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21.
Novel palladium‐doped nanoparticles have been explored to serve as the first metal oxide‐derived heterogeneous catalyst for Ullmann reaction of chloroarenes under mild condition (34 °C). This heterogeneous catalyst exhibited high catalytic activity towards the Ullmann homocoupling of chloroarenes into a series of useful symmetrically biaryl products with good to excellent yields in the presence of ethanol and NaOH, thereby leading to green and economical Ullmann reaction. The produced nanoparticles were successfully characterized by various techniques including PXRD, XPS, HRTEM, SEM‐EDS, BET, TGA techniques, elemental mapping analysis and ICP‐OES. Interestingly, based on characterization and experimental data, a reasonable mechanism has been proposed. Also, the formation of aryl methyl ketone as a by‐product has been further confirmed by isotopic labelling experiments that the acetyl moiety is derived from ethanol. Moreover, the catalyst was stable and could be easily reused up to 5 times under atmospheric air without suffering significant loss in catalytic activity. 相似文献
22.
Santosh Kumar Sejy Lee Reju George Thomas Seung‐Jea Lee Hong‐Joon Lee In‐Kyu Park Yong Yeon Jeong Tae‐Ho Yoon Dong‐Chan Shin Jae‐Suk Lee 《Journal of polymer science. Part A, Polymer chemistry》2019,57(11):1165-1172
Self‐emulsion polymerization (SEP), a green route developed by us for the polymerization of amphiphilic monomers, does not require any emulsifier or an organic solvent except that the water‐soluble initiators such as 2,2′‐azobis[2‐(2‐imidazolin‐2‐yl)propane]dihydrochloride (VA‐044) and potassium persulfate (KPS) are only used. We report here the polymer nanoscaffolds from a number of amphiphilic monomers, which can be used for in situ encapsulation of a variety of nanoparticles. As a demonstration of the efficacy of these nanoscaffolds, the synthesis of a biocompatible hybrid nanoparticle (nanohybrid), prepared by encapsulating Fe3O4 magnetic nanoparticle (Fe3O4 MNPs) in poly(2‐hydroxyethyl methacrylate) in water, for MRI application is presented. The nanohybrid prepared following the SEP in the form of an emulsion does not involve the use of any stabilizing agent, crosslinker, polymeric emulsifier, or surfactant. This water‐soluble, spherical, and stable nanohybrid containing Fe3O4 MNPs of average size 10 ± 2 nm has a zeta potential value of ?41.89 mV under physiological conditions. Magnetic measurement confirmed that the nanohybrid shows typical magnetic behavior having a saturation magnetization (Ms) value of 32.3 emu/g and a transverse relaxivity (r2) value of 29.97 mM?1 s?1, which signifies that it can be used as a T2 contrast agent in MRI. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 相似文献
23.
Bahareh Heidari Majid M. Heravi Mohammad Reza Nabid Roya Sedghi Seyyed Emad Hooshmand 《应用有机金属化学》2019,33(1)
A novel nanocatalyst was designed and prepared. Initially, the surface of magnetic graphene oxide (M‐GO) was modified using thionyl chloride, tris(hydroxymethyl)aminomethane and acryloyl chloride as linkers which provide reactive C═C bonds for the polymerization of vinylic monomers. Separately, β‐cyclodextrin (β‐CD) was treated with acryloyl chloride to provide a modified β‐CD. Then, in the presence methylenebisacrylamide as a cross‐linker, monomers of modified β‐CD and acrylamide were polymerized on the surface of the pre‐prepared M‐GO. Finally, palladium acetate and sodium borohydride were added to this composite to afford supported palladium nanoparticles. This fabricated nanocomposite was fully characterized using various techniques. The efficiency of this easily separable and reusable heterogeneous catalyst was successfully examined in Suzuki–Miyaura cross‐coupling reactions of aryl halides and boronic acid as well as in modified Suzuki–Miyaura cross‐coupling reactions of N‐acylsuccinimides and boronic acid in green media. The results showed that the nanocatalyst was efficient in coupling reactions for direct formation of the corresponding biphenyl as well as benzophenone derivatives in green media based on bio‐based solvents. In addition, the nanocatalyst was easily separable, using an external magnet, and could be reused several times without significant loss of activity under the optimum reaction conditions. 相似文献
24.
