Powdered-photocatalysis of organic wastewater is widely investigated, unfortunately not industrially implemented due to its high energy requirement. Interestingly, such issue may be alleviated via the elimination of mechanical stirring required. Core-shell ZnO-based photocatalysts were developed herein, subsequently demonstrated efficient photocatalytic activities in the absence of mechanical stirring. Results show that the developed SiO2-cored ZnO photocatalyst are highly crystalline, while significantly smaller than coreless, pure ZnO due to the multi-point crystallization prompted. Additionally, it is also inherited with considerable buoyancy ability from SiO2-core in the absence of mechanical stirring, concurrently rendered with UV-active properties due to its ZnO-shell. Experimentally, 55% of particles of ZnO_0.0025 (0.0025 mol of ZnO-deposition) were found stably suspended for 60 min in liquid substrate, as opposed to the instant-settling of pure ZnO particles. In term of photocatalytic activity, ZnO_0.01 manifested the best methylene blue (MB) degradation with 150 mL/min of O2-bubbling. 67.63% of MB was degraded with photocatalyst loading of 0.2 g/L after 120 min UV-irradiation, simultaneously recorded the highest pseudo-first order reaction constant of 9.636 × 10-3 min-1. As summary, the auto-suspending photocatalysis conceptualized in current study offers a high possibility in reducing energy requirement for photo-treatment of wastewater, hence advocating its industrialization potential in near future.
Offretite zeolite synthesis in the presence of cetyltrimethylammonium bromide (CTABr) is reported. The offretite crystals were synthesized with a high crystallinity and hexagonal prismatic shape after only 72 h of hydrothermal treatment at 180 °C. The CTABr has dual-functions during the crystallization of offretite, viz. as structure-directing agent and as mesoporogen. The resulting offretite crystals, with a Si/Al ratio of 4.1, possess more acid sites than the conventional offretite due to their high crystallinity and hierarchical structure. The synthesized offretite is also more reactive than its conventional counterpart in the acylation of 2-methylfuran for biofuel production under non-microwave instant heating condition, giving 83.5% conversion with 100% selectivity to the desired product 2-acetyl-5-methylfuran. Hence, this amphiphile synthesis approach offers another cost-effective and alternative route for crystallizing zeolite materials that require expensive organic templates.
Rubberwood (Hevea brasiliensis), a potential raw material for bioethanol production due to its high cellulose content, was used as a novel feedstock for enzymatic hydrolysis and bioethanol production using biological pretreatment. To improve ethanol production, rubberwood was pretreated with white rot fungus Ceriporiopsis subvermispora to increase fermentation efficiency. The effects of particle size of rubberwood (1 mm, 0.5 mm, and 0.25 mm) and pretreatment time on the biological pretreatment were first determined by chemical analysis and X-ray diffraction and their best condition obtained with 1 mm particle size and 90 days pretreatment. Further morphological study on rubberwood with 1 mm particle size pretreated by fungus was performed by FT-IR spectra analysis and SEM observation and the result indicated the ability of this fungus for pretreatment. A study on enzymatic hydrolysis resulted in an increased sugar yield of 27.67% as compared with untreated rubberwood (2.88%). The maximum ethanol concentration and yield were 17.9 g/L and 53% yield, respectively, after 120 hours. The results obtained demonstrate that rubberwood pretreated by C. subvermispora can be used as an alternative material for the enzymatic hydrolysis and bioethanol production.
The effect of Manganese (Mn) addition on the Vickers hardness and relative density of nanocrystalline hydroxyapatite (HA) dense bodies were studied. The starting Mn doped HA powders was synthesized via sol-gel method with Mn concentration varies from 2 mol% up to 15 mol% Mn. The Mn doped HA disc samples were prepared by uniaxial pressing at 200MPa and subsequently sintered at 1300 degrees C. Characterization was carried out where appropriate to determine the phases present, bulk density, Vickers hardness of the various content of Mn doped HA dense bodies. The addition of Mn was observed to influence the color appearance of the powders and dense bodies as well. Higher Mn concentration resulted in dark grey powders. It was also found that the hardness and relative density of the material increased as the Mn content increased and influenced by the crystallinity of the prepared Mn doped HA powders.
