The work described in this study aimed to express CYP2C8 wild-type and mutant proteins in bacterial expression system and to use the expressed proteins to investigate the structural and functional consequences of a reported allele CYP2C8(*)4 (carrying Ile264Met substitution) on protein activity. Ile264 was replaced by three different amino acids resulting in three mutant constructs, 2C8I264M, 2C8I264R and 2C8I264D. The presence of isoleucine at position 264 in CYP2C8 was found to be important for proper haem insertion and protein folding; whereas bulkier or charged residues were highly disruptive resulting in inactive proteins with minimum spectral and catalytic activities. This was evidenced from the low levels of Soret peak at 450 nm and negligible levels of tolbutamide methylhydroxylase activity. Kinetic study using paclitaxel indicated that all three mutants exhibited only 9.7 to 35.4% of the activity level observed in the wild-type. In addition, the mutants were more sensitive to proteinase K digestion, indicating a possible alteration of conformation. The combined effects of protein instability and compromised catalytic activity resulted in defective CYP2C8 protein which may have clinical implications in carriers of CYP2C8*4, particularly in terms of their capacity to clear potent drugs and their susceptibility to adverse drug reactions.
Recent bioinspired efforts of designing novel nanoenzyme-based electrocatalysts are driven by the urgency of making bioelectrofuels more affordable and efficient. Unlike natural enzymes, nanoenzyme-modified electrodes with large surface areas enclose numerous biomimicking active sites to facilitate enhanced microbial growth followed by increased reactant-to-bioelectrofuel conversion.
In purine metabolism, the xanthine oxidoreductase enzyme converts hypoxanthine (HXN) to xanthine (XN) and XN to uric acid (UA). This leads to the deposition of UA crystals in several parts of the body and the serum UA level might be associated with various multifunctional disorders. The dietary intake of caffeine (CF) and ascorbic acid (AA) decreases the UA level in the serum, which leads to cellular damage. Hence, it is highly needed to monitor the UA level in the presence of AA, XN, HXN, and CF and vice versa. Considering this sequence of complications, the present paper reports the fabrication of an electrochemical sensor using low-cost N-doped carbon dots (CDs) for the selective and simultaneous determination of UA in the presence of AA, XN, HXN, and CF at the physiological pH. The colloidal solution of CDs was prepared by the pyrolysis of asparagine and fabricated on a GC electrode by cycling the potential from -0.20 to +1.2 V in a solution containing CDs and 0.01 M H2SO4. Here, the surface -NH2 functionalities of CDs were used to make a thin film of CDs on the GC electrode. FT-IR spectroscopy confirmed the involvement of the -NH2 group in the formation of the CD film. HR-TEM analysis depicts that the formed CDs showed spherical particles with a size of 1.67 nm and SEM analysis exhibits the 89 nm CD film on the GC electrode surface. The fabricated CD film was successfully used for the sensitive and selective determination of UA. The determination of UA was achieved selectively in a mixture consisting of AA, XN, HXN, and CF with 50-fold high concentration. The CDs-film fabricated electrode has several benefits over the bare electrode: (i) well-resolved oxidation peaks for five analytes, (ii) boosted sensitivity, (iii) shifted oxidation as well as on-set potentials toward less positive potentials, and (iv) high stability. The practical utility of the present sensor was tested by simultaneously determining the multifactorial disorders-causing agents in human fluids. The electrocatalyst developed in the present study is sustainable and can be used for multiple analyses; besides, the electrochemical method used for the fabrication of the CD film is environmentally benign.
