The effect of initial dissolved oxygen concentration (IDOC) on Fenton's reagent degradation of a dyestuff, Reactive Black 5 was explored in this study. The study was designed, conducted and analysed based on Central Composite Rotatable Design using a 3-1 lab-scale reactor. The participation of O2 in the process was experimentally observed and appears to be affected by the dosage of the reagents used in the study. The IDOC was found to have a significant influence on the process. Reducing the IDOC from 7.5 mg l(-1) to 2.5 mg l(-1) increased the removal of TOC by an average of about 10%. Reduction of IDOC from 10 mg l(-1) to 0 mg l(-1) enhanced the TOC removal by about 30%. The negative influence of IDOC is likely to be caused by the competition between the O2 and the reagents for the organoradicals. A model describing the relationship between initial TOC removal, reagent dosage and IDOC has also been developed.
Leachate pollution is one of the main problems in landfilling. Researchers have yet to find an effective solution to this problem. The technology that can be used may differ based on the type of leachate produced. Coliform bacteria were recently reported as one of the most problematic pollutants in semi-aerobic (stabilized) leachate. In the present study, the performance of the Electro-Fenton process in removing coliform from leachate was investigated. The study focused on two types of leachate: Palau Borung landfill leachate with low Coliform content (200 MPN/100 m/L) and Ampang Jajar landfill leachate with high coliform content (>24 × 10(4)MPN/100 m/L). Optimal conditions for the Electro-Fenton treatment process were applied on both types of leachate. Then, the coliform was examined before and after treatment using the Most Probable Number (MPN) technique. Accordingly, 100% removal of coliform was obtained at low initial coliform content, whereas 99.9% removal was obtained at high initial coliform content. The study revealed that Electro-Fenton is an efficient process in removing high concentrations of pathogenic microorganisms from stabilized leachate.
A novel glassy carbon electrode (GCE) modified with a composite film of poly (4-vinylpyridine) (P4VP) and multiwalled carbon nanotubes (P4VP/MWCNT GCE) was used for the voltammetric determination of paracetamol (PCT). This novel electrode displayed a combined effect of P4VP and MWCNT on the electro-oxidation of PCT in a solution of phosphate buffer at pH 7. Hence, conducting properties of P4VP along with the remarkable physical properties of MWCNTs might have combined effects in enhancing the kinetics of PCT oxidation. The P4VP/MWCNT GCE has also demonstrated excellent electrochemical activity toward PCT oxidation compared to that with bare GCE and MWCNT GCE. The anodic peak currents of PCT on the P4VP/MWCNT GCE were about 300 fold higher than that of the non-modified electrodes. By applying differential pulse voltammetry technique under optimized experimental conditions, a good linear ratio of oxidation peak currents and concentrations of PCT over the range of 0.02-450 μM with a limit of detection of 1.69 nM were achieved. This novel electrode was stable for more than 60 days and reproducible responses were obtained at 99% of the initial current of PCT without any influence of physiologically common interferences such as ascorbic acid and uric acid. The application of this electrode to determine PCT in tablets and urine samples was proposed.
The objective of this study was to investigate the performance of employing Fenton's reagent in the advanced oxidation of ozone to treat stabilized landfill leachate in an ozone reactor. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as ozone and Fenton dosage, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following four responses proved to be significant with very low probabilities (<0.0001): chemical oxygen demand (COD), color, NH-N, and ozone consumption (OC). The obtained optimum conditions included a reaction time of 90 min, 30 g/m³ ozone, 0.01 mol/L₂H₂O,0.02 mol/L Fe²⁺, and pH 5. COD, color, and NH₃-N removal rates of 79%, 100%, and 20%, respectively, and 0.18 kg O₃/kg COD OC were obtained. The predictions correspond well with experimental results (COD, color, and NH-N removal rates of 78%, 98.5%, and 19%, respectively, and 0.29 kg O₃/kg COD OC). This method reduces the treatment time and improves the treatment efficiency relative to a previously published method that used Fenton's reagent prior to ozonation.
