The mineralisation kinetics of petroleum refinery effluent (PRE) by Fenton oxidation were evaluated. Within the ambit of the experimental data generated, first-order kinetic model (FKM), generalised lumped kinetic model (GLKM), and generalized kinetic model (GKM) were tested. The obtained apparent kinetic rate constants for the initial oxidation step (k'2), their final oxidation step (k'1), and the direct conversion to endproducts step (k3') were 10.12, 3.78, and 0.24 min(-1) for GKM; 0.98, 0.98, and nil min(-1) for GLKM; and nil, nil, and >0.005 min(-1) for FKM. The findings showed that GKM is superior in estimating the mineralization kinetics.
The binary effect of pulverized fuel ash (PFA) and palm oil fuel ash (POFA) on heat of hydration of aerated concrete was studied. Three aerated concrete mixes were prepared, namely, concrete containing 100% ordinary Portland cement (control sample or Type I), binary concrete made from 50% POFA (Type II), and ternary concrete containing 30% POFA and 20% PFA (Type III). It is found that the temperature increases due to heat of hydration through all the concrete specimens especially in the control sample. However, the total temperature rises caused by the heat of hydration through both of the new binary and ternary concrete were significantly lower than the control sample. The obtained results reveal that the replacement of Portland cement with binary and ternary materials is beneficial, particularly for mass concrete where thermal cracking due to extreme heat rise is of great concern.
Our phytochemical study on the stem bark of Garcinia mangostana has led to the discovery of a new furanoxanthone, mangaxanthone A (1), together with five known analogs. The five known analogs that were isolated are α-mangostin (2), β-mangostin (3), cowagarcinone B (4), and dulcisxanthone F (5). The structural elucidations of these compounds were carried out by interpreting their spectroscopic data, mainly 1D and 2D NMR spectra and MS.
Glycyrrhiza glabra L. (Fabaceae), commonly known as 'liquorice', is one of the most popular ingredients in several traditional herbal medicinal preparations, and glycyrrhizin is the major glycoside present in this plant. The content of glycyrrhizin may vary among G. glabra samples collected from various geographical origins, which may affect the therapeutic efficacy. Thus, quantification of glycyrrhizin in G. glabra samples is important.
This Research Article reports an unusually high efficiency heterogeneous photodegradation of methyl orange (MO) in the presence of Ag nanoparticle-loaded ZnO quasi-nanotube or nanoreactor (A-ZNRs) nanocatalyst grown on FTO substrate. In typical process, photodegradation efficiency of as high as 21.6% per μg per Watts of used catalyst and UV power can be normally obtained within only a 60-min reaction time from this system, which is 10(3) order higher than the reported results. This is equivalent to the turnover frequency of 360 mol mol(-1) h(-1). High-density hexagonal A-ZNRs catalysts were grown directly on FTO substrate via a seed-mediated microwave-assisted hydrolysis growth process utilizing Ag nanoparticle of approximately 3 nm in size as nanoseed and mixture aqueous solution of Zn(NO3)·6H2O, hexamethylenetetramine (HMT), and AgNO3 as the growth solution. A-ZNRs adopts hexagonal cross-section morphology with the inner surface of the reactor characterized by a rough and rugged structure. Transmission electron microscopy imaging shows the Ag nanoparticle grows interstitially in the ZnO nanoreactor structure. The high photocatalytic property of the A-ZNRs is associated with the highly active of inner side's surface of A-ZNRs and the oxidizing effect of Ag nanoparticle. The growth mechanism as well as the mechanism of the enhanced-photocatalytic performance of the A-ZNRs will be discussed.
