Chitosan-tripolyphosphate Beads Research Articles

Biodegradation of Tetracycline Antibiotic by Laccase Biocatalyst Immobilized on Chitosan-Tripolyphosphate Beads

In this study, biodegradation of tetracycline, which is one of the most commonly used antibiotics, was investigated. In order to convert tetracycline into inactive oxidative metabolites, laccase immobilized onto rigid tripolyphosphate-treated chitosan beads was utilized. For immobilization, chitosan surfaces were activated with glutaraldehyde-linker reagents after tripolyphosphate treatment. The glutaraldehyde-linked rigid chitosan beads showed the higher immobilization capacity of laccase, providing thermostability, reusability, and the higher tetracycline transformation activity. Subsequently, synthetic mediators, including 2,2'‑azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and lignophenolic mediators like violuric, syringic and ferulic acids, 1-hydroxybenzotriazole, and vanillin, were investigated to activate laccase as electron mediators with KI assistance. Among them, the immobilized laccase showed highest tetracycline antibiotic inactivation activity when ABTS was used as a mediator. In the presence of KI, violuric and ferulic acids, 1-hydroxybenzotriazole and vanillin functioned as laccase mediators and inactivated tetracycline almost completely, however, the effect was not observed when they did individually. Finally, Vmax of the immobilized laccase was determined as 76.3 ± 4.3 µmoles mg–1 min–1 against tetracycline, which was 2-fold higher than that of the free enzyme. These results will provide novel insights into laccase-based removal of non-biodegradable organic matter.

Removal of erythrosine dye in aqueous solution using chitosan beads and chitosan-tripolyphosphate beads

Chitosan (CHS) and chitosan-tripolyphosphate beads (CTTP) were used for the removal of Erythrosine dye in batch adsorption experiments. The initial pH, agitation period, and adsorbent dosage were studied to determine the influence of these parameters on the adsorption capacity of the beads. Based on the initial pH study, the adsorption capacity for both adsorbents were found to be at pH 6. As the initial pH was increased, the adsorption capacity reduced for both beads. Based on the agitation period study, the kinetics of the adsorption process was determined. It was found that both CHS and CTPP followed the pseudo-second-order kinetic model with the highest adsorption capacity were attained at 50 and 60 minutes, respectively. An additional parameter on the adsorbent dosage was studied for CTTP beads to further improve on the removal capacity. The optimum adsorbent dosage for CHS and CTTP was achieved at 0.05 g and 0.6 g, respectively. An isotherm study was carried out on Erythrosine dye at the concentration of 20 mg/L – 100 mg/L for CHS and 20 mg/L – 150 mg/L for CTPP. It was found that the experimental data for CHS fitted the monolayer Langmuir model. Meanwhile, CTPP favored the multilayer Freundlich model. The CTPP was found to be effective in adsorbing a high concentration of dye, whereby the percentage of removal obtained was 92.6 % at the initial concentration of 150 mg/L of Erythrosine. Meanwhile, for CHS, the percentage of removal attained was 90.0% at the initial concentration of 60 mg/L of Erythrosine.

Development of a first order derivative spectrophotometry method to rapidly quantify protein in the presence of chitosan and its application in protein encapsulation systems

A new protein quantification method based on first order derivative spectrophotometry was established to eliminate various interferences, mainly chitosan, to the utmost using bovine serum albumin (BSA) as a model food protein. Absorbance spectra of BSA solutions were recorded and their first order derivative calculated. The values of derivative absorbance at 288 nm were used to generate linear calibration curve of BSA. The new method was applied in entrapping BSA into chitosan-tripolyphosphate beads. A general calibration curve was established with a CI (width of 95% confidence interval of three repeat measurements of unknown samples) less than 0.0262 g/L and a LOQ (limit of quantification) of 0.11 g/L, showing excellent tolerance to various interferences, which was further verified by the good mass balance of BSA during encapsulation. Overall, the method successfully eliminated the interferences from chitosan and other factors to facilitate the measurement of protein in complicated environments.

