Manganese cobalt-MOF@carbon nanofiber-based non-enzymatic histamine sensor for the determination of food freshness.

Early detection of histamine in foodstuffs/beverages could be useful in preventing various diseases. In this work, we have prepared a free-standing hybrid mat based on manganese cobalt (2-methylimodazole)-metal organic frameworks (Mn-Co(2-MeIm)MOF) and carbon nanofibers (CNFs) and explored as a non-enzymatic electrochemical sensor for determining the freshness of fish and bananas based on histamine estimation. As-developed hybrid mat possesses high porosity with a large specific surface area and excellent hydrophilicity those allow easy access of analyte molecules to the redox-active metal sites of MOF. Furthermore, the multiple functional groups of the MOF matrix can act as active adsorption sites for catalysis. The Mn-Co(2-MeIm)MOF@CNF mat-modified GC electrode demonstrated excellent electrocatalytic activities toward the oxidation of histamine under acidic conditions (pH = 5.0) with a faster electron transfer kinetics and superior fouling resistance. The Co(2-MeIm)MOF@CNF/GCE sensor exhibited a wide linear range from 10 to 1500 µM with a low limit of detection (LOD) of 89.6 nM and a high sensitivity of 107.3 µA mM-1 cm-2. Importantly, as-developed Nb(BTC)MOF@CNF/GCE sensor is enabled to detect histamine in fish and banana samples stored for different periods of time, which thus indicates its practical viability as analytical histamine detector.

Structure of spherical electric double layers with fully asymmetric electrolytes: a systematic study by Monte Carlo simulations and density functional theory.

A systematic investigation of the spherical electric double layers with the electrolytes having size as well as charge asymmetry is carried out using density functional theory and Monte Carlo simulations. The system is considered within the primitive model, where the macroion is a structureless hard spherical colloid, the small ions as charged hard spheres of different size, and the solvent is represented as a dielectric continuum. The present theory approximates the hard sphere part of the one particle correlation function using a weighted density approach whereas a perturbation expansion around the uniform fluid is applied to evaluate the ionic contribution. The theory is in quantitative agreement with Monte Carlo simulation for the density and the mean electrostatic potential profiles over a wide range of electrolyte concentrations, surface charge densities, valence of small ions, and macroion sizes. The theory provides distinctive evidence of charge and size correlations within the electrode-electrolyte interface in spherical geometry.

Structure of fluid mixtures near a solute: a density functional approach.

The structure of fluid mixtures near a spherical solute is studied using a density functional approach and computer simulation. The input direct correlation function is obtained from integral equation theory with an accurate closure relation. The density and concentration profiles of binary as well as ternary hard-sphere mixtures near a large hard-spherical solute compare quite well with the computer simulation results over a wide range of parametric conditions.

Intercalation of V2O5 and Polypyrrole into a Graphene Oxide Layer: A Hybrid Multifunctional Photothermal Structure for Efficient Solar Evaporation, Water Purification, Disinfection, and Power Production.

Development of a hybrid multifunctional photothermal structure with multifunctional capabilities is deliberated as an effective approach for harvesting abundant solar energy for sustainable environmental applications. Achieving enhanced solar to thermal conversion efficiency utilizing a suitably designed, environmentally compatible thermal management structure however remains a significant challenge. Herein, we report the intercalation of V2O5 and polypyrrole into a graphene oxide layer to design a hybrid photothermal assembly (PPy-V2O5-GO) and its multifunctional proficiencies. The hybrid photothermal structure demonstrated synergistic photothermal conversion, buoyant porous structure sustaining water transmission, and efficient steam release. V2O5 and polypyrrole-intercalated optimized graphene oxide structure attained an evaporation rate of 1.9 kg m-2 h-1 with a conversion efficiency of 92% under 1 sun solar radiation. At maximum, the assembly's surface temperature hit 64 ± 2 °C, suggesting its suitability as a solar water purifier. Outdoor experiments suggest the evaporator assembly's capability to accumulate a total output of 15 kg m-2 over a single day. Cell viability investigations revealed strong antimicrobial properties of PPy-V2O5-GO against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus bacteria, eliminating nearly all under 1 sun, making it a potential candidate for photothermal therapy. Furthermore, when combined with a commercial thermoelectric module, the framework displayed exceptional photothermal conversion efficiency, hinting at its potential for electrical power generation. The integration of PPy-V2O5-GO with a Bi2Te3-based thermoelectric module significantly boosted the thermoelectric generator's performance, offering an enhanced power output of 2.8 mW and a high power density of 1.24 mW/cm2, making them suitable for off-grid or remote-area application. Overall, the PPy-V2O5-GO photothermal assembly's stability, lack of leaching, effectiveness in producing pure water from seawater, antimicrobial efficacies, and recyclability make it an excellent choice for sustainable water treatment and power generation.

