Electrochemical Assay to Quantify the Hydroxyl Radical Scavenging Activity of Medicinal Plant Extracts

A new electrochemical assay has been developed which is based on quantifying the attack of OH^. radicals on a self‐assembled thiol monolayer on electrodes in the presence and absence of antioxidants. The OH^. radicals were produced in Fenton solutions. The radical scavengers diminish the concentration of the OH^. radicals in the Fenton solution, and the extent of thiol layer destruction is monitored with the help of a redox probe in solution, the signal of which is only generated at SAM‐free electrode surface. The results of the electrochemical assay were compared with those of the standard DPPH^. assay. In case of each plant extract, an excellent linear correlation was observed between the radical scavenging activity and the concentration of plant extracts; however, the scavenging properties of different plants strongly differ in the electrochemical and the DPPH^. assay. Since the proposed new method probes the reactivity of radical scavengers towards OH^., one of the most important reactive oxygen radicals in tissues, it is supposed to provide much more relevant information than the DPPH^. or other assays.     

Influence of ultrasonication and Fenton oxidation pre-treatment on rheological characteristics of wastewater sludge

The effect of ultrasonication and Fenton oxidation as physico-chemical pre-treatment processes on the change of rheology of wastewater sludge was investigated in this study. Pre-treated and raw sludges displayed non-Newtonian rheological behaviour with shear thinning as well as thixotropic properties for total solids ranging from 10 g/L to 40 g/L. The rheological models, namely, Bingham plastic, Casson law, NCA/CMA Casson, IPC Paste, and power law were also studied to characterize flow of raw and pre-treated sludges. Among all rheological models, the power law was more prominent in describing the rheology of the sludges. Pre-treatment processes resulted in a decrease in pseudoplasticity of sludge due to the decrease in consistency index K varying from 42.4 to 1188, 25.6 to 620.4 and 52.5 to 317.9; and increase in flow behaviour index n changing from 0.5 to 0.35, 0.62 to 0.55 and 0.63 to 0.58, for RS, UlS and FS, respectively at solids concentration 10–40 g/L. The correlation between improvement of biodegradability and dewaterability, decrease in viscosity, and change in particle size as a function of sludge pre-treatment process was also investigated. Fenton oxidation facilitated sludge filterability resulting in capillary suction time values which were approximately 50% of the raw sludges, whereas ultrasonication with high input energy deteriorated the filterability. Biodegradability was also enhanced by the pre-treatment processes and the maximum value was obtained (64%, 77% and 73% for raw, ultrasonicated and Fenton oxidized sludges, respectively) at total solids concentration of 25 g/L. Hence, pre-treatment of wastewater sludge modified the rheological properties so that: (1) the flowability of sludge was improved for transport through the treatment train (via pipes and pumps); (2) the dewaterability of wastewater sludge was enhanced for eventual disposal and; (3) the assimilation of nutrients by microorganisms for further value-addition was increased.     

Chemical biology of salinomycin

Cancer stem cells (CSC) have been shown to be refractory to conventional therapeutic agents, can promote metastasis, and have been linked to cancer relapse. The natural product Salinomycin has been identified by means of high throughput phenotypic screening as a selective killer of CSC in vitro and in vivo. In this article we comprehensively review the chemistry of Salinomycin, documenting early total syntheses, along with strategies that have been developed over the years to effectively modify this natural product at key positions with the view to establish a robust structure-activity-relationship and to delineate the complex mechanism of action of this fascinating molecule in the context of cancer research. Then, we document the biology of Salinomycin, putting forward phenotypic alterations that have been observed in the relevant biological models and highlighting how chemistry has been instrumental in discovering unprecedented physiological features of cancer stem cells that can be exploited for therapeutic benefits.     

Reprogramming the chemical reactivity of iron in cancer stem cells

Cancer stem cells (CSCs) have been shown to be refractory to conventional therapeutic agents, can promote metastasis, and have been linked to cancer relapse. Salinomycin can selectively kill CSCs. We have shown that salinomycin derivatives accumulate in lysosomes and sequester iron in this organelle. As a result, accumulation of iron leads to the production of reactive oxygen species and lysosomal membrane permeabilization, which in turn promotes cell death by ferroptosis. These findings have revealed the prevalence of iron homeostasis in CSCs and paved the way toward the development of next-generation therapeutics.     

