Diacylglycerol (DAG) and monoacylglycerol (MAG) are two natural occurring minor components found in most edible fats and oils. These compounds have gained increasing market demand owing to their unique physicochemical properties. Enzymatic glycerolysis in solvent-free system might be a promising approach in producing DAG and MAG-enriched oil. Understanding on glycerolysis mechanism is therefore of great importance for process simulation and optimization. In this study, a commercial immobilized lipase (Lipozyme TL IM) was used to catalyze the glycerolysis reaction. The kinetics of enzymatic glycerolysis reaction between triacylglycerol (TAG) and glycerol (G) were modeled using rate equation with unsteady-state assumption. Ternary complex, ping-pong bi-bi and complex ping-pong bi-bi models were proposed and compared in this study. The reaction rate constants were determined using non-linear regression and sum of square errors (SSE) were minimized. Present work revealed satisfactory agreement between experimental data and the result generated by complex ping-pong bi-bi model as compared to other models. The proposed kinetic model would facilitate understanding on enzymatic glycerolysis for DAG and MAG production and design optimization of a pilot-scale reactor.
In this research work, carbon nanofibers (CNFs) were synthesized on honeycomb monolith substrates using injection chemical vapor deposition (ICVD) technique. The effect of various wash-coated materials and catalyst promoter on the growth rate of CNFs on monolith substrates were examined. The characteristics of the synthesized CNFs-coated monolith composites were examined using Raman spectroscopy, Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and Transmission electron microscopy (TEM) techniques. According to the textural characterization study, the specific surface area and pore volume of CNFs-coated monolith composites were significantly improved as compared to bare monolith which might be attributed to the growth of highly pure and aligned CNFs over monolith substrate. Besides that, the synthesized CNFs-coated monolith possessed extremely well thermal stability up to the temperature of 550 °C which was corresponded to the strong attachment of highly graphitized CNFs over monolith substrates.
A cost-effective, facile hydrothermal approach was made for the synthesis of SnO2/graphene (Gr) nano-composites. XRD diffraction spectra clearly confirmed the presence of tetragonal crystal system of SnO2 which was maintaining its structure in both pure and composite materials' matrix. The stretching and bending vibrations of the functional groups were analyzed using FTIR analysis. FESEM images illustrated the surface morphology and the texture of the synthesized sample. HRTEM images confirmed the deposition of SnO2 nanoparticles over the surface of graphene nano-sheets. Raman Spectroscopic analysis was carried out to confirm the in-plane blending of SnO2 and graphene inside the composite matrix. The photocatalytic performance of the synthesized sample under UV irradiation using methylene blue dye was observed. Incorporation of grapheme into the SnO2 sample had increased the photocatalytic activity compared with the pure SnO2 sample. The electrochemical property of the synthesized sample was evaluated.
We present a biogenic method for the synthesis of palladium nanoparticle (PdNP)-modified by reducing graphene oxide sheets (rGO) in a one-pot strategy using Ficus carica fruit juice as the reducing agent. The synthesized material was well characterized by morphological and structural analyses, including, Ultraviolet-Visible spectroscopy (UV-Vis), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and Transmission Electron Microscopy (TEM) and Raman spectroscopy. The results revealed that the PdNP modified GO are spherical in shape and estimated to be a dimension of ~0.16 nm. The PdNP/graphene exhibits a great catalytic activity in Suzuki cross-coupling reactions for the synthesis of biaryl compounds with various substrates under both aqueous and aerobic conditions. The catalyst can be recovered easily and is suitable for repeated use because it retains its original catalytic activity. The PdNP/rGO catalyst synthesized by an eco-friendly protocol was used for the Suzuki coupling reactions. The method offers a mild and effective substitute to the existing methods and may significantly contribute to green chemistry.
