全文获取类型
收费全文 | 2695篇 |
免费 | 98篇 |
国内免费 | 5篇 |
专业分类
化学 | 2174篇 |
晶体学 | 16篇 |
力学 | 36篇 |
数学 | 227篇 |
物理学 | 345篇 |
出版年
2023年 | 16篇 |
2022年 | 74篇 |
2021年 | 80篇 |
2020年 | 37篇 |
2019年 | 57篇 |
2018年 | 37篇 |
2017年 | 37篇 |
2016年 | 84篇 |
2015年 | 81篇 |
2014年 | 89篇 |
2013年 | 131篇 |
2012年 | 168篇 |
2011年 | 165篇 |
2010年 | 124篇 |
2009年 | 100篇 |
2008年 | 175篇 |
2007年 | 167篇 |
2006年 | 138篇 |
2005年 | 182篇 |
2004年 | 130篇 |
2003年 | 116篇 |
2002年 | 100篇 |
2001年 | 46篇 |
2000年 | 32篇 |
1999年 | 37篇 |
1998年 | 21篇 |
1997年 | 37篇 |
1996年 | 29篇 |
1995年 | 19篇 |
1994年 | 22篇 |
1993年 | 20篇 |
1992年 | 13篇 |
1991年 | 17篇 |
1990年 | 17篇 |
1989年 | 15篇 |
1988年 | 14篇 |
1987年 | 19篇 |
1986年 | 7篇 |
1985年 | 21篇 |
1984年 | 16篇 |
1983年 | 12篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1976年 | 7篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1972年 | 4篇 |
排序方式: 共有2798条查询结果,搜索用时 0 毫秒
71.
[reaction: see text] Racemic oxodiester 1 undergoes stereoselective cyclocondensation with (S)-tryptophanol, (S)-(3,4-dimethoxyphenyl)alaninol, or the corresponding amino acids, in a process involving a tandem dynamic kinetic resolution/desymmetrization of diastereotopic groups, to give bicyclic lactams, which are cyclized to substituted indolo[2,3-a]- and benzo[a]quinolizidines. 相似文献
72.
Grasso D Grasso G Guantieri V Impellizzeri G La Rosa C Milardi D Micera G Osz K Pappalardo G Rizzarelli E Sanna D Sóvágó I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):537-547
An abnormal interaction between copper and the prion protein is believed to play a pivotal role in the pathogenesis of prion diseases. Copper binding has been mainly attributed to the N-terminal domain of the prion protein, but this hypothesis has recently been challenged in some papers which suggest that the C-terminal domain might also compete for metal anchoring. In particular, the segment corresponding to the helix II region of the prion protein, namely PrP180-193, has been shown both to bind copper and to exhibit a copper-enhanced cytotoxicity, as well as to interact with artificial membranes. The present work is aimed at extending these results by choosing the most representative model of this domain and by determining its copper affinity. With this aim, the different role played by the electrostatic properties of the C- and N-termini of PrP180-193 (VNITIKQHTVTTTT) in determining its conformational behaviour, copper coordination and ability to perturb model membranes was investigated. Owing to the low solubility of PrP180-193, its copper affinity was evaluated by using the shorter PrPAc184-188NH2 (IKQHT) analogue as a model. ESI-MS, ESR, UV/Vis, and CD measurements were carried out on the copper(II)/PrPAc184-188NH2 and copper(II)/PrP180-193NH2 systems, and showed that PrPAc184-188NH2 is a reliable model for the metal interaction with the helix II domain. The affinity of copper(II) for the helix II fragment is higher than that for the octarepeat and PrP106-126 peptides. Finally, the different ability of PrP180-193 analogues to perturb the DPPC model membrane was assessed by DSC measurements. The possible biological consequences of these findings are also discussed briefly. 相似文献
73.
Caseli L Masui DC Furriel RP Leone FA Zaniquelli ME 《Colloids and surfaces. B, Biointerfaces》2005,46(4):248-254
This work investigates the process of incorporation of a glycosylphosphatidyl inositol (GPI)-anchored alkaline phosphatase into Langmuir monolayers of dimyristoyl phosphatidic acid (DMPA). Three different methods of protein incorporation were assayed. When the protein solution was injected below the air–water interface after formation of the lipid monolayer a micro-heterogeneous distribution of alkaline phosphatase throughout the interface was observed. Adsorption kinetics studied by fluorescence microscopy, associated with surface pressure measurements, led to the proposition of a model in which the protein penetration is modulated by the surface packing of the monolayer and intermolecular interactions occurring between the phospholipid and the protein. At initial surface pressures higher than 20 mN m−1, the protein is quickly adsorbed on the interface and the lateral diffusion drives the alkyl chains to turn towards the air phase while the polypeptide moiety faces the aqueous subphase. 相似文献
74.
Miguel A. De La Rosa José A. Navarro Mercedes Roncel 《Applied biochemistry and biotechnology》1991,30(1):61-81
The production of chemicals and fuels, or energy-rich compounds, from water by sunlight is described as a particularly attractive
means for the conversion of solar energy to a valuable renewable resource. The redox properties of photoexcited molecules
and the operating mechanism of light-driven systems are first considered. The mechanism of water oxidation carried out by
higher plants and green algae-which is actually one of the most important biochemical reactions—as well as that of artificial
photosystems, up-to-now designed trying to simulate the natural process with higher efficiency and simplicity, are likewise
discussed. A number of biological and chemical light-driven systems are presented as practical ways to solar energy conversion. 相似文献
75.
76.
