On the redox reactions between allyl radicals and NOx

NO_x mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NO_x can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C₃H₅) and NO_x plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C₃H₅ and NO_x over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C₃H₅ by shock heating of C₃H₅I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C₃H₅ at 220 nm. Unlike low-temperature chemistry, the two target reactions, C₃H₅ + NO → products (R1) and C₃H₅ + NO₂ → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm³/molecule/s):$k_1\left({\mathrm{C}}_3{\mathrm{H}}_5+\text{NO}\right)=1.49\times {10}^{?10}\exp \left(?6083.6\frac{\mathrm{K}}{T}\right)\left(1017?1252K\right)$$k_2\left({\mathrm{C}}_3{\mathrm{H}}_5+\mathrm{N}{\mathrm{O}}_2\right)=1.71\times {10}^{?10}\exp \left(?3675.7\frac{\mathrm{K}}{T}\right)\left(1062?1250K\right)$To our knowledge, these are the first high-temperature measurements of allyl + NO_x reactions. The reported data will be highly useful in understanding the interaction of NO_x with resonantly stabilized radicals as well as the mutual sensitization effect of NO_x on hydrocarbon fuels.     

Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

纳米硅量子线的发现与研究

一维纳米材料是当今介观物理学研究的前沿领域．文章报道了一种利用脉冲激光成功地制备纯度高、直径分布均匀的纳米硅量子线（ＳｉＮＷｓ）的方法，介绍了纳米量子线的形貌、显微结构、生长机理和物理性能研究的最新结果．纳米硅量子线的发现具有重要的科学意义和潜在的应用前景．     

全息散斑条纹的提取及图像处理

介绍了一种新的全息散斑条纹的提取方法.理论和实验表明:对全息散斑底片逐点再现时,两伴生亮斑条纹是全息散斑底片一级衍射光的杨氏干涉条纹,与中央的杨氏条纹是一致的,有较高的条纹对比度且没有背景光晕的影响.利用计算机数字图像处理技术对伴生散斑条纹进行处理,定量测试了受静载物体的面内位移.     

Solid-state synthesis and properties of SmCoO3

In this paper, perovskite oxide SmCoO₃ was prepared by the solid-state reaction method using Co₂O₃ and Sm₂O₃ as raw materials. The structure and properties of the samples were investigated by XRD, Raman spectral techniques, and DC measurements and so on. The results of XRD and Raman spectra showed that the mixtures of Co₂O₃ and Sm₂O₃ can react to produce a single phase perovskite oxide SmCoO₃ around 1353 K. The single-phase SmCoO₃ changes from an insulator to a semi-conductor and transition occurs around 470 K. The thermal expansion coefficient (2.17 × 10⁻⁵ K⁻¹) of the single-phase SmCoO₃ is approximately equal to that of doped LaGaO₃, but much bigger than that of SDC(Ce_0.85Sm_0.15O₂) above 873 K.     

Multilayer poly(vinyl alcohol)-adsorbed coating on poly(dimethylsiloxane) microfluidic chips for biopolymer separation

A poly(dimethylsiloxane) (PDMS) microfluidic chip surface was modified by multilayer-adsorbed and heat-immobilized poly(vinyl alcohol) (PVA) after oxygen plasma treatment. The reflection absorption infrared spectrum (RAIRS) showed that 88% hydrolyzed PVA adsorbed more strongly than 100% hydrolyzed one on the oxygen plasma-pretreated PDMS surface, and they all had little adsorption on original PDMS surface. Repeating the coating procedure three times was found to produce the most robust and effective coating. PVA coating converted the original PDMS surface from a hydrophobic one into a hydrophilic surface, and suppressed electroosmotic flow (EOF) in the range of pH 3-11. More than 1,000,000 plates/m and baseline resolution were obtained for separation of fluorescently labeled basic proteins (lysozyme, ribonuclease B). Fluorescently labeled acidic proteins (bovine serum albumin, beta-lactoglobulin) and fragments of dsDNA phiX174 RF/HaeIII were also separated satisfactorily in the three-layer 88% PVA-coated PDMS microchip. Good separation of basic proteins was obtained for about 70 consecutive runs.     

On Some Model Equations of Euler and Navier-Stokes Equations

The author proposes a two-dimensional generalization of Constantin-Lax-Majda model. Some results about singular solutions are given. This model might be the first step toward the singular solutions of the Euler equations. Along the same line(vorticity formulation), the author presents some further model equations. He possibly models various aspects of difficulties related with the singular solutions of the Euler and Navier-Stokes equations. Some discussions on the possible connection between tur...     

脉冲电流冲击力对电极间距的影响

利用时变场理论和瞬态动力学方程建立了电极及其支撑结构的瞬态耦合模型,分析了瞬态电磁场各参数的分布特点,并求解了电极及其支撑结构的动态响应状态参数。计算结果表明:玻璃钢支撑结构对于脉冲电流形成的冲击力载荷具有很好的缓冲作用;低弹性模量支撑材料在脉冲上升沿和峰值阶段均会产生波动性形变,但该波动性形变对电极间距不会造成太大的影响。     

A theoretical study on the red- and blue-shift hydrogen bonds of cis-trans formic acid dimer in excited states

The excited states of cis-trans formic acid dimer and its monomers have been investigated by time-dependent density functional theory (TDDFT) method. The formation of intermolecular hydrogen bonds O₁-H₁...O₂=C₂ and C₂-H₂...O₄=C₁ induces bond length lengthening of the groups related to the hydrogen bond, while that of the C₂-H₂ group is shortened. It is demonstrated that the red-shift hydrogen bond O₁-H₁...O₂=C₂ and blue-shift hydrogen bond C₂-H₂...O₄=C₁ are both weakened when excited to the S₁ state. Moreover, it is found that the groups related to the formation of red-shift hydrogen bond O₁-H₁...O₂=C₂ are both strengthened in the S1 state, while the groups related to the blue-shift hydrogen bond C₂-H₂...O₄=C₁ are both weakened. This will provide information for the photochemistry and photophysical study of red- and blue-shift hydrogen bond.