This is our initial response towards preparation of nano-inductors garnet for high operating frequencies strontium iron garnet (Sr3Fe5O12) denoted as SrIG and yttrium iron garnet (Y3Fe5O12) denoted as YIG. The garnet nano crystals were prepared by novel sol-gel technique. The phase and crystal structure of the prepared samples were identified by using X-ray diffraction analysis. SEM images were done to reveal the surface morphology of the samples. Raman spectra was taken for yttrium iron garnet (Y3Fe5O12). The magnetic properties of the samples namely initial permeability (micro), relative loss factor (RLF) and quality factor (Q-Factor) were done by using LCR meter. From the XRD profile, both of the Y3Fe5O12 and Sr3Fe5O12 samples showed single phase garnet and crystallization had completely occurred at 900 degrees C for the SrIG and 950 degrees C for the YIG samples. The YIG sample showed extremely low RLF value (0.0082) and high density 4.623 g/cm3. Interesting however is the high Q factor (20-60) shown by the Sr3Fe5O12 sample from 20-100 MHz. This high performance magnetic property is attributed to the homogenous and cubical-like microstructure. The YIG particles were used as magnetic feeder for EM transmitter. It was observed that YIG magnetic feeder with the EM transmitter gave 39% higher magnetic field than without YIG magnetic feeder.
Changes in molecular structure configuration during strain induced crystallisation of an amorphous Poly(Lactic Acid) (PLA 4032D) polymer was monitored in-situ by simultaneously recording the wide angle x-ray scattering (WAXS) and small angle x-ray scattering (SAXS) patterns together with polymer deformation images and force data. The amorphous chain orientation from the beginning of deformation until the onset of crystallisation was studied from the WAXS patterns. The true mechanical behaviour described by the true stress-true strain curve related to an amorphous chain orientation exhibited a linear behaviour. Approaching critical amorphous orientation, the true stress-true strain curve deviated from linear into non-linear behaviour. After the onset of crystallization, when the deformed polymer became a semicrystalline state, the true mechanical behaviour exhibited true strain hardening which greatly affected by the formation of the morphology. The gradual true strain hardening was associated with the formation of micro-fibrillar structure containing thin crystallite morphology whilst sharp increased in true strain hardening was associated with the formation of stacked lamellar morphology in the form of macro-lattice structure. The study was accomplished by the application of high brilliance synchrotron radiation at beamline ID2 of ESRF, Grenoble in France and the usage of the high contrast resolution of WAXS and SAXS charge-couple device (CCD) camera as well as 40 milliseconds temporal resolution of data acquisition system.
In the present work, the dissolution of bamboo biomass was tested using a number of ionic liquids synthesized in laboratory. It was observed that one of the synthesized amino acid-based ionic liquids, namely 1-ethyl-3-methylimidazolium glycinate, was capable of dissolving the biomass completely. The dissolved biomass was then regenerated using a reconstitute solvent (acetone/water) and was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The results were compared to preconditioned bamboo biomass. The regenerated biomass was found to have a more homogenous macrostructure, which indicates that the crystalline form and structure of its cellulose has changed from type Ι to type ΙΙ during the dissolution and regeneration process.
A truncated form of an α-amylase, GTA, from thermophilic Geobacillus thermoleovorans CCB_US3_UF5 was biochemically and structurally characterized. The recombinant GTA, which lacked both the N- and C-terminal transmembrane regions, functioned optimally at 70°C and pH 6.0. While enzyme activity was not enhanced by the addition of CaCl2, GTA's thermostability was significantly improved in the presence of CaCl2. The structure, in complex with an acarbose-derived pseudo-hexasaccharide, consists of the typical three domains and binds one Ca(2+) ion. This Ca(2+) ion was strongly bound and not chelated by EDTA. A predicted second Ca(2+)-binding site, however, was disordered. With limited subsites, two novel substrate-binding residues, Y147 and Y182, may help increase substrate affinity. No distinct starch-binding domain is present, although two regions rich in aromatic residues have been observed. GTA, with a smaller domain B and several shorter loops compared to other α-amylases, has one of the most compact α-amylase folds that may contribute greatly to its tight Ca(2+) binding and thermostability.