Chitosan–tripolyphosphate bead: the interactions that govern its formation

Chitosan–tripolyphosphate beads are a highly stable and biocompatible polymer-network with versatile applications. In this study, we relate the main synthesis parameters of these particles using a design of experiments and a multivariate calibration to understand how some structural characteristics (mass, diameter and water retention capacity) of these spherical hydrogels are achieved from the point of view of the ionotropic association between chitosan chains and tripolyphosphate molecules. The results conduct to a better conceptualization of the crosslinking process, establish the ranges where particles with different structural characteristic can be obtained and a better understanding of how the physicochemical behavior of the chitosan and the tripolyphosphate affect the structural parameters of the chitosan–tripolyphosphate beads. As a novelty, we propose a refined 3D junction zone for the interaction between the raw molecules that allows to conclude that one TPP molecule can associate with up to three amino groups as a maximum.

Protection of astaxanthin from photodegradation by its inclusion in hierarchically assembled nano and microstructures with potential as food

Astaxanthin is a light sensitive molecule which is already approved as a dietary supplement, with a wide range of biological properties in humans and fishes. In this paper, we provide strategies to photostabilize the pigment through its inclusion in easy-to-prepare and scale up formulations, comprising non-toxic excipients. Astaxanthin has been formulated in biocompatible hierarchically assembled structures in order to produce model food to humans and fishes. The structures present increasing complexity in the following order: 1) oily nanodroplets stabilized by phospholipids; 2) chitosan-coated nanoemulsions produced after coating the nanodroplets with chitosan; 3) carrageenan-coated nanoemulsions produced after coating chitosan-coated nanoemulsions with carrageenan; 4) calcium alginate and chitosan tripolyphosphate beads including one of the nanosystems. The sensitivity to UV light of astaxanthin in both the nanosystems and the hydrogels has been evaluated. The nanoformulations produce protection of astaxanthin from photodegradation in the order nanoemulsions > carrageenan-coated nanoemulsions > chitosan-coated nanoemulsions. Chitosan beads furnish higher protection to astaxanthin than alginate beads. In a preliminary assay in fishes, alginate beads of 2–3 mm and 160 μm containing the nutrient were supplied to adult Danio rerio and juvenile Eleginops maclovinus, respectively. Both living species showed high rates of capturing the hydrogels in the water column, corroborating the attractiveness of the formulations as food for fishes. Due to the easy preparation of the formulations (that exclude thermal treatment or the use of toxic solvents), and the flexibility of these hierarchically assembled materials to incorporate other active molecules (proteins, polyunsaturated fatty acids, oligoelements, oral vaccines, antibiotics, antiparasitic, etc.), we postulate these formulations as ideal platforms to create foods for humans and animal species.

RADITYA ISWANDANA, KURNIA SARI SETIO PUTRI, RANDIKA DWIPUTRA, TRYAS YANUARI, SANTI PURNA SARI, JOSHITA DJAJADISASTRA

Objective: Drug delivery to the colon via oral route can be directly treated a variety of diseases in the colon, such as fibrosis. Tetrandrine is a drug that has anti-fibrosis effects. In this study, chitosan-tripolyphosphate (TPP) beads containing tetrandrine was made and evaluated for in vitro release profile and in vivo targeted test.Methods: Chitosan-TPP tetrandrine beads were prepared by ionic gelation method with variation in sodium tripolyphosphate concentration: 3% (Formula 1), 4% (Formula 2), and 5% (Formula 3). All formulae were characterized for its morphology, particle size, moisture content, process efficiency, entrapment efficiency, thermal character, crystallinity, and swelling. Then, the best formula was coated with HPMCP HP-55, CAP, Eudragit L100-55, or Eudragit L100 prior to drug release profile in vitro and in vivo test.Results: Beads from all formulae had an average size: 920.50±0.04 µm, 942.21±0.08 µm, and 1085.95±0.03 µm; Water content: 7.28±0.003%, 5.64±0.005%, and 6.84±0.004%; Process efficiency: 29.70%, 28.96%, and 29.70%; Entrapment efficiency: 16.20±0.63%, 17.02±0.37%, and 20.42±0.70% for Formula 1, 2, and 3, respectively. In addition, the results of in vitro cumulative drug release were 67.36%, 76.04%, 83.12%, 83.21%, 40.16%, 37.98%, 45.86%, 41.71% for Formula 3A-3H, respectively.Conclusion: It can be concluded that Formula 3D (CAP 15%) was chosen as a formulation with the best in vitro profile. Moreover, the in vivo targeted test showed that Formula 3D was able to deliver the beads to the intestine compared to the control beads.

