A theoretical study of a series of five glucose based glycolipid crown ethers and their complexes with Na(+) and K(+) was performed using the density functional theory with B3LYP/6-31 G* to obtain the optimized geometrical structures and electronic properties. The local nucleophilicity of the five molecules was investigated using Fukui function, while the global nucleophilicity was calculated from the ionization potential and electron affinity. The structures and coordination of the complexes were studied to identify the best match of the glycolipid crown ethers with cations. In general, it was found that the oxygen atoms pairs O2 and O3 (or O4 and O6) on the sugar ring are constrained from moving toward the cation, which results in a weaker O-cation coordination strength for the oxygen pair compared to the other oxygen atoms in the crown ether ring. The thermodynamic properties of the binding of the complexes and the exchange reaction in gas phase were evaluated. The cation selectivity pattern among the five molecules was in good agreement with the experiment.
A series of experiments were carried out to determine the best medium for the recovery of cobalt by means of an electrogenerative system. Use of the electrogenerative system with a chloride medium had shown promising performance with the highest free energy of -389.8 kJ mol(-1) compared to that with sulphate and nitrate media. Subsequently, the influence of catholyte concentrations on cobalt recovery using the electrogenerative process was carried out by varying the initial cobalt concentration and sodium chloride concentration. The results showed that almost 100% recovery was attained within 1-4 h of the recovery process. Influence of pH was investigated where the electrogenerative system performed best between pH 5.0 and 7.0. Maximum cell performance of 83% with 99% cobalt removal was obtained at 90 min when 100 mg L(-1) of Co(2+) in 0.5 M NaCl was taken as catholyte solution. The values of ΔH(o) and ΔS(o) of the process were evaluated as 33.41 kJ mol(-1) and 0.13 kJ mol(-1), respectively.
Sunflower seed oil residue, a by-product of sunflower seed oil refining, was utilized as a feedstock for preparation of activated carbon (SSHAC) via microwave induced K(2)CO(3) chemical activation. SSHAC was characterized by Fourier transform infrared spectroscopy, nitrogen adsorption-desorption and elemental analysis. Surface acidity/basicity was examined with acid-base titration, while the adsorptive properties of SSHAC were quantified using methylene blue (MB) and acid blue 15 (AB). The monolayer adsorption capacities of MB and AB were 473.44 and 430.37 mg/g, while the Brunauer-Emmett-Teller surface area, Langmuir surface area and total pore volume were 1411.55 m(2)/g, 2137.72 m(2)/g and 0.836 cm(3)/g, respectively. The findings revealed the potential to prepare high surface area activated carbon from sunflower seed oil residue by microwave irradiation.
New coumarin derivatives, namely 7-[(5-amino-1,3,4-thiadiazol-2-yl)methoxy]-2H-chromen-2-one, 5-[(2-oxo-2H-chromen-7-yloxy)methyl]-1,3,4-thiadiazol-2(3H)-one, 2-[2-(2-oxo-2H-chromen-7-yloxy)acetyl]-N-phenylhydrazinecarbothioamide, 7-[(5-(phenylamino)-1,3,4-thiadiazol-2-yl)methoxy]-2H-chromen-2-one and 7-[(5-mercapto-4-phenyl-4H-1,2,4-triazol-3-yl)methoxy]-2H-chromen-2-one were prepared starting from the natural compound umbelliferone. The newly synthesized compounds were characterized by elemental analysis and spectral studies (IR, ¹H-NMR and ¹³C-NMR).
The secondary structure of RNA pseudoknots has been extensively inferred and scrutinized by computational approaches. Experimental methods for determining RNA structure are time consuming and tedious; therefore, predictive computational approaches are required. Predicting the most accurate and energy-stable pseudoknot RNA secondary structure has been proven to be an NP-hard problem. In this paper, a new RNA folding approach, termed MSeeker, is presented; it includes KnotSeeker (a heuristic method) and Mfold (a thermodynamic algorithm). The global optimization of this thermodynamic heuristic approach was further enhanced by using a case-based reasoning technique as a local optimization method. MSeeker is a proposed algorithm for predicting RNA pseudoknot structure from individual sequences, especially long ones. This research demonstrates that MSeeker improves the sensitivity and specificity of existing RNA pseudoknot structure predictions. The performance and structural results from this proposed method were evaluated against seven other state-of-the-art pseudoknot prediction methods. The MSeeker method had better sensitivity than the DotKnot, FlexStem, HotKnots, pknotsRG, ILM, NUPACK and pknotsRE methods, with 79% of the predicted pseudoknot base-pairs being correct.
