Synthesis, characterization and antimicrobial activity of poly (N-vinyl imidazole) grafted carboxymethyl chitosan

doi:10.1016/j.carbpol.2009.10.024

Carbohydrate Polymers

Volume 79, Issue 4, 17 March 2010, Pages 998-1005

https://doi.org/10.1016/j.carbpol.2009.10.024 Get rights and content

Abstract

Poly (N-vinyl imidazole) (PNVI) has been grafted onto carboxymethyl chitosan in aqueous solution using potassium persulphate (KPS) as initiator. The effect of the monomer and initiator concentration, the reaction temperature and time on the grafting yield have been investigated. The maximum grafting yield was achieved at [KPS] = 8 × 10⁻² mol/L, [M] = 1 mol/L at reaction temperature = 60 °C within reaction time = 2.5 h. The grafted products were characterized by FTIR, elemental analysis, SEM photographs, solubility tests, thermal analysis and antibacterial activity. Grafted products have improved the antimicrobial activity of carboxymethyl chitosan.

Introduction

Chitosan [Poly (β-(1→4)-2-amino-2-deoxy-d-glucan] is N-deacetylated derivative of chitin extracted from the shells of crustaceans like crabs and shrimps. It is obtained through the alkaline hydrolysis of chitin to convert the acetamide group into amino group. Chitosan is a biocompatible polymer and has found many applications as biomaterials in tissue engineering and in controlled drug release systems for various routes of delivery (Kumar, 2000, Mphahlele, 2005, Peng and Zhang, 2009, Rinaudo, 2006, Xie et al., 2002a, Xie et al., 2002b). Chemical modification of Chitosan is an important topic for production of multifunctional material. Graft copolymerization of vinyl monomers onto chitosan and other natural polymers can introduce desired properties and enlarge the field of their potential applications (El-Sherbiny et al., 2005, Jigar and Sinha, 2007, Joshi and Sinha, 2006).

Recently, ceric ion initiated graft copolymerization of N-vinyl imidazole (NVI) onto chitosan was reported (Hamit, Elvan, & Osman, 2007). The maximum grafting yield achieved was 140% in 1.0% (w/v) chitosan solution at 0.2 M N-vinyl imidazole at 70 °C within 3 h under nitrogen atmosphere. Chitosan derivatives soluble in neutral and in basic media in addition to acidic solutions are needed as biomaterials (Sashiwa & Aiba, 2004). Water soluble hydroxyl propyl chitosan was prepared (Xie et al., 2002a, Xie et al., 2002b) with antibacterial activity via grafting by sodium maleate.

Similar to all other vinyl monomers, vinyl imidazoles readily undergo free radical polymerization in water to form high molecular weight water soluble polymers (PNVI). Polymers containing the imidazole ring or its derivatives are known to be useful biomaterials since they show antibacterial activity and have improved biodegradability. The antibacterial activity of some imidazole-5-(4H)-one derivatives was studied (Saravanan, Selvan, Gopal, & Gupta, 2005). Chitosan and imidazole containing polymers have some common properties useful for biomedical applications. They act as antibacterial agents, have metal binding properties and are biocompatible and biodegradable. The advantage of PNVI as a grafting agent is its water solubility.

Wenming et al. (Tao, Peixin, Qing, Jian, & Wenming, 2003) had prepared carboxymethyl chitosan and characterized it by FTIR, ¹H NMR and elemental analysis. Graft copolymerization of methacrylic acid (MAA) onto carboxymethyl chitosan was done using ammonium persulfate (APS) as an initiator and was carried out in an aqueous solution. Evidence of grafting was obtained by comparison of FTIR spectra of carboxymethyl chitosan and the grafted copolymer as well as solubility characteristics of the products. The optimum conditions were reported.

O-Carboxymethyl chitosan was prepared and characterized by FTIR spectroscopy and X-ray diffraction (Jigar & Sinha, 2007). Grafting of Acrylamide (Am) onto carboxymethyl chitosan using ceric ammonium nitrate (CAN) as an initiator was carried out under nitrogen atmosphere in aqueous solution. Optimum grafting conditions were mentioned.

Carboxymethyl chitosan was prepared (El-Sherbiny, 2009) and characterized by FTIR spectroscopy, elemental analysis and X-ray diffraction. Graft copolymerization of N-acryloylglycine (NAGly) onto carboxymethyl chitosan using 2,2-dimethoxy-2-phenyl acetophenone (PI) as photoinitiator was carried out under nitrogen atmosphere in aqueous solution. The effects of concentration of NAGly, PI and reaction time on the extent of grafting were investigated by determining the grafting percentage and grafting efficiency.

In the present study, the various parameters affecting the grafting of PNVI onto carboxymethyl chitosan, characterization of the grafted products and their antibacterial activity results will be reported.

Section snippets

Materials

Chitosan (with a degree of deacetylation 88%) was purchased from Funakoshi Co. Ltd., Japan. Potassium persulfate (KPS) was supplied from S.D. Fine Chemical, India.

N-Vinylimidazole (NVI) was supplied by Merck (Schuchardt OHG, Hohenbrunn, Germany). Monochloro acetic acid was obtained from LOBA chemie pvt. Ltd., Mumbai, India. Other reagents and solvents were of analytical grades and were used as received.

Infrared spectroscopy

FTIR spectra were recorded on Testcan Shimadzu IR-Spectrophotometer (model 8000) within the

IR characterization of CMCh and CMCh-g-PNVI

FTIR spectra of both Chitosan and CMCh – Fig. 1 – show the strong peak at 1412 cm⁻¹ which could be assigned to the symmetrical stretching vibration of COO⁻ group (Brugnerotto et al.,2001). The asymmetrical stretching vibrating of COO⁻ group near 1550 cm⁻¹ is overlapped with the deforming vibration of NH₂ at 1600 cm⁻¹ to obtain a very strong peak. The C–O absorption peak of the secondary hydroxyl group became stronger and moved to 1074 cm⁻¹. The results – which are in accordance with the work of (

Conclusions

1.
In the present work, carboxymethyl chitosan was prepared, characterized by FTIR, SEM and TGA, then it was modified by graft copolymerization of N-vinyl imidazole onto its backbone.
2.
TGA studies showed that the thermal stability of the copolymers CMCh-g-PNVI were found to be better than CMCh and the thermal stability increases with the increase in graft %. Moreover, it was obvious from SEM results that carboxymethylation of chitosan and its graft copolymerization by PNVI modified the flaky nature

Acknowledgement

The authors are much thankful to GRCF (Graduate research challenge fund) of Faculty of Science, Cairo University for facilitating the purchase of chemicals and for making the required analyses of the present work.

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Synthesis, characterization and antimicrobial activity of poly (N-vinyl imidazole) grafted carboxymethyl chitosan

Abstract

Introduction

Section snippets

Materials

Infrared spectroscopy

IR characterization of CMCh and CMCh-g-PNVI

Conclusions

Acknowledgement

Polymer

Polymer

Journal of Food Protection

Carbohydrate Polymer

Polymer

European Polymer Journal

European Polymer Journal

International Journal of Food Microbiology

Reactive and Functional Polymers

Polymer

Polymer

Colloids and Surfaces A: Physicochemical and Engineering Aspects

Progress in Polymer Science

Progress in Polymer Science

International Journal of Antimicrobial Agents

Carbohydrate Polymers

Bioorganic and Medicinal Chemistry

Materials Chemistry and Physics

Carbohydrate Research