Soft Materials that Intercept, Respond to, and Sequester Bacterial Siderophores.

We report the design and characterization of Fe-containing soft materials that respond to, interface with, and/or sequester Fe-chelating 'siderophores' that bacteria use to scavenge for iron and regulate iron homeostasis. We demonstrate that metal-organic network coatings fabricated by crosslinking tannic acid with iron(III) are stable in bacterial growth media, but erode upon exposure to biologically relevant concentrations of enterobactin and deferoxamine B, two siderophores produced by Gram-negative and Gram-positive bacteria, respectively. Our results are consistent with changes in network stability triggered by the extraction of iron(III) and reveal rates of siderophore-induced disassembly to depend upon both siderophore concentration and affinity for iron(III). These coatings also disassemble when incubated in the presence of cultures of wild-type Escherichia coli. Assays using genetically modified strains of E. coli reveal the erosion of these materials by live cultures to be promoted by secretion of enterobactin and not from other factors resulting from bacterial growth and metabolism. This stimuli-responsive behavior can also be exploited to design coatings that release the Fe-chelating antibiotic ciprofloxacin into bacterial cultures. Finally, we report the discovery of Fe-containing polymer hydrogels that avidly sequester and scavenge enterobactin from surrounding media. The materials reported here are (i) capable of interfacing or interfering with mechanisms that bacteria use to maintain iron homeostasis, either by yielding iron to or by sequestering iron-scavenging agents from bacteria, and can (ii) respond dynamically to or report on the presence of populations of iron-scavenging bacteria. Our results thus provide new tools that could prove useful for microbiological research and enable new stimuli-responsive strategies for interfacing with or controlling the behaviors of communities of iron-scavenging bacteria.