Recently, rubber seed oil (RSO) has been considered as a promising potential oil source for biodiesel production. However, RSO is a non-edible feedstock with a significant high free fatty acid (FFA) content which has an adverse impact on the process of biodiesel production. In this study, ultrasonic-assisted esterification process was conducted as a pre-treatment step to reduce the high FFA content of RSO from 40.14% to 0.75%. Response surface methodology (RSM) using central composite design (CCD) was applied to the design of experiments (DOE) and the optimization of esterification process. The result showed that methanol to oil molar ratio was the most influential factor for FFA reduction whereas the effect of amount of catalyst and the reaction were both insignificant. The kinetic study revealed that the activation energy and the frequency factor of the process are 52.577kJ/mol and 3.53×108min-1, respectively.
In this study, performances of mesoporous Mo/Al2O3 catalysts prepared by sol-gel and post-hydrolysis methods in hydrocracking of atmospheric residual oil were compared. In addition, different methods: (i) the single step and (ii) conventional impregnation method to incorporate active metal over the mesoporous support were also investigated. For single step method, Mo/Al2O3 catalysts were synthesized directly by sol-gel and post-hydrolysis method. On the other hand, the impregnation method was a two step procedure which involved the production of alumina via sol-gel or post-hydrolysis method and followed by respective Mo impregnation. In general, mesoporous Mo/Al2O3 catalysts prepared by sol-gel method resulted in relatively higher surface area (> 400 m2/g) and large pore volume (- 0.8 cm3/g). Mo/Al2O3 catalysts prepared by sol-gel method exhibited higher hydrocracking activity as well. The Mo crystal size was found to relate directly with the hydrocracking result.
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.
Highly reactive zinc metal was prepared by electrolysis of a N,N-dimethylformamide (DMF) solution containing naphthalene and a supporting electrolyte in a one-compartment cell fitted with a platinum cathode and a zinc anode. This highly reactive electrogenerated zinc (EGZn/Naph) was used for transformation of ethyl 2-bromoacrylate into the corresponding organozinc compound, which can not be achieved by the use of usual zinc metals. Reaction of the organozinc compounds thus prepared with various aryl halides in the presence of 5 mol% of palladium catalyst gave the corresponding cross-coupling products in high yields. These cross-coupling reactions were successfully applied to a synthesis of the precursor of anti-inflammatory agents such as ibuprofen, naproxen, cicloprofen and suprofen.
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 n-butyramido, isobutyramido, benzamido, and furancarboxamido functions profoundly modulate the electronics of the stilbene olefinic and NH groups and the corresponding radical cations in ways that influence the efficiency of the cyclization due presumably to conformational and stereoelectronic factors. For example, isobutyramido- stilbene undergoes FeCl(3) promoted cyclization to produce only indoline, while n-butyramidostilbene, under the same conditions, produces both indoline and bisindoline.
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.
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.
Titania and ceria incorporated rice husk silica based catalyst was synthesized via sol-gel method using CTAB and glycerol as surface directing agents at room temperature and labeled as RHS-50Ti10Ce. The catalyst was used to study the adsorption and photodegradation of methylene blue (MB) under UV irradiation. The powder XRD pattern of RHS-50Ti10Ce was much broader (2θ=25-30°) than that of the parent RHS (2θ=22°). The catalyst exhibited type IV isotherm with H3 hysteresis loop, and the TEM images showed partially ordered pore arrangements. The TGA-DTG thermograms confirmed the complete removal of the templates after calcination at 500°C. RHS-50Ti10Ce exhibited excellent adsorption capability with more than 99% removal of MB from a 40 mg L(-1) solution in just 15 min. It also decolorized an 80 mg L(-1) MB solution under UV irradiation in 210 min, which was comparable with the commercialized pure anatase TiO2.
Natural enzymes possess several drawbacks which limits their application in industries, wastewater remediation and biomedical field. Therefore, in recent years researchers have developed enzyme mimicking nanomaterials and enzymatic hybrid nanoflower which are alternatives of enzyme. Nanozymes and organic inorganic hybrid nanoflower have been developed which mimics natural enzymes functionalities such as diverse enzyme mimicking activities, enhanced catalytic activities, low cost, ease of preparation, stability and biocompatibility. Nanozymes include metal and metal oxide nanoparticles mimicking oxidases, peroxidases, superoxide dismutase and catalases while enzymatic and non-enzymatic biomolecules were used for preparing hybrid nanoflower. In this review nanozymes and hybrid nanoflower have been compared in terms of physiochemical properties, common synthetic routes, mechanism of action, modification, green synthesis and application in the field of disease diagnosis, imaging, environmental remediation and disease treatment. We also address the current challenges facing nanozyme and hybrid nanoflower research and the possible way to fulfil their potential in future.
