Harnessing Moringa oleifera root powder (MORP) for the sustainable remediation of heavy metal contaminated water.

Heavy metal environmental pollution is rapidly increasing due to the increase in industrialization and urbanization. Industrial processes, such as paint production, mining, and raw materials producing industries release effluents rich in heavy metals, like Pb2+, Cd2+, Cu2+, and Cr3+. These heavy metals are dangerous because they persist in nature, are non-biodegradable and they have high tendency to accumulate in the environment and in living organisms who are exposed to them. This work studied the removal of heavy metals (Cu, Pb, Cr, and Cd) from aqueous solution using Moringa oleifera root powder (MORP) as the adsorbent. The MORP was characterized by SEM, FTIR, BET, and XRD. Batch adsorption experiments carried out investigated the effects of adsorbate concentration, adsorbent dosage, agitation time, pH and temperature on adsorption. The optimum parameters are: contact time (90 min); pH (9); adsorbent dose (0.6); metal ion concentration (30 mg L-1) for Cr and 40 mg L-1 for the rest; and temperature (50 °C) for Cu and Pb, and 70 °C for Cr and Cd. These experimental data were analyzed with 5 isotherm models (Temkin, Flory-Huggins, Langmuir, D-R and Freundlich). The result obtained fitted best to Temkin isotherm in comparison to others. Kinetic studies revealed that the pseudo-second order kinetic model best described the adsorption (with high R2 values ranging from 0.9810-0.9976) compared to pseudo-first order and intra-particle diffusion kinetics model. Results of the thermodynamic study showed that the sorption process was endothermic for Cu and Pb, but exothermic for Cd and Cr. The adsorbent showed good adsorptive tendencies toward the ions studied, and could be applied on an industrial scale for the remediation of metal contaminated water.

Zinc oxide decorated plantain peel activated carbon for adsorption of cationic malachite green dye: Mechanistic, kinetics and thermodynamics modeling.

Reports have shown that malachite green (MG) dye causes various hormonal disruptions and health hazards, hence, its removal from water has become a top priority. In this work, zinc oxide decorated plantain peels activated carbon (ZnO@PPAC) was developed via a hydrothermal approach. Physicochemical characterization of the ZnO@PPAC nanocomposite with a 205.2 m2/g surface area, porosity of 614.68 and dominance of acidic sites from Boehm study established the potency of ZnO@PPAC. Spectroscopic characterization of ZnO@PPAC vis-a-viz thermal gravimetric analyses (TGA), Fourier Transform Infrared Spectroscopy (FTIR), Powdered X-ray Diffraction (PXRD), Scanning Electron Microscopy and High Resolution - Transmission Electron Microscopy (HR-TEM) depict the thermal stability via phase transition, functional group, crystallinity with interspatial spacing, morphology and spherical and nano-rod-like shape of the ZnO@PPAC heterostructure with electron mapping respectively. Adsorption of malachite green dye onto ZnO@PPAC nanocomposite was influenced by different operational parameters. Equilibrium data across the three temperatures (303, 313, and 323 K) were most favorably described by Freundlich indicating the ZnO@PPAC heterogeneous nature. 77.517 mg/g monolayer capacity of ZnO@PPAC was superior to other adsorbents compared. Pore-diffusion predominated in the mechanism and kinetic data best fit the pseudo-second-order. Thermodynamics studies showed the feasible, endothermic, and spontaneous nature of the sequestration. The ZnO@PPAC was therefore shown to be a sustainable and efficient material for MG dye uptake and hereby endorsed for the treatment of industrial effluent.

Effect of hydrothermal carbonization on pyrolysis behavior, nutrients and metal species distribution in municipal sludge.

In this study, the effect of hydrothermal carbonation (HTC) on the pyrolysis behavior and the distribution of nutrients and metal species of waste-activated sludge (WAS) was investigated. Results showed that the pyrolysis activation energy range of WAS decreased from 11 to 57 kJ/mol to 10-36 kJ/mol when the hydrothermal carbonization was at 160 °C. As indicated by thermodynamic parameters, the hydrothermal carbonization process reduces the pyrolysis reaction activity of the hydrochar. The results of the chemical analysis indicate that hydrothermal carbonization significantly enhances the release of phosphorus and nitrogen, with maximum recovery at a temperature of 200 °C. The standard measurement and testing protocol revealed that hydrothermal carbonization increased the content of non-apatite inorganic P fraction in hydrochar and enhanced the availability of P. Heavy metal analysis shows that hydrothermal carbonization can strengthen the stability of heavy metals in WAS.

