Kinetics of adsorption of methylene blue and rhodamine 6G on acrylic acid-based superabsorbents

Superabsorbent polymers (SAPs) of acrylic acid, sodium acrylate, and acrylamide (AM), crosslinked with ethylene glycol dimethacrylate, were synthesized by inverse suspension polymerization. The equilibrium swelling capacities of the SAPs were determined and these decreased with increasing AM content. The adsorption of the two cationic dyes, methylene blue and rhodamine 6G, on the dry as well as equilibrium swollen SAPs was investigated. The amount of the dye adsorbed at equilibrium per unit weight of the SAPs and the rate constants of adsorption were determined. The amount of the dye adsorbed at equilibrium by the SAPs decreased with increasing mol % of AM in the SAPs. The amount of the dye adsorbed at equilibrium was almost equal for the dry and equilibrium swollen SAPs. However, the equilibrium swollen SAPs adsorbed dyes at a higher rate than the dry SAPs. The higher rate of adsorption was attributed to the availability of all the anionic groups present in the fully elongated conformation of the SAPs in the equilibrium swollen state. The effect of initial dye concentration on the adsorption was also investigated and the adsorption was described by Langmuir adsorption isotherms. (C) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Adsorption of anionic dyes on a reversibly swelling cationic superabsorbent polymer

A cationic monomer 2-(methacryloyloxy)ethyl]trimethylammonium chloride was polymerized using N,N'-methylenebisacrylamide as the crosslinker to obtain a cationic superabsorbent polymer (SAP). This SAP was characterized by Fourier transform-infrared spectroscopy, and the equilibrium swelling capacity was determined by swelling in water. The SAP was subjected to cyclic swelling/deswelling in water and NaCl solution. The conductivity of the swelling medium was monitored during the swelling/deswelling and was related to the swelling/deswelling characteristics of the SAP. The adsorption of five anionic dyes of different classes on the SAP was carried out and was found to follow the first-order kinetics. The Langmuir adsorption isotherms were found to fit the equilibrium adsorption data. The dye adsorption capacity of the SAP synthesized in this study was higher than that obtained for other hydrogels reported in the literature. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Optical bio-sensing devices based on etched fiber Bragg gratings coated with carbon nanotubes and graphene oxide along with a specific dendrimer

We demonstrate that etched fiber Bragg gratings (eFBGs) coated with single walled carbon nanotubes (SWNTs) and graphene oxide (GO) are highly sensitive and accurate biochemical sensors. Here, for detecting protein concanavalin A (Con A), mannose-functionalized poly(propyl ether imine) (PETIM) dendrimers (DMs) have been attached to the SWNTs (or GO) coated on the surface modified eFBG. The dendrimers act as multivalent ligands, having specificity to detect lectin Con A. The specificity of the sensor is shown by a much weaker response (factor of similar to 2500 for the SWNT and similar to 2000 for the GO coated eFBG) to detect non specific lectin peanut agglutinin. DM molecules functionalized GO coated eFBG sensors showed excellent specificity to Con A even in the presence of excess amount of an interfering protein bovine serum albumin. The shift in the Bragg wavelength (Delta lambda(B)) with respect to the lambda(B) values of SWNT (or GO)-DM coated eFBG for various concentrations of lectin follows Langmuir type adsorption isotherm, giving an affinity constant of similar to 4 x 10(7) M-1 for SWNTs coated eFBG and similar to 3 x 10(8) M-1 for the GO coated eFBG. (C) 2014 Elsevier B.V. All rights reserved.

Adsopption isotherms-A critique

The possibility or the impossibility of separating the particle and the electrode interactions is discussed in a wider context of the effects due to any two interaction potentials on the equation of state. The involved nature of the pressure dependence on two individually definable forces is illustrated through the Percus Yevick results for the adhesive hard spheres. An alternative form of the adsorption isotherm is given to bring home the intimate relationship between the actual equation of state and the free energy of adsorption. Thermodynamic consequences of congruence with respect to E (or q) as reflected through the linear plots of q (or E) vs. θ are well known. Mathematical consequences of simultaneous congruence have been pointed out recently. In this paper, the physical nature of congruence hypothesis is revealed. In passing "the pseudo-congruence" is also discussed. It is emphasised that the problem is no less ambiguous with regard to modelling the particle/particle interaction. The ad hoc nature of our dependence of the available equations of state is emphasised through a discussion on the HFL theory. Finally, a heuristic method for modelling ΔG mathematically-incorporating its behaviour at saturation coverages-is advanced. The more interesting aspects of this approach, which generalises almost all isotherms hitherto known, are sketched.

