Synthesis of La-incorporated chitosan beads for fluoride removal from water

In this study, lanthanum incorporated chitosan beads (LCB) were synthesized using precipitation method and tested for fluoride removal from drinking water. The effect of various parameters like complexation and precipitation time, lanthanum loading and ammonia strength on fluoride removal have been studied. It is observed that the parameters for the synthesis of LCB have significant influence on development of LCB and in turn on fluoride removal capacity. The optimal condition for synthesis of LCB includes lanthanum loading: 10 wt%, complexation time: 60 min, precipitation time: 60 min, drying temperature: 75 °C for 72 h. The maximum fluoride adsorption capacity of LCB was found to be 4.7 mg/g and negligible release of lanthanum ion was observed. XRD analysis shows the presence of lanthanum hydroxide and amorphous nature of LCB. SEM of LCB shows the presence of oval lanthanum hydroxide particles spread over the chitosan matrix. Fluoride adsorption capacity has been calculated by applying Langmuir and Freundlich isotherms. The comparative study suggests that LCB shows four times greater fluoride adsorption capacity than the commercially used activated alumina.     

Equilibrium, kinetics and thermodynamic aspects of Promethazine hydrochloride sorption by iron rich smectite

Equilibrium, kinetics and thermodynamic aspects of sorption of Promethazine hydrochloride (PHCl) onto iron rich smectite (IRS) from aqueous solution were investigated. The effect of pH on sorption of PHCl onto IRS was also found out. Experimental data were evaluated by using Langmuir, Freundlich and Dubinin–Raduschkevich (DR) isotherm equations. Freundlich and DR equations provided better compatibility than Langmuir equation. Besides, it was determined that the maximum sorption of PHCl takes place at about pH 5. From kinetic studies, it was obtained that sorption kinetics follow pseudo-second-order kinetic model for PHCl sorption onto IRS. When thermodynamic studies are concerned, the values of activation energy (E_a), ΔG°, ΔH° and ΔS° were obtained. ΔG° values are in the range of −8.84 and −9.45 kJ mol⁻¹ indicating spontaneous nature of physisorption. The negative value of the ΔH° (−3.20 kJ mol⁻¹) indicates exothermic nature of adsorption. FTIR analysis and SEM observations of IRS and PHCl adsorbed IRS were also carried out. Sorption experiments indicate that IRS may be used effectively for the adsorption of PHCl.     

Dinitrogen and carbon monoxide hydrogen bonding in protonic zeolites: Studies from variable-temperature infrared spectroscopy

Adsorption (at a low temperature) of nitrogen on the protonic zeolite H-Y results in hydrogen bonding of the adsorbed N₂ molecules with the zeolite Si(OH)Al Brønsted-acid groups. This hydrogen-bonding interaction leads to activation, in the infrared, of the fundamental N–N stretching mode, which appears at 2334 cm⁻¹. From infrared spectra taken over a temperature range, the standard enthalpy of formation of the OH···N₂ complex was found to be ΔH⁰ = −15.7(±1) kJ mol⁻¹. Similarly, variable-temperature infrared spectroscopy was used to determine the standard enthalpy change involved in formation of H-bonded CO complexes for CO adsorbed on the zeolites H-ZSM-5 and H-FER; the corresponding values of ΔH⁰ were found to be −29.4(±1) and −28.4(±1) kJ mol⁻¹, respectively. The whole set of results was analysed in the context of other relevant data available in the literature.     

