Controlled release study of carbaryl insecticide from calcium alginate and nickel alginate hydrogel beads

In this study, controlled release formulations for reducing environmental impact of pesticides have been produced by encapsulating as a model pesticide carbaryl (Carb) in the alginate beads. The various hydrogel bead formulations were prepared by the ionotropic crosslinking of sodium alginate (NaAlg) with calcium and nickel ions. The surface morphology of prepared beads was characterized with scanning electron microscopy (SEM). SEM confirmed the spherical nature and surface morphology of the particles. Bead characteristics, such as carbaryl entrapment efficiency, particle size, equilibrium swelling degree, and carbaryl release kinetics, were determined. The effects of the bead preparation conditions such as crosslinker concentration and type, carbaryl/sodium alginate (Carb/NaAlg) ratio and percentage of NaAlg on the carbaryl release from the calcium alginate (Ca‐Alg) and nickel alginate (Ni‐Alg) beads were investigated in distilled water at 25°C. It was observed that carbaryl release from the Ca‐Alg beads was slower than that of Ni‐Alg beads. The release results indicated that carbaryl release from both of the Ca‐Alg and Ni‐Alg beads decreases with the increasing crosslinker concentration, Carb/NaAlg ratio and percentage of NaAlg. The highest carbaryl release was found to be 100% for the Ni‐Alg beads at 3 days whereas the lowest carbaryl release was found to be 67% for the Ca‐Alg beads at 21 days. The swelling measurements of the beads were also in consistent with the carbaryl release results. The carbaryl release from most of the bead formulations followed Case II transport. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Continuous Production of Uniform Calcium Alginate Beads by Sound Wave Induced Vibration

A new process for the immobilization of sodium alginate, which employs a vibration of membrane induced by sound waves from a horn-type speaker, is developed to produce uniformly-sized beads of predictable diameter. Frequency of sound wave and production rate are varied to find the optimal control ranges for the bead production. The controllable bead size range is 1·50–3·50 mm and the experimental production rates are 0–12 dm³ h^-1 by a single nozzle. This method of bead production is a practical alternative to conventional continuous bead production methods with low apparatus cost and easier and better control of bead size and shape.     

Preparation of interpenetrating polymer network gel beads for dye absorption

Preparation of interpenetrating polymer network (IPN) gel beads for dye absorption was carried out by using simultaneous crosslinking method. First, sodium alginate (SA), 3‐(methacrylamido) propyl trimethyl ammonium chloride (MAPTAC), and/or acrylamide (AM), K₂S₂O₈, and N,N′‐methylenebisacrylamide (MBAM) were mixed in aqueous solution. The beads were prepared using K₂S₂O₈ and MBAM as the initiator and crosslinking agent, respectively. Then, the solution was dropped into CaCl₂ solution mixed with N,N,N′,N′‐tetramethylethylenediamine (TMEDA). The former was used as the crosslinking agent of alginate and the latter was used as the accelerator for the polymerization of monomer in the alginate solution. The gel bead composed of only alginate was also prepared to compare the properties with IPN gel bead. The components in IPN gel bead were examined by FTIR analysis. The factors effecting the particle size of alginate and IPN gel beads were investigated. In alginate gel bead, the concentration of solution affected the particle size, whereas type of monomer affected the particle size of IPN gel bead. The IPN gel bead had smooth surface (from SEM results), different from the alginate bead. Alginate content caused the swelling behavior of dried IPN beads. Cationic dye was absorbed by crosslinked alginate gel bead. The absorption of reactive dye by IPN gel bead was a result of its cationic charge. The absorption density of IPN gel beads was the reciprocal of the absorbent dosage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1585–1591, 2006     

Controlled release formulations of carbaryl based on copper alginate,barium alginate,and alginic acid beads