The adsorption of tributyltin (TBT), onto three mesoporous silica adsorbents functionalized with calix[4]arene, p-tert-butylcalix[4]arene and p-sulfonatocalix[4]arene (MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively) has been compared. Batch adsorption experiments were carried out and the effect of contact time, initial TBT concentration, pH and temperature were studied. The Koble-Corrigan isotherm was the most suitable for data fitting. Based on a Langmuir isotherm model, the maximum adsorption capacities were 12.1212, 16.4204 and 7.5757 mg/g for MCM-TDI-C4, MCM-TDI-PC4 and MCM-TDI-C4S, respectively. The larger uptake and stronger affinity of MCM-TDI-PC4 than MCM-TDI-C4 and MCM-TDI-C4S probably results from van der Waals interactions and the pore size distribution of MCM-TDI-PC4. Gibbs free energies for the three adsorption processes of TBT presented a negative value, reflecting that TBT/surface interactions are thermodynamic favorable and spontaneous. The interaction processes were accompanied by an increase of entropy value for MCM-TDI-C4 and MCM-TDI-C4S (43.7192 and 120.7609 J/mol K, respectively) and a decrease for MCM-TDI-PC4 (-37.4704 J/mol K). It is obviously observed that MCM-TDI-PC4 spontaneously adsorbs TBT driven mainly by enthalpy change, while MCM-TDI-C4 and MCM-TDI-C4S do so driven mainly by entropy changes.
The [Co(Me(2)Salen)(PBu(3))(OH(2))]BF4 and [Co(Me(2)Salen)(PPh(3))(Solv)]BF(4), complexes were synthesized and characterized by FT-IR, UV-Vis, (1)H NMR spectroscopy and elemental analysis techniques. The coordination geometry of [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) was determined by X-ray crystallography. It has been found that the complex is containing [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) and [Co(Me(2)Salen)(PPh(3))(EtOH)]BF(4) hexacoordinate species in the solid state. Cobalt atom exhibits a distorted octahedral geometry and the Me(2)Salen ligand has the N2O2 coordinated environment in the equatorial plane. The [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) complex shows a dimeric structure via hydrogen bonding between the phenolate oxygen and hydrogens of coordinated H2O molecule. These complexes were incorporated into Montmorillonite-K10 nanoclay. The modified clays were identified by FT-IR, XRD, EDX, TGA/DTA, SEM and TEM techniques. According to the XRD results of the new nanohybrid materials, the Schiff base complexes are intercalated in the interlayer spaces of the clay. SEM and TEM micrographs show that the resulting hybrid nanomaterials have layer structures. Also, TGA/DTG results show that the intercalation reaction was taken place successfully.
Through atomistic molecular dynamic simulations using a GROMOS53a6 force field for the carbohydrate, we studied the lyotropic reverse hexagonal phase HII from a glycolipid, namely the Guerbet branched-chain β-d-glucoside, at 14% and 22% water concentrations. Our simulations showed that at low water concentration (14%) the sugar head group overlapped extensively and protruded into the water channel. In contrast, in the 22% concentration system a water column free from the sugar headgroup ('free' water) was formed as expected for the system close to the limit of maximum hydration. In both concentrations, we found anomalous water diffusion in the xy-plane, i.e. the two-dimensional space confined by the surface of the cylinder. On the other hand, along the z-axis, the water diffusion obeyed the Einstein relation for the 22% system, while for the 14% system it was slightly anomalous. For the 22% system, the diffusion along the z-axis of the 'free' water obeyed the Einstein relation, while that of the 'bound' water is slightly anomalous. The xy-plane displacement of the 'bound' water was higher than that for the 'free' water at times longer than 200 ps, as a consequence of the exchange of water molecules between the two regions. Based on our findings, we proposed an alternative explanation to the observed spatial heterogeneity in the HII phase from probe diffusion by Penaloza et al. (Phys. Chem. Chem. Phys., 2012, 14(15), 5247-5250). We found the extent of contact with water was different at different oxygen atoms within the sugar ring. Generally, a higher probability of hydrogen bonding but a shorter lifetime was found in 22% water compared to the case of 14% water. Finally, we examined the extension and compression of the alkyl chain of a columnar.
