全文获取类型
收费全文 | 1181篇 |
免费 | 39篇 |
国内免费 | 4篇 |
专业分类
化学 | 905篇 |
晶体学 | 11篇 |
力学 | 12篇 |
数学 | 50篇 |
物理学 | 246篇 |
出版年
2022年 | 6篇 |
2021年 | 10篇 |
2020年 | 18篇 |
2019年 | 16篇 |
2018年 | 15篇 |
2017年 | 9篇 |
2016年 | 27篇 |
2015年 | 20篇 |
2014年 | 27篇 |
2013年 | 60篇 |
2012年 | 65篇 |
2011年 | 71篇 |
2010年 | 35篇 |
2009年 | 42篇 |
2008年 | 75篇 |
2007年 | 67篇 |
2006年 | 74篇 |
2005年 | 62篇 |
2004年 | 66篇 |
2003年 | 52篇 |
2002年 | 43篇 |
2001年 | 20篇 |
2000年 | 26篇 |
1999年 | 15篇 |
1998年 | 16篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 13篇 |
1994年 | 24篇 |
1993年 | 9篇 |
1992年 | 24篇 |
1991年 | 9篇 |
1990年 | 12篇 |
1989年 | 11篇 |
1988年 | 11篇 |
1986年 | 7篇 |
1985年 | 19篇 |
1984年 | 17篇 |
1983年 | 11篇 |
1982年 | 10篇 |
1981年 | 11篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1974年 | 5篇 |
1973年 | 5篇 |
1972年 | 5篇 |
1970年 | 5篇 |
排序方式: 共有1224条查询结果,搜索用时 78 毫秒
21.
A cationic CpRu(II) complex in combination with quinaldic acid shows high reactivity and chemoselectivity for the catalytic deprotection of hydroxyl groups protected as allyl ethers. The catalyst operates in alcoholic solvents without the need for any additional nucleophiles, satisfying the practical requirements of operational simplicity, safety, and environmental friendliness. The wide applicability of this deprotection strategy to a variety of multifunctional molecules, including peptides and nucleosides, may provide new opportunities in protective group chemistry. [structure: see text] 相似文献
22.
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
23.
24.
Tsai P Ichikawa K Mailer C Pou S Halpern HJ Robinson BH Nielsen R Rosen GM 《The Journal of organic chemistry》2003,68(20):7811-7817
Apparent rate constants, at acidic pH and neutral pH for the reaction of a family of ester-containing 5-carboxyl-5-methyl-1-pyrroline N-oxides with superoxide (O2*-) were estimated, using ferricytochrome c as a competitive inhibitor. It was of interest to note that the rate constants were similar among the different nitrones and not that significantly different from that found for 5-(diethoxyphosphoryl)-5-dimethyl-1-pyrroline N-oxide. At acidic pH, the rate constant for spin trapping O2*- was 3-fold greater than that at physiological pH. Subsequent experiments determined the half-life of aminoxyls, derived from the reaction of these nitrones with O2*-. The EPR spectra were modeled by using a global analysis method. The results clearly demonstrated that EPR spectra of all the aminoxyls were inconsistent with a model that included a single gamma-hydrogen splitting. A better interpretation modeled them as two diastereomers with identical nitrogen splittings and slightly different beta-hydrogen splittings. Detailed line width analyses slightly favored an equal line width-unequal population ratio for the two diastereomers. 相似文献
25.
[reaction: see text] The Sc(OTf)3/FERRODIOL (2) complex was prepared at -78 degrees C in CH2Cl2 in the presence of 2,6-lutidine and MS 4A. The chiral scandium Lewis acid-catalyzed asymmetric Diels-Alder reaction of cyclopentadiene (3) with 3-acyloxazolidin-2-ones (4) effectively produced the adduct (5) in a high yield with good selectivity, i.e., endo/exo = 90:10 up to 91% ee (endo). 相似文献
26.
