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121.
Assumpta C Nwanya Daniel Obi Rose U. Osuji R. Bucher Malik Maaza Fabian I. Ezema 《Journal of Solid State Electrochemistry》2017,21(9):2567-2576
We used a simple chemical synthesis route to deposit nanorod-like cobalt oxide thin films on different substrates such as stainless steel (ss), indium tin oxide (ITO), and microscopic glass slides. The morphology of the films show that the films were uniformly spread having a nanorod-like structure with the length of the nanorods shortened on ss substrates. The electrochemical properties of the films deposited at different time intervals were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS). The film deposited after 20 cycles on ss gave the highest specific capacity of 67.6 mAh g?1 and volumetric capacity of 123 mAh cm?3 at a scan rate 5 mV s?1 in comparison to 62.0 mAh g?1 and 113 mAh cm?3 obtained, respectively, for its counterpart on ITO. The film electrode deposited after 20 cycles on ITO gave the best rate capability and excellent cyclability with no depreciation after 2000 charge–discharge cycles. 相似文献
122.
Natashia Boland Santanu S. Dey Thomas Kalinowski Marco Molinaro Fabian Rigterink 《Mathematical Programming》2017,162(1-2):523-535
We investigate how well the graph of a bilinear function \(b{:}\;[0,1]^n\rightarrow \mathbb {R}\) can be approximated by its McCormick relaxation. In particular, we are interested in the smallest number c such that the difference between the concave upper bounding and convex lower bounding functions obtained from the McCormick relaxation approach is at most c times the difference between the concave and convex envelopes. Answering a question of Luedtke, Namazifar and Linderoth, we show that this factor c cannot be bounded by a constant independent of n. More precisely, we show that for a random bilinear function b we have asymptotically almost surely \(c\geqslant \sqrt{n}/4\). On the other hand, we prove that \(c\leqslant 600\sqrt{n}\), which improves the linear upper bound proved by Luedtke, Namazifar and Linderoth. In addition, we present an alternative proof for a result of Misener, Smadbeck and Floudas characterizing functions b for which the McCormick relaxation is equal to the convex hull. 相似文献
123.
X. Fabian F. Mauger G. Quéméner Ph. Velten G. Ban C. Couratin P. Delahaye D. Durand B. Fabre P. Finlay X. Fléchard E. Liénard A. Méry O. Naviliat-Cuncic B. Pons T. Porobic N. Severijns J. C. Thomas 《Hyperfine Interactions》2015,232(1-3):87-95
We performed classical molecular dynamics (MD) simulations in order to search the conditions for efficient sympathetic cooling of highly charged ions (HCIs) in a linear Paul trap. Small two-component ion Coulomb crystals consisting of laser-cooled ions and HCIs were characterized by the results of the MD simulations. We found that the spatial distribution is determined by not only the charge-to-mass ratio but also the space charge effect. Moreover, the simulation results suggest that the temperature of HCIs do not necessarily decrease with increasing the number of laser-cooled ions in the cases of linear ion crystals. We also determined the cooling limit of sympathetically cooled 165Ho14+ ions in small linear ion Coulomb crystals. The present results show that sub-milli-Kelvin temperatures of at least 10 Ho14+ ions will be achieved by sympathetic cooling with a single laser-cooled Be+. 相似文献
124.
125.
