全文获取类型
收费全文 | 456篇 |
免费 | 28篇 |
专业分类
化学 | 297篇 |
晶体学 | 1篇 |
力学 | 21篇 |
数学 | 66篇 |
物理学 | 99篇 |
出版年
2023年 | 5篇 |
2022年 | 3篇 |
2021年 | 14篇 |
2020年 | 21篇 |
2019年 | 7篇 |
2018年 | 18篇 |
2017年 | 11篇 |
2016年 | 19篇 |
2015年 | 27篇 |
2014年 | 27篇 |
2013年 | 26篇 |
2012年 | 49篇 |
2011年 | 47篇 |
2010年 | 24篇 |
2009年 | 18篇 |
2008年 | 28篇 |
2007年 | 29篇 |
2006年 | 25篇 |
2005年 | 22篇 |
2004年 | 14篇 |
2003年 | 16篇 |
2002年 | 10篇 |
2001年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1992年 | 2篇 |
1989年 | 1篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
排序方式: 共有484条查询结果,搜索用时 71 毫秒
61.
Salaün A Mocquet C Perochon R Lecorgne A Le Grel B Potel M Le Grel P 《The Journal of organic chemistry》2008,73(21):8579-8582
The cyclization of aza-beta(3)-tetrapeptides gives access to new CTP (cyclotetrapeptide) analogues. These stereocontrolled templates are assembled without any asymmetric synthesis. X-ray crystallographic structure and NMR analysis show that the macrocyclic scaffold is characterized by a fully cooperative intramolecular H-bond network, in sharp contrast with the nanotubular assemblies observed for beta(3)-cyclotetrapeptides. This folding property reduces considerably the polarity of aza-beta(3)-tetrapeptides and should be useful in addressing intracellular targets. 相似文献
62.
Souhir Boujday Romain Briandet Michèle Salmain Jean-Marie Herry Pierre-Guy Marnet Michel Gautier Claire-Marie Pradier 《Mikrochimica acta》2008,163(3-4):203-209
We describe the elaboration of ultra-sensitive immunosensors, to detect the bacterial pathogen Staphylococcus aureus. We utilized commercially available polyclonal anti-S. aureus antibody as receptor. Immunosensors were elaborated by building a self-assembled monolayer (SAM) of thiolamine onto planar gold-coated sensor chips. Then, Protein A was covalently linked to the thiolated SAM using glutaraldehyde as cross-linking agent. After a blocking step by Bovine Serum Albumin (BSA), the antibody was immobilized by affinity to Protein A. This step-by-step construction was monitored by Polarization Modulation Reflection Absorption Infrared Spectroscopy (PM-RAIRS) and Quartz Crystal Microbalance with Dissipation (QCM-D). In a first stage, the parameters of immunosensor elaboration were optimized using a model rabbit IgG. The accessibility of receptors and the homogeneity of their distribution were checked by PM-RAIRS, QCM-D, and by immuno-gold scanning electron microscopy. Then, the specific rabbit anti-S. aureus antibody was immobilized and the resulting sensing layer was applied to the detection of the pathogen target. Independent detection of bacteria immobilized on the sensors by fluorescent imaging allowed validation of the specificity of recognition toward the pathogen as well as a quantitative response of the sensor. Using PM-RAIRS as transducing technique allowed us to enhance sensitivity and reach a very competitive detection level (105 CFU mL?1). 相似文献
63.
Gautier F Destribats M Perrier-Cornet R Dechézelles JF Giermanska J Héroguez V Ravaine S Leal-Calderon F Schmitt V 《Physical chemistry chemical physics : PCCP》2007,9(48):6455-6462
We study oil-in-water emulsions stabilised by pH-sensitive colloidal silica or latex particles. Depending on the composition of the continuous phase, the same type of particles and the same emulsification process lead to emulsions characterised either by large drops densely covered by the particles, or to small droplets which are weakly covered. The two kinetically stable states can be tuned reversibly by using pH or salinity as compositional stimuli. We examine the emulsions' behaviour in these two limiting cases and we discuss the possible mechanisms allowing stabilisation, especially in the case of low surface coverage. 相似文献
64.
Romain Valentin Karine Molvinger Françoise Quignard Francesco Di Renzo 《Macromolecular Symposia》2005,222(1):93-102
Nitrogen adsorption at 77 K has been applied to the study of the texture of alginate aerogel microspheres obtained by CO2 supercritical drying of alcogels. The limited volume shrinkage suggests that the aerogels preserve the texture of the hydrogels. Alginate aerogels presents a N2 adsorption at small pressure higher than reference non-porous silica, to be attributed to the polarity of the surface or to a small microporous volume. The aggregated nanobead strings of the guluronic-rich gels accounts for a significant mesoporosity. The N2 adsorption results correspond to electron microscopy observations for features smaller than 50 nm. 相似文献
65.
