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1.
Li-Ngee Ho Tasuku Ikegawa Hiroyasu Nishiguchi Katsutoshi Nagaoka Yusaku Takita 《Applied Surface Science》2006,252(18):6260-6268
A synthesis of molybdenum incorporated mesoporous aluminophosphate with long-chain n-alkylamine as template material had been prepared under non-aqueous condition. These materials were extensively characterized by using X-ray diffraction (XRD), nitrogen sorption isotherms, nuclear magnetic resonance of 27Al and 31P (NMR), inductive coupled plasma (ICP), electron spin resonance (ESR), Fourier transform infrared (FTIR) and thermogravimetric-differential thermal analysis (TG-DTA). Morphology of the materials had been observed by using transmission electron microscope (TEM) that revealed the mesoporous materials possessed wormhole-like structures. Alkaline solvent extraction using n-butylamine/ethanol had been efficiently removed the n-alkylamine from the mesoporous samples which yielded BET surface areas around 550-730 m2/g. BJH analysis showed a narrow pore size distribution which increased with increasing of the carbon chain length of alkylamine (template). Valence state and coordination of the molybdenum in the obtained samples were investigated by using ESR and FTIR where it was found that Mo4+ and Mo6+ molybdenum species existed in the molybdenum incorporated mesoporous aluminophosphate in tetrahedral coordination. 相似文献
2.
Hiroyasu Nishiguchi Hiroshi Yamada Masaru Ogura Tatsumi Ishihara Yusaku Takita 《Research on Chemical Intermediates》2003,29(7-9):755-760
The oxygen storage capacity of CeO2, Ce0.9Pr0.1O2, Pt?Rh/CeO2 and Pt?Rh/Ce0.9Pr0.1O2 was investigated by conventional GC pulse method and transient pulse techniques. It is shown that incorporation of PrOy into CeO2 matrix strongly promotes oxygen storage capacity (OSC) measured using the transient pulse technique. The improvement of OSC at low temperature is observed in Pt?Rh loaded onto CeO2 and Ce?Pr catalysts. 相似文献
3.
Sawada Y. Seki S. Sano M. Miyabayashi N. Ninomiya K. Iwasawa A. Tsugoshi T. Ozao R. Nishimoto Y. 《Journal of Thermal Analysis and Calorimetry》2004,77(3):751-757
Tin-doped indium oxide In2O3 (indium-tin-oxide) transparent conducting films were fabricated on silicon substrates by a dip coating process. The thermal
analysis of the ITO films was executed by temperature-programmed desorption (TPD) or thermal desorption spectroscopy (TDS)
in high vacuum. Gas evolution from the ITO film mainly consisted of water vapor. The total amount of evolved water vapor increased
on increasing the film thickness from approx. 25 to 250 nm and decreased by increasing the preparation temperature from 365
to 600°C and by annealing at the same temperature for extra 10 h. The evolution occurred via two steps; the peak temperatures
for 250 nm thick films were approx. 100-120 and 205-215°C. The 25 nm thick films evolved water vapor at much higher temperatures;
a shoulder at approx. 150-165°C and a peak at approx. 242°C were observed. The evolution temperatures increased by increasing
the preparation and the annealing temperatures except in case of the second peak of the 25 nm thick films. The evolution of
water vapor at high temperature was tentatively attributed to thermal decomposition of indium hydroxide, In(OH)3, formed on the surface of the nm-sized ITO particles.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
4.
Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols 总被引:1,自引:0,他引:1
Iwasawa T Tokunaga M Obora Y Tsuji Y 《Journal of the American Chemical Society》2004,126(21):6554-6555
In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 degrees C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields. 相似文献
5.