Pharmaceutically active compounds from medical plants are attractive as a major source for new drug development. Prenylated stilbenoids with increased lipophilicity are valuable secondary metabolites which possess a wide range of biological activities. So far, many prenylated stilbenoids have been isolated from Morus alba but the enzyme responsible for the crucial prenyl modification remains unknown. In the present study, a stilbenoid-specific prenyltransferase (PT), termed Morus alba oxyresveratrol geranyltransferase (MaOGT), was identified and functionally characterized in vitro. MaOGT recognized oxyresveratrol and geranyl diphosphate (GPP) as natural substrates, and catalyzed oxyresveratrol prenylation. Our results indicated that MaOGT shared common features with other aromatic PTs, e.g. multiple transmembrane regions, conserved functional domains and targeting to plant plastids. This distinct PT represents the first stilbenoid-specific PT accepting GPP as a natural prenyl donor, and could help identify additional functionally varied PTs in moraceous plants. Furthermore, MaOGT might be applied for high-efficiency and large-scale prenylation of oxyresveratrol to produce bioactive compounds for potential therapeutic applications.
The present investigation deals with the development of ethanol-vapour-sensing materials coated with the semiconducting oxide TiO2. Thick films of anatase TiO2 were deposited using the sol-gel dip-coating technique on alumina substrates by conventional alkoxide sol and modified sol added with Degussa P-25 as the sensing medium. It was shown that crystallised TiO2 anatase was obtained at the annealing temperature of 500oC. The fabricated TiO2 sensors exhibited highest sensitivity at the sensing temperature of 350 ºC. Sensitivity towards the ethanol vapour was further increased with UV light effect. The enhancement of the sensitivity of the modified catalytic pellet can be explained by the crystallite of anatase TiO2 and the effect of the photocatalytic of TiO2. The high sensitivity of the TiO2 film deposited with modified sol revealed that the modified sol could be a new alternative in the development of a TiO2 ethanol sensor.
Biocatalytic reaction is a type of reaction which uses enzyme or whole-cell as a (bio)-catalyst to achieve a desired conversion, under controlled conditions in a bioreactor. Temperature produces opposed effects on enzyme activity and stability, and is therefore a key variable in any biocatalytic processes. An exothermic biocatalytic reaction, in a continuous-stirred-tank reactor (CSTR), was analyzed where dynamic equations (non-linear differential equations) could be derived from the Michaelis-Menten and Arrhenius equations, by performing mass and energy balances on the reactor. In this work, the effects of the different parameters such as dilution rate, proportional control constant and dimensionless total enzyme concentration, on the stability of the system, were studied. The stability of the reaction could be analyzed, based on the ODE (ordinary differential equation), solved using the numerical technique in MATLAB® and the analytical investigation using Mathematica.® The numerical analysis can be carried out by considering the hase-plane behaviour and bifurcation diagrams of the dynamic equations, while the analytical analysis using Mathematica® can be undertaken by evaluating the eigenvalues of the system. In order to model the operational stability of biocatalysts, modulation factors need to be considered so that a proper design of bioreactors can be done. Temperature, as a key variable in such bioprocess systems, can be conveniently optimized through the use of appropriate models.
The synthesis of carbon nanotubes (CNTs) using a chemical vapour deposition (CVD) method requires the use of hydrocarbon as the carbon precursor. Among the commonly used hydrocarbons are methane and acetylene, which are both light gas-phase substances. Besides that, other carbon-rich sources, such as carbon monoxide and coal, have also been reportedly used. Nowadays, researches have also been conducted into utilising heavier hydrocarbons and petrochemical products for the production of CNTs, such as kerosene and diesel oil. Therefore, this article reviews the different kind of hydrocarbon sources for CNTs production using a CVD method. The method is used for it allows the decomposition of the carbon-rich source with the aid of a catalyst at a temperature in the range 600-1200°C. This synthesis technique gives an advantage as a high yield and high-quality CNTs can be produced at a relatively low cost process. As compared to other processes for CNTs production such as arc discharge and laser ablation, they may produce high quality CNTs but has a disadvantage for use as large scale synthesis routes.