Photopyroelectric (PPE) spectroscopy is a nondestructive tool that is used to study the optical properties of the ceramics (ZnO + 0.4MnO(2) + 0.4Co(3)O(4) + xV(2)O(5)), x = 0-1 mol%. Wavelength of incident light, modulated at 10 Hz, was in the range of 300-800 nm. PPE spectrum with reference to the doping level and sintering temperature is discussed. Optical energy band-gap (E(g)) was 2.11 eV for 0.3 mol% V(2)O(5) at a sintering temperature of 1025 °C as determined from the plot (ρhυ)(2)versushυ. With a further increase in V(2)O(5), the value of E(g) was found to be 2.59 eV. Steepness factor 'σ(A)' and 'σ(B)', which characterize the slope of exponential optical absorption, is discussed with reference to the variation of E(g). XRD, SEM and EDAX are also used for characterization of the ceramic. For this ceramic, the maximum relative density and grain size was observed to be 91.8% and 9.5 μm, respectively.
The optical band-gap energy (E(g)) is an important feature of semiconductors which determines their applications in optoelectronics. Therefore, it is necessary to investigate the electronic states of ceramic ZnO and the effect of doped impurities under different processing conditions. E(g) of the ceramic ZnO + xBi(2)O(3) + xTiO(2), where x = 0.5 mol%, was determined using a UV-Vis spectrophotometer attached to a Reflectance Spectroscopy Accessory for powdered samples. The samples was prepared using the solid-state route and sintered at temperatures from 1140 to 1260 °C for 45 and 90 minutes. E(g) was observed to decrease with an increase of sintering temperature. XRD analysis indicated hexagonal ZnO and few small peaks of intergranular layers of secondary phases. The relative density of the sintered ceramics decreased and the average grain size increased with the increase of sintering temperature.
Binding constants for the enantiomers of modafinil with the negatively charged chiral selector sulfated-β-CD (S-β-CD) using CE technique is presented. The calculations of the binding constants employing three different linearization plots (double reciprocal, X-reciprocal and Y-reciprocal) were performed from the electrophoretic mobility values of modafinil enantiomers at different concentrations of S-β-CD in the BGE. The highest inclusion affinity of the modafinil enantiomers were observed for the S-enantiomer-S-β-CD complex, in agreement with the computational calculations performed previously. Binding constants for each enantiomer-S-β-CD complex at different temperatures, as well as thermodynamic parameters for binding, were calculated. Host-guest binding constants using the double reciprocal fit showed better linearity (r(2)>0.99) at all temperatures studied (15-30°C) and compared with the other two fit methods. The linear van't Hoff (15-30°C) plot obtained indicated that the thermodynamic parameters of complexation were temperature dependent for the enantiomers.
The feasibility of using papaya seeds (PS), abundantly available waste in Malaysia, for the cationic dye (methylene blue) adsorption has been investigated. Batch adsorption studies were conducted to study the effects of contact time, initial concentration (50-360 mg/L), pH (3-10) and adsorbent dose (0.05-1.00 g) on the removal of methylene blue (MB) at temperature of 30 degrees C. The equilibrium data were analyzed by the Langmuir, the Freundlich and the Temkin isotherms. The data fitted well with the Langmuir model with a maximum adsorption capacity of 555.557 mg/g. The pseudo-second-order kinetics was the best for the adsorption of MB by PS with good correlation. The results demonstrated that the PS is very effective to remove methylene blue from aqueous solutions.
The ability of white-rot fungus, Pycnoporus sanguineus to adsorb copper (II) ions from aqueous solution is investigated in a batch system. The live fungus cells were immobilized into Ca-alginate gel to study the influence of pH, initial metal ions concentration, biomass loading and temperature on the biosorption capacity. The optimum uptake of Cu (II) ions was observed at pH 5 with a value of 2.76mg/g. Biosorption equilibrium data were best described by Langmuir isotherm model followed by Redlich-Peterson and Freundlich models, respectively. The biosorption kinetics followed the pseudo-second order and intraparticle diffusion equations. The thermodynamic parameters enthalpy change (10.16kJ/mol) and entropy change (33.78J/molK) were determined from the biosorption equilibrium data. The FTIR analysis showed that OH, NH, CH, CO, COOH and CN groups were involved in the biosorption of Cu (II) ions onto immobilized cells of P. sanguineus. The immobilized cells of P. sanguineus were capable of removing Cu (II) ions from aqueous solution.
Activated carbon derived from rattan sawdust (ACR) was evaluated for its ability to remove phenol from an aqueous solution in a batch process. Equilibrium studies were conducted in the range of 25-200mg/L initial phenol concentrations, 3-10 solution pH and at temperature of 30 degrees C. The experimental data were analyzed by the Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherm models. Equilibrium data fitted well to the Langmuir model with a maximum adsorption capacity of 149.25mg/g. The dimensionless separation factor RL revealed the favorable nature of the isotherm of the phenol-activated carbon system. The pseudo-second-order kinetic model best described the adsorption process. The results proved that the prepared activated carbon was an effective adsorbent for removal of phenol from aqueous solution.
