Design and Synthesis of a Ruthenium(II) Complex-Based Luminescent Probe for Highly Selective and Sensitive Luminescence Detection of Nitric Oxide

Nitric oxide (NO) is one of the most important intercellular signaling molecules, and plays important roles in various biological systems. In this work, a unique Ru^II complex, tris[(5-(4-methylamino-3-aminobenzylamino)-1,10-phenanthroline)] ruthenium(II) hexafluorophosphate [Ru(MAA-phen)₃][PF₆]₂, has been designed and synthesized as a luminescent probe for the detection of NO in aqueous media. The complex itself is almost non-luminescent, but can specifically react with NO under the aerobic conditions to afford its highly luminescent triazole derivative in aqueous media, [Ru(MTA-phen)₃]²⁺ (MTA-phen: methyl-trazolebenzylamino-1,10-phenanthroline), accompanied by a 302-fold increase in luminescence intensity at 598 nm with a 130 nm Stokes shift. The luminescence response of [Ru(MAA-phen)₃]²⁺ to NO is rapid, highly specific without interferences of other reactive oxygen/nitrogen species, and highly stable against the pH changes in the range of pH 4.5–9.5. These features enable [Ru(MAA-phen)₃]²⁺ to be used as a probe for the highly selective and sensitive luminescence detection of NO in weakly acidic, neutral, and weakly basic media.     

Analytical predictions of shapes of laminar diffusion flames in microgravity and earth gravity

Flame shape is an important observed characteristic of flames that can be used to scale flame properties such as heat release rates and radiation. Flame shape is affected by fuel type, oxygen levels in the oxidiser, inverse burning and gravity. The objective of this study is to understand the effect of high oxygen concentrations, inverse burning, and gravity on the predictions of flame shapes. Flame shapes are obtained from recent analytical models and compared with experimental data for a number of inverse and normal ethane flame configurations with varying oxygen concentrations in the oxidiser and under earth gravity and microgravity conditions. The Roper flame shape model was extended to predict the complete flame shapes of laminar gas jet normal and inverse diffusion flames on round burners. The Spalding model was extended to inverse diffusion flames. The results show that the extended Roper model results in reasonable predictions for all microgravity and earth gravity flames except for enhanced oxygen normal diffusion flames under earth gravity conditions. The results also show trends towards cooler flames in microgravity that are in line with past experimental observations. Some key characteristics of the predicted flame shapes and parameters needed to describe the flame shape using the extended Roper model are discussed.     

Synthesis of a benzoxazine with precisely two phenolic OH linkages and the properties of its high‐performance copolymers

A phenolic OH‐containing benzoxazine ( F‐ap ), which cannot be directly synthesized from the condensation of bisphenol F, aminophenol, and formaldehyde by traditional procedures, has been successfully prepared in our alternative synthetic approach. F‐ap was prepared by three steps including (a) condensation of 4‐aminophenol and 5,5'‐methylenebis(2‐hydroxybenzaldehyde) (1) , (b) reduction of the resulting imine linkage by sodium borohydride, and (c) ring closure condensation by formaldehyde. The key starting material, (1) , was prepared from 2‐hydroxybenzaldehyde and s‐trioxane in the presence of sulfuric acid. F‐ap is structurally similar to bis(3,4‐dihydro‐2H‐3‐phenyl‐1,3‐benzoxazinyl)methane ( F‐a, a commercial benzoxazine based on bisphenol F/aniline/formaldehyde) except for two phenolic OHs. The phenolic OHs can provide reaction sites with epoxy and 1,1'‐(methylenedi‐p‐phenylene)bismaleimide (BMI). The structure–property relationships between the thermosets of F‐ap /epoxy, F‐a /epoxy, F‐ap /BMI, and F‐a /BMI were discussed. Experimental data showed that thermosets based on F‐ap /epoxy and F‐ap /BMI provided much better thermal properties than those based on F‐a /epoxy and F‐a /BMI. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2686–2694     

Determination of bulk viscosity of liquid water via pulse duration measurements in stimulated Brillouin scattering

We present a method by which to determine the bulk viscosity of water from pulse duration measurements of stimulated Brillouin scattering （SBS）. Beginning from a common model of Brillouin scattering, the bulk viscosity is shown to play an important role in Brillouin linewidth determination. Pulse durations of SBS back-reflected optical pulses are measured over the temperature range of 5-40℃. SBS linewidths are de- termined via Fourier transformation of the time-domain results, and the bulk viscosity of water is measured and derived from the obtained values. Our results show that the proposed method for measurement of pulse durations is an effective approach for determining bulk viscosity. The method can be easily extended to determine bulk viscosities of other Newtonian liquids.     