Green synthesis of noble metal nanoparticles is a vastly developing area of research. Metallic nanoparticles have received great attention from chemists, physicists, biologists, and engineers who wish to use them for the development of a new-generation of nanodevices. In this study, silver nanoparticles were biosynthesized from aqueous silver nitrate through a simple and eco-friendly route using Curcuma longa tuber-powder extracts, which acted as a reductant and stabilizer simultaneously. Characterizations of nanoparticles were done using different methods, which included ultraviolet-visible spectroscopy, powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy-dispersive X-ray fluorescence spectrometry, and Fourier-transform infrared spectroscopy. The ultraviolet-visible spectrum of the aqueous medium containing silver nanoparticles showed an absorption peak at around 415 nm. Transmission electron microscopy showed that mean diameter and standard deviation for the formation of silver nanoparticles was 6.30 ± 2.64 nm. Powder X-ray diffraction showed that the particles are crystalline in nature, with a face-centered cubic structure. The most needed outcome of this work will be the development of value-added products from C. longa for biomedical and nanotechnology-based industries.
An organic solvent-tolerant S5 lipase was purified by affinity chromatography and anion exchange chromatography. The molecular mass of the lipase was estimated to be 60 kDa with 387 purification fold. The optimal temperature and pH were 45 degrees C and 9.0, respectively. The purified lipase was stable at 45 degrees C and pH 6-9. It exhibited the highest stability in the presence of various organic solvents such as n-dodecane, 1-pentanol, and toluene. Ca2+ and Mg2+ stimulated lipase activity, whereas EDTA had no effect on its activity. The S5 lipase exhibited the highest activity in the presence of palm oil as a natural oil and triolein as a synthetic triglyceride. It showed random positional specificity on the thin-layer chromatography.
Plastic waste constitutes the third largest waste volume in Malaysian municipal solid waste (MSW), next to putrescible waste and paper. The plastic component in MSW from Kuala Lumpur averages 24% (by weight), whereas the national mean is about 15%. The 144 waste dumps in the country receive about 95% of the MSW, including plastic waste. The useful life of the landfills is fast diminishing as the plastic waste stays un-degraded for more than 50 years. In this study the compostability of polyethylene and pro-oxidant additive-based environmentally degradable plastics (EDP) was investigated. Linear low-density polyethylene (LLDPE) samples exposed hydrolytically or oxidatively at 60 degrees C showed that the abiotic degradation path was oxidative rather than hydrolytic. There was a weight loss of 8% and the plastic has been oxidized as shown by the additional carbonyl group exhibited in the Fourier transform infra red (FTIR) Spectrum. Oxidation rate seemed to be influenced by the amount of pro-oxidant additive, the chemical structure and morphology of the plastic samples, and the surface area. Composting studies during a 45-day experiment showed that the percentage elongation (reduction) was 20% for McD samples [high-density polyethylene, (HDPE) with 3% additive] and LL samples (LLDPE with 7% additive) and 18% reduction for totally degradable plastic (TDP) samples (HDPE with 3% additive). Lastly, microbial experiments using Pseudomonas aeroginosa on carbon-free media with degradable plastic samples as the sole carbon source, showed confirmatory results. A positive bacterial growth and a weight loss of 2.2% for degraded polyethylene samples were evident to show that the degradable plastic is biodegradable.
Cinnamon deodorised aqueous extract (CinDAE) was prepared and evaluated for its total phenolic (315.3 ± 35.4 mg GAE/g) and flavonoid (99.3 ± 9.6 mg RE/g) contents. Stabilizing efficiency of CinDAE, for chicken meatballs, was measured against oxidative deterioration as function of storage time under chilled conditions. For this purpose, oxidative stability [2-thiobarbituric acid reactive substances (TBARS); peroxide value (PV)], colour and sensory acceptability were measured in the control meatballs (C), and those stabilized with 200 ppm of: CinDAE (T1), ascorbic acid (T2), BHA/BHT (50/50; w/w) (T3). In comparison to "C", induction period (IP) and redness (a* value) of the stabilized samples (T1, T2 and T3) were increased, while PV and TBARS were decreased throughout storage (8 ± 1 °C) significantly (p
Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.
