Catalytic action of Mn‐superoxide dismutase in scavenging superoxide radical anion by double hydrogen abstraction from dihydrolipoic acid: A theoretical study

The mechanism of scavenging superoxide radical anion ( ) by dihydrolipoic acid (diLA) in absence and presence of the enzyme Manganese‐superoxide dismutase (Mn‐SOD) has been investigated using density functional theory. Mn‐SOD was modelled by a complex of a manganese cation (Mn²⁺) bonded to three similar molecules having a histidine ring each and a water molecule. It has been shown that the scavenging mechanism involves double hydrogen abstraction by from different pairs of neighboring sites of diLA. It has been found that diLA alone cannot scavenge superoxide radical anions efficiently as the barrier energies involved in the reactions are very high. However, in presence of Mn‐SOD, owing to its catalytic action, the corresponding reactions become barrierless due to which superoxide radical anions would be scavenged highly efficiently. H₂O₂ formed from superoxide radical anion due to double hydrogen abstraction from diLA is scavenged by diLA alone barrierlessly without involving Mn‐SOD or any other catalyst.     

Interrelationship between total volatile organic compounds emissions,structure and properties of natural rubber/polycaprolactone bio-blends cross-linked with peroxides

Natural rubber/polycaprolactone (NR/PCL) bio-based blends with different organic peroxides were prepared using an internal batch mixer and subsequently cross-linked at 170 °C. Two types of commonly used organic peroxides, dicumyl peroxide and di(tert-butylperoxyisopropyl)benzene peroxide, were applied as free-radical initiator. Cross-linking efficiency of NR/PCL blends were investigated using oscillating disc rheometer measurements, followed by infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis and tensile testing. Total volatile organic compounds (TVOCs) emissions were determined using headspace analysis integrated with gas chromatography with flame ionization detector. Determined TVOCs emissions varying in range 21.6–52.1 μg/g and generally value of this parameter decreased with increasing content of PCL phase in studied blends or with application of more efficient di(tert-butylperoxyisopropyl)benzene peroxide as cross-linking agent. It was found that increasing of TVOCs parameter indicated deterioration of mechanical properties of NR/PCL blends, which corresponded with the changes in chemical structure and thermal properties of cross-linked NR/PCL. This confirms that evaluation of TVOCs parameter is interesting alternative for “conventional methods” to characterization of the studied bio-based blends.     

Accurate van der Waals force field for gas adsorption in porous materials

An accurate van der Waals force field (VDW FF) was derived from highly precise quantum mechanical (QM) calculations. Small molecular clusters were used to explore van der Waals interactions between gas molecules and porous materials. The parameters of the accurate van der Waals force field were determined by QM calculations. To validate the force field, the prediction results from the VDW FF were compared with standard FFs, such as UFF, Dreiding, Pcff, and Compass. The results from the VDW FF were in excellent agreement with the experimental measurements. This force field can be applied to the prediction of the gas density (H₂, CO₂, C₂H₄, CH₄, N₂, O₂) and adsorption performance inside porous materials, such as covalent organic frameworks (COFs), zeolites and metal organic frameworks (MOFs), consisting of H, B, N, C, O, S, Si, Al, Zn, Mg, Ni, and Co. This work provides a solid basis for studying gas adsorption in porous materials. © 2017 Wiley Periodicals, Inc.     

碰撞气体的种类和压力对离子阱质谱性能的影响

基于数字离子阱技术,研究了离子阱质谱分析实验过程使用的碰撞气体种类及压力对离子阱质谱性能,如质量分辨能力、信号强度、串级质谱分析,以及低质量截止效应等的影响.实验过程中,在离子的激发和碰撞诱导解离阶段,分别采用质量数不等的氦气(质量数=4 amu)、氮气(质量数=28 amu)、氩气(质量数=40 amu)等作为碰撞气体,以及不同的气体压力,研究了它们对质谱性能的影响.结果表明,当采用质量数较大的氩气作为碰撞气体时,可以有效改善低质量数截止效应和提高离子碰撞过程中的能量转移效率,同时提高离子捕获和解离效率,但是质量分辨率会明显降低.在获得较高质量分辨率方面,氦气作为碰撞气体时效果最好.在气压相同的情况下,质量数大的碰撞气体有利于提高串级质谱分析效率,即获得更多碎片离子峰和更多有关母体离子结构的信息.     