Yoshiyasu Ichikawa Yohei Matsukawa Mari Tamura Fumiyo Ohara Minoru Isobe Hiyoshizo Kotsuki 《化学:亚洲杂志》2006,1(5):717-723
A new method for the synthesis of urea‐linked disaccharides in aqueous media has been developed. The key feature of our approach is two strained Steyermark‐type gluco‐ and galactopyranosyl oxazolidinones. Each oxazolidinone is attached to a pyranose ring in a di‐equatorial trans‐annulation framework. Reaction of these oxazolidinones with 4‐aminohexopyranose in water proceeded smoothly to afford the urea‐tethered cellobiose and lactose analogues. The galactose‐type oxazolidinone proved to be more reactive than the glucose‐type, which is explained by the presence of an axial hydroxy group at C4 in the former. 相似文献
27.
High-performance liquid chromatographic procedure for the simultaneous determination of norfloxacin, fenbufen and felbinac in rat plasma 总被引:1,自引:0,他引:1
Y Katagiri K Naora N Ichikawa M Hayashibara K Iwamoto 《Chemical & pharmaceutical bulletin》1989,37(10):2858-2860
A high-performance liquid chromatographic method for the simultaneous determination of norfloxacin, fenbufen and felbinac extracted from 50 microliters of rat plasma is described. Chromatography was performed on a reversed-phase column with ultraviolet detection. By the present method, quantitative and reproducible determinations were possible for norfloxacin, fenbufen and felbinac over the concentration ranges of 0.2-20, 0.2-120 and 0.4-40 micrograms/ml, respectively. The recoveries of norfloxacin, fenbufen and felbinac added to plasma were nearly 100% with a coefficient of variation of less than 8.0%. This method was found to be applicable to pharmacokinetic studies of each drug after the concomitant administration of norfloxacin and fenbufen. 相似文献
28.
Ichikawa K Shimomura N Yamada M Ohkubo N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3235-3241
In vitro biomimetic mineralization by means of nanotechnology allows the formation of calcium carbonate polymorphs at low temperatures (<25 degrees C) under a CO(2) atmosphere of 500-1500 ppm. A two-dimensional zinc-ion ordered array (zinc array), which acts as an active-site mimic of carbonic anhydrase, has been prepared by immersing the self-organized monolayer of 3-(2-imidazolin-1-y)propyltriethosilane on mica (ImSi substrate) into aqueous zinc solution. The zinc array mounted on the ImSi substrate catalyzed the conversion from CO(2) to HCO(3) (-), and accelerated the formation of calcium carbonate. In situ X-ray diffraction data of the formed calcium carbonate on the poly(L-aspartate)-coated chitin substrate (pAsp substrate), with calcium ion-recognition sites, demonstrated that the interaction between the zinc array and pAsp substrates formed both vaterite and calcite at low temperature (15 degrees C) and mainly vaterite at 25 degrees C; this interaction also controlled the morphology of calcium carbonate formed on pAsp substrate. 相似文献
29.
Sahara R Ichikawa H Mizuseki H Ohno K Kubo H Kawazoe Y 《The Journal of chemical physics》2004,120(19):9297-9301
A Monte Carlo simulation is carried out to study thermodynamic properties of Cu-Au alloys using a face-centered-cubic (fcc) lattice-gas model. To obtain quantitatively accurate results, a Finnis-Sinclair-type potential, which has been widely used for molecular dynamics (MD) simulations, is employed. To overcome some shortcomings of lattice-gas models such as neglecting vibrational entropy, the potential is mapped onto the fcc lattice using the renormalization technique. The renormalized potential gives an improved Cu-Au phase diagram compared to the original MD potential applied directly on the lattice. 相似文献
30.
The nature of the complex europium carbonate ion in concentrated carbonate solution was studied polarographically. A polarographic method for the determination of micro amounts of europium ion in the presence of diverse ions (and especially lanthanides) was developed. 相似文献