The effect of the addition of different concentrations of chitosan (0–2.0% w/w) on the gelling properties of surimi gels made from African catfish (Clarias gariepinus) was tested. Lipid oxidation, total volatile basic nitrogen (TVB-N), and aerobic plate count (APC) changes during 20 days of storage at 4oC also were evaluated. Surimi gels with 1.5% (w/w) chitosan added exhibited the highest improvement in gel strength (58.92%), whiteness (13.18%), and water holding capacity (36.8%). Incorporation of 2.0% (w/w) chitosan in gels resulted in the lowest TVB-N value (36.63 mg N/100 g) at the end of the 20 days storage period. Both the peroxide values and the 2-thiobarbituric acid values increased more slowly in the chitosan-treated gels than in the control gel during the storage period. Chitosan at concentrations of 1.75% and 2.0% (w/w) conferred the best antioxidant effect on catfish surimi gels and resulted in a significant reduction in APC. Based on the microbiological acceptability limit (106 cfu/g), the shelf life
of surimi gels with 1.75% and 2.0% (w/w) chitosan was extended to 12 days in refrigerated storage at 4oC, whereas the other samples lasted only 8 days. Hence, the addition of 1.5–2.0% (w/w) chitosan is a promising approach for the preparation of catfish surimi gels, as it improves texture, prevents lipid oxidation, and inhibits microbial growth.
The emission of waste anaesthetic gas is a growing contributor to global warming and remains a factor in atmospheric ozone depletion. Volatile anaesthetics in medical waste gases could be removed via adsorption using suitable activated carbon materials possessing an enhanced affinity to anaesthetic molecules. In this work, the effects of surface physical and chemical properties on sevoflurane adsorption were investigated by oxidative hydrothermal surface modification of a commercial activated carbon using only distilled water. The hydrothermal surface modification was carried out at different treatment temperatures (150-300 °C) for varying durations (10-30 min), and adsorption was conducted under fixed conditions (bed depth = 10 cm, inlet concentration = 528 mg/L, and flow rate = 3 L/min). The hydrothermal treatment generally increased the BET surface area of the activated carbons. At oxidation temperatures above 200 °C, the micropore volume of the samples diminished. The relative amount of surface oxygen was enriched as the treatment temperature increased. Treatment duration did not significantly affect the introduction of relative amount of surface oxygen, except at higher temperatures. There were no new types of functional groups introduced. However, disappearance and re-formation of oxygen functional groups containing C-O structures (as in hydroxyl and ether groups) occurred when treatment temperature was increased from 150 to 200 °C, and when treatments were conducted above 200 °C, respectively. The ester/acetal groups were enriched under the temperature range studied. The findings suggested that the re-formation of surface oxygen functionalities might lead to the development of functional groups that improve sevoflurane adsorption.
Activated carbons have been reported to be useful for adsorptive removal of the volatile anaesthetic sevoflurane from a vapour stream. The surface functionalities on activated carbons could be modified through aqueous oxidation using oxidising solutions to enhance the sevoflurane adsorption. In this study, an attempt to oxidise the surface of a commercial activated carbon to improve its adsorption capacity for sevoflurane was conducted using 6 mol/L nitric acid, 2 mol/L ammonium persulfate, and 30 wt per cent (wt%) of hydrogen peroxide (H2O2). The adsorption tests at fixed conditions (bed depth: 10 cm, inlet concentration: 528 mg/L, and flow rate: 3 L/min) revealed that H2O2 oxidation gave desirable sevoflurane adsorption (0.510 ± 0.005 mg/m2). A parametric study was conducted with H2O2 to investigate the effect of oxidation conditions to the changes in surface oxygen functionalities by varying the concentration, oxidation duration, and temperature, and the Conductor-like Screening Model for Real Solvents (COSMO-RS) was applied to predict the interactions between oxygen functionalities and sevoflurane. The H2O2 oxidation incorporated varying degrees of both surface oxygen functionalities with hydrogen bond (HB) acceptor and HB donor characters under the studied conditions. Oxidised samples with enriched oxygen functionalities with HB acceptor character and fewer HB donor character exhibited better adsorption capacity for sevoflurane. The presence of a high amount of oxygen functional groups with HB donor character adversely affected the sevoflurane adsorption despite the enrichment of oxygen functional groups with HB acceptor character that have a higher tendency to adsorb sevoflurane.