Three component model of cylindrical electric double layers containing mixed electrolytes: A systematic study by Monte Carlo simulations and density functional theory.

The structure of electric double layer around a hard rigid impenetrable cylindrical polyion is studied using density functional theory as well as Monte Carlo simulations. The three component model, presented here, is an extension of solvent primitive model where the solvent molecules are treated as the neutral hard spheres, counterions and coions as the charged hard spheres, all of equal diameters, and in addition the mixture of mono- and multivalent counterions are also considered. The theory is partially perturbative where the hard sphere interactions are treated within the weighted density approach and the corresponding ionic interactions have been evaluated through second-order functional Taylor expansion with respect to the bulk electrolyte. The theoretical predictions in terms of the density profiles and the mean electrostatic potential profiles are found to be in good agreement with the simulation results. The presence of neutral hard spheres incorporate the effects of exclude volume interactions (ionic size correlations) while the mixture of mono- and multivalent counterions enhance the ionic charge correlation effects. Thus, this model study shows clear manipulations of ionic size and charge correlations in dictating the ionic density profiles as well as mean electrostatic potential profiles of the diffuse layer. The behavior of diffused double layer has been characterized at varying ionic concentrations, at different concentration ratios of mono- and multivalent counterions of mixed electrolytes, at different diameters of hard spheres, and at varying polyion surface charge density.

Size and charge correlations in spherical electric double layers: a case study with fully asymmetric mixed electrolytes within the solvent primitive model.

Size and charge correlations in spherical electric double layers are investigated through Monte Carlo simulations and density functional theory, through a solvent primitive model representation. A fully asymmetric mixed electrolyte is used for the small ions, whereas the solvent, apart from being a continuum dielectric, is also treated as an individual component. A partially perturbative density functional theory is adopted here, and for comparison, a standard canonical ensemble Monte Carlo simulation is used. The hard-sphere free energy is treated within a weighted density approach and the residual ionic contribution is estimated through perturbation around the uniform density. The results from both methods corroborate each other quantitatively over a wide range of physical parameters. The importance of structural correlations is envisaged through the size and charge asymmetry of the supporting electrolytes that includes the solvent as a component.

Molecular solvent model of cylindrical electric double layers: a systematic study by Monte Carlo simulations and density functional theory.

We present the Monte Carlo simulation and density functional study of structure of cylindrical double layers considering solvent as the third component. We have chosen molecular solvent model, where ions and solvent molecules are considered as charged and neutral hard spheres, respectively, having equal diameter. The polyionic cylinder is modeled as an infinite, rigid, and impenetrable charged hard cylinder surrounded by the electrolyte and the solvent spheres. The theory is partially perturbative where the hard-sphere interactions are treated within the weighted density approach, the corresponding ionic interactions have been evaluated through second-order functional Taylor expansion with respect to the bulk electrolyte. The Monte Carlo simulations have been performed in canonical ensemble. The system is studied at varying concentrations of electrolyte ions and the solvent molecules, at different valences of the electrolyte, at different sizes of hard spheres, and at varying surface charge density. The theory and the simulation results are found to be in good agreement at different parametric conditions. The hard-sphere exclusion effects due to molecular nature of the solvent are shown to have special implications in characterizing diffuse layer phenomena such as layering and charge inversion.

Structure of cylindrical electric double layers: a systematic study by Monte Carlo simulations and density functional theory.

We present a systematic study of the structure of cylindrical double layers to envisage the distribution of small ions around a cylindrical polyion through canonical Monte Carlo simulation and density functional theory. The polyion is modeled as an infinite, rigid, and impenetrable charged cylinder surrounded by charged hard spheres of equal diameter modeled for small ions of the electrolyte. The solvent is considered as dielectric continuum. The theory is partially perturbative where the hard sphere contribution to the total excess free energy is evaluated using weighted density approximation, and the ionic interactions are calculated using quadratic Taylor expansion with respect to a uniform fluid. The system is studied over a wide range of parameters, viz., ionic concentrations, valences, and ionic sizes as well as for varying axial charge densities of the polyion. The theoretical predictions are observed to be in good agreement with that of simulation results. Some interesting phenomena relating to the width of the diffuse layer, mean electrostatic potential, and charge inversion have been observed to be dependent on different parametric conditions.

Simple weighted density functional approach to the structure of polymers at interfaces.

