Geometric isomerization can expand the scope of biological activities of natural products. The observed chemical diversity among the pseurotin-type fungal secondary metabolites is in part generated by a trans to cis isomerization of an olefin. In vitro characterizations of pseurotin biosynthetic enzymes revealed that the glutathione S-transferase PsoE requires participation of the bifunctional C-methyltransferase/epoxidase PsoF to complete the trans to cis isomerization of the pathway intermediate presynerazol. The crystal structure of the PsoE/glutathione/presynerazol complex indicated stereospecific glutathione-presynerazol conjugate formation is the principal function of PsoE. Moreover, PsoF was identified to have an additional, unexpected oxidative isomerase activity, thus making it a trifunctional enzyme which is key to the complexity generation in pseurotin biosynthesis. Through the study, we identified a novel mechanism of accomplishing a seemingly simple trans to cis isomerization reaction.
In mangrove ecosystems, litter fall accumulates as refractory organic carbon on the sediment surface and creates anoxic sediment layers. Fiddler crabs, through their burrowing activity, translocate oxygen into the anoxic layers and promote aerobic respiration, iron reduction and nitrification. In this study, the effects of four species of fiddler crabs (Uca triangularis, Uca rosea, Uca forcipata and Uca paradussumieri) on organic content, water content, porosity, redox potential and solid phase iron pools of mangrove sediments were investigated. In each crab's habitat, six cores down to 30 cm depth were taken from burrowed and non-burrowed sampling plots. Redox potential and oxidized iron pools were highest in surface sediment, while porosity, water and organic content were higher in deeper sediment. Reduced iron (Fe (II)) and redox potential were significantly different between burrowed and non-burrowed plots. Crab burrows extend the oxidized surface layer down to 4 cm depth and through the oxidation effect, reduce the organic content of sediments. The effects of burrows varied between the four species based on their shore location. The oxidation effect of burrows enhance the decomposition rate and stimulate iron reduction, which are processes that are expected to play an important role in biogeochemical properties of mangrove sediments.
To overcome the critical limitations of liquid-electrolyte-based dye-sensitized solar cells, quasi-solid-state electrolytes have been explored as a means of addressing long-term device stability, albeit with comparatively low ionic conductivities and device performances. Although metal oxide additives have been shown to augment ionic conductivity, their propensity to aggregate into large crystalline particles upon high-heat annealing hinders their full potential in quasi-solid-state electrolytes. In this work, sonochemical processing has been successfully applied to generate fine Co3O4 nanoparticles that are highly dispersible in a PAN:P(VP-co-VAc) polymer-blended gel electrolyte, even after calcination. An optimized nanocomposite gel polymer electrolyte containing 3 wt % sonicated Co3O4 nanoparticles (PVVA-3) delivers the highest ionic conductivity (4.62 × 10-3 S cm-1) of the series. This property is accompanied by a 51% enhancement in the apparent diffusion coefficient of triiodide versus both unmodified and unsonicated electrolyte samples. The dye-sensitized solar cell based on PVVA-3 displays a power conversion efficiency of 6.46% under AM1.5 G, 100 mW cm-2. By identifying the optimal loading of sonochemically processed nanoparticles, we are able to generate a homogenous extended particle network that effectively mobilizes redox-active species through a highly amorphous host matrix. This effect is manifested in a selective 51% enhancement in photocurrent density (JSC = 16.2 mA cm-2) and a lowered barrier to N719 dye regeneration (RCT = 193 Ω) versus an unmodified solar cell. To the best of our knowledge, this work represents the highest known efficiency to date for dye-sensitized solar cells based on a sonicated Co3O4-modified gel polymer electrolyte. Sonochemical processing, when applied in this manner, has the potential to make meaningful contributions toward the ongoing mission to achieve the widespread exploitation of stable and low-cost dye-sensitized solar cells.