Synthetic branched-chain glycolipids are suitable as model systems in understanding biological cell membranes, particularly because certain natural lipids possess chain branching. Herein, four branched-chain glycopyranosides, namely, 2-hexyl-decyl-α-D-glucopyranoside (α-Glc-OC10C6), 2-hexyl-decyl-β-D-glucopyranoside (β-Glc-OC10C6), 2-hexyl-decyl-α-D-galactopyranoside (α-Gal-OC10C6), and 2-hexyl-decyl-β-D-galactopyranoside (β-Gal-OC10C6), with a total alkyl chain length of 16 carbon atoms have been synthesized, and their phase behavior has been studied. The partial binary phase diagrams of these nonionic surfactants in water were investigated by optical polarizing microscopy (OPM) and small-angle X-ray scattering (SAXS). The introduction of chain branching in the hydrocarbon chain region is shown to result in the formation of inverse structures such as inverse hexagonal and inverse bicontinuous cubic phases. A comparison of the four compounds showed that they exhibited different polymorphism, especially in the thermotropic state, as a result of contributions from anomeric and epimeric effects according to their stereochemistry. The neat α-Glc-OC10C6 compound exhibited a lamellar (Lα) phase whereas dry α-Gal-OC10C6 formed an inverse bicontinuous cubic Ia3d (QII(G)) phase. Both β-anomers of glucoside and galactoside adopted the inverse hexagonal phase (HII) in the dry state. Generally, in the presence of water, all four glycolipids formed inverse bicontinuous cubic Ia3d (QII(G)) and Pn3m (QII(D)) phases over wide temperature and concentration ranges. The formation of inverse nonlamellar phases by these Guerbet branched-chain glycosides confirms their potential as materials for novel biotechnological applications such as drug delivery and crystallization of membrane proteins.
An alkaloid from Maclurodendron porteri has been isolated and characterized. Extraction process was conducted by acid-base extraction method followed by column chromatography. The structure was established by nuclear magnetic resonance spectroscopy and mass spectrometry. The compound was identified as haplophytin B which occurs commonly in the Rutaceae family. However, this is the first time this alkaloid was isolated and reported from the species. The compound showed no inhibition against Staphylococus aureus, Pseudomonas aeruginosa, Bacillus cereus and Escherichia coli and no cytotoxic activity against H199 and A549 cell lines.
Activated carbons are regularly used the treatment of dye wastewater. They can be produced from various organics materials having high level of carbon content. In this study, a novel Pinang frond activated carbon (PFAC) was produced at various CO₂ flow rates in the range of 150-600 mL/min at activation temperature of 800°C for 3 hours. The optimum PFAC sample is found on CO₂ flow rate of 300 mL/min which gives the highest BET surface area and pore volume of 958 m²/g and 0.5469 mL/g, respectively. This sample shows well-developed pore structure with high fixed carbon content of 79.74%. The removal of methylene blue (MB) by 95.8% for initial MB concentration of 50 mg/L and 72.6% for 500 mg/L is achieved via this sample. The PFAC is thus identified to be a suitable adsorbent for removing MB from aqueous solution.
Metal removal potential of both alginate-immobilized and free-cells of Effective Microorganisms (EM-1™ Inoculant) was investigated in this study. Results revealed that removal of Cr(III), Cu(II) and Pb(II) followed a similar trend where alginate-immobilized EM were more efficient compared to free-cells of EM. For these metals, 0.940, 2.695 and 4.011 mg g(-1) of Cr(III), Cu(II) and Pb(II) were removed compared to only 0.160, 0.859 and 0.755 mg ml(-1) removed by free-cells, respectively. The higher efficiency of alginate-immobilized EM was primarily attributed to the alginate matrix. This was evident when both alginate-immobilized EM and plain alginate beads (without EM), were not significantly different in their removal efficacies. Presence of alginate also enhanced the use of the biosorbents as maximum metal sorption was achieved after 120 min as opposed to only 60 min for free-cells. EM per se in immobilized or free-cell forms did not enhance metal removal efficacy.
