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.     

A numerical study on the combustion limits of mesoscale methane jet flames with hydrogen addition

A meso-scale jet flame model was established for the flame ports of domestic gas stoves. The influences of hydrogen addition ratio (β = 0%–25%) on the combustion limits were explored. The results show that with the increase of hydrogen addition ratio, the blow-off limit increases obviously, while the extinction limit decreases slightly, namely, the combustible range expands significantly. Quantitative analysis was carried out in terms of chemical effect and thermal effect. It was found that hydrogen addition will reduce O₂ fraction in the pre-mixture for a constant equivalence ratio. Under near-extinction limit condition, since the flame is located at the nozzle exit, the external O₂ cannot be entrained into or diffuse into the upstream of the flame, which leads to the decrease of reaction rate. However, for the near-blow-off cases, the external O₂ can be entrained and diffuse into the flame, which compensates the difference of O₂ content in the pre-mixture. Therefore, the combustion reaction is enhanced by hydrogen addition because more H radicals can be produced. In addition, as the flame is located closer to the tube with the increase of hydrogen addition ratio, heat transfer between flame and tube wall is augmented and the preheating of fresh mixture is strengthened by the inner tube wall. This heat recirculation effect becomes especially notable in low velocity cases. In conclusion, the extension of extinction limit by hydrogen addition is attributed to the thermal effect, while the increase of blow-off limit is mainly due to the intensification of chemical effect.     

Effects of Bacillus velezensis zk1 on the physiology and metabolism of peaches

Bacillus velezensis zk1 is the dominant bacterium that causing rot in peaches. However, the mechanisms through that this bacterium causes rot have not been elucidated. Here, we explored the mechanisms of peach decay caused by B. velezensis zk1. The invasion of B. velezensis zk1 in peaches resulted in an increase in glucose and arabinose contents in fruit tissues. Moreover, the relative conductivity of the fruit reached 84% after 4 days of culture with bacterial invasion. With the destruction of cells, the malondialdehyde content increased, whereas the vitamin C, dialdehyde, flavonoid and total phenol contents decreased. Polyphenol oxidase, superoxide dismutase, catalase, peroxidase, ascorbate peroxidase and ammonia lyase activities also decreased. Overall, these findings demonstrated that B. velezensis zk1 infection damaged peach chloroplasts, mitochondria, respiratory chain activity and related free radical scavenging enzyme systems, thereby disrupting the normal physiological metabolism of peaches and causing rot.     

Driving performance and road sign identification by multifocal contact lens wearers in a driving simulator

PurposeThe purpose of this study was to compare sign identification distances and driving performance metrics in presbyopic participants while wearing multifocal contact lenses (MFCL) and while wearing progressive addition lens (PAL) spectacles.Methods19 presbyopic participants completed PAL spectacle assessments and contact lens fitting and follow up visits before driving assessments began. These assessments occurred in a simulator equipped with a full-sized sedan on a motion platform and a 260 degree screen. Participants completed the driving task with PAL and with MFCL. Participants followed a lead car and identified signs at various distances from the road. For the two wearing conditions, comparisons of the distance along the road at which signs were identified were made using repeated measures ANOVA. Paired t-tests were used to compare driving performance for the two conditions.ResultsThere was no statistical difference in sign identification distance between PAL and MFLC for signs 32.0 m from the road side of the road (182 ± 46 m for MFCL; 205 ± 45 m for PAL; P = 0.07) or 51.4 m from the side of the road (204 ± 43 m for MFCL; 216 ± 36 m for PAL; P = 0.3). Only signs 70.2 m from the roadside showed a significant difference (207 ± 42 m with MFCL; 232 ± 39 m with PAL; P = 0.01), All distances were greater than those required to safely stop a vehicle. There were no significant differences in the driving performance metrics between the refractive corrections.ConclusionDriving performance metrics were similar for MFCL and PAL spectacles. Sign identification distances with both eyewear types were well within the distances required for safe vehicle stopping.     

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.     

Effects of hydroxyl radical induced oxidation on water holding capacity and protein structure of jumbo squid (Dosidicus gigas) mantle

Protein oxidation is considered as an important issue in food preservation process. In the present study, the potential influence of protein oxidation on water holding capacity and protein structure of jumbo squid (Dosidicus gigas) mantle was investigated. After the hydroxyl radical oxidation, it was found that the carbonyl, surface hydrophobicity and dityrosine content of myofibrillar protein significantly increased (P < 0.05), while the content of total sulphydryl decreased significantly (P < 0.01). Meanwhile, the fluorescence intensity of squid was weakened, and the maximum absorption peak of fluorescence red shift as the H₂O₂ concentration increased. The sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS-PAGE) showed that not only the protein cross-linking but also degradation could have occurred. The content of α-helix decreased, the content of β-sheet, β-turn and the unordered structures increased after oxidation. In addition, oxidation resulted in a decrease in water holding capacity. Taken together, oxidation resulted in the damage of the myofibrillar structure, the increase in muscle loss rate and the decrease in water holding capacity.     

Neural network-based hybrid models developed for free radical polymerization of styrene

In the present work, the free radical polymerization of styrene is modeled by considering the phenomenology of the process (a simplified model, which does not include the diffusional effects, gel, and glass effects) in combination with an empirical model represented by an artificial neural network. Differential evolution (DE) algorithm, belonging to the class of evolutionary algorithms, is applied for developing the neural models in optimal forms. For improving the results—predicted conversion and molecular weights as function of time, temperature, and initiator concentration—different combinations between phenomenological model and neural network are tested; also, individual and stacked neural networks have been developed for the polymerization process. This methodology based on hybrid models, including neural networks aggregated in stacks, provides accurate results.     

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.