Thermodynamic Parameters Research Articles

Effect of the mixed micelles of zwitterionic-anionic surfactant on efficiency of antibiotic azithromycin dihydrate

The study highlights the importance of mixed micelles in enhancing the binding and solubilization properties of partially water-soluble medications, using zwitterionic cocoamidopropyl betaine (CAPB) and anionic sodium tetradecyl sulfate surfactants. Surface tension and fluorescence spectroscopy evaluated the critical micelle concentration (CMC) of CAPB-STS mixed micelle. The thermodynamic parameters were assessed using Clint, Rubingh, and Motomura’s approach, which showed a synergistic interaction between the CAPB and STS. UV spectroscopy technique was used to evaluate the applicability of mixed micelle to enhance the solubility and binding constant (Kb) of antibiotic azithromycin dihydrate (AZI). Kb values of AZI were increased from 2.301 to 3.415 and molar solubilization ratio (MSR) values of AZI were increased from 0.228 to 0.801 by decreasing αCAPB from 0.9 to 0.1. The result indicated that zwitterionic CAPB was an electrostatic interaction consisting of both attractive (−CH2COO¯ group) and repulsive (−N+ group) interactions with AZI (−NH+ group), causing AZI molecules to reside in the Stern layer. While STS consisted of a negative −SO4¯ head group, it caused increased electrostatic interaction, and AZI penetrated the palisade layer of mixed micelles. At 7.00 mmolL-1 concentration of αCAPB 0.1, the solubility of AZI in water was increased to 2.77 mmol/L from 0.0032 mmol/L. Additionally, after 8 h, the controlled release of AZI in PBS at pH 7.4 was 95.58 % and decreased up to 30.77 % at αCAPB 0.1 mixed micelles. The observation of controlled AZI release from αCAPB 0.9 to 0.1 indicates that AZI molecules were strongly bound to mixed micelles by both hydrophobic and electrostatic interactions. In the end, a mixed micelle of CAPB-STS could serve as a useful drug-solubilizing agent in pharmaceutical applications.

Binaphthalene-Assisted Axial Chirality in Porphyrins: Toward Solid-State Circularly Polarized Luminescence from Self-Assembled Nanostructures.

Circularly polarized luminescence (CPL) is emerging as an effective tool to study the excited-state optical activity in molecules and their self-assembled nanostructures. Chiral porphyrins are a class of optically active molecules wherein the ground-state chirality has been extensively studied in recent times using circular dichroism (CD) spectroscopy. However, obtaining CPL from porphyrin nanostructures, which would have vast implications in biological applications, has remained an uphill task. In this work, we design and synthesize a pair of chiral porphyrin enantiomers functionalized by axially chiral binaphthalene units at the four meso-positions. The molecule undergoes self-assembly following an isodesmic polymerization model, leading to the formation of a spherical nanostructure possessing opposite chirality. Favorable thermodynamic parameters achieved through the controlled experimental conditions helped drive the self-assembly in the forward direction. The limitations imposed by a large nonradiative decay constant arising due to the aggregation-induced quenching could be overcome by fabricating self-standing polymeric films of the nanostructures. The films exhibited relatively high radiative decay and, more interestingly, good CPL activity with clear mirror image spectra for the nanostructures with opposite chirality. The work on CPL-active solid-state materials opens avenue for the design and synthesis of a variety of porphyrin-based chromophoric systems and their nanoaggregates that can find potential application in the field of chiral biosensing and bioimaging, security tags, and display devices.

Exploration of transition metal carbides TMCs (TM = V, Ti and Zr): mechanical, electronic structures and thermodynamic properties

The structural, mechanical, electronic, minimum thermal conductivity, tensile and thermodynamic properties of TMCs (M = Ti, V and Zr) have been investigated through first-principles calculations combination with QHA based on density-functional theory. The formation enthalpy, phonon spectrum and elastic constants emphasise that all TMCs are thermodynamically and mechanically stable. The elastic moduli of the VC are higher than the fourth group (TiC and ZrC). The strong covalent bonding between VC is the main reason for the high mechanical properties, while the ionic bonding of ZrC would explain for its low strength. Meanwhile, the weaker mechanical anisotropy of the TMCs favours a higher damage tolerance. Furthermore, the calculated minimum thermal conductivity in different directions of the TMCs demonstrated that is anisotropic. Finally the temperature dependence of thermodynamic parameters including volume, thermal expansion coefficient, bulk modulus and specific heat capacity at constant pressure is evaluated to be stable based on the QHA method.

