Synthesis and characterization of supported metal-based oxygen carriers were carried out to provide information related to the use of oxygen carriers for chemical looping combustion processes. The Cu, Co, Fe, Ni metals supported with Al2O3, CeO2, TiO2, ZrO2 were prepared using the wetness impregnation technique. Then, the X-ray Diffraction (XRD) characterization of oxidized and reduced samples was obtained and presented. The kinetic analysis using Thermogravimetric analyzer (TGA) of the synthesized samples was conducted. The kinetics of reduction reaction of all samples were estimated and explained.
Photocatalytic fuel cell (PFC) was employed to provide renewable power sources to photoelectro-Fenton (PEF) process to fabricate a double-chambered hybrid system for the treatment of azo dye, Amaranth. The PFC-PEF hybrid system was interconnected by a circuit attached to the electrodes in PFC and PEF. Circuit connection is the principal channel for the electron transfer and mobility between PFC and PEF. Thus, different circuit connections were evaluated in the hybrid system for their influences on the Amaranth dye degradation. The PFC-PEF system under the complete circuit connection condition attained the highest decolourization efficiency of Amaranth (PFC: 98.85%; PEF: 95.69%), which indicated that the complete circuit connection was crucial for in-situ formation of reactive species in dye degradation. Besides, the pivotal role of ultraviolet (UV) light irradiation in the PFC-PEF system for both dye degradation and electricity generation was revealed through various UV light-illuminating conditions applied for PFC and PEF. A remarkable influence of UV light irradiation on the production of hydrogen peroxide and generation and regeneration of Fe2+ in PEF was demonstrated. This study provided a comprehensive mechanistic insight into the dye degradation and electricity generation by the PFC-PEF system.
8-OxodGTP is generated by the reaction between dGTP and reactive oxygen species and a considered mutagenic nucleotide. It can be incorporated into the duplex DNA during replication processes by the DNA polymerase, and thus the repair enzyme removes oxodGTP from the nucleotide pools in living cells. On the other hand, the γ-modified triphosphates show interesting properties for use as biological tools. Therefore, the γ-N-pyrenylalkyl-oxodGTP derivatives were synthesized and their effect on the enzymatic reactions were evaluated. The γ-N-pyrenylmethyl-oxodGTP was found to be accepted by the DNA polymerase just like oxodGTP, but showed a competitive inhibition property for the human oxodGTPase.
Microbial arsenite oxidation is an essential biogeochemical process whereby more toxic arsenite is oxidized to the less toxic arsenate. Thiomonas strains represent an important arsenite oxidizer found ubiquitous in acid mine drainage. In the present study, the arsenite oxidase gene (aioBA) was cloned from Thiomonas delicata DSM 16361, expressed heterologously in E. coli and purified to homogeneity. The purified recombinant Aio consisted of two subunits with the respective molecular weights of 91 and 21 kDa according to SDS-PAGE. Aio catalysis was optimum at pH 5.5 and 50-55 °C. Aio exhibited stability under acidic conditions (pH 2.5-6). The V max and K m values of the enzyme were found to be 4 µmol min(-1) mg(-1) and 14.2 µM, respectively. SDS and Triton X-100 were found to inhibit the enzyme activity. The homology model of Aio showed correlation with the acidophilic adaptation of the enzyme. This is the first characterization studies of Aio from a species belonging to the Thiomonas genus. The arsenite oxidase was found to be among the acid-tolerant Aio reported to date and has the potential to be used for biosensor and bioremediation applications in acidic environments.
A non-enzymatic glucose sensor of multi-walled carbon nanotube-ruthenium oxide/composite paste electrode (MWCNT-RuO(2)/CPE) was developed. The electrode was characterized by using XRD, SEM, TEM and EIS. Meanwhile, cyclic voltammetry and amperometry were used to check on the performances of the MWCNT-RuO(2)/CPE towards glucose. The proposed electrode has displayed a synergistic effect of RuO(2) and MWCNT on the electrocatalytic oxidation of glucose in 3M NaOH. This was possible via the formation of transitions of two redox pairs, viz. Ru(VI)/Ru(IV) and Ru(VII)/Ru(VI). A linear range of 0.5-50mM glucose and a limit of detection of 33 μM glucose (S/N=3) were observed. There was no significant interference observable from the traditional interferences, viz. ascorbic acid and uric acid. Indeed, results so obtained have indicated that the developed MWCNT-RuO(2)/CPE would pave the way for a better future to glucose sensor development as its fabrication was without the use of any enzyme.