A controlled release system for reducing environmental impact was produced by encapsulating the pesticide carbaryl (Carb) in the alginate beads. The various bead formulations were prepared by using sodium alginate (NaAlg) as a polymer, CuCl₂, BaCl₂ as a crosslinking agent, and HCl as a linking agent. The surface morphology of prepared beads was characterized with scanning electron microscopy (SEM). SEM confirmed the spherical nature and surface morphology of the particles. Bead characteristics, such as Carb entrapment efficiency, particle size, swelling degree, and Carb release kinetics, were determined. The effects of crosslinker or linker concentration, type, and carbaryl/sodium alginate (Carb/NaAlg) ratio on Carb release from the beads were investigated for 20 days at 25°C. It was observed that Carb release from the beads increased with the increase of Carb/NaAlg ratio whereas decreased with the increase of crosslinker concentration. At the end of 20 days, the Carb release from alginic acid beads was found to be higher than that of copper alginate (Cu‐Alg) and barium alginate (Ba‐Alg) beads. The swelling measurements of the beads supported the release results. Release kinetics were described by Fickian and non‐Fickian approaches. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4245–4253, 2006     

Metal recovery using immobilized cell suspension from a brewery

Lead, copper, and cadmium were adsorbed onto calcium alginate beads containing the cell suspension discarded from a brewery. In the cell suspension, there were many cells under lysis. The cell-suspension immobilized beads were prepared by adding 0.6% (w/v) sodium alginate into the cell suspension from the brewery and then making the cell suspension fall dropwise into the swirling 1% (w/v) calcium alginate solution. The dry weight of insoluble solid in the cell suspension was 96 g dry weight/l and the dry density of the bead containing cell suspension was 140 g dry weight/l of the bead. The specific metal uptake of the cell-suspension immobilized bead was 23.7 mg Pb²⁺, 14.3 mg Cu²⁺, and 13.4 mg Cd²⁺/g bead dry weight, respectively. The cell-suspension immobilized beads retained the initial metal-uptake capacity after 20 repeated batches of adsorption and desorption, but the fraction of metal desorbed from the beads by 1 M HCl solution was only 70% of the adsorbed metal. The beads, which had been contained for 14 successive days in the 0.5% (w/v) CaCl₂ solution at 4 °C just after 20 cycles of adsorption/desorption, retained the initial metal-uptake capacity after 30 repeated cycles, and more than 90% of the copper and cadmium adsorbed on the beads was desorbed by the 1 M HCl solution.     

A Forming Technique to Produce Spherical Ceramic Beads Using Sodium Alginate as a Precursor Binder Phase

The purpose of this study was to improve the forming techniques and parameters for producing spherical ceramic beads using sodium alginate as a sacrificial template. This process has the potential of producing beads for applications such as stress‐wave propagation of granular media, beads for milling, catalyst support, and encapsulation of drugs, as well as water filtration. This simple, inexpensive, and environmentally friendly approach to producing spherical ceramic beads using bead‐forming equipment occurs when a flat‐tipped needle produces droplets that cross‐link, forming green bodies upon contact with CaCl₂ solution. An exchange of ions takes place where sodium alginates substitute their Na⁺ for Ca²⁺ to form semirigid bodies. Spherical ceramic beads using 50 wt% alumina suspension with 0.04 wt% polyacrylate dispersant are produced when: the viscosity of the slurry is below 0.3 Pa·s, the surface tension of the gelling solution is below 50 mN·m, and the distance of the nozzle tip to the reacting solution is ~3 cm. This approach for producing ceramic beads using alginates will allow its use for any type of ceramic material, changing its chemical composition, and controlling the microstructure and shape of the beads.     

