and HB by calorimetric titration were determined across the lanthanoid series at 25 °C.It has been concluded that since the decrement of entropy change caused by the change in the number of released water molecules and in the coordination number of lanthanoids(III) upon complexation is larger than the increment of the enthalpy change, the values of the second formation constants of the complexes decrease with increasing the atomic number across lanthanoid series so that the magnitude of the synergistic extraction decreases with increasing the atomic number. 相似文献
89.
Studer A Amrein S Matsubara H Schiesser CH Doi T Kawamura T Fukuyama T Ryu I 《Chemical communications (Cambridge, England)》2003,(10):1190-1191
4-[(Trimethylstannyl)diphenylsilyl]butanoyl radical, arising from the corresponding 3-(stannylsilyl)propyl radical and CO, undergoes an SHi reaction at Si with extrusion of trimethyltin radical to give silacyclopentanone. The parent 3-(stannylsilyl)propyl radical was also found to isomerize to (3-stannylpropyl)silyl radical via a 1,4-Sn shift from Si to C with a rate constant of 9.3 x 10(4) s-1 at 80 degrees C. Ab initio and DFT MO calculations support a front-side attack mechanism. 相似文献
90.
Wang NH Taniguchi M Tsuji D Doi M Ohishi H Yoza K Baba K 《Chemical & pharmaceutical bulletin》2003,51(1):68-70
Four new guaianolides, sinodielides A-D (1-4), were isolated from Sinodielsia yunnanensis WOLFF together with a known polyacetylene, falcarindiol, and two known coumarins, bergapten and scopoletin. Their structures were established by spectral and X-ray analyses. 相似文献