Sequentially precipitated Mg-promoted nickel-silica catalysts with ageing performed under various ultrasonic intensities were employed to study the catalyst performance in the partial hydrogenation of sunflower oil. Results from various characterisation studies showed that increasing ultrasonic intensity caused a higher degree of hydroxycarbonate erosion and suppressed the formation of Ni silicates and silica support, which improved Ni dispersion, BET surface area and catalyst reducibility. Growth of silica clusters on the catalyst aggregates were observed in the absence of ultrasonication, which explained the higher silica and nickel silicate content on the outer surface of the catalyst particle. Application of ultrasound also altered the electron density of the Ni species, which led to higher activity and enhanced product selectivity for sonicated catalysts. The catalyst synthesised with ultrasonic intensity of 20.78 Wcm-2 achieved 22.6% increase in hydrogenation activity, along with 28.5% decrease in trans-C18:1 yield at IV = 70, thus supporting the feasibility of such technique.
Nanoemulsion is a delivery system used to enhance bioavailability of plant-based compounds across the stratum corneum. Elaeis guineensis leaves are rich source of polyphenolic antioxidants, viz. gallic acid and catechin. The optimal E. guineensis leaves extract water-in-oil nanoemulsion was stable against coalescence, but it was under significant influence of Ostwald ripening over 90 days at 25 °C. The in-vitro permeability revealed a controlled and sustained release of the total phenolic compounds (TPC) of EgLE with a cumulative amount of 1935.0 ± 45.7 µgcm-2 after 8 h. The steady-state flux and permeation coefficient values were 241.9 ± 5.7 µgcm-2 h-1 and 1.15 ± 0.03 cm.h-1, respectively. The kinetic release mechanism for TPC of EgLE was best described by the Korsmeyer-Peppas model due to the highest linearity of R2 = 0.9961, indicating super case II transport mechanism. The in-silico molecular modelling predicted that the aquaporin-3 protein in the stratum corneum bonded preferably to catechin over gallic acid through hydrogen bonds due to the lowest binding energies of - 57.514 kcal/mol and - 8.553 kcal/mol, respectively. Thus, the in-silico study further verified that catechin could improve skin hydration. Therefore, the optimal nanoemulsion could be used topically as moisturizer to enhance skin hydration based on the in-silico prediction.
Sustainable wastewater treatment is one of the biggest issues of the 21st century. Metals such as Zn2+ have been released into the environment due to rapid industrial development. In this study, dried watermelon rind (D-WMR) is used as a low-cost adsorption material to assess natural adsorbents' ability to remove Zn2+ from synthetic wastewater. D-WMR was characterized using scanning electron microscope (SEM) and X-ray fluorescence (XRF). According to the results of the analysis, the D-WMR has two colours, white and black, and a significant concentration of mesoporous silica (83.70%). Moreover, after three hours of contact time in a synthetic solution with 400 mg/L Zn2+ concentration at pH 8 and 30 to 40 °C, the highest adsorption capacity of Zn2+ onto 1.5 g D-WMR adsorbent dose with 150 μm particle size was 25 mg/g. The experimental equilibrium data of Zn2+ onto D-WMR was utilized to compare nonlinear and linear isotherm and kinetics models for parameter determination. The best models for fitting equilibrium data were nonlinear Langmuir and pseudo-second models with lower error functions. Consequently, the potential use of D-WMR as a natural adsorbent for Zn2+ removal was highlighted, and error analysis indicated that nonlinear models best explain the adsorption data.
This investigation of the temperature dependence of DppA interactions with a subset of three dipeptides (AA. AF and FA) by isothermal titration calorimetry has revealed the negative heat capacity ([Formula: see text]) that is a characteristic of hydrophobic interactions. The observation of enthalpy-entropy compensation is interpreted in terms of the increased structuring of water molecules trapped in a hydrophobic environment, the enthalpic energy gain from which is automatically countered by the entropy decrease associated with consequent loss of water structure flexibility. Specificity for dipeptides stems from appropriate spacing of designated DppA aspartate and arginine residues for electrostatic interaction with the terminal amino and carboxyl groups of a dipeptide, after which the binding pocket closes to become completely isolated from the aqueous environment. Any differences in chemical reactivity of the dipeptide sidechains are thereby modulated by their occurrence in a hydrophobic environment where changes in the structural state of entrapped water molecules give rise to the phenomenon of enthalpy-entropy compensation. The consequent minimization of differences in the value of ΔG0 for all DppA-dipeptide interactions thus provides thermodynamic insight into the biological role of DppA as a transporter of all dipeptides across the periplasmic membrane.