In recent years, calcium phosphate-base composites, such as hydroxyapatite (HA) and carbonate apatite (CA) have been considered desirable and biocompatible coating layers in clinical and biomedical applications such as implants because of the high resistance of the composites. This review focuses on the effects of voltage, time and electrolytes on a calcium phosphate-base composite layer in case of pure titanium and other biomedical grade titanium alloys via the plasma electrolytic oxidation (PEO) method. Remarkably, these parameters changed the structure, morphology, pH, thickness and crystallinity of the obtained coating for various engineering and biomedical applications. Hence, the structured layer caused improvement of the biocompatibility, corrosion resistance and assignment of extra benefits for Osseo integration. The fabricated layer with a thickness range of 10 to 20 μm was evaluated for physical, chemical, mechanical and tribological characteristics via XRD, FESEM, EDS, EIS and corrosion analysis respectively, to determine the effects of the applied parameters and various electrolytes on morphology and phase transition. Moreover, it was observed that during PEO, the concentration of calcium, phosphor and titanium shifts upward, which leads to an enhanced bioactivity by altering the thickness. The results confirm that the crystallinity, thickness and contents of composite layer can be changed by applying thermal treatments. The corrosion behavior was investigated via the potentiodynamic polarization test in a body-simulated environment. Here, the optimum corrosion resistance was obtained for the coating process condition at 500 V for 15 min in Ringer solution. This review has been summarized, aiming at the further development of PEO by producing more adequate titanium-base implants along with desired mechanical and biomedical features.
Background. Diurnal rhythms of protein synthesis controlled by the biological clock underlie the rhythmic physiology in the fruit fly, Drosophila melanogaster. In this study, we conducted a proteome-wide investigation of rhythmic protein accumulation in D. melanogaster. Materials and Methods. Total protein collected from fly samples harvested at 4 h intervals over the 24 h period were subjected to two-dimensional gel electrophoresis, trypsin digestion and MS/MS analysis. Protein spots/clusters were identified with MASCOT search engine and Swiss-Prot database. Expression of proteins was documented as percentage of volume contribution using the Image Master 2D Platinum software. Results. A total of 124 protein spots/clusters were identified using MS/MS analysis. Significant variation in the expression of 88 proteins over the 24-h period was observed. A relatively higher number of proteins was upregulated during the night compared to the daytime. The complexity of temporal regulation of the D. melanogaster proteome was further reflected from functional annotations of the differently expressed proteins, with those that were upregulated at night being restricted to the heat shock proteins and proteins involved in metabolism, muscle activity, protein synthesis/folding/degradation and apoptosis, whilst those that were overexpressed in the daytime were apparently involved in metabolism, muscle activity, ion-channel/cellular transport, protein synthesis/folding/degradation, redox homeostasis, development and transcription. Conclusion. Our data suggests that a wide range of proteins synthesized by the fruit fly, D. melanogaster, is under the regulation of the biological clock.
In this study, the catalase-like activity of monomeric tau protein was reported in the presence of of zinc (Zn(II)) ions at low pH value. Monomeric tau protein contains two SH groups that are a target of disulfide bond formation. However these SH groups are able to interact with Zn(II) ion at pH 7.2 which creates a thiol bond as a mimetic model of chloroperoxidase active site which performs catalase like activity at low pH. Zn(II)/tau protein complex decomposed H2O2 with a high rate (Vm) as well as an efficient turn oven number (kcat) at pH 3. This remarkable catalase like activity is may be attributed to the conformational reorientation of protein at low pH. Circular dichroism (CD) studies did not demonstrate any secondary structural changes of tau protein after addition of Zn(II) ions at pH 7.2. In addition, tau protein shows identical CD bands at pH 7.2 and 3. Moreover, fluorescence quenching of tau by Zn(II) at pH 7.2 was initiated by complex formation rather than by dynamic collision. A significant red shift (6nm) was observed in the emission maximum of the fluorescence spectra when the protein was dissolved at pH 3 compared to pH 7.2. This conformational change can provide information regarding the rearrangements of the protein structure and exposure of Cys-Zn(II) group to the solvent which induces easy access of active site to H2O2 molecules and corresponding enhanced catalytic activity of Zn(II)/tau protein complex. This study introduces tau protein as a bio-inspired high performing scaffold for transition metal encapsulation and introducing an engineered apoprotein-induced biomimetic enzyme.
