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101.
Philip Dimitrov Pradeep Iyer Marcel Van Beylen Thieo E. Hogen‐Esch 《Journal of polymer science. Part A, Polymer chemistry》2009,47(8):2198-2206
The anionic polymerization of butadiene initiated with 1,4‐dilithio‐1,1,4,4‐tetraphenylbutane (LiTPB) in diethyl ether (DEE) gives polybutadiene (PBD) with high 1,2 content (>70%), narrow polydispersities (1.04 < Mw/Mn < 1.20), and predicted molecular weights. In THF, this polymerization does not work very well. After removal of DEE and addition of THF, the PBD dianion is end capped quantitatively by addition of 1,1‐diphenylethylene (DPE) to give the diphenylalkyl end capped PBD dianion. Subsequent addition of methyl methacrylate at low temperatures results in the formation of well‐defined PMMA‐b‐PBD‐b‐PMMA triblock copolymers. The results are accounted for by taking into account the effects of Li ion solvation on the BD initiation and end capping of the PBD anion by DPE. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2198–2206, 2009 相似文献
102.
The oxidation of 34 organic sulphides hy 2,2′-hipyridinium chlorochromate (BPCC) resulted in the formation of the corresponding
sulphoxides. The reaction is first order with respect to both BPCC and the sulphide, and is catalysed by hydrogen ions. The
hydrogen-ion dependence has the form:k
obs = a+b[H+]. The oxidation was studied in 19 different organic solvents. An analysis of the solvent effect by Swain’s equation showed
that the both cation-and anion-solvating powers of the solvents play important roles. The rates of oxidation meta- andp-substituted phenyl methyl sulphides were correlated with Charton’s LDR equation. The rates of theo-compounds showed excellent correlation with the LDRS equation. Oxidation of thep-compounds is more susceptible to the delocalizationeffect. Oxidation of themcompounds exhibited a greater dependence on the field effect. In the oxidation of theo-compounds, the contribution of delocalized effect is slightly more than that of the field effect. The oxidation of alkyl
phenyl sulphides is subject to both polar and steric effects of the alkyl groups. Polar reaction constants are negative, indicating
an electron-deficient sulphur centre in the rate-determining step. A mechanism involving formation of a sulphurane intermediate
in the slow step has been proposed. 相似文献
103.
Cover Picture: Electron–Proton Decoupling in Excited‐State Hydrogen Atom Transfer in the Gas Phase (Angew. Chem. Int. Ed. 50/2015) 下载免费PDF全文
104.
The aim of this paper is to find the global solutions of uncertain optimization problems having a quadratic objective function and quadratic inequality constraints. The bounded epistemic uncertainties in the constraint coefficients are represented using either universal or existential quantified parameters and interval parameter domains. This approach allows to model non-controlled uncertainties by using universally quantified parameters and controlled uncertainties by using existentially quantified ones. While existentially quantified parameters could be equivalently considered as additional variables, keeping them as parameters allows maintaining the quadratic problem structure, which is essential for the proposed algorithm. The branch and bound algorithm presented in the paper handles both universally and existentially quantified parameters in a homogeneous way, without branching on their domains, and uses some dedicated numerical constraint programming techniques for finding a robust, global solution. Several examples clarify the theoretical parts and the tests demonstrate the usefulness of the proposed method. 相似文献
105.
Generation of Aryl(2‐lithiophenyl)methanone O‐Methyl Oximes and Their Use for the Synthesis of N‐(3‐Alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines via the Reaction with Nitriles 下载免费PDF全文
Kazuhiro Kobayashi Kota Matsumoto Yuu Shirai Hiroaki Ishikawa Hiroki Inouchi Miyuki Tanmatsu 《Helvetica chimica acta》2014,97(7):915-922
An efficient two‐step procedure for the preparation of a new type of 1H‐isoindoles, i.e., N‐(3‐alkyl‐1‐aryl‐ or 1,3‐diaryl‐1H‐isoindol‐1‐yl)‐O‐methylhydroxylamines 5 , from readily available aryl(2‐bromophenyl)methanones 1 has been developed. Aryl(2‐bromophenyl)methanone O‐methyloximes 2 , derived from the corresponding ketones, were treated with BuLi in Et2O at 0° to generate novel lithium compounds, aryl(2‐lithiophenyl)methanone O‐methyloximes 3 , which were allowed to react with nitriles to give the desired products 5 in moderate‐to‐fair yields. 相似文献
106.
