The structure of 3-iodobenzaldehyde (3IB) was characterized by FT-IR, Raman and single-crystal X-ray diffraction techniques. The conformational isomers, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of 3IB were examined using density functional theory (DFT) method, with the Becke-3-Lee-Yang-Parr (B3LYP) functional and the 6-311+G(3df,p) basis set for all atoms except for iodine. The LANL2DZ effective core basis set was used for iodine. Potential energy distribution (PED) analysis of normal modes was performed to identify characteristic frequencies. 3IB crystallizes in monoclinic space group P21/c with the O-trans form. There is a good agreement between the theoretically predicted structural parameters, and vibrational frequencies and those obtained experimentally. In order to understand halogen effect, 3-halogenobenzaldehyde [XC6H4CHO; X=F, Cl and Br] was also studied theoretically. The free energy difference between the isomers is small but the rotational barrier is about 8kcal/mol. An atypical behavior of fluorine affecting conformational preference is observed.
Bis(dithiolene) tungsten carbonyl complex, W(S2C2Ph2)2(CO)2 was successfully synthesized and the structure, frontier molecular orbital and optical properties of the complex were investigated theoretically using density functional theory calculations. The investigation started with a molecular structure construction, followed by an optimization of the structural geometry using generalized-gradient approximation (GGA) in a double numeric plus polarization (DNP) basis set at three different functional calculation approaches. Vibrational frequency analysis was used to confirm the optimized geometry of two possible conformations of [W(S2C2Ph2)2(CO)2], which showed distorted octahedral geometry. Electronic structure and optical characterization were done on the ground states. Metal to ligand and ligand to metal charge transfer were dominant in this system.
Food manufacturers are interested in developing emulsion-based products into nutritional foods by using beneficial oils, such as fish oil and virgin coconut oil (VCO). In this study, the physicochemical properties of a VCO oil-in-water emulsion was investigated and compared to other commercial oil-in-water emulsion products (C1, C2, C3, and C4). C3 exhibited the smallest droplet size of 3.25 µm. The pH for the emulsion samples ranged from 2.52 to 4.38 and thus were categorised as acidic. In a texture analysis, C2 was described as the most firm, very adhesive and cohesive, as well as having high compressibility properties. From a rheological viewpoint, all the emulsion samples exhibited non-Newtonian behaviour, which manifested as a shear-thinning property. The G'G'' crossover illustrated by the VCO emulsion in the amplitude sweep graph but not the other commercial samples illustrated that the VCO emulsion had a better mouthfeel. In this context, the VCO emulsion yielded the highest zeta potential (64.86 mV), which was attributed to its strong repulsive forces, leading to a good dispersion system. C2 comprised the highest percentage of fat among all emulsion samples, followed by the VCO emulsion, with 18.44% and 6.59%, respectively.
Water bodies with the dye methylene blue pose serious environmental and health risks to humans. Therefore, the creation and investigation of affordable, potential adsorbents to remove methylene blue dye from water resources as a long-term fix is one focus of the scientific community. Food plants and other carbon-source serve as a hotspot for a wider range of application on different pollutants that impact the environment and living organisms. Here, we reviewed the use of treated and untreated biosorbents made from plant waste leaves for removing the dye methylene blue from aqueous media. After being modified, activated carbon made from various plant leaves improves adsorption performance. The range of activating chemicals, activation methods, and bio-sorbent material characterisation using FTIR analysis, Barunauer-Emmett-Teller (BET) surface area, scanning electron microscope (SEM-EDX), and SEM-EDX have all been covered in this review. It has been thoroughly described how the pH solution of the methylene blue dye compares to the pHPZC of the adsorbent surface. The presentation also includes a thorough analysis of the application of the isotherm model, kinetic model, and thermodynamic parameters. The selectivity of the adsorbent is the main focus of the adsorption kinetics and isotherm models. It has been studied how adsorption occurs, how surface area and pH affect it, and how biomass waste compares to other adsorbents. The use of biomass waste as adsorbents is both environmentally and economically advantageous, and it has been discovered to have exceptional color removal capabilities.
