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91.
Numerical approximation of AR‐XPS spectra for rough surfaces considering the effect of electron shadowing 下载免费PDF全文
D. Bianchi L. Katona J. Brenner G. Vorlaufer A. Vernes W. S. M. Werner 《Surface and interface analysis : SIA》2015,47(1):15-21
A computational scheme is presented that takes into account the topography, i.e. the shadowing and hence the local emission angle of the electrons when evaluating AR‐XPS data of macroscopic rough surfaces. The topography of the sample surface is supposed to be recorded by atomic force microscopy and/or optical microscopy. The emitted photoelectrons are simulated based on an extension of the Beer–Lambert law that includes the shadowing, the current local emission angle, and the geometrical instrument setup. The obtained angle‐resolved XPS spectra are optimized in accordance with experimental ones via a self‐consistent minimization algorithm that also allows one to determine the layer thicknesses of the corrugated sample. In order to validate the proposed numerical scheme, the simulation program simulation of electron spectra for surface analysis is used. An additional analysis is then performed considering only experimental data. The numerical scheme gives good agreement in simulation–simulation as well as simulation–experiment comparisons and permits a comprehensible interpretation of the measured data. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
92.
Audrey Llevot Etienne Grau Stphane Carlotti Stphane Grelier Henri Cramail 《Macromolecular rapid communications》2016,37(1):9-28
Nowadays, the synthesis of (semi)aromatic polymers from lignin derivatives is of major interest, as aromatic compounds are key intermediates in the manufacture of polymers and lignin is the main source of aromatic biobased substrates. Phenols with a variety of chemical structures can be obtained from lignin deconstruction; among them, vanillin and ferulic acid are the main ones. Depending on the phenol substrates, different chemical modifications and polymerization pathways are developed, leading to (semi)aromatic polymers covering a wide range of thermomechanical properties. This review discusses the synthesis and properties of thermosets (vinyl ester resins, cyanate ester, epoxy, and benzoxazine resins) and thermoplastic polymers (polyesters, polyanhydrides, Schiff base polymers, polyacetals, polyoxalates, polycarbonates, acrylate polymers) prepared from vanillin, ferulic acid, guaiacol, syringaldehyde, or 4‐hydroxybenzoic acid.
93.
Audrey Roy-Lachapelle Paul B. Fayad Marc Sinotte Christian Deblois Sébastien Sauvé 《Analytica chimica acta》2014
A new approach for the analysis of the cyanobacterial microcystins (MCs) in environmental water matrices has been developed. It offers a cost efficient alternative method for the fast quantification of total MCs using mass spectrometry. This approach permits the quantification of total MCs concentrations without requiring any derivatization or the use of a suite of MCs standards. The oxidation product 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) was formed through a Lemieux oxidation and represented the total concentration of free and bound MCs in water samples. MMPB was analyzed using laser diode thermal desorption-atmospheric pressure chemical ionization coupled to tandem mass spectrometry (LDTD-APCI-MS/MS). LDTD is a robust and reliable sample introduction method with ultra-fast analysis time (<15 s sample−1). Several oxidation and LDTD parameters were optimized to improve recoveries and signal intensity. MCs oxidation recovery yield was 103%, showing a complete reaction. Internal calibration with standard addition was achieved with the use of 4-phenylbutyric acid (4-PB) as internal standard and showed good linearity (R2 > 0.999). Limits of detection and quantification were 0.2 and 0.9 μg L−1, respectively. These values are comparable with the WHO (World Health Organization) guideline of 1 μg L−1 for total microcystin-LR congener in drinking water. Accuracy and interday/intraday variation coefficients were below 15%. Matrix effect was determined with a recovery of 91%, showing no significant signal suppression. This work demonstrates the use of the LDTD-APCI-MS/MS interface for the screening, detection and quantification of total MCs in complex environmental matrices. 相似文献
94.