Removal of hexavalent chromium using coffee husk

The potential to remove chromium(VI) from aqueous solutions through biosorption using coffee husk was investigated. The effects of pH, contact time, initial concentration and adsorbent dosage on the adsorption of Cr(VI) were studied. The data obeyed Langmuir and Freundlich adsorption isotherms. The Langmuir adsorption capacity was found to be 44.95 mg/g. The Freundlich constants K-f and n were 1.027 mg/g (litre/mg)(n)] and 1.493, respectively. Desorption studies indicated the removal of 60% of the hexavalent chromium. Infrared spectral studies revealed the presence of functional groups, such as hydroxyl and carboxyl groups, on the surface of the biomass, which facilitates biosorption of Cr(VI).

Detection of sugar-lectin interactions by multivalent dendritic sugar functionalized single-walled carbon nanotubes

We show that single walled carbon nanotubes (SWNTs) decorated with sugar functionalized poly (propyl ether imine) (PETIM) dendrimer is a very sensitive platform to quantitatively detect carbohydrate recognizing proteins, namely, lectins. The changes in electrical conductivity of SWNT in field effect transistor device due to carbohydrate-protein interactions form the basis of present study. The mannose sugar attached PETIM dendrimers undergo charge-transfer interactions with the SWNTs. The changes in the conductance of the dendritic sugar functionalized SWNT after addition of lectins in varying concentrations were found to follow the Langmuir type isotherm, giving the concanavalin A (Con A)-mannose affinity constant to be 8.5 x 10(6) M-1. The increase in the device conductance observed after adding 10 nM of Con A is same as after adding 20 mu M of a non-specific lectin peanut agglutinin, showing the high specificity of the Con A-mannose interactions. The specificity of sugar-lectin interactions was characterized further by observing significant shifts in Raman modes of the SWNTs. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4739793]

Retention characteristics of Cu2+, Pb2+, and Zn2+ from aqueous solutions by two types of low lime fly ashes

The technical feasibility of utilization of fly ash as a low-cost adsorbent for the removal of metals from water has been studied. For two types of fly ashes, the retention capacities of copper, lead, and zinc metal ions have been studied. Contact time, initial concentration, and pH have been varied and their effect on retention mechanism has been studied. The dominant mechanisms responsible for retention are found to be precipitation due to the presence of calcium hydroxide, and adsorption due to the presence of silica and alumina oxide surfaces in the fly ash. First-order kinetic plots have revealed that the rate constant increases with increase in the initial concentration and pH. Langmuir adsorption isotherms have been plotted to study the maximum adsorption capacities for metal ions considered under different conditions. X-ray diffraction studies revealed the formation of new peaks corresponding to respective metal ions precipitates under alkaline conditions.

Adsorption isotherms-microscopic modelling

The phenomenon of adsorption is governed by the various interactions among the constituents of the interface and the forms of adsorption isotherms hold the clue to the nature of the se in teractions. An understanding of this phenomenon may be said to be complete only when the parameters occurring in such expres - sions for isotherms are interpretable in terms of molecular/electronic interactions.This objective viz. expressing the composition of the isotherm parameters through a microscopic modelling is by no means a simple one. Such a task is particularly made difficult in the case of charged interfaces where idealisation is difficult to make and, when made, not so easy to justify.

