The effect of chemical pretreatments using NaOH, H(2)O(2), and Ca(OH)(2) on Empty Palm Fruit Bunches (EPFB) to degrade EPFB lignin before pyrolysis was investigated. Spectrophotometer analysis proved consecutive addition of NaOH and H(2)O(2) decomposed almost 100% of EPFB lignin compared to 44% for the Ca(OH)(2), H(2)O(2) system while NaOH and Ca(OH)(2) used exclusively could not alter lignin much. Next, the pretreated EPFB was catalytically pyrolyzed. Experimental results indicated the phenolic yields over Al-MCM-41 and HZSM-5 catalysts were 90 wt% and 80 wt%, respectively compared to 67 wt% yield for the untreated sample under the same set of conditions. Meanwhile, the experiments with HY zeolite yielded 70 wt% phenols.
The performance of silver-loaded zeolite (HY and HZSM-5) catalysts in the oxidation of butyl acetate as a model volatile organic compound (VOC) was studied. The objective was to find a catalyst with superior activity, selectivity towards deep oxidation product and stability. The catalyst activity was measured under excess oxygen condition in a packed bed reactor operated at gas hourly space velocity (GHSV)=15,000-32,000 h(-1), reaction temperature between 150 and 500 degrees C and butyl acetate inlet concentration of 1000-4000 ppm. Both AgY and AgZSM-5 catalysts exhibited high activity in the oxidation of butyl acetate. Despite lower silver content, AgY showed better activity, attributed to better metal dispersion, surface characteristics and acidity, and its pore system. Total conversion of butyl acetate was achieved at above 400 degrees C. The oxidation of butyl acetate followed a simple power law model. The reaction orders, n and m were evaluated under differential mode by varying the VOC partial pressure between 0.004 and 0.018 atm and partial pressure of oxygen between 0.05 and 0.20 atm. The reaction rate was independent of oxygen concentration and single order with respect to VOC concentration. The activation energies were 19.78 kJ/mol for AgY and 32.26 kJ/mol for AgZSM-5, respectively.
Catalytic cracking of crude palm oil (CPO) and used palm oil (UPO) were studied in a transport riser reactor for the production of biofuels at a reaction temperature of 450 degrees C, with residence time of 20s and catalyst-to-oil ratio (CTO) of 5 gg(-1). The effect of HZSM-5 (different Si/Al ratios), beta zeolite, SBA-15 and AlSBA-15 were studied as physically mixed additives with cracking catalyst Rare earth-Y (REY). REY catalyst alone gave 75.8 wt% conversion with 34.5 wt% of gasoline fraction yield using CPO, whereas with UPO, the conversion was 70.9 wt% with gasoline fraction yield of 33.0 wt%. HZSM-5, beta zeolite, SBA-15 and AlSBA-15 as additives with REY increased the conversion and the yield of organic liquid product. The transport riser reactor can be used for the continuous production of biofuels from cracking of CPO and UPO over REY catalyst.
Oil palm is widely grown in Malaysia. Palm oil has attracted the attention of researchers to develop an 'environmentally friendly' and high quality fuel, free of nitrogen and sulfur. In the present study, the catalytic cracking of palm oil to biofuel was studied over REY catalyst in a transport riser reactor at atmospheric pressure. The effect of reaction temperature (400-500 degrees C), catalyst/palm oil ratio (5-10) and residence time (10-30s) was studied over the yield of bio-gasoline and gas as fuel. Design of experiments was used to study the effect of operating variables over conversion of palm oil and yield of hydrocarbon fuel. The response surface methodology was used to determine the optimum value of the operating variables for maximum yield of bio-gasoline fraction in the liquid product obtained.
Feedstock recycling of high-density polyethylene (HDPE) over fluid catalytic cracking (FCC) catalysts (1:6 ratio) was carried out using a laboratory fluidized bed reactor operating at 450 degrees C. Fresh and steam deactivated commercial FCC catalysts with different levels of rare earth oxide (REO) were compared as well as used FCC catalysts (E-Cats) with different levels of metal poisoning. Fresh FCC catalysts gave the highest results of HDPE degradation in terms of yield of volatile hydrocarbon product. Meanwhile, steamed FCC catalysts and used FCC catalysts showed similar but lower yields. Overall, the product yields from HDPE cracking showed that the level of metal contamination (nickel and vanadium) did not affect the product stream generated from polymer cracking. This study gives promising results as an alternative technique for the cracking and recycling of polymer waste.