The sorption of basic dye from aqueous solutions by banana stalk waste (BSW), an abundant agricultural waste in Malaysia, was studied in a batch system with respect to pH and initial dye concentration. Sorption isotherm of methylene blue (MB) onto the BSW was determined at 30 degrees C with the initial concentrations of MB in the range of 50-500 mg/L. At pH 2.0, the sorption of dye was not favorable, while the sorption at other pHs (4.0-12.0) was remarkable. Equilibrium data were fitted to the Langmuir, Freundlich and Temkin isotherm models. The equilibrium data were best represented by the Langmuir isotherm model, with maximum monolayer adsorption capacity of 243.90 mg/g. The sorption kinetic data were analyzed using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. It was found that the pseudo-second-order kinetic model was the best applicable model to describe the sorption kinetics. The results showed that BSW sorbent was a promising for the removal of MB from aqueous solutions.
In this paper, the ability of coconut bunch waste (CBW), an agricultural waste available in large quantity in Malaysia, to remove basic dye (methylene blue) from aqueous solution by adsorption was studied. Batch mode experiments were conducted at 30 degrees C to study the effects of pH and initial concentration of methylene blue (MB). Equilibrium adsorption isotherms and kinetics were investigated. The experimental data were analyzed by the Langmuir, Freundlich and Temkin models of adsorption. The adsorption isotherm data were fitted well to Langmuir isotherm and the monolayer adsorption capacity was found to be 70.92 mg/g at 30 degrees C. The kinetic data obtained at different concentrations have been analyzed using a pseudo-first-order, pseudo-second-order equation and intraparticle diffusion equation. The experimental data fitted very well the pseudo-second-order kinetic model.
Calcium borate nanoparticles have been synthesized by a thermal treatment method via facile co-precipitation. Differences of annealing temperature and annealing time and their effects on crystal structure, particle size, size distribution and thermal stability of nanoparticles were investigated. The formation of calcium borate compound was characterized by X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FTIR), Transmission electron microscopy (TEM), and Thermogravimetry (TGA). The XRD patterns revealed that the co-precipitated samples annealed at 700 °C for 3 h annealing time formed an amorphous structure and the transformation into a crystalline structure only occurred after 5 h annealing time. It was found that the samples annealed at 900 °C are mostly metaborate (CaB(2)O(4)) nanoparticles and tetraborate (CaB(4)O(7)) nanoparticles only observed at 970 °C, which was confirmed by FTIR. The TEM images indicated that with increasing the annealing time and temperature, the average particle size increases. TGA analysis confirmed the thermal stability of the annealed samples at higher temperatures.
Oligostilbenoids (e.g., ampelopsin F, viniferin, pallidol) result from homogeneous or heterogeneous coupling of monomeric stilbenoid units, leading to various chemical structures. Oligostilbenoid synthesis is regio- and stereocontrolled. To tackle this regio- and stereocontrol, a supramolecular chemistry approach is required that can be achieved by quantum chemistry. The stability of noncovalent π-stacks, formed between two stilbenoid units prior to oxidation, is accurately evaluated with density functional theory (DFT) including dispersive effects (within the DFT-D formalism). These noncovalent arrangements drive the regiocontrol. The rest of the chemical pathway is a succession of dearomatization and rearomatization stages. The thermodynamics and kinetics of the processes are calculated with classical hybrid functionals. This study allows discrimination between the two main possible chemical pathways, namely, radical-neutral and radical-radical reactions. The former appears more likely, thermodynamics and kinetics being in perfect agreement with the experimental 1:2 ratio obtained for ampelopsin F:pallidol analogues, respectively.
We examined the solubility of simvastatin in water in 0.01 mol·dm(-3), 0.02 mol·dm(-3), 0.04 mol·dm(-3), 0.09 mol·dm(-3), 0.18 mol·dm(-3), 0.36 mol·dm(-3), and 0.73 mol·dm(-3) arginine (ARG) solutions. The investigated drug is termed the solute, whereas ARG the cosolute. Phase solubility studies illustrated a higher extent of solubility enhancement for simvastatin. The aforementioned system was subjected to conductometric and volumetric measurements at temperatures (T) of 298.15 K, 303.15 K, 308.15 K, and 313.15 K to illustrate the thermodynamics involved and related solute-solvent interactions. The conductance values were used to evaluate the limiting molar conductance and association constants. Thermodynamic parameters (ΔG (0), ΔH (0), ΔS (0), and E s) for the association process of the solute in the aqueous solutions of ARG were calculated. Limiting partial molar volumes and expansibilities were evaluated from the density values. These values are discussed in terms of the solute-solvent and solute-cosolute interactions. Further, these systems were analyzed using ultraviolet-visible analysis, Fourier-transform infrared spectroscopy, and (13)C, (1)H, and two-dimensional nuclear overhauser effect spectroscopy nuclear magnetic resonance to complement thermophysical explanation.
