全文获取类型
收费全文 | 677篇 |
免费 | 28篇 |
国内免费 | 3篇 |
专业分类
化学 | 515篇 |
晶体学 | 7篇 |
力学 | 5篇 |
数学 | 27篇 |
物理学 | 154篇 |
出版年
2022年 | 3篇 |
2020年 | 8篇 |
2019年 | 9篇 |
2018年 | 8篇 |
2016年 | 17篇 |
2015年 | 16篇 |
2014年 | 12篇 |
2013年 | 32篇 |
2012年 | 29篇 |
2011年 | 38篇 |
2010年 | 15篇 |
2009年 | 19篇 |
2008年 | 37篇 |
2007年 | 28篇 |
2006年 | 45篇 |
2005年 | 35篇 |
2004年 | 32篇 |
2003年 | 28篇 |
2002年 | 28篇 |
2001年 | 20篇 |
2000年 | 27篇 |
1999年 | 11篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1996年 | 9篇 |
1995年 | 10篇 |
1994年 | 11篇 |
1993年 | 5篇 |
1992年 | 15篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1989年 | 9篇 |
1988年 | 12篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 15篇 |
1984年 | 17篇 |
1983年 | 9篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 4篇 |
1979年 | 7篇 |
1978年 | 4篇 |
1976年 | 3篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1970年 | 4篇 |
1967年 | 2篇 |
1966年 | 3篇 |
排序方式: 共有708条查询结果,搜索用时 15 毫秒
1.
2.
The acute influences of arsenic compounds on the metabolism of porphyrins and heme in various organs of rats after oral or intratracheal administration of disodium arsenate (Na2HAsO4) and gallium arsenide (GaAs) were examined and compared. For the oral administration experiments, 21 or 84 mg of Na2HAsO4, or 2 or 4 g of GaAs, per cm3 saline per kg body weight of each animal was administered to Jcl: Wistar male rats and the organs were removed after exsanguination from the vein of the right axilla under anesthesia with ether, 16 h after administration. In the case of intratracheal administration, rats given 8.2 or 16.4 mg of Na2HAsO4, or 0.2 or 0.4 g GaAs per cm3 saline per kg body weight were examined under the same experimental conditions as for the administration route. Increase in the body weight of rats was suppressed after intratracheal administration of the two arsenic compounds. In these rats the hematocrit value increased significantly. These changes were not shown by the orally administered rats. Elevation in δ-aminolevulinate synthase (ALA-S, EC 2.3.1.37) activity in erythroblasts by Na2HAsO4 was much higher after intratracheal administration than after oral administration. Suppression in the activities of δ-aminolevulinate dehydratase (ALA-D, EC 4.2.1.24) and porphobilinogen deaminase (PBG-D, EC 4.3.1.8) in peripheral erythrocytes by Na2HAsO4 and GaAs were stronger by intratracheal administration than by the oral route. Influences of GaAs on the activity of PBG-D in rat liver were shown to be more effective by oral administration than by the intratracheal route. Oral administration of Na2HAsO4 and GaAs had a stronger suppression effect on the activities of ALA-D and PBG-D in rat kidney. It seems from these results that the different extents of the influence of arsenic compounds might depend on the routes of intake. 相似文献
3.
HPLC determination of (+)-pseudoephedrine and (-)-ephedrine in Japanese herbal medicines containing Ephedra herb using solid-phase extraction 总被引:2,自引:0,他引:2
Ichikawa M Udayama M Imamura K Shiraishi S Matsuura H 《Chemical & pharmaceutical bulletin》2003,51(6):635-639
We developed a rapid and simple HPLC method combined with solid-phase extraction (SPE) for quantitative analysis of (+)-pseudoephedrine (PEP) and (-)-ephedrine (EP) in Japanese herbal (Kampo) medicines such as Kakkon-to, Sho-seiryu-to, Goshaku-san and Bofu-tsusho-san. SPE was performed on TOYOPAK IC-SP M containing propylsulfonic groups. Determination of PEP and EP was carried out using ion-pair reversed-phase HPLC with sodium dodecyl sulfate. N-Benzyldiethylamine was used as an internal standard. The analytical procedure was validated with regard to specificity, linearity, accuracy, and precision. These data suggest that the analytical method developed in this study is useful for quantitative analysis of PEP and EP in various formulations of Kampo medicine containing Ephedra herb. 相似文献
4.
5.
6.
The H2 and CH4 chemical ionization mass spectra of a series of series of substituted benzoic acids and substituted benzyl alcohols have been determined. For the benzoic acids the major fragmentation reactions of the protonated molecule involve elimination of H2O or elimination of CO2, the latter reaction involving migration of the carboxylic hydrogen to the aromatic ring. For the benzyl alcohols the major fragmentation reactions of [MH]+ involve loss of H2O or CH2O, analogous to the CO2 elimination reaction for the benzoic acids. It is shown that the CO2 and CH2O elimination reactions occur only when a conjugated aromatic ring system is present, and that for the carboxylic acid systems, methyl groups and, to a lesser extent, phenyl groups are capable of migrating. The only discernible effect of substituents on the fragmentation of [MH]+ is an enhancement of the H2O loss reaction in the benzoic acid system when an amino, hydroxyl, or halogen substituent is ortho to the carboxyl function. This ‘ortho’ effect, which differs in scope from that observed in electron impact mass spectra, is attributed to an intramolecular catalysis by the ortho substituent of the 1,3 hydrogen migration in the carbonyl protonated acid followed by H2O elimination. Apparently, this route is favoured over the direct elimination of H2O from the carbonyl protonated acid, since the latter has a high activation energy barrier because of unfavourable orbital symmetry restrictions. 相似文献
7.
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
8.
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
9.
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
10.
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