Innovative Sol-gel functionalized polyurethane foam for sustainable water purification and analytical advances.

Nanomaterial combined polymeric membranes such as polyurethane foams (PUFs) have garnered enormous attention in the field of water purification due to their ease of management and surface modification, cost-effectiveness, and mechanical, chemical, and thermal properties. Thus, this study reports the use of novel Sol-gel impregnated polyurethane foams (Sol-gel/PUFs) as new dispersive solid phase microextractors (d- µ SPME) for the efficient separation and subsequent spectrophotometric detection of Eosin Y (EY) textile dye in an aqueous solution with a pH of 3-3.8. The Sol gel, PUFs, and Sol gel-impregnated PUFs were characterized using scanning electron microscopy (SEM), goniometry measurements, dynamic light scattering (DLS), energy dispersive spectroscopy (EDS), UV-Visible, and FTIR spectra. Batch experiment results displayed a remarkable removal percentage (96% ± 5.4%) of the EY from the aqueous solution, with the total sorption time not exceeding 60 min. These data indicate rate-limited sorption via diffusion and/or surface complex ion associate formations after the rapid initial sorption steps. A pseudo-second order kinetic model thoroughly explained the sorption kinetics, providing a sorption capacity (qe) of 37.64 mg g-1, a half-life time (t1/2) of 0.8 ± 0.01 min, and intrinsic penetration control dye retention. The thermodynamic results revealed a negative value for ΔG° (-78.07 kJ mol-1 at 293 K), clearly signifying that the dye uptake was spontaneous, as well as a negative value for ΔH° (-69.58 kJ mol-1) and a positive value for ΔS° (147.65 J mol-1 K-1), making clear the exothermic nature of EY adsorption onto the sorbent, with a growth in randomness at the molecular level. A ternary retention mechanism is proposed, involving the "weak base anion exchanger" of {(-CH2-OH+ -CH2-) (Dye anion)-}Sol-gel/PUF and/or {(-NH2 + -COO-) (Dye anion)-}Sol-gel/PUF via solvent extraction and "surface adsorption" of the dye anion on/in the Sol-gel/PUFs membranes in addition to H-bonding, including surface complexation and electrostatic π-π interaction, between the dye and the silicon/zirconium oxide (Si-O-Zr) and siloxane (Si-O-Si) groups on the sorbent. Complete extraction and recovery (93.65 ± 0.2, -102.28 ± 2.01) of EY dye with NaOH (0.5 M) as a proper eluting agent was achieved using a sorbent-packed mini column. In addition, the established extractor displayed excellent reusability and does not require organic solvents for EY enrichment in water samples, making it a talented nominee as a novel sorbent for EY sorption from wastewater. This study is of great consequence for expanding the applicatio1n of Sol-gel/PUFs in developing innovative spectrophotometric sensing strategies for dye determination. In view of this, it would also be remarkable to perform future studies to explore the analytical implications of this extractor regarding safety and environmental and public health issues associated to the pollutant.

Synthesis of a Porous [14]Annulene Graphene Nanoribbon and a Porous [30]Annulene Graphene Nanosheet on Metal Surfaces.

The electrical and mechanical properties of graphene-based materials can be tuned by the introduction of nanopores, which are sensitively related to the size, morphology, density, and location of nanopores. The synthesis of low-dimensional graphene nanostructures containing well-defined nonplanar nanopores has been challenging due to the intrinsic steric hindrance. Herein, we report the selective synthesis of one-dimensional (1D) graphene nanoribbons (GNRs) containing periodic nonplanar [14]annulene pores on Ag(111) and two-dimensional (2D) porous graphene nanosheet containing periodic nonplanar [30]annulene pores on Au(111), starting from a same precursor. The formation of distinct products on the two substrates originates from the different thermodynamics and kinetics of coupling reactions. The reaction mechanisms were confirmed by a series of control experiments, and the appropriate thermodynamic and kinetic parameters for optimizing the reaction pathways were proposed. In addition, the combined scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations revealed the electronic structures of porous graphene structures, demonstrating the impact of nonplanar pores on the π-conjugation of molecules.

Structural, functional, and physiological properties of anti-(4-hydroxy-3-nitrophenyl)acetyl antibodies during the course of affinity maturation.