A novel samarium-doped spherical-like ZnO hierarchical nanostructure (Sm/ZnO) was synthesized via a facile and surfactant-free chemical solution route. The as-synthesized products were characterized by X-ray diffraction, Brunauer-Emmett-Teller surface area analysis, field emission scanning electron microscopy together with an energy dispersion X-ray spectrum analysis, transmission electron microscopy, UV-visible diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The results revealed that Sm ion was successfully doped into ZnO. It was also observed that the Sm doping increased the visible light absorption ability of Sm/ZnO and a red shift for Sm/ZnO appeared when compared to pure ZnO. The photocatalytic studies revealed that the Sm/ZnO exhibited excellent photocatalytic degradation of 2,4-dichlorophenol (2,4-DCP) compared with the pure ZnO and commercial TiO2 under visible light irradiation. The photocatalytic enhancement of Sm/ZnO products was attributed to their high charge separation efficiency and ·OH generation ability as evidenced by the photoluminescence spectra. The photocatalytic investigation also showed that various parameters exerted their individual influence on the degradation rate of 2,4-DCP. By using a certain of radical scavengers, ·OH was determined to play a pivotal role for the 2,4-DCP degradation. Moreover, the Sm/ZnO could be easily separated and reused, indicating great potential for practical applications in environmental cleanup.
A kinetic study on the aqueous cleavage of N-(2-methoxyphenyl)phthalimide (1) and N-(2-hydroxyphenyl)phthalimide (2), under the buffers of N-methylmorpholine, reveals the equilibrium presence of monocationic amide (Ctam) formed due to nucleophilic reactions of N-methylmorpholine with 1 and 2. Pseudo-first-order rate constants for the reactions of water and HO- with Ctam (formed through nucleophilic reaction of N-methylmorpholine with 1) are 4.60 x 10(-5) s-1 and 47.9 M-1 s-1, respectively. But the cleavage of Ctam, formed through nucleophilic reaction of N-methylmorpholine with 2, involves intramolecular general base (2'-O- group of Ctam)-assisted water attack at carbonyl carbon of cationic amide group of Ctam in or before the rate-determining step.
The production of lignin from empty fruit bunch (EFB) has been carried out using liquefaction method with 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid (IL), in presence of sulfuric acid (H2SO4) as a catalyst. Response surface methodology (RSM) based on a factorial Central Composite Design (CCD) was employed to identify the optimum condition for lignin yield. The result indicated that the second order model was adequate for all the independent variables on the response with R(2)=0.8609. The optimum temperature, time, ionic liquid to EFB ratio, and catalyst concentration were 150.5 °C, 151 min, 3:1 wt/wt and 4.73 wt%, respectively for lignin yield=26.6%. The presence of lignin liquefied product was confirmed by UV-Vis and FTIR analysis. It was also demonstrated lignin extraction from lignocellulosic using recycled IL gave sufficient performance.
In this paper, we report about chemically interaction between Pt Subnano-Clusters on Graphene Nano Sheets (GNS). The aim of this research is to clarify the size effect of Pt clusters on Pt 1-7 wt.%/GNS. This research is an experimental laboratory research. GNS was synthesized by using modified Hummer's method and 1-7 wt.% Pt/GNS were prepared with impregnation method. Then, they were analyzed with TG/DTA, XRD, TEM and XPS, respectively. The results show that Pt clusters are well deposited on GNS (TG/DTA and TEM data). Those data also are consistent with XRD data. The weak and broad peaks appear at 2θ = 39°, indicating Pt metal exists on GNS. The state of Pt is confirmed by using XPS. The appearance of Pt 4f. peaks proves that Pt metal is chemical interaction on GNS. The size of Pt clusters may affect the chemically properties of Pt/GNS catalysts.