Electrospray preparation of propranolol‐loaded alginate beads: Effect of matrix reinforcement on loading and release profile

In the present study, propranolol loaded‐calcium alginate beads were prepared from concentrated solutions of sodium alginate, using combined method of electrospray and ionotropic gelation. The objectives of the study were to increase the propranolol‐HCl loading and to decrease its initial burst release. However, the effects of voltage, nozzle diameter, flow rate, and concentration of sodium alginate on size of the beads and drug entrapment efficiency (DEE) were also investigated. The matrix of alginate beads was reinforced with dextran sulfate and/or coated with chitosan. The mean particle size of the beads, their swelling behavior, and drug entrapment efficiency were characterized. Furthermore, the drug release profiles from the prepared beads in simulated gastric fluid and intestinal fluid were evaluated and compared. Among the parameters that affected the electrospray of alginate, voltage had a pronounced effect on the size of beads. The size of beads was reduced to a minimum value on increasing the voltage. Furthermore, increasing the flow rate, alginate concentration, and nozzle diameter and decreasing the voltage led to improvement in DEE. Enhancing the alginate concentration as well as coating with chitosan and reinforcing with dextran sulfate led to increase of the encapsulation efficiency and therefore decrease of the drug release rate in both pHs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41334.     

Controlled release of diclofenac sodium and ibuprofen through beads of sodium alginate and hydroxy ethyl cellulose blends

Controlled release of diclofenac sodium (DS) and ibuprofen (IB) drugs through sodium alginate (NaAlg)‐hydroxy ethyl cellulose (HEC) blend polymeric beads has been investigated. Beads were prepared by precipitating the viscous solution of NaAlg and HEC blend in alcohol followed by crosslinking with calcium chloride. Different formulations were developed in bead form by varying the amount of HEC, crosslinking agent, and drug concentration. Swelling studies in water, percent encapsulation of drugs, and release studies were carried out. The DS‐loaded beads have shown better release performance than the IB‐loaded beads. Diffusion parameters were evaluated from the Fickian diffusion theory. Mathematical modeling studies and drug release characteristics through bead matrices were studied by solving Fick's diffusion equation. The results are discussed in terms of drug release patterns and theoretical concentration profiles generated through matrices, considering spherical geometry of the beads. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5708–5718, 2006     

Preparation of uniform calcium alginate gel beads by membrane emulsification coupled with internal gelation

With the objective of making calcium alginate gel beads with small and uniform size, membrane emulsification coupled with internal gelation was proposed. Spherical gel beads with mean size of about 50 μm, and even smaller ones in water, and with narrow size distribution were successfully obtained. Experimental studies focusing mainly on the effect of process parameters on bead properties were performed. The size of the beads was mainly dependent on the diameter of the membrane pores. High transmembrane pressure made for large gel beads with wide size distribution. Low sodium alginate concentration produced nonspherical beads, whereas a high concentration was unsuitable for the production of small beads with narrow distribution. Thus 1.5% w/v was enough. A high surfactant concentration favored the formation of small beads, but the adverse effect on mass transfer should be considered in this novel process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 848–852, 2003     

Release behavior of freeze‐dried alginate beads containing poly(N‐isopropylacrylamide) copolymers

Beads composed of alginate, poly(N‐isopropylacrylamide) (PNIPAM), the copolymers of N‐isopropylacrylamide and methacrylic acid (P(NIPAM‐co‐MAA)), and the copolymers of N‐isopropylacrylamide, methacrylic acid, and octadecyl acrylate (P(NIPAM‐co‐MAA‐co‐ODA)), were prepared by dropping the polymer solutions into CaCl₂ solution. The beads were freeze‐dried and the release of blue dextran entrapped in the beads was observed in distilled water with time and pH. The degree of release was in the order of alginate bead < alginate/PNIPAM bead ≈ alginate/P(NIPAM‐co‐MAA) bead < alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead. On the other hand, swelling ratios reached steady state within 20 min, and the values were 200–800 depending on the bead composition. The degree of swelling showed the same order as that of release. Among the beads, only alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead exhibited pH‐dependent release. At acidic condition, inter‐ and intraelectrostatic repulsion is weak and P(NIPAM‐co‐MAA‐co‐ODA) could readily be assembled into an aggregate due to the prevailing hydrophobic interaction of ODA. Thus, it could block the pore of bead matrix, leading to a suppressed release. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Encapsulation of Rhodopseudomonas palustris KTSSR54 using beads from alginate/starch blends

