The binding mode of antineoplastic antimetabolite, floxuridine (FUDR), with human serum albumin (HSA), the leading carrier in blood circulation, was ascertained using multi-spectroscopic, microscopic, and computational techniques. A static fluorescence quenching was established due to decreased Ksv values with rising temperatures, suggesting FUDR-HSA complexation. UV-vis absorption spectral results also supported this conclusion. The binding constant, Ka values, were found within 9.7-7.9 × 103 M-1 at 290, 300, and 310 K, demonstrating a moderate binding affinity for the FUDR-HSA system. Thermodynamic data (ΔS = +46.35 J.mol-1.K-1 and ΔH = -8.77 kJ.mol-1) predicted the nature of stabilizing forces (hydrogen-bonds, hydrophobic, and van der Waals interactions) for the FUDR-HSA complex. Circular dichroism spectra displayed a minor disruption in the protein's 2° and 3° structures. At the same time, atomic force microscopy images proved variations in the FUDR-HSA surface morphology, confirming its complex formation. The protein's microenvironment around Trp/Tyr residues was also modified, as judged by 3-D fluorescence spectra. FUDR-bound HSA showed better resistance against thermal stress. As disclosed from ligand displacement studies, the FUDR binding site was placed in subdomain IIA (Site I). Further, the molecular docking analysis corroborated the competing displacement studies. Molecular dynamics evaluations revealed that the complex achieved equilibrium during simulations, confirming the FUDR-HSA complex's stability.
Odanacatib (ODN) is a selective cathepsin K inhibitor that acts as an anti-resorptive agent to treat osteoporosis. ODN is also found effective in reducing the effect of severe periodontitis. The interaction between ODN and human serum albumin (HSA) was investigated using spectroscopic, microscopic, and in silico approaches to characterize their binding. The fluorescence intensity of HSA increased upon the addition of increasing concentrations of ODN accompanied by blueshift in the fluorescence spectrum, which suggested hydrophobic formation around the microenvironment of the fluorophores upon ODN binding. A moderate binding affinity was obtained for ODN-HSA binding, with binding constant (Ka) values of ∼104 M-1. Circular dichroism results suggested that the overall secondary and tertiary structures of HSA were both only slightly altered upon ODN binding. The surface morphology of HSA was also affected upon ODN binding, showing aggregate formation. Drug displacement and molecular docking results revealed that ODN preferably binds to site III in subdomain IB of HSA, while molecular dynamics simulations indicated formation of a stable protein complex when site III was occupied by ODN. The ODN-HSA complex was mainly stabilized by a combination of hydrogen bonding, hydrophobic interactions, and van der Waals forces. These findings provide additional information to understand the interaction mechanism of ODN in blood circulation and may help in future improvements on the adverse effects of ODN.
The current investigation concerns with preparation eco-friendly and cost-effective adsorbent (mesoporous silica nanoparticles (SBL)) based on black liquor (BL) containing lignin derived from sugarcane bagasse and combining it with sodium silicate derived from blast furnace slag (BFS) for thorium adsorption. Thorium ions were adsorbed from an aqueous solution using the synthesized bio-sorbent (SBL), which was then assessed by X-ray diffraction, BET surface area analysis, scanning electron microscopy with energy dispersive X-ray spectroscopy (EDX), and Fourier transforms infrared spectroscopy (FTIR). Th(IV) sorption properties, including the pH effect, uptake rate, and sorption isotherms across various temperatures were investigated. The maximum sorption capacity of Th(IV) on SBL is 158.88 mg/L at pH value of 4328 K, and 60 min contact time. We demonstrated that the adsorption processes comport well with pseudo-second-order and Langmuir adsorption models considering the kinetics and equilibrium data. According to thermodynamic inspections results, the Th(IV) adsorption process exhibited endothermic and random behavior suggested by positive ΔH° and ΔS° values, while the negative ΔG° values indicated a spontaneous sorption process. The maximum Th(IV) desorption from the loaded SBL (Th/SBL) was carried out at 0.25 M of NaHCO3 and 60 min of contact. Sorption/desorption processes have five successive cycles. Finally, this study suggests that the recycling of BFS and BL can be exploited for the procurement of a promising Th(IV) adsorbents.