Metal nanoclusters have been considered as a new class of chemical sensors due to their unique electronic structures and the particular physicochemical properties. The interaction of N2 molecule with neutral and ionic magnesium nanoclusters Mg17q(q=0,±1), as well as neutral magnesium nanoclusters with the centrality of beryllium and calcium Mg16M (M=Be, Mg, and Ca) have been investigated using CAM-B3LYP/6-311+G(d) level of theory in the gas phase. The electronic properties of magnesium nanoclusters were significantly affected by the adsorption of N2 molecule. The NBO analysis revealed a charge transfer from the adsorbed N2 molecule to the nanocluster. Based on the adsorption energies and enthalpies, a thermodynamically favorable chemisorption process was predicted for the Mg16Ca-N2 complex. The negative value of the Gibbs free energy of Mg16Ca-N2 confirmed the spontaneous adsorption process. The estimated recovery time for Mg16Ca-N2 complex for 8-MR (0.089 s) and 4-MRs (0.075 s) illustrated a possible desorption process for N2 molecule from the surface of Mg16Ca. Our finding also revealed the Mg16Ca has the ability to use as a sensor for detection and absorption of N2 molecule.
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.
Several parts of the world have been facing the problem of nitrite and nitrate contamination in ground and surface water. The acute toxicity of nitrite has been shown to be 10-fold higher than that of nitrate. In the present study, aminated silica carbon nanotube (ASCNT) was synthesised and tested for nitrite removal. The synergistic effects rendered by both amine and silica in ASCNT have significantly improved the nitrite removal efficiency. The IEP increased from 2.91 for pristine carbon nanotube (CNT) to 8.15 for ASCNT, and the surface area also increased from 178.86 to 548.21 m2 g-1. These properties have promoted ASCNT a novel adsorbent to remove nitrite. At optimum conditions of 700 ppm of nitrite concentration at pH 7 and 5 h of contact with 15 mg of adsorbent, the ASCNT achieved the maximal loading capacity of 396 mg/g (85% nitrite removal). The removal data of nitrite onto ASCNT fitted the Langmuir isotherm model better than the Freundlich isotherm model with the highest regression value of 0.98415, and also, the nonlinear analysis of kinetics data showed that the removal of nitrite followed pseudo-second-order kinetic. The positive values of both ΔS° and ΔH° suggested an endothermic reaction and an increase in randomness at the solid-liquid interface. The negative ΔG° values indicated a spontaneous adsorption process. The ASCNT was characterised using FESEM-EDX and FTIR, and the results obtained confirmed the removal of nitrite. Based on the findings, ASCNT can be considered as a novel and promising candidate for the removal of nitrite ions from wastewater.
Enzymatic synthesis of maltooligosaccharides is hampered due to lack of stability of soluble enzyme. This limitation can be tackled by cross linked enzyme aggregates (CLEAs) immobilization approach. However, substrate diffusion is a major bottleneck in cross linking technology. Herein, CLEAs of maltogenic amylase from Bacillus lehensis G1 (Mag1) was developed with addition of porous agent (Mag1-p-CLEAs). Comparison of thermal, pH and kinetic analysis with CLEAs without porous agent (Mag1-CLEAs) and free Mag1 was performed. Mag1-p-CLEAs with porous structure prepared at 0.8% (w/v) of citrus pectin (porous agent), 0.25% (w/v) of chitosan (cross linker) and cross linked for 1.5 h yielded 91.20% activity. 80% of activity is retained after 30 min of incubation at 40 °C and showed longer half-life than free Mag1 and Mag1-CLEAs. Mag1-p-CLEAs also showed pH stability at acidic and alkaline pH. The 1.68-fold increase in Vmax value in comparison to Mag1-CLEAs showed that the presence of pores of Mag1-p-CLEAs enhanced the beta-cyclodextrin accessibility. The increase in high catalytic efficiency (Kcat/Km) value, 1.90-fold and 1.05-fold showed that it also has better catalytic efficiency than free Mag1 and Mag1-CLEAs, respectively. Mag1-p-CLEAs not only improved substrate diffusibility of CLEAs, but also leads to higher thermal and pH stability of Mag1.
Gas Hydrate modelling has gained huge attention in the past decade due to its increase in usage for various energy as well as environmental applications at an industrial scale. As the experimental approach is highly expensive and time-consuming, modelling is the best way to predict the conditions before the actual applications at industrial scales. The commercial software currently existing uses the equation of states (EOS) to predict the thermodynamic conditions of gas hydrates. But, in certain cases, the prediction by using EOS fails to predict the hydrate conditions accurately. Therefore, there arose a need for an accurate prediction model to estimate the hydrate formation conditions. So, in this work, an accurate prediction model has been proposed to predict the thermodynamic equilibrium conditions of the gas hydrate formation. The performance of prediction accuracy for the proposed model is compared with those of the SRK equation of state and Peng Robinson (PR) Equation of state. It was observed that in most of the cases the proposed model has predicted the thermodynamic conditions more accurately than the PR and SRK equation of state. This work helps in understanding the limitations of EOS for the prediction hydrate conditions. Also, the current work helps in strengthening the conventional statistical modelling technique to predict the hydrate conditions for a broader range.
