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排序方式: 共有633条查询结果,搜索用时 984 毫秒
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.
An additive measure in o-minimal expansions of fields 总被引:1,自引:0,他引:1
43.
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
44.
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
45.
Ortiz-Marciales M González E De Jesús M Espinosa S Correa W Martínez J Figueroa R 《Organic letters》2003,5(19):3447-3449
[reaction: see text] Representative B-butyl- and B-methyl-1,3,2-oxazaborolidines derived from ephedrine and norephedrine were prepared in good yield and excellent purity by one-pot treatment of B-H oxazaborolidines with the corresponding organolithium reagent and subsequent hydrolysis of the cyclic borohydride intermediate with anhydrous ammonium chloride. 相似文献
46.
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
47.
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
48.
John C. Graham Xinmin Xu Lonnie Jones Margarita Orticochea 《Journal of polymer science. Part A, Polymer chemistry》1990,28(5):1179-1183
The reaction of bis(ethyl-3-oxo-butanolato-O1,O3)-bis(2-propanolato)titanium(Tyzor DCR and 2-isocyanatoethyl methacrylate (IEM) in refluxing hexane produced a mixture of trimer and polymers of 2-isocyanatoethyl methacrylate which varied considerably from 23 to 92% polymer as the molar ratio of bis(ethyl-3-oxo-butanolato-O1,O3)-bis(2-propanolato)titanium(Tyzor DCR) to 2-isocyanatoethyl methacrylate (IEM) varied from 1:4 to 1:32. The IEM 1-nylon polymer which was soluble in cresol and phenol was characterized by FTIR, 1H-NMR, and 13C-NMR. This analysis also showed that the methacrylate carbon–carbon double bond survived our reaction conditions intact. Based on atomic absorption determination of titanium, the molecular weight of the polymer ranged between 3000 and 4000 g/mol. Thermal gravimetric analysis (TGA) showed the polymer to be stable in air to approximately 250°C. 相似文献
49.
Vapor–liquid equilibria (VLE) data at 100 kPa have been determinated for the ternary system cyclohexane + cyclohexene + morpholine and two constituent binary systems cyclohexane + morpholine and cyclohexene + morpholine. The thermodynamic consistency of experimental data has been verified. Both binary systems deviate moderately from ideality without the presence of an azeotrope. The VLE data have been well correlated using local composition models (Wilson, NRTL and UNIQUAC) and have been also predicted with the original UNIFAC. 相似文献
50.
Dimethylgermylene and its Ge=Ge doubly bonded dimer, tetramethyldigermene, have been characterized directly in solution by
308-nm laser flash photolysis in n-hexane solution, as well as 254-nm photolysis in hydrocarbon glasses at t = 77 K. An absorption band maximum of λ
max ≈ 430 nm and molar absorption coefficient of ε ≈ 2,700 M−1 cm−1 have been shown to be attributable to low-temperature glasses, while the absorption band maximum of λ
max ≈ 480 nm and molar absorption coefficient of ε ≈ 2,400 M−1 cm−1 have been shown to be related to dimethylgermylene in n-hexane solution. The molar absorption coefficient of tetramethyldigermene (λ
max ≈ 380 nm) was determined to be ε ≈ 84,000 M−1 cm−1. The germylene is formed via (formal) cheletropic photocycloreversion of 7,7′-dimethylgerma-1,4,5,6-tetraphenyl-2,3-benzo-norbornadiene.
Tetramethyldigermene and 1,2,3,4-tetraphenylnaphthalene in the triplet state were formed, together with dimethylgermylene.
We attempted to explain the various contradictory interpretations of experimental data existing in the literature on this
reaction. 相似文献