The objective of this study was to investigate the performance of employing H2O2 reagent in persulfate activation to treat stabilized landfill leachate. A central composite design (CCD) with response surface methodology (RSM) was applied to evaluate the relationships between operating variables, such as persulfate and H2O2 dosages, pH, and reaction time, to identify the optimum operating conditions. Quadratic models for the following two responses proved to be significant with very low probabilities (<0.0001): chemical oxygen demand (COD) and NH3-N removal. The obtained optimum conditions included a reaction time of 116 min, 4.97 g S2O8(2-), 7.29 g H2O2 dosage and pH 11. The experimental results were corresponding well with predicted models (COD and NH3-N removal rates of 81% and 83%, respectively). The results obtained in the stabilized leachate treatment were compared with those from other treatment processes, such as persulfate only and H2O2 only, to evaluate its effectiveness. The combined method (i.e., /S2O8(2-)/H2O2) achieved higher removal efficiencies for COD and NH3-N compared with other studied applications.
Secondary metabolite contents (total phenolic, flavonoid, tocopherol, and tocotrienol) and antioxidant activities of Hashemi rice bran extracts obtained by ultrasound-assisted and traditional solvent (ethanol and 50:50 (v/v) ethanol-water) extraction techniques were compared. Phenolic and, flavonoid compounds were identified using ultra-high performance liquid chromatography and method validation was performed. Significant differences (p < 0.05) were observed among the different extraction techniques upon comparison of phytochemical contents and antioxidant activities. The extracts obtained using the ethanol-water (50:50 v/v) ultrasonic technique showed the highest amounts of total phenolics (288.40 mg/100 g dry material (DM)), total flavonoids (156.20 mg/100 g DM), and total tocotrienols (56.23 mg/100 g DM), and the highest antioxidant activity (84.21% 1,1-diphenyl-2-picrylhydrazyl (DPPH), 65.27% β-carotene-linoleic bleaching and 82.20% nitric oxide scavenging activity). Secondary metabolite contents and antioxidant activities of the rice bran extracts varied depending of the extraction method used, and according to their effectiveness, these were organized in a decreasing order as follows: ethanol-water (50:50 v/v) ultrasonic, ethanol-water (50:50 v/v) maceration, ethanol ultrasonic and ethanol maceration methods. Ferulic, gallic and chlorogenic acids were the most abundant phenolic compounds in rice bran extracts. The phytochemical constituents of Hashemi rice bran and its antioxidant properties provides insights into its potential application to promote health.
Although they originated from China, Malays have undergone a lot of intermarriages. A study suggested that CYP2D6 poor metabolism (PM) phenotype was more common in Malays compared to Chinese. CYP2D6 is highly polymorphic and is involved in the metabolism of many drugs and has been implicated in some environmentally-induced diseases. It is therefore useful to further study this polymorphism in Malays.
Hydrogen peroxide and UV radiation have been used in the photochemical degradation of isoprene in aqueous solutions. A kinetic study is carried out taking into account the contribution of the UV radiation reaction and the combined reaction with hydrogen peroxide. An empirical reaction rate expression, which considers the two reactions taking place in parallel, is suggested. Pseudo-first order rate constants are obtained from batch reactor data. As the molar ratio of H(2)O(2):isoprene increases, the rate of reaction increases linearly while the concentration of H(2)O(2) is observed to be nearly constant throughout the reaction; suggesting that the H(2)O(2) acts as a pseudo-catalyst. Nearly complete oxidation of isoprene is achieved. These results indicate that the H(2)O(2)/UV process appears to be a competitive alternative destructive treatment for removing isoprene from water present at low levels.
1. The L-amino acid oxidase of the monocellate cobra (Naja naja kaouthia) venom was purified to electrophoretic homogeneity. The molecular weight of the enzyme was 112,200 as determined by Sephadex G-200 gel filtration chromatography, and 57,400 as determined by SDS-polyacrylamide gel electrophoresis. 2. The enzyme had an isoelectric point of 8.12 and a pH optimum of 8.5. It showed remarkable thermal stability, and, unlike many venom L-amino acid oxidase, was also stable in alkaline medium. The enzyme was partially inactivated by freezing. 3. The enzyme was very active against L-phenylalanine and L-tyrosine, moderately active against L-tryptophan, L-methionine, L-leucine, L-norleucine, L-arginine and L-norvaline. Other L-amino acids were oxidized slowly or not oxidized. 4. Kinetic studies suggest the presence of a side-chain binding site in the enzyme, and that the binding site comprises of at least four hydrophobic subsites.