Supreme capture of Europium(ΙΙΙ) by silica-hyperbranched poly(ethylene imine) composites from aqueous solutions − A mechanistic study

Two bio-inspired variations of the sol–gel technique produced silica-hyperbranched poly (ethylene imine) (PEI) composite nanoparticles (NP) and xerogels (XG). Both methods are performed in ambient conditions and do not require toxic organic solvents or high temperatures. We have investigated the removal efficiency of trivalent europium by these two hybrid species in near-neutral aqueous solutions. The adsorption kinetics and isotherms, including data fitting with the pseudo-first and second order kinetic, and the Langmuir isotherm model are presented and discussed. Thermodynamic parameters indicate exothermic reaction (–180 kJ/mol for NP and –192 kJ/mol for XG, respectively) In addition, spectroscopic (Fourier Transform Infra-Red FTIR, Fluorescence Spectroscopy FS, X-ray Photoelectron Spectroscopy XPS) and microscopic techniques (Scanning Electron Microscopy SEM coupled with Energy Dispersive X-ray analysis EDX), as well as ζ-potential and Dynamic light scattering (DLS) measurements, have been employed to evaluate the interaction mechanism between the surface active moieties and Eu(III). The extremely high and homogeneous dispersion of the amino and silicate groups of the composites has led to the highest capacity value (22 mmol/g or 3343 mg/g and 14 mol/g or 2128 mg/g for the two distinct forms of the nanoparticles and the xerogels, respectively) reported up to today implying a potential application for lanthanide recovery. The adsorption data along with the spectroscopic and microscopic indicate that the adsorption is well described by the Langmuir isotherm model and is based on the formation of inner- and outer-sphere complexes between Eu(III) the amine and −Si-O− moieties.

Thermokinetic study of tannery sludge using combustion and pyrolysis process through non-isothermal thermogravimetric analysis

Sludge from the tannery is produced in enormous amount. This work has investigated the thermal analysis behaviour of the tannery sludge by use of the thermogravimetric analysis (TGA). The TGA experiments is carried out in both air and nitrogen environment at the varied heating rates of 5, 10, 20 and 40 °C/min from the temperature range of 30–900 °C. In the assessment of kinetic parameters, the model fitting (Combined kinetics) method was employed. It was investigated that thermal degradation of the tannery sludge sample occurred in three stages. Majorly the conversions were observed in stage II for both in air and nitrogen environment. The activation energy (Ea) value for the combustion is 165.9 kJ/mol while for the pyrolysis the Ea value is obtained as 65.2 kJ/mol from the conversion range between 0.2 and 0.8 which is a promising approximation supported by a strong R2 value of 0.9719 and 0.93 for combustion and pyrolysis respectively. It is estimated from the master plots that six ideal models A1/2, A1/3, A1/4, F3, F4 and D5 were probably in approximation with the linear fitted data for both air and nitrogen. Various thermodynamic parameters which include the ΔH, ΔG and ΔS are also complimented that indicates the formation of activated complex and non-spontaneity of the reaction. The detailed thermokinetic study of the tannery sludge in combustion and pyrolysis offers a novel approach to understanding how this waste material decomposes under different temperature conditions. This holistic perspective contributes valuable insights into waste management practices, environmental impacts, resource recovery, and process optimization within the leather industry. Furthermore, the optimization of leather production processes on a large scale can minimize waste generation and enhance energy efficiency, strengthening the competitiveness and sustainability of the leather industry.

Surface Plasmon Resonance Allows to Correlate Molecular Properties with Diffusion Coefficients of Linear Chain Alcohols.

Every biological and physicochemical process occurring in a fluid phase depends on the diffusion coefficient (D) of the species in solution. In the present work, a model to describe and fit the behaviour of D as a function of structure and extensive thermodynamics parameters in binary solutions of linear chain organic molecules is developed. Supporting experimental and computational evidences for this model are obtained by measuring D for a series of n-alcohols through a novel surface plasmon resonance method and molecular dynamics simulations. This allows to propose a kind of combined analysis to explain the dependence of D on various thermodynamic and structural parameters. The results suggest that for small linear systems in the range from 0 to 200 g mol-1 and under the assumption that the diffusive activation energy is a linear function of mass, D is strictly dependent on the molecular shape and on the relative strength of the solute-solvent intermolecular forces represented by a parameter named R. The newly proposed approach can be utilized to characterize and monitor progressive changes in physicochemical properties for any investigated species upon increasing the dimension of the aggregate/molecule along a certain direction.

