全文获取类型
收费全文 | 260篇 |
免费 | 12篇 |
专业分类
化学 | 232篇 |
力学 | 5篇 |
数学 | 14篇 |
物理学 | 21篇 |
出版年
2022年 | 6篇 |
2021年 | 5篇 |
2020年 | 2篇 |
2019年 | 13篇 |
2018年 | 3篇 |
2017年 | 4篇 |
2016年 | 10篇 |
2015年 | 12篇 |
2014年 | 7篇 |
2013年 | 14篇 |
2012年 | 20篇 |
2011年 | 23篇 |
2010年 | 19篇 |
2009年 | 12篇 |
2008年 | 25篇 |
2007年 | 25篇 |
2006年 | 19篇 |
2005年 | 8篇 |
2004年 | 14篇 |
2003年 | 11篇 |
2002年 | 6篇 |
2001年 | 5篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1996年 | 2篇 |
1993年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有272条查询结果,搜索用时 31 毫秒
51.
52.
A wide array of synthetic methods are described in the literature for the preparation of xanthones—a prominent class of tricyclic molecules that occur widely in nature. Majority of these reported methods involve linking the two aromatic rings and forming the central pyrone ring using a variety of classical and non-classical cyclization strategies. In a conceptually different approach, we describe here a new xanthone synthesis wherein both the pyrone and the second aromatic rings were forged in a single step by an intramolecular cycloaddition reaction involving 2-(1,2-dichlorovinyloxy) aryldienones. 相似文献
53.
Investigation of phenolic acids in yacon (Smallanthus sonchifolius) leaves and tubers 总被引:5,自引:0,他引:5
Simonovska B Vovk I Andrensek S Valentová K Ulrichová J 《Journal of chromatography. A》2003,1016(1):89-98
Thin-layer chromatographic (TLC) screening of crude extracts of dried leaves and tubers of yacon (Smallanthus sonchifolius, Asteraceae) and products of acid hydrolysis of tubers on the silica gel HPTLC plates using the developing solvents ethyl acetate-formic acid-water (85:10:15, v/v/v) and n-hexane-ethyl acetate-formic acid (20:19:1, v/v/v) proved the presence of chlorogenic, caffeic and ferulic acid. These phenolic acids were isolated from the crude extract of yacon leaves by preparative TLC, and identified after elution by HPLC/MS, as well as by direct injection of the crude extract into the HPLC/MS system. Acid hydrolysis of tubers released the increased amount of phenolic acids (e.g. caffeic acid and ferulic acid), flavonoid quercetin and an unidentified flavonoid, which was detected by TLC analysis. Ferulic acid, isomers of dicaffeoylquinic acid and still an unidentified derivative of chlorogenic acid (Mr = 562) as constituents of yacon leaves and ferulic acid as constituent of yacon tubers are reported here for the first time. These acids gave significant contribution to the radical scavenging activity detected directly on the TLC plate sprayed with 1,1-diphenyl-2-picrylhydrazyl (DPPH). 相似文献
54.
Hynes J Doubleday WW Dyckman AJ Godfrey JD Grosso JA Kiau S Leftheris K 《The Journal of organic chemistry》2004,69(4):1368-1371
A survey of several electrophilic ammonia reagents for the N-amination of indole- and pyrrole-containing heterocycles revealed that monochloramine (NH(2)Cl) is an excellent reagent for this transformation. Pyrroles and indoles containing a variety of substitution were aminated on nitrogen with isolated yields ranging from 45% to 97%. 相似文献
55.