In this study, two biomass-based adsorbents were used as new precursors for optimizing synthesis conditions of a cost-effective powdered activated carbon (PAC). The PAC removed dyes from an aqueous solution using carbonization and activation by KOH, NaOH, and H2SO4. The optimum synthesis, activation temperature, time and impregnation ratio, removal rate, and uptake capacity were determined. The optimum PAC was analyzed and characterized using Fourier-transform infrared spectroscopy (FTIR), x-ray diffraction (XRD), a field emission scanning electron microscope (FESEM), Zeta potential, and Raman spectroscopy. Morphological studies showed single-layered planes with highly porous surfaces, especially PAC activated by NaOH and H2SO4. The results showed that the experimental data were well-fitted with a pseudo-second-order model. Based on Langmuir isotherm, the maximum adsorption capacity for removing methylene blue (MB) was 769.23 mg g-1 and 458.43 mg g-1 for congo red (CR). Based on the isotherm models, more than one mechanism was involved in the adsorption process, monolayer for the anionic dye and multilayer for the cationic dye. Elovich and intraparticle diffusion kinetic models showed that rubber seed shells (RSS) has higher α values with a greater tendency to adsorb dyes compared to rubber seed (RS). A thermodynamic study showed that both dyes' adsorption process was spontaneous and exothermic due to the negative values of the enthalpy (ΔH) and Gibbs free energy (ΔG). The change in removal efficiency of adsorbent for regeneration study was observed in the seventh cycles, with a 3% decline in the CR and 2% decline in MB removal performance. This study showed that the presence of functional groups and active sites on the produced adsorbent (hydroxyl, alkoxy, carboxyl, and π - π) contributed to its considerable affinity for adsorption in dye removal. Therefore, the optimum PAC can serve as efficient and cost-effective adsorbents to remove dyes from industrial wastewater.
Density functional theory calculations on two glycosides, namely, n-octyl-β-D-glucopyranoside (C(8)O-β-Glc) and n-octyl-β-D-galactopyranoside (C(8)O-β-Gal) were performed for geometry optimization at the B3LYP/6-31G level. Both molecules are stereoisomers (epimers) differing only in the orientation of the hydroxyl group at the C4 position. Thus it is interesting to investigate electronically the effect of the direction (axial/equatorial) of the hydroxyl group at the C4 position. The structure parameters of X-H∙∙∙Y intramolecular hydrogen bonds were analyzed, while the nature of these bonds and the intramolecular interactions were considered using the atoms in molecules (AIM) approach. Natural bond orbital analysis (NBO) was used to determine bond orders, charge and lone pair electrons on each atom and effective non-bonding interactions. We have also reported electronic energy and dipole moment in gas and solution phases. Further, the electronic properties such as the highest occupied molecular orbital, lowest unoccupied molecular orbital, ionization energy, electron affinity, electronic chemical potential, chemical hardness, softness and electrophilicity index, are also presented here for both C(8)O-β-Glc and C(8)O-β-Gal. These results show that, while C(8)O-β-Glc possess- only one hydrogen bond, C(8)O-β-Gal has two intramolecular hydrogen bonds, which further confirms the anomalous stability of the latter in self-assembly phenomena.
Finding a proper transition structure for the peptide bond formation process can lead one to a better understanding of the role of ribosome in catalyzing this reaction. Using computer simulations, we performed the potential energy surface scan on the ester bond dissociation of P-site aminoacyl-tRNA and the peptide bond formation of P-site and A-site amino acids. The full fragments of initiator tRNA(i)(met) and elongator tRNA(phe) are attached to both cognate and non-cognate amino acids as the P-site substrate. The A-site amino acid for all four calculations is methionine. We used ONIOM calculations to reduce the computational cost. Our study illustrates the reduced rate of peptide bond formation for misacylated tRNA(i)(met) in the absence of ribosomal bases. The misacylated elongator tRNA(phe), however, did not show any difference in its PES compared with that for the phe-tRNA(phe). This demonstrates the structural specification of initiator tRNA(i)(met) for the amino acids side chain.
