全文获取类型
收费全文 | 2183篇 |
免费 | 91篇 |
国内免费 | 22篇 |
专业分类
化学 | 1395篇 |
晶体学 | 14篇 |
力学 | 78篇 |
数学 | 423篇 |
物理学 | 386篇 |
出版年
2024年 | 2篇 |
2023年 | 20篇 |
2022年 | 45篇 |
2021年 | 45篇 |
2020年 | 53篇 |
2019年 | 58篇 |
2018年 | 58篇 |
2017年 | 40篇 |
2016年 | 76篇 |
2015年 | 76篇 |
2014年 | 93篇 |
2013年 | 143篇 |
2012年 | 173篇 |
2011年 | 237篇 |
2010年 | 115篇 |
2009年 | 101篇 |
2008年 | 156篇 |
2007年 | 132篇 |
2006年 | 138篇 |
2005年 | 107篇 |
2004年 | 98篇 |
2003年 | 76篇 |
2002年 | 54篇 |
2001年 | 27篇 |
2000年 | 18篇 |
1999年 | 10篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 17篇 |
1995年 | 7篇 |
1994年 | 5篇 |
1993年 | 8篇 |
1992年 | 7篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1985年 | 8篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1978年 | 7篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1973年 | 3篇 |
1961年 | 3篇 |
1942年 | 6篇 |
1940年 | 3篇 |
1926年 | 1篇 |
排序方式: 共有2296条查询结果,搜索用时 15 毫秒
21.
Izilda A. Bagatin Alexandre T. Cruz Henrique E. Toma Mário J. Politi Grégoire J. -F. Demets 《Journal of inclusion phenomena and macrocyclic chemistry》2005,52(3):189-193
This article reports the synthesis and the properties of 5,11,17,23-tetra(t-butyl)-25,27-bis-(ethoxy-1,8-naphthalimide)-26,28-hidroxy-calix[4]arene and the formation of an inclusion compound in organic medium. This functionalized calix[4]arene was conceived as the association of a potential host species with a good fluorophore for optical sensoring purposes. Calix[4]-NI as we will call it, maintains its ‘cone-pinched’ configuration and exhibits typical naphthalimide fluorescence bands in non-polar solvents. Its ability to interact with guest species via hydrogen bonding in its endo-hydrophilic cavity to form inclusion compounds was verified with absorption and fluorescence measurements using N-ethanol-1,8-naphthalimide as guest species, which was projected to fit exactly the host cavity and to interact with its naphthalimide π electrons. For this reason, it was possible to follow the formation of the inclusion compound with electronic spectroscopy. 相似文献
22.
Florence Robaut Alexandre Crisci Madeleine Durand-Charre Danielle Jouanne 《Microscopy and microanalysis》2006,12(4):331-334
The carbon contents in carburized steels were investigated by electron probe microanalysis (EPMA) for a range of carbon levels in the solid solution less than 1 wt%. This article describes the difficulties encountered with the classic analytical procedure using the k ratio of X-ray intensities and the phi(rhoz) model. Here, a suitable calibration curve method is presented with emphasis on the metallographic study of standard specimens and on the carbon decontamination of samples. 相似文献
23.
Jo?o?Pedro?Ferreira Jo?o?Alexandre?Rodrigues Inês?Teodora?Elias?da?FonsecaEmail author 《Journal of Solid State Electrochemistry》2004,8(4):260-271
The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater. 相似文献
24.
A simple unequal-sphere packing model is applied to study the iodine (3x3) adlayer on the Pt(111) surface. By using a newly introduced parameter, defined as the average adsorbate height, three characteristic adlattices, (3x3)-sym, (3x3)-asym, and (3x3)-lin, have been selected and characterized in great detail, including the exact adatom registry. The (3x3)-sym iodine adlattice, observed in many experimental studies, appears to be, on average, the closest one to the substrate surface. A special contour plot of average adsorbate height vs X and Y positions of the (3x3) iodine unit cell indicates the existence of two local minima, which are related to preferential formation of (3x3)-sym and (3x3)-asym iodine adlattices. Our model gives good agreement with experimental findings, and explains the mechanism of preferential appearance of (3x3)-sym and (3x3)-asym structures. 相似文献
25.
Alexandre A.M. Lapis Jackson D. Scholten Marcos N. Eberlin 《Tetrahedron letters》2006,47(38):6775-6779
Intermolecular hydroamination or hydroarylation reactions of norbornene and cyclohexadiene performed with catalytic amounts of Brönsted or Lewis acid in ionic liquids were found to provide higher selectivity and yields than those performed in classical organic solvents. The ionic liquid increases the acidity of the media and stabilizes ionic intermediates through the formation of supramolecular aggregates. 相似文献
26.
