Kinetic study of chitosan‐tripolyphosphate complex reaction and acid‐resistive properties of the chitosan‐tripolyphosphate gel beads prepared by in‐liquid curing method

Chitosan gel beads were prepared using an in‐liquid curing method by the ionotropic crosslinking with sodium tripolyphosphate. Crosslinking characteristics of the chitosan‐TPP beads were improved by the modification of in‐liquid curing mechanism of the beads in TPP solution. Chitosan gel beads cured in pH value lower than 6 were really ionic‐crosslinking controlled, whereas chitosan gel beads cured in pH values higher than 7 were coacervation‐phase inversion controlled accompanied with slightly ionic‐crosslinking dependence. According to the result, significantly increasing the ionic‐crosslinking density of chitosan beads could be achieved by transferring the pH value of the curing agent, TPP, from basic to acidic. The swelling behavior of various chitosan beads in acid appeared to depend on the ionic‐crosslinking density of the chitosan‐TPP beads that were deeply affected by the curing mechanism of the beads. The mechanism of chitosan‐TPP beads swollen in weak acid was chain‐relaxation controlled, while the mechanism of chitosan‐TPP beads swollen in strong acid seem to be not only chain‐relaxation but also chain‐scission controlled. Chitosan‐TPP beads prepared in acidic TPP solution decreased the chain‐scission ability due to the increase of ionic crosslinking density of the beads. By the transition of curing mechanism, the swelling degree of chitosan‐TPP beads was depressed, and the disintegration of chitosan‐TPP beads would not occur in strong acid. The mechanism of ionic‐crosslinking reaction of chitosan beads could be investigated by an unreacted core model, and the curing mechanism of the chitosan beads is mainly diffusion controlled when higher than 5% of chitosan was employed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1551–1564, 1999     

氨基酸修饰壳聚糖对胆固醇的吸附作用

通过将不同脱乙酰度的壳聚糖粉末与戊二醛交联,再经苯丙氨酸和色氨酸修饰,得到了两种珠状壳聚糖吸附剂,并进而研究了有关吸附剂对胆因醇的吸附性能。实验表明,交联壳聚糖珠对ＣＨＯ的吸附能力比壳聚糖粉末降低,而经不同氨基酸修饰后的壳聚糖珠对ＣＨＯ吸附能力提高,用Ｐｈｅ修饰比用Ｔｒｙ修饰的珠吸附性能更好些。     

Adsorption of chromium from aqueous solution using chitosan beads

A basic investigation on the removal of Cr(III) and Cr(VI) ions from aqueous solution by chitosan beads was conducted in a batch adsorption system. The chitosan beads were prepared by casting an acidic chitosan solution into an alkaline solution. The influence of different experimental parameters; pH, agitation period and different concentration of Cr(III) and Cr(VI) ions was evaluated. A pH 5.0 was found to be an optimum pH for Cr(III) adsorption, and meanwhile pH 3.0 was the optimum pH for the adsorption of Cr(VI) onto chitosan beads. The Langmuir and Freundlich adsorption isotherm models were applied to describe the isotherms and isotherm constants for the adsorption of Cr(III) and Cr(VI) onto chitosan beads. Results indicated that Cr(III) and Cr(VI) uptake could be described by the Langmuir adsorption model. The maximum adsorption capacities of Cr(III) and Cr(VI) ions onto chitosan beads were 30.03 and 76.92 mg g⁻¹, respectively. Results showed that chitosan beads are favourable adsorbents. The Cr(III) and Cr(VI) ions can be removed from the chitosan beads by treatment with an aqueous EDTA solution.     

Optimization of Enzyme Co-Immobilization with Sodium Alginate and Glutaraldehyde-Activated Chitosan Beads

In this study, two different materials—alginate and glutaraldehyde-activated chitosan beads—were used for the co-immobilization of α-amylase, protease, and pectinase. Firstly, optimization of multienzyme immobilization with Na alginate beads was carried out. Optimum Na alginate and CaCl₂ concentration were found to be 2.5% and 0.1 M, respectively, and optimal enzyme loading ratio was determined as 2:1:0.02 for pectinase, protease, and α-amylase, respectively. Next, the immobilization of multiple enzymes on glutaraldehyde-activated chitosan beads was optimized (3% chitosan concentration, 0.25% glutaraldehyde with 3 h of activation and 3 h of coupling time). While co-immobilization was successfully performed with both materials, the specific activities of enzymes were found to be higher for the enzymes co-immobilized with glutaraldehyde-activated chitosan beads. In this process, glutaraldehyde was acting as a spacer arm. SEM and FTIR were used for the characterization of activated chitosan beads. Moreover, pectinase and α-amylase enzymes immobilized with chitosan beads were also found to have higher activity than their free forms. Three different enzymes were co-immobilized with these two materials for the first time in this study.     