Palm-pressed mesocarp oil has been found to contain plenty of naturally occurring valuable phytonutrients. The application and study of the oil are limited, therefore, quality assessment of refined red palm-pressed mesocarp olein (PPMO) is deemed necessary to provide data in widening the applications as a niche products or raw material for the nutraceutical industry. Results showed that refined PPMO has comparable physicochemical properties and oxidative stability with commercial cooking oil, palm olein (PO). The food safety parameters and contaminants (PAH, 3-MCPD ester, 2-MCPD ester, glycidyl ester and trace metals) analyses proven that refined PPMO is safe to be consumed. Besides, refined PPMO contains remarkably greater concentrations of phytonutrients including carotenoids, phytosterols, squalene and vitamin E than PO, postulating its protective health benefits. The overall quality assessment of refined PPMO showed that it is suitable for human consumption and it is a good source for food applications and dietary nutritional supplements.
The alginate lyase AlyQ from Persicobacter sp. CCB-QB2 is a three-domained enzyme with a carbohydrate-binding module (CBM) from family 32. The CBM32 domain, AlyQB, binds enzymatically cleaved but not intact alginate. Co-crystallisation of AlyQB with the cleaved alginate reveals that it binds to the 4,5-unsaturated mannuronic acid of the non-reducing end. The binding pocket contains a conserved R248 that interacts with the sugar's carboxyl group, as well as an invariant W303 that stacks against the unsaturated pyranose ring. Targeting specifically the non-reducing end is more efficient than the reducing end since the latter consists of a mixture of mannuronic acid and guluronic acid. AlyQB also seems unable to bind these two saturated sugars as they contain OH groups that will clash with the pocket. Docking analysis of YeCBM32, which binds oligogalacturonic acid, shows that the stacking of the pyranose ring is shifted in order to accommodate the sugar's axial C1-OH, and its R69 is accordingly elevated to bind the sugar's carboxyl group. Unlike AlyQB, YeCBM32's binding pocket is able to accommodate both saturated and unsaturated galacturonic acid.
This study investigated the removal of parabens, N,N-diethyl-m-toluamide (DEET), and phthalates by ozonation. The second-order rate constants for the reaction between selected compounds with ozone at pH 7 were of (2.2 +/-0.2) X 10(6) to (2.9 +/-0.3) X 10(6) M 1/s for parabens, (2.1+/- 0.3) to (3.9 +/-0.5) M-1/s for phthalates, and (5.2 +/-0.3) M-1/s for DEET. The rate constants for the reaction between selected compounds with hydroxyl radical ranged from (2.49 +/-0.06) x 10(9) to (8.5 +/-0.2) x 10(9) M-1/s. Ozonation of selected compounds in secondary wastewater and surface waters revealed that ozone dose of 1 and 3 mg/L yielded greater than 99% depletion of parabens and greater than 92% DEET and phthalates, respectively. In addition, parabens were found to transform almost exclusively through the reaction with ozone, while DEET and phthalates were transformed almost entirely by hydroxyl radicals (.OH).