In this study, bamboo waste (BW) was subjected to pyrolysis-assisted ZnCl2 activation to produce mesoporous activated carbon (BW-AC), which was then evaluated for its ability to remove cationic dyes, specifically methylene blue (MB) and crystal violet (CV), from aqueous environments. The properties of BW-AC were characterized using various techniques, including potentiometric-based point of zero charge (pHpzc), scanning electron microscopy with energy dispersive X-rays (SEM-EDX), X-ray diffraction (XRD), gas adsorption with Brunauer-Emmett-Teller (BET) analysis, infrared (IR) spectroscopy. To optimize the adsorption characteristics (BW-AC dosage, pH, and contact time) of PBW, a Box-Behnken design (BBD) was employed. The BW-AC dose of 0.05 g, solution pH of 10, and time of 8 min are identified as optimal operational conditions for achieving maximum CV (89.8%) and MB (96.3%) adsorption according to the BBD model. The dye removal kinetics for CV and MB are described by the pseudo-second-order model. The dye adsorption isotherms revealed that adsorption of CV and MB onto BW-AC follow the Freundlich model. The maximum dye adsorption capacities (qmax) of BW-AC for CV (530 mg/g) and MB (520 mg/g) are favorable, along with the thermodynamics of the adsorption process, which is characterized as endothermic and spontaneous. The adsorption mechanism of CV and MB dyes by BW-AC was attributed to multiple contributions: hydrogen bonding, electrostatic forces, π-π attraction, and pore filling. The findings of this study highlight the potential of BW-AC as an effective adsorbent in wastewater treatment applications, contributing to the overall goal of mitigating the environmental impact of cationic dyes and ensuring the quality of water resources.
This work aims to apply the use of food-grade algae (FGA) composited with chitosan-benzaldehyde Schiff base biopolymer (CHA-BD) as a new adsorbent (CHA-BA/FGA) for methyl violet 2B (MV 2B) dye removal from aqueous solutions. The effect of three processing variables, including CHA-BA/FGA dosage (0.02-0.1 g/100 mL), pH solution (4-10), and contact duration (10-120 min) on the removal of MV 2B was investigated using the Box-Behnken design (BBD) model. Kinetic and equilibrium dye adsorption profiles reveal that the uptake of MV 2B dye by CHA-BA/FGA is described by the pseudo-second kinetics and the Langmuir models. The thermodynamics of the adsorption process (ΔG°, ΔH°, and ΔS°) reveal spontaneous and favorable adsorption parameters of MV 2B dye onto the CHA-BA/FGA biocomposite at ambient conditions. The CHA-BA/FGA exhibited the maximum ability to absorb MV 2B of 126.51 mg/g (operating conditions: CHA-BA/FGA dose = 0.09 g/100 mL, solution pH = 8.68, and temperature = 25 °C). Various interactions, including H-bonding, electrostatic forces, π-π stacking, and n-π stacking provide an account of the hypothesized mechanism of MV 2B adsorption onto the surface of CHA-BA/FGA. This research reveals that CHA-BA/FGA with its unique biocomposite structure and favorable adsorption properties can be used to remove harmful cationic dyes from wastewater.
