Oil and grease remain the dominant contaminants in the palm oil mill effluent (POME) despite the conventional treatment of POME. The removal of residual oil from palm oil-water mixture (POME model) using the progressive freezing process was investigated. An optimization technique called response surface methodology (RSM) with the design of rotatable central composite design was applied to figure out the optimum experimental variables generated by Design-Expert software (version 6.0.4. Stat-Ease, trial version). Besides, RSM also helps to investigate the interactive effects among the independent variables compared to one factor at a time. The variables involved are coolant temperature, XA (4-12 °C), freezing time, XB (20-60 min), and circulation flow, XC (200-600 rpm). The statistical analysis showed that a two-factor interaction model was developed using the obtained experimental data with a coefficient of determination (R2) value of 0.9582. From the RSM-generated model, the optimum conditions for extraction of oil from the POME model were a coolant temperature of 6 °C in 50 min freezing time with a circulation flowrate of 500 rpm. The validation of the model showed that the predicted oil yield and experimental oil yield were 92.56 and 93.20%, respectively.
A new class of liquid crystalline acetylide-imine system was successfully synthesized, characterized
and deposited on indium tin oxide (ITO) coated substrate via electrochemical deposition
method for potential organic film application. The relationship between liquid crystal
molecular structure, phase transition temperature and electrical performance was evaluated.
The mesomorphic properties were identified via polarized optic microscopy (POM) which displayed
fan-shaped texture of smectic A phase and their corresponding transition enthalpies
are in concurrence with DSC and TGA studies. The findings from the conductivity analysis
revealed that the fabricated film exhibits good electrical performance where it displayed
linear current-voltage relationship of I-V curve. Therefore, this proposed type of molecular
framework has given an ideal indication to act as transporting material for application in
optoelectronic devices.
Isonicotinamide-4-methoxybenzoic acid co-crystal (1), C6H6N2O·C8H8O3, is formed through slow evaporation from methanol solution and it undergoes a first-order isosymmetry (monoclinic I2/a ↔ monoclinic I2/a) structural phase transition at Tc= 142.5 (5) K, which has been confirmed by an abrupt jump of crystallographic interaxial angle β from variable-temperature single-crystal XRD and small heat hysteresis (6.25 K) in differential scanning calorimetry measurement. The three-dimensional X-ray crystal structures of (1) at the low-temperature phase (LTP) (100, 140 and 142 K) and the high-temperature phase (HTP) (143, 150, 200, 250 and 300 K) were solved and refined as a simple non-disordered model with final R[F2> 2σ(F2)] ≃ 0.05. The asymmetric unit of (1) consists of crystallographically independent 4-methoxybenzoic acid (A) and isonicotinamide (B) molecules in both enantiotropic phases. Molecule A adopts a `near-hydroxyl' conformation in which the hydroxyl and methoxy groups are positioned on the same side. Both `near-hydroxyl' and `near-carbonyl' molecular conformations possess minimum conformational energies with an energy difference of phases. However, these ABBA arrays are displaced from planarity upon LTP-to-HTP transition and the changes in inter-array interactions are observed in two-dimensional fingerprint plots of their Hirshfeld surfaces. The PIXEL energies of each molecular pair in both phases were calculated to investigate the difference in intermolecular interaction energies before and after the displacement of ABBA arrays from planarity, which directly leads to the single-crystal-to-single-crystal phase transition of (1).
Understanding crystallization behaviors is of utmost importance for developing robust amorphous pharmaceutical solids. Herein, the crystal growth behaviors of amorphous anti-inflammatory drug nimesulide (NIME) are systemically investigated in the glassy and supercooled liquid state as a function of temperature. A sudden over-tenfold increase is observed in the bulk crystal growth of NIME on cooling below its glass transition temperature (Tg). This fast growth behavior is known as a glass-to-crystal (GC) mode and has been reported in some molecular glasses. Fast surface crystal growth of NIME can persist up to Tg + 57°C with a weak jump in its growth rates at 30-40°C. In addition, surface crystal growth and GC growth of NIME exhibit an almost identical temperature dependence, supporting the view that GC growth is indeed a surface-facilitated process. Moreover, the bubble-induced fast crystal growth of NIME is observed in the interior of its supercooled liquid with approximately the same growth kinetics as surface crystal growth. These findings are relevant for a full understanding of the surface-related crystallization behaviors and physical stability of amorphous pharmaceutical formulations.