This study investigated the reaction kinetics and degradation mechanism of parabens (methylparaben, ethylparaben, propylparaben and butylparaben) during ozonation. Experiments were performed at pH 2, 6 and 12 to determine the rate constants for the reaction of protonated, undissociated and dissociated paraben with ozone. The rate constants for the reaction of ozone with dissociated parabens (3.3 × 10(9)-4.2 × 10(9)M(-1)s(-1)) were found to be 10(4) times higher than the undissociated parabens (2.5 × 10(5)-4.4 × 10(5)M(-1)s(-1)) and 10(7) times higher than with the protonated parabens (1.02 × 10(2)-1.38 × 10(2)M(-1)s(-1)). The second-order rate constants for the reaction between parabens with hydroxyl radicals were found to vary from 6.8 × 10(9) to 9.2 × 10(9)M(-1)s(-1). Characterization of degradation by-products (DBPs) formed during the ozonation of each selected parabens has been carried out using GCMS after silylation. Twenty DBPs formed during ozonation of selected parabens have been identified. Hydroxylation has been found to be the major reaction for the formation of the identified DBPs. Through the hydroxylation reaction, a variety of hydroxylated parabens was formed.
Application of ozonation in water treatment involves complex oxidation pathways that could lead to the formation of various by-products, some of which may be harmful to living organisms. In this work, ozonation by-products of ofloxacin (OFX), a frequently detected pharmaceutical pollutant in the environment, were identified and their ecotoxicity was estimated using the Ecological Structure Activity Relationships (ECOSAR) computer program. In order to examine the role of ozone (O3) and hydroxyl radicals (∙OH) in the degradation of ofloxacin, ozonation was performed at pH2, 7 and 12. In this study, 12 new structures have been proposed for the ozonation by-products detected during the ozonation of ofloxacin. According to the identified ozonation by-products, O3 and ∙OH were found to react with ofloxacin during ozonation. The reaction between ofloxacin and O3 proceeded via hydroxylation and breakdown of heterocyclic ring with unsaturated double-bond. The reaction between ofloxacin and ·OH generated various by-products derived from the breakdown of heterocyclic ring. Ecotoxicity assessment indicated that ozonation of OFX could yield by-products of greater toxicity compared with parent compounds.
This study investigated the degradation pathway of metoprolol, a widely used β-blocker, in the ozonation via the identification of generated ozonation by-products (OPs). Structure elucidation of OPs was performed using HPLC coupled with quadrupole time-of-flight high-resolution mass spectrometry. Seven OPs were identified, and four of these have not been reported elsewhere. Identified OPs of metoprolol included aromatic ring breakdown by-products; aliphatic chain degraded by-products and aromatic ring mono-, di-, and tetrahydroxylated derivatives. Based on the detected OPs, metoprolol could be degraded through aromatic ring opening reaction via reaction with ozone (O3) and degradation of aliphatic chain and aromatic ring via reaction with hydroxyl radical (•OH).
Reduction of graphene oxide becomes an alternative way to produce a scalable graphene and the resulting nanomaterial namely reduced graphene oxide (rGO) has been utilized in a wide range of potential applications. In this article, the level of green reduction strategies, especially the solution-based reduction methods are overviewed based on recent progression, to get insights towards biomedical applications. The degrees of gaining tips with the solution-based green reduction methods, conditions, complexity and the resulting rGO characteristics have been elucidated comparatively. Moreover, the application of greenly produced rGO in electrochemical biosensors has been elucidated as well as their electrical performance in term of linear range and limit of detections for various healthcare biological analytes. In addition, the characterization scheme for graphene-based materials and the analyses on the reduction especially for the solution-based green reduction methods are outlined for the future endeavours.
Alzheimer's disease (AD) is a fatal neurodegenerative disease that requires immediate attention. Oxidative stress that leads to the generation of reactive oxygen species is a contributing factor to the disease progression by promoting synthesis and deposition of amyloid-β, the main hallmark protein in AD. It has been previously demonstrated that nanoyttria possesses antioxidant properties and can alleviate cellular oxidative injury in various toxicity and disease models. This review proposed that nanoyttria could be used for the treatment of AD. In this paper, the evidence on the antioxidant potential of nanoyttria is presented and its prospects on AD therapy are discussed.