Metal, carbon and conducting polymer nanoparticles are blended with organic phase change materials (PCMs) to enhance the thermal conductivity, heat storage ability, thermal stability and optical property. However, the existing nanoparticle are expensive and need to be handle with high caution during operation as well during disposal owing to its toxicity. Subsequently handling of solid waste and the disposal of organic PCM after longevity usage are of utmost concern and are less exposed. Henceforth, the current research presents a new dimension of exploration by green synthesized nanoparticles from a thorny shrub of an invasive weed named Prosopis Juliflora (PJ) which is a agro based solid waste. Subsequently, the research is indented to decide the concentration of green synthesized nanoparticle for effective heat transfer rate of organic PCM (Tm = 35-40 °C & Hm = 145 J/g). Furthermore, an in-depth understanding on the kinetic and thermodynamic profile of degradation mechanism involved in disposal of PCM after usage via Coats and Redfern technique is exhibited. Engaging a two-step method, we fuse the green synthesized nanomaterial with PCM to obtain nanocomposite PCM. On experimental evaluation, thermal conductivity of the developed nanocomposite (PCM + PJ) increases by 63.8% (0.282 W/m⋅K to 0.462 W/m⋅K) with 0.8 wt% green synthesized nanomaterial owing to the uniform distribution of nanoparticle within PCM matrix thereby contributing to bridging thermal networks. Subsequently, PCM and PCM + PJ nanocomposites are tested using thermogravimetric analyzer at different heating rates (05 °C/min; 10 °C/min; 15 °C/min & 20 °C/min) to analyze the decomposition kinetic reaction. The kinetic and thermodynamic profile of degradation mechanism involved in disposal of PCM and its nanocomposite of PCM + PJ provides insight on thermal parameters to be considered on large scale operation and to understand the complex nature of the chemical reactions. Adopting thirteen different chemical mechanism model under Coats and Redfern method we determine the reaction mechanism; kinetic parameter like activation energy (Ea) & pre-exponential factor (A) and thermodynamic parameter like change in enthalpy (ΔH), change in Gibbs free energy (ΔG) and change in entropy (ΔS). Dispersion of PJ nanomaterial with PCM reduces Ea from 370.82 kJ/mol-1 to 342.54 kJ/mol-1 (7.7% reduction), as the developed nanomaterial is enriched in carbon element and exhibits a catalytic effect for breakdown reaction. Corresponding, value of ΔG for PCM and PCM + PJ sample within heating rates of 05-20 °C/min varies between 168.95 and 41.611 kJ/mol-1. The current research will unbolt new works with focus on exploring the pyrolysis behaviour of phase change materials and its nanocomposite used for energy storage applications. This work also provides insights on the disposal of PCM which is an organic solid waste. The thermo-kinetic profile will help to investigate and predict the optimum heating rate and temperature range for conversion of micro-scale pyrolysis to commercial scale process.
This study investigates the feasibility of spent tea waste extract (STWE) as a green modifying agent for the modification of chitosan adsorbent towards aspirin removal. Response surface methodology based on Box-Behnken design was employed to find the optimal synthesis parameters (chitosan dosage, spent tea waste concentration, and impregnation time) for aspirin removal. The results revealed that the optimum conditions for preparing chitotea with 84.65% aspirin removal were 2.89 g of chitosan, 18.95 mg/mL of STWE, and 20.72 h of impregnation time. The surface chemistry and characteristics of chitosan were successfully altered and improved by STWE, as evidenced by FESEM, EDX, BET, and FTIR analysis. The adsorption data were best fitted to pseudo 2nd order, followed by chemisorption mechanisms. The maximum adsorption capacity of chitotea was 157.24 mg/g, as fitted by Langmuir, which is impressive for a green adsorbent with a simple synthesis method. Thermodynamic studies demonstrated the endothermic nature of aspirin adsorption onto chitotea.
Binding mechanisms of two selected pesticides, propazine (PRO) and quinoxyfen (QUI) with bovine serum albumin (BSA) was examined using fluorescence, absorption and molecular docking methods. Intrinsic fluorescence of BSA was quenched in the presence of both PRO and QUI. The quenching was ascertained to be conversely linked to temperature, which suggested the contribution of static quenching process in the PRO-BSA and QUI-BSA complex formations. This results were validated by the enhancement in absorption spectrum of BSA upon binding with PRO and QUI. Binding constant values (Kf = 9.55-0.60 × 10-3 M-1 for PRO-BSA system; Kf = 7.08-5.01 × 102 M-1 for QUI-BSA system) and number of binding site (n) values for the PRO-BSA and QUI-BSA systems at different temperatures affirmed a weak binding strength with a set of equivalent binding sites on BSA. Thermodynamic data obtained for both the PRO-BSA and QUI-BSA interactions predicted that the association process was spontaneous and non-covalent contacts such as hydrophobic interactions, van der Waals forces and hydrogen bonds participated in the binding reactions. This result was further supported by the molecular docking assessments. Three-dimensional spectral results revealed the microenvironmental alterations near tryptophan (Trp) and tyrosine (Tyr) residues in BSA by the addition of PRO and QUI. The docking analysis demonstrated the binding pattern for the PRO-BSA and QUI-BSA systems and disclosed the preferred binding site of both PRO and QUI as site I (subdomain IIA) of BSA.
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.