The feasibility of using palm oil fractions as cheap and abundant sources of raw material for the synthesis of amino acid surfactants was investigated. Of a number of enzymes screened, the best results were obtained with the immobilized enzyme, Lipozyme. The effects of temperature, solvent, incubation period, fatty substrate/amino acid molar ratio, enzyme amount, and water removal on the reactions were analyzed and compared to those on reactions with free fatty acids and pure triglycerides as fatty substrates. All reactions were most efficient when carried out at high temperatures (70-80 degrees C) in hexane as a solvent. However, while reactions with free fatty acids proceeded better when a slight excess of the free fatty acids over the amino acids was used, reactions with triglycerides and palm oil fractions were best performed at equimolar ratios. Also, the addition of molecular sieves slightly enhanced reactions with free fatty acids but adversely affected reactions with triglycerides and palm oil fractions. Although reactions with palm oil fractions took longer (6 d) to reach equilibrium compared to reactions with free fatty acids (4 d) and pure triglycerides (4 d), better yields were obtained. Such lipase-catalyzed transacylation of palm oil fractions with amino acids is potentially useful in the production of mixed medium- to long-chain surfactants for specific applications.
The paper reports on the performance of chromium or/and copper supported on H-ZSM-5(Si/Al = 240) modified with silicon tetrachloride (Cr1.5/SiCl4-Z, Cu1.5/SiCl4-Z and Cr1.0Cu0.5/SiCl4-Z) as catalysts in the combustion of chlorinated VOCs (Cl-VOCs). A reactor operated at a gas hourly space velocity (GHSV) of 32,000 h(-1), a temperature between 100 and 500 degrees C with 2500 ppm of dichloromethane (DCM), trichloromethane (TCM) and trichloroethylene (TCE) is used for activity studies. The deactivation study is conducted at a GHSV of 3800 h(-1), at 400 degrees C for up to 12 h with a feed concentration of 35,000 ppm. Treatment with silicon tetrachloride improves the chemical resistance of H-ZSM-5 against hydrogen chloride. TCM is more reactive compared to DCM but it produces more by-products due to its high chlorine content. The stabilization of TCE is attributed to resonance effects. Water vapor increases the carbon dioxide yield through its role as hydrolysis agent forming reactive carbocations and acting as hydrogen-supplying agent to suppress chlorine-transfer reactions. The deactivation of Cr1.0Cu0.5/SiCl4-Z is mainly due to the chlorination of its metal species, especially with higher Cl/H feed. Coking is limited, particularly with DCM and TCM. In accordance with the Mars-van Krevelen model, the weakening of overall metal reducibility due to chlorination leads to a loss of catalytic activity.
L-asparaginase (LA) catalyzes the degradation of asparagine, an essential amino acid for leukemic cells, into ammonia and aspartate. Owing to its ability to inhibit protein biosynthesis in lymphoblasts, LA is used to treat acute lymphoblastic leukemia (ALL). Different isozymes of this enzyme have been isolated from a wide range of organisms, including plants and terrestrial and marine microorganisms. Pieces of information about the three-dimensional structure of L-asparaginase from Escherichia coli and Erwinia sp. have identified residues that are essential for catalytic activity. This review catalogues the major sources of L-asparaginase, the methods of its production through the solid state (SSF) and submerged (SmF) fermentation, purification, and characterization as well as its biological roles. In the same breath, this article explores both the past and present applications of this important enzyme and discusses its future prospects.
In this report, silver nanoparticles (Ag NPs) were successfully deposited on graphene oxide (GO) sheets to form GO-Ag nanocomposite using garlic extract and sunlight and the nanocomposite modified glassy carbon (GC) electrode was applied as an electrochemical sensor for the detection of nitrite ions. The formation of GO-Ag nanocomposite was confirmed by using UV-visible absorption spectroscopy, TEM, XRD and FTIR spectroscopy analyses. Further, TEM pictures showed a uniform distribution Ag on GO sheets with an average size of 19 nm. The nanocomposite modified electrode produced synergistic catalytic current in nitrite oxidation with a negative shift in overpotential. The limit of detection (LOD) values were found as 2.1 µM and 37 nM, respectively using linear sweep voltammetry (LSV) and amperometric i-t curve techniques. The proposed sensor was stable, reproducible, sensitive and selective toward the detection nitrite and could be applied for the detection of nitrite in real water sample.
The photo-degradation of nutrients in stormwater in photocatalytic reactor wet detention pond using nano titanium dioxide (TiO2) in concrete was investigated in a scale model as a new stormwater treatment method. Degradation of phosphate and nitrate in the presence of nano-TiO2 under natural ultra violet (UV) from tropical sunlight was monitored for 3 weeks compared with normal ponds. Two types of cement, including ordinary Portland and white cement mixed with TiO2 nano powder, were used as a thin cover to surround the body of the pond. Experiments with and without the catalyst were carried out for comparison and control. Average Anatase diameter of 25 nm and Rutile 100 nm nano particles were applied at three different mixtures of 3, 10 and 30% weight. The amounts of algae available orthophosphate and nitrate, which cause eutrophication in the ponds, were measured during the tests. Results revealed that the utilization of 3% up to 30% weight nano-TiO2 can improve stormwater outflow quality by up to 25% after 48 h and 57% after 3 weeks compared with the control sample in normal conditions with average nutrient (phosphate and nitrate) removal of 4% after 48 h and 10% after 3 weeks.