全二维气相色谱-飞行时间质谱对催化裂化汽油的定性与定量分析

采用全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)对催化裂化汽油全馏分进行了定性与定量分析,建立了相应的分析方法.结果表明,汽油族组成中的烷烃、烯烃、环烷烃、芳烃在全二维点阵谱图中呈分区域、带状的分布特点.GC×GC-TOF MS根据催化裂化汽油组分内分子的沸点及极性差异对其进行两个维度分离,极大地避免了普通色谱法分析过程中沸点相似化合物共流的弊端,实现催化裂化汽油组分的精确分离和准确定性分析.通过引入响应因子,修正了不同性质的烃类在电离源上电离效率的差异,使得TOF对催化裂化汽油族组成的定量结果与普通气相色谱法的定量结果的相关性较好,且应用GC×GC-TOF MS方法获得了催化裂化汽油更为精确的族组成信息.GC×GC-TOF MS为催化裂化汽油精确表征提供了一种有效方法.     

Similarity solutions for the flow behind an exponential shock in a non-ideal gas

Similarity solutions for the flow of a non-ideal gas behind a strong exponential shock driven out by a piston (cylindrical or spherical) moving with time according to an exponential law are obtained. Similarity solutions exist only when the surrounding medium is of constant density. Solutions are obtained, in both the cases, when the flow between the shock and the piston is isothermal or adiabatic. It is found that the assumption of zero temperature gradient brings a profound change in the density distribution as compare to that of the adiabatic case. Effects of the non-idealness of the gas on the flow-field between the shock and the piston are investigated. The variations of density-ratio across the shock and the location of the piston with the parameter of non-idealness of the gas are also obtained.     

Shocks in local supersonic zones

The results of numerical integration of the Euler equations governing two-dimensional and axisymmetric flows of an ideal (inviscid and non-heat-conducting) gas with local supersonic zones are presented. The subject of the study is the formation of shocks closing local supersonic zones. The flow in the vicinity of the initial point of the closing shock is calculated on embedded, successively refined grids with an accuracy much greater than that previously achieved. The calculations performed, together with the analysis of certain controversial issues, leave no doubt that it is the intersection of C ^?-characteristics proceeding from the sonic line inside the supersonic zone that is responsible for the closing shock formation.     

Acoustics of a Bubbly Liquid with a Weak Chemical Reaction in the Gaseous Phase

The influence of the composition and thermophysical properties of gas-liquid bubbly systems with a dissociating component in the gaseous phase on the laws of small-disturbance propagation and attenuation is investigated. It is found that the reacting gas component in the bubbles significantly affects the sonic-wave attenuation coefficient in the bubbly liquid. This follows from the fact that when a gas bubble is compressed isothermally, a recombination reaction occurs which prevents pressure growth in the bubble.Small-disturbance propagation in bubbly liquids was investigated in a number of publications discussed in review [1]. The acoustics of a bubbly liquid with a gas phase containing active admixtures are of both methodical and practical interest. The dynamics of such multicomponent bubbles were investigated in [2].     

添加剂与RDX的界面作用及对撞击感度的影响研究

研究了石蜡、硬脂酸等添加剂与RDX的界面作用及其对撞击感度的影响。得出添加剂对RDX(Hexogen)的铺展系数越大,钝感效果越好的结论,并获得了铺展系数与特性落高的经验函数关系。     

Large-Scale Streamwise Vortices in the Supersonic Part of a Permeable Nozzle

Large-scale streamwise vortices in the vicinity of a perforated wall in the supersonic part of the nozzle are studied. The governing effect of gas inflow through a perforated wall on origination and parameters of streamwise vortices is experimentally established.__________Translated from Prikladnaya Mekhanika i Tekhnicheskaya Fizika, Vol. 46, No. 5, pp. 68–75, September–October, 2005.