An upsurge in sustainable energy demands has ultimately made supercapattery one of the important choice for energy storage, owing to highly advantageous energy density and long life span. In this work, novel strontium based mixed phased nanostructures were synthesized by using probe sonicator with sonication power 500 W at frequency of 20 kHz. The synthesized material was subsequently calcined at different temperature ranging from 200 to 800 °C. Structural and morphological analysis of the synthesized materials reveals the formation of mixed particle and rod like nanostructures with multiple crystal phases of strontium oxides and carbonates. Crystallinity, grain size and morphology of grown nanomaterials significantly improved with the increase of calcination temperature due to sufficient particle growth and low agglomeration. The electrochemical performance analysis confirms the redox activeness of the Sr-based electrode materials. Material calcined at 600 °C show high specific capacitance of 350 F g-1 and specific capacity of 175 C g-1 at current density of 0.3 A g-1 due to less particle agglomeration, good charge transfer and more contribution of electrochemical active sites for redox reactions. In addition, the developed supercapattery of Sr-based nanomaterials//activated carbon demonstrated high performance with maximum energy density of 21.8 Wh kg-1 and an excellent power density of 2400 W kg-1 for the lower and higher current densities. Furthermore, the supercapattery retain 87% of its capacity after continuous 3000 charge/discharge cycles. The device characteristics were further investigated by analyzing the capacitive and diffusion controlled contributions. The versatile strategy of developing mixed phased nanomaterials pave the way to synthesize other transition metal based nanomaterials with superior electrochemical performance for hybrid energy storage devices.
The application of the anammox process has great potential in treating nitrogen-rich wastewater. The presence of Fe (II) is expected to affect the growth and activity of anammox bacteria. Short-term (acute) and long-term effects (chronic) of Fe (II) on anammox activity were investigated. In the short-term study, results demonstrated that the optimum concentration of Fe (II) that could be added to anammox is 0.08 mM, at which specific anammox activity (SAA) improved by 60% compared to the control assay, 0.00 mM. The inhibition concentration, IC50, of Fe (II) was found to be 0.192 mM. Kinetics of anammox specific growth rate were estimated based on results of the batch test and evaluated with Han-Levenspiel's substrate inhibition kinetics model. The optimum concentration and IC50 of Fe (II) predicted by the Han-Levenspiel model was similar to the batch test, with values of 0.07 mM and 0.20 mM, respectively. The long-term effect of Fe (II) on the performance of a sequencing batch reactor (SBR) was evaluated. Results showed that an appropriate Fe (II) addition enhanced anammox activity, achieving 85% NH4+-N and 96% NO2--N removal efficiency when 0.08 mM of Fe (II) was added. Quantitative polymerase chain reaction (qPCR) was adopted to detect and identify the anammox bacteria.
This study presents a mathematical model examining wastewater pollutant removal through
an oxidation pond treatment system. This model was developed to describe the reaction
between microbe-based product mPHO (comprising Phototrophic bacteria (PSB)), dissolved
oxygen (DO) and pollutant namely chemical oxygen demand (COD). It consists
of coupled advection-diffusion-reaction equations for the microorganism (PSB), DO and
pollutant (COD) concentrations, respectively. The coupling of these equations occurred
due to the reactions between PSB, DO and COD to produce harmless compounds. Since
the model is nonlinear partial differential equations (PDEs), coupled, and dynamic, computational
algorithm with a specific numerical method, which is implicit Crank-Nicolson
method, was employed to simulate the dynamical behaviour of the system. Furthermore,
numerical results revealed that the proposed model demonstrated high accuracy when
compared to the experimental data.
The objective of this study was to optimize the extraction of oil from pre-dried roselle seeds using response surface methodology (RSM). We also determined the oxidative stability of oil extracted from oven and freeze-dried roselle seed in terms of iodine value (IV), free fatty acid (FFA) value, peroxide value (PV), P-anisidine and total oxidation values (TOTOX value). The RSM was designated based on the central composite design with the usage of three optimum parameters ranged from 8 to 16 g of sample weight, 250-350 mL of solvent volume, and 6-8 h of extraction time. The highest oil yielded from roselle seed using the optimization process was 22.11% with the parameters at sample weight of 14.4 g, solvent volume of 329.70 mL, and extraction time of 7.6 h. Besides, the oil extracted from the oven dried roselle seed had the values of 89.04, 2.11, 4.13, 3.76 and 12.03 for IV, FFA, PV, P-anisidine, and TOTOX values, respectively. While for the oil extracted from freeze-dried roselle seed showed IV of 90.31, FFA of 1.64, PV of 2.47, P-anisidine value of 3.48, and TOTOX value of 8.42. PV and TOTOX values showed significant differences whereas; IV, FFA, and P-anisidine values showed no significant differences between the oven and freeze-dried roselle seed oils.