Biodiesel is a green (clean), renewable energy source and is an alternative for diesel fuel. Biodiesel can be produced from vegetable oil, animal fat and waste cooking oil or fat. Fats and oils react with alcohol to produce methyl ester, which is generally known as biodiesel. Because vegetable oil and animal fat wastes are cheaper, the tendency to produce biodiesel from these materials is increasing. In this research, the effect of some parameters such as the alcohol-to-oil molar ratio (4:1, 6:1, 8:1), the catalyst concentration (0.75%, 1% and 1.25% w/w) and the time for the transesterification reaction using ultrasonication on the rate of the fatty acids-to-methyl ester (biodiesel) conversion percentage have been studied (3, 6 and 9 min). In biodiesel production from chicken fat, when increasing the catalyst concentration up to 1%, the oil-to-biodiesel conversion percentage was first increased and then decreased. Upon increasing the molar ratio from 4:1 to 6:1 and then to 8:1, the oil-to-biodiesel conversion percentage increased by 21.9% and then 22.8%, respectively. The optimal point is determined by response surface methodology (RSM) and genetic algorithms (GAs). The biodiesel production from chicken fat by ultrasonic waves with a 1% w/w catalyst percentage, 7:1 alcohol-to-oil molar ratio and 9 min reaction time was equal to 94.8%. For biodiesel that was produced by ultrasonic waves under a similar conversion percentage condition compared to the conventional method, the reaction time was decreased by approximately 87.5%. The time reduction for the ultrasonic method compared to the conventional method makes the ultrasonic method superior.
Bifunctional heterogeneous catalysts have a great potential to overcome the shortcomings of homogeneous and enzymatic catalysts and simplify the biodiesel production processes using low-grade, high-free-fatty-acid feedstock. In this study, we developed ZrO2-based bifunctional heterogeneous catalysts for simultaneous esterification and transesterification of microalgae to biodiesel. To avoid the disadvantage of the low surface area of ZrO2, the catalysts were prepared via a surfactant-assisted sol-gel method, followed by hydrothermal treatments. The response surface methodology central composite design was employed to investigate various factors, like the surfactant/Zr molar ratio, pH, aging time, and temperature on the ZrO2 surface area. The data were statistically analyzed to predict the optimal combination of factors, and further experiments were conducted for verification. Bi2O3 was supported on ZrO2 via the incipient wetness impregnation method. The catalysts were characterized by a variety of techniques, which disclosed that the surfactant-assisted ZrO2 nanoparticles possess higher surface area, better acid-base properties, and well-formed pore structures than bare ZrO2. The highest yield of fatty acid methyl esters (73.21%) was achieved using Bi2O3/ZrO2(CTAB), and the catalytic activity of the developed catalysts was linearly correlated with the total densities of the acidic and basic sites. The mechanism of the simultaneous reactions was also discussed.
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.
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.
Porous Ni, Ni-Co, Ni-Fe, and Ni-Cu magnetic alloys with a morphology similar to a giant barrel sponge were synthesized via a facile co-precipitation procedure and then by hydrogen reduction treatment. For the first time, the non-supported alloys with their unique morphology were employed in catalytic biogas decomposition (CBD) at a reaction temperature of 700 °C and 100 mL min-1 to produce syngas and carbon bio-nanofilaments, and the catalysts' behavior, CH₄ and CO₂ conversion, and the carbon produced during the reaction were investigated. All of the equimolar alloy catalysts showed good activity and stability for the catalytic biogas decomposition. The highest sustainability factor (0.66) and carbon yield (424%) were accomplished with the Ni-Co alloy without any significant inactivation for six hours, while the highest carbon efficiency of 36.43 was obtained with the Ni-Co catalyst, which is considered relatively low in comparison with industry standards, indicating a low carbon production process efficiency, possibly due to the relatively high biogas flow rate. The higher activity of the Ni-Co alloy catalyst was associated with the synergistic impact between nickel and cobalt, allowing the catalyst to maintain a high stability throughout the reaction period. Moreover, highly uniform, interwoven carbon bio-nanofilaments with a parallel and fishbone structure were achieved.
