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901.
Dr. Ilia B. Moroz Dr. Pierre Florian Dr. Jasmine Viger-Gravel Christopher P. Gordon Dr. Anne Lesage Prof. Dr. Christophe Copéret 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16301-16306
A silica-supported monomeric alkylaluminum co-catalyst was prepared via surface organometallic chemistry by contacting tris(neopentyl)aluminum and partially dehydroxylated silica. This system, fully characterized by solid-state 27Al NMR spectroscopy augmented by computational studies, efficiently activates (nBu3P)2NiCl2 towards dimerization of ethene, demonstrating comparable activity to previously reported dimeric diethylaluminum chloride supported on silica. Three types of aluminum surface species have been identified: monografted tetracoordinated Al species as well as two types of bisgrafted Al species—tetra- and pentacoordinated. Of them, only the monografted Al species is proposed to be able to activate the (nBu3P)2NiCl2 complex and generate the active cationic species. 相似文献
902.
Hui Wang Lorenzo Vendrame Dr. Christophe Fliedel Dr. Si Chen Dr. Florence Gayet Dr. Franck D'Agosto Dr. Muriel Lansalot Dr. Eric Manoury Prof. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(16):5205-5214
Unimolecular amphiphilic nanoreactors with a poly(4-vinyl-N-methylpyridinium iodide) (P4VPMe+I−) polycationic outer shell and two different architectures (core-cross-linked micelles, CCM, and nanogels, NG), with narrow size distributions around 130–150 nm in diameter, were synthesized by RAFT polymerization from an R0-4VPMe+I−140-b-S50-SC(S)SPr macroRAFT agent by either chain extension with a long (300 monomer units) hydrophobic polystyrene-based block followed by cross-linking with diethylene glycol dimethacrylate (DEGDMA) for the CCM particles, or by simultaneous chain extension and cross-linking for the NG particles. A core-anchored triphenylphosphine (TPP) ligand functionality was introduced by using 4-diphenylphosphinostyrene (DPPS) as a comonomer (5–20 % mol mol−1) in the chain extension (for CCM) or chain extension/cross-linking (for NG) step. The products were directly obtained as stable colloidal dispersions in water (latexes). After loading with [RhCl(COD)]2 to yield [RhCl(COD)(TPP@CCM)] or [RhCl(COD)(TPP@NG)], respectively, the polymers were used as polymeric nanoreactors in Rh-catalyzed aqueous biphasic hydrogenation of the model substrates styrene and 1-octene, either neat (for styrene) or in an organic solvent (toluene or 1-nonanol). All hydrogenations were rapid (TOF up to 300 h−1) at 25 °C and 20 bar of H2 pressure, the biphasic mixture rapidly decanted at the end of the reaction (<2 min), the Rh loss was negligible (<0.1 ppm in the recovered organic phase), and the catalyst phase could be recycled 10 times without significant loss of catalytic activity. 相似文献
903.
904.
Christophe Louste Zelu Yan Philippe Traoré Roberto Sosa 《Journal of Electrostatics》2013,71(3):504-508
It has been demonstrated that dielectric barrier actuators can be used to induce electrohydrodynamics flows in air as well as in gas. These actuators are often called surface non-thermal plasma actuators in gas applications. Plasma actuators have proved their efficiency for aerodynamics flow control in air. However dielectric barrier devices don't generate plasma in liquids. Electroconvective flows are induced by charge injection at the surface electrode tip. These dielectric barrier injectors (DBI) are particularly well adapted for wall jet production vortex, shedding, and mixing layer applications in dielectric liquids. Dielectric barrier actuators have proved their efficiency on various dielectric liquids. In this study, a dielectric barrier device is tested on silicon oil. Instead of the typical wall jet, a reverse flow is observed in specific configurations. Particle Image Velocimetry and Shlieren measurements are achieved to characterize the unusual electroconvective flow. 相似文献
905.
A Tris(triazolate) Ligand for a Highly Active and Magnetically Recoverable Palladium Catalyst of Selective Alcohol Oxidation Using Air at Atmospheric Pressure 下载免费PDF全文
Dr. Dong Wang Christophe Deraedt Dr. Lionel Salmon Christine Labrugère Laetitia Etienne Dr. Jaime Ruiz Prof. Didier Astruc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(17):6501-6510
High efficiency and selectivity, easy magnetic recovery and recycling, and use of air as the oxidant at atmospheric pressure are major objectives for oxidation catalysis in terms of sustainable and green processes. A tris(triazolyl) ligand, so far only used in copper‐catalyzed alkyne azide cycloadditions, was found to be extremely efficient in SiO2/γ‐Fe2O3‐immobilized palladium complexes. It was characterized by inductively coupled plasma (ICP) analysis, transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), energy‐dispersive X‐ray spectroscopy (EDX), and X‐ray photoelectron spectra (XPS) and found to fulfill the combined conditions for the selective oxidation of alcohols to aldehydes and ketones. 相似文献
906.
907.