Structural and functional analyses of antibodies in the affinity maturation pathway can help us understand the molecular mechanisms of protein recognition. Using one of the haptens, (4-hydroxy-3-nitrophenyl)acetyl (NP), various monoclonal antibodies have been obtained, either at the early or late stage of immunization. The variable regions of monoclonal antibodies and their site-directed mutants can also be obtained as single-chain Fv (scFv) antibodies. The change in antigen-binding affinity and avidity of matured-type antibodies from germline-type antibodies could be evaluated based on binding kinetics and thermodynamics, proposing the antigen recognition mode. Crystal structures of a germline-type antibody, N1G9, and a matured-type antibody, C6, in complex with NP were determined, revealing different antigen-binding mode at atomic resolution. Notably, the Tyr to Gly mutation at the 95th residue of the heavy chain is critical for changing the configuration of complementarity determining region 3, which is involved in antigen binding. Furthermore, thermal stability analyses of scFv antibodies have revealed trade-off between antigen-binding affinity and thermal stability in the antigen-unbound state. To increase affinity, the stability of the variable region may be decreased, possibly due to protein architecture. The high stability of germline-type antibodies and the low stability of matured-type antibodies, which increase upon antigen binding, can be explained by the stability of antibodies required at the respective stages of immunization.

Efficient, rapid and simple adsorption method by polydopamine polystyrene nanofibers mat for removal of multi-class antibiotic residues in environmental water.

Polydopamine polystyrene nanofibers mat (PDA-PS NFsM) was prepared as an adsorbent for the simultaneous removal of multiple antibiotic residues in environmental water for the first time. PDA-PS NFsM can directly be used to adsorb 18 antibiotic residues belonging to 8 classes without any pretreatment of water samples. The adsorption process was completed within 5 min. All antibiotics could be removed at the same time, and the removal rate of each target was above 85%. Moreover, the used PDA-PS NFsM can be easily separated from the environmental water by taking out directly, and can be reused for 10 times after simple regeneration. The thermodynamic and kinetic properties of PDA-PS NFsM adsorption of antibiotic residues were further investigated consequently. It was found that the adsorptions of PDA-PS NFsM to the targets were spontaneous and endothermic process (ΔG<0, ΔH>0, ΔS>0). The results of adsorption kinetic experiments illustrated that the adsorption process was rapid, the adsorption equilibrium of which can be reached in 5 min. Adsorption isotherm experiments proved that the adsorption process of PDA-PS NFsM was consistent with Langmuir adsorption (R2 > 0.994), and the maximum adsorption capacity of PDA-PS NFsM towards all targets were 123.76 mg g-1. The developed method is rapid and simple, and can efficiently adsorb and remove a variety of antibiotics in environmental water, which has good practical application prospect.

Synergistic regulation of nonbinary molecular switches by protonation and light.

We report a molecular switching ensemble whose states may be regulated in synergistic fashion by both protonation and photoirradiation. This allows hierarchical control in both a kinetic and thermodynamic sense. These pseudorotaxane-based molecular devices exploit the so-called Texas-sized molecular box (cyclo[2]-(2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene); 14+, studied as its tetrakis-PF6- salt) as the wheel component. Anions of azobenzene-4,4'-dicarboxylic acid (2H+•2) or 4,4'-stilbenedicarboxylic acid (2H+•3) serve as the threading rod elements. The various forms of 2 and 3 (neutral, monoprotonated, and diprotonated) interact differently with 14+, as do the photoinduced cis or trans forms of these classic photoactive guests. The net result is a multimodal molecular switch that can be regulated in synergistic fashion through protonation/deprotonation and photoirradiation. The degree of guest protonation is the dominating control factor, with light acting as a secondary regulatory stimulus. The present dual input strategy provides a complement to more traditional orthogonal stimulus-based approaches to molecular switching and allows for the creation of nonbinary stimulus-responsive functional materials.

Characteristics, kinetics, thermodynamics and long-term effects of zerovalent iron/pyrite in remediation of Cr(VI)-contaminated soil.