The Binding Mechanism Between Cyclodextrins and Anticancer Drug Noscapine: A Spectroscopic and Molecular Docking Study.

In this paper the binding of noscapine (NOS) as an anticancer drug with poor bioavailability and low solubility with beta and methyl-beta cyclodextrins (β-CD and M-β-CD) as the biocompatible drug carriers were discussed using ultraviolet-visible, fluorescence and nuclear magnetic resonance spectroscopy, as well as molecular docking. The absorption of NOS changed when it was bound to both cyclodextrins, resulting in a hyperchromic shift. It formed a 1:1 stoichiometry inclusion complex with both cyclodextrins according to the Benesi-Hildebrand equation. The binding affinity was larger in NOS-M-β-CD (5.9 (± 0.66) × 103 M- 1) than NOS-β-CD (3.7 (± 0.22) × 103 M- 1) complex. The fluorescence emission band of NOS at 408nm was quenched when NOS was complexed with β-CD, and enhanced in the presence of M-β-CD, while the shoulder at 350nm was enhanced selectively when NOS was complexed with M-β-CD. The fluorescence quenching of NOS with β-CD showed a negative deviation from the Stern-Volmer. The thermodynamic parameters have been estimated with the help of the Van't Hoff equation in different temperatures, and a dynamic mechanism was proposed for quenching. Also, both ΔH and ΔS have positive values thus the main interactions result in hydrophobic forces. Moreover, the negative value of ΔG indicates that the bonding process is spontaneous. 1H NMR chemical shift changes were observable for NOS and both CDs protons due to the chemical environment changes of some nuclei upon complexation. The molecular docking results revealed that the 1:1 inclusion complex possesses a good molecular shape complementarity score for their most probable structures, and indicated that the M-β-CD inclusion system gave the higher complexation efficiency. The binding energy values for β-CD and M-β-CD were determined to be -6.7 and - 9.5kcal/mol, respectively. These findings suggest the same as the result of experimental tests that the NOS-M-β-CD complex is more stable than the NOS-β-CD complex.

Effect of molecular crowders on ligand binding kinetics with G-quadruplex DNA probed by fluorescence correlation spectroscopy

Guanine-rich single-stranded DNA folds into G-quadruplex DNA (GqDNA) structures, which play crucial roles in various biological processes. These structures are also promising targets for ligands, potentially inducing antitumor effects. While thermodynamic parameters of ligand/DNA interactions are well-studied, the kinetics of ligand interaction with GqDNA, particularly in cell-like crowded environments, remain less explored. In this study, we investigate the impact of molecular crowding agents (glucose, sucrose, and ficoll 70) at physiologically relevant concentrations (20% w/v) on the association and dissociation rates of the benzophenoxazine-core based ligand, cresyl violet (CV), with human telomeric antiparallel-GqDNA. We utilized fluorescence correlation spectroscopy (FCS) along with other techniques. Our findings reveal that crowding agents decrease the binding affinity of CV to GqDNA, with the most significant effect—a nearly three-fold decrease—observed with ficoll 70. FCS measurements indicate that this decrease is primarily due to a viscosity-induced slowdown of ligand association in the crowded environment. Interestingly, dissociation rates remain largely unaffected by smaller crowders, with only small effect observed in presence of ficoll 70 due to direct but weak interaction between the ligand and ficoll. These results along with previously reported data provide valuable insights into ligand/GqDNA interactions in cellular contexts, suggesting a conserved mechanism of saccharide crowder influence, regardless of variations in GqDNA structure and ligand binding mode. This underscores the importance of considering crowding effects in the design and development of GqDNA-targeted drugs for potential cancer treatment.

Ultrafast and efficient extraction of heparin via cationic brush magnetic adsorbents

Heparin is a highly sulfated polysaccharide used extensively as an anticoagulant. However, conventional heparin extraction processes remains time-consuming and inefficient. We report cationic brush magnetic adsorbents by grafting poly(3-acrylamidopropyl) trimethylammonium chloride-co-N‑isopropylacrylamide random copolymers onto the surface of Fe3O4 for ultrafast and efficient heparin extraction. The fabricated adsorbent demonstrated an excellent adsorption capacity of 169.36 mg g−1 and a record-breaking adsorption rate towards heparin due to the introduction of N‑isopropylacrylamide, providing more adsorption sites and larger transport channels for the macromolecule heparin to access active sites. In addition, the adsorption capacity and rate for crude heparin were significantly better than those of commercial resin. Thermodynamic parameters implied that the heparin adsorption was spontaneous and endothermic process. The adsorption mechanism can be described by the synergistic effect of electrostatic attraction and hydrogen bond. This study paved an innovative approach to simultaneously enhance the adsorption rate and capacity of the adsorbent for polysaccharide.