A natural pentacyclic triterpenoid oleanolic acid 1 and its biotransformed metabolites 2-3 are potential α-glucosidase inhibitors. To elucidate the inhibitory mechanism of compounds 1, 2 and 3 against α-glucosidase, we calculated (i) their electronic and optical properties using DFT and TD-DFT at the B3LYP/6-31G(d) level in gas and IEF-PCM solvent; and (ii) their binding energies to α-glucosidase via docking study. DFT results showed that the α-glucosidase inhibtion is mainly depend on the polarity parameters of the studied compounds. Docking results revealed that the activity increased with binding energies (i.e. the stability of ligand-receptor complex). The specroscopic data of oleanolic acid 1 and its metabolites 2 and 3 are well predicetd for 13C NMR chemical shifts (R2=99%) and 1H NMR chemical shifts (R2=90%); and for (ii) UV/vis spectra. The assignments and interpretation of NMR chemical shifts and bathochromic shift of λMAX absorption bands are discussed.
Microbial electrosynthesis is a new approach to converting C1 carbon (CO2) to more complex carbon-based products. In the present study, CO2, a potential greenhouse gas, was used as a sole carbon source and reduced to value-added chemicals (acetate, ethanol) with the help of bioelectrochemical reduction in microbial electrosynthesis systems (MES). The performance of MES was studied with varying electrode materials (carbon felt, stainless steel, and cobalt electrodeposited carbon felt). The MES performance was assessed in terms of acetic acid and ethanol production with the help of gas chromatography (GC). The electrochemical characterization of the system was analyzed with chronoamperometry and cyclic voltammetry. The study revealed that the MES operated with hybrid cobalt electrodeposited carbon felt electrode yielded the highest acetic acid (4.4 g/L) concentration followed by carbon felt/stainless steel (3.7 g/L), plain carbon felt (2.2 g/L), and stainless steel (1.87 g/L). The alcohol concentration was also observed to be highest for the hybrid electrode (carbon felt/stainless steel/cobalt oxide is 0.352 g/L) as compared to the bare electrodes (carbon felt is 0.22 g/L) tested, which was found to be in correspondence with the pH changes in the system. Electrochemical analysis revealed improved electrotrophy in the hybrid electrode, as confirmed by the increased redox current for the hybrid electrode as compared to plain electrodes. Cyclic voltammetry analysis also confirmed the role of the biocatalyst developed on the electrode in CO2 sequestration.
Bis(dithiolene) tungsten carbonyl complex, W(S2C2Ph2)2(CO)2 was successfully synthesized and the structure, frontier molecular orbital and optical properties of the complex were investigated theoretically using density functional theory calculations. The investigation started with a molecular structure construction, followed by an optimization of the structural geometry using generalized-gradient approximation (GGA) in a double numeric plus polarization (DNP) basis set at three different functional calculation approaches. Vibrational frequency analysis was used to confirm the optimized geometry of two possible conformations of [W(S2C2Ph2)2(CO)2], which showed distorted octahedral geometry. Electronic structure and optical characterization were done on the ground states. Metal to ligand and ligand to metal charge transfer were dominant in this system.
The presence of phenolic compounds in the aquatic environment has posed severe risks due to their toxicity. Among the phenolic families, nitro- and alkyl-phenolic compounds have been categorized as precedence contaminants by the United States Environmental Protection Agency (US EPA). Therefore, efficient treatment methods for wastewater containing nitro- and alkyl-phenolic compounds are urgently needed. Due to the advantages of creating reactive species and generating efficient degradation of hazardous contaminants in wastewater, advanced oxidation processes (AOPs) are well-known in the field of treating toxic contaminants. In this review paper, the recent directions in AOPs, catalysts, mechanisms, and kinetics of AOPs are comprehensively reviewed. Furthermore, the conclusion summarizes the research findings, future prospects, and opportunities for this study. The main direction of AOPs lies on the optimization of catalyst and operating parameters, with industrial applications remain as the main challenge. This review article is expected to present a summary and in-depth understanding of AOPs development; and thus, inspiring scientists to accelerate the evolution of AOPs in industrial applications.
