全文获取类型
收费全文 | 20218篇 |
免费 | 753篇 |
国内免费 | 55篇 |
专业分类
化学 | 14407篇 |
晶体学 | 121篇 |
力学 | 421篇 |
数学 | 3071篇 |
物理学 | 3006篇 |
出版年
2023年 | 175篇 |
2022年 | 191篇 |
2021年 | 267篇 |
2020年 | 340篇 |
2019年 | 344篇 |
2018年 | 332篇 |
2017年 | 312篇 |
2016年 | 704篇 |
2015年 | 653篇 |
2014年 | 711篇 |
2013年 | 1315篇 |
2012年 | 1519篇 |
2011年 | 1667篇 |
2010年 | 945篇 |
2009年 | 751篇 |
2008年 | 1409篇 |
2007年 | 1379篇 |
2006年 | 1225篇 |
2005年 | 1157篇 |
2004年 | 948篇 |
2003年 | 759篇 |
2002年 | 695篇 |
2001年 | 295篇 |
2000年 | 236篇 |
1999年 | 176篇 |
1998年 | 128篇 |
1997年 | 139篇 |
1996年 | 180篇 |
1995年 | 119篇 |
1994年 | 108篇 |
1993年 | 131篇 |
1992年 | 112篇 |
1991年 | 66篇 |
1990年 | 70篇 |
1989年 | 55篇 |
1988年 | 63篇 |
1987年 | 58篇 |
1986年 | 75篇 |
1985年 | 115篇 |
1984年 | 104篇 |
1983年 | 61篇 |
1982年 | 90篇 |
1981年 | 88篇 |
1980年 | 81篇 |
1979年 | 71篇 |
1978年 | 71篇 |
1977年 | 54篇 |
1976年 | 60篇 |
1974年 | 45篇 |
1973年 | 42篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Manuel Gallardo-Villagrn Lucie Paulus David Yannick Leger Bruno Therrien Bertrand Liagre 《Molecules (Basel, Switzerland)》2022,27(14)
The effect of dimethyl sulfoxide (DMSO) in rheumatoid arthritis (RA) human fibroblast-like synoviocytes (FLSs) has been studied on five different samples harvested from the joints (fingers, hands and pelvis) of five women with RA. At high concentrations (>5%), the presence of DMSO induces the cleavage of caspase-3 and PARP-1, two phenomena associated with the cell death mechanism. Even at a 0.5% concentration of DMSO, MTT assays show a strong toxicity after 24 h exposure (≈25% cell death). Therefore, to ensure a minimum impact of DMSO on RA FLSs, our study shows that the concentration of DMSO has to be below 0.05% to be considered safe. 相似文献
82.
Jos Antonio Andrades Manuel Lojo-Lpez Agata Egea-Corbacho Jos María Quiroga 《Molecules (Basel, Switzerland)》2022,27(14)
Different advanced oxidation processes (AOPs) (ultraviolet radiation, hydrogen peroxide photolysis and photo-Fenton) were applied to test the degradation of terbuthylazine in three types of water: (a) ultrapure water, (b) surface water from the Gaditana area (Los Hurones reservoir, Cádiz, Spain) and (c) groundwater from the Tempul spring in Jerez de la Frontera (Cádiz, Spain). The experiments were carried out on a laboratory scale, using two different types of reactors, batch and semi-continuous. In batch reactors, the most efficient process for the experiments carried out with both ultrapure water and underground groundwater was ultraviolet radiation, whereas for surface water from the Gaditana area, the process that obtained the best results was the photolysis of hydrogen peroxide with 2.5 mg L−1 of H2O2. In semi-continuous reactors, the most efficient process was the photolysis of hydrogen peroxide with 2.5 mg L−1 of H2O2 for all the matrices studied. In both types of reactors, terbuthylazine degradation percentages higher than 90% were achieved; the main difference was in the reaction time, which varied from minutes in the batch reactor to seconds in the semi-continuous reactor. In all the applied AOPs, N-terbutyl-6-hydroxy-N′ethyl-1,3,5-triazine-2,4-diamine (TBA-212) was generated as a reaction intermediate. 相似文献
83.