The title compound, 3,5,7-triaza-1-azoniatricyclo[3.3.1.1(3,7)]decane 2,4-dinitrophenolate monohydrate, C6H13N4+*C6H3N2O5-*H2O, the 1:1 hydrate adduct of hexamethylenetetramine (HMT) and 2,4-dinitrophenol, undergoes a temperature phase transition. In the room-temperature phase, the adduct crystallizes in the monoclinic P2(1)/m space group, whereas in the low-temperature phase, the adduct crystallizes in the triclinic P1 space group. This phase transition is reversible, with the transition temperature at 273 K, and the phase transition is governed by hydrogen bonds and weak interactions. In both these temperature-dependent polymorphs, the crystal structure is alternately layered with sheets of hexamethylenetetramine and sheets of dinitrophenol stacked along the c axis. The hexamethylenetetramine and dinitrophenol moieties are linked by intermolecular hydrogen bonds. The water molecule in the adduct plays an important role, forming O-H...O hydrogen bonds which, together with C-H...O hydrogen bonds, bridge the adducts into molecular ribbons. Extra hydrogen bonds and weak interactions exist for the low-temperature polymorph and these interconnect the molecular ribbons into a three-dimensional packing structure. Also in these two temperature-dependent polymorphs, dinitrophenol acts as a hydrogen-bond acceptor and HMT acts as a hydrogen-bond donor.
A sample of hydronium perchlorate, H(3)O(+) x ClO(4)(-), crystallized from ethanol at ambient temperature, was found to be orthorhombic (space group Pnma) at both 193 and 293 K, with no phase transition observed in this temperature range. This contrasts with the earlier observation [Nordman (1962). Acta Cryst. 15, 18-23] of a monoclinic phase (space group P2(1)/n) at 193 K for crystals grown at that temperature from perchloric acid. The hydronium and perchlorate ions lie across a mirror plane but it is not possible to define at either temperature a simple description of the H-atom positions due to the three-dimensional tumbling of the hydronium cation.
The catalytic activity of free laccase and a novel sol-gel laccase (SOLAC) in ionic liquids and organic solvents was demonstrated by using 2,6-dimethoxyphenol (2,6-DMP) as a substrate. The enhancement of the catalytic activity of the SOLAC was observed and compared to the free laccase in both media. The oxidative biodegradation of o-chlorophenol as a model of phenolic environmental pollutants in organic media shows that the degradation was observed only when using water pre-saturated organic solvents or reverse micelle system. The SOLAC gave higher biodegradation rate in either aqueous or organic solvents, in which the optimum temperature was observed at 40 °C for the reverse micelle system as a reaction medium. All results demonstrated the potential use of the SOLAC for biodegradation of phenolic environmental pollutants in non-conventional media.
An extractive fermentation technique was developed using a thermoseparating reagent to form a two-phase system for simultaneous cell cultivation and downstream processing of extracellular Burkholderia cepacia lipase. A 10% (w/w) solution of ethylene oxide-propylene oxide (EOPO) with a molecular mass of 3900 g/mol and pH 8.5, a 200 rpm speed, and 30 °C were selected as the optimal conditions for lipase production (55 U/ml). Repetitive batch fermentation was performed by continuous replacement of the top phase every 24h, which resulted in an average cell growth mass of 4.7 g/L for 10 extractive batches over 240 h. In scaling-up the process, a bench-scale bioreactor was tested under the conditions that had been optimized in flasks. The production rate and recovery yield were higher in the bioreactor compared to fermentation performed in flasks.
The performance of a compost biofilter inoculated with mixed microbial consortium was optimized for treating a gas-phase mixture of benzene and toluene. The biofilter was acclimated to these VOCs for a period of ∼18d. The effects of concentration and flow rate on the removal efficiency (RE) and elimination capacity (EC) were investigated by varying the inlet concentration of benzene (0.12-0.95g/m(3)), toluene (0.14-1.48g/m(3)) and gas-flow rate (0.024-0.072m(3)/h). At comparable loading rates, benzene removal in the mixture was reduced in the range of 6.6-41% in comparison with the individual benzene degradation. Toluene removal in mixture was even more affected as observed from the reductions in REs, ranging from 18.4% to 76%. The results were statistically interpreted by performing an analysis of variance (ANOVA) to elucidate the main and interaction effects.