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.
Thiol groups of cysteine (Cys) residues in proteins react with quinones, oxidation products of polyphenols, to form protein-polyphenol adducts. The aim of the present work was to quantify the amount of adduct formed between Cys residues and 4-methylcatechol (4MC) in minced beef. A Cys-4MC adduct standard was electrochemically synthesized and characterized by liquid chromatography-mass spectrometry (LC-MS) as well as NMR spectroscopy. Cys-4MC adducts were quantified after acidic hydrolysis of myofibrillar protein isolates (MPIs) and LC-MS/MS analysis of meat containing either 500 or 1500 ppm 4MC and stored at 4 °C for 7 days under a nitrogen or oxygen atmosphere. The concentrations of Cys-4MC were found to be 2.2 ± 0.3 nmol/mg MPI and 8.1 ± 0.9 nmol/mg MPI in meat containing 500 and 1500 ppm 4MC, respectively, and stored for 7 days under oxygen. The formation of the Cys-4MC adduct resulted in protein thiol loss, and ca. 62% of the thiol loss was estimated to account for the formation of the Cys-4MC adduct for meat containing 1500 ppm 4MC. Furthermore, protein polymerization increased in samples containing 4MC as evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), and the polymerization was found to originate from protein-polyphenol interactions as evaluated by a blotting assay with staining by nitroblue tetrazolium.
The immune system is complex and pervasive as it functions to prevent or limit infections in the human body. In a healthy organism, the immune system and the redox balance of immune cells maintain homeostasis within the body. The failure to maintain the balance may lead to impaired immune response and either over activity or abnormally low activity of the immune cells resulting in autoimmune or immune deficiency diseases. Compounds containing α,β-unsaturated carbonyl-based moieties are often reactive. The reactivity of these groups is responsible for their diverse pharmacological activities, and the most important and widely studied include the natural compounds curcumin, chalcone, and zerumbone. Numerous studies have revealed the mainly immunosuppressive and anti-inflammatory activities of the aforesaid compounds. This review highlights the specific immunosuppressive effects of these natural α,β-unsaturated carbonyl-based compounds, and their analogs and derivatives on different types of immune cells of the innate (granulocytes, monocytes, macrophages, and dendritic cells) and adaptive (T cells, B cells, and natural killer cells) immune systems. The inhibitory effects of these compounds have been comprehensively studied on neutrophils, monocytes and macrophages but their effects on T cells, B cells, natural killer cells, and dendritic cells have not been well investigated. It is of paramount importance to continue generating experimental data on the mechanisms of action of α,β-unsaturated carbonyl-based compounds on immune cells to provide useful information for ensuing research to discover new immunomodulating agents.
Excess levels of nitrite ion in drinking water interact with amine functionalized compounds to form carcinogenic nitrosamines, which cause stomach cancer. Thus, it is indispensable to develop a simple protocol to detect nitrite. In this paper, a Cu-metal-organic framework (Cu-MOF) with graphene oxide (GO) composite was synthesized by ultrasonication followed by solvothermal method and then fabricated on a glassy carbon (GC) electrode for the sensitive and selective determination of nitrite contamination. The SEM image of the synthesized Cu-MOF showed colloidosome-like structure with an average size of 8 μm. Interestingly, the Cu-MOF-GO composite synthesized by ultrasonic irradiation followed by solvothermal process produce controlled size of 3 μm colloidosome-like structure. This was attributed to the formation of an exfoliated sheet-like structure of GO by ultrasonication in addition to the obvious influence of GO providing the oxygen functional groups as a nucleation node for size-controlled growth. On the other hand, the composite prepared without ultrasonication exhibited 6.6 μm size agglomerated colloidosome-like structures, indicating the crucial role of ultrasonication for the formation of size-controlled composites. XPS results confirmed the presence of Cu(II) in the as-synthesized Cu-MOF-GO based on the binding energies at 935.5 eV for Cu 2p3/2 and 955.4 eV for Cu 2p1/2. The electrochemical impedance studies in [Fe(CN)6]3-/4- redox couple at the composite fabricated electrode exhibited more facile electron transfer than that with Cu-MOF and GO modified electrodes, which helped to utilize Cu-MOF-GO for trace level determination of nitrite in environmental effluent samples. The Cu-MOF-GO fabricated electrode offered a superior sensitive platform for nitrite determination than the Cu-MOF and GO modified electrodes demonstrating oxidation at less positive potential with enhanced oxidation current. The present sensor detects nitrite in the concentration range of 1 × 10-8 to 1 × 10-4 M with the lowest limit of detection (LOD) of 1.47 nM (S/N = 3). Finally, the present Cu-MOF-GO electrode was successfully exploited for nitrite ion determination in lake and dye contaminated water samples.