Abatement of fluoride from water using manganese dioxide-coated activated alumina

Batch adsorption of fluoride onto manganese dioxide-coated activated alumina (MCAA) has been studied. Adsorption experiments were carried out at various pH (3–9), time interval (0–6 h), adsorbent dose (1–16 g/l), initial fluoride concentration (1–25 mg/l) and in the presence of different anions. Adsorption isotherms have been modeled using Freundlich, Langmuir and Dubinin–Raduskevich isotherms and adsorption followed Langmuir isotherm model. Kinetic studies revealed that the adsorption followed second-order rate kinetics. MCAA could remove fluoride effectively (up to 0.2 mg/l) at pH 7 in 3 h with 8 g/l adsorbent dose when 10 mg/l of fluoride was present in 50 ml of water. In the presence of other anions, the adsorption of fluoride was retared. The mechanism of fluoride uptake by MCAA is due to physical adsorption as well as through intraparticle diffusion which was confirmed by kinetics, Dubinin–Raduskevich isotherm, zeta-potential measurements and mapping studies of energy-dispersive analysis of X-ray.

Combined Atomic Force Microscopy and Modeling Study of The Evolution of Octadecylamine Films on a Mica Surface

The time evolution of the film thickness and domain formation of octadecylamine molecules adsorbed oil a mica surface is investigated Using atomic force microscopy. The adsorbed Film thickness is determined by measuring the height profile across the mica-amine interface of a mica surface partially immersed in a 15 mM solution of octadecylamine in chloroform. Using this novel procedure, adsorption of amine on mica is found to occur in three distinct stages, with morphologically distinct domain Formation and growth occurring during each stage. In the first stage, where adsorption is primarily in the thin-film regime, all average Film thickness of 0.2 (+/- 0.3) nm is formed for exposure times below 30 s and 0.8 (+/- 0.2) nm for 60 s of immersion time. During this stage, large sample spanning domains are observed. The second stage, which occurs between 60-300 s, is associated with it regime of rapid film growth, and the film thickness increases from about 0.8 to 25 nm during this stage. Once the thick-film regime is established, further exposure to the amine solution results in all increase in the domain area, and it regime of lateral domain growth is observed. In this stage, the domain area coverage grows from 38 to 75%, and the FTIR spectra reveal an increased level of crystallinity in the film. Using it diffusion-controlled model and it two-step Langmuir isotherm, the time evolution of the film growth is quantitatively captured. The model predicts the time at which the thin to thick film transition occurs as well its the time required for complete film growth at longer times. The Ward-Tordai equation is also solved to determine the model parameters in the monolayer (thin-film) regime, which occurs during the initial stages of film growth.

Adsorption of anionic dyes on chitosan grafted poly(alkyl methacrylate)s

Chitosan grafted poly(alkyl methacrylate)s (namely chitosan grafted poly(methyl methacrylate) (ChgPMMA), chitosan grafted poly(ethyl methacrylate)(ChgPEMA), chitosan grafted poly(butyl methacrylate) (ChgPBMA) and chitosan grafted poly(hexyl methacrylate) (ChgPHMA)) were synthesized and characterized by using FT-IR and C-13 NMR techniques. The adsorption batch experiments on these grafted copolymers were conducted by using an anionic sulfonated dye. Orange-G. A pseudo-second-order kinetic model was used to determine the kinetics of adsorption. The effect of grafting, effect of process variables and the effect of different sulfonated anionic dyes (Orange-C, Congo Red, Remazol Brill Blue R and Methyl Blue) on the adsorption kinetics was determined. The Langmuir and Freundlich models were used to fit the adsorption isotherms and from the values of correlation coefficients (R-2), it was observed that the experimental data fits very well to the Langmuir model. The values of the maximum adsorption capacity of the adsorbents follow the order: ChgPMMA > ChgPEMA > ChgPBMA > ChgPHMA > chitosan. (C) 2010 Elsevier B.V. All rights reserved.

Studies on interaction of colloidal Ag nanoparticles with Bovine Serum Albumin (BSA)

