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71.
Saad Sene Marc Reinholdt Dr. Guillaume Renaudin Dr. Dorothée Berthomieu Prof. Claudio M. Zicovich‐Wilson Prof. Christel Gervais Dr. Philippe Gaveau Prof. Christian Bonhomme Dr. Yaroslav Filinchuk Prof. Mark E. Smith Prof. Jean‐Marie Nedelec Dr. Sylvie Bégu Dr. P. Hubert Mutin Dr. Danielle Laurencin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):880-891
Boronic acids (R‐B(OH)2) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)3?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C4H9‐B(OH)3]2, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (1H, 13C, 11B and 43Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and 1H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks. 相似文献
72.
Supramolecular Complexes of Multivalent Cholesterol‐Containing Polymers to Solubilize Carbon Nanotubes in Apolar Organic Solvents
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Jules Zeuna Nguendia Weiheng Zhong Alexandre Fleury Guillaume De Grandpré Prof. Armand Soldera Prof. Ribal Georges Sabat Prof. Jerome P. Claverie 《化学:亚洲杂志》2014,9(5):1356-1364
Copolymers of 2‐ethylhexyl acrylate (EHA) and cholesteryloxycarbonyl‐2‐hydroxymethacrylate (CEM) were prepared by reversible addition–fragmentation chain‐transfer (RAFT) polymerization. Supramolecular complexes of these copolymers with carbon nanotubes (CNTs) were soluble in THF, toluene, and isooctane. The colloidal solutions remained stable for months without aggregation. The rationale for the choice of CEM was based on the high adsorption energy of cholesterol on the CNT surface, as computed by DFT calculations. Adsorption isotherms were experimentally measured for copolymers of various architectures (statistical, diblock, and star copolymers), thereby demonstrating that 2–5 cholesterol groups were adsorbed per polymer chain. Once the supramolecular complex had dried, the CNTs could be easily resolubilized in isooctane without the need for high‐power sonication and in the absence of added polymer. Analysis by atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) indicated that the CNTs were devoid of bundles. The supramolecular complexes could also be employed in an inverse emulsion polymerization of 2‐hydroxyethylmethacrylate (HEMA) in isooctane and dodecane, thereby leading to the formation of a continuous polymeric sheath around the CNTs. Thus, this technique leads to the formation of very stable dispersions in non‐polar organic solvents, without altering the fundamental properties of the CNTs. 相似文献
73.
Jonathan Berry Prof. Dr. Thisbe K. Lindhorst Dr. Guillaume Despras 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(39):e202200354
Azobenzene photoswitches are valuable tools for controlling properties of molecular systems with light. We have been investigating azobenzene glycoconjugates to probe carbohydrate-protein interactions and to design glycoazobenzene macrocycles with chiroptical and physicochemical properties modulated by light irradiation. To date, direct conjugation of glycosides to azobenzenes was performed by reactions providing target compounds in limited yields. We therefore sought a more effective and reliable coupling method. In this paper, we report on a straightforward thioarylation of azobenzene derivatives with glycosyl thiols as well as other thiols, thereby increasing the scope of azobenzene conjugation. Even challenging unsymmetrical conjugates can be achieved in good yields via sequential or one-pot procedures. Importantly, red-shifted azoswitches, which are addressed with visible light, were easily functionalized. Additionally, by oxidation of the sulfide bridge to the respective sulfones, both the photochromic and the thermal relaxation properties of the core azobenzene can be tuned. Utilizing this option, we realized orthogonal three-state photoswitching in mixtures containing two distinct azobenzene thioglycosides. 相似文献
74.
Damien Mahaut Dr. Aurélien Chardon Loïc Mineur Prof. Guillaume Berionni Prof. Benoît Champagne 《Chemphyschem》2021,22(19):1958-1966
The activation or heterolytic splitting of methane, a challenging substrate usually restricted to transition metals, has so far proven elusive in experimental frustrated Lewis pair (FLP) chemistry. In this article, we demonstrate, using density functional theory (DFT), that 1-aza-9-boratriptycene is a conceptually simple intramolecular FLP for the activation of methane. Systematic comparison with other FLP systems allows to gain insight into their reactivity with methane. The thermodynamics and kinetics of methane activation are interpreted by referring to the analysis of the natural charges and by employing the distortion-interaction/activation strain (DIAS) model. These showed that the nature of the Lewis base influences the selectivity over the reaction pathway, with N Lewis bases favoring the deprotonation mechanism and P bases the hydride abstraction one. The lower barrier of activation for 1-aza-9-boratriptycene and the higher products stability are due to a better interaction energy than its counterparts, itself due to electrostatic interactions with the methane moiety, favorable orbital overlaps allowed by the side-attack, and space proximity between the B and N atoms. 相似文献
75.
76.