Marczak R Werner F Ahmad R Lobaz V Guldi DM Peukert W 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):3920-3929
Wurtzite ZnO hexagonal nanopyramids were successfully synthesized in the liquid phase from homogeneous methanolic solutions of zinc acetate and tetramethylammonium hydroxide at an excess of zinc ions. The formation and properties of the nanocrystals were examined as a function of synthesis conditions. No significant influence of the [Zn(2+)]/[OH(-)] ratio was noticed on the final particle size, in spite of increased amounts of OH(-) ions, which tend to accelerate the particle nucleation and growth. Nevertheless, the reactant concentration ratio influences the surface properties of the ZnO nanocrystals. Mesoporous ZnO films were prepared by doctor blading ethanolic pastes containing ZnO nanoparticles and ethyl cellulose onto FTO conductive glass substrate followed by calcination. Additionally, the influence of a plasticizer (triacetin)-used during the paste preparation-on the film quality was investigated. A higher content of ZnO nanoparticles and plasticizer in the pastes improved the film quality. Four different temperatures (i.e., 400, 425, 450, and 475 °C) were used for the film calcination and their influence on the structural properties of the films was characterized. In principle, increasing the calcination temperature goes hand in hand with an increase of particle size, as well as the pore diameter and reduction of the surface area. Suitable mesoporous films were employed as photoanodes in dye sensitized solar cells (DSSCs). In order to assess the effect of the varied parameters on complete DSSC devices-using cis-diisothiocyanato-bis(2,2'-bipyridyl-4,4'-dicarboxylato) ruthenium(II)bis(tetrabutylammonium (N719) as a sensitizer-incident photon to current efficiency (IPCE) and current voltage measurements were carried out. The IPCE measurements confirmed photoinduced electron injection from the dye, reaching IPCE values up to 76%. Furthermore, current-voltage characteristics of complete cells emphasized the importance of the proper preparation methods and temperatures. These features are important assets for the preparation of nanocrystalline ZnO based photoelectrodes and for improving the DSSC performance. 相似文献
126.
Braunschweig H Bertermann R Brenner P Burzler M Dewhurst RD Radacki K Seeler F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(42):11828-11837
A stable trans‐(alkyl)(boryl) platinum complex trans‐[Pt(BCat′)Me(PCy3)2] (Cat′=Cat‐4‐tBu; Cy=cyclohexyl=C6H11) was synthesised by salt metathesis reaction of trans‐[Pt(BCat′)Br(PCy3)2] with LiMe and was fully characterised. Investigation of the reactivity of the title compound showed complete reductive elimination of Cat′BMe at 80 °C within four weeks. This process may be accelerated by the addition of a variety of alkynes, thereby leading to the formation of the corresponding η2‐alkyne platinum complexes, of which [Pt(η2‐MeCCMe)(PCy3)2] was characterised by X‐ray crystallography. Conversion of the trans‐configured title compound to a cis derivative remained unsuccessful due to an instantaneous reductive elimination process during the reaction with chelating phosphines. Treatment of trans‐[Pt(BCat′)Me(PCy3)2] with Cat2B2 led to the formation of CatBMe and Cat′BMe. In the course of further investigations into this reaction, indications for two indistinguishable reaction mechanisms were found: 1) associative formation of a six‐coordinate platinum centre prior to reductive elimination and 2) σ‐bond metathesis of B? B and C? Pt bonds. Mechanism 1 provides a straightforward explanation for the formation of both methylboranes. Scrambling of diboranes(4) Cat2B2 and Cat′2B2 in the presence of [Pt(PCy3)2], fully reductive elimination of CatBMe or Cat′BMe from trans‐[Pt(BCat′)Me(PCy3)2] in the presence of sub‐stoichiometric amounts of Cat2B2, and evidence for the reversibility of the oxidative addition of Cat2B2 to [Pt(PCy3)2] all support mechanism 2, which consists of sequential equilibria reactions. Furthermore, the solid‐state molecular structure of cis‐[Pt(BCat)2(PCy3)2] and cis‐[Pt(BCat′)2(PCy3)2] were investigated. The remarkably short B? B separations in both bis(boryl) complexes suggest that the two boryl ligands in each case are more loosely bound to the PtII centre than in related bis(boryl) species. 相似文献
127.
