Promoting Effects of Iron on CO Oxidation over Au/TiO2 Supported Au Nanoparticles

Fe-doped TiO₂ supported gold nanoparticles as high-performance CO oxidation catalysts were prepared. XRD data revealed that TiO₂ support was in an anatase phase. After calcination at 300℃, the sample showed nanotube structure, and the size of gold nanoparticles was 3.1 nm. When calcined at 500℃, most nanotubes broke, and gold nanoparticles grew up to 5.9 nm. XPS spectrum indicated the presence of Fe in the +3 oxidation state. Au/Fe-TiO₂(Au:1.44%, Fe:1.35%) calcined at 300℃ possessed the best catalytic activity, and it could completely convert CO at 25℃. The temperature of 100% CO conversion(T_100%) of Fe-free catalyst was 40℃. After the catalysts were stored at room temperature for 7 d, T_100% of Au/Fe-TiO₂ increased from 25℃ to 30℃, while T_100% of Fe-free catalyst increased from 40℃ to 80℃. The catalytic activity and storage stability of Au/TiO₂ could be improved by Fe-doping. The increase of specific surface area, generation of oxygen vacancies and new adsorption sites, depression of the growth of gold nanoparticles, and strong metal-support interaction were responsible for the promoting effect of iron on the catalytic performance of Au/TiO₂ for CO oxidation.     

Silver nanoparticles embedded temperature-sensitive nanofibrous membrane as a smart free-standing SERS substrate

To develop a smart free-standing surface enhanced Raman scattering(SERS) substrate,silver nanoparticles(AgNPs) embedded temperature-sensitive nanofibrous membrane was fabricated by electrospinning their aqueous solution containing the copolymer poly(N-isopropylacrylamide-co-Nhydroxymethylacrylamide),followed by heat treatment to form crosslinking structure within its constituent nanofibers.To avoid negative effect of the additive like stabilizer and the reactant like reductant on their SERS efficiency,the AgNPs were in-situ synthesized through reducing Ag~+ions dissolved in the polymer solution by ultraviolet irradiation.The prepared hybrid nanofibrous membrane with high stability in aqueous medium can reach its swelling or deswelling equilibrium state within 15 seconds with the medium temperature changing between 25℃and 50℃alternately.When it was used as a free-standing SERS substrate,10~(-12) mol/L of 4-nitrothiophenol in aqueous solution can be detected at room temperature,and elevating detection temperature can further lower its low detection limit.Since its generated SERS signal has desirable reproducibility,it can be used as SERS substrate for quantitative analysis.Moreover,the hybrid membrane as SERS substrate is capable of real-time monitoring the reduction of 4-nitrothiophenol into 4-aminothiophenol catalyzed by its embedded AgNPs,and the detected intermediate indicates that the reaction proceeds via a condensation route.     

Nanostructured Metal Catalysts for Selective Hydrogenation and Oxidation of Cellulosic Biomass to Chemicals

Conversion of biomass to chemicals provides essential products to human society from renewable resources. In this context, achieving atom‐economical and energy‐efficient conversion with high selectivity towards target products remains a key challenge. Recent developments in nanostructured catalysts address this challenge reporting remarkable performances in shape and morphology dependent catalysis by metals on nano scale in energy and environmental applications. In this review, most recent advances in synthesis of heterogeneous nanomaterials, surface characterization and catalytic performances for hydrogenation and oxidation for biorenewables with plausible mechanism have been discussed. The perspectives obtained from this review paper will provide insights into rational design of active, selective and stable catalytic materials for sustainable production of value‐added chemicals from biomass resources.     

表面引发原子转移自由基聚合法合成无机/有机核壳复合纳米粒子

原子转移自由基聚合(ATRP)是目前为止最具工业化应用前景的活性/可控自由基聚合方法之一,其最大特点是可以得到分子量分布窄、链结构规整的聚合物,而且可聚合的单体种类多,反应条件温和并易控制。表面引发ATRP(SI-ATRP)特别适合于无机材料表面接枝聚合物或无机/有机复合材料的制备,近年来引起了国内外研究者的高度关注。本文首先对SI-ATRP的反应过程与特点做了阐述,然后重点述评了用SI-ATRP法合成以非金属氧化物纳米粒子、金属氧化物纳米粒子、金属纳米粒子或其他无机纳米粒子为核的无机/有机复合纳米粒子的研究进展,最后对未来用SI-ATRP法合成无机/有机复合纳米粒子的发展方向和研究前景进行展望。     