TylP is one of five regulatory proteins involved in the regulation of antibiotic (tylosin) production, morphological and physiological differentiation in Streptomyces fradiae. Its function is similar to those of various γ-butyrolactone receptor proteins. In this report, N-terminally His-tagged recombinant TylP protein (rTylP) was overproduced in Escherichia coli and purified to homogeneity. The rTylP protein was crystallized from a reservoir solution comprising 34%(v/v) ethylene glycol and 5%(v/v) glycerol. The protein crystals diffracted X-rays to 3.05 Å resolution and belonged to the trigonal space group P3121, with unit-cell parameters a = b = 126.62, c = 95.63 Å.
This study evaluated the potential of stimuli-responsive bacterial cellulose-g-poly(acrylic acid-co-acrylamide) hydrogels as oral controlled-release drug delivery carriers. Hydrogels were synthesized by graft copolymerization of the monomers onto bacterial cellulose (BC) fibers by using a microwave irradiation technique. The hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FT-IR spectroscopy confirmed the grafting. XRD showed that the crystallinity of BC was reduced by grafting, whereas an increase in the thermal stability profile was observed in TGA. SEM showed that the hydrogels exhibited a highly porous morphology, which is suitable for drug loading. The hydrogels demonstrated a pH-responsive swelling behavior, with decreased swelling in acidic media, which increased with increase in pH of the media, reaching maximum swelling at pH 7. The release profile of the hydrogels was investigated in simulated gastric fluid (SGF) and simulated intestinal fluid (SIF). The hydrogels showed lesser release in SGF than in SIF, suggesting that hydrogels may be suitable drug carriers for oral controlled release of drug delivery in the lower gastrointestinal tract.
Three-dimensional structure of thermostable lipase is much sought after nowadays as it is important for industrial application mainly found in the food, detergent, and pharmaceutical sectors. Crystallization utilizing the counter diffusion method in space was performed with the aim to obtain high resolution diffracting crystals with better internal order to improve the accuracy of the structure. Thermostable T1 lipase enzyme has been crystallized in laboratory on earth and also under microgravity condition aboard Progress spacecraft to the ISS in collaboration with JAXA (Japanese Aerospace Exploration Agency). This study is conducted with the aims of improving crystal packing and structure resolution. The diffraction data set for ground grown crystal was collected to 1.3 Å resolution and belonged to monoclinic C2 space group with unit cell parameters a = 117.40 Å, b = 80.95 Å, and c = 99.81 Å, whereas the diffraction data set for space grown crystal was collected to 1.1 Å resolution and belonged to monoclinic C2 space group with unit cell parameters a = 117.31 Å, b = 80.85 Å, and c = 99.81 Å. The major difference between the two crystal growth systems is the lack of convection and sedimentation in microgravity environment resulted in the growth of much higher quality crystals of T1 lipase.
Two types of palm oil and sal fat based cocoa butter equivalents, namely fCBE (produced by using co-fractionation method) and mCBE (produced by using conventional method) were prepared. Results showed that the fCBE had triglyceride composition and solidification characteristics closer to the Malaysian cocoa butter than the mCBE produced at the same yield percentage. Increasing acetone washing time had little effect on the fCBE if compared to the effect of increasing palm olein to sal fat blend ratio. Co-fractionation technique increase the compatibility between CBE component triglycerides. Thus, more palm oil can be incorporated in the preparation and the process can be carried out at not low temperature as compared to the conventional method.
GDSL esterase J15 (EstJ15) is a member of Family II of lipolytic enzyme. The enzyme was further classified in subgroup SGNH hydrolase due to the presence of highly conserve motif, Ser-Gly-Asn-His in four conserved blocks I, II, III, and V, respectively. X-ray quality crystal of EstJ15 was obtained from optimized formulation containing 0.10 M ammonium sulphate, 0.15 M sodium cacodylate trihydrate pH 6.5, and 20% PEG 8000. The crystal structure of EstJ15 was solved at 1.38 Å with one molecule per asymmetric unit. The structure exhibits α/β hydrolase fold and shared low amino acid sequence identity of 23% with the passenger domain of the autotransporter EstA of Pseudomonas aeruginosa. The active site is located at the centre of the structure, formed a narrow tunnel that hinder long substrates to be catalysed which was proven by the protein-ligand docking analysis. This study facilitates the understanding of high substrate specificity of EstJ15 and provide insights on its catalytic mechanism.