Study on the interaction between antibacterial drug and bovine serum albumin: A spectroscopic approach

The binding of sulfamethoxazole (SMZ) to bovine serum albumin (BSA) was investigated by spectroscopic methods viz., fluorescence, FT-IR and UV–vis absorption techniques. The binding parameters have been evaluated by fluorescence quenching method. The thermodynamic parameters, ΔH°, ΔS°and ΔG° were observed to be −58.0 kJ mol⁻¹, −111 J K⁻¹ mol⁻¹ and −24 kJ mol⁻¹, respectively. These indicated that the hydrogen bonding and weak van der Waals forces played a major role in the interaction. Based on the Forster's theory of non-radiation energy transfer, the binding average distance, r, between the donor (BSA) and acceptor (SMZ) was evaluated and found to be 4.12 nm. Spectral results showed the binding of SMZ to BSA induced conformational changes in BSA. The effect of common ions and some of the polymers used in drug delivery for control release was also tested on the binding of SMZ to BSA. The effect of common ions revealed that there is adverse effect on the binding of SMZ to BSA.     

The effects of pH and ionic strength on fulvic acid uptake by chitosan hydrogel beads

The objective of this work is to investigate the effects of pH and ionic strength on the adsorption capacity for fulvic acid (FA) by chitosan hydrogel beads. The results indicated that the sorption amount increased with decreasing pH and increasing ionic strength concentration. The sorption isotherms were well described by using non-linear Langmuir, Freundlich and Redliche–Peterson equation. The adsorption kinetics of FA onto chitosan hydrogel beads could be described by pseudo-second-order rate model. The extent of FA removal in the presence of other ions decreases in the order Ca²⁺ > Mg²⁺ > Na⁺ ≈ K⁺ and Cl⁻ > NO₃⁻ > CO₃²⁻. FTIR along with XPS analyses revealed the amine groups on the beads were involved in the sorption of FA and the organic complex between the protonated amino groups and FA was formed after FA uptake. Sorption mechanisms including electrostatic interaction and surface complexation were found to be involved in the complex sorption of FA on the chitosan hydrogel beads.     

Kinetics of adsorption of Saccharomyces cerevisiae mandelated dehydrogenase on magnetic Fe3O4–chitosan nanoparticles

The adsorption of Saccharomyces cerevisiae mandelated dehydrogenase (SCMD) protein on the surface-modified magnetic nanoparticles coated with chitosan was studied in a batch adsorption system. Functionalization of surface-modified magnetic particles was performed by the covalent binding of chitosan onto the surface of magnetic Fe₃O₄ nanoparticles. Characterization of these particles was carried out using FTIR spectra, transmission electron micrography (TEM), X-ray diffraction (XRD) and vibrating sample magnetometry (VSM). Magnetic measurement revealed that the magnetic Fe₃O₄–chitosan nanoparticles were superparamagnetic and the saturation magnetization was about 37.3 emu g⁻¹. The adsorption capacities and rates of SCMD protein onto the magnetic Fe₃O₄–chitosan nanoparticles were evaluated. The adsorption capacity was influenced by pH, and it reached a maximum value around pH 8.0. The adsorption capacity increased with the increase in temperature. The adsorption isothermal data could be well interpreted by the Freundlich isotherm model. The kinetic experimental data properly correlated with the first-order kinetic model, which indicated that the reaction is the adsorption control step. The apparent adsorption activation energy was 27.62 kJ mol⁻¹ and the first-order constant for SCMD protein was 0.01254 min⁻¹ at 293 K.     

Glutaraldehyde cross-linked epoxyaminated chitosan as an adsorbent for the removal and recovery of copper(II) from aqueous media

A novel glutaraldehyde cross-linked epoxyaminated chitosan (GA-C-ENCS) prepared through chemical modification was used as an adsorbent for the removal and recovery of Cu(II) from aqueous media. The adsorbent was characterized by FTIR, SEM-EDS, ESR, TG/DTG, BET-surface area and potentiometric titration. The Cu(II) adsorption process, which was pH dependent showed maximum removal at pH 6.0. Adsorption equilibrium was achieved within 3 h. The adsorption of Cu(II) followed a reversible-first-order kinetics. The equilibrium data were evaluated using the Langmuir, Freundlich and Dubinin–Radushkevich isotherm models. The best interpretation for the equilibrium data was given by the Dubinin–Radushkevich isotherm. The adsorption capacity of the adsorbent increased from 3.11 to 3.71 mmol g⁻¹ when the temperature was increased from 20 to 50 °C. The complete removal of 20.7 mg L⁻¹ Cu(II) from electroplating industry wastewater was achieved by 0.4 g L⁻¹ GA-C-ENCS. Regeneration experiments were tried for four cycles and the results indicate a capacity loss of <7.0%.     

