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141.
Balbuena PB Blocker W Dudek RM Cabrales-Navarro FA Hirunsit P 《The journal of physical chemistry. A》2008,112(41):10210-10219
Density functional theory and classical molecular dynamics simulations are used to investigate the vibrational spectra of caffeine and theophylline anhydrous and monohydrate molecules and those of their crystalline anhydrous and monohydrated states, with emphasis in the terahertz region of the spectra. To better understand the influence of water in the monohydrate crystal spectra, we analyze the vibrational spectra of water monomer, dimer, tetramer, and pentamer, and also those of liquid water at two different temperatures. In small water clusters, we observe the progressive addition of translational and librational modes to the terahertz region of the spectra. The water spectra predicted by rigid and flexible water models is examined with classical molecular dynamics, and the respective peaks, especially in the terahertz region, are compared with those found in the small clusters. Similar analysis done for caffeine and theophylline monohydrate molecules using density functional theory clearly shows the presence of water modes in the librational states and in the water stretching region. Molecular dynamics of caffeine and theophylline anhydrous and monohydrate crystals reveal the influence of vibrations from the molecule-molecule (caffeine or theophylline) crystal stacks and those from the water-molecule interactions found in the monohydrate molecules and new modes from molecule-molecule, water-molecule, and water-water hydrogen bonding interactions arising from collective effects in the crystal structure. Findings illustrate challenges of terahertz technology for the detection of specific substances in condensed phases. 相似文献
142.
Leendert van Dalsen Rachel E. Brown James A. Rossi-Ashton David J. Procter 《Angewandte Chemie (International ed. in English)》2023,62(29):e202303104
The photoactivation of electron donor-acceptor complexes has emerged as a sustainable, selective and versatile strategy for the generation of radical species. Electron donor-acceptor (EDA) complexation, however, imposes electronic constraints on the donor and acceptor components and this can limit the range of radicals that can be generated using the approach. New EDA complexation strategies exploiting sulfonium salts allow radicals to be generated from native functionality. For example, aryl sulfonium salts, formed by the activation of arenes, can serve as the acceptor components in EDA complexes due to their electron-deficient nature. This “sulfonium tag” approach relaxes the electronic constraints on the parent substrate and dramatically expands the range of radicals that can be generated using EDA complexation. In this review, these new applications of sulfonium salts will be introduced and the areas of chemical space rendered accessible through this innovation will be highlighted. 相似文献
143.
Ochsenbein ST Tuna F Rancan M Davies RS Muryn CA Waldmann O Bircher R Sieber A Carver G Mutka H Fernandez-Alonso F Podlesnyak A Engelhardt LP Timco GA Güdel HU Winpenny RE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(17):5144-5158
We report the synthesis and structural characterisation of a family of finite molecular chains, specifically [{[R(2)NH(2)](3)[Cr(6)F(11)(O(2)CCMe(3))(10)]}(2)] (in which R=nPr 1, Et 2, nBu 3), [{Et(2)NH}(2){[Et(2)NH(2)](3)[Cr(7)F(12)(O(2)CCMe(3))(12)][HO(2)CCMe(3)](2)}(2)] (4), [{[Me(2)NH(2)](3)[Cr(6)F(11)(O(2)CCMe(3))(10)]2.5 H(2)O}(4)] (5) and [{[iPr(2)NH(2)](3)[Cr(7)F(12)(O(2)CCMe(3))(12)]}(2)] (6). The structures all contain horseshoes of chromium centres, with each Cr...Cr contact within the horseshoe bridged by a fluoride and two pivalates. The horseshoes are linked through hydrogen bonds to the secondary ammonium cations in the structure, leading to di- and tetra-horseshoe structures. Through magnetic measurements and inelastic neutron scattering studies we have determined the exchange coupling constants in 1 and 6. In 1 it is possible to distinguish two exchange interactions, J(A)=-1.1 meV and J(B)=-1.4 meV; J(A) is the exchange interactions at the tips of the horseshoe and J(B) is the exchange within the body of the horseshoe (1 meV=8.066 cm(-1)). For 6 only one interaction was needed to model the data: J=-1.18 meV. The single-ion anisotropy parameters for Cr(III) were also derived for the two compounds as: for 1, D(Cr)=-0.028 meV and |E(Cr)|=0.005 meV; for 6, D(Cr)=-0.031 meV. Magnetic-field-dependent inelastic neutron scattering experiments on 1 allowed the Zeeman splitting of the first two excited states and level crossings to be observed. For the tetramer of horseshoes (5), quantum Monte Carlo calculations were used to fit the magnetic susceptibility behaviour, giving two exchange interactions within the horseshoe (-1.32 and -1.65 meV) and a weak inter-horseshoe coupling of +0.12 meV. Multi-frequency variable-temperature EPR studies on 1, 2 and 6 have also been performed, allowing further characterisation of the spin Hamiltonian parameters of these chains. 相似文献
144.