Biofunctionalization of noble metal nanoparticles like Ag, Au is essential to obtain biocompatibility for specific biomedical applications. Silver nanciparticles are being increasingly used in bio-sensing applications owing to excellent optoelectronic properties. Among the serum albumins, the most abundant proteins in plasma, a wide range of physiological functions of Bovine Serum Albumin (BSA) has made it a model system for biofunctionalization. In absence of adequate prior reports, this study aims to investigate the interaction between silver nanoparticles and BSA. The interaction of BSA [0.05-0.85% concentrations] with Ag nanoparticles [50 ppm concentration] in aqueous dispersion was Studied through UV-vis spectral changes, morphological and surface structural changes. At pH 7, which is More than the isoelectric point of BSA, a decrease in absorbance at plasmon peak of uninteracted nanciparticles (425 mn) was noted till 0.45% BSA, beyond that a blue shift towards 410 urn was observed. The blue shift may be attributed to enhanced electron density on the particle surfaces. Increasing pH to 12 enhanced the blue shift further to 400 rim. The conformational changes in BSA at alkaline pH ranges and consequent hydrophobic interactions also played an important role. The equilibrium adsorption data fitted better to Freundlich isotherm compared to Langmuir Curve. The X-ray diffraction study revealed complete coverage of Ag nanoparticles by BSA. The scanning electron microscopic study of the interacted nanoparticles was also carried Out to decipher morphological changes. This study established that tailoring the concentration of BSA and pH of the interaction it was possible to reduce aggregation of nanoparticles. Biofunctionalized Ag nanoparticles with reduced aggregation will be more amenable towards bio-sensing applications. (C) 2009 Elsevier B.V. All rights reserved.

Biosorption of iron(III) from aqueous solutions using the husk of Cicer arientinum

Iron is a major pollutant released as a by-product during several industrial operations especially during acid mining of metal ores. In this paper, the use of Bengal gram husk (husk of channa dal, Cicer arientinum) in the biosorption of Fe(III) from aqueous solutions is discussed. Parameters like agitation time, adsorbent dosage and pH were studied at different Fe(Ill) concentrations. The adsorption data fit well with Langmuir and Freundlich isotherm models. The adsorption capacity (q(max)) calculated from the Langmuir isotherm was 72.16 mg of Fe(III)/g of the biosorbent at an initial pH of 2.5. Desorption Studies were performed at different concentrations of hydrochloric acid showing that quantitative recovery of the metal ion is possible. The infrared spectra of the biomass before and after treatment with Fe(III), revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Fe(III) ions.

Adsorption Isotherms and Heat of Adsorption of Difluoromethane on Activated Carbons

Experimental adsorption data of difluoromethane (HFC-32) on activated carbon in powder (ACP) and fiber (ACF) forms over a range of (25 to 75) degrees C and pressures up to 1400 kPa are reported. The data are fitted to Toth and Dubinin-Astakhov isotherm equations. Adsorbed phase volume is derived from the data. Isosteric heats of adsorption are extracted, and their dependence on relative loading and relative pressure is analyzed.

Purifying water containing both anionic and cationic species using a (Zn, Cu)O, ZnO, and Cobalt Ferrite based multiphase adsorbent system

For the purpose of water purification, novel and low-cost adsorbents which are promising replacements for activated carbon are being actively pursued. However, a single-phase material that adsorbs both cationic and anionic species remains elusive. Hence, a low-cost, multiphase adsorbent bed that purifies water containing both anionic and cationic pollutants is a desirable alternative. We choose anionic (Congo red, Orange G) and cationic (methylene blue, malachite green) dyes as model pollutants. These dyes are chosen since they are widely found in effluents from textile, leather, fishery, and pharmaceutical industries, and their carcinogenic, mutagenic, genotoxic, and cytotoxic impact on mammalian cells is well-established. We show that ZnO, (Zn0.24Cu0.76)O and cobalt ferrite based multiphase fixed adsorbent bed efficiently adsorbs model anionic (Congo red, Orange G) and cationic (methylene blue and malachite green) pollutants, and their complex mixtures. All adsorbent phases are synthesized using room-temperature, high-yield (similar to 96-100%), green chemical processes. The nanoadsorbents are characterized by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, and zeta potential measurements. The constituent nanophases are deliberately chosen to be beyond 50 nm, in order to avoid the nanotoxic size regime of oxides. Adsorption characteristics of each of the phases are examined. Isotherm based analysis shows that adsorption is both spontaneous and highly favorable. zeta potential measurements indicate that electrostatic interactions are the primary driving force for the observed adsorption behavior. The isotherms obtained are best described using a composite Langmuir-Freundlich model. Pseudo-first-order, rapid kinetics is observed (with adsorption rate constants as high as 0.1-0.2 min(-1) in some cases). Film diffusion is shown to be the primary mechanism of adsorption.