Enhanced and selective adsorption of mercury ions on chitosan beads grafted with polyacrylamide via surface-initiated atom transfer radical polymerization

Enhanced and selective removal of mercury ions was achieved with chitosan beads grafted with polyacrylamide (chitosan-g-polyacrylamide) via surface-initiated atom transfer radical polymerization (ATRP). The chitosan-g-polyacrylamide beads were found to have significantly greater adsorption capacities and faster adsorption kinetics for mercury ions than the chitosan beads. At pH 4 and with initial mercury concentrations of 10-200 mg/L, the chitosan-g-polyacrylamide beads can achieve a maximum adsorption capacity of up to 322.6 mg/g (in comparison with 181.8 mg/g for the chitosan beads) and displayed a short adsorption equilibrium time of less than 60 min (compared to more than 15 h for the chitosan beads). Coadsorption experiments with both mercury and lead ions showed that the chitosan-g-polyacrylamide beads had excellent selectivity in the adsorption of mercury ions over lead ions at pH < 6, in contrast to the chitosan beads, which did not show clear selectivity for either of the two metal species. Mechanism study suggested that the enhanced mercury adsorption was due to the many amide groups grafted onto the surfaces of the beads, and the selectivity in mercury adsorption can be attributed to the ability of mercury ions to form covalent bonds with the amide. It was found that adsorbed mercury ions on the chitosan-g-polyacrylamide beads can be effectively desorbed in a perchloric acid solution, and the regenerated beads can be reused almost without any loss of adsorption capacity.     

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

1. INTRODUCTION Chitosan is the deacetylated chitin which is one of the most abundant natural polymers produced from crab, lobster and shrimp shells or fungal fermentation processes [1]. It is a family of deacetylated β1→4 D-glucosamine polymers. Chitosan has properties including bioactivity, biocompatibility and biodegradability, so it is potentially more useful than cellulose for developing advanced of attention not only as an unutilized biomass resource but also as a novel type of sp…     

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

The present investigation describes a novel method for preparing spherical chitosan particles based on crosslinking with epichlorohydrin.Certain amount of pre-crosslinking agent was added to form chitosan gels by traditional inverse phase suspension polymerization.Then the gels were crosslinked by epichlorohydrin at basic condition to obtain chitosan beads.The effects of reaction conditions,such as crosslinking time,the amount of crosslinking agent and the NaOH concentration,on the physical properties of the chitosan beads were investigated.The beads were found to have more amino groups in the polymer chains than the beads crosslinked by glutaraldehyde.The capacity for copper ions in as high as 40mg/g,The beads have good mechanical strength and can be reused.     

Microscopic examination of chitosan-polyphosphate beads with entrapped spores of the biocontrol agent, Streptomyces melanosporofaciens EF-76.

Spores of the biocontrol agent, Streptomyces melanosporofaciens EF-76, were entrapped by complex coacervation in beads composed of a macromolecular complex (MC) of chitosan and polyphosphate. A proportion of spores entrapped in beads survived the entrapment procedure as shown by treating spores from chitosan beads with a dye allowing the differentiation of live and dead cells. The spore-loaded chitosan beads could be digested by a chitosanase, suggesting that, once introduced in soil, the beads would be degraded to release the biocontrol agent. Spore-loaded beads were examined by optical and scanning electron microscopy because the release of the biological agent depends on the spore distribution in the chitosan beads. The microscopic examination revealed that the beads had a porous surface and contained a network of inner microfibrils. Spores were entrapped in both the chitosan microfibrils and the bead lacuna.     

Radiation synthesis of chitosan beads grafted with acrylic acid for metal ions sorption

Radiation-induced grafting of acrylic acid onto chitosan beads was performed in solution at a dose rate of 20.6 Gy/min of cobalt-60 gamma rays. The effect of absorbed dose on grafting yield was investigated. The characterization of the grafted material was performed by FTIR spectroscopy and the swelling measurements at different pHs. The grafting yield increased with the increase in dose, it reached 80% at 40 kGy irradiation dose.The removal of Pb and Cd ions from aqueous solutions was investigated with both ungrafted and grafted chitosan beads. The sorption behavior of the sorbents was examined through pH, kinetics and equilibrium measurements. Grafted chitosan beads presented higher sorption capacity for both metal ions than unmodified chitosan beads.     