The first purification of the Mo-reducing enzyme from Serratia sp. strain DRY5 that is responsible for molybdenum reduction to molybdenum blue in the bacterium is reported. The monomeric enzyme has an apparent molecular weight of 105 kDalton. The isoelectric point of this enzyme was 7.55. The enzyme has an optimum pH of 6.0 and maximum activity between 25 and 35°C. The Mo-reducing enzyme was extremely sensitive to temperatures above 50°C (between 54 and 70°C). A plot of initial rates against substrate concentrations at 15 mM 12-MP registered a V max for NADH at 12.0 nmole Mo blue/min/mg protein. The apparent K m for NADH was 0.79 mM. At 5 mM NADH, the apparent V max and apparent K m values for 12-MP of 12.05 nmole/min/mg protein and 3.87 mM, respectively, were obtained. The catalytic efficiency (k cat/K m ) of the Mo-reducing enzyme was 5.47 M(-1) s(-1). The purification of this enzyme could probably help to solve the phenomenon of molybdenum reduction to molybdenum blue first reported in 1896 and would be useful for the understanding of the underlying mechanism in molybdenum bioremediation involving bioreduction.
Catalytic depolymerization of mannan composition of palm kernel cake (PKC) by mannanase was optimized to enhance the release of mannan-derived monomeric sugars for further application in acetone-butanol-ethanol (ABE) fermentation. Efficiency of enzymatic hydrolysis of PKC was studied by evaluating effects of PKC concentration, mannanase loading, hydrolysis pH value, reaction temperature and hydrolysis time on production of fermentable sugars using one-way analysis of variance (ANOVA). The ANOVA results revealed that all factors studied had highly significant effects on total sugar liberated (P<0.01). The optimum conditions for PKC hydrolysis were 20% (w/v) PKC concentration, 5% (w/w) mannanase loading, hydrolysis pH 4.5, 45°C temperature and 72h hydrolysis time. Enzymatic experiments in optimum conditions revealed total fermentable sugars of 71.54±2.54g/L were produced including 67.47±2.51g/L mannose and 2.94±0.03g/L glucose. ABE fermentation of sugar hydrolysate by Clostridium saccharoperbutylacetonicum N1-4 resulted in 3.27±1.003g/L biobutanol.
In recent years, environmental problems caused by the use of fossil fuels and the depletion of petroleum reserves have driven the world to adopt biodiesel as an alternative energy source to replace conventional petroleum-derived fuels because of biodiesel's clean and renewable nature. Biodiesel is conventionally produced in homogeneous, heterogeneous, and enzymatic catalysed processes, as well as by supercritical technology. All of these processes have their own limitations, such as wastewater generation and high energy consumption. In this context, the membrane reactor appears to be the perfect candidate to produce biodiesel because of its ability to overcome the limitations encountered by conventional production methods. Thus, the aim of this paper is to review the production of biodiesel with a membrane reactor by examining the fundamental concepts of the membrane reactor, its operating principles and the combination of membrane and catalyst in the catalytic membrane. In addition, the potential of functionalised carbon nanotubes to serve as catalysts while being incorporated into the membrane for transesterification is discussed. Furthermore, this paper will also discuss the effects of process parameters for transesterification in a membrane reactor and the advantages offered by membrane reactors for biodiesel production. This discussion is followed by some limitations faced in membrane technology. Nevertheless, based on the findings presented in this review, it is clear that the membrane reactor has the potential to be a breakthrough technology for the biodiesel industry.
Recently, the discharge of flue gas has become a global issue due to the rapid development in industrial and anthropogenic activities. Various dry and wet treatment approaches including conventional and hybrid hybrid wet scrubbing have been employing to combat against these toxic exhaust emissions. However, certain issues i.e., large energy consumption, generation of secondary pollutants, low regeneration of scrubbing liquid and high efficieny are hindering their practical applications on industrial level. Despite this, the hybrid wet scrubbing technique (advanced oxidation, ionic-liquids and solid engineered interface hybrid materials based techniques) is gaining great attention because of its low installation costs, simultaneous removal of multi-air pollutants and low energy requirements. However, the lack of understanding about the basic principles and fundamental requirements are great hurdles for its commercial scale application, which is aim of this review article. This review article highlights the recent developments, minimization of GHG, sustainable improvements for the regeneration of used catalyst via green and electron rich donors. It explains, various hybrid wet scrubbing techniques can perform well under mild condition with possible improvements such as development of stable, heterogeneous catalysts, fast and in-situ regeneration for large scale applications. Finally, it discussed recovery of resources i.e., N2O, NH3 and N2, the key challenges about several competitive side products and loss of catalytic activity over time to treat toxic gases via feasible solutions by hybrid wet scrubbing techniques.
