全文获取类型
收费全文 | 967篇 |
免费 | 61篇 |
国内免费 | 12篇 |
专业分类
化学 | 1010篇 |
晶体学 | 1篇 |
综合类 | 3篇 |
数学 | 1篇 |
物理学 | 25篇 |
出版年
2024年 | 3篇 |
2023年 | 21篇 |
2022年 | 117篇 |
2021年 | 85篇 |
2020年 | 62篇 |
2019年 | 50篇 |
2018年 | 58篇 |
2017年 | 53篇 |
2016年 | 51篇 |
2015年 | 57篇 |
2014年 | 32篇 |
2013年 | 48篇 |
2012年 | 45篇 |
2011年 | 44篇 |
2010年 | 24篇 |
2009年 | 35篇 |
2008年 | 31篇 |
2007年 | 35篇 |
2006年 | 26篇 |
2005年 | 24篇 |
2004年 | 20篇 |
2003年 | 20篇 |
2002年 | 12篇 |
2001年 | 8篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1998年 | 5篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 5篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 2篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1040条查询结果,搜索用时 9 毫秒
1.
The structure of the strongly cytotoxic marine alkaloid halitulin (1) has been confirmed by total synthesis and its absolute configuration determined as (15S). The synthesis follows a strategy previously reported by one of us and uses an efficient preparation of the quinoline-7,8-diol unit by modified Baeyer-Villiger and Skraup reactions. The O-benzyl protecting groups were removed in the last step of the synthesis by transfer hydrogenolysis without concomitant reduction of the quinoline ring. The method can be applied for the synthesis of halitulin analogues. 相似文献
2.
Paolo Davoli 《Tetrahedron》2005,61(18):4427-4436
The enantioselective total synthesis of the actin-targeting metabolite (−)-microcarpalide is described. Key steps include ring-closing metathesis (RCM) for the final construction of the 10-membered lactone framework and stereoselective homologation of boronic esters for the insertion of all stereocentres with the desired absolute configuration. In particular, the acidic fragment was prepared in seven steps from a suitable chiral bromomethane boronate by means of two sequential stereoselective homologations to install the two stereocentres with the correct final R stereochemistry, employing (−)-pinanediol as the chiral director. Subsequent elaboration to the required C7 backbone entailed nucleophilic displacement with a vinyl Grignard reagent, oxidative cleavage of the boronic scaffold and protection-deprotection manipulations. Interestingly, when the tribenzyloxy diene ester resulting from DCC-mediated coupling of the two key synthons was subjected to RCM in the presence of Grubbs' catalyst, the reaction proceeded stereoselectively to yield the desired trans oxecin-2-one, albeit with poor conversion. 相似文献
3.
T. L. Clemens L. J. Fraher J. L. H. O'Riordan C. J. Little A. Dale 《Chromatographia》1980,13(3):141-144
Summary A simple, reproducible method for the biological synthesis of tritiated 24,25-dihydroxycholecalciferol, 25,26-dihydroxycholecalciferol and 1,25-dihydroxycholecalciferol is described. Kidney homogenates from both vitamin D deficient and replete chicks were usedin vitro to generate these dihydroxylated metabolites using 25 (23,24-3H) hydroxycholecalciferol as the substrate. Tritiated products were purified by Sephadex LH 20 chromatography followed by high-performance liquid chromatography; the identity of each metabolite was established by chromatography with authentic crystalline preparations.Presented at the Symposium organised by the Chromatography Discussion Group, held at Hatfield Lodge on 29 November 1979. 相似文献
4.
Bastien Cochereau Laurence Meslet-Cladire Yves Franois Pouchus Olivier Grovel Catherine Roullier 《Molecules (Basel, Switzerland)》2022,27(10)
In nature, living organisms produce a wide variety of specialized metabolites to perform many biological functions. Among these specialized metabolites, some carry halogen atoms on their structure, which can modify their chemical characteristics. Research into this type of molecule has focused on how organisms incorporate these atoms into specialized metabolites. Several families of enzymes have been described gathering metalloenzymes, flavoproteins, or S-adenosyl-L-methionine (SAM) enzymes that can incorporate these atoms into different types of chemical structures. However, even though the first halogenation enzyme was discovered in a fungus, this clade is still lagging behind other clades such as bacteria, where many enzymes have been discovered. This review will therefore focus on all halogenation enzymes that have been described in fungi and their associated metabolites by searching for proteins available in databases, but also by using all the available fungal genomes. In the second part of the review, the chemical diversity of halogenated molecules found in fungi will be discussed. This will allow the highlighting of halogenation mechanisms that are still unknown today, therefore, highlighting potentially new unknown halogenation enzymes. 相似文献
5.