Development of efficient, green and low-cost natural mineral-based reductive materials is promising to remediation of hexavalent chromium(Cr(VI))-contaminated soil. Considering the synergetic effect between pyrite and zerovalent iron (ZVI), an activated pyrite supported ZVI(ZVI/FeS2) with high reducing activity was developed by ball milling activation of natural pyrite and sulfidation of ZVI. The remediation property of ZVI/FeS2 for Cr(VI)-contaminated soil was evaluated with different ZVI/FeS2 dosage, soil-water ratio, initial pH, time and temperature, as well as the stability of Cr. The results showed that ZVI/FeS2 possessed high reduction activity with soil Cr(VI) removal rate up to 99 % even under alkaline condition, and soil with different pH values eventually converged to neutral after 90 days, indicating that ZVI/FeS2 has a good self-regulating alkaline ability. The reduction process conformed to Langmuir-Hinshelwood first-order kinetics and was a spontaneous and endothermic process. The lower activation energy of 17.97 kJ mol-1 (usually 60-250 kJ mol-1) indicated that the reduction reaction of Cr(VI) was particularly easy to occur. The speciation change of Cr in soil within 30 days demonstrated that the Cr in the soil was converted from a readily migratable state to a more stable state, where the Fe-Mn oxide bound fraction reached 85.03 % due to the generation of Cr(III)/Fe(III) co-precipitation. The results of long-term stability experiments showed that the leaching concentrations of Cr(VI) and total Cr decreased significantly after the ZVI/FeS2 treatment and remained stable at very low levels for 180 days. This study provided a sustainable way to fully utilize natural pyrite minerals to obtain iron-bearing reductive materials for feasible, effective and long-term stable immobilization of Cr(VI) in soil.

Quantify the combined effects of temperature and force on the stability of DNA hairpin.

OxDNA, as a successful coarse-grain model, has been applied to reproduce the thermodynamic and mechanical properties of both single- and double-stranded DNA. In current simulation, oxDNA is extended to explore the combined effects of temperature and force on the stability of DNA hairpin and its free energy landscape. Simulations were carried out at different forces and temperatures, at each temperature, a 18-base-pair DNA hairpin dynamically transited between folded state and unfolded state, and the separation between two states is consistent with the full contour length of single-stranded DNA in the unfolded state. Two methods were used to identify the critical force of DNA hairpin at each temperature and the critical forces obtained from two methods were consistent with each other and gradually decreased with the increasing temperature from 300 K to 326 K. The critical force at 300 K is reasonably consistent with the single molecule result of DNA hairpin with the same stem length. The two-state free energy landscape can be elucidated from the probability distribution of DNA hairpin extension and its dependence on the force and temperature is totally different. The increasing temperature not only reduces the free energy barrier, but also alters the position of transition point along the extension coordinate, resulting in the reduction of folding distance and the extension of unfolding distance, but their sum is not obviously dependent on the temperature. Generally, an assumption that the location of transition state in two-state energy landscape is independent of the stretching force is used to analyze the data of the single molecule experiment, but current simulation results indicate that effects of stretching forces on the location of transition state in two-state energy landscape are dependent on temperature. At relatively high temperature, stretching force can also change the location of transition state in the free energy landscape.

High-temperature liquid chromatography for evaluation of the efficiency of multiwalled carbon nanotubes as nano extraction beds for removal of acidic drugs from wastewater. Greenness profiling and comprehensive kinetics and thermodynamics studies.

The retention behavior of a series of acidic drugs, namely ketoprofen (KET), naproxen (NAP), diclofenac (DIC), and ibuprofen (IBU), on the heat-resisting ZORBAX 300SB-C18 column, was studied thermodynamically using high-temperature liquid chromatography (HTLC). A perfect correlation of the compounds' lipophilicity and the calculated thermodynamic indicators evidenced its contribution to the retention behavior. Besides, the steric fitting has a subsidiary effect on IBU retention. Isocratic HTLC separation of the four compounds was achieved using an aqueous mobile phase containing 30% acetonitrile-0.2% acetic acid-0.2% triethylamine at 60 °C. This method has been utilized to monitor the adsorption efficiency of multiwalled carbon nanotubes (MWCNTs) for the removal of the four NSAIDs from water. Different variables affecting the remediation process have been optimized such as the time of contact, pH, ionic strength, temperature, and the mass of MWCNTs. The kinetics and thermodynamics of the adsorption were investigated. The adsorption was evidenced to take place via pseudo-second-order kinetics and the intraparticle diffusion is the rate-controlling step. The thermodynamic investigation showed that the adsorption process is exothermic and enthalpy-driven, and the adsorption is more extensive at a lower temperature. The MWCNTs showed excellent adsorption efficiency of about 76.4 to 97.6% at the optimum conditions. The obtained results are promising and encouraging for the full-scale application of MWCNTs for remediation of NSAIDs-related water pollution. The green analytical chemistry metric "AGREE" and the analytical eco-scale score tool confirmed that the developed protocol is greener and more favorable to the environment and user than most of the reported literature.