Interaction of flavokawain B (FB), a multitherapeutic flavonoid from Alpinia mutica with the major transport protein, human serum albumin (HSA), was investigated using different spectroscopic probes, i.e., intrinsic, synchronous, and three-dimensional (3-D) fluorescence, circular dichroism (CD), and molecular modeling studies. Values of binding parameters for FB-HSA interaction in terms of binding constant and stoichiometry of binding were determined from the fluorescence quench titration and were found to be 6.88 × 10(4) M(-1) and 1.0 mol of FB bound per mole of protein, respectively, at 25 °C. Thermodynamic analysis of the binding data obtained at different temperatures showed that the binding process was primarily mediated by hydrophobic interactions and hydrogen bonding, as the values of the enthalpy change (ΔH) and the entropy change (ΔS) were found to be -6.87 kJ mol(-1) and 69.50 J mol(-1) K(-1), respectively. FB binding to HSA led to both secondary and tertiary structural alterations in the protein as revealed by intrinsic, synchronous, and 3-D fluorescence results. Increased thermal stability of HSA in the presence of FB was also evident from the far-UV CD spectral results. The distance between the bound ligand and Trp-214 of HSA was determined as 3.03 nm based on the Förster resonance energy transfer mechanism. Displacement experiments using bilirubin and warfarin coupled with molecular modeling studies assigned the binding site of FB on HSA at domain IIA, i.e., Sudlow's site I.
The potential of base treated Shorea dasyphylla (BTSD) sawdust for Acid Blue 25 (AB 25) adsorption was investigated in a batch adsorption process. Various physiochemical parameters such as pH, stirring rate, dosage, concentration, contact time and temperature were studied. The adsorbent was characterized with Fourier transform infrared spectrophotometer, scanning electron microscope and Brunauer, Emmett and Teller analysis. The optimum conditions for AB 25 adsorption were pH 2, stirring rate 500 r/min, adsorbent dosage 0.10 g and contact time 60 min. The pseudo second-order model showed the best conformity to the kinetic data. The equilibrium adsorption of AB 25 was described by Freundlich and Langmuir, with the latter found to agree well with the isotherm model. The maximum monolayer adsorption capacity of BTSD was 24.39 mg/g at 300 K, estimated from the Langmuir model. Thermodynamic parameters such as Gibbs free energy, enthalpy and entropy were determined. It was found that AB 25 adsorption was spontaneous and exothermic.
The molecular structure of a new Schiff base, 2-[4-hydroxy benzylidene]-amino naphthalene (HBAN) has been examined by HF and B3LYP/6-311++G(d,p) calculations. The X-ray structure was determined in order to establish the conformation of the molecule. The compound, C17H13NO, crystallizes in the orthorhombic, P212121 space group with the cell dimension, a=6.2867(2), b=10.2108(3), c=19.2950(6) Å, α=β=γ=90° and z=4. The asymmetric unit contains a molecule of a Schiff base. A strong intermolecular O-H⋯N and a weak C-H⋯O hydrogen bonds stabilized the crystal structure. The vibrational spectra of HBAN have been calculated using density functional theoretical computation and compared with the experimental. The study is extended to the HOMO-LUMO analysis to calculate the energy gap (Δ), Ionization potential (I), Electron Affinity (A), Global Hardness (η), Chemical Potential (μ) and Global Electrophilicity (w). The calculated HOMO and LUMO energy reveals that the charge transfer occurs within the molecule.
The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures.