Alabugin IV Timokhin VI Abrams JN Manoharan M Abrams R Ghiviriga I 《Journal of the American Chemical Society》2008,130(33):10984-10995
Despite being predicted to be stereoelectronically favorable by the Baldwin rules, efficient formation of a C-C bond through a 5-endo-dig radical cyclization remained unknown for more than 40 years. This work reports a remarkable increase in the efficiency of this process upon beta-Ts substitution, which led to the development of an expedient approach to densely functionalized cyclic 1,3-dienes. Good qualitative agreement between the increased efficiency and stereoselectivity for the 5-endo-dig cyclization of Ts-substituted vinyl radicals and the results of density functional theory analysis further confirms the utility of computational methods in the design of new radical processes. Although reactions of Br atoms generated through photochemical Ts-Br bond homolysis lead to the formation of cyclic dibromide side products, the yields of target bromosulfones in the photochemically induced reactions can be increased by recycling the dibromide byproduct into the target bromosulfones through a sequence of addition/elimination reactions at the exocyclic double bond. Discovery of a relatively efficient radical 5-endo-dig closure, accompanied by a C-C bond formation, provides further support to stereoelectronic considerations at the heart of the Baldwin rules and fills one of the last remaining gaps in the arsenal of radical cyclizations. 相似文献
145.
Electrochemical and spectroscopic characterization of a series of mixed-ligand diruthenium compounds
Kadish KM Garcia R Phan T Wellhoff J Van Caemelbecke E Bear JL 《Inorganic chemistry》2008,47(23):11423-11428
The electrochemistry and spectroelectrochemistry of a novel series of mixed-ligand diruthenium compounds were examined. The investigated compounds having the formula Ru(2)(CH(3)CO(2))(x)(Fap)(4-x)Cl where x = 1-3 and Fap is 2-(2-fluoroanilino)pyridinate anion were made from the reaction of Ru(2)(CH(3)CO(2))(4)Cl with 2-(2-fluoroanilino)pyridine (HFap) in refluxing methanol. The previously characterized Ru(2)(Fap)(4)Cl as well as the three newly isolated compounds represented as Ru(2)(CH(3)CO(2))(Fap)(3)Cl (1), Ru(2)(CH(3)CO(2))(2)(Fap)(2)Cl (2), and Ru(2)(CH(3)CO(2))(3)(Fap)Cl (3) possess three unpaired electrons with a Ru(2)(5+) dimetal core. Complexes 1 and 2 have well-defined Ru(2)(5+/4+) and Ru(2)(5+/6+) redox couples in CH(2)Cl(2), but 3 exhibits a more complicated electrochemical behavior due to equilibria involving association or dissociation of the anionic chloride axial ligand on the initial and oxidized or reduced forms of the compound. The E(1/2) values for the Ru(2)(5+/4+) and Ru(2)(5+/6+) processes vary linearly with the number of CH(3)CO(2)(-) bridging ligands on Ru(2)(CH(3)CO(2))(x)(Fap)(4-x)Cl and plots of reversible half-wave potentials vs the number of acetate groups follow linear free energy relationships with the largest substituent effect being observed for the oxidation. The major UV-visible band of the examined compounds in their neutral Ru(2)(5+) form is located between 550 and 800 nm in CH(2)Cl(2) and also varies linearly with the number of CH(3)CO(2)(-) ligands on Ru(2)(CH(3)CO(2))(x)(Fap)(4-x)Cl. The electronic spectra of the singly oxidized and singly reduced forms of each diruthenium species were characterized by UV-visible spectroelectrochemistry in CH(2)Cl(2). 相似文献
146.
