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81.
Transition Metal Free Cycloamination of Prenyl Carbamates and Ureas Promoted by Aryldiazonium Salts 下载免费PDF全文
Roman Abrams Dr. Quentin Lefebvre Prof. Jonathan Clayden 《Angewandte Chemie (International ed. in English)》2018,57(41):13587-13591
Upon treatment with aryldiazonium salts, prenyl carbamates and ureas undergo redox‐neutral azocycloamination. In general, N‐aryl O‐prenyl carbamates cyclize in a photocatalytic reaction with visible light and an organic dye. With electron‐deficient diazonium salts, electronic matching with an electron‐rich N‐aryl substituent results in a reaction proceeding in the ground state, without either light or photocatalyst. Cyclic voltammetry suggests that this radical reaction is initiated by hydrogen‐atom abstraction mediated by an aryl radical, followed by a radical addition cascade and proton‐coupled hole propagation. The reaction proceeds at room temperature in short reaction times, and a range of functional groups is tolerated. 相似文献
82.
83.
Boisselier E Diallo AK Salmon L Ruiz J Astruc D 《Chemical communications (Cambridge, England)》2008,(39):4819-4821
Gold nanoparticles (AuNPs) are synthesized and stabilized by new "clicked" dendrimers of generations zero to two (G(0)-G(2)) containing tri- and tetra-ethyleneglycol tethers; they are either encapsulated by G(1) (81 tethers) and G(2) (243 tethers) or stabilized without encapsulation by G(0) (27 tethers). 相似文献
84.
Legent G Delaune A Norris V Delcorte A Gibouin D Lefebvre F Misevic G Thellier M Ripoll C 《The journal of physical chemistry. B》2008,112(17):5534-5546
Localizing two or more components of assemblies in biological systems requires both continued development of fluorescence techniques and invention of entirely new techniques. Candidates for the latter include dynamic secondary ion mass spectrometry (D-SIMS). The latest generation of D-SIMS, the Cameca NanoSIMS 50, permits the localization of specific, isotopically labeled molecules and macromolecules in sections of biological material with a resolution in the tens of nanometers and with a sensitivity approaching in principle that of a single protein. Here we use two different systems, crystals of glycine and mixtures of proteins, to show that the formation of recombinant CN secondary ions under Cs bombardment can be exploited to create a new colocalization technique. We show experimentally that the formation of the recombinant (13)C(15)N secondary ion between (13)C- and (15)N-labeled macromolecules is indeed an indicator of the distance between the interacting macromolecules and on their shape. We build up a convolution model of the mixing-recombination process in D-SIMS that allows quantitative interpretations of the distance-dependent formation of the recombinant CN. Our results show that macromolecules can be colocalized if they are within 2 nm of one another. We discuss the potential advantages of this new technique for biological applications. 相似文献
85.
Telomere length is an important measure of cell and tissue regenerative capacities. The mean telomere length is classically used as global indicator of a tissue telomere length. In skeletal muscle, which is made of postmitotic myonuclei and satellite cells (muscle stem cells), minimum telomere length is also used to assess the telomere length of satellite cells and newly incorporated myonuclei. At present, the estimation of the method reproducibility during the assessment of mean and minimum telomere length using Southern blot analysis has never been documented. The aim of this report is to describe a signal modelization for improved precision of assessment of minimum and mean telomere lengths and to document the method reproducibility. Telomeres are assessed using a Southern technique where the gel is directly hybridized with the specific probe without the membrane-transferring step in order to prevent telomeric low signal loss. We found that the improved signal analysis for determination of telomere length is associated with coefficients of variation ranging from 1.37 to 4.29% for the mean telomeric restriction fragment (TRF) length and from 2.04 to 4.95% for the minimum TRF length. Improved method reproducibility would allow saving time and biological material as duplicate and triplicate measurement of the same sample is no longer required. 相似文献
86.
Vivares D Soussan E Blanzat M Rico-Lattes I 《Langmuir : the ACS journal of surfaces and colloids》2008,24(17):9260-9267
The aggregation behavior of the cationic-rich side of a sugar-based tricatenar catanionic mixture was investigated in water, and it was shown that the excess of cationic sugar-based surfactant enhanced vesicle stability as well as encapsulation properties. Moreover, when the system was diluted, the vesicular solution collapsed into a lamellar phase, whereas, when it was concentrated, no major impact on the shape and stability of the aggregates was observed. We also showed that both an increase in temperature and the addition of salt induced reversible vesicle aggregation, which appeared to be salt-specific, following the direct order of the Hofmeister series. A proper adjustment of these parameters should then enable better control of the shape, stability, and even encapsulation ability of the aggregates formed by these tricatenar cationic/anionic mixtures. 相似文献
87.