Pradeep P. KapadiaJohn C. Widen Mackenzie A. MagnusDale C. Swenson F. Christopher Pigge 《Tetrahedron letters》2011,52(19):2519-2522
Two tetrapyridyl-substituted tetraphenylethylenes have been prepared via Suzuki coupling between tetrabromo tetraphenylethylene and 3- or 4-pyridine boronic acid. Both compounds exhibit aggregation-induced emission as determined by solid state fluorescence spectroscopy and solution phase fluorescence measurements performed in aqueous/organic solvent mixtures. Solution phase fluorescence was also found to be switchable as a function of pH. 3-Pyridyl-substituted tetraphenylethylene has been structurally characterized by X-ray crystallography. 相似文献
107.
Nunes SP Karunakaran M Pradeep N Behzad AR Hooghan B Sougrat R He H Peinemann KV 《Langmuir : the ACS journal of surfaces and colloids》2011,27(16):10184-10190
The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. 相似文献
108.
A hypothesis concerning the exponential buildup of polyelectrolyte multilayer films prepared by layer-by-layer assembly has become widely accepted in the scientific community. This model was first introduced with experimental data in Langmuir. It was subsequently described in Proceedings of the National Academy of Sciences and extended and amended in papers in Langmuir and other journals. According to the "in and out diffusion" hypothesis, as it is called, or "common rule" of exponential multilayer film buildup, as it is widely regarded, "a diffusion-based buildup mechanism ... explains most of the exponential-like growth process of polyelectrolyte multilayers reported in the literature." The present work offers an alternative viewpoint to specific elements of the hypothesis and the model as a whole. 相似文献
109.
Choonara YE Pillay V Ndesendo VM du Toit LC Kumar P Khan RA Murphy CS Jarvis DL 《Colloids and surfaces. B, Biointerfaces》2011,87(2):243-254
This study focused on evaluating four emulsion-based processing strategies for polymeric nanoparticle synthesis to explicate the mechanisms of nanoparticle formation and the influence on achieving sustained-release of two anti-tuberculosis drugs, isoniazid and rifampicin. Poly(lactic-co-glycolic acid) (PLGA) nanoparticles were formulated with and without sorbitan mono-oleate as a stabilizer using emulsion-solvent-surfactant-evaporation (ESSE) and emulsion-solvent-evaporation (ESE) approaches. An alginate solution gelled by ionic crosslinking with calcium chloride was employed to prepare alginate hydrogel nanoparticles via reverse-emulsion-cationic-gelification (RECG) and reverse-emulsion-surfactant-cationic-gelification (RESCG) approaches. In vitro drug release analysis was performed. The size, zeta potential and morphology of the nanoparticles were analyzed. Molecular mechanics energy relationships (MMER) were employed to explore the spatial disposition of alginate and PLGA with respect to the emulsifying profile of sorbitan monooleate and to corroborate the experimental findings. Results revealed that particle size of the PLGA nanoparticles was influenced by the stabilizer concentration. Nanoparticles synthesized by the ESSE approach had smaller sizes of 240±8.7 nm and 195.5±5.4 nm for rifampicin- and isoniazid-loaded nanoparticles, respectively. This was a substantial size reduction from nanoparticles generated by the ESE approach (>1000 nm). The RESCG approach produced stable and higher nanoparticle yields with desirable size (277±1.0 nm; 289±1.2 nm), a low polydispersity index (27.1±0.3 mV; 28.5±0.5 mV) and drug entrapment efficiency of 73% and 75% for isoniazid and rifampicin, respectively. Drug release from the ESSE and RESCG synthesized nanoparticles displayed desirable release of the two anti-TB drugs with sustained zero-order kinetics over a period of 8h. MMER supported the mechanisms of nanoparticle formation with a sphericalized interlaced network configuration. 相似文献
110.
Yury Torubaev Pradeep Mathur Alexander Pasynskii. 《Journal of organometallic chemistry》2011,696(4):832-834
Treatment of ruthenium carbonyl, [Ru3(CO)12] with phenylseleno tribromide PhSeBr3 afforded a new triruthenium cluster, [(CO)10Br4Ru3(μ-SePh)2] (1). Its molecular structure was determined by single crystal XRD method (P21/c; a = 10.514(3) Å; b = 10.814(3) Å; c = 19.063(5) Å; β = 105.064(4)°; V = 2093.1(10) Å3) and shown to have two lateral Ru(CO)3Br2 units attached via two PhSe bridges to a Ru(CO)4 center forming a chain-like Ru-Se-Ru-Se-Ru cluster core. This is in contrast with a recently reported reaction of PhTeBr3 with [Ru3(CO)12] which formed a monomeric complex of ruthenium-dicarbonyl-dibromo fragment coordinating two PhTeBr ligands, [(CO)2RuBr2(PhTeBr)2]. 相似文献