A series of fibrous aminated adsorbents for CO2 adsorption were prepared by covalent incorporation of poly (glycidyl methacrylate) (PGMA) by graft copolymerization of GMA onto electron beam (EB) irradiated polyethylenepolypropylene (PE/PP) fibrous sheets and subsequent amination with ethylenediamine (EDA), diethylenetriamine (DETA), or tetraethylenepentamine (TEPA). The physico-chemical properties of the adsorbents were evaluated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), thermogravimetric (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) analysis. All the adsorbents displayed typic primary and secondary amine features combined with a decrease in both of crystallinity and surface area of PE/PP, and such a decrease was higher in adsorbents with longer aliphatic chain of the amine. Of all adsorbents, TEPA-containing fibres showed the highest CO2 adsorption capacity and thus was further investigated for CO2 capture from CO2/CH4 mixtures of different gas ratios under various pressures and temperatures. The selectivity of CO2 over CH4 and equilibrium isotherms, kinetics, and thermodynamics of the adsorption on the fibrous aminated adsorbent were all investigated. The Sips model was found to best fit the isotherm of CO2 adsorption suggesting the presence of a combination of monolayer and multilayer adsorptions. The adsorption kinetic data was found to best fit Elovich model reflecting chemisorption. The ΔG°, ΔS°, and ΔH° showed positive values suggesting that the adsorption of CO2 on the present fibrous adsorbent was non-spontaneous with an increase in randomness implying that the process was endothermic. Overall, it can be suggested that PE/PP-g-PGMA/TEPA adsorbent has a strong potential for separation of CO2 from NG.
This study presents the kinetics and thermodynamics of biomass pyrolysis. The kinetics of the pyrolysis process was estimated using ten kinetic models from three different mechanisms, namely chemical reaction, diffusion, and nucleation and growth. Results showed that each pyrolysis subdivision was described by a different reaction model, signifying the complex nature of the pyrolysis process. The average values of activation energy determined from the kinetic models for empty fruit bunch, coconut shell, bamboo, and cardboard are 10.2-64.6 kJ/mol, 18.7-186.2 kJ/mol, 8.0-70.8 kJ/mol, and 13.1-277.3 kJ/mol, respectively. The biomass pyrolysis is endothermic and non-spontaneous and would require external energy to initiate the degradation process. The findings are helpful in characterizing the thermal degradation of biomass in exploring its potential as a source of alternative solid fuel.
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.
This study investigated the efficacy of using phosphate-modified zeolite (PZ) as an adsorbent for removing thorium from aqueous solutions. The effects of various factors such as contact time, adsorbent mass, initial thorium concentration, and pH value of the solution on the removal efficiency were analyzed using the batch technique to obtain optimum adsorption condition. The results revealed that the optimal conditions for thorium adsorption were a contact time of 24 h, 0.03 g of PZ adsorbent, pH 3, and a temperature of 25 °C. Isotherm and kinetics parameters of the thorium adsorption on PZ were also determined, with equilibrium studies showing that the experimental data followed the Langmuir isotherm model. The maximum adsorption capacity (Qo) for thorium was found to be 17.3 mg/g with the Langmuir isotherm coefficient of 0.09 L/mg. Using phosphate anions to modify natural zeolite increased its adsorption capacity. Furthermore, adsorption kinetics studies demonstrated that the adsorption of thorium onto PZ adsorbent fitted well with the pseudo-second-order model. The applicability of the PZ adsorbent in removing thorium from real radioactive waste was also investigated, and nearly complete thorium removal was achieved (> 99%) from the leached solution obtained from cracking and leaching processes of rare earth industrial residue under optimized conditions. This study elucidates the potential of PZ adsorbent for efficient removal of thorium from rare earth residue via adsorption, leading to a reduction in waste volume for ultimate disposition.