1. Substrate specificity of purified king cobra (Ophiophagus hannah) venom L-amino acid oxidase was investigated. 2. The enzyme was highly specific for the L-enantiomer of amino acid. Effective oxidation of L-amino acid by the enzyme requires the presence of a free primary alpha-amino group but the alpha-carboxylate group is not as critical for the catalysis. 3. The enzyme was very active against L-Lys, L-Phe, L-Leu, L-Tyr, L-Tryp, L-Arg, L-Met, L-ornithine, L-norleucine and L-norvaline and moderately active against L-His, L-cystine and L-Ileu. Other L-amino acids were oxidized slowly or not oxidized. 4. The data suggest the presence of a side chain binding site in the enzyme, and that the binding site comprises at least five 'subsites': the hydrophobic subsites a, b and c; and the two 'amino' binding subsites d and e. Subsite b appears to be able to accommodate two methylene/methyl carbons.
The description of comammox Nitrospira spp., performing complete ammonia-to-nitrate oxidation, and their co-occurrence with canonical β-proteobacterial ammonia oxidizing bacteria (β-AOB) in the environment, calls into question the metabolic potential of comammox Nitrospira and the evolutionary history of their ammonia oxidation pathway. We report four new comammox Nitrospira genomes, constituting two novel species, and the first comparative genomic analysis on comammox Nitrospira. Unlike canonical Nitrospira, comammox Nitrospira genomes lack genes for assimilatory nitrite reduction, suggesting that they have lost the potential to use external nitrite nitrogen sources. By contrast, compared to canonical Nitrospira, comammox Nitrospira harbor a higher diversity of urea transporters and copper homeostasis genes and lack cyanate hydratase genes. Additionally, the two comammox clades differ in their ammonium uptake systems. Contrary to β-AOB, comammox Nitrospira genomes have single copies of the two central ammonia oxidation pathway operons. Similar to ammonia oxidizing archaea and some oligotrophic AOB strains, they lack genes involved in nitric oxide reduction. Furthermore, comammox Nitrospira genomes encode genes that might allow efficient growth at low oxygen concentrations. Regarding the evolutionary history of comammox Nitrospira, our analyses indicate that several genes belonging to the ammonia oxidation pathway could have been laterally transferred from β-AOB to comammox Nitrospira. We postulate that the absence of comammox genes in other sublineage II Nitrospira genomes is the result of subsequent loss.
Aims: To understand the molecular pathways involved in oxidative stress (OS)-mediated sperm dysfunction against a hypoxic and hyperthermic microenvironment backdrop of varicocele through a proteomic approach. Results: Protein selection (261) based on their role in redox homeostasis and/or oxidative/hyperthermic/hypoxic stress response from the sperm proteome data set of unilateral varicocele (UV) in comparison with fertile control displayed 85 to be differentially expressed. Upregulation of cellular oxidant detoxification and glutathione and reduced nicotinamide adenine dinucleotide (NADH) metabolism accompanied with downregulation of protein folding, energy metabolism, and heat stress responses were observed in the UV group. Ingenuity pathway analysis (IPA) predicted suppression of oxidative phosphorylation (OXPHOS) (validated by Western blotting [WB]) along with augmentation in OS and mitochondrial dysfunction in UV. The top affected networks indicated by IPA involved heat shock proteins (HSPs: HSPA2 and HSP90B1). Their expression profile was corroborated by immunocytochemistry and WB. Hypoxia-inducible factor 1A as an upstream regulator of HSPs was predicted by MetaCore. Occurrence of reductive stress in UV spermatozoa was corroborated by thiol redox status. Innovation: This is the first evidence of a novel pathway showing aberrant redox homeostasis against chronic hypoxic insult in varicocele leading to sperm dysfunction. Conclusions: Upregulation of antioxidant system and dysfunctional OXPHOS would have shifted the redox balance of biological redox couples (GSH/GSSG, NAD+/NADH, and NADP+/NADPH) to a more reducing state leading to reductive stress. Chronic reductive stress-induced OS may be involved in sperm dysfunction in infertile men with UV, where the role of HSPs cannot be ignored. Intervention with antioxidant therapy warrants proper prior investigation.