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991.
Hyun Ook Seo Dae Han Kim Kwang-Dae Kim Eun Ji Park Chae Won Sim Young Dok Kim 《Adsorption》2013,19(6):1181-1187
Adsorption and desorption of toluene on bare and TiO2-coated silica with a mean pore size of 15 nm under dry and humid conditions were studied using toluene breakthrough curves and temperature programmed desorption (TPD) of toluene and CO2. Two TiO2/silica samples (either partially or fully covered with TiO2) were prepared with 50 and 200 cycles of TiO2 atomic layer deposition (ALD), respectively. The capacity of silica to adsorb toluene improved significantly with TiO2-thin film coating under dry conditions. However, toluene desorption from the surface due to displacement by water was more pronounced for TiO2-coated samples than bare samples under humid conditions. In TPD experiments, silica with a thinner TiO2 film (50-ALD cycled) had the highest reactivity for toluene oxidation to CO2 both in the absence and presence of water. Toluene adsorption and oxidation reactivity of silica can be controlled by modifying the silica surface with small amount of TiO2 using ALD. 相似文献
992.
Nature and population of Li+ cationic sites in MCM-22 zeolite and its pillared form (MCM-36) were investigated by means of adsorption of CO as a probe molecule. CO stretching frequency and adsorption heat were measured by FTIR spectroscopy and adsorption microcalorimetry. Intrazeolitic carbonyl complexes on Li+ cations in MCM-22 and MCM-36 are characterized by two main vibrational bands at 2,195 and 2,188 cm?1. Band at higher wavenumbers is ascribed to carbonyls on Li+ ions coordinated only to two oxygen atoms at the intersection of 10-ring channels and interacting with CO molecule by energy around 45 kJ mol?1. Band at 2,188 cm?1 was assigned to the carbonyls on Li+ cations located on top of 5 or 6-rings on the channel walls and coordinated to three or four oxygen atoms, interacting with CO molecule by energy 33–36 kJ mol?1. Effect of pillaring and layered form of zeolite on nature and population of Li+ cationic sites is also discussed, as well as the formation of dicarbonyl complexes. 相似文献
993.
Dr. Qingsong Dong Prof. Xiao‐Juan Yang Shida Gong Dr. Qiong Luo Prof. Qian‐Shu Li Prof. Ji‐Hu Su Dr. Yanxia Zhao Prof. Biao Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(45):15240-15247
A nickel? nickel‐bonded complex, [{Ni(μ‐L.?)}2] ( 1 ; L=[(2,6‐iPr2C6H3)NC(Me)]2), was synthesized from reduction of the LNiBr2 precursor by sodium metal. Further controllable reduction of 1 with 1.0, 2.0 and 3.0 equiv of Na, respectively, afforded the singly, doubly, and triply reduced compounds [Na(DME)3] ? [{Ni(μ‐L.?)}2] ( 2 ; DME=1,2‐dimethoxyethane), [Na(Et2O)]Na[(L.?)Ni? NiL2?] ( 3 ), and [Na(Et2O)]2Na[L2?Ni? NiL2?] ( 4 ). Here L represents the neutral ligand, L.? denotes its radical monoanion, and L2? is the dianion. All of the four compounds feature a short Ni? Ni bond from 2.2957(6) to 2.4649(8) Å. Interestingly, they display two different structures: the perpendicular ( 1 and 2 ) and the coaxial ( 3 and 4 ) structure, in which the metal? metal bond axis is perpendicular to or collinear with the axes of the α‐diimine ligands, respectively. The electronic structures, Ni? Ni bonding nature, and energetic comparisons of the two structure types were investigated by DFT computations. 相似文献
994.