Membrane-bound fatty acid desaturases perform oxygenated desaturation reactions to insert double bonds within fatty acyl chains in regioselective and stereoselective manners. The Δ9-fatty acid desaturase strictly creates the first double bond between C9 and 10 positions of most saturated substrates. As the three-dimensional structures of the bacterial membrane fatty acid desaturases are not available, relevant information about the enzymes are derived from their amino acid sequences, site-directed mutagenesis and domain swapping in similar membrane-bound desaturases. The cold-tolerantPseudomonassp. AMS8 was found to produce high amount of monounsaturated fatty acids at low temperature. Subsequently, an active Δ9-fatty acid desaturase was isolated and functionally expressed inEscherichia coli. In this paper we report homology modeling and docking studies of a Δ9-fatty acid desaturase from a Cold-tolerantPseudomonassp. AMS8 for the first time to the best of our knowledge. Three dimensional structure of the enzyme was built using MODELLER version 9.18 using a suitable template. The protein model contained the three conserved-histidine residues typical for all membrane-bound desaturase catalytic activity. The structure was subjected to energy minimization and checked for correctness using Ramachandran plots and ERRAT, which showed a good quality model of 91.6 and 65.0%, respectively. The protein model was used to preform MD simulation and docking of palmitic acid using CHARMM36 force field in GROMACS Version 5 and Autodock tool Version 4.2, respectively. The docking simulation with the lowest binding energy, -6.8 kcal/mol had a number of residues in close contact with the docked palmitic acid namely, Ile26, Tyr95, Val179, Gly180, Pro64, Glu203, His34, His206, His71, Arg182, Thr85, Lys98 and His177. Interestingly, among the binding residues are His34, His71 and His206 from the first, second, and third conserved histidine motif, respectively, which constitute the active site of the enzyme. The results obtained are in compliance with thein vivoactivity of the Δ9-fatty acid desaturase on the membrane phospholipids.
A gene encoding a thermotolerant lipase with broad pH was isolated from an Antarctic Pseudomonas strain AMS3. The recombinant lipase AMS3 was purified by single-step purification using affinity chromatography, yielding a purification fold of approximately 1.52 and a recovery of 50%. The molecular weight was approximately ∼60 kDa including the strep and affinity tags. Interestingly, the purified Antarctic AMS3 lipase exhibited broad temperature profile from 10-70 °C and stable over a broad pH range from 5.0 to pH 10.0. Various mono and divalent metal ions increased the activity of the AMS3 lipase, but Ni(2+) decreased its activity. The purified lipase exhibited the highest activity in the presence of sunflower oil. In addition, the enzyme activity in 25% v/v solvents at 50 °C particularly to n-hexane, DMSO and methanol could be useful for catalysis reaction in organic solvent and at broad temperature.
The first enantioselective synthesis of (-)-conolutinine was achieved in 10 steps. The synthesis featured a catalytic asymmetric bromocyclization of tryptamine to forge the tricycle intermediate. Hydration of an alkene catalyzed by Co(acac)2 was also employed as a key step to diastereoselectively introduce the tertiary alcohol moiety. The absolute configuration of (-)-conolutinine was established to be (2S,5aS,8aS,13aR) based on this asymmetric total synthesis.
The syntheses of fourteen unusual o-carboxamido stilbenes by the Heck protocol revealed surprising complexity related to intriguing substituent effects with mechanistic implications. The unexpected cytotoxic and chemopreventive properties also seem to be substituent dependent. For example, although stilbene 15d (with a 4-methoxy substituent) showed cytotoxicity on HT29 colon cancer cells with an IC(50) of 4.9 μM, the 3,4-dimethoxy derivative (15c) is inactive. It is interesting to observe that the 3,5-dimethoxy derivative (15e) showed remarkable chemopreventive activity in WRL-68 fetal hepatocytes, surpassing the gold standard, resveratrol. The resveratrol concentration needed to be 5 times higher than that of 15e to produce comparable elevation of NQO1.