NMR study of the dynamic behaviour of the system 2-ethylhexylsodium-2-ethylhexyllithium in heptane

Mixtures of 2-ethylhexylsodium and 2-ethylhexyllithium are studied by ¹H- and ¹³C-NMR spectroscopy in the temperature range from 20 to −50°C in hydrocarbon solutions. Characteristic temperature-dependent spectra obtained are indicative of dynamic exchange processes taking place in the system. The following activation parameters are found: ΔH^≠=31.7±2.7 kJ mol⁻¹; ΔG^≠₃₁₃=58.7±0.6 kJ mol⁻¹; ΔS^≠=−86.37±10.8 J mol⁻¹ K⁻¹. The negative value of the activation entropy indicates that the exchange proceeds through the associative mechanism. The participation in exchange reactions of aggregates, containing both sodium and lithium derivatives, is suggested.     

Adsorption mechanism of Cu from aqueous solution by chitosan-coated magnetic nanoparticles modified with α-ketoglutaric acid

In order to better understand the adsorption mechanism of chitosan-coated magnetic nanoparticles modified with α-ketoglutaric acid (α-KA-CCMNPs), the removal of Cu²⁺ by α-KA-CCMNPs from aqueous solution was investigated in a batch system at 18, 35 and 50 °C. Different experimental approaches were applied to show mechanistic aspects, such as adsorption isotherms, kinetics and thermodynamics studies. Adsorption equilibrium studies showed that Cu²⁺ adsorption followed Langmuir model. The kinetics of the interactions was best described by pseudo-second-order mechanism. The thermodynamic parameters (ΔG°, ΔH° and ΔS°) analysis predicted that the adsorption process was strongly dependent on temperature of medium, and spontaneous and endothermic process. The XPS combined with FT-IR spectra revealed that N atom of –NH– group and O atom of carboxyl group in α-KA-CCMNPs coordinated with Cu²⁺. Experimental results from this study provide data that would be required if this heavy metal adsorption system was to be “scaled up” for industrial application.     

The standard partial molar entropy of the aqueous tetra-n-butylammonium cation

The standard partial molar entropy of the aqueous tetrabutylammonium cation, not known previously, has now been obtained, based on the molar entropy of two of its crystalline salts, the iodide and the tetraphenylborate, recently determined experimentally for this purpose. The calculation required also published molar enthalpies of solution and solubilities of these two salts as well as of the perchlorate. The choice of the anions depended mainly on the limited solubilities of the examined salts in water, facilitating the estimation of the relevant activity coefficients. The result is S^∞(Bu₄N⁺, aq) = (380 ± 20) J · K⁻¹ · mol⁻¹ at T = 298.15 K, on the mol · dm⁻³ scale and based on S^∞(H⁺, aq) = (−22.2 ± 1.2) J · K⁻¹ · mol⁻¹ (yielding the ‘absolute’ value). The molar entropy of this cation in the ideal gas standard state, S(Bu₄N⁺, g) = (798 ± 8) J · K⁻¹ · mol⁻¹ then yielded the molar entropy of hydration Δ_hydS^∞ (Bu₄N⁺) = (−418 ± 23) J · K⁻¹ · mol⁻¹.     

