The role of transition metals in oxidative degradation of cellulose

The role of transition metals in oxidative degradation of cellulose has been studied. Degradation experiments with model papers and studies of hydroxyl radical production in solution have been performed with Fe, Cu, Mn, Co, Cr, Ni, and Zn. Rates of production of hydroxyl radicals in solution have been estimated using the radical scavenger N,N′-(5-nitro-1,3-phenylene)bisglutaramide in the pH interval 7-9. Hydroxyl radical production during degradation of Cu-containing cellulose has been studied. To gain a better insight into chemistry behind degradation processes, chemiluminometric experiments were also performed.The experiments provide strong evidence that the role of transition metals during the oxidative degradation of cellulose is catalytic. A correlation between the behaviour of transition metals in solution and in paper was established at low contents of transition metal in paper.     

Synthesis of Iron Nanometallic Glasses and Their Application in Cancer Therapy by a Localized Fenton Reaction

Metallic glasses and cancer theranostics are emerging fields that do not seem to be related to each other. Herein, we report the facile synthesis of amorphous iron nanoparticles (AFeNPs) and their superior physicochemical properties compared to their crystalline counterpart, iron nanocrystals (FeNCs). The AFeNPs can be used for cancer theranostics by inducing a Fenton reaction in the tumor by taking advantage of the mild acidity and the overproduced H₂O₂ in a tumor microenvironment: Ionization of the AFeNPs enables on‐demand ferrous ion release in the tumor, and subsequent H₂O₂ disproportionation leads to efficient ^.OH generation. The endogenous stimuli‐responsive ^.OH generation in the presence AFeNPs enables a highly specific cancer therapy without the need for external energy input.     

On‐surface Fenton and Fenton‐like reactions appraised by paper spray ionization mass spectrometry

On‐surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe²⁺/H₂O₂) and Fenton‐like (Mⁿ⁺/H₂O₂; Mⁿ⁺ = Fe³⁺, Co²⁺, Cu²⁺, Mn²⁺) systems was investigated by using paper spray ionization mass spectrometry (PS‐MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS‐MS analyzes). The results indicated the following order in the rates of such reactions: Fe²⁺/H₂O₂ ≫ H₂O₂ ≫ Cu²⁺/H₂O₂ > Mⁿ⁺/H₂O₂ (Mⁿ⁺ = Fe³⁺, Co²⁺, Mn²⁺) ~ Mⁿ⁺ (Mⁿ⁺ = Fe²⁺, Fe³⁺, Co²⁺, Cu²⁺, Mn²). The superior capability of Fe²⁺/H₂O₂ in causing the degradation of sildenafil indicates that Fe²⁺ efficiently decomposes H₂O₂ to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H₂O₂ can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, ie, Fe³⁺, Co²⁺, Cu²⁺, and Mn²⁺. A unique oxidation by‐product was detected in the reaction between Fe²⁺/H₂O₂ with sildenafil, and a possible structure for it was proposed based on the MS/MS data. The on‐surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS‐MS shows to be a convenient platform to promptly monitor on‐surface oxidation reactions.     

A new sono-electrochemical method for enhanced detoxification of hydrophilic chloroorganic pollutants in water

A new method for detoxification of hydrophilic chloroorganic pollutants in effluent water was developed, using a combination of ultrasound waves, electrochemistry and Fenton's reagent. The advantages of the method are exemplified using two target compounds: the common herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) and its derivative 2,4-dichlorophenol (2,4-DCP). The high degradation power of this process is due to the large production of oxidizing hydroxyl radicals and high mass transfer due to sonication. Application of this sono-electrochemical Fenton process (SEF) treatment (at 20 kHz) with quite a small current density, accomplished almost 50% oxidation of 2,4-D solution (300 ppm, 1.2 mM) in just 60 s. Similar treatments ran for 600 s resulted in practically full degradation of the herbicide; sizable oxidation of 2,4-DCP also occurs. The main intermediate compounds produced in the SEF process were identified. Their kinetic profile was measured and a chemical reaction scheme was suggested. The efficiency of the SEF process is tentatively much higher than the reference degradation methods and the time required for full degradation is considerably shorter. The SEF process maintains high performance up to concentrations which are higher than reference methods. The optimum concentration of Fe²⁺ ions required for this process was found to be of about 2 mM, which is lower than that in reference techniques. These findings indicate that SEF process may be an effective method for detoxification of environmental water.     

Spin-trapping of oxygen free radicals in chemical and biological systems: new traps, radicals and possibilities

The choice of the spin-trap that is to be applied in any EPR study represents the crossroad between a comprehensive investigation and an "ordinary" quantification of production of radicals. So, the scope of our study was to compare the performance of different spin-traps for qualitative analysis of radical-generating systems, and their ability to recognize previously unnoticed radicals. In addition, we present a brief account of the difficulties involved in the detection of oxygen-centered radicals in chemical and biological systems accompanied by the rationale for using the EPR spin-trapping technique in quantitative studies of such reactive species. Certain technical aspects of EPR experiments related to efficient trapping of free radicals in biochemical systems are also discussed. As an example we present here results obtained using EPR spectroscopy and the spin-trap DEPMPO, which show that the Fenton reaction, as well as various biological systems generate a previously unappreciated hydrogen (*H) atom.     