A combinative effect of two or more individual material properties, such as lattice parameters and chemical properties, has been well-known to generate novel nanomaterials with special crystal growth behavior and physico-chemical performance. This paper reports unusually high catalytic performance of AgPt nanoferns in the hydrogenation reaction of acetone conversion to isopropanol, which is several orders higher compared to the performance shown by pristine Pt nanocatalysts or other metals and metal-metal oxide hybrid catalyst systems. It has been demonstrated that the combinative effect during the bimetallisation of Ag and Pt produced nanostructures with a highly anisotropic morphology, i.e., hierarchical nanofern structures, which provide high-density active sites on the catalyst surface for an efficient catalytic reaction. The extent of the effect of structural growth on the catalytic performance of hierarchical AgPt nanoferns is discussed.
Polylactic acid (PLA)/Epoxidized natural rubber (ENR-50) blends were prepared by melt extrusion followed by injection
molding to fabricate the test samples. The effect of ENR-50 loadings on the morphological, mechanical, chemical
resistance and water absorption properties of the blends were studied using standard methods. The toughness of the
blend improved with ENR loading up to 20 wt. % but flexural and tensile strength decreased. The balanced mechanical
properties were obtained at 20 wt. % ENR-50 loading. SEM showed good distribution and increased ENR particle size
as ENR content increased from 10 to 30 wt. %. The differential scanning calorimeter (DSC) showed a steady drop in
crystallization temperature (Tc
) as ENR content increases while the glass transition temperature (Tg
) remained unchanged.
Water absorption was observed to increase with ENR loadings. Increase in ENR content was also observed to reduce the
chemical resistance of the blends.
The experiment aims to investigate the effect of high energy milling to the crystallite size of α-alumina. The starting material used is α-alumina powder with starting crystal size of 86nm. This powder was milled at different time ranges from 0 to 60 minutes and milling speed ranges from 400 rpm to 1100 rpm using a wet milling technique in corundum abrasive materials. The wet milling technique involved the use of water with the alumina to water ratio of 1:6.1. Samples prepared were then examined using the X-Ray Diffraction (XRD) to calculate the crystallite size and scanning electron microscope (SEM) was also used to determine changes in the morphology. Results from these analysis showed that the crystallite size will get smaller when milling speed and time of more than 600rpm and 30 minutes respectively were used. Optimum conditions to achieve the smallest crystal size of 79.7nm are 1000 rpm and 60 minutes.
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 3-(4-fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazole-1-carbaldehyde have been investigated experimentally and theoretically. The title compound was optimized using at HF and DFT levels of calculations. The B3LYP/6-311++G(d,p) (5D,7F) results and in agreement with experimental infrared bands. The normal modes are assigned using potential energy distribution. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using natural bonding orbital analysis. The frontier molecular orbital analysis is used to determine the charge transfer within the molecule. From molecular electrostatic potential map, it is evident that the negative electrostatic potential regions are mainly localized over the carbonyl group and mono substituted phenyl ring and are possible sites for electrophilic attack and, positive regions are localized around all para substituted phenyl and pyrazole ring, indicating possible sites for nucleophilic attack. First hyperpolarizability is calculated in order to find its role in nonlinear optics. The geometrical parameters are in agreement with experimental data. From the molecular docking studies, it is evident that the fluorine atom attached to phenyl ring and the carbonyl group attached to pyrazole ring are crucial for binding and the results draw us to the conclusion that the compound might exhibit phosphodiesterase inhibitory activity.