时变水声信道的动态压缩感知估计

水声多径信道具有的稀疏特性已被应用于设计稀疏估计方法提高信道估计性能。然而,水声信道具有的快速时变特性,给传统稀疏信道估计方法带来了很大的困难。考虑到水声信道除了高时变性多径,还存在着相对静止,缓慢变化的直达径或者海底反射径,通过将水声信道建模为由静态和时变稀疏支撑集组成,把时变水声信道估计转化为动态压缩感知问题。结合卡尔曼滤波和压缩感知理论,并采用原始对偶追踪算法求解Dantzig selector模型,从而实现对复数域基于卡尔曼滤波器的压缩感知稀疏求解问题的处理。信道时变条件下的数值仿真及基于信道估计的判决反馈均衡器的海上实验结果表明,该算法相对经典的正交匹配追踪和最小二乘QR分解算法具有较明显的性能改善。从而说明,通过对时变水声信道进行动态压缩感知估计可有效提高估计性能。     

液相色谱-串联质谱法同时测定生物组织全基因组DNA甲基化和羟甲基化水平

测定全基因组DNA甲基化和羟甲基化水平对于研究环境污染物暴露的影响及致病机理具有重要的作用。本文建立了液相色谱-串联质谱（LC-MS/MS）同时测定动物组织中全基因组DNA甲基化和羟甲基化水平的方法。从动物组织样品中提取DNA,并将其酶解成单核苷,利用液相色谱-串联质谱法测定5-甲基胞嘧啶核苷、5-羟甲基胞嘧啶核苷和鸟嘌呤核苷的含量,计算全基因组DNA甲基化率和羟甲基化率。利用该方法研究了砷暴露对大鼠肝脏和小脑全基因组DNA甲基化和羟甲基化水平的影响,得到了砷影响DNA甲基化及羟甲基化的初步数据。该方法具有良好的重现性、灵敏度和稳定性,可以同时检测差异较大的DNA甲基化和羟甲基化水平。为同时研究DNA甲基化和羟甲基化水平提供了有力的支持。     

弹性撞击作用下弯扭耦合梁的动力响应

对于质量块以一定初速度撞击悬臂梁端部问题,基于弯扭耦合Timoshenko梁模型,把质量块与悬臂梁作为一个整体振动,动力响应以Duhamel积分表示,使用模态叠加法给出动力响应与撞击力的结果.对于悬臂梁受质量块撞击的算例,分别分析了弯扭耦合梁、弯扭耦合系数很小的梁和各向同性Timoshenko梁,对比讨论了撞击力结果.     

A high-resolution accurate mass approach to identification of graveoline metabolites using ultra-high-performance liquid chromatography combined with a photo diode array detector and quadrupole/time-of-flight tandem mass spectrometry

Graveoline is a biologically active ingredient extracted from Ruta graveolens. Current work aimed at investigating in vitro metabolism of graveoline using rat or human liver microsomes and hepatocytes. Graveoline (20 μM) was incubated with nicotinamide adenine dinucleotide phosphate–supplemented rat and human liver microsomes as well as hepatocytes. LC coupled to a photo diode array detector and quadrupole/time-of-flight tandem mass spectrometry was used to detect and identify the metabolites. The structures of the metabolites were identified by accurate mass, elemental composition, and indicative fragment ions. A total of 12 metabolites, comprising 6 phase I and 6 phase II metabolites, were obtained. The metabolic pathways included demethylenation, demethylation, hydroxylation, glucuronidation, and glutathion conjugation. The metabolite (M10) produced by opening the ring of the methylenedioxyphenyl moiety was detected as the most abundant in both liver microsomes and hepatocytes, mainly catalyzed by CYP1A2, 2C8, 2C9, 2C19, 2D6, 3A4, and 3A5. This study provides valuable information on the in vitro metabolism of graveoline, which is indispensable for further development and safety evaluation of this compound.     

Janus Metastructure Based on Magnetized Plasma Material with and Logic Gate and Multiple Physical Quantity Detection

In this paper, a Janus metastructure (JMS) is proposed that can act both as a logic gate and detect multiple physical quantities. By adjusting the incident angle of electromagnetic waves, arranging the dielectrics asymmetrically, and using the anisotropy of the plasma, the Janus function can be obtained, which gives the metastructure a multiscale property. Sharp transmission peak (TP) is generated by located defect mode resonance. The AND logic gate on the positive and negative scales can be realized by judging the TP value. By locking the point frequency of the TP, the refractive index, magnetic field strength, incident angle, and plasma density can be detected simultaneously on the two scales in the GHz range, which is rarely studied. Good sensing performances are also owned, and the corresponding optimal sensitivities are 0.095 (2πc/d)/RIU, 9.42 × 10⁻³ (2πc/d)/T, 1.48 × 10⁻³ (2πc/d)/°, and 0.035 (2πc/d) m³/10¹⁹, respectively. Compared with the traditional sensors, the proposed JMS equipped with two scales not only can realize the logic gate but also measure multiple physical quantities, which has a certain application potential.     

Revealing the Formation Mechanism and Optimizing the Synthesis Conditions of Layered Double Hydroxides for the Oxygen Evolution Reaction

Layered double hydroxides (LDHs), whose formation is strongly related to OH⁻ concentration, have attracted significant interest in various fields. However, the effect of the real-time change of OH⁻ concentration on LDHs’ formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH₃ gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi-LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported.