Novel Sm doped Cr2O3 decorated MWCNTs nanocomposite photocatalyst was successfully prepared by a facile hydrothermal method for metoprolol (MET) degradation. A heterogeneous photo -Fenton like system was formed with the addition of H2O2 for ultrasonic irradiation (US), visible light irradiation (Vis) and dual irradiation (US/Vis) systems. The intrinsic characteristics of Sm doped Cr2O3 decorated MWCNTs nanocomposite was comprehensively performed using state-of-art characterization tools. Optical studies confirmed that Sm doping shifted the absorbance of Cr2O3 towards the visible-light region, further enhanced by MWCNTs incorporation. In this study, degradation of metoprolol (MET) was investigated in the presence of Cr2O3 nanoparticles, Sm doped Cr2O3 and Sm doped Cr2O3 decorated MWCNTs nanocomposites using sonocatalysis and photocatalysis and simultaneously. Several different experimental parameters, including irradiation time, H2O2 concentration, catalyst amount, initial concentration, and pH value, were optimized. The remarkably enhanced sonophotocatalytic activity of Sm doped Cr2O3 decorated MWCNTs could be attributed to the more formation of reactive radicals and the excellent electronical property of Sm doping and MWCNTs. The rate constant of degradation using sonophotocatalytic system was even higher than the sum of rates of individual systems due to its synergistic performance based on the kinetic data. A plausible mechanism for the degradation of MET over Sm-Cr2O3/MWCNTs is also demonstrated by using active species scavenger studies and EPR spectroscopy. Our findings imply that (•OH), (h+) and (•O2-) were the reactive species responsible for the degradation of MET based on the special three-way Fenton-like mechanism and the dissociation of H2O2. The durability and stability of the nanocomposite were also performed, and the obtained results revealed that the catalysts can endure the harsh sonophotocatalytic conditions even after fifth cycles. Mineralization experiments using the optimized parameters were evaluated as well. The kinetics and the reaction mechanism with the possible reasons for the synergistic effect were presented. Identification of degraded intermediates also investigated.
The application of hydrogen peroxide (H2O2) as a management tool to control Microcystis blooms has become increasingly popular due to its short lifetime and targeted action. H2O2 increases intracellular reactive oxygen species resulting in oxidative stress and subsequently cell death. H2O2 is naturally produced in freshwater bodies as a result of photocatalytic reactions between dissolved organic carbon and sunlight. Previously, some studies have suggested that this environmental source of H2O2 selectively targets for toxigenic cyanobacteria strains in the genus Microcystis. Also, past studies only focused on the morphological and biochemical changes of H2O2-induced cell death in Microcystis with little information available on the effects of different H2O2 concentrations on growth, esterase activity and membrane integrity. Therefore, this study investigated the effects of non-lethal (40-4000 nM) concentrations on percentage cell death; with a focus on sub-lethal (50 μM) and lethal (275 μM; 500 μM) doses of H2O2 on growth, cells showing esterase activity and membrane integrity. The non-lethal dose experiment was part of a preliminary study. Results showed a dose- and time-dependent relationship in all three Microcystis strains post H2O2 treatment. H2O2 resulted in a significant increase in intracellular reactive oxygen species, decreased chlorophyll a content, decreased growth rate and esterase activity. Interestingly, at sub-lethal (50 μM H2O2 treatment), percentage of dead cells in microcystin-producing strains was significantly higher (p
The feasibility and performance of Jicama peroxidase (JP) immobilized Buckypaper/polyvinyl alcohol (BP/PVA) membrane for methylene blue (MB) dye removal was investigated in a customized multi-stage filtration column under batch recycle mode. The effect of independent variables, such as influent flow rate, ratio of H2O2/MB dye concentration, and contact time on the dye removal efficiency, were investigated using response surface methodology (RSM). To capture the inherent characteristics and better predict the removal efficiency, a data-driven adaptive neuro-fuzzy inference system (ANFIS) is implemented. Results indicated that the optimum dye removal efficiency of 99.7% was achieved at a flow rate of 2 mL/min, 75:1 ratio of H2O2/dye concentration with contact time of 183 min. The model predictions of ANFIS are significantly good compared with RSM, thus resulting in R2 values of 0.9912 and 0.9775, respectively. The enzymatic kinetic parameters, Km and Vmax, were evaluated, which are 1.98 mg/L and 0.0219 mg/L/min, respectively. Results showed that JP-immobilized BP/PVA nanocomposite membrane can be promising and cost-effective biotechnology for the practical application in the treatment of industrial dye effluents.
In this study, the zinc oxide (ZnO) layer was synthesised on the surface of Zn plates by three different techniques, i.e. electrolysis, hydrogen peroxide and heat treatment. The synthesised ZnO layers were characterised using scanning electron microscopy, X-ray diffraction, UV-visible diffuse reflectance and photoluminescence spectroscopy. The photocatalytic activity of the ZnO layer was further assessed against methylene blue (MB) degradation under UV irradiation. The photocatalytic degradation of MB was achieved up to 84%, 79% and 65% within 1 h for ZnO layers synthesised by electrolysis, heat and hydrogen peroxide treatment, respectively. The reusability results show that electrolysis and heat-treated ZnO layers have considerable photocatalytic stability. Furthermore, the results confirmed that the photocatalytic efficiency of ZnO was directly associated with the thickness and enlarged surface area of the layer. Finally, this study proved that the ZnO layers synthesised by electrolysis and heat treatment had shown better operational stability and reusability.
In the present study, a comparison of central composite design (CCD) and Taguchi method was established for Fenton oxidation. [Dye]ini, Dye:Fe(+2), H2O2:Fe(+2), and pH were identified control variables while COD and decolorization efficiency were selected responses. L 9 orthogonal array and face-centered CCD were used for the experimental design. Maximum 99% decolorization and 80% COD removal efficiency were obtained under optimum conditions. R squared values of 0.97 and 0.95 for CCD and Taguchi method, respectively, indicate that both models are statistically significant and are in well agreement with each other. Furthermore, Prob > F less than 0.0500 and ANOVA results indicate the good fitting of selected model with experimental results. Nevertheless, possibility of ranking of input variables in terms of percent contribution to the response value has made Taguchi method a suitable approach for scrutinizing the operating parameters. For present case, pH with percent contribution of 87.62% and 66.2% was ranked as the most contributing and significant factor. This finding of Taguchi method was also verified by 3D contour plots of CCD. Therefore, from this comparative study, it is concluded that Taguchi method with 9 experimental runs and simple interaction plots is a suitable alternative to CCD for several chemical engineering applications.
The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k'2), their final oxidation step (k'1), and the direct conversion to endproducts step (k3') were 10.12, 3.78, and 0.24 min(-1) for GKM; 0.98, 0.98, and nil min(-1) for GLKM; and nil, nil, and >0.005 min(-1) for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics.
Palm oil mill effluent (POME) is a highly contaminating wastewater due to its high chemical oxygen demand (COD) and biochemical oxygen demand (BOD). Conventional treatment methods require longer residence time (10-15 days) and higher operating cost. Owing to this, finding a suitable and efficient method for the treatment of POME is crucial. In this investigation, ultrasound cavitation technology has been used as an alternative technique to treat POME. Cavitation is the phenomenon of formation, growth and collapse of bubbles in a liquid. The end process of collapse leads to intense conditions of temperature and pressure and shock waves which assist various physical and chemical transformations. Two different ultrasound systems i.e. ultrasonic bath (37 kHz) and a hexagonal triple frequency ultrasonic reactor (28, 40 and 70 kHz) of 15 L have been used. The results showed a fluctuating COD pattern (in between 45,000 and 60,000 mg/L) while using ultrasound bath alone, whereas a non-fluctuating COD pattern with a final COD of 27,000 mg/L was achieved when hydrogen peroxide was introduced. Similarly for the triple frequency ultrasound reactor, coupling all the three frequencies resulted into a final COD of 41,300 mg/L compared to any other individual or combination of two frequencies. With the possibility of larger and continuous ultrasonic cavitational reactors, it is believed that this could be a promising and a fruitful green process engineering technique for the treatment of POME.
The mineralisation of remazol black B (RBB) was studied at concentrations ranging from 20-1000 mgL(-1). The work was aimed at investigating the Fenton-like peroxidation of RBB at a concentration typically obtained in Batik cottage industries. Other response parameters were degradation and colour removal efficiencies. The parameters that were measured included total organic carbon (TOC), chemical oxygen demand (COD) as well as absorbance for mineralisation, degradation and colour. To optimise the process, the interaction effects of several controlling variables on the treatment process were examined using dispersion matrix-optimal design and response surface analysis. Four specific variables: initial dye concentration (Dye)o; the molar ratio of oxidant to dye organic strength (H2O2):(COD); the mass ratio of the oxidant to the catalyst (H2O2):(Fe3+) and reaction time (t(r)), were observed. Three reduced empirical models, one for each response, were developed for describing the treatment process. For 20, 510 and 1000 mgL(-1), the optimum %TOC reduction and oxidation times were 44% for 95 min, 52% for 52.5 min and 68% for 10 min corresponding to 67, 81 and 75% COD reduction, respectively. The optimum COD reduction and oxidation times were 89% for 95 min, 91% for 10 min and 84% for 95 min for concentrations of 20, 510 and 1000 mg L(-1), respectively. For all concentrations, total colour removal was achieved. A comparison of the results obtained in this study with literature values for traditional Fenton, photo-Fenton and photo-Fenton-like oxidation indicated that the TOC reduction obtained using the Fenton-like process was satisfactory.
The resource availability hypothesis predicts an increase in the allocation to secondary metabolites when carbon gain is improved relative to nutrient availability, which normally occurs during periods of low irradiance. The present work was carried out to confirm this hypothesis by investigating the effects of decreasing irradiance on the production of plant secondary metabolites (flavonoids and phenolics) in the herbal plant Orthosiphon stamineus, and to characterize this production by carbohydrate, H(2)O(2), and malondialdehyde (MDA) levels, net photosynthesis, leaf chlorophyll content and carbon to nitrogen ratio (C/N). Four levels of irradiance (225, 500, 625 and 900 µmol/m(2)/s) were imposed onto two-week old seedlings for 12 weeks in a randomized complete block design experiment. Peak production of total flavonoids, phenolics, soluble sugar, starch and total non-structural carbohydrate ocurred under low irradiance of 225 µmol/m(2)/s, and decreased with increasing irradiance. The up-regulation of secondary metabolites could be explained by the concomitant increases in H(2)O(2) and MDA activities under low irradiance. This condition also resulted in enhanced C/N ratio signifying a reduction in nitrogen levels, which had established significant negative correlations with net photosynthesis, total biomass and total chlorophyll content, indicating the possible existence of a trade-off between growth and secondary metabolism under low irradiance with reduced nitrogen content. The competition between total chlorophyll and secondary metabolites production, as exhibited by the negative correlation coefficient under low irradiance, also suggests a sign of gradual switch of investment from chlorophyll to polyphenols production.
This study evaluated the effectiveness of Fenton's technique for the treatment of semi-aerobic landfill leachate collected from Pulau Burung Landfill Site (PBLS), Penang, Malaysia. The Fe2+ or Fe3+ as catalyst and H2O2 as oxidizing agent are commonly used for the classical Fenton's reaction. In present study, the effect of operating conditions such as pH, reaction time, molar ratio, agitation rate, feeding mode and Fenton reagent concentrations which are important parameters that affect the removal efficiencies of Fenton method were investigated. Under the most favorable conditions, the highest removals of 58.1 and 78.3% were observed for COD and color, respectively. In general, the best operating conditions were pH = 3, Fe = 560 mg L(-1), H2O2 = 1020 mg L(-1), H2O2/Fe2+ molar ratio = 3, agitation rate = 400 rpm and reaction time = 120 minutes. The results highlighted that stepwise addition of Fenton's reagent was more effective than adding the entire volume in a single step. Excessive hydrogen peroxide and iron have shown scavenging effects on hydroxyl radicals and reduced degradation of refractory organics in the landfill leachate.
Oxidative stress has been implicated as an important pathogenic factor in the pathophysiology of various life-threatening diseases such as cancer, cardiovascular diseases and diabetes. It occurs when the production of free radicals (generated during aerobic metabolism, inflammation, and infections) overcome the antioxidant defences in the body. Although previous studies have implied that oxidative stress is present in serum of patients with parasitic infection there have been no studies confirming oxidative stress levels in the Malaysian population infected with intestinal parasites. Three biochemical assays namely hydrogen peroxide (H2O2), lipid peroxidation (LP) and advanced oxidative protein product (AOPP) assays were carried out to measure oxidative stress levels in the urine of human subjects whose stools were infected with parasites such as Blastocystis hominis, Ascaris, Trichuris, hookworm and microsporidia. The levels of H2O2, AOPP and LP were significantly higher (P<0.001, P<0.05 and P<0.05 respectively) in the parasite-infected subjects (n=75) compared to the controls (n=95). In conclusion, the study provides evidence that oxidative stress is elevated in humans infected by intestinal parasites. This study may influence future researchers to consider free radical-related pathways to be a target in the interventions of new drugs against parasitic infection and related diseases.
In this study, advanced oxidation process utilizing Fenton's reagent was investigated for degradation of malachite green (MG). The effects of different reaction parameters such as the initial MG concentration, initial pH, the initial hydrogen peroxide concentration, the initial ferrous concentration and the reaction temperature on the oxidative degradation of MG have been investigated. The optimal reacting conditions were experimentally found to be pH 3.40, initial hydrogen peroxide concentration=0.50mM and initial ferrous concentration=0.10mM for initial MG concentration of 20mg/L at 30 degrees C. Under optimal conditions, 99.25% degradation efficiency of dye in aqueous solution was achieved after 60 min of reaction.
New derivatives of 7-hydroxy-4-methylcoumarin were synthesized using a chemical method and a microwave-assisted method to compare the feasibility, reaction times, and yields of the product. The newly synthesized coumarins were characterized by different spectroscopic techniques (FT-IR and NMR) and micro-elemental analysis (CHNS). In vitro antioxidant activities of these compounds were evaluated against hydrogen peroxide and were compared with standard natural antioxidant, vitamin C. Our results reveal that these compounds exhibit excellent radical scavenging activities.
In this work, the direct electrochemistry of hemoglobin (Hb), which was immobilized on carbonyl functionalized single walled carbon nanotube (SWCNT) and deposited onto a gold (Au) electrode has been described. The synthesis of the network of crosslinked SWCNT/Hb was done with the help of crosslinking agent EDC (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide). The UV-Vis and FTIR spectroscopy of SWCNT/Hb networks showed that Hb maintained its natural structure and kept good stability. In addition with this, scanning electron microscopy (SEM) illustrated that SWCNT/Hb networks had a featured layered structure and Hb being strongly liked with SWCNT surface. Cyclic voltammetry (CV) was used to study and to optimize the performance of the resulting modified electrode. The cyclic voltammetric (CV) responses of SWCNT/Hb networks in pH 7.0 exhibit prominent redox couple for the FeIII/II redox process with a midpoint potential of -0.46 V and -0.34, cathodic and anodic respectively. Furthermore, SWCNT/Hb networks are utilized for the detection of hydrogen peroxide (H2O2). Electrochemical measurements reveal that the resulting SWCNT/Hb electrodes display high electrocatalytic activity to H2O2 with high sensitivity, wide linear range, and low detection limit. Overall, the electrochemical results are due to excellent biocompatibility and excellent electron transport efficiency of CNT as well as high Hb loading and synergistic catalytic effect of the modified electrode toward H2O2.