The complementary effect between biochar and ferrihydrite in sustainable Fenton-like oxidation of pollutant

Biochar (BC) and ferrihydrite (Fh) were used together in activation of H₂O₂ for removal of sulfamethazine (SMZ), a refractory antibiotic pollutant. The results show a complementary effect between biochar and ferrihydrite on activation of H₂O₂, namely biochar accelerated Fe(Ⅲ)/Fe(Ⅱ) cycle through electron donation/transfer, while ferrihydrite enhanced the yield of ^•OH through a sustainable release of dissolved Fe. Thus several times more ^•OH was produced in the co-activated system (BC + Fh/H₂O₂) than either in the ferrihydrite-catalyzed Fenton-like system (Fh/H₂O₂) or in the biochar-activated system (BC/H₂O₂). Consequently, a more efficient oxidation of SMZ was observed in BC + Fh/H₂O₂, in which the reaction rate constant (k_obs) is 30.7 times in Fh/H₂O₂ and 6.08 times in BC/H₂O₂, respectively. This research provides a simple and sustainable strategy for enhancing the efficiency of Fenton-like oxidation of pollutants.     

Nanosilver resonance scattering spectral method for determination of hydroxyl radical and its application

Silver nanoparticles were prepared under a microwave high-pressure condition using citric acid sodium as a reducer while the excess citrate was removed under high speed centrifugation. There is a resonance scattering (RS) peak at 470 nm for silver nanoparticles. In a pH 4.0 HAc-NaAc buffer solution, hydroxyl radicals from the Fenton reaction can oxidize silver nanoparticles to Ag , resulting in the RS intensity decreasing. The decreased RS intensity at 470 nm (△I 470 nm) is linear with respect to the concentration of H2O2 (C) in the range of 0.27-7.56 μmol/L with a detection limit of 0.23 μmol/L. Its regression equation is △I 470 nm = 24.3 C 13.8 with a correlation coefficient of 0.9959. This method was applied to screening the antioxidants with satisfactory results.     

Antioxidant Activity of Deferasirox and Its Metal Complexes in Model Systems of Oxidative Damage: Comparison with Deferiprone

Deferasirox is an orally active, lipophilic iron chelating drug used on thousands of patients worldwide for the treatment of transfusional iron overload. The essential transition metals iron and copper are the primary catalysts of reactive oxygen species and oxidative damage in biological systems. The redox effects of deferasirox and its metal complexes with iron, copper and other metals are of pharmacological, toxicological, biological and physiological importance. Several molecular model systems of oxidative damage caused by iron and copper catalysis including the oxidation of ascorbic acid, the peroxidation of linoleic acid micelles and the oxidation of dihydropyridine have been investigated in the presence of deferasirox using UV-visible and NMR spectroscopy. Deferasirox has shown antioxidant activity in all three model systems, causing substantial reduction in the rate of oxidation and oxidative damage. Deferasirox showed the greatest antioxidant activity in the oxidation of ascorbic acid with the participation of iron ions and reduced the reaction rate by about a 100 times. Overall, deferasirox appears to have lower affinity for copper in comparison to iron. Comparative studies of the antioxidant activity of deferasirox and the hydrophilic oral iron chelating drug deferiprone in the peroxidation of linoleic acid micelles showed lower efficiency of deferasirox in comparison to deferiprone.     

芬顿试剂对田菁胶的氧化降解

考察了芬顿试剂对田菁胶的氧化降解行为. 系统研究了H_2O_2和Fe~(2+)用量、温度和降解时间对田菁胶粘度的影响. 结果表明,H_2O_2和Fe~(2+)合适的体积比为2:1. 在较低的温度(25 ℃)和较短的时间(20 min)内芬顿试剂就能使田菁胶粘度下降90%以上. 另外,pH值的变化对其降解性能影响不大,显示了较好的降解效果.