全文获取类型
收费全文 | 1470篇 |
免费 | 53篇 |
国内免费 | 14篇 |
专业分类
化学 | 1135篇 |
晶体学 | 27篇 |
力学 | 9篇 |
数学 | 67篇 |
物理学 | 299篇 |
出版年
2023年 | 10篇 |
2022年 | 13篇 |
2021年 | 22篇 |
2020年 | 30篇 |
2019年 | 35篇 |
2018年 | 23篇 |
2017年 | 15篇 |
2016年 | 43篇 |
2015年 | 43篇 |
2014年 | 30篇 |
2013年 | 64篇 |
2012年 | 70篇 |
2011年 | 111篇 |
2010年 | 44篇 |
2009年 | 44篇 |
2008年 | 81篇 |
2007年 | 76篇 |
2006年 | 80篇 |
2005年 | 63篇 |
2004年 | 69篇 |
2003年 | 54篇 |
2002年 | 45篇 |
2001年 | 52篇 |
2000年 | 28篇 |
1999年 | 30篇 |
1998年 | 18篇 |
1997年 | 14篇 |
1996年 | 21篇 |
1995年 | 11篇 |
1994年 | 9篇 |
1993年 | 12篇 |
1992年 | 13篇 |
1991年 | 14篇 |
1990年 | 16篇 |
1989年 | 11篇 |
1988年 | 13篇 |
1987年 | 19篇 |
1986年 | 14篇 |
1985年 | 23篇 |
1984年 | 17篇 |
1983年 | 15篇 |
1982年 | 10篇 |
1981年 | 9篇 |
1980年 | 12篇 |
1979年 | 13篇 |
1977年 | 8篇 |
1976年 | 12篇 |
1975年 | 13篇 |
1974年 | 6篇 |
1972年 | 6篇 |
排序方式: 共有1537条查询结果,搜索用时 15 毫秒
51.
Harayama T Akiyama T Nakano Y Nishioka H Abe H Takeuchi Y 《Chemical & pharmaceutical bulletin》2002,50(4):519-522
A palladium-assisted coupling reaction of aryl triflate with arene was investigated, and a novel Pd reagent prepared from equimolar Pd(OAc)2, 1,3-Bis[diphenylphosphino]propane (DPPP), and Bu3P was developed. This method is useful for intramolecular biaryl coupling reactions, not only between aryl triflate and arene (triflate-amide), but also between aryl halide and arene (halo-amide). 相似文献
52.
Chiral cationic palladium[bond]phosphinooxathiane complexes have been found to be effective catalysts for enantioselective Diels-Alder (DA) reaction of cyclopentadiene with acyl-1,3-oxazolidin-2-ones to give the corresponding DA adducts in good yield and high enantioselectivity up to 93% ee. 相似文献
53.
Makoto Kunisada Taro Masaki Ryusuke Ono Hironobu Morinaga Eiji Nakano Flandiana Yogianti Kunihiro Okunishi Hiroshi Sugiyama Chikako Nishigori 《Photochemistry and photobiology》2013,89(3):649-654
The UVA is currently thought to be carcinogenic because, similar to UVB, it induces the formation of cyclobutane pyrimidine dimers (CPDs). Various drugs have been reported to cause photosensitive drug eruptions as an adverse effect. Although the precise mechanism of photosensitive drug eruption remains to be elucidated, it is generally accepted that free radicals and other reactive molecules generated via UV‐irradiated drugs play important roles in the pathogenesis of photosensitive drug eruptions. The waveband of concern for photo‐reactive drugs is UVA‐visible light, but some extend into the UVB region. We tested whether photosensitive drugs could enhance CPD formation after UVA exposure by using isolated DNA in the presence of several reported photosensitive drugs using high‐performance liquid chromatography. We found that the diuretic agent hydrochlorothiazide (HCT) significantly enhanced the production of TT dimers over a wide range of UVA. Furthermore, we investigated whether UVA plus HCT could enhance CPD production in xeroderma pigmentosum model mice defective in nucleotide excision repair. Immunofluorescence studies showed that CPD formation in the skin significantly increased after 365 nm narrow‐band UVA irradiation in the presence of HCT, compared with that in wild‐type mice. HCT could be used with caution because of its enhancement of UVA‐induced DNA damage. 相似文献
54.
O-Glycosylations using thiomethyl glycosides as donors were compared under both frozen and unfrozen conditions. In the presence of MeOTf as a promoter, enormous rate acceleration was observed when the glycosylation was conducted in p-xylene below its freezing point. 相似文献
55.