Modeling of Equilibrium Adsorption and Surface Tension of Cationic Gemini Surfactants

A series of equilibrium tension models are used to evaluate the adsorption behavior of a novel class of lipoaminoacid gemini cationic surfactants, N^α,N^ω-bis(long-chain N^α-acylarginine)α,ω-dialkylamides or bis(Args). For purposes of comparison, the monomer LAM (the methyl ester of N^α-lauroyl arginine) was also examined. These surfactants are of particular interest for both their low toxicity and biocompatibility. The tension models are based on the Gibbs adsorption isotherm and classified as “ionic” when the surface charge and the electric double layer are accounted for or as “pseudo-nonionic” when the surface charge is ignored. Both model predictions and fitted parameter values are evaluated with respect to physical plausibility and overall goodness of fit to the available tension and density data. In particular, the inferred values for the standard Gibbs free energy of adsorption ΔG°, determined from an equilibrium constant defined on a nondimensional basis, without including artifacts due to an electrostatic contribution, are analyzed. The most reliable values of ΔG° are found with the combined model to range from −110 to −120 kJ mol⁻¹ for the three dimers examined and −80 kJ mol⁻¹ for the monomer. For spacer chain lengths n=3, 6, or 9, the maximum surface area of surfactant adsorption and the maximum free energy of adsorption are observed for the surfactant with the spacer chain length of 6.     

Vapor pressure, kinetics and enthalpy of sublimation of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II)

The kinetics of sublimation of bis(2,2,6,6-tetramethyl-3,5-heptanedionato)copper(II), [Cu(tmhd)₂] was studied by non-isothermal and isothermal thermogravimetric (TG) methods. The non-isothermal sublimation activation energy values determined following the procedures of Friedman, Kissinger, and Flynn–Wall methods yielded 93 ± 5, 67 ± 2, and 73 ± 4 kJ mol⁻¹, respectively and the isothermal sublimation activation energy was found to be 97 ± 3 kJ mol⁻¹ over the temperature range of 375–435 K. The dynamic TG run proved the complex to be completely volatile and the equilibrium vapor pressure (p_e)_T of the complex over the temperature range of 375–435 K determined by a TG-based transpiration technique, yielded a value of 96 ± 2 kJ mol⁻¹ for its standard enthalpy of sublimation (Δ_subH°).     

Chitosan–magnetite nanocomposites (CMNs) as magnetic carrier particles for removal of Fe(III) from aqueous solutions

This research focuses on removal of Fe(III) from aqueous solution using chitosan–magnetite nanocomposites as potential sorbent. The presence of nanosized magnetic particles within the nanocomposites was confirmed by TEM and SAED analysis. The particles with diameter 508 μm and 84 μm, follow Frendlich sorption isotherm at 30 °C, and the Frendlich constants (K_F, 1/n) have been found to be 5.974 mg g⁻¹, 2.66 and 35.98 mg g⁻¹, 1.385, respectively. Out of various kinetic models, the experimental data for dynamic uptake of Fe(III) is best fitted on ‘pseudo-second order’ kinetic model. The linear nature of plots between log (% sorption) and log (time) is indicative of intra-particle diffusion. For the particles with diameters 508 μm and 84 μm, the value of k_id was found to be 1.78 mg l⁻¹ min^−0.5 and 2.13 mg l⁻¹ min^−0.5. The sorption mean free energy from the Dubinin–Radushkevic isotherm was found to be 7.04 kJ mol⁻¹ indicating chemical nature of sorption. The increase in chitosan content in sorbent particles is found to enhance the Fe(III) uptake. The various thermodynamic parameters have also been evaluated. Finally, the presence of Cu²⁺ ions in the sorbate is found to decrease the uptake of Fe(III).     