Biochar (BC) has attracted much attention owing to its superior sorption capacity towards ionized organic contaminants. However, the mechanism of ionized organics sorption occurring within BC containing large amounts of minerals is still controversial. In this study, we demonstrate the physicochemical structure of high-salinity microalgal residue derived biochar (HSBC) and elucidate the corresponding sorption mechanisms for four ionized dyes along with determining the crucial role of involved minerals. The results indicate that sodium and calcium minerals mainly exist within HSBCs, and the pyrolysis temperature can dramatically regulate the phases and interfacial property of both carbon matrix and minerals. As a result, the HSBC shows a higher sorption potential, benefiting from abundant functional groups and high content of inorganic minerals. Using theoretical calculations, the activities of electron donor-acceptor interaction between HSBCs and different dyes are clearly illustrated, thereby identifying the critical role of Ca2+ in enhancing the removal of ionized dyes in HSBCs. In addition, Ca-containing minerals facilitate the sorption of ionized dyes in HSBCs by forming ternary complexes through metal-bridging mechanism. These results of mineral-induced dye sorption mechanisms help to better understand the sorption of ionized organics in high-salt containing BC and provide a new disposal strategy for hazardous microalgal residue, as well as provide a breakthrough in making the remediation of ionized organic contaminated microalgal residue derived absorbent feasible.
This investigation explores the efficacy of employing ultrasonic cavitation and coupling it with advanced oxidation processes (hydrogen peroxide and Fenton's reagent) for reducing the levels of total ammonia nitrogen in fish pond water containing Tilapia fishes. Ultrasonic cavitation is a phenomenon where the formation, growth and collapse of vaporous bubbles occur in a liquid medium producing highly reactive free radicals. Ultrasonic probe system (20 kHz with 750 W and 1000 W) was used to induce cavitation. Besides, to intensify the process, ultrasonic cavitation was coupled with hydrogen peroxide and Fenton's reagent. Using SERA colour indicator test kits, the levels of ammonium, nitrite and carbonate hardness were measured. The results obtained from this study clearly show that the advanced oxidation processes are more efficient in reducing the ammonium and nitrite levels in fish pond water than using ultrasound alone. The pH and carbonate hardness levels were not affected significantly by ultrasonic cavitation. The optimal treatment time and ultrasound power to treat the water samples were also established. Energy efficiency and cost analysis of this treatment have also been presented, indicating that ultrasonic cavitation coupled with hydrogen peroxide appears to be a promising technique for reducing total ammonia nitrogen levels in the fish pond water.
A total of 20 new indole alkaloids comprising mainly oxidized derivatives of macroline- (including alstofonidine, a macroline indole incorporating a butyrolactone ring-F), pleiocarpamine-, and sarpagine-type alkaloids were isolated from the bark and leaf extracts of Alstonia angustifolia. The structures and relative configurations of these alkaloids were determined using NMR and MS analyses and in some instances confirmed by X-ray diffraction analyses. Alkaloids 3, 7, 35, and 41 showed moderate to weak activity, while 21 showed strong activity in reversing multidrug resistance in vincristine-resistant KB cells.
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.
Lubricant oils take significant part in current health and environmental considerations since they are an integral and indispensable component of modern technology. Antioxidants are probably the most important additives used in oils because oxidative deterioration plays a major role in oil degradation. Zeolite nanoparticles (NPs) have been proven as another option as green antioxidants in oil formulation. The anti-oxidative behavior of zeolite NPs is obvious; however, the phenomenon is still under investigation. Herein, a study of the effect of extra-framework cations stabilized on Linde Type L (LTL) zeolite NPs (ca. 20 nm) on inhibition of oxidation in palm oil-based lubricant oil is reported. Hydrophilic LTL zeolites with a Si/Al ratio of 3.2 containing four different inorganic cations (Li(+), Na(+), K(+), Ca(2+)) were applied. The oxidation of the lubricant oil was followed by visual observation, colorimetry, fourier transform infrared (FTIR) spectroscopy, (1)H NMR spectroscopy, total acid number (TAN), and rheology analyses. The effect of extra-framework cations to slow down the rate of oil oxidation and to control the viscosity of oil is demonstrated. The degradation rate of the lubricant oil samples is decreased considerably as the polarizability of cation is increased with the presence of zeolite NPs. More importantly, the microporous zeolite NPs have a great influence in halting the steps that lead to the polymerization of the oils and thus increasing the lifetime of oils.
The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species.