Preparation and adsorption properties of diethylenetriamine‐modified chitosan beads for acid dyes

This work has demonstrated that the novel chitosan derivative, synthesized by phase transition and grafting diethylenetriamine, has a great potential for the adsorption of acid dyes from aqueous solutions. Four acid dyes with different molecular sizes and structures were used to investigate the adsorption performance of diethylenetriamine‐modified chitosan beads (CTSN‐beads). Results indicated that the adsorption of dyes on CTSN‐beads was largely dependent on the pH value and controlled by the electrostatic attraction. In addition, the adsorption rate (AO10 > AO7 > AR18 > AG25) and adsorption capacities (AO7 > AR18 > AO10 > AG25) were directly related to the molecular size of the dye and the amount of the sulfonate groups on the dye molecules. The equilibrium and kinetic data fitted well with the Langmuir–Freundlich and pseudo‐second‐order model. Furthermore, thermodynamic parameters indicated that the adsorption processes occurred spontaneously and higher temperature made the adsorption easier. The reuse tests indicated that the CTSN‐beads can be recovered for multiple uses. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4090–4098, 2013     

Preparation of water‐soluble chitosan

An improved method of preparing water soluble chitosan was studied by N‐acetylation with acetic anhydride. Its merits were a simple processing technique, very short reaction time, little agent, high molecular weight of the product, and good water solubility. This article not only discusses the effect of several factors, such as the amount of reactants, concentration of hydrogen ions in the solution, and solvent system, on N‐acetylation but also some influential factors on the water solubility of N‐acetylated chitosan. Experiments showed that the amount of acetic anhydride was the most important factor affecting the N‐acetylation degree of the chitosan. The effect of the means of adding materials and the amount of solvent on the reaction could not be ignored. The solubility of half N‐acetylated chitosan was not changed with an increase in the molecular weight in water, and the water solubility decreased with increasing molecular weight in the alkaline region. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3497–3503, 2004     

Poly (methacrylic acid) modified biomass for enhancement adsorption of Pb2+, Cd2+ and Cu2+

In this study, the graft copolymerization of methacrylic acid onto the biomass of baker's yeast was carried out in aqueous medium using potassium persulfate (PPS) as initiator. The poly (methacrylic acid) modified biomass obtained was characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS) and microscopic analyses. The number of functional groups was determined by potentiometric titration. The adsorption capacity of the modified biomass for Pb²⁺, Cd²⁺ and Cu²⁺ showed a significant increase compared with the pristine biomass, due to the presence of a large number of functional groups. According to the Langmuir equation, the maximum uptake capacities (q_m) for Pb²⁺, Cd²⁺ and Cu²⁺ were 243.9, 108.7 and 73.5 mg g^?1, respectively. Adsorption kinetics study showed that completion of the adsorption process needed only 30 min. The loaded biosorbent was regenerated using EDTA solution and used repeatedly three times with little loss of uptake capacity. Good results were obtained when the modified biomass was used to treat simulated wastewater containing Pb²⁺, Cd²⁺ and Cu²⁺. Copyright © 2007 Society of Chemical Industry     

Competitive adsorption of acid dyes from aqueous solution on diethylenetriamine‐modified chitosan beads

The interaction between two dyes (AO7 and AG25) during adsorption was studied in detail with diethylenetriamine‐modified chitosan beads (CTSN‐beads) as the adsorbent. Results indicate that the adsorption capacities and rates were directly related to the molecular size of the dye. The adsorption capacity and rate of AO7 could be greatly weakened by interaction with AG 25 during adsorption, which has a larger molecular size. The adsorption followed the pseudo‐second‐order kinetic equation and Freundlich model gave a satisfying correlation with the equilibrium data both in the single and binary component system. Adsorption could be divided into three stages, each controlled by different mechanisms. Temperature experiments showed high temperature was beneficial to the mass transfer of dyes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41168.     

