title: Interaction of O-acylated chitosans with biomembrane models: probing the effects from hydrophobic interactions and hydrogen bonding.
abstract: One of the major challenges in establishing the mechanisms responsible for the chitosan action in biomedical applications lies in the determination of the molecular-level interactions with the cell membrane. In this study, we probed hydrophobic interactions and H-bonding in experiments with O,O'-diacetylchitosan (DACT) and O,O'-dipropionylchitosan (DPPCT) incorporated into monolayers of distinct phospholipids, the zwitterionic dipalmitoyl phosphatidyl choline (DPPC), and the negatively charged dipalmitoyl phosphatidyl glycerol (DPPG) and dimyristoyl phosphatidic acid (DMPA). The importance of hydrophobic interactions was confirmed with the larger effects observed for DACT and DPPCT than for parent chitosan (Chi), particularly for the more hydrophobic DPPCT. Such larger effects were noted in surface pressure isotherms and elasticity of the monolayers. Since H-bonding is hampered for the chitosan derivatives, which have part of their hydroxyl groups shielded by O-acylation, these effects indicate that H-bonding does not play an important role in the chitosan-membrane interactions. Using polarization-modulated infrared reflection absorption (PM-IRRAS) spectroscopy, we found that the chitosan derivatives were incorporated into the hydrophobic chain of the phospholipids, even at high surface pressures comparable to those in a real cell membrane. Taken together, these results indicate that the chitosan derivatives containing hydrophobic moieties would probably be more efficient than parent chitosan as antimicrobial agents, where interaction with the cell membrane is crucial.
authors.affiliation: Institute of Chemistry of São Carlos, USP, PO Box 780, 13560-970 São Carlos, SP, Brazil. Electronic address: adrianapavinatto@iqsc.usp.br.
authors.forename: Adriana
authors.initials: A
authors.lastname: Pavinatto
authors.affiliation: Institute of Physics of São Carlos, USP, PO Box 369, 13566-590 São Carlos, SP, Brazil.
authors.forename: Adriano L
authors.initials: AL
authors.lastname: Souza
authors.affiliation: Institute of Physics of São Carlos, USP, PO Box 369, 13566-590 São Carlos, SP, Brazil.
authors.forename: Jorge A M
authors.initials: JA
authors.lastname: Delezuk
authors.affiliation: Institute of Physics of São Carlos, USP, PO Box 369, 13566-590 São Carlos, SP, Brazil.
authors.forename: Felippe J
authors.initials: FJ
authors.lastname: Pavinatto
authors.affiliation: Institute of Chemistry of São Carlos, USP, PO Box 780, 13560-970 São Carlos, SP, Brazil.
authors.forename: Sérgio P
authors.initials: SP
authors.lastname: Campana-Filho
authors.affiliation: Institute of Physics of São Carlos, USP, PO Box 369, 13566-590 São Carlos, SP, Brazil.
authors.forename: Osvaldo N
authors.initials: ON
authors.lastname: Oliveira
mesh_terms: D015060:1,2-Dipalmitoylphosphatidylcholine / Q000737:chemistry; D000215:Acylation; D002462:Cell Membrane / Q000378:metabolism*; D048271:Chitosan / Q000378:metabolism*; D006860:Hydrogen Bonding; D057927:Hydrophobic and Hydrophilic Interactions; D008567:Membranes, Artificial; D008954:Models, Biological; D011312:Pressure; D013055:Spectrophotometry, Infrared; D017550:Spectroscopy, Fourier Transform Infrared; D013696:Temperature
chemical_list: D008567:Membranes, Artificial; D015060:1,2-Dipalmitoylphosphatidylcholine; D048271:Chitosan
keywords: Hydrogen bonds; Hydrophobic interactions; Langmuir films; Membrane models; O-acylated chitosan