The radius of spatial analyticity for solutions of the KdV equation is studied. It is shown that the analyticity radius does not decay faster than as time t goes to infinity. This improves the works of Selberg and da Silva (2017) [30] and Tesfahun (2017) [34]. Our strategy mainly relies on a higher order almost conservation law in Gevrey spaces, which is inspired by the I-method. 相似文献
25.
Dr. Fabian O. von Rohr Alice Ryser Dr. Huiwen Ji Dr. Karoline Stolze Dr. Jing Tao Jessica J. Frick Prof. Greta R. Patzke Prof. Robert J. Cava 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(8):2082-2088
We describe the previously unreported oxygen excess hexagonal antimony tungsten bronze with composition Sb0.5W3O10, in the following denoted as h-SbxWO3+2x with x=0.167, to demonstrate its analogy to classical AxWO3 tungsten bronzes. This compound forms in a relatively narrow temperature range between 580 °C<T<620 °C. It was obtained as a dark-blue polycrystalline powder, and as thin, needle-shaped, blue single crystals. h-SbxWO3+2x crystallizes in the hexagonal space group P6/mmm with the cell parameters a=7.4369(4) Å and c=3.7800(2) Å. The antimony and excess oxygen occupy the hexagonal channels within the network of corner-sharing WO6 octahedra. h-SbxWO3+2x has a resistivity of ρ300 K≈1.28 mΩ cm at room temperature, with little if any temperature-dependence on cooling. DFT calculations on a simplified model for this compound find a metallic-like electronic structure with the Fermi level falling within rather flat bands, especially around the Γ point. 相似文献
26.
Maurice Dörr Sebastian Lips Prof. Dr. Carlos Alberto Martínez-Huitle Dr. Dieter Schollmeyer Prof. Dr. Robert Franke Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7835-7838
We report an innovative, sustainable and straightforward protocol for the synthesis of N,N-diarylamides equipped with nonprotected hydroxyl groups by using electrosynthesis. The concept allows the application of various substrates furnishing diarylamides with yields up to 57 % within a single and direct electrolytic protocol. The method is thereby easy to conduct in an undivided cell with constant current conditions offering a versatile and short-cut alternative to conventional pathways. 相似文献
27.
A novel N‐doped MoO 3 @SiC hollow nanosphere has been synthesized through two steps. Due to the first step, N‐doped MoO2@C nanosphere was synthesized using the hydrothermal method and in the second step, Si‐C bonds were formed through the low‐temperature magnesiothermic method and MoO 3 @SiC hollow nanosphere was produced. The prepared nanostructures were identified by various techniques such as IR, XRD, XPS, BET/BJH, SEM/EDS, and Raman spectroscopy. Results show that converting of C to SiC increase the surface area from 17 to 241 m2/g with remarkably decrease in pore diameter. Also, molybdenum is present in the form of MoO2 in carbon catalyst while during magnesiothermic process, it transfers to MoO3 form in the SiC catalyst. The synthesized products were employed as catalysts in oxidative desulfurization of model fuel. The results displayed that MoO 3 @SiC hollow nanostructure shows a superior catalytic activity (99.9%, 40 min) compared to C support (56%, 60 min). Furthermore, the recycling of MoO2@C catalyst shows a dramatic decrease even after the first run, while, SiC support exhibit higher stability during the stronger interaction between molybdenum catalyst and SiC support. 相似文献
28.
Saddam Saqib Wajid Zaman Fazal Ullah Imran Majeed Asma Ayaz Muhammad Farooq Hussain Munis 《应用有机金属化学》2019,33(11)
The ever‐increasing resistance of plant microbes towards fungicides and bactericides has been causing serious threat to plant production in recent years. For the development of an effective antifungal agent, we introduce a novel hydrothermal protocol for synthesis of chitosan iron oxide nanoparticles (CH‐Fe2O3 NPs) using acetate buffer of low pH 5.0 for intermolecular interaction of Fe2O3 NPs and CH. The composite structure and elemental elucidation were carried out by using X‐ray power diffraction (XRD), Scanning Electron Microscopy (SEM), Energy Dispersive X‐ray (EDX), Transmission Electron Microscopy (TEM), Fourier Transformed Infrared Spectroscopy (FTIR) and Ultraviolet Visible Absorption Spectroscopy (UV–vis spectroscopy). Additionally, antifungal activity was evaluated both In vitro and In vivo against Rhizopus oryzae which is causing fruit rot disease of strawberry. We compared different concentrations (0.25%, 0.50%, 075% and 1%) of CH‐Fe2O3 NPs and 50% synthetic fungicide (Matalyxal Mancozab) to figure out suitable concentration for application in the field. XRD analysis showed a high crystalline nature of the NPs with average size of 52 nanometer (nm). SEM images revealed spherical shape with size range of 50–70 nm, whereas, TEM also revealed spherical shape, size ranging from 0 nm to 80 nm. EDX and FTIR results revealed presence of CH on surface of Fe2O3 NPs. The band gap measurement showed peak 317–318 nm for bare Fe2O3 NPs and CH‐Fe2O3 NPs respectively. Antifungal activity in both In vitro and In vivo significantly increased with increase in concentration. The overall results revealed high synergetic antifungal potential of organometallic CH‐Fe2O3 NPs against Rhizopus oryzae and suggest the use of CH‐Fe2O3 NPs against other Phyto‐pathological diseases due to biodegradable nature. 相似文献
29.
Kinetics and mechanism of nitration of aromatic compounds using trichloroisocyanuric acid (TCCA)/NaNO2, TCCA-N,N-dimethyl formamide (TCCA-DMF)/NaNO2, and TCCA-N,N-dimethyl acetamide (TCCA-DMA)/NaNO2 under acid-free and Vilsmeier-Haack conditions. Reactions followed second-order kinetics with a first-order dependence on [Phenol] and [Nitrating agent] ([TCCA], [(TCCA-DMF)], or [(TCCA-DMA)] >> [NaNO2]). Reaction rates accelerated with the introduction of electron-donating groups and retarded with electron-withdrawing groups, but did not fit well into the Hammett's theory of linear free energy relationship or its modified forms like Brown-Okamoto or Yukawa-Tsuno equations. Rate data were analyzed by Charton's multiple linear regression analysis. Isokinetic temperature (β) values, obtained from Exner's theory for different protocols, are 403.7 K (TCCA-NaNO2), 365.8 K (TCCA-DMF)/NaNO2, and 358 K (TCCA-DMA)/NaNO2. These values are far above the experimental temperature range (303-323 K), indicating that the enthalpy factors are probably more important in controlling the reaction. 相似文献
30.
Ethan M. Cunningham Alexander S. Gentleman Peter W. Beardsmore 《Molecular physics》2019,117(21):2990-3000
ABSTRACTWe present the results of a combined experimental and computational study of the structures of gas-phase M+(N2O)n (M?=?Li, Al) complexes. Infrared spectra were recorded in the region of the N2O asymmetric (N?=?N) stretch using photodissociation spectroscopy employing the inert messenger technique. Unlike in our previous studies on M+(N2O)n (M?=?Cu, Ag, Au and M?=?Co, Rh, Ir) complexes, N– and O–bound isomers in this case are near isoenergetic and are not distinguished spectroscopically at this resolution. In the case of Li+ complexes, there is, however, evidence for the presence of bound N2 moieties, indicating the presence of inserted, OLi+N2(N2O)n–type structures. The weak N2 band lies to the blue of the signature of molecularly N– and O–bound ligands and is well–reproduced in the simulated spectra of energetically low-lying structures computed from density functional theory. No such inserted isomers are observed in the case of Al+(N2O)n complexes whose infrared spectra can be understood on the basis of molecularly-bound N2O ligands. The differences in M+(N2O)n structures observed for these closed–shell, ns2, metal centres relative to other metal cations are discussed in terms of the likely bonding motifs. 相似文献