Supercritical Fenton Oxidation: A New Method for Total Organic Carbon Measurement

A new method for total organic carbon (TOC) measurement was established based on supercritical Fenton oxidation. The organic pollutants in wastewater were oxidized to carbon dioxide in supercritical water by Fenton reagents that was detected using a nondispersive infrared detector. The influence of temperature from 380 to 480°C, oxidant coefficient from 1 to 20, pH from 2.2 to 5.2, and Fe²⁺ concentration from 0.2 to 0.8?mg?L^?1 was characterized; the optimal conditions were at 420°C, an oxidant coefficient n?≥?5, a pH of 4.4, and Fe²⁺ concentration of 0.8?mg?L^?1. Using these parameters, the recovery of potassium hydrogen phthalate exceeded 98.2%. The introduction of Fenton oxidation based on supercritical water lowered the temperature and reduced the oxidant coefficient required for TOC determination.     

Enhanced sonochemical degradation of azure B dye by the electroFenton process

The degradation of azure B dye (C₁₅H₁₆ClN₃S; AB) has been studied by Fenton, sonolysis and sono-electroFenton processes employing ultrasound at 23 kHz and the electrogeneration of H₂O₂ at the reticulated vitreous carbon electrode. It was found that the dye degradation followed apparent first-order kinetics in all the degradation processes tested. The rate constant was affected by both the pH of the solution and initial concentration of Fe²⁺, with the highest degradation obtained at pH between 2.6 and 3. The first-order rate constant decreased in the following order: sono-electroFenton > Fenton > sonolysis. The rate constant for AB degradation by sono-electroFenton is ∼10-fold that of sonolysis and ∼2-fold the one obtained by Fenton under silent conditions. The chemical oxygen demand was abated ∼68% and ∼85% by Fenton and sono-electroFenton respectively, achieving AB concentration removal over 90% with both processes.     

Hydrogen peroxide-generating nanomedicine for enhanced chemodynamic therapy

Chemodynamic therapy(CDT) is an emerging endogenous stimulation activated tumor treatment approach that exploiting iron-containing nanomedicine as catalyst to convert hydrogen peroxide(H_2O_2)into toxic hydroxyl radical(·OH) through Fenton reaction.Due to the unique characteristics(weak acidity and the high H_2O_2 level) of the tumor microenvironment,CDT has advantages of high selectivity and low side effect.However,as an important substrate of Fenton reaction,the endogenous H_2O_2 in tumor is still insufficient,which may be an important factor limiting the efficacy of CDT.In order to optimize CDT,various H_2O_2-generating nanomedicines that can promote the production of H_2O_2 in tumor have been designed and developed for enhanced CDT.In this review,we summarize recently developed nanomedicines based on catalytic enzymes,nanozymes,drugs,metal peroxides and bacteria.Finally,the challenges and possible development directions for further enhancing CDT are prospected.     

Synthesis of N-TiO2@NH2-MIL-88(Fe) Core-shell Structure for Efficient Fenton Effect Assisted Methylene Blue Degradation Under Visible Light

Core-shell TiO₂-based photocatalysts with specific composition, morphology, and functionality have attracted considerable attention for their excellent degradation properties on organic pollutants via a photocatalytic oxidation process. Herein, a N-TiO₂@NH₂-MIL-88(Fe) core-shell structure was prepared by coating NH₂-MIL-88(Fe) on nitrogen-doped TiO₂(N-TiO₂) nanoparticles. Introduction of heteroatom nitrogen to pure TiO₂ expands the spectral response range, leading to enhanced quantum efficiency of photocatalyst. Furthermore, loading NH₂-MIL-88(Fe) on N-TiO₂ improved the adsorption ability of the nanocomposites due to the porous tunnels of NH₂-MIL-88(Fe). The resulted core-shell N-TiO₂@NH₂-MIL-88(Fe) nanocomposites realized the transfer of photo excited electrons from N-TiO₂ to NH₂-MIL-88(Fe) rapidly, partially reduced Fe³⁺ to Fe²⁺ in NH₂-MIL-88(Fe), and further enhanced the Fenton effect on efficiently degrading methylene blue dye(MB) under visible light(λ ≥ 420 nm) with the assistance of H₂O₂.     

Simultaneous Removal of Antibiotics and Heavy Metals with Poly(Aspartic Acid)-Based Fenton Micromotors

The discharge of diverse pollutants has led to a complex water environment and posed a huge health threat to humans and animals. Self-propelled micromotors have recently attracted considerable attention for efficient water remediation due to their strong localized mass transfer effect. However, a single functionalized component is difficult to tackle with multiple contaminants and requires to combine different decontamination effects together. Here, we introduced a multifunctional micromotor to implement the adsorption and degradation roles simultaneously by integrating the poly(aspartic acid) (PASP) adsorbent with a MnO₂-based catalyst. The as-prepared micromotors are well propelled in contaminated waters by MnO₂ catalyzing hydrogen peroxide. In addition, the catalytic ramsdellite MnO₂(R-MnO₂) inner layer is decorated with Fe₂O₃ nanoparticles to improve their catalytic performance, contributing to an excellent degradation ability with 90% tetracycline (TC) removal in 50 minutes by enhanced Fenton-like reactions. Combining the attractive adsorption capability of poly (aspartic acid) (PASP), the composite micromotors offer an efficient removal of heavy metal ions in short time. Moreover, the designed micromotors are able to simultaneously remove antibiotic and heavy metals in mixed contaminants circumstance just in single treatment. This multifunctional micromotor with distinctive decontamination ability exhibits a promising prospective in treating multiple pollutants in the future.     

Current Use of Fenton Reaction in Drugs and Food

Iron is the most abundant mineral in the human body and plays essential roles in sustaining life, such as the transport of oxygen to systemic organs. The Fenton reaction is the reaction between iron and hydrogen peroxide, generating hydroxyl radical, which is highly reactive and highly toxic to living cells. “Ferroptosis”, a programmed cell death in which the Fenton reaction is closely involved, has recently received much attention. Furthermore, various applications of the Fenton reaction have been reported in the medical and nutritional fields, such as cancer treatment or sterilization. Here, this review summarizes the recent growing interest in the usefulness of iron and its biological relevance through basic and practical information of the Fenton reaction and recent reports.     

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.     

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.