Rosa Ortiz Joaquín Borrás Lourdes Perelló Horacio Jimenez 《Monatshefte für Chemie / Chemical Monthly》1986,117(4):443-451
The formation constants of the binary complexes Cu(CM)2+ and Cu(CM)
2
2+
as well as those of the ternary complexes Cu(CM)L
+ and Cu(CM)2
L
+ (CM=Cimetidine=N-Cyano-N-methyl-N[(5-methyl-1H-imidazol-4-yl)methyltioethyl]-guanidine; HL=Phenobarbital=5-ethyl-5-phenyl-barbituric acid) have been determined in 0.1 and 1.0 mol dm–3 NaClO4 methanol solutions at 25±0.2°C. The values of logX, log stat.., and logK confirm the stability of the ternary complexes.
Ternäre Komplexe von Cimetidin und Phenobarbital mit Cu(II) in methanolischer Lösung
Zusammenfassung Die Stabilitätskonstanten der binären Komplexe Cu(CM)2+ und Cu(CM) 2 2+ sowie die der ternären Komplexe Cu(CM)L + und Cu(CM)2 L + (CM=Cimetidin=N-Cyan-N-methyl-N-[(5-methyl-1H-imidazol-4-yl)methylthioethyl]-guanidin; HL=Phenobarbitalum=5-Ethyl-5-phenyl-barbitursäure) wurden in 0.1 und 1.0M Lösungen von NaClO4 in Methanol bei 25±0.2°C bestimmt. Die Werte von logX, log stat. und logK bestätigen die Stabilität der ternären Komplexe.相似文献
77.
[reaction: see text] A cheap and efficient iodination of hydrocarbons can be achieved by generating tert-butyl hypoiodite from iodine and sodium tert-butoxide. The alkane is reactant and solvent, and this metal-free process provides a clean solution for their direct iodination. 相似文献
78.
Qiong Dai Rosa Lebrn-Aguilar Elena Fernndez-Snchez Jos Antonio García-Domínguez Jesus Eduado Quintanilla-Lpez 《Journal of separation science》1993,16(12):721-724
Four poly(methyl 3,3,3-trifluoropropyl siloxanes) with trifluoro-propyl group content (group substitution) between 8 and 35 percent have been synthesized and characterized as stationary phases for gas chromatography in borosilicate glass capillary columns. Results are compared with those from two commercial stationary phases–a polydimethylsiloxane and a poly(methyl 3,3,3-trifluoropropyl siloxane) with a fifty percent trifluoropropyl group content (group substitution). Retention index values, McReynolds constants, polarity (as defined by McReynolds) and retention polarity (as defined by Takács) increase regularly with the trifluoropropyl group content of the stationary phase. The temperature coefficient of the retention indices of the McReynolds probes, and that of the polarities, have been determined at temperatures between 60 and 180 °C. Specific retention volumes do not follow the linear dependence on trifluoropropyl group content observed for retention indices or polarities. Substances with electron-donor groups show maximum retention for a trifluoropropyl group content of ca 30%, whereas the retention of hydrocarbons, halogenated compounds, and alcohols decreases as the degree of trifluoropropyl group substitution increases from 0 to 50%. It is felt that a polysiloxane with a trifluoropropyl group content of ca 30 to 35% would be the best choice for the separation of ketones, nitro compounds or amines. 相似文献
79.
Rosa Caballol Josep M. Ribó Francesc R. Trull Asunción Vallés 《Monatshefte für Chemie / Chemical Monthly》1987,118(8-9):993-1010
The applicability of the MINDO/3 method is evaluated for calculations on dipyrrolic partial structures of bile pigments. It is shown that this method cannot be used for an accurate conformational analysis. However, when applying the frontier orbital model for reactivity parameters, a good picture of the HOMO and the LUMO distribution can be obtained in this type of molecules.
Reaktivität von Pyrrolpigmenten, 9. Mitt. MINDO/3-Rechnungen von dipyrrolischen Partialmodellen von Gallenpigmenten
Zusammenfassung Es werden die Einsatzmöglichkeiten von MINDO/3 für den Fall dipyrrolischer Partialstrukturen der Gallenpigmente aufgezeigt. Die Methode ist für eine genaue Konformationsanalyse nicht geeignet. Unter Verwendung der Reaktionsparameter des Frontier-Orbital-Modells läßt sich jedoch ein gutes Bild der HOMO- und LUMO-Verteilung für diesen Verbindungstyp gewinnen.相似文献
80.
Alexis Rojas-Gonzlez Claudia Yuritzi Figueroa-Hernndez Oscar Gonzlez-Rios Mirna Leonor Surez-Quiroz Rosa María Gonzlez-Amaro Zorba Josu Hernndez-Estrada Patricia Rayas-Duarte 《Molecules (Basel, Switzerland)》2022,27(11)
The demand of foods with high antioxidant capacity have increased and research on these foods continues to grow. This review is focused on chlorogenic acids (CGAs) from green coffee, which is the most abundant source. The main CGA in coffee is 5-O-caffeoylquinic acid (5-CQA). Coffee extracts are currently the most widely used source to enhance the antioxidant activity of foods. Due to the solubility of CGAs, their extraction is mainly performed with organic solvents. CGAs have been associated with health benefits, such as antioxidant, antiviral, antibacterial, anticancer, and anti-inflammatory activity, and others that reduce the risk of cardiovascular diseases, type 2 diabetes, and Alzheimer’s disease. However, the biological activities depend on the stability of CGAs, which are sensitive to pH, temperature, and light. The anti-inflammatory activity of 5-CQA is attributed to reducing the proinflammatory activity of cytokines. 5-CQA can negatively affect colon microbiota. An increase in anthocyanins and antioxidant activity was observed when CGAs extracts were added to different food matrices such as dairy products, coffee drinks, chocolate, and bakery products. The fortification of foods with coffee CGAs has the potential to improve the functionality of foods. 相似文献