Modulation of the intensity of light by high quality reflective micro-displays is predominantly carried out by liquid crystal over silicon (LCoS) spatial light modulator (SLM) technology for applications such as pico-projectors. Wider use of these devices, in applications such as computer-generated holography and optical correlation, is limited by their phase modulation ability and illumination polarisation state dependence. These devices rely on planar or twisted nematic liquid crystals to modulate the light, but due to their viscoelastic properties they are inherently slow. Research into the use of the polymer stabilised blue phase has already shown that it can offer high speed phase modulation. However, other chiral nematic orientations are yet to be compared in LCoS devices. In this article, we demonstrate that polymer-stabilised chiral nematic liquid crystal electro-optical effects can offer phase modulation in silicon backplane devices. The uniform standing helix and focal conic textures are shown to be independent of the input light polarisation state and the uniform lying helix is shown to be polarisation dependent. These optical responses are then compared with that of the blue phase to identify a suitable orientation for further development in LCoS technology in order to find a high-speed, full phase modulating material. 相似文献
147.
Ma Y Luciani T Porter RA Russell AT Johnson D Marston G 《Physical chemistry chemical physics : PCCP》2007,9(37):5084-5087
The mechanism of formation of pinonic and norpinonic acids from alpha-pinene ozonolysis has been investigated by studying the products of the ozonolysis of an enone derived from alpha-pinene using gas chromatography coupled to mass spectrometry. 相似文献
148.
Improved STR typing of telogen hair root and hair shaft DNA 总被引:1,自引:0,他引:1
Today the STR typing of telogen hair and hair shafts is regarded as a challenge. The small DNA quantity in the hair is highly degraded. Another problem are PCR inhibitors in the hair. In particular hair pigments, the melanins, are known to inhibit PCR. Hairs are exposed to sunlight and partly to chemical oxidation processes, which make them even more difficult to analyze. To increase the chances of a correct typing of hair, the small amount of DNA must be successfully isolated and the inhibitors have to be removed or neutralized. Furthermore, miniSTR typing improves the analysis of stains with degraded DNA like it is the case with hair. We introduce a nonorganic extraction method and in addition a miniSTR concept which is promising in typing stains with little and degraded DNA, especially hairs. The miniSTR concept including five database STRs (SE33, VWA, TH01, FGA, D3S1358) and the gender typing system Amelogenin was optimized for the amplification of hair DNA. Compared to commercial STR kits, this approach resulted in considerably higher success rates. 相似文献
149.
150.
Watari M Galbraith J Lang HP Sousa M Hegner M Gerber C Horton MA McKendry RA 《Journal of the American Chemical Society》2007,129(3):601-609
Free-standing cantilevers, which directly translate specific biochemical reactions into micromechanical motion, have recently attracted much attention as label-free biosensors and micro/nano robotic devices. To exploit this mechanochemical sensing technology, it is essential to develop a fundamental understanding of the origins of surface stress. Here we report a detailed study into the molecular basis of stress generation in aqueous environments focusing on the pH titration of model mercaptohexadecanoic acid self-assembled monolayers (SAMs), using in situ reference cantilevers coated with nonionizable hexadecanethiol SAMs. Semiautomated data analysis and a statistical model were developed to quantify cyclic deprotonation/protonation reactions on multiple arrays. In-plane force titrations were found to have the sensitivity to detect ionic hydrogen bond formation between protonated and nonprotonated carboxylic acid groups in the proximity of the surface pK1/2, which generated a mean tensile differential surface stress of +1.2 +/- 0.3 mN/m at pH 6.0, corresponding to 1 pN attractive force between two adjacent MHA molecules. Conversely, the magnitude of compressive differential surface stress was found to increase progressively with pH >/= 7.0, reaching a maximum of -14.5 +/- 0.5 mN/m at pH 9.0, attributed to enhanced electrostatic repulsion between deprotonated carboxylic acid groups. However, striking differences were observed in the micromechanical responses to different ionic strength and ion species present in the aqueous environment, highlighting the critical role of counter- and co-ions on surface stress. Our findings provide fundamental insights into the molecular mechanisms of in-plane mechanochemistry, which may be exploited for biosensing and nanoactuation applications. 相似文献