PREPARATION OF CHITOSAN COATED METAL AFFINITY CHROMATOGRAPHY ADSORBENT

A new and an inexpensive adsorbent of chitosan coated silica for immobilized metal affinity chromatography(IMAC) was studied.After a double coating,the chitosan coated on silica beads could be up to 53.4mg/g silica beads.When pH&gt;3.8,the metal ligand Cu^2+ was chelated on the coated chitosan with a bound capacity of 14.6mg/g chitosan without introducing iminodiacetic acid(IDA).     

Comparative Adsorption of Lead(II) on Flake and Bead‐Types of Chitosan

The adsorption of Pb(II) ions from aqueous solutions by chitosan flakes and beads was studied. The chitosan beads were prepared by casting an acidic chitosan solution into alkaline solution. Experiments were carried out as a function of pH, agitation period and initial concentration of Pb²⁺ ions. The uptake of Pb²⁺ ions from aqueous solution was determined from changes in concentration as measured by atomic absorption spectroscopy. The maximum uptake of Pb²⁺ ions on chitosan beads was greater than that on chitosan flakes. Adsorption isothermal data could be interpreted by the Langmuir equation. The experimental data of the adsorption equilibrium from Pb²⁺ ion solutions correlated well with the Langmuir isotherm equation. SEM analyses were also conducted for visual examination of the chitosan flakes and beads. Physical properties including surface area and average pore diameter were characterized by N₂ adsorption experiment.     

Radiation grafting of ionically crosslinked alginate/chitosan beads with acrylic acid for lead sorption

Radiation-induced grafting of acrylic acid onto alginate/chitosan beads was performed in solution at a dose rate of 20.6 Gy/min of Co-60 gamma rays. The effect of absorbed dose on grafting yield was investigated. The characterization of the grafted and un-grafted beads was performed by FTIR spectroscopy and the swelling measurements at different pHs was studied. It is found that as the pH value increases the swelling degree increases up to pH 6 but with further increase in pH value the swelling decreases. Also, it is noticed that the grafting yield increased with increase the irradiation dose. Both un-grafted and grafted alginate/chitosan beads were examined as sorbents for the removal of Pb ions from aqueous solutions. The sorption behavior of the sorbents was examined through pH, and equilibrium measurements. Grafted alginate/chitosan beads presented higher sorption capacity for Pb ions than un-grafted beads.     

Adsorption of tannic acid, humic acid, and dyes from water using the composite of chitosan and activated clay

Chitosan is a well-known excellent adsorbent for a number of organics and metal ions, but its mechanical properties and specific gravity should be enhanced for practical operation. In this study, activated clay was added in chitosan slurry to prepare composite beads. The adsorption isotherms and kinetics of two organic acids (tannic acid, humic acid) and two dyes (methylene blue, reactive dye RR222) using composite beads, activated clay, and chitosan beads were compared. With composite beads as an adsorbent, all the isotherms were better fitted by the Freundlich equation. The adsorption capacities with composite beads were generally comparable to those with chitosan beads but much larger than those with activated clay. The pseudo-first-order and pseudo-second-order equations were then screened to describe the adsorption processes. It was shown that the adsorption of larger molecules such as tannic acid (MW, 1700 g mol(-1)), humic acid, and RR222 from water onto composite beads was better described by the pseudo-first-order kinetic model. The rate parameters of the intraparticle diffusion model for adsorption onto such adsorbents were also evaluated and compared to identify the adsorption mechanisms.     

Simple functionalization of cellulose beads with pre-propargylated chitosan for clickable scaffold substrates

Concerning the increased market for bio-based materials and environmentally safe practices, cellulose-based beads are one of the more attractive alternatives. Thus, this work focuses on the generation of functional cellulose-based beads with a relatively simple and direct method of blending a pre-modified chitosan bearing the targeted functional groups and cellulose, prior to the formation of the beads, as a mean to have functional groups in the formed structure. To this end, chitosan was chemically modified with propargyl bromide in homogenous reaction conditions and then combined with cellulose in sodium hydroxide/urea solution and coagulated in nitric acid to produce spherical shaped beads. The successful chemical modification of chitosan was assessed by elemental analysis, as well as by Fourier-transform infrared spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The alkynyl moieties from the chitosan derivative, served as reactive functional groups for click-chemistry as demonstrated by the tagging of the commercial fluorophore Azide-Fluor 488 via CuI-catalysed alkyne-azide cycloaddition reaction, in aqueous media. This work demonstrates the one-step processing of multiple polysaccharides for functional spherical beads as a template for bio-based scaffolds such as enzyme immobilization for stimuli-response applications and bioconjugations.

