Biased Brownian motion as the operating principle for microscopic engines

The hydrolysis of adenosine triphosphate (ATP) has been shown to drive the motion of motor proteins along a biopolymer. These motor proteins are the smallest engines known and, in the absence of an ATP-to-adenosine diphosphate chemical potential, they execute Brownian motion. Therefore, it is reasonable to imagine that the energy released in ATP hydrolysis is used to bias, or rectify, Brownian motion in one direction. In this paper, we show, in terms of Fokker-Planck equations that we solve analytically, how a net flow can occur along a periodic potential, provided that this potential has an anisotropy and that there is an energy input. We work out two cases: one case where the energy input comes from a fluctuation of the periodic potential in time and one case where a variation of temperature within a period is maintained. An interesting feature of these systems is that they need “the correct amount” of thermal noise. Without thermal noise or with too much thermal noise, no net flow occurs and, in this sense, the systems we discuss are one more example of the lately much discussed phenomenon of stochastic resonance.     

Kinetically controlled catalytic formation of zinc oxide thin films at low temperature

We developed a unique method to produce ZnO thin films by kinetically controlled catalytic hydrolysis of a molecular precursor at low temperature, operating in conjunction with the vectorial control of crystal growth. Using a system in which the diffusion of a volatile catalyst into a solution of molecular precursor of the metal oxide limits the rate of hydrolysis and establishes a gradient of catalyst concentration, we investigated the nucleation of textured nanoparticles at the gas-liquid interface and characterized their subsequent growth. Use of this slow diffusion method combined with prediction of molecular species using a partial charge model enables a higher level of organizational control than obtained in other low-temperature synthesis methods, without the use of organic molecules. Various metal oxides and their morphologies and chemical compositions can be tailored for specific applications using this relatively simple approach.     

The escape process of carbon monoxide from myoglobin to solution at physiological temperature

The carbon monoxide (CO) docking sites involved in the ligand escape process from the iron atom in hem of myoglobin (Mb) to solution at physiological temperature were studied on the basis of the effect of xenon (Xe) on the ligand escape rate by the transient grating (TG) technique. The TG method provides a direct measurement of the changes in molecular volume. The apparent CO escaping rate and the volume contraction increase with increasing Xe pressure. The pressure dependence of the rate is consistent with that of the Xe population at the Xe(1) site. This result clearly shows that CO is trapped at the Xe(1) site before escaping to solvent in a Xe-free solution at room temperature. It is shown that only CO but not the trapped Xe is released by the photoexcitation of the Xe-trapped MbCO. A dissociation scheme is proposed to explain the enhancement of the escaping rate by the presence of Xe(1). There are two branches for the CO escaping pathway. The dominant part of the dissociated CO escapes to the solvent through the Xe(1) trapping site under the Xe-free condition, and there are at least three intermediate states along this pathway. When a Xe atom blocks the Xe(1) site, the CO escapes through another route.     

An efficient catalytic asymmetric addition of trimethylsilyl cyanide to aldehydes at room temperature

The BINOL-salen compound (S)-5c in combination with Ti(OⁱPr)₄ is found to catalyze the addition of TMSCN to aldehydes to form chiral cyanohydrins with very good enantioselectivity (75-85% ee). The reactions are carried out in one-pot at room temperature without the need to isolate the chiral Lewis acid catalyst.     

Chemical inhomogeneity of SiOx dissociation by catalytic Au at a relatively low temperature

Sporadic catalytic decomposition because of the presence of Au grains is a significant issue to be clarified in electronic devices. Here, we report the inhomogeneous dissociation of native silicon oxide depending on the electronic structure of Au grains using scanning photoelectron microscopy. Upon annealing, the oxygen atoms dissociated from native SiO_x layer out‐diffuses in non‐uniform manner, resulting in oxidize the Au layer. Valence band spectra showed that the spit‐orbit splitting, directly related to the coordination number, differs from site to site. Scanning photoelectron microscopy images show that dissociated SiO_x coincides with the regions where low‐coordinated Au resides. These results imply that Au with low coordination number activated the dissociation of SiO_x and open new pathway to remove undesirable oxide layer at relatively low temperature. Copyright © 2016 John Wiley & Sons, Ltd.     

Synergistic catalytic ozonation of toluene with manganese and cerium varies at low temperature

The temperature of waste gas in refuse transfer station, airport smoking area, and RTO terminal is low,which needs deep oxidation. Catalytic ozonation is one of the most effective treatment techniques in these scenarios. In this study, we reported that catalysts were modified under the condition of magnetic field to simulate the low temperature dynamic conditions of low concentration toluene for catalytic ozonation. This paper aims to explore the relationship between oxygen vacancy and active ox...     

