Oxidation of toluenes to benzoic acids by oxygen in non-acidic solvents

Oxidation of substituted toluenes by molecular oxygen at one atmosphere to the corresponding substituted benzoic acids in non-acidic solvents was investigated. Satisfactory oxidation of halo-, methoxy-, and cyano-toluenes were achieved using Co(C₁₈H₃₅O₂)₂/NH₄Br or Co(OAc)₂/NaBr/AcOH as catalysts in the presence of a radical initiator.     

Two efficient four-step routes to marine toxin tanikolide

We have presented two facile four-step syntheses of (±)-tanikolide from ethyl 2-oxocyclopentanecarboxylate. The overall chemical yields of the two sequences reached as high as 76 and 85%, respectively. The first strategy involved alkylation, Baeyer-Villiger reaction, saponification, and reduction/lactonization. The second approach for synthesizing tanikolide took advantage of the same intermediate, the alkylated ketoester 2, which was converted to the target molecule in such three steps as deethoxycarbonylation, hydroxymethylation, and Baeyer-Villiger reaction. Our strategies are advantageous because of their high yields and suitability for the preparation of 1 in multigram or larger quantities.     

A New Method for Constructing Williamson Matrices

For every prime power q 1 (mod 4) we prove the existence of (q; x, y)-partitions of GF(q) with q=x²+4y² for some x, y, which are very useful for constructing SDS, DS and Hadamard matrices. We discuss the transformations of (q; x,y)-partitions and, by using the partitions, construct generalized cyclotomic classes which have properties similar to those of classical cyclotomic classes. Thus we provide a new construction for Williamson matrices of order q².The research supported by NSF of China (No. 10071029).     

季铵盐功能化的钛硅分子筛催化丙烯氧化酯化合成碳酸丙烯酯

将有机卤素季铵盐以硅烷化键合方式嫁接到钛硅分子筛上,制备了兼备催化氧化烯烃合成环氧化物和环氧化物碳酸酯化反应的新型双功能催化剂,考察了其在丙烯、过氧化氢和二氧化碳一步合成碳酸丙烯酯的催化性能.研究表明,具有大外表面积的层剥离的钛硅分子筛是一种嫁接季铵盐合适的载体,丙基三丁基卤化铵是酯化催化性能优良的功能化基团,两者的偶合使一步法催化丙烯环氧化酯化合成碳酸丙烯酯的收率达48%.该催化剂具有较好的稳定性和重复使用性能.     

Ti-MWW/H2O2体系催化官能化烯烃环氧化

研究了Ti-MWW/H2O2催化体系对多种官能化烯烃液相环氧化的催化性能.结果表明,与钛硅分子筛TS-1相比,Ti-MWW具有更高的催化活性和环氧化产物选择性.溶剂对Ti-MWW催化环氧化反应的活性影响较大,其中水是催化丙烯酸乙酯和乙酸烯丙酯的最佳溶剂,随着C=C双键相邻官能团吸电子能力的增强,环氧化反应的催化活性下降.     

Multiple Mechanisms of the Synthesized Antimicrobial Peptide TS against Gram-Negative Bacteria for High Efficacy Antibacterial Action In Vivo

The emergence of drug-resistant bacteria emphasizes the urgent need for novel antibiotics. The antimicrobial peptide TS shows extensive antibacterial activity in vitro and in vivo, especially in gram-negative bacteria; however, its antibacterial mechanism is unclear. Here, we find that TS without hemolytic activity disrupts the integrity of the outer bacterial cell membrane by displacing divalent cations and competitively binding lipopolysaccharides. In addition, the antimicrobial peptide TS can inhibit and kill E. coli by disintegrating the bacteria from within by interacting with bacterial DNA. Thus, antimicrobial peptide TS’s multiple antibacterial mechanisms may not easily induce bacterial resistance, suggesting use as an antibacterial drug to be for combating bacterial infections in the future.     

Novel microfibrous composite bed reactor: high efficiency H2 production from NH3 with potential for portable fuel cell power supplies

A novel microfibrous composite bed reactor was developed and was demonstrated for high efficiency hydrogen production by the decomposition of ammonia at moderate temperatures in portable fuel cell power system applications. By using a high-speed and low-cost papermaking technology combined with a subsequent sintering process, sinter-locked three-dimensional microfibrous networks consisting of approximately 3 vol% 8 microm (dia.) nickel microfibers were utilized to entrap approximately 35 vol% 100-200 microm dia. porous Al(2)O(3) support particulates. A CeO(2) promoter and active Ni component were then dispersed onto the pore surface of the entrapped Al(2)O(3) support particulates by a stepwise incipient wetness impregnation method. The microfibrous structure took advantage of a large void volume, entirely open structure, high heat/mass transfer, high permeability, good thermal stability, and unique form factors. Addition of ceria significantly promoted the low-temperature activity of Ni/Al(2)O(3) catalyst particulates incorporated into the micorfibrous structure. The use of fine particles of catalyst significantly attenuated the intraparticle mass transport limitations. As a result, the present novel microfibrous composite bed reactor provided excellent activity and structure stability in ammonia decomposition, as well as low pressure drop and high efficiency reactor design. At a 90% conversion of a 145 sccm ammonia feed rate, the microfibrous entrapped Ni/CeO(2)-Al(2)O(3) catalyst composite bed could provide a 4-fold reduction of catalytic bed volume and a 5-fold reduction of catalytic bed weight (or 9-fold reduction of catalyst dosage), while leading to a reduction of reaction temperature of 100 degrees C, compared to a packed bed with 2 mm dia. Ni/CeO(2)-Al(2)O(3) catalyst pellets. This composite bed was capable of producing roughly 22 W of hydrogen power, with an ammonia conversion of 99% at 600 degrees C in a bed volume of 0.5 cm(3) throughout a 100 h continuous test. These initial and promising results established that the microfibrous nickel-based catalyst composites were effective for high efficiency production of hydrogen by ammonia decomposition, while achieving a significant reduction of overall catalytic bed weight and volume. We anticipate our assay to be a new point for small-scale hydrogen production, where the microfibrous catalytic reactors considered in isolation can satisfy several of the most fundamental criteria needed for useful operation.     

双离子液体基多孔炭的制备与电化学性能

以质子型离子液体1-氢-3-乙烯基咪唑硫酸氢盐(HVImHSO₄)为主炭源, 以1-丁基-3-甲基咪唑六氟磷酸盐(BMImPF₆)为助剂, 在氮气气氛、 1000 ℃下一步炭化得到氮、 磷、 硫共掺杂多孔炭. 通过N₂吸附-脱附、 扫描电子显微镜(SEM)、 透射电子显微镜(TEM)、 X射线衍射(XRD)、 拉曼光谱(Raman)、 热重分析(TGA)和X射线光电子能谱(XPS)等技术对多孔炭进行了分析表征. 结果表明, 多孔炭的孔结构以微孔为主, 最高比表面积可达1111 m²/g, 其微晶结构中无定形碳和石墨化碳并存; 多孔炭中的氮主要以季氮(N-Q)、 吡咯氮(N-5)和吡啶氮(N-6)的形式存在, 磷以磷-氧(N—O—P)键合形式为主, 硫主要以噻吩硫(C—S—C)为主. 在6 mol/L KOH溶液、 三电极体系中, 多孔炭在0.5 A/g电流密度下的比电容为138 F/g; 在10 A/g电流密度下的比电容为100 F/g; 在2 A/g电流密度下循环充放电10000次, 其比电容保持率为95.8%, 显示出良好的电化学性能.