Poly(methacrylic acid)‐bound dihydroxybenzene units: Redox polymers

Poly(methacrylic acid) (PMAA) was functionalized with a hydroquinone/catechol under the reaction conditions of Minisci. Optimum conditions for maximum functionalization (52%) were found to be as follows: [benzoquinone]/[PMAA] ratio, 0.75; reaction time, 3 h; temperature, 75°C; and a nitrogen atmosphere. Redox properties of hydroquinone/catechol‐modified PMAA (PMAA‐HQ) were evaluated by their midpotentials potentiometrically estimated to be 898 mV at 20°C. At 35°C, a two‐stage oxidation was observed with a midpotential of 1000 mV. These midpotentials were found to be higher than those of hydroquinone, catechol, and a 1 : 1 hydroquinone‐catechol mixture, under the same conditions of potentiometric titration. Under the modification reaction conditions, the modified PMAA underwent severe degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 954–961, 2006     

Preparation of nanometer‐sized poly(methacrylic acid) particles in water‐in‐oil microemulsions

A water‐in‐oil microemulsion, water‐in‐cyclohexane stabilized by poly(ethylene glycol) tert‐octylphenyl, was developed to prepare poly(methacrylic acid) (PMAA) particles. Up to 100% conversion of the amphiphilic monomer, methacrylic acid (MAA), which could not be converted to the polymer efficiently in a dioctylsulfosuccinate sodium salt/toluene microemulsion, was achieved. The viscosity‐average molecular weight of the PMAA prepared was 1.45 × 10⁵ g/mol. The effects of some polymerization parameters, including the reaction temperature and the concentrations of the initiator and the monomer, on the polymerization of MAA were investigated. The results showed that the polymerization rate of MAA was slower than that of acrylamide in the microemulsions reported in the literature. The degree of conversion increased with the initiator concentration, reaction temperature, and monomer concentration. However, the stable microemulsions became turbid during the polymerization when the reaction temperature was at 70°C or at a high monomer concentration (40 wt %) The synthesized PMAA particles were spherical and had diameters in the range of ～50 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2497–2503, 2006     

Inhibition of water‐soluble cationic cellulosic polymers to clay hydration

The inhibition of water‐soluble cationic graft terpolymers of hydroxyethylcellulose with the vinyl monomers dimethyldiallylammonium chloride and acrylamide to the hydration of water‐sensitive clay in oilfields was investigated by clay hydration‐swelling tests, XRD analyses, zeta‐potential measurements, and SEM observation. It has been shown that grafting enhances the hydration‐inhibition effectiveness and the performances of these cationic cellulosic polymers are strongly dependent on their cationicity, relative molecular weight, and solution concentration. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3088–3093, 1999     

Preparation of water‐soluble chitosan derivatives and their antibacterial activity

Carboxymethyl chitosan sodium (CMCTS) was synthesized by chitosan and chloroacetic acid under an alkali catalyst. Acrylic acid sodium salt and methylacrylic acid sodium salt were grafted onto CMCTS to obtain copolymers with good water solubility. The graft reaction was carried out at 70°C for 2 h, and ammonium persulfate was used as an initiator. The structure changes of chitosan and its derivatives were investigated by the FTIR. The antibacterial activity of chitosan derivatives against Staphylococcus aureus and Escherichia coli were explored by the viable cell counting method. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1357–1361, 2002     

Synthesis of highly swellable hydrogels of water‐soluble carboxymethyl chitosan and poly(ethylene glycol)

Highly swellable hydrogels were produced by crosslinking of high molecular weight carboxymethylated chitosan (CmCHT) with poly(ethylene glycol) (PEG) oligomers. The hydrogel swelling capacity could be controlled via the crosslinking density and ranged from 900% to 5600%. The hydrogels showed good homogeneity with a high interconnected porosity in the swollen state and with nanodomains rich in CmCHT and others rich in PEG diglycidyl ether. Oscillatory frequency sweep analysis showed a storage modulus of 27 kPa for the hydrogel with the highest crosslinking density, which together with the exhibited enzyme degradability with lysozyme at 59 days indicate that these hydrogels have potential use in delivery systems or soft tissue regeneration. © 2017 Society of Chemical Industry     