The solid acid Ferric-manganese doped tungstated/molybdena nananoparticle catalyst was prepared via impregnation reaction followed by calcination at 600°C for 3 h. The characterization was done using X-ray diffraction (XRD), Raman spectroscopy, thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), X-ray fluorescence (XRF), Transmission electron microscope (TEM) and Brunner-Emmett-Teller surface area measurement (BET). Moreover, dependence of biodiesel yield on the reaction variables such as the reaction temperature, catalyst loading, as well as molar ratio of methanol/oil and reusability were also appraised. The catalyst was reused six times without any loss in activity with maximum yield of 92.3% ±1.12 achieved in the optimized conditions of reaction temperature of 200°C; stirring speed of 600 rpm, 1:25 molar ratio of oil to alcohol, 6 % w/w catalyst loading as well as 8 h as time of the reaction. The fuel properties of WCOME's were evaluated, including the density, kinematic viscosity, pour point, cloud point and flash point whereas all properties were compared with the limits in the ASTM D6751 standard.
In the current research work, effect of microwave irradiation energy on the esterification of palm fatty acid distillate (PFAD) to produce PFAD methyl ester / biodiesel was intensively appraised. The PFAD is a by-product from refinery of crude palm oil consisting >85% of free fatty acid (FFA). The esterification reaction process with acid catalyst is needed to convert the FFA into fatty acid methyl ester or known as biodiesel. In this work, fabricated microwave-pulse width modulation (MPWM) reactor with controlled temperature was designed to be capable to increase the PFAD biodiesel production rate. The classical optimization technique was used in order to study the relationship and the optimum condition of variables involved. Consequently, by using MPWM reactor, mixture of methanol-to-PFAD molar ratio of 9:1, 1 wt.% of sulfuric acid catalyst, at 55°C reaction temperature within 15 min reaction time gave 99.5% of FFA conversion. The quality assessment and properties of the product were analyzed according to the American Society for Testing and Materials (ASTM), European (EN) standard methods and all results were in agreement with the standard requirements. It revealed that the use of fabricated MPWM with controlled temperature was significantly affecting the rate of esterification reaction and also increased the production yield of PFAD methyl ester.
A highly active and stable nano structured Pt/Mg1-xNixO catalysts was developed by a simple co-precipitation method. The obtained Pt/Mg1-xNixO catalyst exhibited cubic structure nanocatalyst with a size of 50-80 nm and realized CH4 and CO2 conversions as high as 98% at 900°C with excellent stability in the dry reforming of methane. The characterization of catalyst was performed using various kinds of analytical techniques including XRD, BET, XRF, TPR-H2, TGA, TEM, FESEM, FT-IR, and XPS analyses. Characterization of spent catalyst further confirms that Pt/Mg1-xNixO catalyst has high coke-resistance for dry reforming. Thus, the catalyst demonstrated in this study, offers a promising catalyst for resolving the dilemma between dispersion and reducibility of supported metal, as well as activity and stability during high temperature reactions.
The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods.
In this study, an optimized mesoporous sulfonated carbon (OMSC) catalyst derived from palm kernel shell biomass was developed using template carbonization and subsequent sulfonation under different temperatures and time conditions. The OMSC catalyst was characterized using acid-base titration, elemental analysis, XRD, Raman, FTIR, XPS, TPD-NH3, TGA-DTA, SEM, and N2 adsorption-desorption analysis to reveal its properties. Results proved that the OMSC catalyst is mesoporous and amorphous in structure with improved textural, acidic, and thermal properties. Both FTIR and XPS confirmed the presence of -SO3H, -OH, and -COOH functional groups on the surface of the catalyst. The OMSC catalyst was found to be efficient in catalyzing glycerol conversion to acetin via an acetylation reaction with acetic acid within a short period of 3 h. Response surface methodology (RSM), based on a two-level, three-factor, face-centered central composite design, was used to optimize the reaction conditions. The results showed that the optimized temperature, glycerol-to-acetic acid mole ratio, and catalyst load were 126 °C, 1:10.4, and 0.45 g, respectively. Under these optimum conditions, 97% glycerol conversion (GC) and selectivities of 4.9, 27.8, and 66.5% monoacetin (MA), diacetin (DA), and triacetin (TA), respectively, were achieved and found to be close to the predicted values. Statistical analysis showed that the regression model, as well as the model terms, were significant with the predicted R2 in reasonable agreement with the adjusted R2 (<0.2). The OMSC catalyst maintained excellent performance in GC for the five reaction cycles. The selectivity to TA, the most valuable product, was not stable until the fourth cycle, attributable to the leaching of the acid sites.