多铁材料BaCoF$lt;sub$gt;4$lt;/sub$gt;电子结构的第一性原理研究

采用基于密度泛函理论的广义梯度近似方法和赝势平面波法,对多铁材料BaCoF₄的铁电反铁磁相和可能的顺电相的电子结构进行了第一性原理研究.研究表明,反铁磁态很可能有利于低温下的铁电稳定性,F的强负电性使得体系内原子间主要是离子键相互作用.Co离子与在bc面上的F（2）,F（3）离子间完全是离子键作用,而与F（4）间有较弱的共价作用,与F（1）间作用介于两者之间.铁电畸变主要来源于Ba离子与F（1）, F（2）, F（3）离子沿着c轴方向的相对位移,F（4）对铁电性的贡献最少.铁电相中F（2）, F（3）离子的能量低于中心对称相,最大位移贡献者F（1）的化学键性由弱共价作用到离子键的变化也是最大的,这均有利于体系的稳定. 关键词： 第一性原理 铁电性 铁电畸变 反铁磁性     

射流抛光多相紊流流场的数值模拟

 理论分析了射流抛光的紊动冲击射流特点,构建了射流抛光的垂直冲击射流模型和斜冲击射流模型。根据射流抛光冲击射流的特点,比较各种流体模型后,采用RNG k-e 模型应用于射流抛光模型的计算。利用计算流体力学理论的二阶迎风格式对抛光模型方程离散,用SIMPLEC数值计算方法对射流抛光过程的紊动冲击射流和离散相磨粒分布进行数值模拟,得到了射流抛光过程的连续流场和离散相磨粒与水溶液的耦合流场,同时计算出了抛光液射流在工件壁面上的压力、速度、紊动强度、剪切力分布和磨粒体积质量分布,分析了垂直射流抛光模型和斜冲击射流抛光模型紊流流场的特点。     

利用频谱仪提取双反馈混沌半导体激光器的外腔长度密钥

光反馈半导体激光器产生的高维宽带混沌载波,应用于光混沌通信系统中.主器的外腔长度用作混沌保密通信的附加密钥.本文实验研究了光反馈混沌半导体激光器外腔长度密钥的识别.通过对长腔光反馈产生的混沌频谱进行局部放大,分析其精细结构,结果表明:无论是单反馈半导体激光器还是有不同外腔长度比的双反馈半导体激光器,都可以利用频谱仪直接提取出激光器的外腔长度信息.     

用于乙烯环氧化反应的CuCs掺杂银基催化剂设计

最近的理论研究筛选出CuCs掺杂Ag基催化剂是一种高效的乙烯环氧化催化剂[ACS Catal. 11,3371 (2021)]. 然而,该工作是基于研究表面建模预测Ag基催化剂的性能,在实际反应过程中,Ag基催化剂是颗粒状的. 本文结合密度函数理论、Wulff构造理论和微观动力学分析来研究Ag基催化剂在颗粒模型上的催化性能. 研究表明,CuCs掺杂Ag基催化剂在选择性和活性方面都优于纯Ag基催化剂,这一点通过实验得到了证明. 进一步地表征分析发现,CuCs掺杂能促进颗粒的生长以及颗粒的分散,从而形成富含晶界的Ag颗粒. 此外,CuCs促进了催化剂表面亲电氧的形成,这均有利于环氧乙烷的形成和解吸. 本工作为理论与实验相结合的催化剂设计提供了一个案例研究.     

Coupled intramolecular/heterointerfacial electron transfer in polyelectrolyte-shielded Iso-type black phosphorus hetero-structure boosts oxygen reduction kinetics

Searching new structured black phosphorus (BP) and exploring intriguing functions and applications have become a hot topic so far.Here,we introduce a novel Iso-...     

掺杂对CH样品Rayleigh-Taylor不稳定性增长的影响

在神光II激光装置上进行了辐射驱动不同掺杂样品的单模Rayleigh-Taylor(RT)不稳定性实验.结果显示:与纯碳氢(CH)样品相比,掺Br的CH样品的扰动更早、更快地进入非线性区,产生二次谐波,并且掺Br比例越高,CH样品扰动进入非线性区的时间越早,相同时刻扰动的二次谐波的幅度越高.这是因为密度梯度效应抑制了二次谐波的产生,掺Br比例越高,密度梯度标长越小;同时密度梯度效应还抑制三次谐波对基模增长的负反馈,造成基模具有更大的线性增长,导致线性饱和幅值大于经典值0.1λ.