Lambs L Léopold A Zeller B Herteman M Fromard F 《Rapid communications in mass spectrometry : RCM》2011,25(19):2777-2784
Mangrove forests could be a simple and effective alternative to conventional sewage treatment, particularly for island communities given its low cost and low maintenance. Due to their high adaptation capacity, these plants are able to tolerate and bioremediate the high levels of nutrients and pollutants found in sewage water. This solution could be applied to small tropical islands with high population density such as Mayotte in the Indian Ocean. This paper reports on a trial by stable isotopic (15)N tracing of such a bioremediation process on pre-treated wastewater near the village of Malamani, in the middle of the large coastal mangrove in the bay near Chirongui. The first results show a boost in the mangrove growth, but a longer period of observation is needed to confirm the beneficial effects, and also to clarify the role of the local crab population, whose engineering activities play an important part in the ecosystem. The exact denitrification process is not yet understood, and the mass balance equation also reveals loss of nitrogen-containing compounds, which needs to be analyzed more closely. 相似文献
95.
Choi W Hashimoto M Ellerbee AK Chen X Bishop KJ Garstecki P Stone HA Whitesides GM 《Lab on a chip》2011,11(23):3970-3978
This paper describes the behavior of bubbles suspended in a carrier liquid and moving within microfluidic networks of different connectivities. A single-phase continuum fluid, when flowing in a network of channels, partitions itself among all possible paths connecting the inlet and outlet. The flow rates along different paths are determined by the interaction between the fluid and the global structure of the network. That is, the distribution of flows depends on the fluidic resistances of all channels of the network. The movement of bubbles of gas, or droplets of liquid, suspended in a liquid can be quite different from the movement of a single-phase liquid, especially when they have sizes slightly larger than the channels, so that the bubbles (or droplets) contribute to the fluidic resistance of a channel when they are transiting it. This paper examines bubbles in this size range; in the size range examined, the bubbles are discrete and do not divide at junctions. As a consequence, a single bubble traverses only one of the possible paths through the network, and makes a sequence of binary choices ("left" or "right") at each branching intersection it encounters. We designed networks so that, at each junction, a bubble enters the channel into which the volumetric flow rate of the carrier liquid is highest. When there is only a single bubble inside a network at a time, the path taken by the bubble is, counter-intuitively, not necessarily the shortest or the fastest connecting the inlet and outlet. When a small number of bubbles move simultaneously through a network, they interact with one another by modifying fluidic resistances and flows in a time dependent manner; such groups of bubbles show very complex behaviors. When a large number of bubbles (sufficiently large that the volume of the bubbles occupies a significant fraction of the volume of the network) flow simultaneously through a network, however, the collective behavior of bubbles-the fluxes of bubbles through different paths of the network-can resemble the distribution of flows of a single-phase fluid. 相似文献
96.
Bilé EG Sassine R Denicourt-Nowicki A Launay F Roucoux A 《Dalton transactions (Cambridge, England : 2003)》2011,40(24):6524-6531
Novel anionic species, such as hydrogen carbonate (HCO(3)(?)), fluoride (F(?)), triflate (CF(3)SO(3)(?)), tetrafluoroborate (BF(4)(?)) and chloride (Cl(?)) were investigated as new partners of water soluble N,N-dimethyl-N-cetyl-N-(2-hydroxyethyl) ammonium salts, used as a protective agent of rhodium colloids. The effect of the surfactant polar head on the micellar behavior, size and morphology of the nanospecies was studied by adapted physico-chemical experiments (surface tension measurements, dynamic light scattering, thermogravimetric and TEM analyses) and discussed in terms of strong or weak stabilization of the growing nanoparticles surface. Finally, the influence of the nanoenvironment generated by the surfactant with various counter-anions was evaluated via the hydrogenation of aromatics. 相似文献
97.
Baker ML Piligkos S Bianchi A Carretta S Collison D McDouall JJ McInnes EJ Mutka H Timco GA Tuna F Vadivelu P Weihe H Güdel HU Winpenny RE 《Dalton transactions (Cambridge, England : 2003)》2011,40(34):8533-8539
An investigation into the physical consequences of including a Jahn-Teller distorted Cu(II) ion within an antiferromagnetically coupled ring, [R(2)NH(2)][Cr(7)CuF(8)((O(2)C(t)Bu)(16))] is reported. Inelastic neutron scattering (INS) and electron paramagnetic resonance (EPR) spectroscopic data are simulated using a microscopic spin Hamiltonian, and show that the two Cr-Cu exchange interactions must be inequivalent. One Cr-Cu exchange is found to be antiferromagnetic and the other ferromagnetic. The geometry of the Jahn-Teller elongation is deduced from these results, and shows that a Jahn-Teller elongation axis must lie in the plane of the Cr(7)Cu wheel; the elongation is not observed by X-ray crystallography, due to positional disorder of the Cu site within the wheel. An electronic structure calculation confirms the structural distortion of the Cu site. 相似文献
98.