Immobilization of a nonspecific chitosan hydrolytic enzyme for application in preparation of water‐soluble low‐molecular‐weight chitosan

A nonspecific chitosan hydrolytic enzyme, cellulase, was immobilized onto magnetic chitosan microspheres, which was prepared in a well spherical shape by the suspension crosslinking technique. The morphology characterization of the microspheres was carried out with scanning electron microscope and the homogeneity of the magnetic materials (Fe₃O₄) in the microspheres was determined from optical micrograph. Factors affecting the immobilization, and the properties and stabilities of the immobilized enzyme were studied. The optimum concentration of the crosslinker and cellulase solution for the immobilization was 4% (v/v) and 6 mg/mL, respectively. The immobilized enzyme had a broader pH range of high activity and the loss of the activity of immobilized cellulase was lower than that of the free cellulase at high temperatures. This immobilized cellulase has higher apparent Michaelis–Menten constant K_m (1.28 mg/mL) than that of free cellulase (0.78 mg/mL), and the maximum apparent initial catalytic rate V_max of immobilized cellulase (0.39 mg mL^?1 h^?1) was lower than free enzyme (0.48 mg mL^?1 h^?1). Storage stability was enhanced after immobilization. The residual activity of the immobilized enzyme was 78% of original after 10 batch hydrolytic cycles, and the morphology of carrier was not changed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1334–1339, 2006     

Studies of adsorption of alkaline trypsin by poly(methacrylic acid) brushes on chitosan membranes

Poly(methacrylic acid)‐grafted chitosan membranes (chitosan‐g‐poly(MAA)) were prepared in two sequential steps: in the first step, chitosan membranes were prepared by phase‐inversion technique and then epichlorohydrin was used as crosslinking agent to increase its chemical stability in acidic media; in the second step, the graftcopolymerization of methacrylic acid onto the chitosan membranes was initiated by ammonium persulfate (APS) under nitrogen atmosphere. The chitosan‐g‐poly(MAA) membranes were first used as an ion‐exchange support for adsorption of trypsin from aqueous solution. The influence of pH, equilibrium time, ionic strength, and initial trypsin concentration on the adsorption capacity of the chitosan‐g‐poly(MAA) membranes have been investigated in a batch system. Maximum trypsin adsorption onto chitosan‐g‐poly(MAA) membrane was found to be 92.86 mg mL^?1 at pH 7.0. The experimental equilibrium data obtained for trypsin adsorption onto chitosan‐g‐poly(MAA) membranes fitted well to the Langmuir isotherm model. The adsorption data was analyzed using the first‐ and second‐order kinetic models, and the experimental data was well described by the second‐order equation. More than 97% of the adsorbed trypsin was desorbed using glutamic acid solution (0.5M, pH 4.0). In addition, the chitosan‐g‐ poly(MAA) membrane prepared in this work showed promising potential for various biotechnological applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(ethylene glycol)‐containing cationic hydrogels with lipophilic character

Not much effort has been focused towards the development of hydrogels that swell in nonpolar solvents. We have synthesized a new set of polyelectrolyte hydrogels and demonstrated their ability to absorb a less‐polar or nonpolar organic solvent, as well as their ability to resist gel‐collapse in a predominantly nonpolar medium. The hydrogels were prepared by free radical polymerization of different molar ratios of poly(ethylene glycol) methyl ether acrylate and (3‐(methacryloylamino)propyl)‐trimethyl ammonium chloride as comonomers in an aqueous medium. Their swelling behavior in organic solvents was studied by varying the dielectric constant of the swelling medium including mixed‐solvent systems. Besides a high degree of swelling (up to 200 times) in polar solvents, some of the hydrogels also exhibited moderate swelling (up to 15 times) in less‐polar organic solvents. Hydrogels samples with high cationic content showed drastic change in swelling extent in some of the mixed‐solvent systems. It was also interesting to note that the retention of significant swelling in dimethyl sulphoxide–toluene mixture with even 90% toluene content for some compositions. These polyelectrolyte hydrogels with improved lipophilicity opens up greater opportunities for the development of even superior soft materials through proper structural optimizations that would successfully function for a wider range of solvents. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39873.     

