全文获取类型
收费全文 | 13521篇 |
免费 | 601篇 |
国内免费 | 56篇 |
专业分类
化学 | 9031篇 |
晶体学 | 82篇 |
力学 | 353篇 |
数学 | 2428篇 |
物理学 | 2284篇 |
出版年
2023年 | 89篇 |
2022年 | 184篇 |
2021年 | 249篇 |
2020年 | 288篇 |
2019年 | 293篇 |
2018年 | 313篇 |
2017年 | 289篇 |
2016年 | 512篇 |
2015年 | 466篇 |
2014年 | 486篇 |
2013年 | 880篇 |
2012年 | 1010篇 |
2011年 | 1060篇 |
2010年 | 613篇 |
2009年 | 571篇 |
2008年 | 817篇 |
2007年 | 774篇 |
2006年 | 751篇 |
2005年 | 672篇 |
2004年 | 534篇 |
2003年 | 459篇 |
2002年 | 402篇 |
2001年 | 208篇 |
2000年 | 175篇 |
1999年 | 137篇 |
1998年 | 106篇 |
1997年 | 95篇 |
1996年 | 126篇 |
1995年 | 68篇 |
1994年 | 103篇 |
1993年 | 71篇 |
1992年 | 84篇 |
1991年 | 82篇 |
1990年 | 81篇 |
1989年 | 76篇 |
1988年 | 60篇 |
1987年 | 50篇 |
1986年 | 39篇 |
1985年 | 64篇 |
1984年 | 83篇 |
1983年 | 43篇 |
1982年 | 58篇 |
1981年 | 52篇 |
1980年 | 56篇 |
1979年 | 42篇 |
1978年 | 41篇 |
1977年 | 53篇 |
1976年 | 41篇 |
1975年 | 41篇 |
1973年 | 35篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
141.
In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation. 相似文献
142.
Coe BJ Harris JA Brunschwig BS Asselberghs I Clays K Garín J Orduna J 《Journal of the American Chemical Society》2005,127(38):13399-13410
In this article, we describe a series of new complex salts in which electron-rich transition-metal centers are coordinated to three electron-accepting N-methyl/aryl-2,2':4,4' ':4',4' '-quaterpyridinium ligands. These complexes contain either Ru(II) or Fe(II) ions and have been characterized by using various techniques, including electronic absorption spectroscopy and cyclic voltammetry. Molecular quadratic nonlinear optical (NLO) responses beta have been determined by using hyper-Rayleigh scattering at 800 nm and also via Stark (electroabsorption) spectroscopic studies on the intense, visible d --> pi* metal-to-ligand charge-transfer bands. The latter experiments reveal that these putatively octupolar D(3) chromophores exhibit two substantial components of the beta tensor which are associated with transitions to dipolar excited states. Computations involving time-dependent density-functional theory and the finite field method serve to further illuminate the electronic structures and associated linear and NLO properties of the new chromophoric salts. 相似文献
143.
Y. Aguilera R. Consuegra A. Abreú F. Baldassarre M. Rendueles 《Journal of Radioanalytical and Nuclear Chemistry》2003,258(1):93-99
The ion exchange chromatography displacement technique was used for the enrichment of 15N. The runs were conducted in laboratory and bench scales using two systems of columns filled with Wofatit KPS ion exchange resin (medium porosity type). Ammonia NH4
+/NH3 aq. was chosen as the isotopic exchange system. The ammonium bands formed in the columns were eluted by means of sodium hydroxide solution. Hydrodynamic patterns in the column beds was evaluated in terms of dimensionless Reynolds number. The results show that separation process can be performed in the turbulent or laminar flow regime. 相似文献
144.
Base hydrolysis of bis-bipyridylplatinum(II) occurs via a 1:1 intermediate adduct with hydroxide ion. The equilibrium constants for this 1:1 addition of hydroxide inwater to complex ions [PtL2]2+, where L=one of theisoelectronic set 2,2-bipyridyl (bpy); 2,2- bipyrazine (bpz); 3,3-bipyridazine (bpdz) and 2,2- bipyrimidine (bpym) are respectively (as log10K at 25°C): 4.23; 4.59; 3.82; 6.14. This result is rationalized in terms of addition at the 6–position of the ligand. 相似文献
145.
A new software-controlled volume-based system for sample introduction in process flow injection analysis was developed. By using a multi-syringe burette coupled with one or two additional commutation valves, the multi-commuted injection of precise sample volumes was accomplished. Characteristics and performance of the injection system were studied by injecting an indicator in a buffered carrier. Three configurations were implemented in order to achieve two different tasks: the single injection of a sample in a two- or three-channels manifold, and the dual injection into different streams. The two channel flow system using the single injection was applied to the determination of free acidity in diluted samples containing high levels of iron(III), by employing the single point titration methodology. The precipitation of ferric hydroxide was prevented using the ammonium and sodium salts of oxalate and acetate as buffer titrant. Methyl Red was employed as indicator. The procedure allows determination of acid concentration in solutions with a Fe(III)/H+ molar ratio up to 0.2. Samples with higher Fe(III)/H+ molar ratios were spiked with a known strong acid at dilution. The three-channel configuration was applied to the determination of ferric ions, using, as reagent, a merging mixture of sulfuric acid and potassium thiocyanate. The double injection system was implemented in series in a single (three-channel) manifold in such a way that a different injection volume and a changed reagent were used for each analyte. It was applied to the separated or sequential determination of free acidity and ferric ions. In this configuration, iron(III) was determined using 0.5-0.7% (w/v) sodium salicylate solution as reagent. The systems can operate at up to 100, 84 and 78 injections per hour, respectively. Determinations on synthetic and process samples compared well with the reference values and procedures. Recoveries of 95-102% with a maximum RSD value of 5.4% were found for acidity. The respective values obtained for iron determinations were 96-105% and 4.3%. 相似文献
146.