A brief review of the experimental methods used to evaluate vapour pressures and sublimation enthalpies is presented. The methods discussed have been used for determining the results of several substituted benzenes that were collected in a database, with the main purpose of developing new estimation methods of these thermodynamic properties. A critical evaluation of the two most used calorimetric techniques for determining enthalpies of sublimation is also addressed. 相似文献
84.
Rui M. Novais Frank Simon Petra Pötschke Tobias Villmow José A. Covas Maria C. Paiva 《Journal of polymer science. Part A, Polymer chemistry》2013,51(17):3740-3750
This work reports the study of the effect of chemical functionalization of carbon nanotubes on their dispersion in poly(lactic acid). The nanotubes were functionalized by the 1,3‐dipolar cycloaddition reaction, generating pyrrolidine groups at the nanotube surface. Further reaction of the pyrrolidine groups with poly(lactic acid) was studied in solution and in the polymer melt. The former involved refluxing the nanotubes in a dimethylformamide/polymer solution; the latter was carried out by direct melt mixing in a microcompounder. The carbon nanotubes collected after each process were characterized by thermogravimetry and by X‐ray photoelectron spectroscopy, showing evidence of polymer bonded to the nanotube surface only when the reaction was carried out in the polymer melt. The composites with polymer modified nanotubes present smaller average agglomerate area and a narrower agglomerate area distribution. In addition, they show improved tensile properties at low CNT concentration and present lower electrical resistivity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3740–3750 相似文献
85.
José L. Domínguez M. Carmen Villaverde Fredy Sussman 《Journal of computer-aided molecular design》2013,27(5):403-417
In this work we propose a protocol for estimating the effect of pH on the docking performance to BACE-1, which affords the charge state of the inhibitor as well as the protonation state of all ionisable residues in the protein at a given pH value. To the best of our knowledge, this is the first report of a protocol predicting the BACE-1 ligand docking poses not only at the neutral pH at which most crystallographic structures were obtained, but also at the optimal pH of the enzyme (in the acidic range), at which most of the BACE-1 binding affinity assays are performed. We have applied this protocol to a set of 23 fragment-like BACE-1 ligands that span four orders of magnitude in their binding affinities. The pK a values of the BACE-1 acidic residues deviate substantially from the estimates for model compounds in solution and display a ligand dependent variability, especially in the case of the catalytic Asp dyad residues. This outcome should have a strong bearing on the design of protocols for docking based BACE-1 screening campaigns. Finally, we were able to find an explanation for the poor docking success rate of some fragments based on the availability of anchoring points, a rationale that could help to improve hit rates in BACE-1 screening campaigns. 相似文献
86.
Abstract Anomeric pairs of per-O-acetylated-D-xylopyranosyl halides were individually treated with a wide variety of nucleophiles under mild PTC conditions. Thus, 2,3,4-tri-O-acetyl-α-D-xylopyranosyl bromide 1 provided exclusively the β-D-xylopyranosyl anomers 2-11 in good to excellent yields (65-95%). Alternatively, under the same PTC conditions, 2,3,4-tri-O-acetyl-β-D-xylopyranosyl chloride 13 afforded solely the inverted α-D-anomers 15 (82%) and 16 (67%) upon treatment with thiophenol and sodium azide, respectively. Similarly, 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl chloride 19 provided the analogous products 20 (63%) and 21 (31%) upon treatment with thiophenol and sodium azide. In the presence of tetrabutylammonium chloride as PTC catalyst, β-xylopyranosyl chloride 13 was shown to slowly equilibrate to the α-chloride 14. Therefore, care must be taken to avoid PTC catalyst for which counter anions can cause anomerization of the starting glycosyl halides. 相似文献
87.
