In this study, a novel water-insoluble polyelectrolyte complex between chitosan and poly(acrylic acid-co-maleic acid) was prepared and characterized. The chitosan used (M̅v = 23,000–60,000 g/mol) formed water-insoluble polyelectrolyte complexes at pH 2.2–4.8 and water-soluble chitosan oligomers (M̅v = 2,700 g/mol) at pH 2.2–7.4. The polyelectrolyte complexes formed were used in the preparation of novel carriers for a Trichoderma spp. biocontrol agent. Three types of beads were prepared: noncross-linked chitosan beads, coated with a chitosan/poly(acrylic acid-co-maleic acid) polyelectrolyte complex; genipin-cross-linked chitosan beads; and cross-linked chitosan beads, coated with a chitosan/poly(acrylic acid-co-maleic acid) polyelectrolyte complex. Trichoderma viride was immobilized either in the bulk or in the surface layer of the beads. The microbiological tests confirmed that T. viride immobilized in either mode maintained viability and the capacity to develop and to inhibit the growth of the pathogenic soil microorganisms, Alternaria and Fusarium.
PanevaDIgnatovaMManolovaN. Novel chitosan-containing micro- and nanofibrous materials by electrospinning. Preparation and biomedical application. In: ChangWN (ed.) Nanofibers: fabrication, performance, and applications. New York: Nova Science Publishers, 2009, pp.73–151.
2.
LeeDWLimHChongHN. Advances in chitosan material and its hybrid derivatives: a review. Open Biomater J2009; 1: 10–20.
3.
NussinovitchA. Beads and special applications of polymers for agricultural uses. In: Polymer macro- and micro-gel beads: fundamentals and applications. New York: Springer, 2009, pp.231–253.
4.
HadramiAEAdamLRHadramiIE. Chitosan in plant protection. Mar Drugs2010; 8(4): 968–987.
5.
StoilovaOKosevaNManolovaN. Polyelectrolyte complex between chitosan and poly(2-acryloylamido-2-methylpropanesulfonic acid). Polym Bull1999; 43(1): 67–73.
6.
PanevaDMinchevaRStoilovaO. Degradation of chitosan in the presence of poly(vinyl alcohol) and poly(acrylic acid) by a crude enzyme complex from Trichoderma viride. e-Polymers2003; 019: 1–9.
7.
BoninaPPetrovaTsManolovaN. Degradation of networks composed of chitosan and polyacrylamide by a crude enzyme complex from Bacillus subtilis. e-Polymers2004; 062: 1–8.
8.
SpasovaMManolovaNNaydenovM. Electrospun biohybrid materials for plant biocontrol containing chitosan and Trichoderma viride spores. J Bioact Compat Pol2011; 26(1): 48–55.
9.
RinaudoM. Chitin and chitosan: properties and applications. Progr Polym Sci2006; 31(7): 603–632.
10.
GeorgeMEmilia AbrahamT. Polyionic hydrocolloids for the intestinal delivery of protein drugs: alginate and chitosan—a review. J Control Release2006; 114(1): 1–14.
11.
TsaoCTChangCHLinYY. Antibacterial activity and biocompatibility of a chitosan-γ-poly(glutamic acid) polyelectrolyte complex hydrogel. Carbohyd Res2010; 345(12): 1774–1780.
12.
ChavasitVKienzle-SterzerCAntonio TorresJ. Formation and characterization of an insoluble polyelectrolyte complex: chitosan-polyacrylic acid. Polym Bull1988; 19(3): 223–230.
13.
TsaoCTChangCHLinYY. Tissue response to chitosan/γ-PGA polyelectrolyte complex using a rat model. J Bioact Compat Polym2011; 26(2): 191–206.
14.
YoshizawaTShin-yaYHongK-J. pH- and temperature-sensitive permeation through polyelectrolyte complex films composed of chitosan and polyalkyleneoxide-maleic acid copolymer. J Membrane Sci2004; 241(2): 347–354.
15.
YoshizawaTShin-yaYHongK-J. pH- and temperature-sensitive release behaviors from polyelectrolyte complex films composed of chitosan and PAOMA copolymer. Eur J Pharm Biopharm2005; 59(2): 307–313.
16.
SeoJAKohJHRohDK. Preparation and characterization of crosslinked proton conducting membranes based on chitosan and PSSA-MA copolymer. Solid State Ionics2009; 180(14–16): 998–1002.
17.
KosevaNStoilovaOManolovaN. Chitosan beads as carriers of 8-hydroxy-7-iodoquinoline-5-sulfonic acid—loading, coating by interpolymer complex formation and drug release. J Bioact Compat Pol2001; 16(1): 3–19.
18.
StoilovaOKosevaNPetrovaTs. Hydrolysis of chitosan, chitosan-polyoxyethylene and chitosan-poly(2-acryloylamido-2-methylpropanesulfonic acid) by a crude enzyme complex from Trichoderma viride. J Bioact Compat Pol2001; 16(5): 379–392.
19.
RajendiranRJegadeeshkumarDSureshkumarBT. In vitro assessment of antagonistic activity of Trichoderma viride against post harvest pathogens. J Agric Technol2010; 6(1): 31–35.
20.
DomardA. pH and c.d measurements on a fully deacetylated chitosan: application to CuII-polymer interactions. Int J Biol Macromol1987; 9(2): 98–104.
21.
EdwardsMBenjaminMMRyanJN. Role of organic acidity in sorption of natural organic matter (NOM) to oxide surfaces. Colloid Surf A1996; 107: 297–307.
22.
LeclercqLBousttaMVertM. Dynamics of polyelectrolyte complex formation and stability when a polycation is progressively added to a polyanion under physicochemical conditions modeling blood. J Bioact Compat Pol2011; 26: 3–19.
23.
HaradaAKataokaK. Effect of charged segment length on physicochemical properties of core-shell type polyion complex micelles from block ionomers. Macromolecules2003; 36(13): 4995–5001.
24.
AnderssonTHolappaSAseyevV. Effect of polycation length on its complexation with DNA and with poly(oxyethylene-block-sodium methacrylate). Biomacromolecules2006; 7(11): 3229–3238.
25.
MinchevaRBougardFPanevaD. Natural polyampholyte-based core-shell nanoparticles with N-carboxyethylchitosan-containing core and poly(ethylene oxide) shell. Biomacromolecules2009; 10(4): 838–844.
26.
MiF-LSungH-WShyuS-S. Synthesis and characterization of a novel chitosan-based network prepared using naturally occurring crosslinker. J Polym Sci A: Polym Chem2000; 38(15): 2804–2814.