A γ-NA5 catalyst in the form of pellet was first to be reported and was pioneering in gasification to accelerate the production of syngas through biomass (palm empty fruit brunch) conversion. The synthesised γ-NA5 pellet possesses a high surface area of 212.32 m2 g-1, which renders more active sites for hydrocarbon cracking, subsequently leading to high H2 production (0.0716 m3 kg-1). Additionally, the pellet exhibits remarkable reversibility and reusability with 91% H2 production efficiency being retained after five consecutive gasification cycles. Distinctively, the feature of the synthesised γ-NA5 pellet from the conventional powder-like catalyst is that it eases the separation of the used catalyst from the biomass ash, and subsequently facilitates regeneration solely by calcination process. The loading of 20 wt.% optimised amount of catalyst itself has successfully shorten the completion of gasification process up to 135 min, which is highly feasible for a large scale industrial usage after considering the cost of the catalyst, facile preparation method, and catalyst's effectiveness towards gasification.
Solid acid catalyzed cracking of waste oil-derived fatty acids is an attractive route to hydrocarbon fuels. HZSM-5 is an effective acid catalyst for fatty acid cracking; however, its microporous nature is susceptible to rapid deactivation by coking. We report the synthesis and application of hierarchical HZSM-5 (h-HZSM-5) in which silanization of pre-crystallized zeolite seeds is employed to introduce mesoporosity during the aggregation of growing crystallites. The resulting h-HZSM-5 comprises a disordered array of fused 10-20 nm crystallites and mesopores with a mean diameter of 13 nm, which maintain the high surface area and acidity of a conventional HZSM-5. Mesopores increase the yield of diesel range hydrocarbons obtained from oleic acid deoxygenation from ~20% to 65%, attributed to improved acid site accessibility within the hierarchical network.
Since the complexity of photocatalyst synthesis process and high cost of noble cocatalyst leftovers a major hurdle to producing hydrogen (H2) from water, a noble metal-free Ni-Si/MgO photocatalyst was realized for the first time to generate H2 effectively under illumination with visible light. The catalyst was produced by means of simple one-pot solid reaction using self-designed metal reactor. The physiochemical properties of photocatalyst were identified by XRD, FESEM, HRTEM, EDX, UV-visible, XPS, GC and PL. The photocatalytic activities of Ni-Si/MgO photocatalyst at different nickel concentrations were evaluated without adjusting pH, applied voltage, sacrificial agent or electron donor. The ultrathin-nanosheet with hierarchically porous structure of catalyst was found to exhibit higher photocatalytic H2 production than hexagonal nanorods structured catalyst, which suggests that the randomly branched nanosheets are more active surface to increase the light-harvesting efficiency due to its short electron diffusion path. The catalyst exhibited remarkable performance reaching up to 714 µmolh-1 which is higher among the predominant semiconductor catalyst. The results demonstrated that the photocatalytic reaction irradiated under visible light illumination through the production of hydrogen and hydroxyl radicals on metals. The outcome indicates an important step forward one-pot facile approach to prepare noble ultrathin photocatalyst for hydrogen production from water.
Visible light driven C-doped mesoporous TiO2 (C-MTiO2) nanorods have been successfully synthesized through green, low cost, and facile approach by sol-gel bio-templating method using regenerated cellulose membrane (RCM) as nanoreactor. In this study, RCM was also responsible to provide in-situ carbon sources for resultant C-MTiO2 nanorods in acidified sol at low temperatures. The composition, crystallinity, surface area, morphological structure, and optical properties of C-MTiO2 nanorods, respectively, had been characterized using FTIR, XRD, N2 adsorption/desorption, TEM, UV-vis-NIR, and XPS spectroscopy. The results suggested that the growth of C-MTiO2 nanorods was promoted by the strong interaction between the hydroxyl groups of RCMs and titanium ion. Optical and XPS analysis confirmed that carbon presence in TiO2 nanorods were responsible for band-gap narrowing, which improved the visible light absorption capability. Photocatalytic activity measurements exhibited the capability of C-MTiO2 nanorods in degradation of methyl orange in aqueous solution, with 96.6% degradation percentage under visible light irradiation.
Fibrous silica-titania (FST) catalysts were synthesized by microemulsion followed by silica seed-crystal crystallization methods under various molar ratios of toluene to water (T/W). The catalysts were characterized by XRD, UV-DRS, FESEM, TEM, AFM, N2 adsorption-desorption, FTIR, and ESR. The results revealed that altering the T/W ratio affected the growth of the silica and titania and led to different size, fiber density, silica-titania structure, and number of hydroxyl groups, as well as oxygen vacancies in the FSTs, which altered their behavior toward subsequent application. Photodegradation of ibuprofen (IBP) are in the following order: FST(6:1) (90%) > FST(5:1) (84%) > FST(7:1) (79%) > commercial TiO2 (67%). A kinetics study using Langmuir-Hinshelwood model illustrated that the photodegradation followed the pseudo-first-order and adsorption was the rate-limiting step. Optimization by response surface methodology (RSM) showed that the pH, initial concentration, and catalyst dosage were the remarkable parameters in photodegradation of IBP. The FST (6:1) maintained its photocatalytic activities for up to five cycles reaction without serious catalyst deactivation, and was also able to degrade other endocrine-disrupting chemicals, indicating its potential use for the treatment of those chemicals in wastewater.