Metal ion sorption by chitosan–tripolyphosphate beads

ABSTRACTHeavy metal removal from wastewater is crucial for the proper management of discharged water from mining operations. This residual water is typically unusable for other purposes such as for human/animal, crop, or industrial consumption. Eco‐friendly adsorption materials are necessary to ensure the sustainable treatment of this wastewater. Therefore, the sorption of Cu(II), Cd(II), Pb(II), and Zn(II) ions onto chitosan–tripolyphosphate (CTPP) beads was investigated using real mining wastewater and prepared ion metal solutions. The effects of pH, contact time, temperature, selectivity, and maximum sorption capacity in successive batches at different concentrations were studied. The optimum sorption of cations, except for copper (pH 3) was found at pH 5. Equilibrium in the adsorption of all metals was reached at 24 h of contact. Studies of the maximum sorption capacity at different concentrations showed that the CTPP beads could adsorb 158, 55, 47, and 47 mg/g of Pb(II), Cu(II), Cd(II), and Zn(II), respectively. Experimental data for the sorption of Pb(II) were optimally correlated with the Langmuir model. The thermodynamic parameters such as the changes in enthalpy (ΔH0), entropy (ΔS0), and free energy (ΔG0) were determined. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45511.

Entrapment of protein in chitosan-tripolyphosphate beads and its release in an in vitro digestive model.

This research sought to evaluate the entrapment and in vitro release behaviour of bovine serum albumin (BSA) in chitosan-tripolyphosphate (TPP) hydrogel beads. Beads were manufactured by extruding gel forming solutions containing varying concentrations of chitosan (1-2.5%w/w) and BSA (0.25-10%w/w) into TPP solutions ranging in concentration from 0.1 to 10%w/w and in ionic strength from 0.16 to 0.67M at pH values of 4, 5 and 9.4. Beads produced at a low TPP concentration of 0.4% w/w had the highest BSA entrapment efficiency (71.6±0.7%) and inhibited BSA release in simulated gastric fluid (SGF) to a greater extent. Increasing chitosan concentration resulted in a higher protein entrapment efficiency, but lowered the overall release. Increasing TPP concentration or the BSA concentration loaded, led to early release in SGF. The results indicate that the utilization of lower concentrations of TPP is a good approach to improve the protein retention ability of chitosan-TPP beads in a simulated gastric environment.

In vitro evaluation of encapsulated primary rat hepatocytes pre- and post-cryopreservation at −80°C and in liquid nitrogen

Encapsulation techniques have the potential to protect hepatocytes from cryoinjury. In this study, we comparatively evaluated the viability and metabolic function of primary rat hepatocytes encapsulated in calcium alginate microbeads, in chitosan tripolyphosphate beads, and in three-layered alginate–chitosan–alginate (ACA) microcapsules, before and after cryopreservation at −80°C and in liquid nitrogen (LN2) for 1 and 3 months. Findings demonstrated that LN2 was atop of −80°C in regard to preservation of viability (> 90%) and hepatic functions. LN2-cryopreserved hepatocytes encapsulated in ACA microcapsules retained metabolic function post-thawing, with > 90% of the albumin, total protein and urea syntheses activities, and > 80% of oxidative function.