Romain Valentin Raluca Horga Barbara Bonelli Edoardo Garrone Francesco Di Renzo Françoise Quignard 《Macromolecular Symposia》2005,230(1):71-77
Supercritical drying of alginate gels is an efficient way to prepare aerogels with high surface area (>300 m2 · g−1). FTIR spectroscopy allows to monitor the adsorption of NH3 from the gas phase onto the acid sites of the alginate. Free carboxylic groups are effective Brønsted sites, whereas the divalent cations used in the ionotropic gelation present the properties of Lewis sites. The ratio between Brønsted and Lewis sites provides infomation on the role of pH in alginate gelation and suggests that non-buffered gelation by transition-metal cations is a mixed ionotropic-acid process. 相似文献
66.
Romain Mougeot Philippe Jubault Julien Legros Thomas Poisson 《Molecules (Basel, Switzerland)》2021,26(23)
Herein, we report a continuous flow process for the synthesis of 2,6-diisopropylphenol—also known as Propofol—a short-acting intravenous anesthesia, widely used in intensive care medicine to provide sedation and hypnosis. The synthesis is based on a two-step procedure: a double Friedel–Crafts alkylation followed by a decarboxylation step, both under continuous flow. 相似文献
67.
Florian Boutenel Myriam Delhomme Vincent Velay Romain Boman 《Comptes Rendus Mecanique》2018,346(8):665-677
Cold tube drawing is a metal forming process that allows manufacturers to produce high-precision tubes. The dimensions of the tube are reduced by pulling it through a conical converging die with or without inner tool. In this study, finite element modelling has been used to give a better understanding of the process.This paper presents a model that predicts the final dimensions of the tube with very high accuracy. It is validated thanks to experimental tests. Moreover, five studies are performed with this model, such as investigating the influence of the die angle on the drawing force or the influence of relative thickness on tube deformation. 相似文献
68.
Romain Fardel Matthias Nagel Thomas Lippert Alexander Wokaun 《Applied Surface Science》2009,255(10):5430-5434
Thin films of a photodecomposible triazene polymer are used as sacrificial layer for the micro-deposition of sensitive materials by laser-induced forward transfer. To understand the ablation process of this sacrificial layer, the ultraviolet laser ablation of triazene films was investigated by time-resolved shadowgraphy. Irradiation from the film side shows a complete decomposition into gaseous fragments, while ablation through the substrate causes ejection of a solid flyer of polymer. The occurence of the flyer depends on the film thickness as well as on the applied fluence, and a compact flyer is obtaind when these two parameters are optimized. 相似文献
69.
Romain Fardel Lukas Urech Thomas Lippert Claude Phipps James M. Fitz-Gerald Alexander Wokaun 《Applied Physics A: Materials Science & Processing》2009,94(3):657-665
Laser plasma thrusters are a new kind of propulsion system for small satellites, and work with the thrust created by the laser
ablation of a target. Liquid polymer solutions are very promising fuels for such systems, provided that no splashing of the
target occurs, because ejection of droplets strongly decreases the performances of the system. We have investigated the nanosecond
infrared laser ablation of glycidyl azide polymer solutions containing carbon nanoparticles as absorber. Shadowgraphy imaging
revealed two cases, namely splashing regime and solid-like behavior. The transition between both regimes depends on the viscosity
of the solution and on the laser fluence, and is explained by the recoil force acting on the target. Appropriate conditions
to avoid splashing were identified, showing that this liquid polymer solution is a suitable fuel for laser plasma thrusters. 相似文献
70.
Romain Siegrist Corinne Baumgartner Paul Seiler Franois Diederich 《Helvetica chimica acta》2005,88(8):2250-2261
We report a short synthetic route that provides optically active 2‐substituted hexahydro‐1H‐pyrrolizin‐3‐ones in four steps from commercially available Boc (tert‐but(oxy)carbonyl))‐protected proline. Diastereoisomers (−)‐ 11 and (−)‐ 12 were assembled from the proline‐derived aldehyde (−)‐ 8 and ylide 9 via a Wittig reaction and subsequent catalytic hydrogenation (Scheme 3). Cleavage of the Boc protecting group under acidic conditions, followed by intramolecular cyclization, afforded the desired hexahydro‐1H‐pyrrolizinones (−)‐ 1 and (+)‐ 13 . Applying the same protocol to ylide 19 afforded hexahydro‐1H‐pyrrolizinones (−)‐ 25 and (−)‐ 26 (Scheme 5). The absolute configuration of the target compounds was determined by a combination of NMR studies (Figs. 1 and 2) and X‐ray crystallographic analysis (Fig. 3). 相似文献