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.
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.
HOMO and LUMO of organic compounds are basic parameters for the design and fabrication of an organic solar cell. This paper presents a technique to obtain HOMO and LUMO of an n-type polymer of [6,6]-phenyl C61-butyric acid 3-ethylthiophene ester (PCBE) and a p-type polymer of poly (3-octyl-thiophene-2, 5-diyl) (P3OT). The energy of band gap for each material has been calculated using optical absorption spectrum. Cyclic Voltammetry was used to estimate the oxidation potential and energy band diagram consequently. The experiments were carried out in a three-electrode cell consisting of a platinum working electrode, a platinum counter electrode and a SCE reference electrode. P3OT showed energy band gap equal to 1.83 eV with HOMO and LUMO equal to 5.59 eV and 3.76 eV, respectively. PCBE showed energy band gap equal to 1.96 eV with HOMO and LUMO equal to 5.87 eV and 3.91 eV, respectively. Based on energy band diagram that was constructed from this experimental result, the couple materials may be successfully used to fabricate the feasible organic solar cells.
Wide spread documentation of antibiotic pollution is becoming a threat to aquatic environment. Erythromycin (ERY), a macrolide belonging antibiotic is at the top of this list with its concentrations ranging between ng/L to a few μg/L in various global waterbodies giving rise to ERY-resistance genes (ERY-RGs) and ERY- resistance bacteria (ERY-RBs) posing serious threat to the aquatic organisms. ERY seems resistant to various conventional water treatments, remained intact and even increased in terms of mass loads after treatment. Enhanced oxidation potential, wide pH range, elevated selectivity, adaptability and greater efficiency makes advance oxidation processes (AOPs) top priority for degrading pollutants with aromatic rings and unsaturated bonds like ERY. In this manuscript, recent developments in AOPs for ERY degradation are reported along with the factors that affect the degradation mechanism. ERY, marked as a risk prioritized macrolide antibiotic by 2015 released European Union watch list, most probably due to its protein inhibition capability considered third most widely used antibiotic. The current review provides a complete ERY overview including the environmental entry sources, concentration in global waters, ERY status in STPs, as well as factors affecting their functionality. Along with that this study presents complete outlook regarding ERY-RGs and provides an in depth detail regarding ERY's potential threats to aquatic biota. This study helps in figuring out the best possible strategy to tackle antibiotic pollution keeping ERY as a model antibiotic because of extreme toxicity records.
This study evaluated the impact of Vernonia amygdalina (VA) on the transcription of key enzymes involved in cellular modulation of glucose in streptozotocin-induced diabetic rats in a bid to understand the possible anti-diabetic mechanism of VA.
