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961.
The lanthanum strontium titanate (LST) has to be calcined at significantly high temperature (above 1,300 °C) to obtain its pure perovskite structure when synthesized by conventional solid-state method, which is main reason for reducing active surface area. In this study, A-site deficient (La0.3Sr0.7)0.93TiO3 was synthesized by Pechini method. Although the prepared powders were calcined at 600 °C, the pure perovskite structure can be obtained without any secondary phase such as TiO2. Moreover, the porosity and surface area are 6 times and one order of magnitude higher in the LST powders synthesized by Pechini method than in the powders synthesized by solid-state method. Based on these results, the LST electrode (Pechini) leads to two times lower electrode resistance than the LST electrode (solid-state). Thus, the LST powders synthesized by Pechini can contributes to saving the energy needed for calcination process as well as increasing the porosity and active surface area, enhancing physical and electrochemical properties in SOFC anode. 相似文献
962.
Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles
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Dr. Jinsen Chen Pei Chen Chao Song Prof. Dr. Jin Zhu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(44):14245-14249
RhIII‐catalyzed N‐nitroso‐directed C?H addition to ethyl 2‐oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N‐nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C?H functionalization‐based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tricyclic‐fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles. 相似文献
963.
Back Cover: Two‐Dimensional Tetrathiafulvalene Covalent Organic Frameworks: Towards Latticed Conductive Organic Salts (Chem. Eur. J. 45/2014)
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964.
Shan She Shengtai Bian Prof. Dr. Jian Hao Dr. Jiangwei Zhang Jin Zhang Prof. Dr. Yongge Wei 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16987-16994
A series of aliphatic organoimido derivatives of hexamolybdate based on amantadine, namely (nBu4N)2[Mo6O18(?NC10H15)] ( 1 ), (nBu4N)2 {cis‐[Mo6O17(?NC10H15)2]} ( 2 ), (nBu4N)2{trans‐[Mo6O17(?NC10H15)2]} ( 3 ), and (nBu4N)2[Mo6O16(?NC10H15)3] ( 4 ), was synthesized in reasonable yield by dehydration with N,N′‐dicyclohexylcarbodiimide (DCC). They were characterized by IR and UV/Vis spectroscopy, elemental analysis, ESI mass spectrometry, and single‐crystal X‐ray structure analysis. The spectral and structural similarities and differences between monosubstituted, cis‐disubstituted, and trans‐disubstituted organoimido derivatives were elucidated and may provide guidance for related work on organoimido‐functionalized Lindqvist‐type polyoxometalates. In addition, trans‐disubstituted and polysubstituted derivatives containing aliphatic organoimido ligands have not yet been reported, and the crystal structure of the trans isomer may lead us to a deeper understanding of disubstituted derivatives. Furthermore, proliferation and morphology of MCF‐7 cells were studied with compound 1 . The present results show that the DCC‐dehydrating protocol could be an efficient approach to covalently graft bioactive ligands such as amantadine onto POMs and enhance their application in clinical cancer treatment. 相似文献
965.
Synthesis of Site‐Specifically Phosphate‐Caged siRNAs and Evaluation of Their RNAi Activity and Stability
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Dr. Li Wu Fen Pei Jinhao Zhang Junzhou Wu Mengke Feng Yuan Wang Dr. Hongwei Jin Prof. Liangren Zhang Prof. Xinjing Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12114-12122
A complete set of new photolabile nucleoside phosphoramidites were synthesized, then site‐specifically incorporated into sense or antisense strands of siRNA for phosphate caging. Single caging modification was made along siRNA strands and their photomodulation of gene silencing were examined by using the firefly luciferase reporter gene. Several key phosphate positions were then identified. Furthermore, multiple caging modifications at these key positions led to significantly enhanced photomodulation of gene silencing activity, suggesting a synergistic effect. The caging group on both the terminally phosphate‐caged siRNA and the single‐stranded caged RNA has comparatively high stability, whereas hydrolysis of the caged group from the internally caged siRNA was observed, irrespective of the presence of Mg2+. Molecular dynamic simulations demonstrated that enhanced hydrolysis of the caging group on internally phosphate‐caged siRNAs was due to easy fragmentation of the caging group upon formation of the pentavalent intermediate of the phosphotriester with attack by water. The caging group in the terminally phosphate‐caged siRNA or single‐stranded caged RNA prefers to form π–π stacks with nearby nucleobases. In addition to providing explanations for previous observations, this study sheds further light on the design of caged oligonucleotides and indicates the direction of future development of nucleic acid drugs with phosphate modifications. 相似文献
966.
Cube‐in‐Cube Hollow Cu9S5 Nanostructures with Enhanced Photocatalytic Activities in Solar H2 Evolution
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Miao Xu Min Wang Tiannan Ye Na Liang Lun Jin Dr. Jiantao Zai Prof. Xuefeng Qian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(42):13576-13582
Hydrogen produced from water under solar energy is an ideal clean energy source, and the efficiency of hydrogen production usually depends on the catalytic systems based on new compounds and/or a unique nanostructure. Herein, well‐defined cube‐in‐cube hollow Cu9S5 nanostructures have been successfully prepared with Cu2O nanocubes and CS2 as precursors, and single‐shell hollow Cu9S5 nanocubes could be obtained by replacing CS2 with Na2S. The formation mechanism of cube‐in‐cube hollow nanostructures has been proposed based on the Kirkendell effect and an outward self‐assembly process. Further studies revealed that the cube‐in‐cube hollow Cu9S5 nanostructures exhibited better photocatalytic activity toward solar H2 evolution and would be a promising photocatalyst in the solar hydrogen industry. 相似文献
967.