Synthesis of green ceramic adsorbent for the treatment of tire factory effluent containing lead, zinc, aluminum, cobalt, iron and manganese ions

In this study, a novel nano-composite ceramic adsorbent was synthesized and characterized for the removal of heavy metal ions from industrial wastewater. The adsorbent was prepared using low-cost materials including clay and human hair, and hydroxyapatite nanoparticles derived from bovine bones. The synthesis method, material properties, and adsorption performance were thoroughly investigated wed XRD, FT-IR, FE-SEM and, BET. The adsorption process was optimized using Design Expert software, resulting in optimal conditions of pH 6.5, adsorbent mass of 22.5 g, temperature of 44.5 °C, initial concentration of 281 mgL−1, and retention time of 192 min. Thermodynamic parameters indicated that the adsorption process was spontaneous, endothermic, and followed the Freundlich isotherm model. The adsorption mechanism involved ion exchange, physical and chemical surface adsorption, facilitated by the unique surface properties of the nano-composite adsorbent. Moreover, the adsorbent exhibited high regeneration efficiency, with up to 73 cycles of reuse without a decrease in removal efficiency.

Investigation on Heterostructured SeO2–TiO2 Nanofluoroprobe for Highly Selective and Sensitive Detection of a Neonicotinoid Insecticide, Imidacloprid in Soil and Water Matrixes

Heterostructured SeO2–TiO2 nanoparticles were used as a highly sensitive and selective fluoroprobe for the detection and determination of neonicotinoid insecticide imidacloprid. The sonication-assisted co-precipitation technique was used to create nanoparticles, which were then characterized using UV–Vis, SEM–EDS, HRTEM, XRD, and TGA. These analyses revealed that the nanoparticles had globular morphology, a crystallite size of 14 nm, a bandgap of 2.45 eV, and stability at high temperatures. Fluorescence emission at 548 nm wavelength exhibits high sensitivity and selectivity for imidacloprid over other pesticides with complete fluorescent quenching at 2 × 10–4 M concentration of imidacloprid. Stern–Volmer equation and thermodynamic parameters applied to the experimental data over a temperature range of 20–50 °C provide the Ksv value in the range of 1.56 × 105 to 2.69 × 105 M−1 and indicate strong interactions, dynamic, spontaneous, and endothermic quenching process. Furthermore, the excellent salient features and notably the unaffected performance even in the presence of various anions, fertilizer, and binary mixture of pesticides often sprayed on plants, will pave the way for the development of rapid, affordable, selective fluoroprobe for onsite monitoring of imidacloprid. The reliability for determination is also examined for spiked soil samples to develop a hybrid SeO2–TiO2 nanoparticles fluoroprobe as a simple alternative to existing techniques for the detection of imidacloprid.Graphical

Computational Assessment of the Phytochemicals of Panax ginseng C.A. Meyer Against Dopamine Receptor D1 for Early Huntington's Disease Prophylactics.

A herb, Panax ginseng C.A. Meyer has been used traditionally for the treatment of various diseases. In this work, its chemical components have been explored by computational methods for the possibility of therapeutic potential against early Huntington's disease. The molecular docking calculations against dopamine receptor D1 (PDB ID: 7X2F) involved in pathogenesis of early Huntington's disease gave the binding affinities (kcal/mol) of schizandrin (-10.530), ergosterol (-10.124), protopanaxadiol (-9.650), panaxydol (-9.399), diphenhydramine (-9.358), and panasenoside (-9.358). The values for native ligand (-7.748) and some selected drugs, Nefazodone (-9.880), Risperidone (-9.752), and Haloperidol (-9.712) were higher revealing weaker interactions. The stability assessment of top protein-ligand adducts in terms of various geometrical and thermodynamical parameters extracted from 200 ns molecular dynamics simulations pointed to schizandrin, protopanaxadiol, and panasenoside as hit molecules. The minimal translational and rotational motion of the docked ligands at orthosteric pocket of the receptor at near physiological conditions hinted at the probability of it restricting or inhibiting over-activation of DRD1. The sustained thermodynamic spontaneity of complex formation reaction augmented the inferences derived from spatial results. The phytochemicals from Panax ginseng could be used in the prophylactics of early Huntington's disease and recommendation is made for further evaluation by experimental work.