The aim of this study was to determine hydrolytic stability [acid value (AV)] and oxidative stability [peroxide value (PV) and conjugated dienes (CD)] of selected blended oils during potato frying. The blended oils were prepared by blending palm oil with corn oil (POCO), sesame oil (POSO) and rice bran oil (PORBO). Blended vegetable oils were prepared in a ratio of 1 to 1 (v/v) and tested for 0, 10 and 20 times after frying potato. AV and PV were determined by titration method, while CD was determined using the spectrophotometric method. Increasing frequency of oil frying contributed to increased level of AV in all blended oils. PVs were increased in all samples, with most noticeable increment observed in POSO, followed by PORBO and POCO. CD levels of the blended oils were also increased after 20 times of potato frying compared with the unused oil and after 10 times of frying. POCO was the most stable oil in terms of hydrolytic and oxidative stabilities. It is most suitable for deep-fat frying of potato chips and industrial application.
The co-existence of heavy metals and organic compounds including Cr(VI) and p-cresol (pC) in water environment becoming a challenge in the treatment processes. Herein, the synchronous photocatalytic reduction of Cr(VI) and oxidation of pC by silver oxide decorated on fibrous silica zirconia (AgO/FSZr) was reported. In this study, the catalysts were successfully developed using microemulsion and electrochemical techniques with various AgO loading (1, 5 and 10 wt%) and presented as 1, 5 and 10-AgO/FSZr. Catalytic activity was tested towards simultaneous photoredox of hexavalent chromium and p-cresol (Cr(VI)/pC) and was ranked as followed: 5-AgO/FSZr (96/78%) > 10-AgO/FSZr (87/61%) > 1-AgO/FSZr (47/24%) > FSZr (34/20%). The highest photocatalytic activity of 5-AgO/FSZr was established due to the strong interaction between FSZr and AgO and the lowest band gap energy, which resulted in less electron-hole recombination and further enhanced the photoredox activity. Cr(VI) ions act as a bridge between the positive charge of catalyst and cationic pC in pH 1 solution which can improve the photocatalytic reduction and oxidation of Cr(VI) and pC, respectively. The scavenger experiments further confirmed that the photogenerated electrons (e-) act as the main species for Cr(VI) to be reduced to Cr(III) while holes (h+) and hydroxyl radicals are domain for photooxidation of pC. The 5-AgO/FSZr was stable after 5 cycles of reaction, suggesting its potential for removal of Cr(VI) and pC simultaneously in the chemical industries.
Ternary CuO/AgO/FSZr photocatalysts were fabricated via the hydrothermal and electrochemical methods with three different CuO loading (1, 3 and 5 wt%), indicated as 1CuO/AgO/FSZr, 3CuO/AgO/FSZr and 5CuO/AgO/FSZr. The photocatalytic reaction was tested towards simultaneous chromium (VI) photoreduction and p-cresol photooxidation and the performance in order as follow: 3CuO/AgO/FSZr > 5CuO/AgO/FSZr > 1CuO/AgO/FSZr > AgO/FSZr > FSZr. CuO/AgO/FSZr photocatalysts showed an improvement in photocatalytic activity compared to AgO/FSZr and FSZr due to the reduction potential of chromium (VI) aligned closer to the conduction band of CuO and provided abundant free active electrons (e-) and holes (h+) with efficient transportation and migration. Interestingly, the 3CuO/AgO/FSZr was established as the best photocatalyst with 98% reduction of chromium (VI) and 83% oxidation of p-cresol simultaneously, owing to its strong corporation between the metal oxides and support and higher total pore volume. The Langmuir-Hinshelwood model were employed for kinetics which followed the pseudo-first-order kinetics model well. Based on the simultaneous photocatalytic mechanism, chromium (VI) and p-cresol were directly reduced and oxidized by e- and h+, respectively. The response surface methodology (RSM) discovered that the quadratic term initial concentration of chromium (VI) is the main significant factor in photocatalytic performance. The optimum parameters for simultaneous photoredox of chromium (VI) and p-cresol predicted from RSM are 9.6 mg L-1 of chromium (VI) concentration, 9.8 mg L-1 of p-cresol concentration and 0.32 g L-1 of catalyst dosage. Under these conditions the error between the predicted and experimental values is only 3.7%. The 3CuO/AgO/FSZr sustained the photocatalytic performance after reused for five cycles and could oxidized various organic pollutants as well as reduced chromium (VI) simultaneously.
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.