Superfast electrophoresis of electron-type conducting particles

The features of concentration polarization caused by electric current through a unipolar conductive particle are considered. The peculiarities of the formation of an induced space charge near a particle with electron-type conductivity are analysed. It has been shown that the theoretical values of electrophoretic velocity for these particles are essentially smaller than those calculated for particles with ion-type conductivity.A new method to observe the superfast electrophoresis is developed. The electrophoretic velocity of graphite and activated carbon particles of different size (diameter, 200–500 μm) displaced in distilled water and electrolyte solutions in strong electric fields (100–500 V cm⁻¹) was measured. It is shown that, in contrast to classical electrophoresis, the electrophoretic mobility of such particles increases with the particle size and the external field strength. The experimental and theoretical results are compared. The discrepancy between theory and experiment is analysed.     

An acyclic enediyne anticancer compound attributed to a Bergman cyclization at physiological temperature

Enediyne cytotoxic drugs have attracted much attention because of their unique structure and potent anticancer activity. However, acyclic enediynes are long considered as inactive at physiological temperature due to their long C1-C6 distance. By adjusting the steric bulkiness of the functional groups at the alkynyl termini and the electron-withdrawing effect at the ene moiety, herein, a simple acyclic enediyne was designed and synthesized to achieve the onset of thermal Bergman cyclization at physiological temperature in polar solvents. The spontaneous generation of diradical intermediates was confirmed through EPR analysis and further supported by spin trapping experiment, radical indicator experiment, and high resolution MS analysis. The reactive diradicals generated in aqueous media induced single and double stranded cleavage of DNA, and showed high cytotoxicity to Hela cells. The IC₅₀ value of the enediyne compound is comparable to many clinical used anti-tumor agents.     

Structural and functional design of catalytic converters for emissions from internal combustion engines

We consider some features of technology for manufacturing advanced three-way (CO/NO _x /C _n H _m ) catalytic converters for emissions of internal combustion engines, namely, application, stabilization, and modification of γ-Al₂O₃ second supports on synthetic cordierite matrices and Pt, Pd, and Rh active components, as well as oxidation of finely divided carbon on the surface of soot filters coated with a catalyst coating in the form of binary oxide compositions (CuCr₂O₄ and CuCo₂O₄) using a number of oxidizers (O₂, O₃, NO, NO₂, H₂O, and CO₂).     

焙烧温度对Pd-Cu/凹凸棒土CO常温催化氧化性能的影响

以凹凸棒土(APT)作载体,采用等体积浸渍法制备了Pd-Cu/APT催化剂,以CO氧化为探针反应,在连续流动微反装置上,考察了焙烧温度对催化剂CO常温催化氧化性能的影响。通过N2-物理吸附、XRD、TG、FT-IR和H2-TPR等手段对催化剂的结构和性质进行了表征。结果表明,随焙烧温度升高,Pd-Cu/APT中载体逐步脱水,进而引起催化剂结构和织构变化,其中,Cu物种由Cu(OH)Cl逐渐向CuO转变,同时,高分散的Pd物种与Cu物种间相互作用先增强后减弱。经300℃焙烧的催化剂比表面积大,Cu物种以Cu(OH)Cl形式存在,且具有良好的分散状态,与Pd物种之间产生较强的相互作用,显著提高了其还原性能。在空速6 000 h-1、CO体积分数0.5%、水蒸气体积分数3.3%的反应条件下,常温可将CO完全转化800 min以上。焙烧温度高于或低于300℃均引起CO常温催化氧化性能的下降。     

Single atom catalytic oxidation mechanism of formaldehyde on Al doped graphene at room temperature

Formaldehyde (HCHO) is one kind of common indoor toxic pollutant, the catalytic oxidation degradation of formaldehyde at room temperature is desired. In this work, a new single atomic catalyst (SAC), Al doped graphene, for the catalytic oxidation of HCHO molecules was proposed through density function theory (DFT) calculations. It is found that Al atoms can be adsorbed on graphene stably without aggression. Then HCHO can be effectively oxidized into CO₂ and H₂O in the presence of O₂ molecules on Al doped graphene with a low energy barrier of 0.82 eV and releasing energy of 2.29 eV with the pathway of HCHO → HCOOH → CO → CO₂. The oxidation reaction can happen promptly with reaction time τ = 56.9 s at the speed control step at room temperature. Therefore, this work proposed a high-performance catalyst Al-doped graphene without any noble metal for HCHO oxidation at ambient temperature, and corresponding oxidation pathway and mechanism are also deeply understood.     