Controlled ring‐opening polymerization of trimethylene carbonate and access to PTMC‐PLA block copolymers mediated by well‐defined N‐heterocyclic carbene zinc alkoxides 下载免费PDF全文
Four novel Zinc–NHC alkyl/alkoxide/chloride complexes ( 4 , 5 , 9 and 9′ ) were readily prepared and fully characterized, including X‐ray diffraction crystallography for 5 and 9′ . The reaction of N‐methyl‐N′‐butyl imidazolium chloride ( 3.HCl ) with ZnEt2 (2 equiv.) afforded the corresponding [(CNHC)ZnCl(Et)] complex ( 4 ) via a protonolysis reaction, as deduced from NMR data. The alcoholysis of 4 with BnOH led to quantitative formation of the dinuclear Zn(II) alkoxide species [(CNHC)ZnCl(OBn)]2 ( 5 ), as confirmed by X‐ray diffraction analysis. The NMR data are in agreement with species 5 retaining its dimeric structure in solution at room temperature. The protonolysis reaction of N‐(2,6‐diisopropylphenyl)‐N′‐ethyl methyl ether imidazolium chloride ( 8.HCl ) with ZnEt2 (2 equiv.) yielded the [(CNHC)ZnCl(Et)] species 9 . The latter was found to be reactive with CH2Cl2 in solution and to cleanly convert to the corresponding Zn(II) dichloride [(CNHC)ZnCl2]2 ( 9′ ), whose molecular structure was also elucidated using X‐ray diffractometry. Unlike Zn(II)–NHC alkoxide species 1 and 2 , which contain a NHC flanked with an additional N‐functional group (i.e. thioether and ether, respectively), the Zn(II) alkoxide species 5 incorporates a monodentate NHC ligand. The Zn(II) complexes 1 , 2 and 5 were tested in the ring‐opening polymerization (ROP) of trimethylene carbonate (TMC). All three species are effective initiators for the controlled ROP of trimethylene carbonate, resulting in the production of narrow disperse PTMC material. Initiator 1 (incorporating a thioether moiety) was found to perform best in the ROP of TMC. Notably, the latter also readily undergoes the sequential ROP of TMC and rac‐LA in the presence of a chain‐transfer agent, leading to well‐defined and high‐molecular‐weight PTMC/PLA block copolymers. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
908.
12/14/14‐Helix Formation in 2:1 α/β‐Hybrid Peptides Containing Bicyclo[2.2.2]octane Ring Constraints 下载免费PDF全文
Dr. Baptiste Legrand Dr. Christophe André Laure Moulat Dr. Claude Didierjean Dr. Patrick Hermet Prof. Jean‐Louis Bantignies Prof. Jean Martinez Dr. Muriel Amblard Dr. Monique Calmès 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):11986-11990
The highly constrained β‐amino acid ABOC induces different types of helices in β urea and 1:1 α/β amide oligomers. The latter can adopt 11/9‐ and 18/16‐helical folds depending on the chain length in solution. Short peptides alternating proteinogenic α‐amino acids and ABOC in a 2:1 α/β repeat pattern adopted an unprecedented and stable 12/14/14‐helix. The structure was established through extensive NMR, molecular dynamics, and IR studies. While the 1:1 α‐AA/ABOC helices diverged from the canonical α‐helix, the helix formed by the 9‐mer 2:1 α/β‐peptide allowed the projection of the α‐amino acid side chains in a spatial arrangement according to the α‐helix. Such a finding constitutes an important step toward the conception of functional tools that use the ABOC residue as a potent helix inducer for biological applications. 相似文献
909.
Mitsuhiko Miyazaki Ryuhei Ohara Kota Daigoku Kenro Hashimoto Jonathan R. Woodward Claude Dedonder Christophe Jouvet Masaaki Fujii 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(50):15304-15308
Hydrogen‐release by photoexcitation, excited‐state‐hydrogen‐transfer (ESHT), is one of the important photochemical processes that occur in aromatic acids and is responsible for photoprotection of biomolecules. The mechanism is described by conversion of the initial state to a charge‐separated state along the O(N)‐H bond elongation, leading to dissociation. Thus ESHT is not a simple H‐atom transfer in which a proton and a 1s electron move together. Here we show that the electron‐transfer and the proton‐motion are decoupled in gas‐phase ESHT. We monitor electron and proton transfer independently by picosecond time‐resolved near‐infrared and infrared spectroscopy for isolated phenol–(ammonia)5, a benchmark molecular cluster. Electron transfer from phenol to ammonia occurred in less than 3 picoseconds, while the overall H‐atom transfer took 15 picoseconds. The observed electron‐proton decoupling will allow for a deeper understanding and control of of photochemistry in biomolecules. 相似文献
910.
Antoine Charbonnier Cyril Brochon Eric Cloutet Christophe Navarro Georges Hadziioannou 《Journal of polymer science. Part A, Polymer chemistry》2013,51(21):4608-4617
In this article, a simple route to obtain particles in one step from functional ionizable monomers in organic media by the use of acrylate‐based macroinitiator synthesized by nitroxide‐mediated radical polymerization is presented. Different positively ionizable monomers like 4‐vinylpyridine, (dimethylamino)ethyl methacrylate, or negatively ionizable ones like methacrylic acid and acrylic acid were tested. Several parameters were studied to control the particles size, their stability in different organic media, and the possibility to crosslink them. Finally, well‐defined, depending of conditions, functional latexes in organic media were produced in a simple way. This synthetic process constitutes the first step to produce electrophoretic inks for display applications such as electronic paper. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4608–4617 相似文献