全文获取类型
收费全文 | 691篇 |
免费 | 32篇 |
国内免费 | 1篇 |
专业分类
化学 | 534篇 |
晶体学 | 4篇 |
力学 | 7篇 |
数学 | 104篇 |
物理学 | 75篇 |
出版年
2023年 | 2篇 |
2022年 | 13篇 |
2021年 | 27篇 |
2020年 | 11篇 |
2019年 | 9篇 |
2018年 | 4篇 |
2017年 | 7篇 |
2016年 | 29篇 |
2015年 | 19篇 |
2014年 | 18篇 |
2013年 | 40篇 |
2012年 | 41篇 |
2011年 | 46篇 |
2010年 | 38篇 |
2009年 | 29篇 |
2008年 | 39篇 |
2007年 | 37篇 |
2006年 | 50篇 |
2005年 | 42篇 |
2004年 | 34篇 |
2003年 | 33篇 |
2002年 | 28篇 |
2001年 | 12篇 |
2000年 | 7篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 11篇 |
1996年 | 8篇 |
1995年 | 7篇 |
1994年 | 8篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1972年 | 1篇 |
1921年 | 1篇 |
1919年 | 1篇 |
排序方式: 共有724条查询结果,搜索用时 250 毫秒
41.
Elisabetta Massolo Maurizio BenagliaDavide Parravicini Davide BrennaRita Annunziata 《Tetrahedron letters》2014
Starting from (E)-β-substituted-β-nitroacrylates and α,β-unsaturated ketones, a stereoselective organocatalyzed one-pot methodology allowed to synthesize highly decorated chiral 2-nitro-cyclohexane carboxylic esters. The reaction is promoted by Cinchona alkaloid-derived primary amines in the presence of an acidic co-catalyst and affords two diastereoisomers, in good yields and high enantiomeric excess (often higher than 90% ee). By replacing conventional heating with microwave irradiation, cleaner reactions in shortened times (from 48 h to 30 min) were obtained, with improved dr (80:20) and high ee (up to 94%). The application of microwave technology to this organocatalytic methodology allowed also employing C1 substituted enones, leading to cyclohexanones with four contiguous stereocenters in two isomers only, and up to 99% enantioselectivity. 相似文献
42.
Novel processes have recently been developed that provide for the enhancement of ozonation through combination with electrochemical treatments. These are processes that can be included among those defined as advanced oxidation processes as they proceed via electrogeneration of highly oxidizing radical species.These processes are generally carried out by sparging ozone in both divided and undivided electrochemical cells in order to promote its decomposition through different mechanisms, depending on the electrode materials adopted, and in some cases still debated.This mini review presents the most recent advances in the field of electrochemically assisted ozonation.In particular, the first section is focused on the process known as electroperoxone (EP) where the ozone decomposition is enhanced by the adoption of carbon-based cathodes, due to the electrogeneration of hydrogen peroxide, while the second section is focused on the process that implies ozonation in a cell adopting metal-based cathodes. 相似文献
43.
44.
Lorella Guadagnini Elisabetta Salatelli Anastasiia Kharina Domenica Tonelli 《Journal of Solid State Electrochemistry》2014,18(10):2731-2742
A composite material based on overlapped layers of electrochemically synthesized Prussian Blue (PB) and terthiophene-derived polymer is described, aiming at enhancing the stability of the hexacyanoferrate thanks to the protective action of the polymer. Two bilayer configurations and deposition methods (for the polymer component) were tested. The morphology and electrochemical behavior in organic solvent and in aqueous solutions containing different supporting electrolytes were carried out. The best performances of electrodes modified with films of the composite material as to increased stability of PB were achieved with the potentiostatically deposited polymer covering the PB layer, in acetate buffer at pH 5.5. As for potential cycling stress, the anodic and cathodic peak currents due to PB were not decreased after 20 cycles. Conversely, PB alone displayed the anodic peak currents relevant to PB/Prussian White (PW) and PB/Berlin Green (BG) systems decreased by about 30 %. The stability to local pH increase was assessed by cyclic voltammetry after electrochemical reduction of H2O2. For example, the anodic peak currents were decreasing by 15 % and 5 % for the two PB redox systems, while for PB alone the same currents decreased by 35 % and 10 %. The response sensitivity to hydrogen peroxide was improved by 54 %, with respect to PB alone, as evaluated by chronoamperometry. 相似文献
45.