Dr. Zhao‐Yang Fei Bo Sun Liang Zhao Prof. Wei‐Jie Ji Prof. Chak‐Tong Au 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6480-6487
Gold nanoparticles (3–4 nm) were deposited on Mn3O4 nanocrystallites with three distinct morphologies (cubic, hexagonal, and octahedral). The resulting structures were characterized, and their activities for benzene combustion were evaluated. The dominant exposed facets for the three kinds of Mn3O4 polyhedrons show the activity order: (103)≈(200)>(101). A similar activity order was derived for the interfaces between the Au and the Mn3O4 facet: Au/(200)≈Au/(103)>Au/(101). The metal–support interactions between the Au nanoclusters and specific facets of the Mn3O4 polyhedrons lead to a unique interfacial synergism in which the electronic modification of the Au nanoparticles and the morphology of the Mn3O4 substrate have a joint effect that is responsible for a significant enhancement in the catalytic activity of the Au/Mn3O4 system. 相似文献
995.
Fangyuan Zheng Prof. Fang Zeng Changmin Yu Xianfeng Hou Prof. Shuizhu Wu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):936-942
Owing to the considerable significance of fluoride anions for health and environmental issues, it is of great importance to develop methods that can rapidly, sensitively and selectively detect the fluoride anion in aqueous media and biological samples. Herein, we demonstrate a robust fluorescent turn‐on sensor for detecting the fluoride ion in a totally aqueous solution. In this study, a biocompatible hydrophilic polymer poly(ethylene glycol) (PEG) is incorporated into the sensing system to ensure water solubility and to enhance biocompatibility. tert‐Butyldiphenylsilyl (TBDPS) groups were then covalently introduced onto the fluorescein moiety, which effectively quenched the fluorescence of the sensor. Upon addition of fluoride ion, the selective fluoride‐mediated cleavage of the Si? O bond leads to the recovery of the fluorescein moiety, resulting in a dramatic increase in fluorescence intensity under visible light excitation. The sensor is responsive and highly selective for the fluoride anion over other common anions; it also exhibits a very low detection limit of 19 ppb. In addition, this sensor is operative in some real samples such as running water, urine, and serum and can accurately detect fluoride ions in these samples. The cytotoxicity of the sensor was determined to be Grade I toxicity according to United States Pharmacopoeia and ISO 10993‐5, suggesting the very low cytotoxicity of the sensor. Moreover, it was found that the senor could be readily internalized by both HeLa and L929 cells and the sensor could be utilized to track fluoride level changes inside the cells. 相似文献
996.
Zheng Wang Shuai Luo Dr. Shoude Zhang Wu‐Lin Yang Yang‐Zi Liu Prof. Dr. Honglin Li Prof. Dr. Xiaoyan Luo Prof. Dr. Wei‐Ping Deng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(21):6739-6745
The first catalytic enantioselective 1,3‐dipolar cycloaddition of azomethine ylides to α‐aminoacrylate catalyzed by a AgOAc/ferrocenyl oxazolinylphosphine (FOXAP) system was developed, which exhibits excellent exo‐ and enantioselectivity (92–99 % ee). This process provides efficient access to useful 4‐aminopyrrolidine‐2,4‐dicarboxylic acid (APDC)‐like compounds containing a unique quaternary α‐amino acid unit. 相似文献
997.
Dr. Yaqi Jiang Yanyan Jia Jiawei Zhang Lei Zhang Huang Huang Prof. Dr. Zhaoxiong Xie Prof. Dr. Lansun Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):3119-3124
Pt? Cu alloy octahedral nanocrystals (NCs) have been synthesized successfully by using N,N‐dimethylformamide as both the solvent and the reducing agent in the presence of cetyltrimethylammonium chloride. Cu underpotential deposition (UPD) is found to play a key role in the formation of the Pt? Cu alloy NCs. The composition in the Pt? Cu alloy can be tuned by adjusting the ratio of metal precursors in solution. However, the Cu content in the Pt? Cu alloy NCs cannot exceed 50 %. Due to the fact that Cu precursor cannot be reduced to metallic copper and the Cu content cannot exceed 50 %, we achieved the formation of the Pt? Cu alloy by using Cu UPD on the Pt surface. In addition, the catalytic activities of Pt? Cu alloy NCs with different composition were investigated in electrocatalytic oxidation of formic acid. The results reveal that the catalytic performance is strongly dependent on Pt? Cu alloy composition. The sample of Pt50Cu50 exhibits excellent activity in electrocatalytic oxidation of formic acid. 相似文献
998.