Alginate beads are a promising carrier for biofertilizer delivery, but still possess drawbacks of low mechanical strength and bead shrinkage that result in poor appearance and inadequate cell protection. Blending alginate with starch was proposed as a solution to these problems, and here alginate hydrogels were prepared using a 2% (w/v) alginate dispersion blended with varying contents of gelatinized starch (0–5% w/v). The interaction produced a viscosity synergism that increased the complexity of the matrix network in the alginate/starch blends, producing a more suitable matrix for cell entrapment. Hydrogen bonding between alginate and starch influenced the viscosity of the various solutions in a way that was consistent with the FTIR spectra. The starch content also helped beads retain their spherical shape after drying. The starch supported the entrapment of bacterial cells (plant growth-promoting bacterium Rhodopseudomonas palustris KTSSR54 as biofertilizer) in the matrix, which reduced cell loss. The highest entrapment efficiency of 70.83% was obtained at 4% (w/v) starch, while the entrapment efficiency of control beads was 50.56%. Overall, the appropriate content of starch mixed with alginate is conducive to changes in the morphology of microcapsules and increases in the amount of biological encapsulation.     

Metal recovery by aged beads prepared using cell-suspension from the waste of beer fermentation broth

Lead, copper, and cadmium were adsorbed onto aged calcium alginate beads containing cell-suspension from the waste of beer fermentation broth. Beads prepared by adding 0.6% (w/v) sodium alginate into the cell suspension from the waste of beer fermentation broth and making the cell suspension drop into the 1% (w/v) calcium alginate solution were stored in the 1% (w/v) calcium chloride solution for 1 year. The specific metal uptake of the aged cell-suspension immobilized bead was 312 mg Pb²⁺, 158 mg Cu²⁺, and 112 mg Cd²⁺/g bead dry weight at pH 7.5 of the metal solution, respectively. The relation between the specific metal uptake by the aged cell-suspension immobilized beads and the equilibrium metal concentration was nonlinearly regressed and well described by the Freundlich isotherm. The specific cadmium uptake capacity of aged cell-suspension immobilized beads was between the specific cadmium uptake capacities of commercial beads Duolite GT-73 and Amberite IRA-400 and higher than those of the fresh Saccharomyces cerevisiae ATCC 834 and Saccharomyces cerevisiae ATCC 24858 immobilized beads.     

Evaluation of alginate–chitosan bioadhesive beads as a drug delivery system for the controlled release of theophylline

This study describes the preparation of mucoadhesive alginate–chitosan beads containing theophylline intended for colon‐specific delivery. The calcium alginate beads were coated with chitosan by the ionotropic hydrogelation method with a polyelectrolyte complex reaction between two oppositely charged polyions. The release profiles of theophylline from the beads were determined by ultraviolet–visible absorption measurement at 272 nm. Scanning electron microscopy was used for morphology observation. The in vitro mucoadhesive tests for particles were carried out with the freshly excised jejunum of Sprague‐Dawley rats. The bead particles, which ranged in size from 200 to 400 μm, exhibited excellent mucoadhesive properties. The results showed that the formulated coated beads succeeded in controlling the release of theophylline over a 24‐h period. In conclusion, the release of theophylline was found to be dependent on the composition of the beads, the component polymer and its possible interactions, and the bioadhesiveness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Purification of anthocyanins from red cabbage using semi interpenetrating network hydrogel beads in a packed bed column

Anthocyanins are polyphenols, water-soluble pigments that have increased acceptability to food and pharmaceutical products. In this investigation, semi interpenetrating network hydrogel beads were developed to purify anthocyanins present in red cabbage. Effect of bead size and refluxing on anthocyanin purification and carbohydrates elimination were studied. Hydrogel bead with 1% gelatin, 5% sodium alginate, and 1% calcium chloride resulted in maximum two-fold increase in anthocyanin purity with 35 mg/g carbohydrate elimination. Further, hydrogel bead size and refluxing exhibited inversely proportional anthocyanin purity and carbohydrate elimination. Thereby, confirmed that anthocyanin purity is highly dependent on sugars. The results suggested that the developed hydrogel beads could be suitable for purifying bioactive compounds.     