Adsorption of Pb(II) Ions Using Humic Acid Coated Chitosan-Tripolyphosphate (HA-CTPP) Beads

A new humic acid (HA) based adsorbent was prepared by coating humic acid on chitosan tripolyphosphate (CTPP) beads. Humic acid-chitosan tripolyphosphate (HA-CTPP) beads thus obtained were characterized using Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. Swelling capacity studies of CTPP and HA-CTPP beads conducted in the pH range, pH = 1–10 showed that HA-CTPP beads are more stable against swelling than CTPP beads. Equilibration of HA-CTPP beads in water for different pH showed that leaching of HA from the beads is negligible and the beads are stable for adsorption applications. Adsorption of Pb(II) ions onto HA-CTPP beads were studied as a function of various operational parameters such as initial pH, metal ion concentration, and contact time. The results showed that HA-CTPP beads are suitable for Pb(II) ions adsorption and the kinetics of sorption very well fit into pseudo-second order model. The Langmuir model was found to be more suitable for explaining the observed adsorption data, giving a theoretical maximum adsorption capacity of 223.7 mg/g. HA-CTPP beads could possibly find application in the treatment of waste water contaminated with other toxic and/or heavy metals.

Fe(II) and Fe(III) adsorption by chitosan-tripolyphosphate beads: kinetic and equilibrium studies

The purpose of this research was to analyze the adsorption behavior of Fe(II) and Fe(III) ions in aqueous solution onto beads of naturally derived chitosan cross-linked with tripolyphosphate in a batch system. Effects of solution pH, contact time and amount of adsorbent were regarded in the kinetic and equilibrium studies. The optimum conditions of adsorption for Fe(II) and Fe(III) were obtained as pH 5 and 3, amount of adsorbent 2 and 1.9 g and contact time 70 and 60 min, respectively. The kinetic and equilibrium experimental data were integrated into different models using the non-linear regression method. As a result, the pseudo-second-order and the Redlich–Peterson isotherm were the best evaluated models. The adsorption capacity, based on Langmuir, was 11.65 mg g −1 for Fe(II) and 13.72 mg g −1 for Fe(III). The beads of chitosan cross-linked with tripolyphosphate may be used as an effective bioadsorbent for the removal of Fe(II) and Fe(III) from an aqueous solution. This study confirms that the chitosan isolated from shrimp waste can be used to remove certain heavy metals in wastewater, without adversely affecting the ecosystem.

Preparation and characterization of porous chitosan–tripolyphosphate beads for copper(II) ion adsorption

AbstractPorous chitosan–tripolyphosphate beads, prepared by the ionotropic crosslinking and freeze‐drying, were used for the adsorption of Cu(II) ion from aqueous solution. Batch studies, investigating bead adsorption capacity and adsorption isotherm for the Cu(II) ion, indicated that the Cu(II) ion adsorption equilibrium correlated well with Langmuir isotherm model. The maximum capacity for the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, deduced from the use of the Langmuir isotherm equation, was 208.3 mg/g. The kinetics data were analyzed by pseudo‐first, pseudo‐second order kinetic, and intraparticle diffusion models. The experimental data fitted the pseudo‐second order kinetic model well, indicating that chemical sorption is the rate‐limiting step. The negative Gibbs free energy of adsorption indicated a spontaneous adsorption, while the positive enthalpy change indicated an endothermic adsorption process. This study explored the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, and used SEM/EDS, TGA, and XRD to examine the properties of adsorbent. The use of porous chitosan–tripolyphosphate beads to adsorb Cu(II) ion produced better and faster results than were obtained for nonporous chitosan–tripolyphosphate beads. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Adsorptive removal of Cr(III) from aqueous solution using tripolyphosphate cross-linked chitosan beads

Chitosan tripolyphosphate (CTPP) beads were prepared at two different cross-linking densities and adsorption of Cr(III) onto it were studied as a function of different operational parameters such as solution pH, equilibration time and initial Cr(III) ion concentration. Higher cross-linked beads were found to have more adsorption capacity at all the experimental pH employed (pH = 3–5), whereas adsorption capacity is found to increase with increase in pH. Adsorption data were analyzed using Langmuir and Freundlich isotherm models. Langmuir model is found be more suitable to explain the experimental results with a monolayer adsorption capacity of 469.5 mg/g. Among the kinetic models used, pseudo-second order kinetic model could best describe the adsorption process. Competition experiments done in presence of Na(I), Mg(II), Ca(II), Al(III) and Fe(III) revealed that, except in the case of Al(III), adsorption of Cr(III) is not significantly affected by the presence of foreign cations. NaCl is found to be a suitable leaching agent for the desorption of adsorbed Cr(III) from CTPP beads. FTIR spectroscopic investigations confirmed that phosphate groups are the principal binding site responsible for the sorption of Cr(III) onto CTPP beads.