Preparation of core-shell structured polystyrene @ graphene oxide composite microspheres with high adsorption capacity and its removal of dye contaminants.

Styrene was added dropwise to graphene dispersion solution by Pickering emulsion method to fabricate polystyrene @ graphene oxide layered composite microspheres (Pst@GO) for the removal of dye pollutants from water solution. Field emission scanning electron microscope, transmission electron microscopy, energy dispersive spectrometer, Brunauer emmett teller, zeta potential analyser and Fourier transform infrared spectrometer were adopted to analyse the changes in the microstructure and functional group of Pst@GO before and after the adsorption. The effects of initial concentration, adsorbent dose, pH, adsorption temperature and time on the adsorption behaviour of RhB and MB onto Pst@GO were studied by batch experiments. The results showed that a lot of folds on the surface of Pst@GO were beneficial to improve its adsorption capacity. The maximum adsorption capacity of RhB and MB onto Pst@GO was 49.70 and 59.07 mg g-1 at the initial concentration of 300 mg L-1, dose 0.1 g, pH = 7.0, adsorption temperature 55°C, adsorption time 2 h. The adsorption kinetics and thermodynamics analysis indicated that the adsorption of two dyes onto Pst@GO was endothermic reaction, while electrostatic attraction and hydrogen bonding are the main driving forces for the adsorption reaction.Polystyrene @ graphene oxide layered composite microspheres (Pst@GO) were prepared by Pickering emulsion method to remove dye pollutants in water. The preparation process of Pst@GO is as follows:Figure 1 Schematic fabrication process of Pst@GO.

Investigating the thermodynamic and kinetics properties of acid phosphatase extracted and purified from seedlings of Chenopodium murale.

Herein acid phosphatase isoenzyme was extracted from the C. murale seedlings. The purification was accomplished by chromatographic techniques and passing through DEAE-cellulose and Sephadex G-100 column. The specific activity of acid phosphatase 5.75 U/mg of protein was obtained with 66 purification fold 15.8% yield and molecular mass was 29 kDa with very faint bands corresponding to 18 kDa and 14 kDa. The maximal activity at pH 5.0 and 50 °C best illustrated by first order kinetics. When temperature was raised (55 °C to 75 °C), the deactivation rate constant was increased from 0.001 to 0.014 min-1, while half-life was decreased from 693 to 49 min-1. The results of activity collected at different temperature were then used to estimate, activation energy of hydrolysis reaction (Ea = 47.59 kJmol-1). A high Z-value (18.86 °C min-1) was obtained indicating a less sensitivity towards temperatures. The residual activity examinations were carried out from 55 °C to 75 °C and assessing the Deactivation Energy (Ed 116.39 kJmol-1), Enthalpy change (ΔH° 113.55kJmol-1), Entropy change (ΔS° 110.33kJmol-1) and change in Gibbs free energy (ΔG° 10.02 kJmol-1). Taken together, thermodynamic parameters confirm the high stability of enzyme and show potential commercial applicability.

Indirect Nano-sensing approach: A universal potentiometric silver ion selective sensor for inline quantitative profiling of the kinetics and thermodynamics of formation and decay of silver nanoparticles.