Boisselier E Ornelas C Pianet I Aranzaes JR Astruc D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(18):5577-5587
Water-soluble benzoate-terminated dendrimers of four generations (from G0 with 9 branches to G3 with 243 branches) were synthesized and fully characterized. They form water-soluble assemblies by ion-pairing interactions with three cations of medicinal interest (acetylcoline, benzyltriethylammonium, and dopamine), which were characterized and investigated by 1H NMR spectroscopy, whereas such interactions do not provoke any significant shift of 1H NMR signals with the monomeric benzoate anion. The calculated association constants confirm that the dendritic carboxylate termini reversibly form ion pairs and aggregates. Diffusion coefficients and hydrodynamic diameters of the dendrimers, as well as changes thereof on interaction with the cations, were evaluated by DOSY experiments. The lack of increase of dendrimer size on addition of the cations and the upfield shifts of the 1H NMR signals of the cation indicate encapsulation within the hydrophobic dendrimer interiors together with probable backfolding of the benzoate termini. 相似文献
88.
Groni S Dorlet P Blain G Bourcier S Guillot R Anxolabéhère-Mallart E 《Inorganic chemistry》2008,47(8):3166-3172
In the present work we report the reactivity of [LMnII]2+ toward addition of hydrogen peroxide (H2O2) in acetonitrile solution, where L is a pentadentate polypyridine ligand. Formation of peroxo complexes is evidenced by low-temperature UV-visible spectroscopy, ESI-mass spectrometry, and EPR spectroscopy using parallel as well as perpendicular mode detection. The influence of the medium (basicity, water content) on the formation of various species is investigated. In basic nonanhydrous medium the fate of the reaction mixture solution is the formation of the di-mu-oxo mixed-valent Mn(III)Mn(IV) dinuclear complex. In acidic medium the building of the oxo bridges is avoided and the reaction mixture evolves toward oxidation of the ligand L. This reaction route offers new opportunities for the study of oxidation reactivity of Mn (hydro)peroxo complexes. 相似文献
89.
B. Scherrer A. Godard I. Ribet P. Bouchardy T. Pot M. Lefebvre 《Applied physics. B, Lasers and optics》2000,71(6):859-864
Time-domain coherent anti-Stokes Raman scattering experiments have been carried out by probing vibrational and pure rotational
lines of nitrogen in the Doppler broadened regime. The theoretical analysis of the transient responses outlines the role of
the geometrical effects. For pure rotational CARS, it is shown that the main contribution to the dephasing of the Raman coherence
results from the change in direction between the pump and anti-Stokes wave vectors whereas the difference between the modulus
of these two wave vectors accounts for dephasing in vibrational CARS. Furthermore, we demonstrate that the range of operation
of time-domain CARS velocimetry is extended by probing pure rotational lines. The predictions are validated by experiments
which are performed both in a static gas cell and in a Mach 10 supersonic flow.
Received: 30 March 2000 / Revised version: 9 June 2000 / Published online: 13 September 2000 相似文献
90.
Patrick Cancouët Elodie Daudet Grard Hlary Michel Moreau Georges Sauvet 《Journal of polymer science. Part A, Polymer chemistry》2000,38(5):826-836
Poly(hydrogenmethylsiloxane‐co‐dimethylsiloxane)s of various compositions have been prepared by cationic ring‐opening polymerization of octamethylcyclotetrasiloxane (D4) and 1,3,5,7‐tetramethylcyclotetrasiloxane (D) in the presence of hexamethyldisiloxane as end‐blocker or by rearrangement of poly(hydrogenmethylsiloxane) in the presence of D4. These copolymers were examined by high resolution 1H NMR (500.13 MHz) and 29Si NMR (99.37 MHz) spectroscopies. Triad effects were observed by 1H and up to heptad effects by 29Si NMR. The chemical shifts were assigned for these stereosequences. The intensities of the triad signals were used to calculate the quantitative parameters describing the microstructure of the copolymer chains: number‐average block length (L̄) and persistence ratio (η). The values of these parameters for copolymers prepared in various experimental conditions show that the time necessary for redistribution reactions (backbiting) is much larger than the time required to establish the equilibrium between linear polymer and cyclic oligomers. However, redistribution is fast enough to prevent the formation of block copolymers even in the case of the rearrangement of poly(hydrogenmethylsiloxane) in the presence of D4. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 826–836, 2000 相似文献