A study was conducted to detect and quantify lard stearin (LS) content in canola oil (CaO) using differential scanning calorimetry (DSC). Authentic samples of CaO were obtained from a reliable supplier and the adulterant LS were obtained through a fractional crystallization procedure as reported previously. Pure CaO samples spiked with LS in levels ranging from 5 to 15% (w/w) were analyzed using DSC to obtain their cooling and heating profiles. The results showed that samples contaminated with LS at 5% (w/w) level can be detected using characteristic contaminant peaks appearing in the higher temperature regions (0 to 70°C) of the cooling and heating curves. Pearson correlation analysis of LS content against individual DSC parameters of the adulterant peak namely peak temperature, peak area, peak onset temperature indicated that there were strong correlations between these with the LS content of the CaO admixtures. When these three parameters were engaged as variables in the execution of the stepwise regression procedure, predictive models for determination of LS content in CaO were obtained. The predictive models obtained with single DSC parameter had relatively lower coefficient of determination (R(2) value) and higher standard error than the models obtained using two DSC parameters in combination. This study concluded that the predictive models obtained with peak area and peak onset temperature of the adulteration peak would be more accurate for prediction of LS content in CaO based on the highest coefficient of determination (R(2) value) and smallest standard error.
The rational design of a glycolipid application (e.g. drug delivery) with a tailored property depends on the detailed understanding of its structure and dynamics. Because of the complexity of sugar stereochemistry, we have undertaken a simulation study on the conformational dynamics of a set of synthetic glycosides with different sugar groups and chain design, namely dodecyl β-maltoside, dodecyl β-cellobioside, dodecyl β-isomaltoside and a C12C10 branched β-maltoside under anhydrous conditions. We examined the chain structure in detail, including the chain packing, gauche/trans conformations and chain tilting. In addition, we also investigated the rotational dynamics of the headgroup and alkyl chains. Monoalkylated glycosides possess a small amount of gauche conformers (∼20%) in the hydrophobic region of the lamellar crystal (LC) phase. In contrast, the branched chain glycolipid in the fluid Lα phase has a high gauche population of up to ∼40%. Rotational diffusion analysis reveals that the carbons closest to the headgroup have the highest correlation times. Furthermore, its value depends on sugar type, where the rotational dynamics of an isomaltose was found to be 11-15% and more restrained near the sugar, possibly due to the chain disorder and partial inter-digitation compared to the other monoalkylated lipids. Intriguingly, the present simulation demonstrates the chain from the branched glycolipid bilayer has the ability to enter into the hydrophilic region. This interesting feature of the anhydrous glycolipid bilayer simulation appears to arise from a combination of lipid crowding and the amphoteric nature of the sugar headgroups.
In recent years, there has been considerable interest in the use of natural fibers as potential reinforcing fillers in polymer composites despite their hydrophilicity, which limits their widespread commercial application. The present study explored the fabrication of nanocomposites by melt mixing, using an internal mixer followed by a compression molding technique, and incorporating rice husk (RH) as a renewable natural filler, montmorillonite (MMT) nanoclay as water-resistant reinforcing nanoparticles, and polypropylene-grafted maleic anhydride (PP-g-MAH) as a compatibilizing agent. To correlate the effect of MMT delamination and MMT/RH dispersion in the composites, the mechanical and thermal properties of the composites were studied. XRD analysis revealed delamination of MMT platelets due to an increase in their interlayer spacing, and SEM micrographs indicated improved dispersion of the filler(s) from the use of compatibilizers. The mechanical properties were improved by the incorporation of MMT into the PP/RH system and the reinforcing effect was remarkable as a result of the use of compatibilizing agent. Prolonged water exposure of the prepared samples decreased their tensile and flexural properties. Interestingly, the maximum decrease was observed for PP/RH composites and the minimum was for MMT-reinforced and PP-g-MAH-compatibilized PP/RH composites. DSC results revealed an increase in crystallinity with the addition of filler(s), while the melting and crystallization temperatures remained unaltered. TGA revealed that MMT addition and its delamination in the composite systems improved the thermal stability of the developed nanocomposites. Overall, we conclude that MMT nanoclay is an effective water-resistant reinforcing nanoparticle that enhances the durability, mechanical properties, and thermal stability of composites.