Liquid crystalline side-chain polysiloxanes containing mesogenic groups attached by esterification

Summary Liquid crystalline side-chain polysiloxanes were prepared without metal complex catalyst. Mesogenic groups such as cholesteryl, 4-cyano-4-biphenyl and 4-methoxy-4-biphenyl group were introduced into polysiloxane by esterification and from DSC measurements they were compatible with other liquid crystalline polysiloxanes reported previously.     

Immobilization of multicopper oxidase from Pyrobaculum aerophilum onto an electrospun-aligned single-walled carbon nanotube surface via a carbon-nanotube-binding peptide for biocathode

Biofuel cells (BFCs) that produce electrical energy from organic resources through enzymatic reactions have been attracting significant attention. Owing to the high electrical conductivity of carbon nanotubes (CNTs), their modification on the electrode surface of a BFC is expected to increase the current, and their high specific surface area may be useful in increasing the power output. Previously, we constructed a biocathode by immobilizing multicopper oxidase from Pyrobaculum aerophilum (McoP) with a carbon nanotube binding peptide (CBP) sequence on the CNTs. This resulted in higher current densities than when using enzymes without CBP sequences. However, owing to the randomly stacked CNTs on the surface of the electrodes, their conductive properties were impaired and performance as biocathodes was poor. Herein, we constructed a biocathode in which single-walled CNTs (SWCNTs) were oriented one-dimensionally and McoP is immobilized on the surface of an SWNCT via CBP. The current density was successfully increased by two-fold by orienting the CNTs and orienting and immobilizing McoP on their surfaces. This technology provides insights into the development of biodevices with controlled orientation of both the SWCNTs and enzymes immobilized on their surfaces.     

Focus on Extracellular Vesicles: Development of Extracellular Vesicle-Based Therapeutic Systems

Many types of cells release phospholipid membrane vesicles thought to play key roles in cell-cell communication, antigen presentation, and the spread of infectious agents. Extracellular vesicles (EVs) carry various proteins, messenger RNAs (mRNAs), and microRNAs (miRNAs), like a “message in a bottle” to cells in remote locations. The encapsulated molecules are protected from multiple types of degradative enzymes in body fluids, making EVs ideal for delivering drugs. This review presents an overview of the potential roles of EVs as natural drugs and novel drug-delivery systems.     

Gene expression within cell-sized lipid vesicles

Functional protein synthesis was observed in cell-sized lipid vesicles following encapsulation of a gene-expression system. Expression of rsGFP (red-shifted green fluorescent protein) within individual vesicles was observed by fluorescence microscopy. Interestingly, at the early stage of the reaction, the expression efficiency inside the vesicle was remarkably higher than that in the solution outside. The synthesized rsGFP in individual vesicles is safe from attack by proteinase K added to the external aqueous solution. Studies on cell-sized vesicles expressing protein should contribute to a fundamental understanding of certain aspects of living systems and will be useful for practical applications, such as the construction of microreactors.     

Methanol synthesis from CO2 over Cu/ZnO catalysts prepared from various coprecipitated precursors

Various precursors of Cu/ZnO catalysts were prepared by coprecipitation methods. By varying the conditions of coprecipitation, precursors having different structures (aurichalcite, malachite, hydrozincite, or their mixture) were obtained at given Cu/Zn ratios, ranging from 30/70 to 70/30. In a wide range of the Cu/Zn ratios, the catalysts derived from the precursors containing aurichalcite exhibited high performance in the methanol synthesis from CO₂.     

Selective hydrogenation of chloronitrobenzene to chloroaniline in supercritical carbon dioxide over Ni/TiO2: Significance of molecular interactions

The hydrogenation of chloronitrobenzene to chloroaniline was investigated over Ni/TiO₂ at 35 °C in supercritical CO₂ (scCO₂), ethanol, and n-hexane. The reaction rate followed the order of scCO₂ > n-hexane > ethanol. In scCO₂, the selectivity to chloroaniline and to aniline over Ni/TiO₂ were 97–99.5% and <1%, respectively, in the conversion range of 9–100%. The high chemoselectivity to chloroaniline cannot be achieved over Ni/TiO₂ in ethanol and n-hexane. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions of CO₂ with the following reactant and reaction intermediates: chloronitrobenzene, chloronitrosobenzene, and N-chlorophenylhydroxylamine. The molecular interaction modifies the reactivity of each species and accordingly the reaction rate and the selectivity. The influence of Cl substituent on the interaction modes of CO₂ with these reacting species is discussed. Possible reaction pathways for the hydrogenation of chloronitrobenzene in scCO₂ over Ni/TiO₂ are also proposed.     

Theoretical study on interaction between CO2 and carbonyl compounds: Influence of CO2 on infrared spectroscopy and activity of CO

The interactions between CO₂ and carbonyl compounds at different CO₂ pressures have been studied both experimentally and theoretically. In situ high-pressure FTIR on carbonyl compounds, i.e., acetaldehyde, acetone, and crotonaldehyde, in supercritical CO₂ have been measured at various CO₂ pressures varying from 6 to 22 MPa. In order to get insights into the mechanism, theoretical study has been conducted concerning the effect of CO₂ on frequency shift of CO in acetaldehyde, acetone, benzaldehyde, crotonaldehyde and cinnamaldehyde at different CO₂ pressures. It has been shown that the experimental frequency shifts can be well simulated by the theoretical model calculations using particular structures, in which a carbonyl compound interacts with a few CO₂ molecules, depending on the carbonyl compounds examined, except for acetaldehyde.The interaction energies between CO₂ and those carbonyl compounds are also given. In addition, the effect of CO₂ on hydrogenation of crotonaldehyde and benzaldehyde has been discussed by means of the local softness (s⁺) calculated at CO₂ pressures of 0-22 MPa, which can explain the reactivity difference in the crotonaldehyde and benzaldehyde hydrogenations in supercritical CO₂.     

基于光子带隙的双平板太赫兹传输系统研究

研究了一种利用光子晶体带隙特性工作的双平板太赫兹传输系统,它结合了光子晶体波导传输能量集中、损耗低以及双平板波导低色散和单模传输的优点.具体设计了工作在O.32THz的传输系统,研究结果表明:光子晶体双平板波导不但可以实现单模的高效传输,而且也具有良好的输入输出匹配性能.该设计中,采用矩形波导的输入输出结构在316～360 GHz的带宽内可以获得S11<-10 dB的匹配.而且,和普通双平板波导相比更具有结构紧凑、易于集成等优点,因此具有较高的实用价值.