René Csuk Alois Fürstner Heinz Sterk Hans Weidmann 《Journal of carbohydrate chemistry》2013,32(3):459-467
Hexopyranoside- and hexofuranose uloses with either ethyl 2-(branamethyl)acrylate in the presence of laminar Zn/Ag-graphite or ethyl 2-(trimethylsilylinethyl)acrylate/tetra-n-butylanrnonium fluoride undergo stereoselective branching, mainly with formation of spiro α-methylene-γ-lactones. 相似文献
88.
Mario Gómez José Quincoces Klaus Peseke Manfred Michalik Helmut Reinke 《Journal of carbohydrate chemistry》2013,32(7):851-865
ABSTRACT 1,6-Anhydro-2-(dicyanomethylene)-2,3-dideoxy-4-S-ethyl-4-thio-β-D-erythro-hexopyranose (1) reacted with tosyl azide or sulfur and triethylamine to furnish the 5-aza-10, 11-dioxatricyclo[6.2.1.02,6]undeca-2(6),3-diene-3-carbonitrile 2 and the 10,11-dioxa-5-thiatricyclo[6.2.1.02,6]undeca-2(6),3-diene-3-carbonitrile 3, respectively. The reactions of 1 with arylisothiocyanates furnished the 11,12-dioxa-5-thiatricyclo[7.2.1.02,7]dodeca-2(7),3-diene-3-carbonitriles 4 and 5. 3 underwent cyclization with triethyl orthoformate and ammonia or hydrazine hydrate to afford the 5,7-diaza-14,15-dioxa-9-thiatetracyclo[10.2.1.02,10.03.8]pentadecatetra(tri)enes 7 and 8, respectively. 相似文献
89.
María José Camarasa Ana San-Félix María Jesús Pérez-Pérez Sonsoles Velázquez Rosa Alvarez Cristina Chamorro 《Journal of carbohydrate chemistry》2013,32(4-5):451-469
1. INTRODUCTION AIDS will still be one of the most important challenges for the Scientific Community in the approaching new century. Since the identification, in 1983-84,1,2 of human immunodeficiency virus (HIV) as the etiological agent of AIDS, significant progress has been made in the treatment of HIV-infected patients. This has been in part due to the discovery and clinical use of an increasing number of anti-HIV drugs. However, while highly active antiretroviral therapy (HAART)3 approaches have reduced the morbidity and mortality, the intertwined problems of drug induced viral resistance, poor compliance with complex regimens and therapy failure continue. Therefore, there remains a pressing need for the development of new antiviral agents that can be used not only as first line therapeutic candidates, but also in the antiretroviral-experienced patient population. 相似文献
90.
David A. M. C. van de Vijver Mattia C. F. Prosperi José J. Ramasco 《The European physical journal. Special topics》2013,222(6):1403-1411
We are reviewing the literature regarding sexual networks and HIV transmission in sub-Saharan Africa and Europe. On Likoma Island in Malawi, a sexual network was reconstructed using a sociometric survey in which individuals named their sexual partners. The sexual network identified one giant component including half of all sexually active individuals. More than 25% of respondents were linked through independent chains of sexual relations. HIV was more common in the sparser regions of the network due to over-representation of groups with higher HIV prevalence. A study from KwaZulu-Natal in South-Africa collected egocentric data about sexual partners and found that new infections in women in a particular area was associated with the number of life-time partners in men. Data about sexual networks and HIV transmission are not reported in Europe. It is, however, found that the annual number of sexual partners follows a scale-free network. Phylogenetic studies that determine genetic relatedness between HIV isolates obtained from infected individuals, found that patients in the early stages of infections explain a high number of new infections. In conclusion, the limited information that is available suggest that sexual networks play a role in spread of HIV. Obtaining more information about sexual networks can be of benefit for modeling studies on HIV transmission and prevention. 相似文献