(Au)核(Ag)壳纳米微粒光度法快速检测过氧化氢

以粒径为10 nm的纳米金为晶种, 用柠檬酸钠还原硝酸银制备了平均粒径为30 nm的(Au)核(Ag)壳纳米微粒, 用高速离心纯化除去过量的柠檬酸三钠获得了较纯的(Au)核(Ag)壳纳米微粒, 其吸收峰位于393 nm处. 在pH 4.4的HAc-NaAc缓冲溶液中, Fenton反应产生的羟基自由基可以氧化(Au)核(Ag)壳纳米微粒银层生成银离子, 导致393 nm处的吸光度降低. H2O2的浓度(c)在6.58～421.1 μmol/L范围内与393 nm处的吸光度降低值ΔA 393 nm呈良好的线性关系, 回归方程为ΔA393 nm=0.00111c+0.0210, 相关系数为0.9908, 检出限为1.73 μmol/L. 本方法用于废水样品测定, 结果满意.     

A Light-Responsive Injectable Hydrogel with Remodeling Tumor Microenvironment for Light-Activated Chemodynamic Therapy

Chemodynamic therapy (CDT) based on Fenton-like reaction is often limited by the tumor microenvironment (TME), which has insufficient hydrogen peroxide, and single CDT treatment is often less efficacious. To overcome these limitations, a hydrogel-based system is designed to enhance the redox stress (EOH) by loading the composite nanomaterial Cu-Hemin-Au, into the agarose hydrogels. The hydrogels can reach the tumor site upon intratumoral injection, and then coagulate and stay for extended period. Once irradiated with near-infrared light, the Cu-Hemin-Au act as a photothermal agent to convert the light energy into heat, and the EOH gradually heated up and softened, releasing the Cu-Hemin-Au residing in it to achieve photothermal therapy (PTT). Benefiting from the glucose oxidase (GOx)-like activity of the Au nanoparticles, glucose in the tumor cells is largely consumed, and hydrogen peroxide (H₂O₂) is generated in situ, and then Cu-Hemin-Au react with sufficient H₂O₂ to generate a large amount of reactive oxygen species, which promote the complete inhibition of tumor growth in mice during the treatment cycle. The hydrogel system for the synergistic enhancement of oxidative stress achieves good PTT/CDT synergy, providing a novel inspiration for the next generation of hydrogels for application in antitumor therapy.     

Green synthesis and application of nanoscale zero-valent iron/rectorite composite material for P-chlorophenol degradation via heterogeneous Fenton reaction

A zero-valent iron/rectorite nanocomposite (NZVI/rectorite) was developed as a heterogeneous H₂O₂ catalyst for P-chlorophenol degradation. The physicochemical properties of NZVI/rectorite were characterized by various techniques including X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive spectrometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and Brunauer–Emmett–Teller analysis. Results showed that NZVI sphere nanoparticles were successfully loaded on the rectorite surface with less aggregation and good dispersion. Moreover, compared with acid-leached rectorite (30.91 m²/g), the NZVI/rectorite appeared to have larger surface area (50.75 m²/g). In addition, the effects of pH, reaction time, initial P-chlorophenol concentration, catalyst amount, and H₂O₂ dosage on the P-chlorophenol degradation were systematically investigated. Results showed that NZVI/rectorite presents better properties for the degradation and mineralization of P-chlorophenol compared with pristine NZVI due to the large surface area, low aggregation, and good dispersion of the former. The degradation mechanisms of P-chlorophenol by NZVI/rectorite were adsorption and reduction coupled with a Fenton-like reaction. Four successive runs of the stability and regeneration study also showed that the NZVI/rectorite were unchanged even after 100% of P-chlorophenol degradation ratio. This study has extended the application of NZVI/rectorite as environment function material for the removal of P-chlorophenol from the environment.     

Fe(0)/Cu双金属还原与Fenton氧化集成工艺处理印染生化尾水树脂脱附液的研究

通过比较Fe(0)和Fe(0)/Cu还原工艺处理印染生化尾水树脂脱附液的效果,发现Fe(0)/Cu双金属还原对脱附液TOC和UV254去除率均优于Fe(0)。若将Fe(0)/Cu双金属还原与Fenton氧化工艺集成可以进一步提高处理效果。该组合工艺处理后,TOC去除率高达66%,UV254去除率高于90%,脱附液的BOD5/CODcr从低于0.1升高至0.38左右。由此可见,该组合工艺对复合功能树脂碱脱附液具有良好的处理效果,处理后废水的毒性降低,可生化性显著提高,为其返回生物系统进一步生化降解提供了较好的保证。