Biosorption of nickel from aqueous solutions by Acacia leucocephala bark: Kinetics and equilibrium studies

The biosorption of nickel(II) ions from aqueous solution by Acacia leucocephala bark was studied in a batch adsorption system as a function of pH, initial metal ion concentration, adsorbent dosage, contact time and temperature. The maximum Ni(II) adsorption was obtained at pH 5. Further, the biosorbents were characterized by Fourier Transformer Infrared Spectroscopy (FTIR). The experimental data were analysed using three sorption kinetic models viz., the pseudo-first- and second-order equations and the intraparticle diffusion model. Results show that the pseudo-second-order equation provides the best correlation for the biosorption process. The equilibrium nature of Ni(II) adsorption at different temperatures of 30, 40 and 50 °C have been described by the Langmuir and Freundlich isotherm models. The equilibrium data fit well Langmuir isotherm. The monolayer adsorption capacity of A. leucocephala bark as obtained from Langmuir isotherm at 30 °C was found to be 294.1 mg/g. The Chi-square (χ²) and Sum of the square errors (SSE) tests were also carried out to find the best fit adsorption isotherm and kinetic model. Isotherms have been used to determine thermodynamic parameters of the process, viz., free energy change (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were calculated indicating that this system was a spontaneous and endothermic process. Present investigation emphasized that A. leucocephala bark may be utilized as a low cost adsorbent for nickel removal.     

Grafting of organosilane derived from 3-glycidoxypropyltrimethoxysilane and thiourea onto magnesium phyllosilicate by sol–gel process and investigation of metal adsorption properties

A layered inorganic–organic magnesium silicate (Mg-GTPS-TU) has been successfully synthesized by using sol–gel based precursor under mild temperature conditions and a new silylaing agent (GTPS-TU) derived from 3-glycidoxypropyltrimethoxysilane (GTPS) and thiourea (TU) as the silicon source. The hybrid material was characterized through elemental analysis, infrared spectroscopy, X-ray diffractometry, thermogravimetry, and carbon and silicon solid-state nuclear magnetic resonance spectroscopy. The result confirmed the attachment of organic functionality to the inorganic silicon network. The inter-lamellar distance for the hybrid material was found to be 18.8 Å. Metal adsorption characteristics follows Cr(III) >Mn(II)>Zn(II) with more affinity towards Cr(III) in dilute aqueous solution. Evaluation of thermodynamic parameters ΔH and ΔS for Cr(III) were found to be 25.44 J mol⁻¹ and 79.9 J mol⁻¹ K⁻¹, respectively, indicating adsorption process to be endothermic in nature. The negative value of ΔG indicated the feasibility and spontaneity of ongoing adsorption process at relatively higher temperature. The presence of multiple coordination sites in the attached organic functionality expresses the potentiality of the hybrid material containing new silylating agent for heavy cation removal from eco-system.     

Surface modification of Mitoxantrone-loaded PLGA nanospheres with chitosan

The purpose of this research was to develop polylactic-co-glycolic acid (PLGA) nanospheres surface modified with chitosan (CS). Mitoxantrone- (MTO-) loaded PLGA nanospheres were prepared by a solvent evaporation technique. The PLGA nanospheres surface was modified with CS by two strategies (adsorption and covalent binding). PLGA nanospheres of 248.4 ± 21.0 nm in diameter characterized by the laser light scattering technique, scanning electron microscopy (SEM) are spherical and its drug encapsulation efficiency is 84.1 ± 3.4%. Zeta potential of unmodified nanospheres was measured to be negative −21.21 ± 2.13 mV. The positive zeta potential of modified nanospheres reveals the presence of CS on the surface of the modified nanospheres. Modified nanospheres were characterized for surface chemistry by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR). FT-IR spectra exhibited peaks at 3420 cm⁻¹ and 1570 cm⁻¹, XPS spectra shows the N 1s (atomic orbital 1s of nitrogen) region of the surface of the nanospheres, corresponding to the primary amide of CS. In vitro drug release demonstrated that CS-modified nanospheres have many advantages such as prolonged drug release property and decreased the burst release over the unmodified nanospheres, and the modified nanospheres by covalent binding method could achieve the release kinetics of a relatively constant release. These data demonstrate high potential of CS-modified PLGA nanospheres for the anticancer drug carrier.     

