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771.
Tetsuya Kawano 《Journal of solid state chemistry》2011,184(9):2466-2471
Single crystals of new oxyborates, Mg5NbO3(BO3)3 and Mg5TaO3(BO3)3, were prepared at 1370 °C in air using B2O3 as a flux. They were colorless and transparent with block shapes. X-ray diffraction analysis of the single crystals revealed Mg5NbO3(BO3)3 and Mg5TaO3(BO3)3 to be isostructural. The X-ray diffraction reflections were indexed to the orthorhombic Pnma (No. 62) system with a=9.3682(3) Å, b=9.4344(2) Å, c=9.3379(3) Å and Z=4 for Mg5NbO3(BO3)3 and a=9.3702(3) Å, b=9.4415(3) Å, c=9.3301(2) Å and Z=4 for Mg5TaO3(BO3)3. The crystal structures of Mg5NbO3(BO3)3 and Mg5TaO3(BO3)3 are novel warwickite-type superstructures having ordered arrangements of Mg and Nb/Ta atoms. Polycrystals of Mg5NbO3(BO3)3 prepared by solid state reaction at 1200 °C in air showed broad blue-to-green emission with a peak wavelength of 470 nm under 270 nm ultraviolet excitation at room temperature. 相似文献
772.
Periodic Mesoporous Organosilica with Molecular‐Scale Ordering Self‐Assembled by Hydrogen Bonds 下载免费PDF全文
Dr. Norihiro Mizoshita Dr. Shinji Inagaki 《Angewandte Chemie (International ed. in English)》2015,54(41):11999-12003
Nanoporous materials with functional frameworks have attracted attention because of their potential for various applications. Silica‐based mesoporous materials generally consist of amorphous frameworks, whereas a molecular‐scale lamellar ordering within the pore wall has been found for periodic mesoporous organosilicas (PMOs) prepared from bridged organosilane precursors. Formation of a “crystal‐like” framework has been expected to significantly change the physical and chemical properties of PMOs. However, until now, there has been no report on other crystal‐like arrangements. Here, we report a new molecular‐scale ordering induced for a PMO. Our strategy is to form pore walls from precursors exhibiting directional H‐bonding interaction. We demonstrate that the H‐bonded organosilica columns are hexagonally packed within the pore walls. We also show that the H‐bonded pore walls can stably accommodate H‐bonding guest molecules, which represents a new method of modifying the PMO framework. 相似文献
773.
The hydrogenation of ethylene on Ni(1 0 0) surface has been studied by TDS. The decrease in the bonding energy with increasing coverage is revealed for both of adsorbed hydrogen and ethylene by the shift of desorption to lower temperatures. Ethane formation is only observed on the preadsorbed hydrogen coverage exceeding 0.5 monolayer (ML), coupled with the growth of H2 shoulder peak at lower temperatures. Further increase of H coverage to saturation reduces the bonding energy of subsequently adsorbed ethylene by 15 kJ/mol and decreases the saturation coverage of ethylene to about one-third on the clean surface. This leads to the shift of ethane desorption from 250 to 220 K and an appearance of additional ethane peak at 180 K. The latter ethane formation coincides with the hydrogenation of surface ethyl species derived from ethyl iodide as a precursor. It indicates that the rate of ethyl formation on the surface would be comparable to that of subsequent hydrogen addition to the surface ethyl species in the hydrogenation of ethylene when the preadsorbed hydrogen coverage approaches 1.0 ML. 相似文献
774.
The K absorption-edge spectra of the ligand chlorine ion in square-planar complex compounds cis- and trans-[Pt(NH3)2Cl2], trans-[Pd(NH3)2Cl2], and (NH4)2PdCl4 are reported and discussed in connection with the chlorine K absorption spectra of K2PtCl4 and K2PdCl4, reported previously. The observed chemical shift of a white line at the absorption threshold is interpreted in terms of the difference of the ligand-field splitting of electronic states for metal ions. The white line is attributed to the electronic transition from the Cl? ls level to the lowest unoccupied antibonding molecular orbital (MO), which is specified by a in the square-planar complex with D4h symmetry. The other absorption structures are regarded as continuum “shape resonances” of the outgoing electron trapped by the cage of the surrounding atoms. The effect of geometrical isomerism is found in the chlorine K absorption spectra of cis- and trans-[Pt(NH3)2Cl2]. 相似文献
775.