Exploring Weak Ligand–Protein Interactions by Long‐Lived NMR States: Improved Contrast in Fragment‐Based Drug Screening 下载免费PDF全文
Roberto Buratto Daniele Mammoli Dr. Elisabetta Chiarparin Dr. Glyn Williams Prof. Geoffrey Bodenhausen 《Angewandte Chemie (International ed. in English)》2014,53(42):11376-11380
Ligands that have an affinity for protein targets can be screened very effectively by exploiting favorable properties of long‐lived states (LLS) in NMR spectroscopy. In this work, we describe the use of LLS for competitive binding experiments to measure accurate dissociation constants of fragments that bind weakly to the ATP binding site of the N‐terminal ATPase domain of heat shock protein 90 (Hsp90), a therapeutic target for cancer treatment. The LLS approach allows one to characterize ligands with an exceptionally wide range of affinities, since it can be used for ligand concentrations [L] that are several orders of magnitude smaller than the dissociation constants KD. This property makes the LLS method particularly attractive for the initial steps of fragment‐based drug screening, where small molecular fragments that bind weakly to a target protein must be identified, which is a difficult task for many other biophysical methods. 相似文献
46.
Graziano Baccolini Giorgio Orsolan Elisabetta Mezzina Paolo Sgarabotto Corrado Rizzoli 《Heteroatom Chemistry》1994,5(1):37-42
Fused 1,3-benzothiaphospholes 2 (cis-2,6,10-trimethyl-[1, 3]benzothiaphospholo[2,3-b][1, 3]benzothiaphosphole) reacts with H2O2 and S8, giving the corresponding oxide and sulfide, respectively. The reactions of 2 with diethyl azodicarboxylate (DEAD)/catechol or DEAD/o-aminophenol, o-azidophenol, and tetrachloro-o-benzoquinone (TOB) give the first examples of spiro pentacoordinated phosphorus derivatives of this heterocyclic system. The X-ray structural analysis of spiro compound 3 showed a trigonal bipyramidal configuration at phosphorus in which the three rings assume axial-equatorial positions. 相似文献
47.
Elva Morretta Antonella DAgostino Elisabetta Cassese Barbara Maglione Antonello Petrella Chiara Schiraldi Maria Chiara Monti 《Molecules (Basel, Switzerland)》2022,27(3)
Plant extracts have shown beneficial properties in terms of skin repair, promoting wound healing through a plethora of mechanisms. In particular, the poly-/oligosaccharidic aqueous extract of Triticum vulgare (TVE), as well as TVE-based products, shows interesting biological assets, hastening wound repair. Indeed, TVE acts in the treatment of tissue regeneration mainly on decubitus and venous leg ulcers. Moreover, on scratched monolayers, TVE prompts HaCat cell migration, correctly modulating the expression of metalloproteases toward a physiological matrix remodeling. Here, using the same HaCat-based in vitro scratch model, the TVE effect has been investigated thanks to an LFQ proteomic analysis of HaCat secretomes and immunoblotting. Indeed, the unbiased TVE effect on secreted proteins has not yet been fully understood, and it could be helpful to obtain a comprehensive picture of its bio-pharmacological profile. It has emerged that TVE treatment induces significant up-regulation of several proteins in the secretome (153 to be exact) whereas only a few were down-regulated (72 to be exact). Interestingly, many of the up-regulated proteins are implicated in promoting wound-healing-related processes, such as modulating cell–cell interaction and communication, cell proliferation and differentiation, and prompting cell adhesion and migration. 相似文献
48.