Characteristics of X-ray transmissions were investigated for epoxy composites filled with 2-10 vol% WO3 loadings using synchrotron X-ray absorption spectroscopy (XAS) at 10-40 keV. The results obtained were used to determine the equivalent X-ray energies for the operating X-ray tube voltages of mammography and radiology machines. The results confirmed the superior attenuation ability of nano-sized WO3-epoxy composites in the energy range of 10-25 keV when compared to their micro-sized counterparts. However, at higher synchrotron radiation energies (i.e., 30-40 keV), the X-ray transmission characteristics were similar with no apparent size effect for both nano-sized and micro-sized WO3-epoxy composites. The equivalent X-ray energies for the operating X-ray tube voltages of the mammography unit (25-49 kV) were in the range of 15-25 keV. Similarly, for a radiology unit operating at 40-60 kV, the equivalent energy range was 25-40 keV, and for operating voltages greater than 60 kV (i.e., 70-100 kV), the equivalent energy was in excess of 40 keV. The mechanical properties of epoxy composites increased initially with an increase in the filler loading but a further increase in the WO3 loading resulted in deterioration of flexural strength, modulus and hardness.
A new microextraction procedure termed agarose gel liquid phase microextraction (AG-LPME) combined with gas chromatography-mass spectrometry (GC-MS) was developed for the determination of selected polycyclic aromatic hydrocarbons (PAHs) in water. The technique utilized an agarose gel disc impregnated with the acceptor phase (1-octanol). The extraction procedure was performed by allowing the solvent-impregnated agarose gel disc to tumble freely in the stirred sample solution. After extraction, the agarose gel disc was removed and subjected to centrifugation to disrupt its framework and to release the impregnated solvent, which was subsequently withdrawn and injected into the GC-MS for analysis. Under optimized extraction conditions, the new method offered high enrichment factors (89-177), trace level LODs (9-14ngL(-1)) and efficient extraction with good relative recoveries in the range of 93.3-108.2% for spiked drinking water samples. AG-LPME did not exhibit any problems related to solvent dissolution, and it provided high extraction efficiencies that were comparable to those of hollow fiber liquid phase microextraction (HF-LPME) and significantly higher than those of agarose film liquid phase microextraction (AF-LPME). This technique employed a microextraction format and utilized an environmentally compatible solvent holder that supported the green chemistry concept.
A new homoleptic dithiolene tungsten complex, tris-{1,2-bis(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten, was successfully synthesized via a reaction of the thiophosphate ester and sodium tungstate. The thiophosphate ester was prepared from 3,5-dimethoxybenzaldehyde via benzoin condensation to produce the intermediate 1,2-bis-(3,5-dimethoxyphenyl)-2-hydroxy-ethanone compound, followed by a reaction of the intermediate with phosphorus pentasulfide. FTIR, UV-Vis spectroscopy, 1H NMR and 13C NMR and elemental analysis confirmed the product as tris{1,2-bis-(3,5-dimethoxyphenyl)-1,2-ethylenodithiolene-S,S'}tungsten with the molecular formula of C54H54O12S6W. Crystals of the product adopted a monoclinic system with space group of P2(1)/n, where a=12.756(2) Å, b=21.560(3) Å, c=24.980(4) Å and β=103.998(3)°. Three thioester ligands were attached to the tungsten as bidentate chelates to form a distorted octahedral geometry. Density functional theory calculations were performed to investigate the molecular properties in a generalized-gradient approximation framework system using Perdew-Burke-Ernzerhof functions and a double numeric plus polarization basis set. The HOMO was concentrated on the phenyl ligands, while the LUMO was found along the W(S2C2)3 rings. The theoretical optical properties showed a slight blue shift in several low dielectric solvents. The solvatochromism effect was insignificant for high polar solvents.