Indirect Nano-sensing are indispensable chemical sensory points that make use of the unique properties of nanoparticles to derive information about it to our macroscopic world. Precious Silver nanoparticles have become more attractive in many areas of healthcare and life sciences leading to massive industrial production and increase of environmental exposure which may lead to Nanotoxicity accompanied by the release of Ag+ ions. A reversible silver selective screen-printed electrode was fabricated, optimized, and validated. A wide linearity range of 1 × 10-6 - 1 × 10-2 M was obtained, with a LOD that reaches 1.5 × 10-7 M and a typical slope of monovalent cationic compounds of 59.6 mV/decade. It showed high selectivity towards the cationic Ag+ ion activity in presence of the negatively charged citrate capped silver nanoparticles (Cit-AgNPs). The fabricated sensor has been used for tracking the decrease of Ag+ activity during the reduction of AgNO3 with tri-sodium citrate during the Bottom-up synthesis of Cit-AgNPs at different temperature (60, 70 and 80 °C). The kinetic parameters (Activation energy (Ea) and Reaction rate (K)) and the thermodynamic characteristics (free activation energy (ΔG), entropy (ΔS), enthalpy (ΔH)) have been calculated. Furthermore, it has been used for tracking the release of Ag+ during the spontaneous and stimulated decay of Cit-AgNPs. The present work could be a junction between nanotechnology and recent advances in design of a reproducible, portable real-time analyzer for in-process monitoring of the production of Cit-AgNPs and its environmental hazards with many advantages in comparison to the reported techniques in terms of portability, simplicity, cost-efficient, fast inline tracking, no sampling, real-time profiles at high temperatures and it does not need professional operators.

High-performance of activated biocarbon based on agricultural biomass waste applied for 2,4-D herbicide removing from water: adsorption, kinetic and thermodynamic assessments.

Activated biocarbons were prepared using biomass wastes: sugarcane bagasse, coconut shell and endocarp of babassu coconut; as a renewable source of low-cost raw materials and without prior treatments. These activated biocarbons were characterized by textural analysis, solid-state 13C nuclear magnetic resonance spectroscopy, X-ray diffraction and scanning electronic microscopy. Textural analysis results revealed that those activated biocarbons were microporous, with specific surface area values of 547, 991 and 1,068 m2 g-1 from sugarcane bagasse, coconut shell and endocarp of babassu coconut, respectively. The innovation of this work was to evaluate which biomass residue was able to offer the best performance in removing 2,4-dichlorophenoxyacetic acid herbicide (2,4-D) from water by adsorption. Adsorption process of 2,4-D was investigated and the Langmuir and Redlich-Peterson models described best the adsorption process, with R2 values within 0.96-0.99. The 2,4-D removal performance were 97% and 99% for the coconut and babassu biocarbons, respectively. qM parameter values obtained from Langmuir model were 153.9, 233.0 and 235.5 mg g-1 using sugarcane bagasse, coconut shell and endocarp of babassu, respectively. In addition, the adsorption kinetics were described nicely by the second-order model and the Gibbs free energy parameter values were negative, pointing to a spontaneous adsorption, as well.

Synthesis of chitosan composite iron nanoparticles for removal of diclofenac sodium drug residue in water.

Iron composite nanoparticles were prepared (90% yield) using macromolecule chitosan and characterized by spectroscopic techniques (FT-IR, XRD, SEM, TEM & EDX). These were utilized to remove diclofenac sodium in water. The adjusted parameters were 400 µg/ L, 50.0 min., 5.0, 2.0 g/ L and 25.0 °C as concentration, contact time, pH, adsorbent amount and temperature for the elimination of diclofenac sodium in water with maximum 85% elimination. The sorption was spontaneous with exothermic. Data followed Langmuir, Temkin and Dubinin-Radushkevich models. Thermodynamic parameter ΔG° values were -12.19, -13.74 and -15.67 kJ/mol at 20, 25 and 30 °C temperatures. The values of ΔH° and ΔS° were 8.58 and 20.84 kJ/mol. Pseudo-first-order and liquid film diffusion mechanisms were proposed for the adsorption. This adsorption method is fast, effective eco-friendly and low-cost as it may be used in natural circumstances of water resources. The sorption method may be applied for the elimination of diclofenac sodium in any water body at a huge and financial scale.

Preparation of a carboxymethylcellulose-iron composite for uptake of atorvastatin in water.

Many water bodies are being contaminated by atorvastatin, which has certain side effects and problems on healthy individuals through contaminated water. For this purpose, effective and selective carboxymethylcellulose macromolecule iron composite nanoparticles were synthesized by green methods, characterized and used for uptake of atorvastatin drug residue from water. Atorvastatin in water was analyzed by HPLC using Aqua C28 (250 mm × 46 mm id) column and buffer-ACN (35:65, v/v) as eluent. The maximum elimination of atorvastatin was 80% with 40 µg L-1 concentration; 40 min agitated time, 5.0 pH, 1.0 g L-1 dose and 298 K temp. The removal data obeyed Freundlich, Langmuir, Dubinin-Radushkevich and Temkin models. The values of free energy were -8.79, -8.73 and -8.65 kJ mol-1 at 20.0, 25.0 and 30.0 °C temperatures. Enthalpy value was -14.16 kJ mol-1; showing exothermic removal. Entropy was -18.74 × 10-3 kJ mol-1 K; presenting decrease in entropy in the process. The kinetics modeling showed pseudo-first-order and liquid film diffusion mechanisms of removal. The removal technology was quick, conservation pleasant and lucrative. It is because of it capability with little dose and interaction time. Hence, the reported technology is practical for the exclusion of atorvastatin in water resource.