A multiporous nanofiber (MPNFs) of SnO₂ and chitosan has been used for the immobilization of a redox protein, hemoglobin (Hb), onto the surface of glassy carbon electrode (GCE). The multiporous nanofiber of SnO₂ that has very high surface area is synthesized by using electrospinning technique through controlling the tin precursor concentration. Since the constructed MPNFs of SnO₂ exposes very high surface area, it increases the efficiency for biomolecule-loading. The morphology of fabricated electrodes is examined by SEM observation and the absorbance spectra of Hb/(MPNFs) of SnO₂ are studied by UV-Vis analysis. Cyclic Voltammetry and amperometry are employed to study and optimize the performance of the resulting fabricated electrode. After fabrication of the electrode with the Hb and MPNFs of SnO₂, a direct electron transfer between the protein's redox centre and the glassy carbon electrode was established. The modified electrode has showed a couple of redox peak located at -0.29 V and -0.18 V and found to be sensitive to H₂O₂. The fabricated electrode also exhibited an excellent electrocatalytic activity towards the reduction of H₂O₂. The catalysis currents increased linearly to the H₂O₂ concentration in a wide range of 5.0×10-6-1.5×10-4 M. Overall experimental results show that MPNFs of SnO₂ has a role towards the enhancement of the electroactivity of Hb at the electrode surface. Thus the MPNFs of SnO₂ is a very promising candidate for future biosensor applications.
Dicofol, an extensively used organochlorine pesticide and a recommended Stockholm convention persistent organic pollutant (POP) candidate is well known for its endocrine disruptive properties. The sonochemical degradation of Dicofol in aqueous media has been investigated using a 20-kHz probe type sonicator with power inputs from 150 to 450 W. The degradation rate was determined as a function of concentration of Dicofol, solution pH, bulk phase temperature, ultrasonic power density and H2O2 addition. At optimum operating conditions, the pseudo-first-order degradation rate constant (k) was determined to be 0.032 min-1 and the extent of degradation was found to be 86% within 60 min of ultrasound treatment. High performance liquid chromatography (HPLC) and Gas chromatography coupled with mass spectroscopy (GC-MS) analysis indicated the presence of degraded products. The obtained results of Dicofol degradation and control experiments in the presence of H2O2 and radical scavenger test suggest thermal decomposition along with radical attack at bubble-vapor interface to be the dominant degradation pathway. Sonochemical treatment is effective and promising for successful removal of harmful pesticides such as Dicofol and superior removal efficiency for other POPs is expected in the near future with the successful implementation of ultrasound-based wastewater treatment.
Lignosus rhinocerotis (Cooke) Ryvarden has been reported to possess numerous pharmacological effects. However, little is known about its potential role in mitigating the detrimental effects of oxidative stress. The present study investigated the cytoprotective effects of L. rhinocerotis extracts against hydrogen peroxide (H2O2)-induced oxidative stress of rat pheochromocytoma (PC12) cells. In the pre-treatment model, PC12 cells were pre-treated with aqueous (LRAQ) or ethanolic (LRET) extracts of L. rhinocerotis for 24 h, followed by 30 μM of H2O2 for 24 h. In the co-treatment model, the cells were incubated with LRAQ or LRET and H2O2 for 2 or 24 h to induce oxidative stress. Cell viability, intracellular reactive oxygen species (ROS) levels, mitochondrial membrane potential (MMP), and apoptotic cells with activated caspase-3/7 were quantified. Additionally, LRET was separated into fractions by chromatographic methods prior to analysis by gas chromatography-mass spectrometry (GCMS). 320 μg/ml aqueous extract showed a significant cytoprotective effect of 70.0 ± 22.4% and 133.92 ± 8.8% in the pre-treatment and co-treatment models, respectively, compared to untreated H2O2-challenged cells. LRAQ also showed a reduction (p < 0.05) in the percentage of depolarized cells of 37.6 ± 0.6% at 640 ug/ml and 53.4 ± 4.5% at 320 ug/ml in the pre-treatment and co-treatment models, respectively, compared to untreated H2O2-challenged cells. LRAQ or LRET showed a reduction (p < 0.01) in caspase 3/7 activity compared to untreated H2O2-challenged cells in the co-treatment model. However, LRAQ or LRET did not reduce excessive ROS formation (p > 0.05). The cytoprotective effects could be attributed to the presence of fatty acids, phenols, phytosterols, and dicarboxylic acids. In conclusion, L. rhinocerotis extracts demonstrated cytoprotective effects against H2O2-induced oxidative stress in an in vitro model, contributing to the maintenance of cellular integrity through the regulation of mitochondrial function and apoptosis.