Photocatalysis utilizing semiconductors offer a cost-effective and promising solution for the removal of pollutants. MXene and perovskites, which possess desirable properties such as a suitable bandgap, stability, and affordability, have emerged as a highly promising material for photocatalytic activity. However, the efficiency of MXene and perovskites is limited by their fast recombination rates and inadequate light harvesting abilities. Nonetheless, several additional modifications have been shown to enhance their performance, thereby warranting further exploration. This study delves into the fundamental principles of reactive species for MXene-perovskites. Various methods of modification of MXene-perovskite-based photocatalysts, including Schottky junction, Z-scheme and S-scheme are analyzed with regard to their operation, differences, identification techniques and reusability. The assemblance of heterojunctions is demonstrated to enhance photocatalytic activity while also suppressing charge carrier recombination. Furthermore, the separation of photocatalysts through magnetic-based methods is also investigated. Consequently, MXene-perovskite-based photocatalysts are seen as an exciting emerging technology that necessitates further research and development.
Burkholderia pseudomallei is a highly versatile pathogen with ~25% of its genome annotated to encode hypothetical proteins. One such hypothetical protein, BPSL1038, is conserved across seven bacterial genera and 654 Burkholderia spp. Here, we present a 1.55 Å resolution crystal structure of BPSL1038. The overall structure folded into a modified βαββαβα ferredoxin fold similar to known Cas2 nucleases. The Cas2 equivalent catalytic aspartate (D11) pairs are conserved in BPSL1038 although B. pseudomallei has no known CRISPR associated system. Functional analysis revealed that BPSL1038 is a nuclease with endonuclease activity towards double-stranded DNA. The DNase activity is divalent ion independent and optimum at pH 6. The concentration of monovalent ions (Na+ and K+) is crucial for nuclease activity. An active site with a unique D11(X20)SST motif was identified and proposed for BPSL1038 and its orthologs. Structure modelling indicates the catalytic role of the D11(X20)SST motif and that the arginine residues R10 and R30 may interact with the nucleic acid backbone. The structural similarity of BPSL1038 to Cas2 proteins suggests that BPSL1038 may represent a sub-family of nucleases that share a common ancestor with Cas2.
Nickel (Ni), cobalt (Co), and zinc (Zn) loaded on fibrous silica KCC-1 was investigated for CO2 methanation reactions. Ni/KCC-1 exhibits the highest catalyst performance with a CH4 formation rate of 33.02 × 10-2 molCH4 molmetal-1 s-1, 1.77 times higher than that of Co/KCC-1 followed by Zn/KCC-1 and finally the parent KCC-1. A pyrrole adsorption FTIR study reveals shifting of perturbed N-H stretching decreasing slightly with the addition of metal oxide, suggesting that the basic sites of catalyst were inaccessible due to metal oxide deposition. The strengths of basicity were found to follow sthe equence KCC-1, Ni/KCC-1, Zn/KCC-1, and Co/KCC-1. The data were supported by N2 adsorption desorption analysis, where Co/KCC-1 displayed the greatest reduction in total surface area whereas Ni/KCC-1 displayed the least reduction. The elucidation of difference mechanism pathways has also been studied by in situ IR spectroscopy studies to determine the role of different metal oxides in CO2 methanation. It was discovered that Ni/KCC-1 and Co/KCC-1 follow a dissociative mechanism of CO2 methanation in which the CO2 molecule was dissociated on the surface of the metal oxide before migration onto the catalyst surface. This was confirmed by the evolution of a peak corresponding to carbonyl species (COads) on a metal oxide surface in FTIR spectra. Zn/KCC-1, on the other hand, showed no such peak, indicating associative methanation pathways where a hydrogen molecule interacts with an O atom in CO2 to form COads and OH. These results offers a better understanding for catalytic studies, particularly in the field of CO2 recycling.