Enhanced extraction of hydroxytyrosol, maslinic acid and oleanolic acid from olive pomace: Process parameters, kinetics and thermodynamics, and greenness assessment.

Three techniques of ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE) and solvent extraction (SE) were used for enhancing the hydroxytyrosol (HT), maslinic acid (MA) and oleanolic acid (OA) extraction from olive pomace, being evaluated and compared through process parameters, kinetics and thermodynamics, plus greenness assessment analysis. Results showed that UAE yielded the maximum compounds due to a strong cavitation effect and the strongest mass and heat transfer efficiency involving the kinetic constants (h, Ce and K) and thermodynamic parameters (△H, △S and △G). Additionally, the optimal extraction conditions were acquired: ethanol concentration of 90%, extraction temperature of 50 °C, extraction time of 5 min, liquid to solid ratio of 30 mL/g, ultrasound intensity of 135.6 W/cm2, and ultrasound frequency of 60 kHz. UAE was confirmed as an effective and greener technique with the lowest E factor, energy consumption and carbon emission during the extraction process of bioactive compounds from olive pomace.

Kinetic and thermodynamic features of nanomagnetic cross-linked enzyme aggregates of naringinase nanobiocatalyst in naringin hydrolysis.

In this work, the structural thermostabilization of the characterized nanomagnetic cross-linked enzyme aggregates of naringinase have been considered. Comparisons have been made between free and immobilized enzyme by the determination of temperature-dependent half-lives (t1/2), energy barriers of thermal inactivation (Ea(in)) process, and thermodynamic parameters (ΔH*, ΔG*, and ΔS*) in a storage thermostability approach. Samples of NM-NGase-CLEAs were treated at different temperatures in the range of 40-80 °C for 90 min. The Km values of immobilized enzyme was reduced about 10.7 folds compared to the free one. The catalytic efficiency (kcat/Km) was raised about 10.5 folds after immobilization. Enzyme half-life (t1/2) of NM-NGase-CLEAs increased from 18.7 to 52.9 min (about 3 folds) at 80 °C. The thermodynamics study indicated that Ea(in) of the free enzyme increased from 38.51 to 49.14 (KJ·mol-1) and ΔH* increased from 35.57 to 46.20 (KJ·mol-1) after immobilization, which indicates an increase in the thermostability of this multimeric enzyme after nanomagnetic CLEAs fabrication. The NM-CLEAs of naringinase preserved 73% of its original activity after 10 cycles, which implies strong operational stability. Thus, the developed method for nanomagnetic CLEAs preparation has provided an efficient and simple approach for the productive and reusable nanobiocatalyst together with ease in enzyme handling.

Kinetics and thermodynamics of the thermal inactivation and chaperone assisted folding of zebrafish dihydrofolate reductase.

The maintenance of thermal stability is a major issue in protein engineering as many proteins tend to form inactive aggregates at higher temperatures. Zebrafish DHFR, an essential protein for the survival of cells, shows irreversible thermal unfolding transition. The protein exhibits complete unfolding and loss of activity at 50 °C as monitored by UV-Visible, fluorescence and far UV-CD spectroscopy. The heat induced inactivation of zDHFR follows first-order kinetics and Arrhenius law. The variation in the value of inactivation rate constant, k with increasing temperatures depicts faster inactivation at elevated temperatures. We have attempted to study the chaperoning ability of a shorter variant of GroEL (minichaperone) and compared it with that of conventional GroEL-GroES chaperone system. Both the chaperone system prevented the aggregation and assisted in refolding of zDHFR. The rate of thermal inactivation was significantly retarded in the presence of chaperones which indicate that it enhances the thermal stability of the enzyme. As minichaperone is less complex, and does not require high energy co-factors like ATP, for its function as compared to conventional GroEL-GroES system, it can act as a very good in vitro as well as in vivo chaperone model for monitoring assisted protein folding phenomenon.