In this work, an electrochemical method for detection of trace amount of aluminium (Al3+), a heavy metal ion, based on a bare gold electrode (AuE) was developed. Current responses of the AuE under various type of electrolytes, redox indicators, pH, scan rate and accumulation time were investigated using cyclic voltammetry (CV) method to obtain the optimum conditions for Al3+ detection. The sensing properties of the AuE towards the target ion with different concentrations were investigated using differential pulse voltammetry (DPV) method. From the CV results, the optimal conditions for the detection of Al3+ were Tris-HCl buffer (0.1 M, pH 2) supported by 5 mM Prussian blue with scan rate and accumulation time respectively of 100 mVs−1 and 15 s. Under the optimum conditions, the DPV method was detected with different concentrations of aluminium ion ranging from 0.2 to 1.0 ppm resulted in a good linear regression r² = 0.9806. This result suggests that the optimisation of the basic parameters in electrochemical detection using AuE is crucial before further modification of the Au-electrode to improve the sensitivity and selectivity especially for the low concentration of ion detection. The developed method has a great potential for rapid detection of heavy metal ion (Al3+) in drinking water samples.
Over the past decade, research involving immunometabolism, has been gaining much interest. The immune cell re-sponses of an individual may be influenced by metabolites released by the host or derived from the microbiota. How-ever, the immune response of an individual may vary depending on the health condition of an individual. During infection, the metabolic processes derived from the infectious diseases can effect the function of immune cells and thus determine the response or survival of the host during infection. Immunometabolism also has a role in tumor development although the mechanism of how tumor cells influence immune cell function is not well understood. Among the major meatbolic pathways that have been studied in immune cells include glycolysis, the tricarboxylic acid cycle, the pentose phosphate pathway, fatty acid oxidation, fatty acid synthesis and amino acid metabolism. Understanding the tight connection between metabolomics and immunity in health and disease will be crucial as this could lead to therapeutic interventions or in developing metabolomic biomarkers in immunology.
A systematic study on the FeCl3-induced oxidation of 1,2-diarylalkenes was carried out with the focus on the variation of product type as a function of aromatic substitution, as well as to compare the reactivity of stilbene cation radicals generated via Fe(III) oxidation with those generated by anodic oxidation. The aromatic substituents were found to fall into three main categories, namely those that give rise to tetralins and/or dehydrotetralins, those that give products possessing pallidol and ampelopsin F-type carbon skeletons, and last, those that give rise to trimeric products, indanes, and dehydrotetralins/tetralins. The latter are those stilbenes with a para-methoxy substituent in one ring and a para- or meta-EWG (CF3, NO2, Cl, F) in the other, and represent the most prominent departure when compared with the behavior of the same stilbenes under the conditions of anodic oxidation. Reaction pathways to rationalize the formation of the different products are presented.
The present work focuses on the development of cellulose nanofibrils (CNF) film that derived from sustainable biomass resources, which potentially to work as bio-based conductive membranes that assembled into supercapacitors. The chemically purified cellulose was isolated from different parts of coconut (coconut shell and its husk) and further subjected to 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation for CNF preparation. Physicochemical properties of prepared CNFs were studied in terms of chemical characteristics & crystallinity, surface functionalities, surface morphology, and thermal properties. Both coconut shell-derived CNF and coconut husk-derived CNF fulfilled with nanocellulose's characteristics with fibres width ranged of 70-120 nm and 150-330 nm, respectively. CNF films were further prepared by solvent casting method to measure the modulus elasticity, piezoelectric and dielectric properties of the films. Mechanical study indicated that coconut shell-derived CNF film showed a higher value of elastic modulus than the coconut husk-derived CNF film, which was 8.39 GPa and 5.36 GPa, respectively. The effectiveness of electrical aspects for CNF films are well correlated with the crystallinity and thermal properties, associated with it's composition of different coconut's part.