Tao Zheng Prof. Dr. Juan M. Clemente‐Juan Prof. Dr. Jing Ma Prof. Dr. Lin Dong Dr. Song‐Song Bao Dr. Jian Huang Prof. Dr. Eugenio Coronado Prof. Dr. Li‐Min Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16394-16402
Two cobalt phosphonates, [Co2(2,2′‐bpy)2(H2O)(pbtcH)] ( 1 ) and [Co2(H2O)(pbtcH)(phen)2] ( 2 ; pbtcH5=5‐phosphonatophenyl‐1,2,4‐tricarboxylic acid, 2,2′‐bpy=2,2′‐bipyridine, phen=1,10‐phenanthroline), with layer structures are reported. Compound 1 contains O‐C‐O and O‐P‐O bridged tetramers of Co4, which are further connected by pbtcH4? units to form a layer. In compound 2 , the cobalt tetramers made up of water‐bridged Co2 dimers and O‐P‐O linkages are connected into a layer by pbtcH4? units. Upon dehydration, compounds 1 and 2 experience single‐crystal‐to‐single‐crystal (SC–SC) structural transformations to form [Co2(2,2′‐bpy)2(pbtcH)] ( 1 a ) and [Co2(pbtcH)(phen)2] ( 2 a ), respectively. The process is reversible in each case. Notably, a breathing effect is observed for 1 , accompanied by pore opening and closing due to the reorientation of the coordinated 2,2′‐bpy molecules. The transformation was also monitored by in situ IR measurements. Magnetic studies reveal that antiferromagnetic interactions are mediated between the magnetic centers in compounds 1 and 1 a , whereas ferromagnetic interactions are dominant in compound 2 . 相似文献
999.
Dr. Qiuhua Zhu Lan Huang Dr. Zhipeng Chen Sichao Zheng Longyun Lv Dr. Zhibo Zhu Prof. Derong Cao Prof. Huanfeng Jiang Prof. Shuwen Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1268-1280
A new series of C‐6 unsubstituted tetrahydropyrimidines 6 have been directly synthesized via a convenient urea‐catalyzed chemoselective five‐component reaction (5CR) under mild conditions. Compounds 6 show typical aggregation‐induced emission enhancement (AIEE) characteristics because they are practically no emissive in solution but emit blue or green fluorescence in aggregates with fluorescence yield up to 93 %. One of the 5CR products, 6 aa , exhibits blue‐ and green‐fluorescence aggregates (bf‐ and gf‐aggregates). The bf‐ and gf‐aggregates are prepared under different conditions and proved to result from different J‐aggregations by single‐crystal X‐ray analysis. In addition, the bf‐ and gf‐aggregates of 6 aa show unusual size‐independent emission (SIE) characteristics because their maximum emission wavelengths in different sizes (suspension particles, film, powder and crystals) are the same, 434 and 484 nm, respectively. Based on the obtained experimental results, the 5CR mechanism, the origins of AIEE and SIE characteristics are discussed. 相似文献
1000.
Ji Ha Lee Sunwoo Kang Prof. Dr. Jin Yong Lee Prof. Dr. Justyn Jaworski Prof. Dr. Jong Hwa Jung 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16665-16671
There is an ongoing need for explosive detection strategies to uncover threats to human security including illegal transport and terrorist activities. The widespread military use of the explosive trinitrotoluene (TNT) for landmines poses another particular threat to human health in the form of contamination of the surrounding environment and groundwater. The detection of explosives, particularly at low picogram levels, by using a molecular sensor is seen as an important challenge. Herein, we report on the use of a fluorescent metal–organic framework hydrogel that exhibits a higher detection capability for TNT in the gel state compared with that in the solution state. A portable sensor prepared from filter paper coated by the hydrogel was able to detect TNT at the picogram level with a detection limit of 1.82 ppt (parts per trillon). Our results present a simple and new means to provide selective detection of TNT on a surface or in aqueous solution, as afforded by the unique molecular packing through the metal–organic framework structure in the gel formation and the associated photophysical properties. Furthermore, the rheological properties of the MOF‐based gel were similar to those of a typical hydrogel. 相似文献