Biophysical studies of human serum albumin with cocaine and cocaethylene: Understanding the drug-protein interaction in simulated physiological conditions

In this study, HSA was used as a transport protein model to simulate the transport dynamics and availability of cocaine (COC) and its pharmacologically active metabolite, cocaethylene (CE). In the interaction studies between the alkaloids and HSA, the binding constant (Kb) values were higher for CE (2.92 to 8.33 × 104 M−1) than COC (1.15 to 3.77 × 104 M−1) at different temperatures. Thermodynamic parameter calculations indicate that COC preferentially interacts through van der Waals forces and hydrogen bonds, while CE interacts hydrophobically. Competition studies using the ANS probe confirmed the more hydrophobic characteristics of CE. Synchronized fluorescence indicated that both compounds preferentially interact in the microregion of the Trp214 residue. Based on 3D fluorescence, UV–vis, and circular dichroic results, changes in the secondary structure of the protein were confirmed. Studies to assess the HSA binding site were carried out using warfarin (site I), diazepam (site II), and digitoxin (subdomain IIIB) as markers, and it was verified that both compounds interact preferentially at the site I. Finally, based on the 1H NMR and theoretical studies, it was possible to propose the alkaloid epitope in the interaction with HSA. In conclusion, when compared to COC, CE presented greater HSA protein affinity, justifying its longer plasma lifetime and increasing the drug’s effects on the body.

Efficient CO2 capture using a novel Zn-doped activated carbon developed from agricultural liquid biomass: Adsorption study, mechanism and transition state

A Zn-doped carbon was prepared and used as an effective CO2 adsorbent. This carbonaceous material was developed from olive mill wastewater (OMWW) by an innovative process using thermal shock flash pyrolysis followed by zinc chloride impregnation at ambient temperature. The developed Zn-doped carbon is highly porous (1406.56 m2.g−1), thermally stable and rich in active sites. The Temkin isotherm and the pseudo-second order kinetic model best describe the adsorption of CO2 on the developed material, and the storage capacity is of 370.41 mg g−1 (293 K). Thermodynamic parameters showed favorable, exothermic, and orderly adsorption. Two new isotherms, based on the number of layers formed at the surface, developed by advanced statistical modelling, were adapted and used to understand the mechanism in depth. The analysis of the results showed that CO2 adsorption occurs through the appearance of double layers on the adsorbent surface. Adapted models showed: only one molecule was adsorbed per surface active site, a very low degree of aggregation of CO2 molecules before adsorption and the molecules were adsorbed in a parallel orientation. The activation parameters showed a rapid and physical adsorption with a drop in entropy at the transition state. The mechanisms involved were governed by thermodynamic control with the possibility of easy desorption at high temperature. Zn-doped carbon is an ecological approach to reduce CO2 emissions on the globe.

Study on the adsorption performance of zeolite imidazole frameworks materials for Co(II) and Mn(II) in solution

Abstract The radionuclides 60Co and 54Mn are the main activation products produced in the operation of nuclear power facilities. Wastewater with these radionuclides must be treated to meet standards before being discharged. A variety of zeolite imidazole frameworks (ZIFs) materials were synthesized at room temperature, and the adsorption effect of ZIF-67 was found to be the best through adsorption experiments on Co(II) and Mn(II). The thermal stability test and structural characterization of ZIF-67 were carried out. At the same time, the influence of the initial pH value, adsorption time, and initial concentration of the solution on the adsorption of Co(II) and Mn(II) by ZIF-67 was investigated. The results show that: ZIF-67 has a microporous structure with a BET surface area of 1,035.72 m2/g. In addition, ZIF-67 has good thermal stability, under the condition of pH = 6, a temperature of 303 K and the initial concentration of 500 mg/L. The saturated adsorption capacity for Co(II) and Mn(II) reached 230.25 mg/g and 338.75 mg/g, respectively. ZIF-67 exhibits good selective adsorption performance for Co(II) and Mn (II) in high concentration interfering ion solutions and multi-ion solutions. The adsorption process of ZIF-67 was analyzed by kinetics, thermodynamics, isotherms, and adsorption diffusion models. The analysis of thermodynamic parameters shows that the adsorption process of ZIF-67 to Co(II) and Mn(II) is spontaneous and endothermic. The pseudo-second-order kinetic model, Langmuir isotherm model, and Boyd model are more in line with the adsorption process of Co(II) and Mn(II) by ZIF-67. It shows that the active sites on the surface of ZIF-67 are evenly distributed, and the adsorption process is single-molecule chemical layer adsorption. In addition, the liquid film diffusion dominates the adsorption rate during the adsorption process of Co(II) and Mn(II) by ZIF-67.

