全文获取类型
收费全文 | 1049篇 |
免费 | 43篇 |
专业分类
化学 | 847篇 |
晶体学 | 4篇 |
力学 | 8篇 |
数学 | 17篇 |
物理学 | 216篇 |
出版年
2023年 | 6篇 |
2022年 | 8篇 |
2021年 | 13篇 |
2020年 | 22篇 |
2019年 | 22篇 |
2018年 | 15篇 |
2017年 | 9篇 |
2016年 | 17篇 |
2015年 | 25篇 |
2014年 | 28篇 |
2013年 | 40篇 |
2012年 | 63篇 |
2011年 | 77篇 |
2010年 | 36篇 |
2009年 | 32篇 |
2008年 | 56篇 |
2007年 | 73篇 |
2006年 | 66篇 |
2005年 | 64篇 |
2004年 | 60篇 |
2003年 | 48篇 |
2002年 | 36篇 |
2001年 | 35篇 |
2000年 | 19篇 |
1999年 | 11篇 |
1998年 | 3篇 |
1997年 | 6篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 10篇 |
1987年 | 10篇 |
1986年 | 12篇 |
1985年 | 30篇 |
1984年 | 14篇 |
1983年 | 5篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1979年 | 13篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 6篇 |
排序方式: 共有1092条查询结果,搜索用时 15 毫秒
11.
Abstract— As a model for studies involving biologic systems, rates of hematoporphyrin and protopor-phyrin-sensitized photooxidation of tryptophan were measured in water-methanol mixtures. Absorption and fluorescence-emission spectra associated with solutions of porphyrins in different water-methano! mixtures were also examined. The optimal rate of photooxidation by hematoporphyrin occurred in 30% methanol; by protoporphyrin, in 60% methanol. Absorption spectra were examined to characterize dispersion of hematoporphyrin into monomeric form in 90% methanol, and the dimer formation which predominates in 30% methanol. With the more hydrophobic protoporphyrin, an absorption spectrum characteristic of drug monomer was seen in 100% methanol, a dimer spectrum was observed in 60% methanol. At methanol concentrations < 60%, we observed impaired photooxidation and another alteration in the absorption pattern apparently reflecting drug aggregation beyond the dimer stage. Fluorescence emission maxima of both porphyrins were blue-shifted with increasing solvent dielectric constant, but an additional blue shift was detected in an aqueous environment which was apparently related to porphyrin aggregation. Absorption and fluorescence-emission spectra appear helpful for characterizing environmental determinants of porphyrin-sensitized photooxidation. 相似文献
12.
Five new natural labdane-type diterpenoids (5-9), designated leoheteronins A-E, together with four known diterpenoids (1-4), two phytosterols as a mixture of beta-sitosterol and stigmasterol, and the flavone genkwanin (10) were isolated from the aerial parts of Leonurus heterophyllus SW. (Lamiaceae) collected in northern Vietnam. Compound 1 was isolated for the first time from a Leonurus species, and 10 is considered to be a chemotaxonomic marker of the Leonurus genus. Their structures were determined using spectroscopic analyses. 相似文献
13.
A sensitive assay for acyl CoA-cholesterol acyltransferase (EC 2.3.1.26) in rat liver microsomal and mitochondrial preparations is described. The lowered cholesterol concentration in the enzyme reaction with oleoyl CoA is determined spectrofluorimetrically by using the cholesterol oxidase/peroxidase/p-hydroxyphenylpropionic acid system. The assay requires as little as 20 μg of protein in the enzyme preparation. 相似文献
14.
Tsuyoshi Otsuka 《Tetrahedron letters》2004,45(12):2643-2647
A novel and efficient oxidative dimerization of 1-naphthols 1 with dioxygen in the presence of several semiconductors including SnO2, ZrO2, and activated charcoal as catalytic mediators took place selectively to give the corresponding 2,2′-binaphthols 2 or 2,2′-binaphthyl-1,1′-quinones 3 in excellent yields without light irradiation. Among these semiconductors, the catalytic activity of SnO2 could be fully restored by appropriate reactivation treatment after oxidation. The products 2 and 3 should be useful as synthetic intermediates for natural binaphthyls. 相似文献
15.
Eight 1,2-diarylethylenediamines in the meso- or DL-form produce fluorescence when heated with reducing carbohydrates in an alkaline medium. Of the diamines, meso-1,2-bis(4-methoxyphenyl)ethylenediamine is the most favourable reagent for reducing carbohydrates, including 2- deoxy sugars, amino sugars and sialic acids. The reagent permits the fluorimetric determination of reducing carbohydrates at concentrations as low as 0.2–0.9 nmol ml?1. 相似文献
16.
Ooi Y Hobara D Yamamoto M Kakiuchi T 《Langmuir : the ACS journal of surfaces and colloids》2005,21(24):11185-11189
In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates. 相似文献
17.
Staphylionosides A-K: megastigmane glucosides from the leaves of Staphylea bumalda DC 总被引:1,自引:0,他引:1
Chemical investigation of leaves of Staphylea bumalda DC., collected in the suburbs of Hiroshima City, afforded 11 new megastigmane glucosides, named staphylionosides A-K (3-13), along with two known megastigmane glucosides (1, 2). The relative structures were elucidated from spectroscopic evidence, and the absolute structures of the aglycones were determined by means of the combination of beta-D-glucosylation-induced shift-trends and the modified Mosher's method. 相似文献
18.
From the leaves of Alangium paltanifolium var. platanifolium, collected in Fukuoka Prefecture, twelve further megastigmane glycosides were isolated. Seven of them, named platanionosides D-J (1-7), were found to be new compounds. Their structures were elucidated from spectroscopic evidence and their absolute structures were determined from beta-D-glucosylation-induced shift trends of 13C-NMR and by application of a modified Mosher's method. 相似文献
19.
Nakamura Y O-kawa K Nishimura T Yashima E Nishimura J 《The Journal of organic chemistry》2003,68(8):3251-3257
The optical resolution of trans-2 and trans-3 [60]fullerene bisadducts with an inherent chiral addition pattern, modified by Bingel reaction, cycloaddition by benzyne, Prato reaction, and cycloaddition by o-quinodimethane, was systematically investigated by using chiral HPLC columns (Chiralcel OD and Chiralpak AD). The chiroptical properties of enantiomers separated were also examined. 相似文献
20.
Makoto Yuasa Aritomo Yamaguchi Kenichi Oyaizu Yosuke Fujito Mizuki Kitao Tsuyoshi Sato 《先进技术聚合物》2005,16(9):702-705
meso‐Substituted cobalt porphyrins adsorbed on carbon black were prepared as catalysts for the electroreduction of O2. The catalyst, which was prepared by using a homogenizer in mixing cobalt tetraethylporphyrin and carbon black, gave rise to electroreduction of O2 at a remarkably positive potential (Ep = 0.45 V versus saturated calomel electrode (SCE)) and showed a high selectively for the four‐electron reduction (n = 3.8). Electrochemical study and extended X‐ray absorption fine structure (EXAFS) analysis revealed that the adsorbed face‐to‐face dimeric aggregates of cobalt porphyrin molecules were highly efficient catalysts for electroreduction of O2. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献