One major source of inter-individual variability in drug pharmacokinetics is genetic polymorphism of the cytochrome P450 (CYP) genes. This study aimed to elucidate the enzyme kinetic and molecular basis for altered activity in three major alleles of CYP2D6, namely CYP2D6*2, CYP2D6*10 and CYP2D6*17. The E. coli-expressed allelic variants were examined using substrate (venlafaxine and 3-cyano-7-ethoxycoumarin[CEC]) and inhibitor (quinidine, fluoxetine, paroxetine, terbinafine) probes in enzyme assays as well as molecular docking. The kinetics data indicated that R296C and S486T mutations in CYP2D6*2 have caused enhanced ligand binding (enhanced intrinsic clearance for venlafaxine and reduced IC50 for quinidine, paroxetine and terbinafine), suggesting morphological changes within the active site cavity that favoured ligand docking and binding. Mutations in CYP2D6*10 and CYP2D6*17 tended to cause deleterious effect on catalysis, with reduced clearance for venlafaxine and CEC. Molecular docking indicated that P34S and T107I, the unique mutations in the alleles, have negatively impacted activity by affecting ligand access and binding due to alteration of the substrate access channel and active site morphology. IC50 values however were quite variable for quinidine, fluoxetine and terbinafine, and a general decrease in IC50 was observed for paroxetine, suggesting ligand-specific altered susceptibility to inhibition in the alleles. This study indicates that CYP2D6 allele selectivity for ligands was not solely governed by changes in the active site architecture induced by the mutations, but that the intrinsic properties of the substrates and inhibitors also played vital role.
Metal nanoparticles prepared by exsolution at the surface of perovskite oxides have been recently shown to enable new dimensions in catalysis and energy conversion and storage technologies owing to their socketed, well-anchored structure. Here we show that contrary to general belief, exsolved particles do not necessarily re-dissolve back into the underlying perovskite upon oxidation. Instead, they may remain pinned to their initial locations, allowing one to subject them to further chemical transformations to alter their composition, structure and functionality dramatically, while preserving their initial spatial arrangement. We refer to this concept as chemistry at a point and illustrate it by tracking individual nanoparticles throughout various chemical transformations. We demonstrate its remarkable practical utility by preparing a nanostructured earth abundant metal catalyst which rivals platinum on a weight basis over hundreds of hours of operation. Our concept enables the design of compositionally diverse confined oxide particles with superior stability and catalytic reactivity.
In recent years, carbon nanotubes have received widespread attention as promising carbon-based nanoelectronic devices. Due to their exceptional physical, chemical, and electrical properties, namely a high surface-to-volume ratio, their enhanced electron transfer properties, and their high thermal conductivity, carbon nanotubes can be used effectively as electrochemical sensors. The integration of carbon nanotubes with a functional group provides a good and solid support for the immobilization of enzymes. The determination of glucose levels using biosensors, particularly in the medical diagnostics and food industries, is gaining mass appeal. Glucose biosensors detect the glucose molecule by catalyzing glucose to gluconic acid and hydrogen peroxide in the presence of oxygen. This action provides high accuracy and a quick detection rate. In this paper, a single-wall carbon nanotube field-effect transistor biosensor for glucose detection is analytically modeled. In the proposed model, the glucose concentration is presented as a function of gate voltage. Subsequently, the proposed model is compared with existing experimental data. A good consensus between the model and the experimental data is reported. The simulated data demonstrate that the analytical model can be employed with an electrochemical glucose sensor to predict the behavior of the sensing mechanism in biosensors.
Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.
The ceaseless increase of pollution cases due to the tremendous consumption of fossil fuels has steered the world towards an environmental crisis and necessitated urgency to curtail noxious sulfur oxide emissions. Since the world is moving toward green chemistry, a fuel desulfurization process driven by clean technology is of paramount significance in the field of environmental remediation. Among the novel desulfurization techniques, the oxidative desulfurization (ODS) process has been intensively studied and is highlighted as the rising star to effectuate sulfur-free fuels due to its mild reaction conditions and remarkable desulfurization performances in the past decade. This critical review emphasizes the latest advances in thermal catalytic ODS and photocatalytic ODS related to the design and synthesis routes of myriad materials. This encompasses the engineering of metal oxides, ionic liquids, deep eutectic solvents, polyoxometalates, metal-organic frameworks, metal-free materials and their hybrids in the customization of advantageous properties in terms of morphology, topography, composition and electronic states. The essential connection between catalyst characteristics and performances in ODS will be critically discussed along with corresponding reaction mechanisms to provide thorough insight for shaping future research directions. The impacts of oxidant type, solvent type, temperature and other pivotal factors on the effectiveness of ODS are outlined. Finally, a summary of confronted challenges and future outlooks in the journey to ODS application is presented.