A simple weighted density functional approach is employed here for predicting the structure of polymers at interfaces where the polymer molecules are modeled as freely rotating fused-hard-sphere chains with fixed bond lengths and bond angles. The approach treats the ideal gas free energy functional exactly while the excess free energy functional is evaluated using a weighted density approximation. The weight function and the bulk fluid direct correlation function required in the theory are obtained using the Denton-Ashcroft recipe and the polymer reference interaction site model integral equation theory, respectively. The calculated density profiles are shown to be in good agreement with computer simulation results.

Effect of ionic size on the structure of cylindrical electric double layers: a systematic study by Monte Carlo simulations and density functional theory.

The effect of ionic size on the diffuse layer characteristics of a cylindrical electric double layer is studied using density functional theory and Monte Carlo simulations for the restricted primitive model and solvent primitive model. The double layer is comprised of an infinitely long, rigid, impenetrable charged cylinder also referred to as the polyion, located at the center of a cylindrical cell containing the electrolyte, which is composed of charged hard spheres and the solvent molecules as neutral hard spheres (in the case of the solvent primitive model). The diameters of all the hard spheres are taken to be the same. The theory is based on a partially perturbative scheme, where perturbation is used to approximate the ionic interactions and the hard sphere contribution is treated within the weighted density approach. The Monte Carlo simulations are performed in the canonical ensemble. The zeta potential profiles as a function of the polyion surface charge density are presented for cylindrical double layers at different ionic concentrations, ionic valences, and different hard sphere (ionic and the solvent) diameters of 2, 3, and 4 Å. The theory agrees quite well with the simulation results for a wide range of system parametric conditions and is capable of showing the maximum and minimum in the zeta potential value for systems having divalent counterions. The steric effects due to the presence of solvent molecules play a major role in characterizing the zeta potential and the ionic density profiles. A noticeable change in the concavity of the zeta potential plots with increasing particle size at very low concentrations of monovalent electrolytes is suggestive of the occurrence of infinite differential capacitance for such systems.

Structure of colloidal solution in presence of mixed electrolytes: a solvent restricted primitive model study.

The structure of colloidal solution in presence of mixed electrolytes is studied using Monte Carlo simulation and density functional theory, based on a four-component model of the spherical double layer. In this model the ions and solvent molecules are treated as charged and neutral hard spheres, respectively, having equal diameter, and in addition the mixture of mono- and multivalent co-ions are also considered. The macroion is considered as a uniformly charged hard sphere surrounded by the electrolyte and the solvent. The density functional theory is based on a partially perturbative scheme, where the electrical part is calculated through perturbation with respect to uniform density and the hard sphere contribution is approximated using a weighted density approach. The theory is found to be in quantitative agreement with the Monte Carlo simulation results, for singlet density as well as the mean electrostatic potential profiles. The system is studied over a wide range of parametric conditions, viz. with different ionic valences as well as size, at varying electrolyte concentration ratio of mono- and multivalent co-ions of mixed electrolytes, at different surface charge densities, and radius of the macroion. The present work reflects that even a simple primitive model for the solvent is able to manipulate the hard-sphere and electrostatic correlations of the diffuse double layer in the ionic density as well as mean electrostatic potential profiles.

Structure of spherical electric double layers containing mixed electrolytes: a systematic study by Monte Carlo simulations and density functional theory.

The structure of spherical electric double layers in the presence of mixed electrolytes is studied using Monte Carlo simulation and density functional theory within the restricted primitive model. The macroion is modeled as an impenetrable charged hard sphere carrying a uniform surface charge density, surrounded by the small ions represented as charged hard spheres, and the solvent is taken as a dielectric continuum. The density functional theory uses a partially perturbative scheme, where the hard-sphere contribution to the one-particle correlation function is evaluated using weighted density approximation and the ionic interactions are calculated using a second-order functional Taylor expansion with respect to a bulk electrolyte. The Monte Carlo simulations have been performed in canonical ensemble. The system is studied at varying ionic concentrations, at different concentration ratios of mono- and multivalent counterions of mixed electrolytes, at different diameters of hard spheres, at different macroion radius, and at varying polyion surface charge densities. The theoretical predictions in terms of the density profiles and the mean electrostatic potential profiles are found to be in good agreement with the simulation results. This model study shows clear manipulations of ionic size and charge correlations in dictating a number of interesting phenomena relating to width of the diffuse layer and charge inversion under different parametric conditions.

Molecular solvent model of spherical electric double layers: a systematic study by Monte Carlo simulations and density functional theory.