We present an electrochemical long period fiber grating (LPFG) sensor for electroactive species with an optically transparent electrode. The sensor was fabricated by coating indium tin oxide onto the surface of LPFG using a polygonal barrel-sputtering method. LPFG was produced by an electric arc-induced technique. The sensing is based on change in the detection of electron density on the electrode surface during potential application and its reduction by electrochemical redox of analytes. Four typical electroactive species of methylene blue, hexaammineruthenium(III), ferrocyanide, and ferrocenedimethanol were used to investigate the sensor performance. The concentrations of analytes were determined by the modulation of the potential as the change in transmittance around the resonance band of LPFG. The sensitivity of the sensor, particularly to methylene blue, was high, and the sensor responded to a wide concentration range of 0.001 mM to 1 mM.
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.
Pharmaceutical delivery systems are developed to improve the physicochemical properties of therapeutic compounds. Emulsions are one of these drug delivering systems formulated using water, oils and lipids as main ingredients. Extensive data are usually generated on the physical and chemical characteristics of these oil-in-water and lipid emulsions. However, the oxidative tendency of emulsions is often overlooked. Oxidation impacts the overall quality and safety of these pharmaceutical emulsions. Additionally, introducing oxidatively unstable emulsions into biological systems further promotes oxidation in situ. Products of these reactions then continue to pose serious harm to cells and fuel other physiological oxidation reactions. Consequently, the increase of oxidation products leads to oxidative damage to biological systems. Thus, emulsions with lower lipid peroxidation are more stable and will reduce the negative effects of oxidation in situ. Preventive measures during the formulation of emulsions are important. Many naturally occurring and cost effective substances possess low oxidation tendencies and confer oxidative protection when used in emulsions. Additionally, certain preparatory methods should be employed to reduce or better control lipid peroxidation. Finally, emulsions must be evaluated for their oxidation susceptibility using the various techniques available. Careful attention to the preparation of emulsions and assessment of their oxidative stability will help produce safer emulsions without compromising efficacy.
This study investigates the potential of using small amounts of ionic liquids (IL) to enhance ultrasound-assisted extraction of lipids content from green microalgae. Three imidazolium-based ILs (butyl, octyl and dodecyl), each of them with two anions (bromide and acetate) were tested as additives. Viscosity and surface tension of the ILs aqueous mixtures were analyzed to determine the influence of ILs' anions and alkyl chain length, whereas KI dosimetry experiments were used as an indicator of radicals formation. A key finding suggests that the small addition of ILs improves the ultrasonication either by enhancing the viscosity and reducing the water surface tension, leading to a more powerful acoustic cavitation process or by increasing HO° production likely to oxidize the microalgae cells membranes, and consequently disrupting them on a more efficient manner. KI dosimetry also revealed that long ILs alkyl chain is detrimental. This experimental observation is confirmed thus strengthened as the yield of extracted lipids from green microalgae has shown an incremental trend when the IL concentration also increased. These hypotheses are currently under investigation to spot detailed impact of ILs on cavitation process.
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.
Glycerol electro-oxidation offers a green route to produce the high value added chemicals. Here in, we report the glycerol electro-oxidation over a series of multi walled carbon nano tubes supported monometallic (Pt/CNT and Pd/CNT) and bimetallic (Pt-Pd/CNT) catalysts in alkaline medium. The cyclic voltammetry, linear sweep voltammetry and chronoamperometry measurements were used to evaluate the activity and stability of the catalysts. The Pt-Pd/CNT electrocatalyst exhibited the highest activity in terms of higher current density (129.25 A/m²) and electrochemical surface area (382 m²/g). The glycerol electro-oxidation products formed at a potential of 0.013 V were analyzed systematically by high performance liquid chromatography. Overall, six compounds were found including mesoxalic acid, 1,3-dihydroxyacetone, glyceraldehyde, glyceric acid, tartronic acid and oxalic acid. A highest mesoxalic acid selectivity of 86.42% was obtained for Pt-Pd/CNT catalyst while a maximum tartronic acid selectivity of 50.17% and 46.02% was achieved for Pd/CNT and Pt/CNT respectively. It was found that the introduction of Pd into Pt/CNT lattice facilitated the formation of C3 products in terms of maximum selectivity achieved (86.42%) while the monometallic catalysts (Pd/CNT and Pt/CNT) showed a poor performance in comparison to their counterpart.