This study explores the plausible molecular interaction between a potent hepatitis C virus inhibitor, PSI-6206 (PSI), and human serum albumin (HSA), a primary transporter in blood plasma. Results obtained from both computational viz. molecular docking and molecular dynamics (MD) simulation and wet lab techniques such as UV absorption, fluorescence, circular dichroism (CD), and atomic force microscopy (AFM) complemented each other. While docking results identified PSI binding to subdomain IIA (Site I) of HSA by forming six hydrogen bonds, MD simulations signified the complex stability throughout the 50,000 ps. A consistent cutback in the Stern-Volmer quenching constant (Ksv) along with rising temperatures supported the static mode of fluorescence quenching in response to PSI addition and implied the development of the PSI-HSA complex. This discovery was backed by the alteration of the HSA UV absorption spectrum, a larger value (>1010 M-1.s-1) of the bimolecular quenching rate constant (kq) and the AFM-guided swelling of the HSA molecule, in the presence of PSI. Moreover, the fluorescence titration results revealed a modest binding affinity (4.27-6.25×103 M-1) in the PSI-HSA system, involving hydrogen bonds, van der Waals and hydrophobic interactions, as inferred from ΔS = + 22.77 J mol-1 K-1 and ΔH = - 11.02 KJ mol-1values. CD and 3D fluorescence spectra reminded significant adjustment in the 2° and 3° structures and modification in the Tyr/Trp microenvironment of the protein in the PSI-bound state. The results obtained from drug competing experiments also advocated the binding location of PSI in HSA as Site I.
Fig leaf, an environmentally friendly byproduct of fruit plants, has been used for the first time to treat of methylene blue dye. The fig leaf-activated carbon (FLAC-3) was prepared successfully and used for the adsorption of methylene blue dye (MB). The adsorbent was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and the Brunauer-Emmett-Teller (BET). In the present study, initial concentrations, contact time, temperatures, pH solution, FLAC-3 dose, volume solution, and activation agent were investigated. However, the initial concentration of MB was investigated at different concentrations of 20, 40, 80, 120, and 200 mg/L. pH solution was examined at these values: pH3, pH7, pH8, and pH11. Moreover, adsorption temperatures of 20, 30, 40, and 50 °C were considered to investigate how the FLAC-3 works on MB dye removal. The adsorption capacity of FLAC-3 was determined to be 24.75 mg/g for 0.08 g and 41 mg/g for 0.02 g. The adsorption process has followed the Langmuir isotherm model (R2 = 0.9841), where the adsorption created a monolayer covering the surface of the adsorbent. Additionally, it was discovered that the maximum adsorption capacity (Qm) was 41.7 mg/g and the Langmuir affinity constant (KL) was 0.37 L/mg. The FLAC-3, as low-cost adsorbents for methylene blue dye, has shown good cationic dye adsorption performance.
Due to increasing antibiotic pollution in the water environment, green and efficient adsorbents are urgently needed to solve this problem. Here we prepare magnetic bamboo-based activated carbon (MDBAC) through delignification and carbonization using ZnCl2 as activator, resulting in production of an activated carbon with large specific surface area (1388.83 m2 g-1). The influencing factors, such as solution pH, initial sulfadiazine (SD) concentration, temperature, and contact time, were assessed in batch adsorption experiments. The Langmuir isotherm model demonstrated that MDBAC adsorption capacity on SD was 645.08 mg g-1 at its maximum, being higher than majority of previously reported adsorbents. In SD adsorption, the kinetic adsorption process closely followed the pseudo-second kinetic model, and the thermodynamic adsorption process was discovered to be exothermic and spontaneous in nature. The MDBAC exhibited excellent physicochemical stability, facile magnetic recovery and acceptable recyclability properties. Moreover, the synergistic interactions between MDBAC and SD mainly involved electrostatic forces, hydrogen bonding, π-π stacking, and chelation. Within the benefits of low cost, ease of production and excellent adsorption performance, the MDBAC biosorbent shows promising utilization in removing antibiotic contaminants from wastewater.
The presence of chloride ion as an environmental pollutant is having a devastating and irreversible effect on aquatic and terrestrial ecosystems. To ensure safe and clean drinking water, it is vital to remove this substance using non-toxic and eco-friendly methods. This study presents a novel and highly efficient Ag NPs-modified bentonite adsorbent for removing chloride ion, a common environmental pollutant, from drinking water using a facile approach. The surface chemical properties and morphology of the pristine Na-bentonite and Ag NPs-Modified bentonite were characterized by field emission scanning electron microscopy (FESEM) and X-ray spectroscopy (EDX), X-Ray diffraction (XRD), Fourier transform infrared (FTIR), and zeta potential (ζ). To achieve maximum chloride ion removal, the effects of experimental parameters, including adsorbent dosage (1-9 g/L), chloride ion concentration (100-900 mg/L), and reaction time (5-25 h), were examined using the Response Surface Methodology (RSM). The chloride ion removal of 90% was obtained at optimum conditions (adsorbent dosage: 7 g/L, chloride ion concentration: 500 mg/L, and reaction time: 20 h). The adsorption isotherm and kinetics results indicated that the Langmuir isotherm model and pseudo-second-order kinetics were found suitable to chloride ion removal. Additionally, the regeneration and reusability of the Ag NPs-modified bentonite were further studied. In the regeneration and reusability study, the Ag NPs-modified bentonite has shown consistently ≥90% and ≥87% chloride ion removal even up to 2 repeated cycles, separately. Thus, the findings in this study provided convincing evidence for using Ag-NPs modified bentonite as a high-efficiency and promising adsorbent to remove chloride ion from drinking water.
