双对苯醌的抗氧化活性分析及其固体发酵条件优化

为探索生物活性未知的双对苯醌（2,7-dihydroxy-3,6,9-trimethyl-9H-xanthene-1,4,5,8-tetraone，DTXT）的抗氧化活性，并提高其发酵产量，考察DTXT的还原力以及对超氧阴离子自由基、羟自由基、1,1-二苯基-2-三硝基苯肼（1,1-diphenyl-2-picrylhydrazyl，DPPH）自由基的清除效果，在单因素试验基础上，采用响应面法优化了DTXT产生菌瓶生顶孢霉（Acremonium cavaraeanum）CA022菌株的固体发酵培养基。结果表明：在200 μg/mL质量浓度下，DTXT的还原力与芦丁差异不显著，高于VE和2,6-二叔丁基-4甲基苯酚，对超氧阴离子自由基清除率达到67.00%，对羟自由基清除率达到78.83%，对DPPH自由基清除率达到76.53%。通过响应面试验，得到最佳培养基配方为葡萄糖0.773%、硝酸钠0.185%、H3BO3 0.032%、VB1 100 μg/100 g，在此条件下实际获得的DTXT产量为4 150.8 mg/kg，是优化前产量的（2 864.83 mg/kg）1.45 倍。     

Piezoelectric properties of PVDF-conjugated polymer nanofibers

This study presents the development and characterization of PVDF-conjugated polymer nanofiber-based systems. Five different conducting polymers (CPs) were synthesized successfully and used to create the nanofiber systems. The CPs used are polyaniline (PANI), polypyrrole (PPY), polyindole (PIN), polyanthranilic acid (PANA), and polycarbazole (PCZ). Nanofiber systems were produced utilizing the Forcespinning® technique. The nanofiber systems were developed by mechanical stretching. No electrical field or post-process poling was used in the nanofiber systems. The morphology, structure, electrochemical and piezoelectric performance was characterized. All of the nanofiber PVDF/CP systems displayed higher piezoelectric performance than the fine fiber PVDF systems. The PVDF/PPY nanofiber system displays the highest piezoelectric performance of 15.56 V. The piezoelectric performance of the PVDF/CP nanofiber systems favors potential for an attractive source of energy where highly flexible membranes could be used in power actuators, sensors and portable, and wireless devices to mention some.     

Organofluorine Hydrazone Derivatives as Multifunctional Anti-Alzheimer's Agents with CK2 Inhibitory and Antioxidant Features

A set of novel hydrazone derivatives were synthesized and analyzed for their biological activities. The compounds were tested for their inhibitory effect on the phosphorylating activity of the protein kinase CK2, and their antioxidant activity was also determined in three commonly used assays. The hydrazones were evaluated for their radical scavenging against the DPPH, ABTS and peroxyl radicals. Several compounds have been identified as good antioxidants as well as potent protein kinase CK2 inhibitors. Most hydrazones containing a 4-N(CH₃)₂ residue or perfluorinated phenyl rings showed high activity in the radical-scavenging assays and possess nanomolar IC₅₀ values in the kinase assays.     

The Chemistry of DPPH· Free Radical and Congeners

Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH^·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.     

基于α-FeOOH催化H2O2蒸气的低温烟气脱硝实验

针铁矿是分布广泛、储量丰富的铁氧化物，其主要成分为α-羟基氧化铁（α-FeOOH）。为了探究针铁矿在催化H₂O₂烟气脱硝反应中的性能，本文通过沉淀-水解法制备了α-FeOOH，并在自行搭建的实验台上开展了α-FeOOH催化H₂O₂的低温烟气脱硝实验研究，深入分析了H₂O₂流量、H₂O₂浓度、汽化温度、反应温度和共存气体浓度等工况参数对脱硝性能的影响。采用离子色谱（IC）分析了单独脱硝反应和同时脱硫脱硝反应后的含氧酸成分，结合各项表征分析技术考察了催化剂反应前后的理化特性和稳定性。实验结果显示，随着汽化温度和反应温度的升高，NO的脱除效率先增加后降低；增加H₂O₂浓度对脱硝效率有明显的促进作用。当汽化温度为140℃、反应温度为160℃时，以2.5mL/h注入10mol/L的H₂O₂脱硝效率达到80%。当SO₂浓度为1000μL/L时，脱硝效率提高至86.4%。离子色谱分析结果显示，单独脱硝反应和同时脱硫脱硝反应后含氧酸产物为HNO₃和H₂SO₄。反应前后催化剂的表征结果显示，α-FeOOH在脱硝反应后依然具有良好的稳定性，显示出针铁矿在低温烟气脱硝工艺中的潜在应用前景。     

基于OH-PLIF的狭长受限空间油气爆炸中间基团浓度分布研究

为了精确测量狭长受限空间油气爆炸过程中的关键自由基团，从而实现对其爆炸流场、火焰传播的精确分析，基于先进的平面激光诱导荧光测量技术（PLIF），设计构建了油气爆炸PLIF测量系统，开展了不同工况下狭长受限空间汽油-空气混合气爆炸实验研究，获得了该爆炸中间基团OH基的浓度分布。实验结果表明，1.1%~2.4%（体积分数）油气浓度之间，OH基浓度先增大后减小；随火焰的传播发展，OH基浓度不断变大，表明爆炸不断强化；爆燃不同时期OH基分布情况不同，表明不同爆燃阶段的燃烧反应区域有较大差异；爆燃前期火焰与壁面之间有“隔离带”，是由未燃气浓度增大导致火焰传播变慢的结果。主要创新点在于通过设计时序控制子系统，解决了非稳态预混燃烧中自由基分布瞬态测量。     

Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.