     

Immobilization of cellulose extracted from Robinia Pseudoacacia seed fibers onto chitosan: Chemical characterization and study of methylene blue removal

The design of economical adsorbents to remove pollutants from contaminated water is attracting more attention. In this study, cellulose was successfully extracted from Robinia Pseudoacacia seed fibers and immobilized onto chitosan beads. The prepared spherical beads were then used for the biosorption of methylene blue dye from aqueous media. Samples were investigated using several analytical methods, namely FT-IR, XRD, EDX, SEM, and TGA analyses. The adsorption experiments showed that combining cellulose with chitosan improved the removal of methylene blue. The maximum uptake amount of methylene blue using cellulose–chitosan composite beads was 55 mg/g. However, it was about 35 mg/g at 20 °C for chitosan beads. The kinetic data complied strongly with the pseudo-second order equation, suggesting that the biosorption phenomenon has predominantly a chemical nature. Overall, the current study has shown a promising technique to design new adsorbents from abundant natural polymers for eliminating cationic dyes from water.     

STRUCTURAL CHANGES AND RELEASE CHARACTERISTICS OF CROSSLINKED CHITOSAN BEADS IN RESPONSE TO SOLUTION pH

The present investigation describes a novel method for preparing beads based on crosslinked chitosan with glutaraldehyde interpenetrating glycine polymer network. Four type of beads, viz., CHI1 (composed of chitosan, glycine and glutaraldehyde); CHI2 (composed of chitosan and glutaraldehyde); CHI3 (composed of chitosan and glycine) and CHI4 (only chitosan) were prepared and their release characteristics were studied using thyamine hydrochloride (Thy-HCl) as a model drug. Structural changes during swelling of CHI1 beads in solutions of different pH were studied using IR and UV spectroscopy.     

Studies in the development of nateglinide loaded calcium alginate and chitosan coated calcium alginate beads

Nateglinide loaded alginate-chitosan beads were prepared by ionic gelation method for controlling the drug release by using various combinations of chitosan and Ca2+ as cation and alginate as anion. IR spectrometry, scanning electron microscopy, differential scanning calorimetry and X-ray powder diffractometry were used to investigate the physicochemical characteristics of the drug in the bead formulations. The calcium content in beads was determined by atomic absorption spectroscopy. The swelling ability of the beads in different media (pH 1.2, 4.5, 6.8) has been found to be dependent on the presence of polyelectrolyte complex of the beads and the pH of the media. The ability to release the Nateglinide was examined as a function of chitosan and calcium chloride content in the gelation medium. It is evident that the rate of drug release and its kinetics could be controlled by changing the chitosan and the calcium chloride concentrations. Calcium alginate beads released more than 95% of drug with in 8 h; whereas coated beads sustained the drug release and released only 75-80% of drug. The drug release mechanism analyzed indicates that the release follows either "anomalous transport" or "case-II transport".     

The separation of GMP from milk whey using the modified chitosan beads

The cationic property of chitosan was used to adsorb glycomacropeptide (GMP) molecules from milk whey proteins. β-cyclodextrin was immobilized to native chitosan beads by cross-linking with 1,6-hexamethylene diisocyanate (HMDI). The resultant modified beads (CS-HMDI-BCD) presented superior adsorption affinity and capacity towards GMP. At pH 3.0, 90.23% of GMP was adsorbed with a maximum adsorption capacity corresponding to 12.87 mg of sialic acid/g-adsorbent. Desorption experiments showed that the modified beads could be regenerated and used in many cycles without significant decreases in the capacity and selectivity.     

Preparation of electrospun chitosan/poly(vinyl alcohol) membranes

Electrospinning of chitosan from its solutions in 2% aqueous acetic acid was studied by adding poly(vinyl alcohol) (PVA) as a “guest” polymer. Properties of the chitosan/PVA solutions including viscosity, conductivity, and surface tension were measured, and effects of the polymer concentration, chitosan/PVA mass ratio and processing parameters (applied voltage, flow rate, capillary-to-collector distance) on the electrospinnability of chitosan/PVA were investigated. Analyses of scanning electron micrographs and transmission electron micrographs suggested that the chitosan/PVA ultrafine fibers were often obtained along with beads, and chitosan was located in the elctrospun fibers as well as in the beads. Uniform chitosan/PVA fibers with an average diameter of 99 ± 21 nm could be prepared from a 7% chitosan/PVA solution in 40:60 mass ratio. Results of Fourier transform infrared spectroscopy and X-ray diffraction demonstrated that there were possible hydrogen bonds between chitosan and PVA molecules, which could weaken the strong interaction in chitosan itself and facilitate chitosan/PVA electrospinnability. The electrospun chitosan/PVA membranes showed higher water uptake and would have potential applications in wound dressings.