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41.
Häkkinen H Moseler M Kostko O Morgner N Hoffmann MA von Issendorff B 《Physical review letters》2004,93(9):093401
We present high resolution UV-photoelectron spectra of cold mass selected Cun-, Agn-, and Aun- with n=53-58. The observed electron density of states is not the expected simple electron shell structure, but is strongly influenced by electron-lattice interactions. Only Cu55- and Ag55- exhibit highly degenerate states. This is a direct consequence of their icosahedral symmetry, as is confirmed by density functional theory calculations. Neighboring sizes exhibit perturbed electronic structures, as they are formed by removal or addition of atoms to the icosahedron and therefore have lower symmetries. Gold clusters in the same size range show completely different spectra with almost no degeneracy, which indicates that they have structures of much lower symmetry. This behavior is related to strong relativistic bonding effects in gold, as demonstrated by ab initio calculations for Au55-. 相似文献
42.
Herrera-Alonso M McCarthy TJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(21):9184-9189
Electrophilic aromatic substitution reactions were studied at poly(p-xylylene) (PPX) film surface-reaction medium interfaces. The extent of the reactions (depth of penetration and degree of substitution) was determined by the interaction of the polymer with the reaction solution. Reaction with chlorosulfonic acid to produce sulfonyl chloride and sulfone functionalities occurred readily in the bulk of PPX, and yields were sensitive to time and temperature. Confinement of this reaction to the PPX surface was achieved by controlling the concentration of the acid. Functionalization of PPX with N-methylol-2-chloroacetamide in sulfuric acid to produce the chloroamidomethylated derivative occurred in high yield and was confined to the surface region of PPX. Hydrolysis of the amide to generate aminomethylated PPX was assessed by XPS and a derivatization reaction. Friedel-Crafts type chemistry (acylation and alkylation reactions) also produced functionalized surfaces, but with lower degrees of substitution than the other two reactions and was strictly surface-confined. 相似文献
43.
A prototype calix[4]arene-based receptor for carbohydrate recognition containing peptide and phosphate binding groups 总被引:2,自引:0,他引:2
Segura M Bricoli B Casnati A Muñoz EM Sansone F Ungaro R Vicent C 《The Journal of organic chemistry》2003,68(16):6296-6303
A novel class of macrobicyclic receptors for carbohydrate recognition based on upper rim, peptide-bridged calix[4]arenes has been designed and synthesized. Receptor 12, in which a charged phosphate group cooperates with peptide hydrogen-bonding donor and acceptor groups in the binding process, is the most efficient and selective in the complexation of simple carbohydrate derivatives. The selectivity observed is toward beta-glucoside 13a, which is better bound (DeltaG degrees = 19.6 kJ mol(-)(1)) compared to the corresponding alpha anomer 13b (DeltaG degrees = 17.0 kJ mol(-)(1)) and to the beta-galactoside 13c (DeltaG degrees = 17.7 kJ mol(-)(1)) in CDCl(3). A substantial drop in the stability constant is observed by esterification of the phosphate group in the host 12 or by alkylation of the OH groups in the 2 and 3 positions in the beta-glucoside and beta-galactoside derivatives. On the basis of a careful analysis of the (1)H NMR data available, a binding mode of the beta-octylglucoside 13a to receptor 12 is proposed. 相似文献
44.
Gianni Bosi Juan Carlos Candeal Esteban Induráin Esteban Oloriz Margarita Zudaire 《Order》2001,18(2):171-190
In the framework of the analysis of orderings whose associated indifference relation is not necessarily transitive, we study the structure of an interval order and its representability through a pair of real-valued functions. We obtain a list of characterizations of the existence of a representation, showing that the three main techniques that have been used in the literature to achieve numerical representations of interval orders are indeed equivalent. 相似文献
45.
Margarita A. Deneva Pepa I. Uzunova Marin N. Nenchev 《Optical and Quantum Electronics》2007,39(3):193-212
We report (theory, experimental check) an improved approach for generation of a tunable, subnanosecond pulse (0.1–0.4 ns),
based on a single pulsation (“spike”) separation from the transient oscillations in a dye laser with active mirror (AMIR).