Nakano S Kitagawa Y Kawakami T Okumura M Nagao H Yamaguchi K 《Molecules (Basel, Switzerland)》2004,9(9):792-807
A possible mechanism for a ferromagnetic interaction in the rhombic (Rh) form of C60 (Rh-C60) is suggested on the basis of theoretical studies in relation to cage distortion of the C60 unit in the polymerized 2D-plane. Band structure calculations on Rh-C60 show that cage distortion leads to competition between diamagnetic and ferromagnetic states,which give rise to the possibility of thermally populating the ferromagnetic state. 相似文献
56.
[structure: see text] Synthesis and fluorescence properties of pi-conjugated compounds having alternately an aromatic ring such as benzene, pyridine, and thiophene and an enediyne unit in the backbone are described. 相似文献
57.
Synthesis and analgesic activity of novel heterocycles, [1]benzothiopyrano[3,4-b]pyrrole derivatives
M Hori T Kataoka H Shimizu E Imai N Iwata N Kawamura M Kurono K Nakano M Kido 《Chemical & pharmaceutical bulletin》1989,37(5):1282-1286
In order to develop analgesic compounds possessing a sulfur atom in the alicyclic ring, novel cis-fused heterocycles, [1]benzothiopyrano[3,4-b]pyrrole derivatives (II) were synthesized via a unique cyclization reaction starting from 4-(4-methoxyphenylthio)-2-butanone (1) or 6-methoxy-3,4-dihydro-2H-1-benzothiopyran-4-one (7). The analgesic effects of benzothiopyranopyrroles (16, 18) were measured by means of the writhing test. The phenolic derivative 18 completely inhibited the appearance of writhing at the dose of 50 mg/kg, but the methoxy derivative 16 had no analgesic effect. 相似文献
58.
Chiral cationic palladium-phosphinooxazolidine catalysts in ionic liquid afforded excellent enantioselectivity in Diels-Alder reactions and the catalyst was easily recycled eight times without any significant decrease in chemical yields or enantioselectivity (89-99%, 88-99% ee). 相似文献
59.
A Kamizono N Inotsume K Miyamoto K Ueda T Miyakawa H Arimoto M Nakano 《Journal of chromatography. A》1991,567(1):113-120
A sensitive and selective method has been developed for the determination of sultopride and tiapride in serum using gas chromatography with a surface ionisation detector. No interfering peaks from endogenous substances were observed. The method showed good reproducibility and accuracy, and the standard curve was linear up to 2 micrograms/ml with a correlation coefficient of 0.999. This method is applicable to pharmacokinetic studies and therapeutic drug monitoring of sultopride and tiapride. 相似文献
60.
Saito S Nakano Y Hikichi A Suzuki R Yoshimoto K Maeda M Aoyama M Shibukawa M 《The Analyst》2011,136(13):2697-2705
Novel fluorescent probes have been developed for the ultratrace detection of heavy metal ions by capillary electrophoresis using laser-induced fluorescence detection. Based on a molecular design, the probes are composed of an octadentate chelating moiety, a macrocyclic DOTA (tetraazacyclododecanetetraacetic acid) and an acyclic DTPA (diethylenetriaminepentaacetic acid) frame, a spacer and a fluorophore (fluorescein). These were chosen on the basis of their ability to form kinetically inert and highly emissive complexes, and to prevent a quenching effect even with heavy and paramagnetic metal ions. Addition of a cationic polymer, polybrene, in the separation buffer provided high resolution and simultaneous detection of Ca(2+), Mg(2+), Cu(2+), Zn(2+), Ni(2+), Co(2+), Mn(2+), Cd(2+) and Pb(2+). The direct fluorescence detection of these metal ions with high sensitivity at lower ppt levels, typically 2-7 × 10(-11) M (potentially sub-ppt), was successfully achieved. While separation of anionic compounds using a counter cation ("Ion Association (IA)" mode) is typically controlled by the ion association equilibrium constants, K(ass), it was found that differences in the mobilities, μ(ep(IAC)), of the ion association complexes formed between the probe complexes and counter cations are the driving forces for separation in this new method. This suggests that each of the polybrene-probe complexes has different chemical structures among metal ions, which were able to be determined by CD spectra in this investigation. This novel separation mode was termed the "Ion Association Complex (IAC)" mode, distinct from the IA mode. 相似文献