Over the last few years, several attempts have been made to replace petrochemical products with renewable and biodegradable components. The most challenging part of this approach is to obtain bio-based materials with properties and functions equivalent to those of synthetic products. Various naturally occurring polymers such as starch, collagen, alginate, cellulose, and chitin represent attractive candidates as they could reduce dependence on synthetic products and consequently positively impact the environment. Chitosan is also a unique bio-based polymer with excellent intrinsic properties. It is known for its anti-bacterial and film-forming properties, has high mechanical strength and good thermal stability. Nanotechnology has also applied chitosan-based materials in its most recent achievements. Therefore, numerous chitosan-based bionanocomposites with improved physical and chemical characteristics have been developed in an eco-friendly and cost-effective approach. This review discusses various sources of chitosan, its properties and methods of modification. Also, this work focuses on diverse preparation techniques of chitosan-based bionanocomposites and their emerging application in various sectors. Additionally, this review sheds light on future research scope with some drawbacks and challenges to motivate the researchers for future outstanding research works.
This study is based on the removal of methylene blue (MB) from aqueous solution by cost effective and biodegradable adsorbent carboxymethyl starch grafted polyvinyl pyrolidone (Car-St-g-PVP). The Car-St-g-PVP was synthesized by grafting vinyl pyrolidone onto carboxymethyl starch by free radical polymerization reaction. The structure and different properties of Car-St-g-PVP were determined by 1H NMR, FT-IR, XRD, TGA and SEM. A series of batch experiments were conducted for the removal of MB, The adsorption affecting factors such as temperature, contact time, initial concentration of MB dye, dose of Car-St-g-PVP and pH were studied in detail. The other parameters like the thermodynamic study, kinetics and isothermal models were fitted to the experimental data. The results showed that pseudo 2nd order kinetics and Langmuir's adsorption isotherms were best fitted to experimental data with regression coefficient R2 viz. 0.99 and 0.97. The kinetic study showed that the adsorption mechanism favored chemisorption. The Gibbs free energy (ΔG°) for the adsorption process was found to be -7.31 kJ/mol, -8.23 kJ/mol, -9.00 kJ/mol and -10.10 kJ/mol at 25 °C, 35 °C, 45 °C and 55 °C respectively. The negative values of ΔG° suggested the spontaneous nature of the adsorption process. Similarly, the positive values of entropy (ΔS°) and enthalpy (ΔH°) 91.27 J/k.mol and 19.90 kJ/mol showed the increasing randomness and endothermic nature of the adsorption process. The value of separation factor (RL) was found to be less than one (RL
Thermodynamic chemical equilibrium analysis using, total Gibbs energy minimization method, was carried out for methane oxidation to higher hydrocarbons. For a large methane conversion and a high selectivity to higher hydrocarbons, the system temperature and oxygen concentration played a vital role, whereas, the system pressure only slightly influenced the two variables. Numerical results showed that the conversion of methane increased with the concentration of oxygen and reaction temperature, but it decreased with pressure. Nevertheless, the presence of oxygen suppressed the formation of higher hydrocarbons which mostly consisted of aromatics, but enhanced the formation of hydrogen. As the system pressure increased, the aromatics, olefins and hydrogen yields diminished, but the paraffin yield improved. Carbon monoxide seemed to be the major oxygen-containing equilibrium product from methane oxidation, whilst almost no H2O, CH3OH and HCOH were detected although traces amount of carbon dioxide were formed at relatively lower temperature and higher pressure. The total Gibbs energy minimization method is useful to theoretically analyze the feasibility of methane conversion to higher hydrocarbons and syngas at the selected temperature and pressure.
Renewable energy systems are vital for a sustainable future, where solid-state hydrogen storage can play a crucial role. Perovskite hydride materials have attracted the scientific community for hydrogen storage applications. The current work focuses on the theoretical study using density functional theory (DFT) to evaluate the characteristics of MgXH3 (X = Co, Cu, Ni) hydrides. The structural, vibrational, electronic, mechanical, thermodynamic, and hydrogen storage properties of these hydrides were investigated. The equilibrium lattice parameters were calculated using the Birch-Murnaghan equation of state-to-energy volume curves. The elastic constants (Cij) and relevant parameters, such as Born criteria, were calculated to confirm the mechanical stability of the hydrides. The Cauchy pressure (Cp) revealed brittle or ductile behavior. The outcomes of the Pugh ratio, Poisson ratio, and anisotropy were also calculated and discussed. The absence of negative lattice vibrational frequencies in phonon dispersion confirmed the lattice's dynamic stability. The heat capacity curves of thermodynamic properties revealed that hydrides can conduct thermal energy. The metallic character and ample interatomic distances of hydrides were confirmed by the band structure and population analysis, which confirmed that hydrides can conduct electrical energy and adsorb hydrogen. The density of state (DOS) and partial DOS unveiled the role of specific atoms in the DOS of the crystal. The calculated gravimetric hydrogen storage capacity of MgCoH3, MgCuH3, and MgNiH3 hydrides was 3.64, 3.32, and 3.49wt%, respectively. Our results provide a deeper understanding of its potential for hydrogen storage applications through a detailed analysis of MgXH3 (X = Co, Cu, Ni) perovskite hydride material.