Titanium dioxide (TiO2) is one of the most widely investigated metal oxides due to its extraordinary surface, electronic and catalytic properties. However, the large band gap of TiO2 and massive recombination of photogenerated electron-hole pairs limit its photocatalytic and photovoltaic efficiency. Therefore, increasing research attention is now being directed towards engineering the surface structure of TiO2 at the most fundamental and atomic level namely morphological control of {001} facets in the range of microscale and nanoscale to fine-tune its physicochemical properties, which could ultimately lead to the optimization of its selectivity and reactivity. The synthesis of {001}-faceted TiO2 is currently one of the most active interdisciplinary research areas and demonstrations of catalytic enhancement are abundant. Modifications such as metal and non-metal doping have also been extensively studied to extend its band gap to the visible light region. This steady progress has demonstrated that TiO2-based composites with {001} facets are playing and will continue to play an indispensable role in the environmental remediation and in the search for clean and renewable energy technologies. This review encompasses the state-of-the-art research activities and latest advancements in the design of highly reactive {001} facet-dominated TiO2via various strategies, including hydrothermal/solvothermal, high temperature gas phase reactions and non-hydrolytic alcoholysis methods. The stabilization of {001} facets using fluorine-containing species and fluorine-free capping agents is also critically discussed in this review. To overcome the large band gap of TiO2 and rapid recombination of photogenerated charge carriers, modifications are carried out to manipulate its electronic band structure, including transition metal doping, noble metal doping, non-metal doping and incorporating graphene as a two-dimensional (2D) catalyst support. The advancements made in these aspects are thoroughly examined, with additional insights related to the charge transfer events for each strategy of the modified-TiO2 composites. Finally, we offer a summary and some invigorating perspectives on the major challenges and new research directions for future exploitation in this emerging frontier, which we hope will advance us to rationally harness the outstanding structural and electronic properties of {001} facets for various environmental and energy-related applications.
Metal-free carbonaceous nanomaterials have witnessed a renaissance of interest due to the surge in the realm of nanotechnology. Among myriads of carbon-based nanostructures with versatile dimensionality, one-dimensional (1D) carbon nanotubes (CNTs) and zero-dimensional (0D) carbon dots (CDs) have grown into a research frontier in the past few decades. With extraordinary mechanical, thermal, electrical and optical properties, CNTs are utilized in transparent displays, quantum wires, field emission transistors, aerospace materials, etc. Although CNTs possess diverse characteristics, their most attractive property is their unique photoluminescence. On the other hand, another growing family of carbonaceous nanomaterials, which is CDs, has drawn much research attention due to its cost-effectiveness, low toxicity, environmental friendliness, fluorescence, luminescence and simplicity to be synthesized and functionalized with surface passivation. Benefiting from these unprecedented properties, CDs have been widely employed in biosensing, bioimaging, nanomedicine, and catalysis. Herein, we have systematically presented the fascinating properties, preparation methods and multitudinous applications of CNTs and CDs (including graphene quantum dots). We will discuss how CNTs and CDs have emerged as auspicious nanomaterials for potential applications, especially in electronics, sensors, bioimaging, wearable devices, batteries, supercapacitors, catalysis and light-emitting diodes (LEDs). Last but not least, this review is concluded with a summary, outlook and invigorating perspectives for future research horizons in this emerging platform of carbonaceous nanomaterials.
As an indispensable energy source, ammonia plays an essential role in agriculture and various industries. Given that the current ammonia production is still dominated by the energy-intensive and high carbon footprint Haber-Bosch process, photocatalytic nitrogen fixation represents a low-energy consuming and sustainable approach to generate ammonia. Heterostructured photocatalysts are hybrid materials composed of semiconductor materials containing interfaces that make full use of the unique superiorities of the constituents and synergistic effects between them. These promising photocatalysts have superior performances and substantial potential in photocatalytic reduction of nitrogen. In this review, a wide spectrum of recently developed heterostructured photocatalysts for nitrogen fixation to ammonia are evaluated. The fundamentals of solar-to-ammonia conversion, basic principles of various heterojunction photocatalysts and modification strategies are systematically reviewed. Finally, a brief summary and perspectives on the ongoing challenges and directions for future development of nitrogen photofixation catalysts are also provided.