The structure of spherical electric double layers is studied using Monte Carlo simulation and density functional theory by considering solvent as the third component. In this molecular solvent model (MSM), ions and solvent molecules are considered as charged and neutral hard spheres, respectively, having equal diameter. The macroion is considered as an isolated hard sphere having uniform surface charge density surrounded by the electrolyte and the solvent. The theory is partially perturbative as the hard-sphere contribution to the one particle correlation function is evaluated using suitably averaged weighted density, and the ionic part is obtained through a second-order functional Taylor expansion around the bulk electrolyte. The Monte Carlo simulations have been performed in a canonical ensemble. The system is studied at varying concentrations of electrolytes, and the solvent molecules, at different valences of the electrolyte, at different macroion radii, and at varying surface charge densities. The theory is found to be in good agreement with the simulation results over a wide range of parametric conditions. The excluded volume effects due to the molecular nature of the solvent are shown to have much richer features in diffuse layer phenomena like layering and charge inversion.

Effect of attractions on the structure of polymer solutions confined between surfaces: a density functional approach.

A density functional theory is presented to study the effect of attractions on the structure of polymer solutions confined between surfaces. The polymer molecules have been modeled as a pearl necklace of freely jointed hard spheres and the solvent as hard spheres, both having Yukawa-type attractions and the mixture being confined between attractive Yukawa-type surfaces. The present theory treats the ideal gas free energy functional exactly and uses weighted density approximation for the hard chain and hard sphere contributions to the excess free energy functional. The attractive interactions are calculated using the direct correlation function obtained from the polymer reference interaction site model theory along with the mean spherical approximation closure. The theoretical predictions on the density profiles of the polymer and the solvent molecules are found to agree quite well with the Monte Carlo simulation results for varying densities, chain lengths, wall separations, and different sets of interaction potentials.

Structure of spherical electric double layers: a density functional approach.

A density functional theory is presented for the structure of spherical electric double layers within the restricted primitive model, where the macroion is considered as a hard sphere having uniform surface charge density, the small ions as charged hard spheres, and the solvent is taken as a dielectric continuum. The theory is partially perturbative as the hard-sphere contribution to the one-particle correlation function is evaluated using suitably averaged weighted density and the ionic part is obtained through a second-order functional Taylor expansion around the uniform fluid. The theory is in quantitative agreement with Monte Carlo simulation for the density profiles and the zeta potentials over a wide range of macroion sizes and electrolyte concentrations. The theory is able to provide interesting insights about the layering and the charge inversion phenomena occurring at the interface.

Effect of attractive interactions on the structure of polymer melts confined between surfaces: a density-functional approach.

A density-functional theory is presented to study the structure of polymers, having attractive interactions, confined between attractive surfaces. The theory treats the ideal-gas free-energy functional exactly and uses weighted density approximation for the hard-chain contribution to the excess free-energy functional. The bulk interactions of freely jointed hard spheres are obtained from generalized Flory equation of state and the attractive interactions are calculated using the direct correlation function obtained from the polymer reference interaction site model theory along with the mean spherical approximation closure. The theoretical predictions are found to be in quite good agreement with the Monte Carlo simulation results for varying densities, chain lengths, and different interaction potentials. The results confirm important implications of using different approximations for the hard-sphere and attractive interactions.

Structure of inhomogeneous polymer solutions: a density functional approach.

The structure of polymer solutions confined between surfaces is studied using a density functional theory where the polymer molecules have been modeled as a pearl necklace of freely jointed hard spheres and the solvent as hard spheres. The present theory uses the concept of universality of the free energy density functional to obtain the first-order direct correlation function of the nonuniform system from that of the corresponding uniform system, calculated through the Verlet-modified type bridge function. The uniform bulk fluid direct correlation function required as input has been calculated from the reference interaction site model integral equation theory using the Percus-Yevick closure relation. The calculated results on the density profiles of the polymer as well as the solvent are shown to compare well with computer simulation results.

Structure of short polymers at interfaces: a combined simulation and theoretical study.

The structure of polymers confined between surfaces is studied using computer simulation and a density functional approach. The simple model system considers the polymer molecule as a pearl necklace of freely jointed hard spheres, having attractions among the beads, confined between attractive surfaces. This approach uses the universality of the free-energy functional to obtain the self-consistent field required in the single chain simulation. The second-order direct correlation function for the uniform bulk fluid required as input has been calculated from the reference interaction site model integral equation theory using mean spherical approximation. The theoretical results are shown to compare well with the Monte Carlo simulation results for varying densities, chain lengths, and with different attractive interaction parameters. The simulation results on the conformational properties give important indications regarding the behavior of chains as they approach the surfaces.