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.
Polyethylene glycol functionalized with oxygenated multi-walled carbon nanotubes (O-PEG-MWCNTs) as an efficient nanomaterial for the in vitro adsorption/release of curcumin (CUR) anticancer agent. The synthesized material was morphologically characterized using scanning electron microscopy, Fourier transform infrared spectroscopy and transmission electron microscopy. In addition, the CUR adsorption process was assessed with kinetic and isotherm models fitting well with pseudo-second order and Langmuir isotherms. The results showed that the proposed O-PEG-MWCNTs has a high adsorption capacity for CUR (2.0 × 103 mg/g) based on the Langmuir model. The in vitro release of CUR from O-PEG-MWCNTs was studied in simulating human body fluids with different pHs (ABS pH 5, intestinal fluid pH 6.6 and body fluid pH 7.4). Lastly, to confirm the success compliance of the O-PEG-MWCNT nanocomposite as a drug delivery system, the parameters affecting the CUR release such as temperature and PEG content were investigated. As a result, the proposed nanocomposite could be used as an efficient carrier for CUR delivery with an enhanced prolonged release property. Graphical Abstract ᅟ.
Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (DeltaH degrees), Gibbs free energy (DeltaG degrees) and entropy (DeltaS degrees) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.
Among numerous methods developed in purification and separation industries, the adsorption process has received considerable attention due to its inexpensive, facile, and eco-friendly nature. The importance of the adsorption process causes extraordinary endeavors for modeling the adsorption isotherms during the years; thus, myriads of research have been conducted and many reviews have been published. In this paper, we have attempted to gather the most widely used adsorption isotherms and their related definitions, along with examples of correlated work of the recent decade. In the present review, 37 adsorption isotherms with about 400 references have been collected from the research published in the period of 2010-2020. The adsorption isotherms utilized are alphabetically organized for ease of access. The parameters of each isotherm, as well as the applicable definitions, are presented in the table, in addition to being discussed in the text. Another table is provided for the practical use of researchers, featuring the usage of the related isotherms in peer-reviewed studies.
The adsorption characteristics of 2,4,6-trichlorophenol (TCP) on activated carbon prepared from oil palm empty fruit bunch (EFB) were evaluated. The effects of TCP initial concentration, agitation time, solution pH and temperature on TCP adsorption were investigated. TCP adsorption uptake was found to increase with increase in initial concentration, agitation time and solution temperature whereas adsorption of TCP was more favourable at acidic pH. The adsorption equilibrium data were best represented by the Freundlich and Redlich-Peterson isotherms. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The mechanism of the adsorption process was determined from the intraparticle diffusion model. Boyd plot revealed that the adsorption of TCP on the activated carbon was mainly governed by particle diffusion. Thermodynamic parameters such as standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), standard free energy (DeltaG degrees ) and activation energy were determined. The regeneration efficiency of the spent activated carbon was high, with TCP desorption of 99.6%.
The adsorption of rhodamine B (RhB) using acid modified banana peels has been examined. Chemical characteristics of the adsorbents were observed in order to determine active functional groups. The major functional groups on the surface were OH, C = O, C = C and C-O-C. Interactions between operational parameters were studied using the central composite design (CCD) of response surface methodology (RSM). The predictions of the model output indicated that operational factors influenced responses at a confidence level of 95% (P<0.05). The optimum conditions for adsorption were pH 2 at a 0.2 g/L dose within 60 minutes of contact time. Isotherm studies were carried out using the optimized process variables. The data revealed that RhB adsorption fitted the Langmuir isotherm equation while the reduction of COD followed the Freundlich isotherm. Kinetic experiments fitted the pseudo second order model for RhB removal and COD reduction. The adsorption mechanism was not the only rate controlling step. Diffusion through the boundary layer described the pattern of adsorption.
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.