The bound site of Mo atoms and its local structure in a Mo/HY catalyst have been determined by detailed analysis of extended X-ray absorption fine structure (EXAFS). Molybdenum was introduced in the supercage of HY zeolite by cycles of saturated adsorption of Mo(CO)6 at room temperature and subsequent thermal decomposition at 573 K. Two Mo atoms per supercage were immobilized in each CVD-thermal treatment cycle. The Mo loading increased linearly with the cycles up to three cycles at saturation, where six Mo atoms were supported. Temperature-programmed decomposition of the adsorbed Mo(CO)6 was also characterized by GC, QMS, and FT-IR, respectively. The EXAFS analysis including multiple scattering based on theoretical calculations revealed that Mo bound with two oxygen atoms connects to Al, where one of the two oxygen atoms had been associated with a proton. The bound site is called the S(III)' site. The zeolite framework was significantly distorted by the introduction of low-valent Mo, resulting in isolation of the [MoO2Al] unit from the surrounding zeolite framework due to a quasi-disruption of Si-O bonds adjacent to the unit. In the mild oxidation of the low-valent Mo/HY sample two Mo=O bonds were newly formed and the position of Mo was displaced by 0.06 nm so that the distortion of zeolite framework around the Al atom was relieved. The structures were also supported by DFT calculations. This study is the first example that the position of metal cation in zeolite was determined unambiguously by the EXAFS analysis. 相似文献
6.
Komatsu H Iwasawa N Citterio D Suzuki Y Kubota T Tokuno K Kitamura Y Oka K Suzuki K 《Journal of the American Chemical Society》2004,126(50):16353-16360
The role of intracellular magnesium ions is of high interest in the fields of pharmacology and cellular biology. To accomplish the dynamic and three-dimensional imaging of intracellular Mg2+, there is a strong desire for the development of optimized Mg2+ fluorescent probes. In this paper we describe the design, synthesis, and cellular application of the three novel Mg2+ fluorescent probes KMG-101, -103, and -104. The compounds of this series feature a charged beta-diketone as a binding site specific for Mg2+ and a fluorescein residue as the fluorophore that can be excited with an Ar+ laser such as is widely used in confocal scanning microscopy. This molecular design leads to an intensive off-on-type fluorescent response toward Mg2+ ions. The two fluorescent probes KMG-103 and -104 showed suitable dissociation constants (Kd,Mg2+ = 2 mM) and nearly a 10-fold fluorescence enhancement over the intracellular magnesium ion concentration range (0.1-6 mM), allowing high-contrast, sensitive, and selective Mg2+ measurements. For intracellular applications, the membrane-permeable probe KMG-104AM was synthesized and successfully incorporated into PC12 cells. Upon application of the mitochondria uncoupler FCCP to the probe-incorporated cells, the resulting increase in the free magnesium ion concentration could be followed over time. By using a confocal microscope, the intracellular 3D magnesium ion concentration distributions were satisfactorily observed. 相似文献
7.
The hydronaphthalene moieties of mevinic acids are synthesized enantioselectively by using the asymmetric intramolecular Diels-Alder reaction catalyzed by a chiral titanium reagent. 相似文献
8.
Ichikawa S Tada M Iwasawa Y Ikariya T 《Chemical communications (Cambridge, England)》2005,(7):924-926
Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed. 相似文献
9.
Tada M Taniike T Kantam LM Iwasawa Y 《Chemical communications (Cambridge, England)》2004,(22):2542-2543
The self-dimerized chiral assembly of vanadium-Schiff-base complexes was found to occur on a SiO2 surface and to be the first heterogeneous catalyst for the asymmetric oxidative coupling of 2-naphthol with 100% selectivity and 90% enantioselectivity. 相似文献
10.
A complexation-initiated intramolecular Diels-Alder reaction was demonstrated for the first time. On adsorbing the alkyne-Co(2)(CO)(6) complexes having a diene and a dienophile on opposite ends of the alkyne on silica gel, the Diels-Alder reaction was accelerated and the equilibrium was shifted toward the adduct formation to a greater extent compared to that in solution. Seven-membered ring formation was apparently favorable in this system. 相似文献