Carbohydrate Polymers 91 (2013) 333–338 Contents lists available at SciVerse ScienceDirect Carbohydrate Polymers jo u rn al hom epa ge: www.elsevier.com/locate/carbpol Synthesis and photobiocidal properties of cationic porphyrin-grafted paper Jean-Pierre Mbakidi a , Klara Herke a , Sandra Alvès b , Vincent Chaleix a , Robert Granet a , Pierre Krausz a , Stéphanie Leroy-Lhez a , Tan-Sothea Ouk a , Vincent Sol a,∗ a Université de Limoges, Laboratoire de Chimie des Substances Naturelles, EA 1069, 123 avenue Albert Thomas, 87060 Limoges, France b Laboratoire de Chimie Structurale Organique et Biologique, Université Pierre et Marie Curie, CNRS UMR7613, 4 Place Jussieu, 75252 Paris Cedex 05, France a r t i c l e i n f o Article history: Received 25 June 2012 Received in revised form 24 July 2012 Accepted 3 August 2012 Available online 11 August 2012 Keywords: Antibacterial surfaces Paper Porphyrin PACT mechanism Cyanuric chloride a b s t r a c t We report on the synthesis of cellulose paper bearing a cationic porphyrin, designed for antimicrobial applications. Tricationic porphyrin has been covalently grafted on paper, without previous chemical modification of the cellulosic support, using 1,3,5-triazine derivative as linker. The obtained porphyrin- grafted paper was characterized by infrared (ATR-FTIR), UV–visible and diffuse reflectance UV–vis (DRUV) spectroscopies to confirm the triazine linkage. Thermogravimetric analysis (TGA) was used to investigate thermal properties of grafted paper. Antimicrobial activity of porphyrin–cellulose material was tested under visible light irradiation against Staphylococcus aureus and Escherichia coli. The two bacterial strains deposited on the resulting photosensitizing filter paper are efficiently killed after illumination. © 2012 Elsevier Ltd. All rights reserved. 1. Introduction Microbial contamination is of great concern in a variety of areas including medical devices, healthcare products, water purifica- tion systems, hospitals, dental office equipment, food packaging, food storage, household sanitation, etc. In the last years, major interest has grown in the preparation of materials endowed with antibacterial properties for use in a wide range of fields such as food packaging and transportation, housekeeping, and handling of medical and military items (El-Khouly et al., 2010; Hasmen, Ibrahim, El-Sayed, EL-Husseiny, & El-Enany, 2009; Hou, Zhou, & Wang, 2009; Hsu & Klibanov, 2011; Kenawy, Worley, & Broughton, 2007; Kenawy, 2001; Ngo, Li, Simon, & Garnier, 2011; Tankhiwale & Bajpai, 2009). The need for a control of potentially pathogenic microorganisms in exposed environments has led to the develop- ment of antibacterial products. Antimicrobial surfaces have been obtained by incorporating active agents, currently under study or commercially available, among which can be mentioned quaternary ammonium salts (Lee et al., 2004), N-halamines (Ren, Kocer, Worley, Broughton, & Huang, 2009), guanidine polymers (Kawabata & Taylor, 2007), antibi- otics (Cassano et al., 2009), or Ag/TiO 2 nanoparticles (Dastjerdi & Montazer, 2010). However, these agents are not entirely sat- isfactory because material can loose antibacterial properties in ∗ Corresponding author. Tel.: +33 05 5545 7490; fax: +33 05 5545 7202. E-mail address: vincent.sol@unilim.fr (V. Sol). noncovalent systems, release of environmentally hazardous agents, obligation on direct contact between antimicrobial molecules and microorganism, and emergence of antimicrobial resistance. Our strategy was to develop a new cellulosic material bearing a covalent linker between polymeric surface and new antimicrobial molecules. Indeed, cellulose is an excellent starting material for developing a more sustainable material from renewable resources. So, paper has a visible market-share in hygiene products or in packaging materials. The degradable nature of filter paper makes it an attractive alternative for these uses. Concerning the type of new antimicrobial agents, photosensitizers (PS) such as porphyrins have been intensively studied for their photobactericidal effects in Photodynamic Antimicrobial ChemoTherapy (PACT) (Hamblin & Hassan, 2004; Jori & Spikes, 1984; Nitzan, Balzam-Sudakevitz, & Ashkenazi, 1998; Wainwright, 1998). This treatment involves the use of photosensitive compound which is activated by expo- sure to visible light (MacDonald & Dougherty, 2001). Although the cellular mechanism of the photodynamic process is not yet fully understood, it is presently admitted that phototoxic effects rely primarily on the formation of singlet oxygen ( 1 O 2 ) after illu- mination (DeRosa & Crutchley, 2002; Ochsner, 1997). This highly reactive species is able to react with almost every cellular com- ponent, bringing irreversible damages that ultimately lead to cell death (Dolmans, Fukumura, & Jain, 2003; Dougherty, 1987; Soukos, Ximenez-Fyvie, Hamblin, Socransky, & Hasan, 1998). Recent works have shown that porphyrins keep their antimicrobial properties when grafted on carbon nanotubes, nylon fabrics, polyvinylidene fluoride, chitosan or cellulose and that these modified polymers 0144-8617/$ – see front matter © 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.carbpol.2012.08.013