In this paper, the kinetics of palm oil ethanolysis with various models have been investigated in a temperature range of 25-55 °C. The highest yield was achieved when the conversion to ethyl ester was 97.5±0.5% in the stated temperature range, using ethanol:oil molar ratio of 12:1, and 1.0 wt.% sodium ethoxide. The level of conformity of the reaction with reversible second order, irreversible second order and first order kinetic models were evaluated by means of the R(2) values of the linear curves. The ethanolysis showed the best conformity with irreversible second order kinetic model with 92-98% level of confidence. The reaction rate constants were within 0.018-0.088 dm(3)/mol min and the activation energy of the reaction was 42.36 kJ/mol.
Cobalt oxide nanocubes incorporated with reduced graphene oxide (rGO-Co3O4) was prepared by using simple one-step hydrothermal route. Crystallinity and structural characteristics of the nanocomposite were analyzed and confirmed using X-ray diffraction (XRD) and Raman analysis, respectively. The cubical shape of the Co3O4 nanostructures and the distribution of Co3O4 nanocubes on the surface of rGO sheets were identified through field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) mapping analysis, respectively. Raman spectra depicted the presence of D and G bands for GO and rGO with different ID/IG values and thus confirmed the reduction of GO into rGO. The electrochemical study reflects that the rGO-Co3O4 nanocomposite shows good electrocatalytic activity in oxidation of depression biomarker serotonin (5-HT) in phosphate buffer (pH 7.2). The detection of 5-HT was carried out by using rGO-Co3O4 nanocomposite modified glassy carbon electrode under dynamic condition using amperometry technique with a linear range of 1-10 μM. The limit of detection and limit of quantification were calculated and found to be 1.128 and 3.760 μM, respectively with a sensitivity value of 0.133 μΑ·μM-1. The sensor showed selectivity in the presence of different interferent species such as ascorbic acid, dopamine and uric acid.
Air gasification of the Wood-Plastic Composite (WPC) was performed over Ni-loaded HZSM-5 catalysts to generate H2-rich gas. Increasing SiO2/Al2O3 ratio (SAR) of HZSM-5 adversely affected catalytic activity, where the highest gas yield (51.38 wt%) and H2 selectivity (27.01 vol%) were acquired using 20 %Ni/HZSM-5(30) than those produced over 20 %Ni/HZSM-5(80) and 20 %Ni/HZSM-5(280). Reducing SAR was also favorably conducive to increasing the acyclic at the expense of cyclic compounds in oil products. These phenomena are attributed to enhanced acid strength and Ni dispersion of 20 %Ni/HZSM-5(30) catalyst. Moreover, catalytic activity in the terms of gas yield and H2 selectivity enhanced with growing Ni loading to 20 %. Also, the addition of promoters (Cu and Ca) to 20 %Ni/HZSM-5(30) boosted the catalytic efficiency for H2-rich gas generation. Raising temperature indicated a positive relevance with the gas yield and H2 selectivity. WPC valorization via gasification technology would be an outstanding outlook in the terms of a waste-to-energy platform.