Polymethyl methacrylate/montmorillonite nanocomposite beads through a suspension polymerization‐derived process

Polymethyl methacrylate (PMMA) polymer beads with montmorillonite (MMT) were prepared using a suspension polymerization method for applying acrylic bone cements. The polymer beads were characterized by X‐ray diffraction and transmission electron microscopy to examine MMT dispersion. The change in the shape and size of the polymer beads due to the preparation conditions, such as stirring speed, degree of polymerization, and concentration of polyvinyl alcohol (PVA) as a suspension stabilizer, and MMT contents, etc. was observed by scanning electron microscopy and particle size analysis. The prepared polymer beads were composed of polymer‐intercalated nanocomposites with partially exfoliated MMT layers. The size of the polymer beads was decreased by increasing the stirring speed. The bead size was decreased with increasing the degree of polymerization and the concentration of PVA molecules. MMT addition into the monomer portion increased the size of the corresponding polymer beads. The bead size was slightly reduced by adding of styrene to the MMA solution. The incorporation of PMMA into monomer portion enlarged the bead size. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2340–2349, 2005     

Characterization of the structure and diffusion behavior of calcium alginate gel beads

A simple and novel method using gel shrinkage to indirectly characterize the structure of calcium alginate gel (CAG) beads during the calcium alginate gelation process was presented in this study. The effect of preparation process parameters (gelling cations, bead diameter, and alginate M _w and concentration) on the structure of the CAG bead formation process was thoroughly investigated. It was found that (a) the concentration of the Na⁺ and Ca²⁺ ion in gel bath was found to be the determining factor in the gel structure formation process by regulating the dissociation of alginate and the complexation of the calcium; (b) Na⁺ acts as a competitor with calcium and a screen in the electrostatic repulsion; (c) the effect of beads size below 700 μm on the structure of CAG beads can be neglected; and (d) the sodium alginate concentration has no significant effect on the gel formation process. Furthermore, the diffusion of bovine serum albumin (BSA) was controlled by the density of CAG bead. Consequently, a faster diffusion rate of BSA within the looser structure of beads can be observed. These results are keys to understanding the behavior and performance of beads in their utilization medium. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48923.     

Ethanol production by alginate immobilised yeast in a fluidised bed bioreactor

Yeast, immobilised in alginate beads of known standard size and mechanical strength, has been utilised in a novel design of fluidised bed bioreactor which avoids problems of particle flotation and gas logging. Circulating substrate simultaneously entered the top and bottom of the bed. The bioreactor operated reliably for periods of up to 20 days. Increasing alginate concentration in the range 1–5% (w/w) had little effect on the performance of the immobilised yeast in converting ethanol to glucose but reduced the tendency of beads to split. Increasing bead diameter in the range 1–5 mm increased the tendency to split and reduced overall conversion of glucose. A model was developed to describe the consumption of glucose within beads based on Michaelis–Menten kinetics and the diffusion of glucose into beads. Application of the model to experimental results showed maximum reaction velocity to be independent of bead diameter and alginate concentration. The model confirmed that the observed reduction in ethanol yield compared with free yeast cells was caused by the lower substrate concentration towards the centre of the bead as opposed to any change in the metabolic rate of the immobilised cells.     