GR15 is a short molecule or peptide composed of aliphatic amino acids and possesses to have antioxidant properties. The GR15, 1GGGAFSGKDPTKVDR15 was identified from the protein S-adenosylmethionine synthase (SAMe) expressed during the sulfur departed state of Arthrospira platensis (spirulina or cyanobacteria). The in-silico assessment and the structural features of GR15 showed its antioxidant potency. Real-time PCR analysis found the up-regulation of ApSAMe expression on day 15 against oxidative stress due to 10 mM H2O2 treatment in A. platensis (Ap). The antioxidant activity of GR15 was accessed by the cell-free antioxidant assays such as ABTS, SARS, HRAS and NO; the results showed dose-dependent antioxidant activity. The toxicity assay was performed in both in vitro and in vivo models, in which peptide does not exhibit any toxicity in MDCK cell and zebrafish embryos. The intercellular ROS reduction potential of GR15 peptide was also investigated in both in vitro and in vivo models including LDH assay, antioxidant enzymes (SOD and CAT), and fluorescent staining assay (DCFDA, Hochest and Acridine orange sting) was performed; the results showed that the GR15 peptide was effectively reduced the ROS level. Further, RT-PCR demonstrated that GR15 enhanced the antioxidant property and also up-regulated the antioxidant gene, thus reduced the ROS level in both in vitro and in vivo models. Based on the results obtained from this study, we propose that GR15 has the potential antioxidant ability; hence further research can be directed towards the therapeutic product or drug development against disease caused by oxidative stress.
A simple and rapid screening of biomarkers in clinical and food matrices is urgently needed to diagnose cardiovascular diseases. The cholesterol (Chol) and hydrogen peroxide (H2O2) are critical bio-indicators, which require more inventive detection techniques to be applied to real food, and bio-samples. In this study, a robust dual sensor was developed for Chol and H2O2 using hybrid catalyst. Bovine serum albumin (BSA)-capped nanocatalyst was potentially catalyzed 3,3',5,5'-tetramethylbenzidine (TMB), and H2O2. The enzymatic nanoelectrocatalyst delivered a wide range of signaling concentrations from 250 nM to 3.0 mM and 100 nM to 10 mM, limit of detection (LOD) of 53.2 nM and 18.4 nM for Chol and H2O2. The cholesterol oxidase-BSA-AuNPs-metal-free organic framework (ChOx-BSA-AuNPs-MFOF) based electrode surface effectively operated in live-cells and real-food samples. The enzymatic sensor exhibits adequate recovery of real-food samples (96.96-99.44%). Finally, the proposed system is a suitable choice for the potential applications of Chol and H2O2 in clinical and food chemistry.
Neuronal models are an important tool in neuroscientific research. Hydrogen peroxide (H2O2), a major risk factor of neuronal oxidative stress, initiates a cascade of neuronal cell death. Polygonum minus Huds, known as 'kesum', is widely used in traditional medicine. P. minus has been reported to exhibit a few medicinal and pharmacological properties. The current study aimed to investigate the neuroprotective effects of P. minus ethanolic extract (PMEE) on H2O2-induced neurotoxicity in SH-SY5Y cells. LC-MS/MS revealed the presence of 28 metabolites in PMEE. Our study showed that the PMEE provided neuroprotection against H2O2-induced oxidative stress by activating the Nrf2/ARE, NF-κB/IκB and MAPK signaling pathways in PMEE pre-treated differentiated SH-SY5Y cells. Meanwhile, the acetylcholine (ACH) level was increased in the oxidative stress-induced treatment group after 4 h of exposure with H2O2. Molecular docking results with acetylcholinesterase (AChE) depicted that quercitrin showed the highest docking score at -9.5 kcal/mol followed by aloe-emodin, afzelin, and citreorosein at -9.4, -9.3 and -9.0 kcal/mol, respectively, compared to the other PMEE's identified compounds, which show lower docking scores. The results indicate that PMEE has neuroprotective effects on SH-SY5Y neuroblastoma cells in vitro. In conclusion, PMEE may aid in reducing oxidative stress as a preventative therapy for neurodegenerative diseases.