Igor Dovgan Alexandre Hentz Oleksandr Koniev Anthony Ehkirch Steve Hessmann Sylvain Ursuegui Sbastien Delacroix Margaux Riomet Frdric Taran Sarah Cianfrani Sergii Kolodych Alain Wagner 《Chemical science》2020,11(5):1210
Controlled protein functionalization holds great promise for a wide variety of applications. However, despite intensive research, the stoichiometry of the functionalization reaction remains difficult to control due to the inherent stochasticity of the conjugation process. Classical approaches that exploit peculiar structural features of specific protein substrates, or introduce reactive handles via mutagenesis, are by essence limited in scope or require substantial protein reengineering. We herein present equimolar native chemical tagging (ENACT), which precisely controls the stoichiometry of inherently random conjugation reactions by combining iterative low-conversion chemical modification, process automation, and bioorthogonal trans-tagging. We discuss the broad applicability of this conjugation process to a variety of protein substrates and payloads.Controlled protein functionalization holds great promise for a wide variety of applications.Applications of protein conjugates are limitless, including imaging, diagnostics, drug delivery, and sensing.1–4 In many of these applications, it is crucial that the conjugates are homogeneous.5 The site-selectivity of the conjugation process and the number of functional labels per biomolecule, known as the degree of conjugation (DoC), are crucial parameters that define the composition of the obtained products and are often the limiting factors to achieving adequate performance of the conjugates. For instance, immuno-PCR, an extremely sensitive detection technique, requires rigorous control of the average number of oligonucleotide labels per biomolecule (its DoC) in order to achieve high sensitivity.6 In optical imaging, the performance of many super-resolution microscopy techniques is directly defined by the DoC of fluorescent tags.7 For therapeutics, an even more striking example is provided by antibody–drug conjugates, which are prescribed for the treatment of an increasing range of cancer indications.8 A growing body of evidence from clinical trials indicates that bioconjugation parameters, DoC and DoC distribution, directly influence the therapeutic index of these targeted agents and hence must be tightly controlled.9Standard bioconjugation techniques, which rely on nucleophile–electrophile reactions, result in a broad distribution of different DoC species (Fig. 1a), which have different biophysical parameters, and consequently different functional properties.10Open in a separate windowFig. 1Schematic representation of the types of protein conjugates.To address this key issue and achieve better DoC selectivity, a number of site-specific conjugation approaches have been developed (Fig. 1b). These techniques rely on protein engineering for the introduction of specific motifs (e.g., free cysteines,11 selenocysteines,12 non-natural amino acids,13,14 peptide tags recognized by specific enzymes15,16) with distinct reactivity compared to the reactivity of the amino acids present in the native protein. These motifs are used to simultaneously control the DoC (via chemo-selective reactions) and the site of payload attachment. Both parameters are known to influence the biological and biophysical parameters of the conjugates,11 but so far there has been no way of evaluating their impact separately.The influence of DoC is more straightforward, with a lower DoC allowing the minimization of the influence of payload conjugation on the properties of the protein substrate. The lowest DoC that can be achieved for an individual conjugate is 1 (corresponding to one payload attached per biomolecule). It is noteworthy that DoC 1 is often difficult to achieve through site-specific conjugation techniques due to the symmetry of many protein substrates (e.g., antibodies). Site selection is a more intricate process, which usually relies on a systematic screening of conjugation sites for some specific criteria, such as stability or reactivity.17Herein, we introduce a method of accessing an entirely new class of protein conjugates with multiple conjugation sites but strictly homogenous DoCs (Fig. 1c). To achieve this, we combined (a) iterative low conversion chemical modification, (b) process automation, and (c) bioorthogonal trans-tagging in one workflow.The method has been exemplified for protein substrates, but it is applicable to virtually any native bio-macromolecule and payload. Importantly, this method allows for the first time the disentangling of the effects of homogeneous DoC and site-specificity on conjugate properties, which is especially intriguing in the light of recent publications revealing the complexity of the interplay between payload conjugation sites and DoC for in vivo efficacy of therapeutic bioconjugates.18 Finally, it is noteworthy that this method can be readily combined with an emerging class of site-selective bioconjugation reagents to produce site-specific DoC 1 conjugates, thus further expanding their potential for biotechnology applications.19 相似文献
27.
The asymmetric Michael addition of propionaldehyde to (2E)-(3-nitro-but-2-enyloxymethyl)-benzene 8, catalyzed by the chiral diamine (S,S)-N-iPr-2,2′-bipyrrolidine, afforded, with 93% ee, a precursor 9 of (−)-botryodiplodin. The nitro functionality of 9 was converted to a ketone via a Nef reaction to give, after a few steps, the enantiomerically enriched (−)-botryodiplodin. 相似文献
28.
Solvolysis of asymmetric homoallylic triflates bearing a terminal stannyl substituent gives disubstituted cyclopropanes and bicyclopropanes bearing differentiated termini in high enantiopurity. 相似文献
29.
A phytochemical investigation in plantlets of the Brazilian medicinal tree Virola surinamensis resulted in the isolation and structural determination of four new compounds: 3-hydroxy-4-methyl-2-(11'-piperonyl-n-undecyl)-butenolide; 3-hydroxy-4-methyl-2-(7'-piperonyl-n-heptyl)-butanolide; 9'-(3,4-methylenedioxy-phenyl)-nonanoic acid and 13'-(3,4-methylene-dioxyphenyl)-tridecanoic acid. Thirteen compounds previously isolated from seeds and adult plants were also reported. 相似文献
30.
The present work discusses the grafting by electron beam irradiation of poly(ethylene oxide) (PEO) star-shaped polymers onto porous expanded polytetrafluoroethylene (EXPTFE) surfaces. The resulting materials are intended to combine the good biocompatible properties of PEO with the outstanding mechanical properties of PTFE. The star-shaped PEOs were synthesized via anionic polymerization. 3 Mev electron beam irradiation was applied to graft these PEO stars onto porous EXPTFE surfaces. The hydrophobic EXPTFE surface had to be pre-modified with N-vinylpyrrolidone. ESCA was used to quantify the amount of grafted star-shaped PEO. Unmodified EXPTFE surfaces are well known, when implanted in a body, to be rapidly covered by a layer of cells and fibrin. The EXPTFE coated with PEO were implanted in the peritoneal cavity of rats (or under the back skin). This implantation did not induce any inflammation reactions and SEM analysis had attested the absence of adsorbed cells and fibrin. The glucose diffusion properties of these membranes were studied by a lag time analysis method and compared to those of pure PEO hydrogels. As expected, glucose diffuses through the hydrogel coated membrane and diffusion is not affected by the presence of the EXPTFE membrane. 相似文献