Adsorption of uranium from aqueous solution using chitosan-tripolyphosphate (CTPP) beads

Chitosan-tripolyphosphate (CTPP) beads were prepared using in-liquid curing method and used for the adsorption of uranium from aqueous solution. Beads were prepared at two different cross-linking densities by adjusting the pH of the tripolyphosphate solution. The synthesized beads were characterized using FTIR spectroscopy before and after adsorption of uranium. Beads having higher cross-linking are found to have better adsorption capacity for uranium. Factors that influence the uranium adsorption onto CTPP beads such as solution pH, contact time and initial uranium concentration were studied in detail. The experimental results were fitted into Langmuir and Freundlich adsorption isotherms. From Langmuir adsorption model the adsorption capacity of CTPP beads for uranium is estimated as 236.9mg/g. Pseudo-first order, pseudo-second order and intraparticle diffusion model were applied to the observed kinetics data and the results shows that the pseudo-second order model is more suitable to explain the kinetics of adsorption of uranium on CTPP beads. FTIR spectroscopic characterization of the beads showed that the phosphate groups may be more responsible for the adsorption of uranium on CTPP beads.

Adsorption characterization of Pb(II) and Cu(II) ions onto chitosan-tripolyphosphate beads: Kinetic, equilibrium and thermodynamic studies

Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (Δ H°), Gibbs free energy (Δ G°) and entropy (Δ S°) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.

Synthesis of zero-valent copper-chitosan nanocomposites and their application for treatment of hexavalent chromium

This study used ionotropic crosslinking to synthesize chitosan-tripolyphosphate chelating resin beads, which are used to fabricate zero-valent copper-chitosan nanocomposites. The copper nanoparticles were dispersed on chitosan-tripolyphosphate beads, and were thus able to maintain appropriate dispersion and stability, which greatly improves their applicability. The fabrication process contains two steps: using chitosan-tripolyphosphate beads to adsorb Cu(II) ions, followed by chemical reduction to reduce Cu(II) ions to zero-valent copper. This study explored the adsorption of synthesized chitosan-tripolyphosphate beads to Cu(II) ions, and used SEM/EDS, XPS, and TEM to examine the properties of zero-valent copper-chitosan nanocomposites. The results showed that, the adsorption behavior of hexavalent chromium from aqueous solution onto fabricated nanocomposites has better adsorption capacity than that of the chitosan-tripolyphosphate beads.

Investigation on the development of sturdy bioactive hydrogel beads

AbstractBiocatalytic hydrogel beads, which retain higher activity, expand, and contract with changes in pH, having biocompatibility, are developed. Composite spherical beads of chitosan having a diameter of 1–2 mm were prepared by ionic gelation using sodium tripolyphosphate (TPP). Above 3% TPP, the activity of the enzyme decreases. The mechanical strength of the chitosan–TPP beads was further improved by the addition of clay or cassava starch granules. The immobilization of protease (fungal, Aspergillus) was done with glutaraldehyde crosslinking. The chitosan–starch hydrogel beads showed significant increase in firmness and stiffness when compared with chitosan–clay beads. The swelling studies show that the particles expand at pH 1.2 and contract at pH 7.4. The activity retention of the immobilized protease was as high as 70% and exhibited a high pH and lower temperature optima than the free enzyme. Chitosan–starch hydrogel beads exhibited degradation peaks at about 90–110°C in TGA analysis. The biocatalyst beads retained 85% of the original catalytic activity even after eight cycles of repeat use. The freeze‐dried beads has good storage stability and can be used either as artificial bioreactor systems in detergent or in therapeutic formulations © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008