Morphology of Poly(1‐olefin)s from Poly(1‐octene) to Poly(1‐eicosene)

Poly(1‐olefin)s from poly(1‐octene) to poly(1‐eicosene) synthesized by isospecific metallocene catalysts are investigated by wide and small angle X‐ray scattering (WAXS and SAXS) and by atomic force microscopy. The crystal structure of poly(1‐eicosene) is determined and the scattering peaks are assigned. Additionally, 1‐dodecene is polymerized using a constrained geometry catalyst and the obtained atactic polymer is compared with the isotactic species. Using this sample it is possible to determine the amorphous halo in the small angle regime at room temperature. For poly(1‐decene), poly(1‐dodecene), and poly(1‐hexadecene) a long period can be measured by small angle X‐ray scattering which coincides with the results from AFM measurements.     

Poly(ethylene‐co‐methacrylic acid)–lithium ionomer as a compatibilizer for poly(ethylene terephthalate)/linear low‐density polyethylene blends

Poly(ethylene terephthalate) (PET)/linear low‐density polyethylene (LLDPE) blends (75/25), with contents of poly(ethylene‐co‐methacrylic acid) partially neutralized with lithium (PEMA–Li) that were systematically changed from 0 to 45% relative to the LLDPE, were obtained by direct injection molding in an attempt to (1) ameliorate the performance of the binary blend and (2) find the best compatibilizer content. PEMA–Li did not modify the PET or LLDPE amorphous‐phase compositions or the crystalline content of PET. However, PEMA–Li did lead to a nucleation effect and to the presence of a second smaller and less perfect crystalline structure. PET induced a fractional crystallization in LLDPE that remained in the presence of PEMA–Li and reduced the crystallinity of LLDPE. The ternary blends showed two similar dispersed LLDPE and PEMA–Li phases with small subparticles, probably PET, inside. The compatibilizing effect of PEMA–Li was clearly shown by the impressive increase in the break strain, along with only small decreases in the modulus of elasticity and in the tensile strength. With respect to the recycling possibilities of LLDPE, a ternary blend with the addition of 22.5% PEMA–Li, which led to very slight modulus and yield stress decreases with respect to the binary blend and a break strain increase of 480%, appeared to be the most attractive. However, the highest property improvement appeared with the addition of 37.5% PEMA–Li, which led to elasticity modulus and tensile strength decreases of only 9%, along with a very high break strain increase (760%). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1322–1328, 2003     

A chemometric approach to understanding the bioelimination of anionic,water‐soluble dyes by a biomass ‐ Part 4: Reactive dyes**

The bioelimination of a series of hydrolysed reactive dyes of known chemical structure has been determined using a new, rapid and robust laboratory method and a chemometric analysis conducted on the bioelimination results. The level of bioelimination varies from 0% up to only 25% and the chemometric analysis indicates that if either the number of aromatic rings increases or the number of 2‐hydroxyethylsulphone groups decreases, then the bioelimination increases. To maximise the bioelimination of reactive dyes, large, planar triazine‐based dyes should be used.     

Poly[ethylene‐co‐(methacrylic acid)] Healing Agents for Mendable Carbon Fiber Laminates

The first reported use of two‐dimensional mesh thermoplastic fibers in an epoxy matrix for mendable composites is presented, yielding 100% restoration of G_IC, failure energy, and peak loads over repeated damage‐healing cycles. SEM imaging and EDS mapping showed different surface structures between CFRP_p and CFRP_f and confirmed strength recoveries were attained by delivery of EMAA to the fracture plane which enabled the fractured surfaces to rebind after heating to 150 °C for 30 min.

