Biofilm-responsive encapsulated-phage coating for autonomous biofouling mitigation in water storage systems.

Biofilms in water storage systems may harbor pathogens that threaten public health. Chemical disinfectants are marginally effective in eradicating biofilms due to limited penetration, and often generate harmful disinfection byproducts. To enhance biofouling mitigation in household water storage tanks, we encapsulated bacteriophages (phages) in chitosan crosslinked with tri-polyphosphate and 3-glycidoxypropyltrimethoxysilane. Phages served as self-propagating green biocides that exclusively infect bacteria. This pH-responsive encapsulation (244 ± 11 nm) enabled autonomous release of phages in response to acidic pH associated with biofilms (corroborated by confocal microscopy with pH-indicator dye SNARF-4F), but otherwise remained stable in pH-neutral tap water for one month. Encapsulated phages instantly bind to plasma-treated plastic and fiberglass surfaces, providing a facile coating method that protects surfaces highly vulnerable to biofouling. Biofilm formation assays were conducted in tap water amended with 200 mg/L glucose to accelerate growth and attachment of Pseudomonas aeruginosa, an opportunistic pathogen commonly associated with biofilms in drinking water distribution and storage systems. Biofilms formation on plastic surfaces coated with encapsulated phages decreased to only 6.7 ± 0.2% (on a biomass basis) relative to the uncoated controls. Likewise, biofilm surface area coverage (4.8 ± 0.2 log CFU/mm2) and live/dead fluorescence ratio (1.80) were also lower than the controls (6.6 ± 0.2 log CFU/mm2 and live/dead ratio of 11.05). Overall, this study offers proof-of-concept of a chemical-free, easily implementable approach to control problematic biofilm-dwelling bacteria and highlights benefits of this bottom-up biofouling control approach that obviates the challenge of poor biofilm penetration by biocides.

Persistent free radicals in biochar enhance superoxide-mediated Fe(III)/Fe(II) cycling and the efficacy of CaO2 Fenton-like treatment.

Superoxide radicals (O2•-) produced by the reaction of Fe(III) with H2O2 can regenerate Fe(II) in Fenton-like reactions, and conditions that facilitate this function enhance Fenton treatment. Here, we developed an efficient Fenton-like system by using calcium peroxide/biochar (CaO2/BC) composites as oxidants and tartaric acid-chelated Fe(III) as catalysts, and tested it for enhanced O2•--based Fe(II) regeneration and faster sulfamethoxazole (SMX) degradation. SMX degradation rates and peroxide utilization efficiencies were significantly higher with CaO2/BC than those with CaO2 or H2O2 lacking BC. The CaO2/BC system showed superior activity to reduce Fe(III), while kinetic analyses using chloroform as a O2•- probe inferred that the O2•- generation rate by CaO2/BC was one-half of that by CaO2. Apparently, O2•- is utilized more efficiently in this system to regenerate Fe(II) and enhance SMX degradation. Additionally, a positive correlation between SMX degradation rate constants and EPR signal intensities of biochar-derived persistent free radicals (PFRs) in CaO2/BC was obtained. We postulate that PFRs enhanced Fe(III) reduction by shuttling electrons donated by O2•-. This represents a new strategy to augment the ability of superoxide to accelerate Fe(III)/Fe(II) cycling for increased hydroxyl radical production and organic pollutant removal in Fenton-like reactions.

A 3D Plasmonic Antenna-Reactor for Nanoscale Thermal Hotspots and Gradients.

Plasmonic nanoantennas focus light below the diffraction limit, creating strong field enhancements, typically within a nanoscale junction. Placing a nanostructure within the junction can greatly enhance the nanostructure's innate optical absorption, resulting in intense photothermal heating that could ultimately compromise both the nanostructure and the nanoantenna. Here, we demonstrate a three-dimensional "antenna-reactor" geometry that results in large nanoscale thermal gradients, inducing large local temperature increases in the confined nanostructure reactor while minimizing the temperature increase of the surrounding antenna. The nanostructure is supported on an insulating substrate within the antenna gap, while the antenna maintains direct contact with an underlying thermal conductor. Elevated local temperatures are quantified, and high local temperature gradients that thermally reshape only the internal reactor element within each antenna-reactor structure are observed. We also show that high local temperature increases of nominally 200 °C are achievable within antenna-reactors patterned into large extended arrays. This simple strategy can facilitate standoff optical generation of high-temperature hotspots, which may be useful in applications such as small-volume, high-throughput chemical processes, where reaction efficiencies depend exponentially on local temperature.