Investigating the synergetic effect of tungsten oxide doping into the 1,3-dicarbonyl moiety grafted chitosan and phytic acid impregnated sodium alginate for efficient U(VI) adsorption

In this work, chemical modification of the chitosan with ethyl acetoacetate was performed through a base-catalyzed reaction in which epichlorohydrin facilitated the insertion as well as nucleophilic substitution reaction to graft the 1,3-dioxo moiety across the linear chains of the base biopolymer to establish specificity and selectivity for U(VI) removal. The modified chitosan (EAA-CS) was intercalated into phosphate rich alginate matrix (PASA). Later on, the WO3-doped composites with different WO3 to PASA mass ratio were prepared and characterized using FTIR, XPS, SEM-EDS, XRD, and elemental mapping analysis. WO3 significantly contributed to chemically stable inorganic-organic composites with improved porous texture. Among the prepared composites, MCPS-3 microspherical beads, having mass ratio of 30.0 % w/w, exhibited excellent sorption capacity for U(VI) at an optimal pH 4.5. The successful U(VI) sorption was validated by the existence of two U4f peaks at 392.25 and 381.36 eV due to U4f5/2 and U4f7/2 sub-peaks with an intensity ratio of 3:4, respectively. Batch mode sorption kinetics followed pseudo-second-order rate equation (R2 ≈ 0.99, qe,th ≈ 116.88 mg/g, k2 = 0.86 × 10−4 g/mg.min−1) and equilibrium sorption data aligns with Langmuir (R2 = 0.99, qm = 343.85 mg/g at 310 K and pH = 4.5, KL = 2.00 × 10−2 L/mg) and Temkin models (R2 ≈ 0.99). Thermodynamic parameters ΔHo (30.51 kJ/mol), ΔSo (0.19 kJ/mol.K) and ΔGo (−25.64, −26.89, and − 27.91 kJ/mol) at 298, 305, and 310 K, respectively, suggested that the uptake process is feasible, endothermic and spontaneous. Based on these findings, it is reasonable to conclude that MCPS-3 could be a better hydrogel-based biomaterial for appreciable uranium recovery.

Pyranine Interaction with Amines in Micelles.

The fluorescence behavior of pyranine in anionic micellar system of sodium dodecyl sulphate was studied in the presence of selected amines. The amines included cyclopropylamine (CPA), ethylenediamine (EDA), benzylamine (BA), dibutylamine (DBA), cyclohexylamine (CHA), and polyethylenediamine (PEDA). All the studied amines quenched the intensity of pyranine. Study was performed in 0.05M and 0.1M SDS. The thermodynamic parameters were determined in order to understand the quenching of pyranine by the studied amines. Change in Gibbs free energy and quenching was found higher in 0.05M SDS concentration and was found lower when SDS concentration was increased to 0.1M SDS. Pyranine quenching by the amines studied were treated with an extended Stern-Volmer equation that produced the Stern-Volmer constant ([Formula: see text]). Binding constant (Kb), number of binding stoichiometry (n) and Gibbs free energy change (ΔGbinding) were found higher for lower surfactant concentration as compare to higher surfactant concentration. More negative (-ve) the Gibbs free energies more will be the quenching, higher will be the sensitivity and vice versa. The Gibbs free energies for all the studied amines were found in the order as cyclopropylamine > ethylenediamine > benzylamine > dibutylamine > cyclohexylamine > polyethylenediamine. Fluorescence quenching of pyranine by amines in aqueous SDS is reproducible and is useful for the determination of amines in environmental samples.