Baker ML Bianchi A Carretta S Collison D Docherty RJ McLnnes EJ McRobbie A Muryn CA Mutka H Piligkos S Rancan M Santini P Timco GA Tregenna-Piggott PL Tuna F Güdel HU Winpenny RE 《Dalton transactions (Cambridge, England : 2003)》2011,40(12):2725-2734
We report a detailed physical analysis on a family of isolated, antiferro-magnetically (AF) coupled, chromium(III) finite chains, of general formula (Cr(RCO(2))(2)F)(n) where the chain length n = 6 or 7. Additionally, the chains are capped with a selection of possible terminating ligands, including hfac (= l,l,l,5,5,5-hexafluoropentane-2,4-dionate(l-)), acac (= pentane-2,4-dionate(l-)) or (F)(3). Measurements by inelastic neutron scattering (INS), magnetometery and electron paramagnetic resonance (EPR) spectroscopy have been used to study how the electronic properties are affected by n and capping ligand type. These comparisons allowed the subtle electronic effects the choice of capping ligand makes for odd member spin 3/2 ground state and even membered spin 0 ground state chains to be investigated. For this investigation full characterisation of physical properties have been performed with spin Hamiltonian parameterisation, including the determination of Heisenberg exchange coupling constants and single ion axial and rhombic anisotropy. We reveal how the quantum spin energy levels of odd or even membered chains can be modified by the type of capping ligand terminating the chain. Choice of capping ligands enables Cr-Cr exchange coupling to be adjusted by 0, 4 or 24%, relative to Cr-Cr exchange coupling within the body of the chain, by the substitution of hfac, acac or (F)(3) capping ligands to the ends of the chain, respectively. The manipulation of quantum spin levels via ligands which play no role in super-exchange, is of general interest to the practise of spin Hamilton modelling, where such second order effects are generally not considered of relevance to magnetic properties. 相似文献
99.
An Fe(3)O(4) nanoparticle-supported copper(I) pybox catalyst, which exhibits excellent reactivity and yields products with good enantioselectivity, was developed. As a proof of concept, six optically active propargyl amines were obtained in excellent yields. The catalyst can be magnetically removed and recycled easily six times without a decrease in activity or enantioselectivity. 相似文献
100.
Okadaic acid (OA), responsible for gastrointestinal problems, inhibits protein phosphatase 2A (PP2A). Therefore, the inhibition exerted by the toxin on PP2A could be used to detect the presence of OA in aqueous solution and in shellfish sample.In this work, two commercial PP2As (from ZEU Immunotec and Millipore) and one produced by molecular engineering (from GTP Technology) were tested. Enzymes were used in solution and also immobilized within a polymeric gel. In solution, best performances were obtained using PP2A purchased from ZEU Immunotec (Spain). OA was detected in aqueous solution in concentration as low as 0.0124 μg L−1 using the enzyme from ZEU Immunotec whereas the detection limits were 0.47 μg L−1 and 0.123 μg L−1 with PP2As from Millipore and GTP Technology, respectively. Considering that the immobilization step contributes to stabilize the PP2A activity, enzymes were entrapped within a photopolymer and an agarose gel. These different polymeric matrices were optimized, tested and compared. Agarose gel seems to be a good alternative to the photopolymer largely used in our group. For instance, the IC50 value obtained with the test based on PP2A from ZEU Immunotec immobilized within an agarose gel was 1.98 μg L−1. This value was 1.8-fold lower than those obtained with the photopolymer test using the same enzyme. The proposed test is sensitive, fast and does not require expensive equipment. To evaluate the efficiency of the assay, PP inhibition tests based on PP2A from ZEU Immunotec in solution or immobilized within a gel were used for OA detection in contaminated shellfish. 相似文献