The purpose of exploring protein interactions between human adenovirus and heat shock protein 70 is to exploit a potentially synergistic interaction to enhance anti-tumoral efficacy and decrease toxicity in cancer treatment. However, the protein interaction of Hsp70 with E1A32 kDa of human adenovirus serotype 5 remains to be elucidated. In this study, two residues of ATPase domain of human heat shock 70 kDa protein 1 (PDB: 1 HJO) were mutated. 3D mutant models (K71L and T204V) using PyMol software were then constructed. The structures were evaluated by PROCHECK, ProQ, ERRAT, Verify 3D and ProSA modules. All evidence suggests that all protein models are acceptable and of good quality. The E1A32 kDa motif was retrieved from UniProt (P03255), as well as subjected to docking interaction with NBD, K71L and T204V, using the Autodock 4.2 program. The best lowest binding energy value of -9.09 kcal/mol was selected for novel T204V. Moreover, the protein-ligand complex structures were validated by RMSD, RMSF, hydrogen bonds and salt bridge analysis. This revealed that the T204V-E1A32 kDa motif complex was the most stable among all three complex structures. This study provides information about the interaction between Hsp70 and the E1A32 kDa motif, which emphasizes future perspectives to design rational drugs and vaccines in cancer therapy.
This work describes methacrylic acid functionalized β-cyclodextrin (MAA-βCD) as a novel functional monomer in the preparation of molecular imprinted polymer (MIP MAA-βCD) for the selective removal of 2,4-dichlorophenol (2,4-DCP). The polymer was characterized using Fourier Transform Infrared (FTIR) spectroscopy, Brunauer-Emmett-Teller (BET) and Field Emission Scanning Electron Microscopy (FESEM) techniques. The influence of parameters such as solution pH, contact time, temperature and initial concentrations towards removal of 2,4-DCP using MIP MAA-βCD have been evaluated. The imprinted material shows fast kinetics and the optimum pH for removal of 2,4-DCP is pH 7. Compared with the corresponding non-imprinted polymer (NIP MAA-βCD), the MIP MAA-βCD exhibited higher adsorption capacity and outstanding selectivity towards 2,4-DCP. Freundlich isotherm best fitted the adsorption equilibrium data of MIP MAA-βCD and the kinetics followed a pseudo-second-order model. The calculated thermodynamic parameters showed that adsorption of 2,4-DCP was spontaneous and exothermic under the examined conditions.
Hispidin oligomers are styrylpyrone pigments isolated from the medicinal fungi Inonotus xeranticus and Phellinus linteus. They exhibit diverse biological activities and strong free radical scavenging activity. To rationalize the antioxidant activity of a series of four hispidin oligomers and determine the favored mechanism involved in free radical scavenging, DFT calculations were carried out at the B3P86/6-31+G (d, p) level of theory in gas and solvent. The results showed that bond dissociation enthalpies of OH groups of hispidin oligomers (ArOH) and spin density delocalization of related radicals (ArO•) are the appropriate parameters to clarify the differences between the observed antioxidant activities for the four oligomers. The effect of the number of hydroxyl groups and presence of a catechol moiety conjugated to a double bond on the antioxidant activity were determined. Thermodynamic and kinetic studies showed that the PC-ET mechanism is the main mechanism involved in free radical scavenging. The spin density distribution over phenoxyl radicals allows a better understanding of the hispidin oligomers formation.
Oil palm shell, a waste from palm oil industry, was cleaned and utilized as adsorbent. Its particle size distribution gave the uniformity coefficient of approximately two indicating that it can be used as filter bed media for continuous operation without resting. Its measured pH(pzc) of 4.1 is below the common pH of constructed wetland water body suggesting positive adsorption for heavy metal. The effect of various parameters on its adsorption was studied via batch experiments. The adsorption of Cu(II) and Pb(II) ions by oil palm shell showed a slightly better fit with the Freundlich compared to Langmuir. Its monolayer adsorption capacities were found to be 1.756 and 3.390mg/g for Cu(II) and Pb(II), respectively. High correlation coefficient of over 0.99 given by the pseudo-second-order model suggests that the rate limiting factor may be chemisorption. These findings suggest its potential application as constructed wetland media for the removal of heavy metal.