Evaluation of two fast and easy methods for pesticide residue analysis in fatty food matrixes 总被引:11,自引:0,他引:11
Two rapid methods of sample preparation and analysis of fatty foods (e.g., milk, eggs, and avocado) were evaluated and compared for 32 pesticide residues representing a wide range of physicochemical properties. One method, dubbed the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method for pesticide residue analysis, entailed extraction of 15 g sample with 15 mL acetonitrile (MeCN) containing 1% acetic acid followed by addition of 6 g anhydrous magnesium sulfate and 1.5 g sodium acetate. After centrifugation, 1 mL of the buffered MeCN extract underwent a cleanup step (in a technique known as dispersive solid-phase extraction) using 50 mg each of C18 and primary secondary amine sorbents plus 150 mg MgSO4. The second method incorporated a form of matrix solid-phase dispersion (MSPD), in which 0.5 g sample plus 2 g C18 and 2 g anhydrous sodium sulfate was mixed in a mortar and pestle and added above a 2 g Florisil column on a vacuum manifold. Then, 5 x 2 mL MeCN was used to elute the pesticide analytes from the sample into a collection tube, and the extract was concentrated to 0.5 mL by evaporation. Extracts in both methods were analyzed concurrently by gas chromatography/mass spectrometry and liquid chromatography/tandem mass spectrometry. The recoveries of semi-polar and polar pesticides were typically 100% in both methods (except that basic pesticides, such as thiabendazole and imazalil, were not recovered in the MSPD method), but recovery of nonpolar pesticides decreased as fat content of the sample increased. This trend was more pronounced in the QuEChERS method, in which case the most lipophilic analyte tested, hexachlorobenzene, gave 27 +/- 1% recovery (n=6) in avocado (15% fat) with a<10 ng/g limit of quantitation. 相似文献
56.
We study the mobility of short ssDNA fragments (approximately 30-500 bases) separated by capillary electrophoresis in entangled polymer solutions. Although this corresponds to what is commonly called the Ogston regime, the corresponding sieving concept has never been defined properly nor tested quantitatively. We consider three formulas that have been suggested to fit data in this range of ssDNA sizes, and we discuss how their free parameters are related to actual physical parameters. We test these formulas with new data obtained in our laboratory using a commercial poly-N,N-dimethylacrylamide sieving matrix. Our results show that all three formulas provide decent fits. However, the traditional Ogston equation produces fitting parameters that appear to lack physical meaning. Surprisingly, all three approaches predict that the effective pore size and fiber radius are almost equal. This is the first step towards the development of a systematic approach to optimizing sequencing systems for this size range. 相似文献
57.
Andreeva A Stoitchkova K Busheva M Apostolova E 《Journal of photochemistry and photobiology. B, Biology》2003,70(3):153-162
The low-temperature (77 K) emission and excitation chlorophyll fluorescence spectra in thylakoid membranes isolated from pea mutants were investigated. The mutants have modified pigment content, structural organization, different surface electric properties and functions [Dobrikova et al., Photosynth. Res. 65 (2000) 165]. The emission spectra of thylakoid membranes were decomposed into bands belonging to the main pigment protein complexes. By an integration of the areas under them, the changes in the energy distribution between the two photosystems as well as within each one of them were estimated. It was shown that the excitation energy flow to the light harvesting, core antenna and RC complexes of photosystem II increases with the total amount of pigments in the mutants, relative to the that to photosystem I complexes. A reduction of the fluorescence ratio between aggregated trimers of LHC II and its trimeric and monomeric forms with the increase of the pigment content (chlorophyll a, chlorophyll b, and lutein) was observed. This implies that the closer packing in the complexes with a higher extent of aggregation regulates the energy distribution to the PS II core antenna and reaction centers complexes. Based on the reduced energy flow to PS II, i.e., the relative increased energy flow to PS I, we hypothesize that aggregation of LHC II switches the energy flow toward LHC I. These results suggest an additive regulatory mechanism, which redistributes the excitation energy between the two photosystems and operates at non-excess light intensities but at reduced pigment content. 相似文献
58.
Gregory B. Kharas Subha Ramnarayan Sonia E. Chavez Ramneek K. Mangat Janet C. Chappell Katerina Chernik 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):275-278
Novel copolymers of trisubstituted ethylene monomers, alkyl and alkoxy ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC6H4CH=C(CN)2 (where R is 2-ethyl, 4-i-propyl, 4-butyl, 4-i-butyl, 4-t-butyl, 2-ethoxy, and 4-hexyloxy) and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C-NMR. The order of relative reactivity (1/r 1) for the monomers is 4-t-butyl (1.45) > 4-i-propyl (1.38) > 2-ethyl (1.37) > 4-hexyloxy (1.33) > 4-i-butyl (1.24) > 2-ethoxy (1.13) > 4-butyl (1.04). High T g of the copolymers, in comparison with that of polystyrene) indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1–10% wt.), which then decomposed in the 500–800°C range. 相似文献
59.
60.
A novel one-pot procedure for the preparation of N,6-disubstituted-1,3,5-triazine-2,4-diamines and its scope of application are demonstrated with a number of examples. The new procedure involves the treatment of isothiocyanates with sodium hydrogencyanamide, followed by amidines in the presence of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride. 相似文献