Jaqueline Cornejo-Campos Yenny Adriana Gmez-Aguirre Jos Rodolfo Velzquez-Martínez Oscar Javier Ramos-Herrera Carolina Estefanía Chvez-Murillo Francisco Cruz-Sosa Carlos Areche Emmanuel Cabaas-García 《Molecules (Basel, Switzerland)》2022,27(12)
Acanthocereus tetragonus (L.) Hummelinck is used as an alternative food source in some Mexican communities. It has been shown that the young stems of A. tetragonus provide crude protein, fiber, and essential minerals for humans. In this work, we analyzed the phytochemical profile, the total phenolic content (TPC), and the antioxidant activity of cooked and crude samples of A. tetragonus to assess its functional metabolite contribution to humans. The phytochemical profile was analyzed using Ultra-High-Performance Liquid Chromatography coupled to High-Resolution Mass Spectrometry (UHPLC-PDA-HESI-Orbitrap-MS/MS). Under the proposed conditions, 35 metabolites were separated and tentatively identified. Of the separated metabolites, 16 occurred exclusively in cooked samples, 6 in crude samples, and 9 in both crude and cooked samples. Among the detected compounds, carboxylic acids, such as threonic, citric, and malic acids, phenolic acids, and glycosylated flavonoids (luteolin-O-rutinoside) were detected. The TPC and antioxidant activity were analyzed using the Folin–Ciocalteu method and the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical inhibition method, respectively. The TPC and antioxidant activity were significantly reduced in the cooked samples. We found that some metabolites remained intact after the cooking process, suggesting that A. tetragonus represents a source of functional metabolites for people who consume this plant species. 相似文献
6.
Changyao Shan Baishu Li Li Li Beibei Li YongLin Ren Tao Liu 《Molecules (Basel, Switzerland)》2022,27(14)
The metabolites produced by the larvae of Bactrocera dorsalis (Diptera: Tephritidae) exposed to different doses of irradiation were analyzed using solid phase microextraction (SPME) and gas chromatography-mass spectrometry (GC-MS), and a metabonomic analysis method of irradiated insects based on GC-MS was established. The analysis revealed 67 peaks, of which 23 peaks were identified. The metabolites produced by larvae treated with different irradiation doses were compared by multivariate statistical analysis, and eight differential metabolites were selected. Irradiation seriously influenced the fatty acid metabolic pathway in larvae. Using the R platform combined with the method of multivariate statistical analysis, changes to metabolite production under four irradiation doses given to B. dorsalis larvae were described. Differential metabolites of B. dorsalis larvae carried chemical signatures that indicated irradiation dose, and this method is expected to provide a reference for the detection of irradiated insects. 相似文献
7.
R. G. Stebbins T. Roy T. R. Doane 《International journal of environmental analytical chemistry》2013,93(3):127-137
Abstract The 1-ethylmonocarboxylic acid of Malathion (MCA) was identified as a metabolite of Malathion in the gut of golden shiners (N. Chrysoleucas) (7.11 × 102±0.66 × 102 ng/g tissue). As noted in the literature the rate of hydrolysis of Malathion above pH 7 is first order with respect to Malathion and pH dependent. In addition, the rate of hydrolysis of Malathion in aquaria housing these fish was found to be dependent on the concentration of Ca+2; sparging the aquaria with air affected the rate. Some of the hydrolysis products of Malathion were identified by gc/ms and found to be pH dependent above pH 7. The half-life of Malathion under different conditions, the identification of some hydrolytic products and a general scheme for the analysis of Malathion, along with some of its metabolic and hydrolytic products are included in this paper. 相似文献
8.
《Analytical letters》2012,45(20):2537-2549
Abstract The structure of the derivative formed during the reaction of 1,3-dimethyluric acid, the major metabolite of theophylline in humans, with iodopropane was elucidated. GC-MS analysis indicated the presence of a single dipropylated product even though three positional isomers are possible. The stability of the product was lower than anticipated since one of the alkyl groups added was readily removed by acid hydrolysis. Carbon-13 NMR proved to be the most useful technique for establishing the positions of alkylation. Assignment of carbon-13 resonances were consistent with placement of propyl groups on N-7 and on the oxygen at C-8. The structure of the product was assigned as 1,3-dimethyl-7-(1-propyl)-8-(1-propyloxy)xanthine. This O-alkylated structure is unusual since most heterocycles that can exist as lactim-lactam tautomers alkylate primarily on ring nitrogens. 相似文献
9.
《Analytical letters》2012,45(11):697-707
Abstract An analytical procedure based on electron capture gas chromatography for the determination of o,p′-DDD, a drug used for the treatment of Cushing′s syndrome, is presented. Detection of a metabolite, identified as o,p′-DDE, is also described. 相似文献
10.
Taro Amagata Makoto Tanaka Takeshi Yamada Yi-Pei Chen Katsuhiko Minoura Atsushi Numata 《Tetrahedron letters》2013
A continuous investigation of secondary metabolites produced by the sponge-derived fungus, Gymnascella dankaliensis, has yielded a new polyketide tyrosine derivative, dankastatin C (3) and the known steroid, demethylincisterol A3 (4), which was originally found from a Homaxinella marine sponge. The stereostructure of the new compound has been determined based on the analysis of 1D and 2D NMR data. Dankastatin C (3) showed potent cell growth inhibitory activity against the murine P388 cell line. 相似文献