In this study, the interactions of α-tocopherol (α-TOH) in PVOH-starch blends were investigated. α-TOH is an interacting agent possesses a unique molecule of polar chroman "head" and non-polar phytyl "tail" which can improve surface interaction of PVOH and starch. It showed favorable results when blending PVOH-starch with α-TOH, where the highest tensile strengths were achieved at 60 wt.% PVOH-starch blend for 1 phr α-TOH and 50 wt.% for 3 phr α-TOH, respectively. This due to the formation of miscible PVOH-starch as resulted by the compatibilizing effect of α-TOH. Moreover, the enthalpy of melting (ΔHm) of 60 wt.% PVOH-starch and 50 wt.% PVOH-starch added with 1 and 3 phr α-TOH respectively were higher than ΔHm of the neat PVOH-starch blends. The thermogravimetry analysis also showed that α-TOH can be used as thermal stabilizer to reduce weight losses at elevated temperature. The surface morphologies of the compatible blends formed large portion of continuous phase where the starch granules interacted well with α-TOH by acting as compatilizer to reduce surface energy of starch for embedment into PVOH matrix.
Natural styrylpyrones isolated from fungi are known for various biological activities including antioxidant activity by scavenging free radicals. UV/vis spectra play an important role in elucidating chemical structures of these compounds via identification of chromophore units. With the aim of predicting the UV/vis spectra of a series of natural styrylpyrones, we tested TD-DFT, CIS and ZINDO methods in gas and in PCM solvent. The results showed that the individual or combined B3P86 and B3LYP hybrid functionals are suitable to predict the maximum wavelength absorption bands (λmax) for styrylpyrones. The structure property relationship (SPR) study emphasized the role of (i) structural parameters (e.g., hydrogen bond and the length of conjugated double bonds) and (ii) electronic descriptors (e.g., ionization potential, electronic affinity, hardness and electrophilicity) in bathochromic and hypsochromic shifts of maximum wavelength absorption bands (λmax) of styrylpyrone derivatives.
Two new indole alkaloids, voatinggine (1) and tabertinggine (2), which are characterized by previously unencountered natural product skeletons, were isolated from a Malayan Tabernaemontana species. The structures and absolute configuration of these alkaloids were determined using NMR and MS analysis, and X-ray diffraction analysis. A possible biogenetic pathway to these novel alkaloids from an iboga precursor, and via a common cleavamine-type intermediate, is presented.
Ozone-oxidised starches were prepared from the native starches isolated from white and red cocoyam, and white and yellow yam cultivars. The native and oxidised starches were evaluated for functional, thermal and molecular properties. The correlations between the amount of reacted ozone and carbonyl and carboxyl contents of the starches were positive, as ozone generation time (OGT) increased. Significant differences were obtained in terms of swelling power, solubility, pasting properties and textural properties of the native starches upon oxidation. The DSC data showed lower transition temperatures and enthalpies for retrograded gels compared to the gelatinized gels of the same starch types. The native starches showed CB-type XRD patterns while the oxidised starches resembled the CA-type pattern. As amylose content increased, amylopectin contents of the starches decreased upon oxidation. Similarly, an increase in Mw values were observed with a corresponding decrease in Mn values upon oxidation.
We describe a server that allows the interrogation of the Protein Data Bank for hypothetical 3D side chain patterns that are not limited to known patterns from existing 3D structures. A minimal side chain description allows a variety of side chain orientations to exist within the pattern, and generic side chain types such as acid, base and hydroxyl-containing can be additionally deployed in the search query. Moreover, only a subset of distances between the side chains need be specified. We illustrate these capabilities in case studies involving arginine stacks, serine-acid group arrangements and multiple catalytic triad-like configurations. The IMAAAGINE server can be accessed at http://mfrlab.org/grafss/imaaagine/.