Dhont Guillaume Cassam-Chenaï Patrick Patras Frédéric 《Journal of mathematical chemistry》2021,59(10):2294-2326
Journal of Mathematical Chemistry - The construction of integrity bases for invariant and covariant polynomials built from a set of three dimensional vectors under the $${{\mathrm {SO(3)}}}$$ and... 相似文献
77.
78.
Scott B. Ficarro Jessica M. Biagi Jinhua Wang Jenna Scotcher Rositsa I. Koleva Joseph D. Card Guillaume Adelmant Huan He Manor Askenazi Alan G. Marshall Nicolas L. Young Nathanael S. Gray Jarrod A. Marto 《Journal of the American Society for Mass Spectrometry》2014,25(4):636-650
We assemble a versatile molecular scaffold from simple building blocks to create binary and multiplexed stable isotope reagents for quantitative mass spectrometry. Termed Protected Amine Labels (PAL), these reagents offer multiple analytical figures of merit including, (1) robust targeting of peptide N-termini and lysyl side chains, (2) optimal mass spectrometry ionization efficiency through regeneration of primary amines on labeled peptides, (3) an amino acid-based mass tag that incorporates heavy isotopes of carbon, nitrogen, and oxygen to ensure matched physicochemical and MS/MS fragmentation behavior among labeled peptides, and (4) a molecularly efficient architecture, in which the majority of hetero-atom centers can be used to synthesize a variety of nominal mass and sub-Da isotopologue stable isotope reagents. We demonstrate the performance of these reagents in well-established strategies whereby up to four channels of peptide isotopomers, each separated by 4 Da, are quantified in MS-level scans with accuracies comparable to current commercial reagents. In addition, we utilize the PAL scaffold to create isotopologue reagents in which labeled peptide analogs differ in mass based on the binding energy in carbon and nitrogen nuclei, thereby allowing quantification based on MS or MS/MS spectra. We demonstrate accurate quantification for reagents that support 6-plex labeling and propose extension of this scheme to 9-channels based on a similar PAL scaffold. Finally, we provide exemplar data that extend the application of isotopologe-based quantification reagents to medium resolution, quadrupole time-of-flight mass spectrometers. Figure
115F 相似文献
79.
Dr. Luke D. Elliott Dr. Jonathan P. Knowles Dr. Paul J. Koovits Katie G. Maskill Michael J. Ralph Dr. Guillaume Lejeune Lee J. Edwards Richard I. Robinson Ian R. Clemens Brian Cox David D. Pascoe Guido Koch Martin Eberle Malcolm B. Berry Prof. Kevin I. Booker‐Milburn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15226-15232
The use of flow photochemistry and its apparent superiority over batch has been reported by a number of groups in recent years. To rigorously determine whether flow does indeed have an advantage over batch, a broad range of synthetic photochemical transformations were optimized in both reactor modes and their yields and productivities compared. Surprisingly, yields were essentially identical in all comparative cases. Even more revealing was the observation that the productivity of flow reactors varied very little to that of their batch counterparts when the key reaction parameters were matched. Those with a single layer of fluorinated ethylene propylene (FEP) had an average productivity 20 % lower than that of batch, whereas three‐layer reactors were 20 % more productive. Finally, the utility of flow chemistry was demonstrated in the scale‐up of the ring‐opening reaction of a potentially explosive [1.1.1] propellane with butane‐2,3‐dione. 相似文献
80.
A General Method for Preparing Bridged Organosilanes with Pendant Functional Groups and Functional Mesoporous Organosilicas
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Prof. Jana Hodačová Dr. Guillaume Toquer Dr. Xavier Cattoën Dr. Michel Wong Chi Man 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10371-10382
New organosilica precursors containing two triethoxysilyl groups suitable for the organosilica material formation through the sol‐gel process were designed and synthesised. These precursors display alkyne or azide groups for attaching targeted functional groups by copper‐catalysed azide–alkyne cycloaddition (CuAAC) and can be used for the preparation of functional organosilicas following two strategies: 1) the functional group is first appended by CuAAC under anhydrous conditions, then the functional material is prepared by the sol‐gel process; 2) the precursor is first subjected to the sol‐gel process, producing porous, clickable bridged silsesquioxanes or periodic mesoporous organosilicas (PMOs), then the desired functional groups are attached by means of CuAAC. Herein, we show the feasibility of both approaches. A series of bridged bis(triethoxysilane)s with different pending organic moieties was prepared, demonstrating the compatibility of the first approach with many functional groups. In particular, we demonstrate that organic functional molecules bearing only one derivatisation site can be used to produce bridged organosilanes and bridged silsesquioxanes. In the second approach, clickable PMOs and porous bridged silsesquioxanes were prepared from the alkyne‐ or azide‐containing precursors, and thereafter, functionalised with complementary model azide‐ or alkyne‐containing molecules. These results confirmed the potential of this approach as a general methodology for preparing functional organosilicas with high loadings of functional groups. Both approaches give rise to a wide range of new functional organosilica materials. 相似文献