Structure,antioxidative potency and potential scavenging of OH and OOH of phenylethyl-3,4-dihydroxyhydrocinnamate in protic and aprotic media: DFT study

DFT methods including B3LYP, B3PW91 and M05–2 x associated to 6–31 + G(d,p) were used for the structural and antioxidant potency studies of phenylethyl-3,4-dihydroxy-hydrocinnamate (PDH). Solvents were employed according to their protric and aprotic character. So, calculated structures agree with the experimental data. O₄H₄ is propitious to scavenge radicals whatever the medium except in water where O₃H₃ and O₄H₄ are competitive. The explicit solvents of dichloromethane (DCM) and water present a disparity of OH bond dissociation enthalpy and free energy (BDE and BDFE). These parameters are low in continuum except in water. The ionization potentials (IP) and potential affinities (PA) are low in solvents. BDE, IP and PA are each, approximatively constant in mixed solvent treatment in water using n-H₂O (n = 3,5,8). Elsewhere, H-atom transfer (HAT) mechanism is favoured in vacuum and DCM, whereas sequential proton loss electron transfer (SPLET) is likely in protic solvents. A discord between HAT and SPLET in benzene is observed. The PDH compound is more antioxidant and resistant to oxidation than caffeic acid phenethyl ester (CAPE). The potential of scavenging of OH and OOH whatever the reaction channel shows that they decay rapidly in any media through HAT. PDH is easily deprotonated in the protic solvents and the resulting product is the most antioxidant and the least resistant to oxidation.     

工程陶瓷预压应力下超声振动辅助划痕实验研究

目的结合超声振动加工方法,探究工程陶瓷预压应力加工过程的工件表面损伤特性。方法建立预压应力下工程陶瓷超声振动辅助加工过程的工程学模型,结合Al_2O_3陶瓷划痕过程的离散元仿真结果和实验结果进行分析,采用扫描电镜对加工表面进行观察,使用三向动态压电测力仪测量划痕力。结果预压应力下超声振动辅助划痕过程能够去除沟槽边缘处的材料堆积,并且划痕沟槽边缘破碎呈现周期性。当预压应力为200 MPa、理论划痕深度为10μm时,普通划痕深度为7.58μm,宽度107.5μm,超声振动辅助划痕深度为8.55μm,宽度为143.5μm。结合仿真结果,超声振动辅助划痕过程可减小划痕沟槽的径向裂纹数量,增大径向裂纹深度。同时,两种划痕过程动态切向力出现明显差异,超声振动辅助划痕过程动态切向力较小,变化相对平稳。结论超声振动辅助加工过程可以减小工程陶瓷预压应力加工过程的切削力,提高材料加工效率。