Mátyás Milen László Hazai Pál Kolonits György Kalaus Lajos Szabó Ágnes Gömöry Csaba Szántay 《Central European Journal of Chemistry》2005,3(1):118-136
Transformation of β-carboline derivatives into optically active entities were studied and the de and ee values of the resulted compounds were detected.
Dedicated to Professor Károly Lempert on his 80th birthday. 相似文献
147.
López-Alarcón C Squella JA Núñez-Vergara LJ Baez H Camargo C 《Rapid communications in mass spectrometry : RCM》2002,16(24):2229-2238
A gas chromatography/mass spectrometry (GC/MS) method for the qualitative and quantitative determination of the calcium-channel antagonists C-4-substituted 1,4-dihydropyridines, and their corresponding N-ethyl derivatives, is presented. Also, the electrochemical oxidation and the reactivity of the compounds with alkyl radicals derived from 2,2'-azobis-(2-amidinopropane) were monitored by GC/MS. Mass spectral fragmentation patterns for the C-4-substituted 1,4-dihydropy-ridine parent drugs were significantly different from those of their oxidation products, generated either by electrochemical oxidation or by reaction with alkyl radicals. However, for N-ethyl-1,4-dihydropyridine compounds it was not possible to detect the final products (pyridinium salts) using these experimental conditions. 相似文献
148.
Bernardi A Potenza D Capelli AM García-Herrero A Cañada FJ Jiménez-Barbero J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(20):4598-4612
As a step to delineate a strategy of ligand design for cholera toxin (CT), NMR studies were performed on several mimics of the GM1 ganglioside oligosaccharide. The conformation of these analogues was investigated first in solution and then upon binding to cholera toxin by transferred nuclear Overhauser effect (TR-NOE) measurements. It was demonstrated that CT selects a conformation similar to the global minima of the free saccharides from the ensemble of presented conformations. No evidence of major conformational distortions was obtained, but one or two of the available conformers of the hydroxyacid side chain appear to be selected in the bound state. The NMR data were interpreted with the aid of computer models, generated and analyzed by using a combination of different approaches (MacroModels' MC/EM and MC/SD, Autodock, and GRID). Analysis of the NMR data supported by computational studies allowed us to interpret the experimental observations and to derive workable models of the ligand:toxin complexes. These models suggest that the higher affinity of the (R)-lactic acid derivative 3 may stem from lipophilic interactions with a hydrophobic area in the toxin binding site located in the vicinity of the sialic acid side chain binding region of the CT:GM1 complex, and formed by the side chain of Ile-58 and Lys-34. Thus, the models obtained have allowed us to make useful design suggestions for the improvement of ligand affinity. 相似文献
149.
José Sepúlveda-Arques M. José Alvarez de Laviada Mercedes Medio-Simón 《Monatshefte für Chemie / Chemical Monthly》1990,121(1):81-84
Summary The reaction of methyl propiolate (MP) with 1-phenyl-4-vinylpyrazole deuterated in the five position has clarified the1H NMR spectrum of the mixture of the adducts 1:2 which are obtained as a result of a Diels-Alder cycloaddition followed by a non-regioselective ene reaction. The deuterated substrate allowed at the same time to establish the stereochemistry of the ene reaction as a concertedcis process.
Cycloadditionsreaktionen von 5-Deutero-1-phenyl-4-vinylpyrazol. Stereoselektivecis-en-Reaktion und Vereinfachung von NMR-Spektren von Mischungen der Cycloaddukte (Kurze Mitt.)
Zusammenfassung Die Reaktion von Methylpropiolat (MP) mit an der 5-Stellung deuteriertem 1-Phenyl-4-vinylpyrazol wurde zur vereinfachten Interpretation der1H-NMR-Spektren einer 1:2 Mischung von Addukten aus der Diels-Alder-Cycloaddition mit nachfolgender nicht-regioselektiver en-Reaktion eingesetzt. Das deuterierte Substrat erlaubte zugleich auch die Bestimmung der Stereochemie der en-Reaktion als einen konzertiertencis-Prozeß.相似文献
150.
J. Trekoval P. Kratochvíl 《Journal of polymer science. Part A, Polymer chemistry》1972,10(5):1391-1398
A viscometric determination of the degree of branching γ, of poly(methyl methacrylate) obtained by anionic polymerization proved the reaction of the growing center of poly(methyl methacrylate) with the ester group of another polymer molecule, accompanied by the formation of a trifunctional branch point. This reaction occurs if the solution polymerization of methyl methacrylate is initiated: (1) with butyllithium at ?78°C only on attaining 100% conversion and after a long time or at +20°C immediately after the polymerization has set in; (2) with lithium tert-butoxide at +20°C after a long time. The degree of branching of poly(methyl methacrylates) obtained under similar conditions in the presence of tetrahydrofuran reaches higher values than for polymers prepared in toluene. The tacticity of polymers does not affect the experimentally determined γ values. 相似文献