In this work, crude oil biodegradation has been optimized in a solid-liquid two phase partitioning bioreactor (TPPB) by applying a response surface methodology based d-optimal design. Three key factors including phase ratio, substrate concentration in solid organic phase, and sodium chloride concentration in aqueous phase were taken as independent variables, while the efficiency of the biodegradation of absorbed crude oil on polymer beads was considered to be the dependent variable. Commercial thermoplastic polyurethane (Desmopan®) was used as the solid phase in the TPPB. The designed experiments were carried out batch wise using a mixed acclimatized bacterial consortium. Optimum combinations of key factors with a statistically significant cubic model were used to maximize biodegradation in the TPPB. The validity of the model was successfully verified by the good agreement between the model-predicted and experimental results. When applying the optimum parameters, gas chromatography-mass spectrometry showed a significant reduction in n-alkanes and low molecular weight polycyclic aromatic hydrocarbons. This consequently highlights the practical applicability of TPPB in crude oil biodegradation.
Composite sago starch-based system was developed and characterized with the aim to find an alternative to gelatin in the processing of pharmaceutical capsules. Dually modified (Hydrolyzed-Hydroxypropylated) sago starches were combined with κ-carrageenan (0.25, 0.5, 0.75, and 1%). The rheological properties of the proposed composite system were measured and compared with gelatin as reference material. Results show that combination of HHSS12 (Hydrolysed-hydroxypropylated sago starch at 12h) with 0.5% κ-carrageenan was comparable to gelatin rheological behavior in pharmaceutical capsule processing. The solution viscosity at 50 °C and sol-gel transition of the proposed composite system were comparable to those of gelatin. The viscoelastic moduli (G' and G") for the proposed system were lower than those of gelatin. These results illustrate that by manipulation of the constituents of sago starch-based composite system, a suitable alternative to gelatin can be produced with comparable properties and this could find potential application in pharmaceutical capsule industry.
Graft copolymerisation of methyl methacrylate (MMA) onto Agave angustifolia was conducted with ceric ammonium nitrate (CAN) as the redox initiator. The maximum grafting efficiency was observed at CAN and MMA concentrations of 0.91 × 10(-3) and 5.63 × 10(-2)M, respectively, at 45°C for 3h reaction time. Four characteristic peaks at 2995, 1738, 1440, and 845 cm(-1), attributed to PMMA, were found in the IR spectrum of grafted cellulose. The crystallinity index dropped from 0.74 to 0.46, while the thermal stability improved upon grafting. The water contact angle increased with grafting yield, indicating increased hydrophobicity of cellulose. SEM images showed the grafted cellulose to be enlarged and rougher. The changes in the physical nature of PMMA-grafted cellulose can be attributed to the PMMA grafting in the amorphous regions of cellulose, causing it to expand at the expense of the crystalline component.
The control effects on the convection dynamics in a viscoelastic fluid-saturated porous medium heated from below and cooled from above are studied. A truncated Galerkin expansion was applied to balance equations to obtain a four-dimensional generalized Lorenz system. The dynamical behavior is mainly characterized by the Lyapunov exponents, bifurcation, and isospike diagrams. The results show that within a range of moderate and high Rayleigh numbers, proportional controller gain is found to enhance the stabilization and destabilization effects on the thermal convection. Furthermore, due to the effect of viscoelasticity, the system exhibits remarkable topological structures of regular regions embedded in chaotic domains.
The optical properties of a ZnO photocatalyst were enhanced with various dopant concentrations of Fe(3+). Doped ZnO nanoparticles were synthesized via a sol-gel method without the use of capping agents or surfactants and was then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet-visible (UV-Vis) spectroscopy. The results showed that ZnO has a wurtzite, hexagonal structure and that the Fe(3+) ions were well incorporated into the ZnO crystal lattice. As the Fe(3+) concentration increased from 0.25 wt.% to 1 wt.%, the crystal size decreased in comparison with the undoped ZnO. The spectral absorption shifts of the visible light region (red shift) and the band gap decreases for each Fe-ZnO sample were investigated. The photocatalytic activities of the ZnO and Fe-ZnO samples were evaluated based on the degradation of 2-chlorophenol in aqueous solution under solar radiation. The samples with a small concentration of Fe(3+) ions showed enhanced photocatalytic activity with an optimal maximum performance at 0.5 wt.%. The results indicated that toxicity removal of 2-chlorophenol at same line of degradation efficiency. Small crystallite size and low band gap were attributed to high activities of Fe-ZnO samples under various concentrations of Fe(3+) ions compared to undoped ZnO.
A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL(-1) for phosphamidon and dimethoate, and 10-100 pg mL(-1) for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL(-1) for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL(-1)) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g(-1)) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.