Efficient catalytic performance of tetra-alkyl orthotitanates for the oxidative desulfurization of dibenzothiophene at room temperature

Desulfurization of fuel oil is of great importance for producing clean energy. In this study, we report that tetra-alkyl orthotitanates exhibited efficient catalytic performance in the oxidative desulfurization of dibenzothiophene. The sulfur content in model oil (1000 ppmw) could be reduced to less than 10 ppmw within 10 min at room temperature and ambient pressure. In addition, the formed sulfones can be easily separated from the oil phase without extraction process. This work will provide a basis for the design of novel oxidative desulfurization catalysts with high desulfurization efficiency.     

Enhanced hydrogen selectivity from catalytic decomposition of formic acid over FeZnIr nanocatalyst at room temperature

Research on Chemical Intermediates - Hydrogen is considered a promising energy carrier for the future, especially for clean energy generation via fuel cell technologies. Formic acid is one of the...     

Superfast thermal decomposition reactions of polymers and crystallohydrates

Evidence of the existence of a high-limit degradation temperature for polymers is reported. At this high-limit temperature, the rate of polymer thermolysis exceeds the reaction rate predicted by the Arrhenius law by many orders of magnitude. An explanation is proposed for the observed behaviour, based on the disappearance of intermolecular interactions. For the study of degradation reactions under high-limit temperature conditions, new methods of fast (pulsed) thermal analysis are presented. The investigated samples, as very thin films, are brought into tight contact with a hot moving metal surface. Under these conditions, the heating rate exceeds 10⁴ deg/s, allowing estimation of accompanying decomposition rates for heating times of the order of 0.01 s.     

Viscosity reduction of citric-Fe(III) in catalytic aquathermolysis of heavy oil at low temperature

A Fe(III) coordination complex was synthesized, characterized, and then used in aquathermolysis of heavy oil as catalyst at relatively low temperature, 180°C. The effects of water amount, catalyst concentration on aquat hermolysis were investigated in this work. The crude oil before and after aquathermolysis was fully characterized, and the mechanism of viscosity reduction was discussed in detail. The results show that heavy oil can undergo aquathermolysis in the present of water and citric-F e(III) complex at low temperature. Besides, the catalytic aquathermolysis could not only decrease the viscosity of heavy oil, but also remove some heteroatoms, finally make the flow properties better and the quality upgraded.     

活性炭（焦）低温吸附催化脱除H2S的基础研究

以活性炭、活性焦作为脱硫剂,并应用BET、XPS等测试手段对其进行分析表征。结果表明,活性炭（焦）的脱硫能力与其表面酸碱性有着密切的关系,增加表面上起碱性作用的π-π^﹡键,羰基官能团（C-O和醚基官能团（C-O）的浓度,可增加其表面催化作用,特别是C-O官能团;反应温度对活性炭（焦）的脱硫性能有很大的影响,脱硫剂在150℃～180℃活性高,硫容大,副反应少;水蒸气对活性炭（焦）脱除H₂S有促进作用。     

低品质生物质的热解及低温催化气化研究

利用TG及小型固定床反应器对不同来源的三种低品质生物质--禽畜粪便样品的热解特性及其低温催化气化过程进行了研究。结果表明,各种粪便的主要热解温度为473K~823K。猪粪与禽粪中的有机组分及矿物质组分性质的不同,导致了它们的热解行为存在着较大的差异。在其主要热解区间内,猪粪的热解经历两个明显的失重过程,表明猪粪中的有机成分包括半纤维素、纤维素和木质素。鸡粪中的主要有机组分为纤维素,导致其有一个明显的热解失重过程。鸡粪中含有大量的CaCO₃,在热解过程中受热分解以CaO的形式存在于鸡粪半焦中。禽畜粪便的低温催化气化过程可以将热解焦油全部转化为小分子气相产物和碳,气相产物中有效组分(H₂和CO)产率明显增加。每克猪粪(daf.)低温催化气化过程氢的产量为960mL,鸡粪的氢气产率为680mL/(g鸡粪(daf.))。     

Direct observation of the direction of motion for spherical catalytic swimmers

Nonconductive Janus particle swimmers made by coating fluorescent polymer beads with hemispheres of platinum have been fully characterized using video microscopy to reveal that they undergo propulsion in hydrogen peroxide fuel away from the catalytic platinum patch. The platinum coating shadows the fluorescence signal from half of each swimmer to allow the orientation to be observed directly and correlated quantitatively with the resulting swimming direction. The observed swimmer direction is consistent with both the bubble release and diffusiophoretic propulsion mechanisms.