Recently, microbial-based iron reduction has been considered as a viable alternative to typical chemical-based treatments. The iron reduction is an important process in kaolin refining, where iron-bearing impurities in kaolin clay affects the whiteness, refractory properties, and its commercial value. In recent years, Gram-negative bacteria has been in the center stage of iron reduction research, whereas little is known about the potential use of Gram-positive bacteria to refine kaolin clay. In this study, we investigated the ferric reducing capabilities of five microbes by manipulating the microbial growth conditions. Out of the five, we discovered that Bacillus cereus and Staphylococcus aureus outperformed the other microbes under nitrogen-rich media. Through the biochemical changes and the microbial behavior, we mapped the hypothetical pathway leading to the iron reduction cellular properties, and found that the iron reduction properties of these Gram-positive bacteria rely heavily on the media composition. The media composition results in increased basification of the media that is a prerequisite for the cellular reduction of ferric ions. Further, these changes impact the formation of biofilm, suggesting that the cellular interaction for the iron(III)oxide reduction is not solely reliant on the formation of biofilms. This article reveals the potential development of Gram-positive microbes in facilitating the microbial-based removal of metal contaminants from clays or ores. Further studies to elucidate the corresponding pathways would be crucial for the further development of the field.
Synthetic antioxidants are added to food in the powdered form to preserve it. However these compounds posed serious health concern since they have been associated with causing cancer. Thus using fresh herbs with antioxidant activities would be good alternative. The objectives of this study were to evaluate and compare the total phenolic contents and antioxidant activities of both powdered and fresh forms of turmeric leaf, pandan leaf and torch ginger flower. Total phenolic content (TPC) was assayed based on the redox reaction between Folin-Ciocalteu with phenolics in the sample extracts. Antioxidant activity (AA) was assayed using the ß-carotene linoleate model system and the percentage of antioxidant activity was calculated from the values of degradation rate. Scavenging activity (SA) was assayed using the DPPH radical scavenging model system whereby EC50 value was determined from the plotted graph of scavenging activity against the concentration of sample extracts. Analyses revealed that powdered forms of turmeric leaf, pandan leaf and torch ginger flower had higher TPC (2013.09 ± 5.13, 1784.25 ± 7.59 and 1937.42 ± 6.61 mg GAE/100g, respectively) than their respective fresh forms (348.75 ± 1.26, 356.42 ± 1.32 and 211.59 ± 6.29 mg GAE/100g, respectively). Similarly, powdered forms of turmeric leaf, pandan leaf and torch ginger flower possessed better AA (64.31 ± 0.99, 65.09 ± 0.74 and 11.80 ± 0.40 %, respectively) than their respective fresh forms (24.93 ± 0.71, 16.91 ± 0.70 and 1.45 ± 0.10 %, respectively). Powdered forms of turmeric leaf, pandan leaf and torch ginger flower were also better radical scavenger as compared to their respective fresh forms. In conclusion, all samples in their powdered forms have high total phenolic contents, antioxidant and scavenging activities than their respective fresh forms.
Consumption of mushroom has increased remarkably because of their desirable aroma, taste and high nutritional content. This study was undertaken to measure and compare the antioxidant activity, total phenolic content (TPC) and total flavonoid content (TFC) of Agaricus bisporous (white button mushroom) and Agaricus brasiliensis (Brazilian mushroom) in aqueous and 60% ethanol extract. Results showed that button mushroom (21.47 ± 0.48 mg GAE/g of dry weight) had significant higher TPC in aqueous whereas Brazilian mushroom (12.50 ± 0.22 mg GAE/g of dry weight) had significant higher TPC in 60% ethanol (p< 0.05). In terms of TFC, Brazilian mushroom had higher content than button mushroom in both types of solvents. For FRAP assay, Brazilian mushroom had significantly higher total antioxidant activity than the button mushroom in 60% ethanol (p < 0.05) but opposite trend with aqueous. For DPPH radical scavenging activity, Brazilian mushroom (60% ethanol) had the lowest EC50 value, followed by button mushroom (60% ethanol), Brazilian mushroom (aqueous) and button mushroom (aqueous). Pearson correlation test (p < 0.05) showed strong positive correlation between TPC and FRAP assay in both extracts (r = 0.969 for 60% ethanol extract; r = 0.973 for aqueous extract). For TFC, there was a strong positive, correlation with FRAP assay (r = 0.985) in aqueous extract. In conclusion, high antioxidant activity in ethanol extract of mushrooms due to presence of phenolic content can potentially be used as a source of natural antioxidants.