Efficient Copper‐Catalyzed Direct Intramolecular Aminotrifluoromethylation of Unactivated Alkenes with Diverse Nitrogen‐Based Nucleophiles
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Dr. Jin‐Shun Lin Ya‐Ping Xiong Can‐Liang Ma Li‐Jiao Zhao Prof. Dr. Bin Tan Prof. Dr. Xin‐Yuan Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1332-1340
A mild, convenient, and step‐economical intramolecular aminotrifluoromethylation of unactivated alkenes with a variety of electronically distinct, nitrogen‐based nucleophiles in the presence of a simple copper salt catalyst, in the absence of extra ligands, is described. Many different nitrogen‐based nucleophiles (e.g., basic primary aliphatic and aromatic amines, sulfonamides, carbamates, and ureas) can be employed in this new aminotrifluoromethylation reaction. The aminotrifluoromethylation process allows straightforward access to diversely substituted CF3‐containing pyrrolidines or indolines, in good to excellent yields, through a direct difunctionalization strategy from the respective acyclic starting materials. Mechanistic studies were conducted and a plausible mechanism was proposed. 相似文献
968.
Tailoring 3,3′‐Dihydroxyisorenieratene to Hydroxystilbene: Finding a Resveratrol Analogue with Increased Antiproliferation Activity and Cell Selectivity
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Yan‐Fei Kang Wen‐Jing Yan Ting‐Wen Zhou Dr. Fang Dai Dr. Xiu‐Zhuang Li Xia‐Zhen Bao Yu‐Ting Du Cui‐Hong Yuan Hai‐Bo Wang Xiao‐Rong Ren Dr. Qiang Liu Dr. Xiao‐Ling Jin Prof. Dr. Bo Zhou Prof. Dr. Jie Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):8904-8908
Four novel compounds were designed by “tailoring” 3,3′‐dihydroxyisorenieratene (a natural carotenoid) based on an isoprene unit retention truncation strategy. Among them, the smallest molecule 1 (2,3,6,2′,3′,6′‐hexamethyl‐4,4′‐dihydroxy‐trans‐stilbene) was concisely synthesized in a one‐pot Stille–Heck tandem sequence, and surfaced as a promising lead molecule in terms of its selective antiproliferative activity mediated by blocking the NCI‐H460 cell cycle in G1 phase. Additionally, theoretical calculations and cell uptake experiments indicate that the unique polymethylation pattern of compound 1 significantly induces a conformational change shift out of planarity and increases its cell uptake and metabolic stability. The observation should be helpful to rationally design resveratrol‐inspired antiproliferative agents. 相似文献
969.
Highly Enantioselective Catalytic System for Asymmetric Copolymerization of Carbon Dioxide and Cyclohexene Oxide
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Yuan‐Zhao Hua Liu‐Jie Lu Pei‐Jin Huang Dong‐Hui Wei Prof. Ming‐Sheng Tang Prof. Dr. Min‐Can Wang Prof. Dr. Jun‐Biao Chang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12394-12398
A new ligand can be easily prepared, and its intramolecular dinuclear zinc complexes act as a high performance catalyst for the asymmetric alternating copolymerization of cyclohexene oxide and CO2 under very mild conditions (1 atm CO2, room temperature), affording completely alternating polycarbonates with up to 93.8 % enantiomeric excess (ee) and 98 % yield. A high Mn value of 28 600 and a relatively narrow polydispersity (Mw/Mn ratio) of 1.43 were also achieved. 相似文献
970.
Well‐Defined Iron Complexes as Efficient Catalysts for “Green” Atom‐Transfer Radical Polymerization of Styrene,Methyl Methacrylate,and Butyl Acrylate with Low Catalyst Loadings and Catalyst Recycling
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So‐ichiro Nakanishi Dr. Mitsunobu Kawamura Hidetomo Kai Prof. Dr. Ren‐Hua Jin Dr. Yusuke Sunada Prof. Dr. Hideo Nagashima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(19):5802-5814
Environmentally friendly iron(II) catalysts for atom‐transfer radical polymerization (ATRP) were synthesized by careful selection of the nitrogen substituents of N,N,N‐trialkylated‐1,4,9‐triazacyclononane (R3TACN) ligands. Two types of structures were confirmed by crystallography: “[(R3TACN)FeX2]” complexes with relatively small R groups have ionic and dinuclear structures including a [(R3TACN)Fe(μ‐X)3Fe(R3TACN)]+ moiety, whereas those with more bulky R groups are neutral and mononuclear. The twelve [(R3TACN)FeX2]n complexes that were synthesized were subjected to bulk ATRP of styrene, methyl methacrylate (MMA), and butyl acrylate (BA). Among the iron complexes examined, [{(cyclopentyl)3TACN}FeBr2] ( 4 b ) was the best catalyst for the well‐controlled ATRP of all three monomers. This species allowed easy catalyst separation and recycling, a lowering of the catalyst concentration needed for the reaction, and the absence of additional reducing reagents. The lowest catalyst loading was accomplished in the ATRP of MMA with 4 b (59 ppm of Fe based on the charged monomer). Catalyst recycling in ATRP with low catalyst loadings was also successful. The ATRP of styrene with 4 b (117 ppm Fe atom) was followed by precipitation from methanol to give polystyrene that contained residual iron below the calculated detection limit (0.28 ppm). Mechanisms that involve equilibria between the multinuclear and mononuclear species were also examined. 相似文献