Fluorination of an Alumina Surface: Modeling Aluminum–Fluorine Reaction Mechanisms

Density functional theory (DFT) calculations were performed to examine exothermic surface chemistry between alumina and four fluorinated, fragmented molecules representing species from decomposing fluoropolymers: F^–, HF, CH₃F, and CF₄. The analysis has strong implications for the reactivity of aluminum (Al) particles passivated by an alumina shell. It was hypothesized that the alumina surface structure could be transformed due to hydrogen bonding effects from the environment that promote surface reactions with fluorinated species. In this study, the alumina surface was analyzed using model clusters as isolated systems embedded in a polar environment (i.e., acetone). The conductor-like screening model (COSMO) was used to mimic environmental effects on the alumina surface. Four defect models for specific active −OH sites were investigated including two terminal hydroxyl groups and two hydroxyl bridge groups. Reactions involving terminal bonds produce more energy than bridge bonds. Also, surface exothermic reactions between terminal −OH bonds and fluorinated species produce energy in decreasing order with the following reactant species: CF₄ > HF > CH₃F. Additionally, experiments were performed on aluminum powders using thermal equilibrium analysis techniques that complement the calculations. Consistently, the experimental results show a linear relationship between surface exothermic reactions and the main fluorination reaction for Al powders. These results connect molecular level reaction kinetics to macroscopic measurements of surface energy and show that optimizing energy available in surface reactions linearly correlates to maximizing energy in the main reaction

Reaction Dynamics of Rocket Propellant with Magnesium Oxide Nanoparticles

The combustion behavior of rocket propellant grade 2 (RP-2) was investigated as a function of magnesium oxide (MgO) nanoparticles (i.e., 20 nm diameter) added at varied concentrations. The MgO nanoparticles were surface-treated with a long-chain carboxylic acid to aid their dispersion in RP-2. The fuel droplet regression rate, surface tension, and heat of combustion of RP-2 with MgO nanoparticle additives were measured to characterize combustion behavior. Heat of combustion and surface tension measurements varied negligibly among all samples indicating that calorific output and surface tension are not controlling parameters influencing fuel combustion behavior. However, fuel droplet regression rates were considerably increased by adding 0.5 wt % MgO from 0.225 to 66.16 mm/s, which is an improvement by 2 orders of magnitude. Further analysis showed that MgO particles enhance diffusive heat transfer, which promotes nucleation and disruptive burning throughout the three stages of regression, heating/evaporation (stage 1), combustion of RP-2 (stage 2), and combustion of carboxylic acid dispersant (stage 3), and, thus, lead to improved fuel droplet combustion

Porphyrin Immobilized Nanographene Oxide for Enhanced and Targeted Photothermal Therapy of Brain Cancer

Brain cancer is a fatal disease that is difficult to treat because of poor targeting and low permeability of chemotherapeutic drugs through the blood brain barrier. In a comparison to current treatments, such as surgery followed by chemotherapy and/or radiotherapy, photothermal therapy is a remarkable noninvasive therapy developed in recent years. In this work, porphyrin immobilized nanographene oxide (PNG) was synthesized and bioconjugated with a peptide to achieve enhanced and targeted photothermal therapy for brain cancer. PNG was dispersed into the agar based artificial tissue model and demonstrated a photo-to-thermal conversion efficiency of 19.93% at a PNG concentration of only 0.5 wt %, with a heating rate of 0.6 °C/s at the beginning of irradiation. In comparison, 0.5 wt % graphene oxide (GO) indicated a photo-to-thermal conversion efficiency of 12.20% and a heating rate of 0.3 °C/s. To actively target brain tumor cells without harming healthy cells and tissues surrounding the laser path, a tripeptide l-arginyl-glycyl-l-aspartic (RGD) was further grafted to PNG. The photothermal therapy effects of PNG-RGD completely eliminated the tumor <i>in vivo</i>, indicating its excellent therapeutic effect for the treatment of brain cancer