Two novel glycolipids have been synthesized and their phase behaviour studied. They have been characterized using FT-IR, FAB and 13C NMR and 1H NMR to ensure the purity of novel glycolipids. The two glycolipids are distinguished based on the head group of glycolipids (monosaccharide/glucose and disaccharide/maltose). These two novel glycolipids have been used as surfactant to perform two phase diagrams. Phase behaviours that have been investigated are 2-hexyldecyl-beta-D-glucopyranoside (2-HDG)/n-octane/water ternary system and 2-hexyldecyl-beta-D-maltoside (2-HDM)/n-octane/water ternary system. SAXS and polarizing optical microscope have been used to study the phase behaviours of these two surfactants in ternary phase diagram. Study of effect of the head group on branched-alkyl chain surfactants in ternary system is a strategy to derive the structure-property relationship. For comparison, 2-HDM and 2-HDG have been used as surfactant in the same ternary system. The phase diagram of 2-hexyldecyl-beta-D-maltoside/n-octane/water ternary system exhibited a Lalpha phase at a higher concentration regime, followed with two phases and a micellar solution region in a lower concentration regime. The phase diagram of 2-HDG/water/n-octane ternary system shows hexagonal phase, cubic phase, rectangular ribbon phase, lamellar phase, cubic phase as the surfactant concentration increase.
The purpose of this study was to select appropriate surfactants or blends of surfactants to study the ternary phase diagram behavior of newly introduced palm kernel oil esters.
The problem of entropy generation analysis and natural convection in a nanofluid square cavity with a concentric solid insert and different temperature distributions is studied numerically by the finite difference method. An isothermal heater is placed on the bottom wall while isothermal cold sources are distributed along the top and side walls of the square cavity. The remainder of these walls are kept adiabatic. Water-based nanofluids with Al 2 O 3 nanoparticles are chosen for the investigation. The governing dimensionless parameters of this study are the nanoparticles volume fraction ( 0 ≤ ϕ ≤ 0.09 ), Rayleigh number ( 10 3 ≤ R a ≤ 10 6 ) , thermal conductivity ratio ( 0.44 ≤ K r ≤ 23.8 ) and length of the inner solid ( 0 ≤ D ≤ 0.7 ). Comparisons with previously experimental and numerical published works verify a very good agreement with the proposed numerical method. Numerical results are presented graphically in the form of streamlines, isotherms and local entropy generation as well as the local and average Nusselt numbers. The obtained results indicate that the thermal conductivity ratio and the inner solid size are excellent control parameters for an optimization of heat transfer and Bejan number within the fully heated and partially cooled square cavity.
Marine biofouling causes problems to marine structure and obstructs condenser tubes in cooling systems which use sea water as the coolant. The main purpose of this study is to investigate the seasonal ecology of biofouling organisms such as the green mussel, Perna viridis, the dominant fouling species in the Eastern Johore Straits at the Senoko Power Station. The spawning time and its relationship with environmental conditions were studied. The physical, chemical and biological conditions of the sea at Senoko were monitored for a year. Settling slides were used to study the fouling succession in different monsoon seasons. The study showed that there were two main spawning peaks for the green mussel and that these peaks occurred during the intermonsoon months of November and April. These peaks were also correlated with the bimodal patterns for salinity, dissolved oxyen, bivalve veliger larval density and total plankton biomass of the Eastern Johore Strait water. Succession patterns were similar during the two monsoon seasons, however, the rate of fouling was probably greater during the southwest monsoon months. It is therefore advisable that the control or reduction of biofouling in Eastern Johore Strait should take into account the seasonal fluctuations and spawning of the fouling organisms.
For the synthesis of a highly active TiO2-chitosan nanocomposite, pH plays a crucial role towards controlling its morphology, size, crystallinity, thermal stability, and surface adsorption properties. The presence of chitosan (CS) biopolymer facilitates greater sustainability to the photoexcited electrons and holes on the catalysts' surface. The variation of synthesis pH from 2 to 5 resulted in different physico-chemical and photocatalytic properties, whereby a pH of 3 resulted in TiO2-chitosan nanocomposite with the highest photocatalytic degradation (above 99 %) of methylene orange (MO) dye. This was attributed to the efficient surface absorption properties, high crystallinity, and the presence of reactive surfaces of -NH2 and -OH groups, which enhances the adsorption-photodegradation effect. The larger surface oxygen vacancies coupled with reduced electron-hole recombination further enhanced the photocatalytic activity. It is undeniable that the pH during synthesis is critical towards the development of the properties of the TiO2-chitosan nanocomposite for the enhancement of photocatalytic activity.