     

Hydrolyzed collagen‐grafted‐poly[(acrylic acid)‐co‐(methacrylic acid)] hydrogel for drug delivery

Hydrolyzed collagen‐grafted‐poly[(acrylic acid)‐co‐(methacrylic acid)] hydrogels were synthesized by solution polymerization and confirmed by infrared spectroscopy. From sequential univariate analysis, the optimal molar ratio of acrylic acid: methacrylic acid was 92:8 in the presence of N,N′‐methylenebisacrylamide, ammonium persulfate, and N,N,N′,N′‐tetramethylethylenediamine at 0.12, 0.015, and 0.2% mol of the monomers, respectively. The water absorbency of this hydrogel was both pH‐ and temperature‐dependent, but was higher in nonbuffered water than in boric acid/citric acid/phosphate buffer under the same conditions. The optimal hydrogel could swiftly swell and deswell in neutral and acid solutions, respectively. Its potential application in drug delivery was examined using insulin and methylene blue as model payload drugs. Loading in a 50% (v v^?1) ethanol solution gave a higher insulin loading level than in the buffer water. Insulin and methylene blue were both released at pH 6.8 but not at pH 1.2, but followed first order kinetics and the Higuchi equation, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45654.     

Isothermal kinetics of (E)‐4‐(4‐metoxyphenyl)‐4‐oxo‐2‐butenoic acid release from a poly(acrylic acid‐co‐methacrylic acid) hydrogel

A kinetic study of the release of the drug (E)‐4‐(4‐metoxyphenyl)‐4‐oxo‐2‐butenoic acid (MEPBA) from a poly(acrylic acid‐co‐methacrylic acid) (PAA‐co‐MA) hydrogel was performed. The isothermal kinetic curves of MEPBA release from the PAA‐co‐MA hydrogel in bidistilled water at different temperatures ranging from 20 to 40°C were determined. The reaction rate constants of the investigated process were determined with the initial rate, the saturation rate, and Peppas's semiempirical equation. Also, a model‐fitting method for the determination of the kinetics model of drug release was applied. The influence of α at the values of the kinetic parameters and the presence of a compensation effect was established. A procedure for the determination of the distribution function of the activation energies was developed. This procedure was based on the experimentally determined relationship between the activation energy and α. The mechanism of active compound release is discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of chemically modified chitosan with 2,5‐dimercapto‐1,3,4‐thiodiazole and its adsorption abilities for Au(III), Pd(II), and Pt(IV)

A new chemically modified chitosan hydrogel with 2,5‐dimercapto‐1,3,4‐thiodiazole (CTS‐DMTD) has been synthesized. The structure of CTS‐DMTD was confirmed by elemental analysis and FTIR. It was found that adsorption capacities were significantly affected by the pH of solution, with optimum pH values of 3.0 for Au(III), 2.0 for Pd(II) and Pt(IV). The saturated adsorption capacities were 198.5 mg/g for Au(III), 16.2 and 13.8 mg/g for Pd(II) and Pt(IV), respectively. Langmuir and Freundlich isotherm adsorption models were applied to analyze the experimental data. The results showed that adsorption isotherms of Pd(II) and Pt(IV) could be well described by the Langmuir equation. The adsorption kinetic investigations indicated that the kinetic data correlated well with the pseudo‐second‐order model. The recovery experimental data showed that CTS‐DMTD had a higher affinity toward Au(III), Pd(II), and Pt(IV) in the coexistence system containing Cu(II), Fe(III), Cd(II), Ni(II), Mg(II), and Zn(II). The studies of desorption were carried out using various reagents and the optimum effect was obtained using thiourea. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009