A pumping by 20–50 ns pulses from Q-switched Nd:YAG laser is considered. The separation is in original, two-spectral selective
channels cavity, where the forced by AMIR quenched generation at one of the wavelength stops initially started spiking generation
at the other wavelength after the first spike development. The AMIR quickly starts the quenching generation at a precisely
controlled moment and with necessary intensity thus assuring the desired separation. An advantage is a high reproducibility
of the separation for high (~250%) pump power fluctuations combined with tuning in large range (~20 nm). To obtain such an
operation we form ~1 ns leading front pump pulse by electrooptical temporal cutting of the input pump pulse and use an optical
delay line. This increases also a few times the power in the separated spike (to be ~100 kW). Our approach widens the combinations
of lasers for effective applications of spike separation technique (dye lasers excited by Q-switched solid-state or Cu-vapor
lasers). 相似文献
46.
Margarita Suárez Hector Novoa Yamila Verdecia Amaury Alvarez Rolando Pérez Dolores Molero Norbert M. Blaton Nazario Martín 《Tetrahedron》2006,62(7):1365-1371
Unprecedented 2-iminium chloride salts of 5,8-dihydro-2H-pyrido[3,2-e][1,3]thiazines derivatives (8) were easily synthesized in one step from the corresponding o-chloroformyl-1,4-dihydropyridine (2) and thiourea. The structural study has been carried out by X-ray crystallography and theoretical calculations at the B3LYP/6-31G* levels and reveal that the new salts exhibit appropriate structural features to behave as calcium channel modulators. 相似文献
47.
Demikhovsky Y Kolusheva S Geyzer M Jelinek R 《Journal of colloid and interface science》2011,364(2):428-434
Mesostructured silica films have attracted interest as potential platforms for sensing, molecular sieving, catalysis, and others. The fabrication of free-standing silica films on water, however, is challenging due to the need for scaffolding agents that would constitute effective templates. We describe the assembly of thin film at the air/water interface comprising quaternary silicates and polydiacetylene (PDA), a unique chromatic polymer forming two-dimensional conjugated networks, and the use of these films for biological sensing. PDA exhibits a dual role in the system-both as the amphiphilic matrix facilitating immobilization of the silicate colloidal units at the air/water interface and additionally a chromatic reporter that undergoes visible blue-red transitions, accompanied by fluorescence transformations, in the presence of analytes. We demonstrate the application of the silicate/PDA thin films for the detection of bacterial proliferation. 相似文献
48.
A solid-phase extraction methodology, followed by high-performance liquid chromatography (HPLC) quantification with UV absorbance
detection (λ=267 nm), was developed in order to study the stability of 3′-azido-3′-deoxy-5′-O-isonicotinoylthymidine (AZT-Iso), a novel derivative of the antiretroviral AZT, in different matrixes. The half-lives (t
1/2) for AZT-Iso were 1.19, 1.13 and 0.30 h for human, rat and rabbit plasma, respectively, and 14.91 and 25.49 h for potassium
phosphate buffer (pH 7.4) and human serum albumin solution, respectively. The HPLC method proved to be selective, sensitive
and accurate. Good recovery, linearity and precision were achieved using p-fluorophenol as an internal standard. The validity of this method was tested using synthetic mixtures of the intact drug
with its decomposition products. In conclusion, the method presented is applicable to in vivo pharmacokinetics studies of
AZT-Iso in rats. 相似文献
49.
50.
Roman E. Enrique Castro W. Veronica Camus O. Margarita 《Journal of organometallic chemistry》1985,293(1):93-101
The reactions between the phosphine-organoiron [CpFeII-η6-C6Me5CH2PPh2]+ PF6? (1) and [RhCl(η4-diolefin)(μ-Cl)]2 in CH2Cl2 at reflux give the new heterobinuclear air-stable crystalline complexes [CpFeII-η6-C6Me5CH2)P(Ph)2Rh(η4-diene)Cl]PF6,(D'*-diene=cyclooctadiene (COD): 65%, 2; trimethylfluorobenzobicyclo[2.2.2]octadiene (Me3TFB): 48%, 3). Complexes 2 and 3 have been studied by 1H, 13C and 31P NMR spectroscopy and they are carbonylated (CO, 1 atm). Cyclic voltammetry experiments with addition of MeOH show electron transfer FeIRhI → FeIIRh0, the presence of a catalytic wave FeI/FeII and the possible formation of Rh hydrides. Under normal conditions 2 is a catalyst for hydrogenation of cyclohexene, but it is less efficient than the known mononuclear Rh1 analogues. 相似文献