Liquid natural rubber (LNR) was functionalized into liquid epoxidized natural rubber (LENR) and hydroxylated LNR (LNROH)
via oxidation using a Na2
WO4
/CH3
COOH/H2
O2
catalytic system. Microstructures of LNR and functionalized LNRs
were characterized using Fourier Transform Infrared (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopies. The
effect of CH3
COOH, H2
O2
, Na2
WO4
, reaction time and temperature. reaction time and temperature on epoxy content were
investigated. LNR-OH was obtained when oxidation reaction was conducted at a longer reaction time, higher temperature
or excess amount of catalyst. Thermogravimetric analysis (TGA) reported the thermal behavior of functionalized LNRs.
Molecular weight and polydispersity index (PDI) were determined using gel permeation chromatography (GPC).
FK506-binding protein35 of Plasmodium knowlesi (Pk-FKBP35) is a member of peptidyl prolyl cis-trans isomerase (PPIase) and is considered as a promising avenue of antimalarial drug target development. This protein is organized into the N-terminal domain responsible for PPIase catalytic activity followed and the tetratricopeptide repeat domain for its dimerization. The protease-coupling and protease-free assays are known to be the common methods for investigating the catalytic properties of PPIase. Earlier, the protease-coupling assay was used to confirm the catalytic activity of Pk-FKBP35 in accelerating cis-trans isomerization of the peptide substrate. This report is aimed to re-assess the catalytic and substrate specificity of Pk-FKBP35 using an alternative method of a protease-free assay. The result indicated that while Pk-FKBP35 theoretically contained many possible cleavage sites of chymotrypsin, experimentally, the catalytic domain was relatively stable from chymotrypsin. Furthermore, under protease-free assay, Pk-FKBP35 also demonstrated remarkable PPIase catalytic activity with kcat/KM of 4.5 + 0.13 × 105 M−1 s−1, while the kcat/KM of active site mutant of D55A is 0.81 + 0.05 × 105 M−1 s−1. These values were considered comparable to kcat/KM obtained from the protease-coupling assay. Interestingly, the substrate specificities of Pk-FKBP35 obtained from both methods are also similar, with the preference of Pk-FKBP35 towards Xaa at P1 position was Leu>Phe>Lys>Trp>Val>Ile>His>Asp>Ala>Gln>Glu. Altogether, we proposed that protease-free and protease-coupling assays arereliable for Pk-FKBP35.
Comparison studies in suspension and hybrid photocatalytic membrane reactor (HPMR) system was investigated by using Reactive Black 5 (RB5) as target pollutant under UVA light irradiation. To achieve this aim, hybrid TiO2/clinoptilolite (TCP) photocatalyst powder was prepared by solid-state dispersion (SSD) methods and embedded at the outer layer of dual layer hollow fiber (DLHF) membranes fabricated via single step co-spinning process. TiO2 and CP photocatalyst were also used as control samples. The samples were characterized by Scanning Electron Microscopy (SEM), Energy Dispersion of X-ray (EDX), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analyses. The result shows that TCP was actively functioned as photocatalyst in suspension system and 86% of RB5 photocatalytic degradation achieved within 60 min; however the additional step is required to separate the catalyst with treated water. In the HPMR system, even though the RB5 photocatalytic degradation exhibits lower efficiency however the rejection of RB5 was achieved up to 95% under UV irradiation due to the properties of photocatalytic membranes. The well dispersed of TCP at the outer layer of DLHF membrane have improved the surface affinity of DL-TCP membrane towards water, exhibit the highest pure water flux of 41.72 L/m2.h compared to DL-TiO2 membrane. In general, CP can help on improving photocatalytic activity of TiO2 in suspension, increased the RB5 removal and the permeability of DLHF membrane in HPMR system as well.
Structured lipid is a type of modified form of lipid that is "fabricated" with the purpose to improve the nutritional and functional properties of conventional fats and oils derived from animal and plant sources. Such healthier choice of lipid received escalating attention from the public for its capability to manage the rising prevalence of metabolic syndrome. Of which, medium-chain triacylglycerol (MCT) and medium-and long-chain triacylglycerol (MLCT) are the few examples of the "new generation" custom-made healthful lipids which are mainly composed of medium chain fatty acid (MCFA). MCT is made up exclusively of MCFA whereas MLCT contains a mixture of MCFA and long chain fatty acid (LCFA), respectively. Attributed by the unique metabolism of MCFA which is rapidly metabolized by the body, MCFA and MCT showed to acquire multiple physiological and functional properties in managing and reversing certain health disorders. Several chemically or enzymatically oils and fats modification processes catalyzed by a biological or chemical catalyst such as acidolysis, interesterification and esterification are adopted to synthesis MCT and MLCT. With their purported health benefits, MCT and MLCT are widely being used as nutraceutical in food and pharmaceutical sectors. This article aims to provide a comprehensive review on MCT and MLCT, with an emphasis on the basic understanding of its structures, properties, unique metabolism; the current status of the touted health benefits; latest routes of production; its up-to-date applications in the different food systems; relevant patents filed and its drawbacks.