The effects of organic solvents and their binary mixture in the glucose functionalization of bacterial poly-3-hydroxyalkanoates catalyzed by Lecitase™ Ultra were studied. Equal volume binary mixture of DMSO and chloroform with moderate polarity was more effective for the enzyme catalyzed synthesis of the carbohydrate polymer at ≈38.2 (±0.8)% reactant conversion as compared to the mono-phasic and other binary solvents studied. The apparent reaction rate constant as a function of medium water activity (aw) was observed to increase with increasing solvent polarity, with optimum aw of 0.2, 0.4 and 0.7 (±0.1) observed in hydrophilic DMSO, binary mixture DMSO:isooctane and hydrophobic isooctane, respectively. Molecular sieve loading between 13 to 15gL(-1) (±0.2) and reaction temperature between 40 to 50°C were found optimal. Functionalized PHA polymer showed potential characteristics and biodegradability.
In this work, preparation of granular activated carbon from oil palm biodiesel solid residue, oil palm shell (PSAC) by microwave assisted KOH activation has been attempted. The physical and chemical properties of PSAC were characterized using scanning electron microscopy, volumetric adsorption analyzer and elemental analysis. The adsorption behavior was examined by performing batch adsorption experiments using methylene blue as dye model compound. Equilibrium data were simulated using the Langmuir, Freundlich and Temkin isotherm models. Kinetic modeling was fitted to the pseudo-first-order, pseudo-second-order and Elovich kinetic models, while the adsorption mechanism was determined using the intraparticle diffusion and Boyd equations. The result was satisfactory fitted to the Langmuir isotherm model with a monolayer adsorption capacity of 343.94mg/g at 30°C. The findings support the potential of oil palm shell for preparation of high surface area activated carbon by microwave assisted KOH activation.
The aim of the present work was to investigate the feasibility of grass waste (GW) for methylene blue (MB) adsorption. The adsorption of MB on GW material was studied as a function of GW dose (0.05-1.20 g), solution pH 3-10, contact time and initial concentration (70-380 mg/L). The influence of these parameters on the adsorption capacity was studied using the batch process. The experimental data were analyzed by the Langmuir and Freundlich isotherms. The adsorption isotherm was found to follow the Langmuir model. The monolayer adsorption capacity was found to be 457.640 mg/g. The kinetic data were fitted to the pseudo-first-order and pseudo-second-order models, and were found to follow closely the pseudo-second-order kinetic model. The results revealed that GW adsorbent is potentially low-cost adsorbent for adsorption of MB.
In this paper, pineapple stem (PS) waste, an agricultural waste available in large quantity in Malaysia, was utilized as low-cost adsorbent to remove basic dye (methylene blue, MB) from aqueous solution by adsorption. Batch mode experiments were conducted at 30 degrees C to study the effects of initial concentration of methylene blue, contact time and pH on dye adsorption. Equilibrium adsorption isotherms and kinetic were investigated. The experimental data were analyzed by the Langmuir and Freundlich models and the isotherm data fitted well to the Langmuir isotherm with monolayer adsorption capacity of 119.05mg/g. The kinetic data obtained at different concentrations were analyzed using a pseudo-first-order and pseudo-second-order equation and intraparticle diffusion equation. The experimental data fitted very well the pseudo-second-order kinetic model. The PS was found to be very effective adsorbent for MB adsorption.
This study aimed at investigating the feasibility of using jackfruit peel (JFP), a solid waste, abundantly available in Malaysia, for the adsorption of methylene blue, a cationic dye. Batch adsorption studies were conducted to evaluate the effects of contact time, initial concentration (35-400mg/L), pH (2-11), and adsorbent dose (0.05-1.20g) on the removal of dye at temperature of 30 degrees C. The experimental data were analyzed by the four different types of linearized Langmuir isotherm, the Freundlich isotherm and the Temkin isotherm. The experimental data fitted well with the type 2 Langmuir model with a maximum adsorption capacity of 285.713mg/g. Pseudo-first and pseudo-second-order kinetics models were tested with the experimental data, and pseudo-second-order kinetics was the best for the adsorption of MB by JFP with coefficients of correlation R(2)> or =0.9967 for all initial MB concentrations studied. The results demonstrated that the JFP is very effective for the adsorption of methylene blue (MB) from aqueous solutions.