In this study, the removal of natural organic matter (NOM) using coconut fiber (CF) and palm oil fiber (POF) was investigated. Preliminary analysis was performed using a jar test for the selection of optimal medium before the fabricated column model experiment. The equilibrium studies on isotherms and kinetic models for NOM adsorption were analyzed using linearized correlation coefficient. Results showed that the equilibrium data were fitted to Langmuir isotherm model for both CF and POF. The most suitable adsorption model was the pseudo-first-order kinetic model for POF and pseudo-second-order kinetic model for CF. The adsorption capacities achieved by the CF and POF were 15.67 and 30.8 mg/g respectively. Based on this investigation, it can be concluded that the POF is the most suitable material for the removal of NOM in semi polluted river water.
Polyhydroxyalkanoate (PHA) recovery from aerobic granules was investigated using four cell digestion agents, namely, sodium hypochlorite, sodium hydroxide, acetone and sodium chloride. Simultaneously, the removal of extracellular polymeric substances (EPS) and its effect on PHA yield were investigated. The highest PHA recovery yield was obtained using sodium hypochlorite, accounting for 89% cell dry weight (CDW). The highest PHA was recovered after the sodium hypochlorite completely removed the EPS from the aerobic granules. The average molecular weight (Mw) of the PHA recovered using sodium hypochlorite was 5.31 × 10(5)g/mol with only 1.8% molecular weight degradation. The energy and duration analysis for PHA recovery revealed that the sodium hypochlorite method required the least amount of energy and time at 0.0561 MJ/g PHA and 26 h, respectively. The PHA that was recovered was a P3(HB-co-HV) co-polymer.
The refining of the crude palm oil (CPO) generates the palm oil refinery effluent (PORE). The presence of high contents of biochemical oxygen demand (BOD), chemical oxygen demand (COD), turbidity, and suspended solids (SS) in PORE encourages the determination of an effective treatment process to minimize the environmental pollution and preserve aquatic life. In the present study, a biodegradable natural polymer, namely tannin, was utilized as a coagulant to treat PORE. The coagulation experiment was conducted using a jar test apparatus. The tannin coagulation efficiency was evaluated based on the BOD, COD, turbidity, and SS removal from PORE by varying the tannin dose (50-300 mg/L), pH (pH 4-10), treatment time (15-90 min), and sedimentation time (15-90 min). It was found that the maximum removal of BOD, COD, turbidity, and SS was 97.62%, 88.89%, 93.01%, and 90.21%, respectively, at pH 6, a tannin dose of 200 mg/L, 60 min of coagulation time, and 60 min of sedimentation time. Analyses of isotherm models revealed that the Freundlich isotherm model was well fitted with the coagulation study. Kinetics studies show that the pseudo-second-order kinetics model was the well-fitted kinetics model for the BOD, COD, turbidity, and SS removal from PORE using tannin as a polymeric coagulant. The determination of thermodynamics parameters analyses revealed that BOD, COD, turbidity, and SS removal from PORE was spontaneous, exothermic, and chemical in nature. The finding of the present study shows that tannin as a natural polymeric coagulant would be utilized in PORE treatment to avoid toxic sludge generation.
Different fractions of fully hydrogenated soybean oil (FHSBO) in soybean oil (10-30% w/w) and the addition of 1% salt (sodium chloride) were used to investigate the effect of high-pressure treatments (HP) on the crystallization behaviors and physical properties of the binary mixtures. Sample microstructure, solid fat content (SFC), thermal and rheological properties were analyzed and compared against a control sample (crystallized under atmospheric condition). The crystallization temperature (Ts) of all model fats under isobaric conditions increased quadratically with pressure until reaching a pressure threshold. As a result of this change, the sample induction time of crystallization (tc) shifted from a range of 2.74-0.82 min to 0.72-0.43 min when sample crystallized above the pressure threshold under adiabatic conditions. At the high solid mass fraction, the addition of salt reduced the pressure threshold to induce crystallization during adiabatic compression. An increase in pressure significantly reduced mean cluster diameter in relation to the reduction of tc regardless of the solid mass fraction. In contrast, the sample macrostructural properties (SFC, storage modulus) were influenced more significantly by solid mass fractions rather than pressure levels. The creation of lipid gel was observed in the HP samples at 10% FHSBO. The changes in crystallization behaviors indicated that high-pressure treatments were more likely to influence crystallization mechanisms at low solid mass fraction.