Growing concerns of water pollution by dye pollutants from the textile industry has led to vast research interest to find green solutions to address this issue. In recent years, heterogeneous photocatalysis has harvested tremendous attention from researchers due to its powerful potential applications in tackling many important energy and environmental challenges at a global level. To fully utilise the broad spectrum of solar energy has been a common aim in the photocatalyst industry. This study focuses on the development of an efficient, highly thermal and chemical stable, environmentally friendly and metal-free graphitic carbon nitride (g-C3N4) to overcome the problem of fast charge recombination which hinders photocatalytic performances. Nitrogen-doped carbon quantum dots (NCQDs) known for its high electronic and optical functionality properties is believed to achieve photocatalytic enhancement by efficient charge separation through forming heterogeneous interfaces. Hence, the current work focuses on the hybridisation of NCQDs and g-C3N4 to produce a composite photocatalyst for methylene blue (MB) degradation under LED light irradiation. The optimal hybridisation method and the mass loading required for maximum attainable MB degradation were systematically investigated. The optimum photocatalyst, 1 wt% NCQD/g-C3N4 composite was shown to exhibit a 2.6-fold increase in photocatalytic activity over bare g-C3N4. Moreover, the optimum sample displayed excellent stability and durability after three consecutive degradation cycles, retaining 91.2% of its original efficiency. Scavenging tests were also performed where reactive species, photon-hole (h+) was identified as the primary active species initiating the pollutant degradation mechanism. The findings of this study successfully shed light on the hybridisation methods of NCQDs which improve existing g-C3N4 photocatalyst systems for environmental remediation by utilising solar energy.
The Prins cyclization of styrene (SE) with paraformaldehyde (PFCHO) was conducted with mesoporous ZnAlMCM-41 catalysts for the synthesis of 4-phenyl-1,3-dioxane (4-PDO) using a liquid phase heterogeneous catalytic method. For a comparison study, the Prins cyclization reaction was also conducted over different nanoporous catalysts, e.g. mesoporous solid acid catalysts, AlMCM-41(21) and ZnMCM-41(21), and microporous catalysts, USY, Hβ, HZSM-5, and H-mordenite. The recyclable mesoporous ZnAlMCM-41 catalysts were reused in this reaction to evaluate their catalytic stabilities. Since ZnAlMCM-41(75) has higher catalytic activity than other solid acid catalysts, washed ZnAlMCM-41(75)/W-ZnAlMCM-41(75) was prepared using an efficient chemical treatment method and used with various reaction parameters to find an optimal parameter for the highly selective synthesis of 4-PDO. W-ZnAlMCM-41(75) was also used in the Prins cyclization of olefins with PFCHO and formalin (FN, 37% aqueous solution of formaldehyde (FCHO)) under different reaction conditions to obtain 1,3-dioxanes, which are widely used as solvents or intermediates in organic synthesis. Based on the nature of catalysts used under different reaction conditions, a reasonable plausible reaction mechanism for the Prins cyclization of SE with PFCHO is proposed. Notably, it can be seen from the catalytic results of all catalysts that the W-ZnAlMCM-41(75) catalyst has higher 4-PDO selectivity with exceptional catalytic activity than other microporous and mesoporous catalysts.
5-Hydroxymethylfurfural (HMF) has been identified as a promising biomass-derived platform chemical. In this study, one pot production of HMF was studied in ionic liquid (IL) under probe sonication technique. Compared with the conventional heating technique, the use of probe ultrasonic irradiation reduced the reaction time from hours to minutes. Glucose, cellulose and local bamboo, treated with ultrasonic, produced HMF in the yields of 43%, 31% and 13% respectively, within less than 10min. The influence of various parameters such as acoustic power, reaction time, catalysts and glucose loading were studied. About 40% HMF yield at glucose conversion above 90% could be obtained with 2% of catalyst in 3min. Negligible amount of soluble by-product was detected, and humin formation could be controlled by adjusting the different process parameters. Upon extraction of HMF, the mixture of ionic liquid and catalyst could be reused and exhibited no significant reduction of HMF yield over five successive runs. The purity of regenerated [C4C1im]Cl and HMF was confirmed by NMR spectroscopy, indicating neither changes in the chemical structure nor presence of any major contaminants during the conversion under ultrasonic treatment. 13C NMR suggests that [C4C1im]Cl/CrCl3 catalyses mutarotation of α-glucopyranose to β-glucopyranose leading to isomerization and finally conversion to HMF. The experimental results demonstrate that the use of probe sonication technique for conversion to HMF provides a positive process benefit.