Highly stable mesoporous Co/Ni mixed metal-organic framework [Co/Ni(μ3-tp)2(μ2-pyz)2] for Co (II) heavy metal ions (HMIs) remediation

A bimetallic cobalt/nickel-based metal-organic framework (MOF), [Co/Ni(μ3-tp)2(μ2-pyz)2], denoted as Co/Ni-MOF, has been successfully prepared by a hydrothermal method. The MOF was prepared by incorporating mixed O− and N− donor ligands, specifically terephthalic acid (tp) and pyrazine (pyz). The Mesoporous Co/Ni-MOF was comprehensively characterized using various analytical methods such as XRD, BET, FT-IR, TGA (23 % char yields), SEM, and EDS analyses. The synthesized mesoporous Co/Ni-MOF was then used to absorb Co (II) from aquatic areas efficiently. Several critical parameters, such as the beginning Co (II) concentration (25–150 mg/L), the effect of pH (2–10), the duration of time (5–30 min), and the amount of adsorbent (0.003–0.02 g), were systematically investigated. Remarkably, the Mesoporous Co/Ni MOF displayed a significant adsorption capacity of 372.66 mg g−1 in the optimum conditions, including pH = 6, amount of adsorbent = 0.003 g, duration of time = 25 min, and beginning Co (II) concentration = 150 mg/L. Adsorption data from the experimental studies of the mesoporous Co/Ni MOF are matched based on the non-linear pseudo-first-order (PSO) kinetic model (R2 = 0.9999), and a chemical process is suggested for chemisorption. Furthermore, the adsorption isotherms of Co (II) heavy metal ions (HMIs) are an excellent fit with the non-linear Temkin, indicating that they explain the sorbent/sorbate interactions concerning the heat of adsorption. It is evident from the thermodynamic parameters that adsorption is a spontaneous and favorable exothermic process. These results highlight the promising adsorption performance and potential applications of the mesoporous Co/Ni-MOF as an effective adsorbent for Co (II) elimination from aquatic areas. Four-cycle regeneration studies were the most effective for the Co (II) under study.

Comparative analysis of multi-effect evaporators in an ammonium acetate concentration process for L-methionine production

The process of treating an acetic acid aqueous solution generated during L-methionine production with ammonia and recovering a highly concentrated ammonium acetate aqueous solution using a multi-effect evaporator process was studied. The electrolyte non-random two-liquid model was applied to calculate the activity in the electrolyte solution, and the Hayden-O’Connell model was used to consider the dimerization reaction of acetic acid in the vapor phase. The dissociation equilibrium constant of acetic acid was modeled based on experimental values, and all other thermodynamic property models and parameters were used as implemented in the Aspen Plus software. Economic evaluation was carried out with various sensitivity tests, considering the loss of acetic acid and ammonia, as well as the steam cost. Evaporator operation was found to be more economical when the molar ratio of acetic acid to ammonia was equal, feed concentration was high, feed flow rate was low, and evaporator temperature was low. These results were confirmed in actual plant operations, with significant correlations between the feed flow rate and evaporator temperature. Our findings have significant implications for the development of sustainable and economical L-methionine production methods that enable the recycling of ammonium acetate.

Exploring the Fibrous Nature of Single-Stranded DNA-Collagen Complexes: Nanostructural Observations and Physicochemical Insights.

Nucleic acid-collagen complexes (NACCs) are a self-assembled biomimetic fibrillary platform arising from the spontaneous complexation of single-stranded DNA (ssDNA) oligonucleotides and collagen. NACCs merge the extracellular matrix functionality of collagen with the tunable bioactivity of ssDNA as aptamers for broad biomedical applications. We hypothesize that NACCs offer a hierarchical architecture across multiple length scales that significantly varies compared to native collagen. We investigate this using atomic force microscopy and electron microscopy (transmission electron microscopy and cryogenic electron microscopy). Results demonstrate key topographical differences induced by adding ssDNA oligonucleotides to collagen type I. NACCs form a dense network of intertwined collagen fiber bundles in the microscale and nanoscale while retaining their characteristic D-band periodicities (∼67 nm). Additionally, our exploration of thermodynamic parameters governing the interaction indicates an entropically favorable NACC formation driven by ssDNA. Thermal analysis demonstrates the preservation of collagen's triple helical domains and a more stabilized polypeptide structure at higher temperatures than native collagen. These findings offer important insights into our understanding of the ssDNA-induced complexation of collagen toward the further establishment of structure-property relationships in NACCs and their future development into practical biomaterials. They also provide pathways for manipulating and enhancing collagenous matrices' properties without requiring complex chemical modifications or fabrication procedures.