Arndt M Salih KS Fromm A Goossen LJ Menges F Niedner-Schatteburg G 《Journal of the American Chemical Society》2011,133(19):7428-7449
The ruthenium-catalyzed hydroamidation of terminal alkynes has evolved to become a broadly applicable tool for the synthesis of enamides and enimides. Depending on the catalyst system employed, the reaction leads chemo-, regio-, and stereoselectively to a single diastereoisomer. Herein, we present a comprehensive mechanistic study of the ruthenium-catalyzed hydroamidation of terminal alkynes, which includes deuterium-labeling, in situ IR, in situ NMR, and in situ ESI-MS experiments complemented by computational studies. The results support the involvement of ruthenium-hydride and ruthenium-vinylidene species as the key intermediates. They are best explained by a reaction pathway that consists of an oxidative addition of the amide, followed by insertion of a π-coordinated alkyne into a ruthenium-hydride bond, rearrangement to a vinylidene species, nucleophilic attack of the amide, and finally reductive elimination of the product. 相似文献
128.
Conrady FM Fröhlich R Schulte to Brinke C Pape T Hahn FE 《Journal of the American Chemical Society》2011,133(30):11496-11499
The β,β'-bis(triisopropylsiloxy)phenyl-1,4-diisocyanide 3 and [Ir(Cp*)Cl(2)](2) were used for the stepwise assembly of the [Ir(Cp*)Cl] cornered molecular square [6](Cl)(4). Synthesis of the tetrakis(diisocyanide) bridged molecular square [Ir(Cp*)Cl(3)](4)(BF(4))(4) [5](BF(4))(4) followed by cleavage of the O-Si(i-Pr)(3) bonds of the diisocyanide bridges with HCl/i-PrOH led to an intramolecular attack of the liberated hydroxyl groups at the isocyanide carbon atoms with formation of molecular square [6](Cl)(4) featuring four dicarbene linkers. 相似文献
129.
Guo S Fabian O Chang YL Chen JT Lackowski WM Barbara PF 《Journal of the American Chemical Society》2011,133(31):11994-12000
A new phenomenon is presented in which electrogenerated chemiluminescence (ECL) is generated and propagates laterally as self-reinforcing waves as a result of the oxidation of a poly(9,9-dioctylfluorene-co-benzothiadiazole) thin film. In an ordered array of Au electrode posts that act as effective ECL nucleation sites, soliton-like waves were observed to expand from each site and annihilate upon collision with each other. Simulations of the ECL response supported the experimental observations that the ECL waves propagate at a constant speed. A correlated diffusion mechanism involving the correlated motion of ions, injected holes, and solvent molecules is proposed to interpret the experimental data qualitatively. A rapid increase in the diffusion coefficient of these species in the polymer results in a sharp interface between non-oxidized and oxidized polymer phases wherein the electrochemical (EC) oxidation and mass transport of all pertinent species take place. EC oxidation of conjugated polymers of this type has important implications for the understanding of these materials and their modes of operation in EC conjugated polymer devices. 相似文献
130.
Bolisetty S Vallooran JJ Adamcik J Handschin S Gramm F Mezzenga R 《Journal of colloid and interface science》2011,361(1):90-96
We report for the first time on the templating effect of β-lactoglobulin amyloid-like fibrils to synthesize gold single crystals of several decades of μm in dimensions. The gold single crystals were produced by reducing an aqueous solution of chloroauric acid by β-lactoglobulin amyloid protein fibrils. Atomic force microscopy, conventional and scanning transmission electron microscopy, electron diffraction and optical microscopy techniques were combined to characterize the structure of the gold crystals. The single-crystalline features of these macroscopic gold crystals are witnessed by their distinctive hexagonal and triangular shape and are confirmed by selected area electron diffraction (SAED). UV-vis absorption spectrum, recorded after a reaction time of 6h at the heating temperature of 55°C showed a surface plasmon resonance peak at 540 nm. With the increase of reaction time to 24h, the absorption spectrum peaks shift to a very broad and higher wavelength region extending up to near infrared region. Remarkably, these single crystalline gold crystals show auto fluorescence when illuminated to UV lamp. Further increase in β-lactoglobulin amyloid fibrils concentration above the isotropic-nematic transition, drives the formation of gold single crystals microplates stacking together and self-assembling into new hierarchical, layered protein-gold hybrid composites. 相似文献