Ramn Rodrigo Catalina Retamal Denisse Schupper Diego Vergara-Hernndez Sarmistha Saha Elisabetta Profumo Brigitta Buttari Luciano Saso 《Molecules (Basel, Switzerland)》2022,27(8)
Ischemia-reperfusion myocardial damage is a paradoxical tissue injury occurring during percutaneous coronary intervention (PCI) in acute myocardial infarction (AMI) patients. Although this damage could account for up to 50% of the final infarct size, there has been no available pharmacological treatment until now. Oxidative stress contributes to the underlying production mechanism, exerting the most marked injury during the early onset of reperfusion. So far, antioxidants have been shown to protect the AMI patients undergoing PCI to mitigate these detrimental effects; however, no clinical trials to date have shown any significant infarct size reduction. Therefore, it is worthwhile to consider multitarget antioxidant therapies targeting multifactorial AMI. Indeed, this clinical setting involves injurious effects derived from oxygen deprivation, intracellular pH changes and increased concentration of cytosolic Ca2+ and reactive oxygen species, among others. Thus, we will review a brief overview of the pathological cascades involved in ischemia-reperfusion injury and the potential therapeutic effects based on preclinical studies involving a combination of antioxidants, with particular reference to resveratrol and quercetin, which could contribute to cardioprotection against ischemia-reperfusion injury in myocardial tissue. We will also highlight the upcoming perspectives of these antioxidants for designing future studies. 相似文献
49.
Elisabetta Coppi Federica Cherchi Martina Venturini Elena Lucarini Renato Corradetti Lorenzo Di Cesare Mannelli Carla Ghelardini Felicita Pedata Anna Maria Pugliese 《Molecules (Basel, Switzerland)》2022,27(6)
Ligands of the Gi protein-coupled adenosine A3 receptor (A3R) are receiving increasing interest as attractive therapeutic tools for the treatment of a number of pathological conditions of the central and peripheral nervous systems (CNS and PNS, respectively). Their safe pharmacological profiles emerging from clinical trials on different pathologies (e.g., rheumatoid arthritis, psoriasis and fatty liver diseases) confer a realistic translational potential to these compounds, thus encouraging the investigation of highly selective agonists and antagonists of A3R. The present review summarizes information on the effect of latest-generation A3R ligands, not yet available in commerce, obtained by using different in vitro and in vivo models of various PNS- or CNS-related disorders. This review places particular focus on brain ischemia insults and colitis, where the prototypical A3R agonist, Cl-IB-MECA, and antagonist, MRS1523, have been used in research studies as reference compounds to explore the effects of latest-generation ligands on this receptor. The advantages and weaknesses of these compounds in terms of therapeutic potential are discussed. 相似文献
50.
Paolo Ferruti Elisabetta Ranucci Amedea Manfredi Nicolò Mauro Elena Ferrari Riccardo Bruni Francesco Colombo Patrizia Mussini Manuela Rossi 《Journal of polymer science. Part A, Polymer chemistry》2012,50(24):5000-5010
Traditional precipitation methods for inorganic micropollutant removal from waters are increasingly being replaced by sorption methods based on both natural and synthetic materials. In this context, two novel effective heavy metal ions absorbers are presented. These resins, LYMA and LMT85, were crosslinked poly(amidoamine)s carrying amine and carboxyl groups in their repeating units. In particular, the LYMA‐repeating unit contains one carboxyl and two amine groups and is a mimic of L ‐lysine, whereas LMT85 contains two amine and five carboxyl groups and is a mimic of EDTA. Both resins were prepared at moderate cost by simple eco‐friendly procedures. The heavy metal ion set adopted as benchmark was Cu2+, Cd2+, Pb2+, Zn2+, Ni2+, and Co2+. LYMA proved selective for Cu2+ and Ni2+, the other ions tested being negligibly absorbed, whereas LMT85 proved capable of rapidly and quantitatively absorbing all the ions tested either singly or in mixed solution. The absorption process was reversible, and the resins were easily regenerated by acidification. The absorption of several metal ions imparted intense coloring to the resins, a feature possibly exploitable for analytical purposes. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献