Self-Organized Amphiphiles are Poor Hydroxyl Radical Scavengers in Fast Photochemical Oxidation of Proteins Experiments

ABSTRACTThe analysis of membrane protein topography using fast photochemical oxidation of protein (FPOP) has been reported in recent years, but still underrepresented in literature. Based on the hydroxyl radical reactivity of lipids and other amphiphiles, it is believed that the membrane environment acts as a hydroxyl radical scavenger decreasing effective hydroxyl radical doses and resulting in less observed oxidation of proteins. Here, we investigated the effect of bulk hydroxyl radical scavenging in FPOP using both isolated cellular membranes as well as detergent micelles. We found no significant change in radical scavenging activity upon the addition of disrupted cellular membranes with the membrane concentration in the range of 0-25600 cell/μL using an inline radical dosimeter. We confirmed the non-scavenging nature of the membrane with the FPOP results of a soluble model protein in the presence of cell membranes, which showed no significant difference in oxidation with or without membranes. The use of detergents revealed that, while soluble detergent below the critical micelle concentration acts as a potent hydroxyl radical scavenger as expected, additional detergent has little to no hydroxyl radical scavenging effect once the critical micelle concentration is reached. These results suggest that any scavenging effect of membranes or organized amphiphilic membrane mimetics in FPOP experiments are not due to bulk hydroxyl radical scavenging, but may be due to a localized scavenging phenomenon.

On the Nature of Hydrodynamic Cavitation Process and Its Application for the Removal of Water Pollutants

Cavitation is considered a high energy demanding process for water treatment. For this study, we used a simple experimental setup to generate cavitation at a low pressure (low energy) and test it for hydroxyl radical production using a well-known chemical probe as a hydroxyl radical scavenger. The conditions for generating the cavitation process (eg, pressure, flow velocity, temperature, and other significant variables) were used to degrade model contaminants, an azo dye and an antibiotic. The amount of hydroxyl radicals generated by the system was estimated using N,N-dimethyl-p-nitrosoaniline (pNDA) as hydroxyl radical scavenger. The capability of hydrodynamic cavitation (HC) to degrade contaminants was assessed using Congo red (CR) and sulfamethoxazole (SMX) as model contaminants. Different chemical models were analyzed using UV-visible spectrophotometry (for pNDA and CR) and high-performance liquid chromatography (HPLC) (for SMX) after HC treatment under different process conditions (ie, pressure of 13.7 and 10.3 kPa, and flow rates of 0.14 to 3.6 × 10−4 m3/s). No pNDA bleaching was observed for any of the reaction conditions tested after 60 minutes of treatment, which suggests that there was no hydroxyl radical generation during the process. However, 50% degradation of CR and 25% degradation of SMX were observed under the same process conditions, comparable with previously reported results. These results suggest that the process is most likely thermally based rather than radically based, and therefore, it can degrade organic pollutants even if no hydroxyl radicals are produced. Hydrodynamic cavitation, either alone or coupled with other advanced water technologies, has been identified as a promising technology for removing organic contaminants entering the water cycle; however, more research is still needed to determine the specific mechanisms involved in the process and the optimal operation conditions for the system.

Degradation of p-Chloronitrobenzene in Aqueous Solution by Iron Silicate Catalytic Ozonation

Iron silicate, a stable and efficient catalyst prepared in the laboratory has been successfully used as a catalyst combined with ozonation in the degradation of p-Chloronitrobenzene (pCNB). The catalytic ozonation removal effectiveness of pCNB was investigated under various physicochemical conditions. Both the adsorption and the single ozonation were not effective for the degradation of pCNB, but the presence of iron silicate in ozonation process could substantially enhance the pCNB removal efficiency. The hydroxyl radical scavenger experiment confirmed that iron silicate catalytic ozonation followed a radical-type mechanism. The increasing of both the iron silicate dosage and the ozone dosage could enhance the removal effectiveness of pCNB. The iron silicate catalyst could be recycled easily without decreasing any ozone catalytic activity after four successive reuses. It is concluded that the iron silicate was an efficient green catalyst for pCNB degradation in drinking water.

Visible light photooxidative performance of a high-nuclearity molecular bismuth vanadium oxide cluster

The visible light photooxidative performance of a new high-nuclearity molecular bismuth vanadium oxide cluster, H3[{Bi(dmso)3}4V13O40], is reported. Photocatalytic activity studies show faster reaction kinetics under anaerobic conditions, suggesting an oxygen-dependent quenching of the photoexcited cluster species. Further mechanistic analysis shows that the reaction proceeds via the intermediate formation of hydroxyl radicals which act as oxidant. Trapping experiments using ethanol as a hydroxyl radical scavenger show significantly decreased photocatalytic substrate oxidation in the presence of EtOH. Photocatalytic performance analyses using monochromatic visible light irradiation show that the quantum efficiency Φ for indigo photooxidation is strongly dependent on the irradiation wavelength, with higher quantum efficiencies being observed at shorter wavelengths (Φ395nm ca. 15%). Recycling tests show that the compound can be employed as homogeneous photooxidation catalyst multiple times without loss of catalytic activity. High turnover numbers (TON ca. 1200) and turnover frequencies up to TOF ca. 3.44 min−1 are observed, illustrating the practical applicability of the cluster species.