Encapsulation of herbal aqueous extract through absorption with ca-alginate hydrogel beads

Encapsulation of herbal aqueous extract through absorption with ca-alginate hydrogel beads was studied. A model herbal aqueous extract, Piper sarmentosum, was used in this study. The effect of process variables (i.e. alginate M/G ratio, alginate concentration, extract concentration, bead size and bead water content) on encapsulation efficiency and biochemical compounds stability were studied. The stability of biochemical compounds was evaluated by using mass balance analysis and FT-IR spectroscopy. The results show that the encapsulation efficiency was mainly affected by alginate M/G ratio and bead water content. In general, ca-alginate beads made of higher alginate M/G ratio or dried to a lower water content were found to absorb significantly more aqueous extract. However, the beads made of higher M/G ratio were less rigid after the absorption process. Besides, the mass balance analysis reveals that the encapsulation process and material did not degrade the bioactive compounds, as the total antioxidant content remained unchanged. This is well supported by the FT-IR analysis where the characteristic bands of chemical groups remained unaltered. Interestingly, the beads made of lower alginate M/G ratio were found to have higher antioxidant affinity. In conclusion, this study demonstrates the potential of using absorption process and hydrogel material for encapsulation of herbal aqueous extract.     

Size adjustment of spherical temperature-sensitive hydrogel beads by liquid–liquid dispersion using a Kenics static mixer

Temperature-sensitive hydrogel beads were prepared by Kenics static mixer technology. The temperature-sensitive monomer N,N-diethylacrylamide and photo-crosslinkable pre-polymer ENT were used as model hydrogel materials. Drop dispersion of high viscosity polymer material in low viscosity hexadecane was made using the static mixer. Drops of a solution of the mixed materials were rapidly photo-crosslinked by UV irradiation after mixing in the static mixer, and spherical hydrogel beads with narrow, normal size distribution were thus prepared. The Kenics static mixer is a useful device for the preparation of spherical beads of temperature-sensitive hydrogels. The Sauter Mean Diameter of the hydrogel beads swollen in deionized water at 293 K was measured. The experimentally determined dimensionless swollen hydrogel bead diameter was well correlated with the Weber number, degree of swelling and viscosity ratio. The effects of gelation and ENT addition on the bead size were evaluated from the degree of swelling. The correlation equation can be used for size adjustment of temperature-sensitive spherical hydrogel beads.     

One pot synthesis of nano Ag in calcium alginate beads and its catalytic application in p‐Nitrophenol reduction with kinetic parameter estimation and model fitting

In this work, one step process of synthesis of silver nanoparticles (Agnp) embedded in insitu formed calcium alginate (CA) beads is stated. CA, formed from the reaction between sodium alginate and calcium hydroxide, acts as reducing and stabilizing agent as well as support for nanoparticles. The reaction mechanism for the formation and stabilization of Agnp is proposed where the vicinal dihydroxy groups of alginate are assumed to act as the reducing agent for Ag⁺ to Ag°. Transmission electron microscopy (TEM), x‐ray diffraction (XRD), UV‐vis spectroscopy, field emission scanning electron microscopy (FESEM), and atomic absorption spectroscopy (AAS) were used to characterize the Agnp. The formation of spherical nanoparticles with average size range of 4‐5 nm was confirmed by TEM. Catalytic activity of this nano silver‐calcium alginate (Agnp‐CA) composite was evaluated in the reduction of p‐nitrophenol. Concentrations of sodium alginate, calcium hydroxide, and AgNO₃ are found to be the parameters that critically affect the synthesis of Agnp. The efficacy of the catalyst is expressed on the basis of suitable reaction parameters. Both pseudo‐homogeneous and heterogeneous kinetic models are proposed for the reaction to find the best model and the Eley‐Riedel model is found to fit well with the experimental data. The novelty of this work is that the tandem process of CA bead formation, Agnp formation, and Agnp entrapment in CA have been transformed into a single‐step process. Moreover, elaborations of each step of the ionic mechanisms of Agnp formation and p‐NP reduction with Agnp and the establishment of a heterogeneous kinetic model for the reaction are reported for the first time here.