Piezoelectric Sensor in Situ Monitoring Adsorption of Fibrinogen and Surfactant onto a Self-Assembled Monolayer of Alkanethiols

This report describes the use of a piezoelectric quartz crystal (PQC) sensor to investigate the nonspecific adsorption of fibrinogen (FN) and sodium dodecyl sulfate (SDS) onto a self-assembled monolayer (SAM) of alkanethiols on gold. The change in adsorption mass was monitored in situ by the PQC sensor. A kinetics model was proposed to describe the adsorption of the FN and SDS on the hydrophobic SAM surface. The adsorption kinetics parameters were determined from the responses of the PQC. The adsorption and desorption rate constants of the FN on the SAM surface were estimated to be (6.18 ± 0.53) × 10³ M⁻¹ s⁻¹ and (6.74 ± 0.72) × 10⁻³ s⁻¹, respectively. The rate constants for the adsorption and desorption of SDS on the SAM are (24.3 ± 1.4 M⁻¹ s⁻¹) and (1.52 ± 0.11) × 10⁻² s⁻¹, respectively. The adsorption of SDS on the SAM was reversible. The fractional coverage of the FN on the SAM surface was estimated from kinetics analyses to be 42–86% for the FN concentration range 25–400 μg/ml. Over 80% of the FN is irreversibly adsorbed on the SAM surface with respect to dilution of the bulk phase. The fraction of FN reversibly adsorbed increases with the bulk concentration of FN.     

Isotherm, kinetic and thermodynamic studies of lead and copper uptake by H2SO4 modified chitosan

The kinetic and thermodynamic adsorption and adsorption isotherms of Pb(II) and Cu(II) ions onto H₂SO₄ modified chitosan were studied in a batch adsorption system. The experimental results were fitted using Freundlich, Langmuir and Dubinin–Radushkevich isotherms; the Langmuir isotherm showed the best conformity to the equilibrium data. The pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models were employed to analyze the kinetic data. The adsorption behavior of Pb(II) and Cu(II) was best described by the pseudo-second order model. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) were determined; the adsorption process was found to be both spontaneous and exothermic. No physical damage to the adsorbents was observed after three cycles of adsorption/desorption using EDTA and HCl as eluents. The mechanistic pathway of the Pb(II) and Cu(II) uptake was examined by means of Fourier transform infrared (FTIR) and Energy dispersive X-ray (EDX) spectroscopy. The equilibrium parameter (R_L) indicated that chitosan–H₂SO₄ was favorable for Pb(II) and Cu(II) adsorption.     

Mesoporous silica functionalized with diethylenetriamine moieties for metal removal and thermodynamics of cation–basic center interactions

The inorganic–organic hybrid material was synthesized by co-condensation of tetraethylorthosilicate and the organosilane N-[3-(trimethoxysilyl)propyl]diethylenetriamine. Spectroscopic analysis of the hybrid material by FTIR showed bands at 2937 and 2839 cm⁻¹ related to ν(CH); ²⁹Si NMR spectrum gave signals at −108, −99, −68 and −59 ppm, Q⁴, Q³, T⁴ and T² species related to the silica backbone structure. The well-defined peaks obtained in the ¹³C NMR spectrum in the 10–58 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous silica. Particle morphology evaluated by a scanning electron microscopic (SEM) study showed the formation of spherical particles in the nanometer range. The X-ray diffraction pattern showed a peak at a 2θ of 2.3°, demonstrating the mesoporous characteristic of the synthesized material. Adsorption evaluated by batch equilibrium processes gave the maximum adsorption of 2.2 and 2.8 mmol g⁻¹ for copper and nickel, respectively. From these values a stoichiometry of 2:1 for cation/ligand was established, considering the amount of 1.2 mmol of pendant groups per gram of the hybrid material. Thermodynamic parameters related to the adsorption of metal ions, evaluated using the calorimetric titration technique presented a negative Gibbs free energy value, in agreement with the spontaneity of cation removal on the basic center in the mesoporous silica at the solid/liquid interface.