776.
Takashi Kaneko Dr. Go M. Russell Yutaro Kawano Prof. Dr. Hiroshi Masai Prof. Dr. Jun Terao 《Angewandte Chemie (International ed. in English)》2023,62(26):e202305374
Photopolymerization and photoprocessing are core technologies for molding and tuning polymer materials. However, they are incompatible with single materials owing to their contradictory photoreactivity. Herein, an acid-induced photocleavable crosslinker, a platinum–acetylide complex covered by permethylated cyclodextrins, enables the fabrication of photoprocessable materials via photopolymerization with N-(2-hydroxyethyl)acrylamide. The polymer networks are molded by 365 nm irradiation as well as softened and degraded by a cooperative reaction with HCl as an acidic additive under 365 nm UV light, or 470 nm visible light in the presence of a photosensitizer. Moreover, the crosslinker is applied to a photoadhesive triggered by 365 nm irradiation. The adhesion is detachable on-demand through acid-induced photodegradation with the same wavelength and intensity of irradiation. Thus, acid-induced photocleavage allows the integration of light-induced molding and processing under various lights of various wavelengths, opening up new strategies for polymer technologies. 相似文献
777.
778.
Mart-Rujas J Islam N Hashizume D Izumi F Fujita M Kawano M 《Journal of the American Chemical Society》2011,133(15):5853-5860
With the use of ab initio X-ray powder diffraction, a family of isostructural crystalline porous coordination networks, [(ZnX(2))(3)(TPT)(2)](n)· (solvent) (X = I, Br, Cl), has been studied at elevated temperatures of 573-723 K. Upon heating, all three networks exhibited crystalline-to-amorphous-to-crystalline (CAC) phase transformations to three new networks, [(ZnI(2))(3)(TPT)(2)](n), [(ZnBr(2))(3)(TPT)(2)](n)·(H(2)O) and [(ZnBr(2))(μ-Br)(ZnBr)(TPT)](n), and [(ZnCl(2))(μ-Cl)(ZnCl)(TPT)](n), respectively. A set of control experiments was used to obtain detailed mechanistic aspects of the CAC transformations. We demonstrate how bonds are broken and formed in these significant molecular rearrangements and how the initial arrangement plays a crucial role in the formation of the new networks after the CAC transformations. The structural information in the amorphous phase is retained and passed from a metastable to a more stable crystal, thus, reinforcing the notion that coordination networks are flexible and chemically active. 相似文献
779.
Asaumi T Chatani N Matsuo T Kakiuchi F Murai S 《The Journal of organic chemistry》2003,68(19):7538-7540
The reaction of 1-arylpyrazoles with CO and ethylene in the presence of Ru(3)(CO)(12) resulted in regioselective carbonylation at the ortho C-H bonds. While it is found that the pyrazole ring also functions as the directing group for C-H bond cleavage, the efficiency of the reaction depends on the position of the pyrazole ring. 相似文献
780.
Mikio Fujii Shinji Sudo Yasuyuki Kitagawa Keisuke Kato 《Journal of carbohydrate chemistry》2013,32(7):424-437
While D-glucose is the natural substrate of aldose reductase (AR) in the polyol pathway, the K m value of D-glucose against AR is large. A glucoamide 1 was designed as a tool to investigate whether AR has a strong affinity for the open form of D-glucose. Glucoamide 1 was synthesized in high yield by modification of the reaction condition for click chemistry. It was found that our modified condition was applicable for highly polar alkynes and gave coupling products in excellent yield (90% to 100%). Although weak inhibitory activity against AR was observed, kinetic studies showed that AR does not accept glucoamide 1 in its active site. 相似文献