The present study intended to develop efficient hydrogel spheres in treating simulated wastewater contaminated with p-chlorophenol. Herein, copper-modified nanocellulose was grafted onto alginate to produce eco-friendly hydrogel spheres to utilize as a viable biosorbent. Fabricated spheres were characterized through scanning electron microscopy, thermogravimetry, surface area measurement, point of zero charge and zeta potential analyses. The adsorption of p-chlorophenol was optimized by altering various experimental conditions. Pseudo second order kinetics and Langmuir adsorption isotherm best described the adsorption of p-chlorophenol onto copper-modified cellulose nanocrystal-based spheres. The maximum adsorption capacity was 66.67 mg g-1 with a reusability up to five regeneration cycles. The thermodynamic study directed that p-chlorophenol adsorption was exothermic, spontaneous, and reversible within the analyzed temperature range. Weber-Morris model revealed that intraparticle diffusion was not the singular rate-controlling step in the adsorption process. Hence, copper-modified nanocellulose spheres could be employed as a sustainable and effective biosorbent for p-chlorophenol adsorption from wastewater.
In this research article, novel starch phosphate grafted polyvinyl imidazole (StP-g-PIMDZs) was synthesized. Firstly, a phosphate group was attached to starch polymer via a phosphorylation reaction. Next, 1-vinyl imidazole (VIMDZ) was grafted on the backbone of starch phosphate (StP) through a free radical polymerization reaction. The synthesis of these modified starches was confirmed by 1H NMR, 31P NMR and FT-IR techniques. The grafting of vinyl imidazole onto StP diminished the crystallinity. Due to the insertion of the aromatic imidazole ring, the StP-g-PIMDZs demonstrated greater thermal stability. The StP and StP-g-PIMDZs were used as sorbents for the adsorption of methylene blue dye (MBD) from the model solution. The maximum removal percentage for starch, StP, StP-g-PIMDZ 1, StP-g-PIMDZ 2 and StP-g-PIMDZ 3 was found to be 60.6%, 66.7%, 74.2%, 85.3 and 95.4%, respectively. The Pseudo second order kinetic model and Langmuir adsorption isotherm were best suited to the experimental data with R2 = 0.999 and 0.99, respectively. Additionally, the thermodynamic parameters showed that the adsorption process was feasible, spontaneous, endothermic and favored chemi-sorption mechanism.
Interactive association of an antifungal drug, climbazole (CBZ) with the carrier protein in bovine circulation, bovine serum albumin (BSA) was explored by fluorescence and absorption spectroscopy along with in silico techniques. The fluorescence and absorption spectral alterations of the protein upon addition of CBZ affirmed the complex foration between CBZ and BSA. The inverse temperature dependence behaviour of the KSV values as well as the hyperchromic result of the protein's absorption signals characterized CBZ-triggered quenching of BSA fluorescence as the static quenching. A weak binding affinity (Ka = 3.12-1.90-× 103 M-1) was reported towards the CBZ-BSA association process. Interpretation of thermodynamic data (entropy change = +14.68 J mol-1 K-1 and enthalpy change = -15.07 kJ mol-1) and in silico analyses anticipated that hydrophobic forces, van der Waals forces and hydrogen bonds were the key intermolecular forces in the complex stabilization. Inclusion of CBZ to BSA produced microenvironmental perturbations around Tyr and Trp residues, and also significantly defended temperature-induced destabilization of BSA. The binding locus of CBZ was detected in the proximity of Sudlow's sites I (subdomain IIA) and II (subdomain IIIA) of BSA, exhibiting greater preference towards site II, as revealed by competitive site-marker displacement investigations and in silico analysis. The stability of the CBZ-BSA complex was further validated by the molecular dynamics simulation assessments.