We report pH/bacteria-responsive nanocomposite coatings with multiple mechanisms of antibacterial protection that include the permanent retention of antimicrobials, bacteria-triggered release of antibiotics and bacteria-induced film swelling. A novel small-molecule-hosting film was constructed using layer-by-layer deposition of montmorillonite (MMT) clay nanoplatelets and polyacrylic acid (PAA) components, both of which carry a negative charge at neutral pH. The films were highly swollen in water, and they exhibited major changes in swelling as a function of pH. Under physiologic conditions (pH 7.5, 0.2 M NaCl), hydrogel-like MMT/PAA films took up and sequestered B45% of the dry film matrix mass of the antibiotic gentamicin, causing dramatic film deswelling. Gentamicin remained sequestrated within the films for months under physiologic conditions and therefore did not contribute to the development of antibiotic resistance. When challenged with bacteria (Staphylococcus aureus, Staphylococcus epidermidis or Escherichia coli), the coatings released PAA-bound gentamicin because of bacteria-induced acidification of the immediate environment, whereas gentamicin adsorbed to MMT nanoplatelets remained bound within the coating, affording sustained antibacterial protection. Moreover, an increase in film swelling after gentamicin release further hindered bacterial adhesion. These multiple bacteria-triggered responses, together with nontoxicity to tissue cells, make these coatings promising candidates for protecting biomaterial implants and devices against bacterial colonization.
INTRODUCTIONPolymer nanocomposites uniquely combine the properties of inorganic and organic components that is central to the development of novel advanced materials. The naturally occurring smectite clays, which are chemically and thermally stable and biocompatible, are attractive nanocomposites. Exfoliated clay nanoplatelets strongly impact the mechanical, transport, optical, fire retardant and gas barrier properties of nanocomposite materials. 1,2 For many biomedical applications, however, hydrophilic rather than hydrophobic nanocomposites are of great interest, and responsive properties are essential. 3 Reports on responsive hydrophilic nanocomposites are rare, and those few known to us advantageously use the complementary properties of temperature/pH-responsive polymers and clay nanosheets to yield environmentally controlled free-standing materials. 4 A promising way to leverage the favorable properties of hydrophilic-responsive nanocomposites on surfaces is to use the layer-by-layer (LbL) technique to construct 'smart' surface coatings. 5 To construct clay-containing LbL films, electrostatic interactions of positively charged polymers with negatively charged basal planes of silicate nanosheets, 6,7 neutral polymer/nanoplatelet hydrogen bonding 8 or a combination of the two have been explored. 9