"Built to Last": Plant-based Eco-friendly Durable Antibacterial Coatings.

The demand for effective and long-term durable antibacterial surfaces has been ever-growing in the past decades. A wide variety of long-lasting antibacterial surfaces developed from release-killing, active-killing, and anti-fouling strategies have demonstrated the desired effectiveness and durability so far. Most of these successful designs were developed from toxic and fossil-based materials, which failed to comply with the green design criteria. Furthermore, the longevity of these surfaces remained an unaddressed challenge. Herein, we present a disruptive paradigm that emphasizes both eco-friendliness and long-lasting antibacterial properties. A bio-based active-killing essential oil, namely carvacrol, and nonfouling carboxybetaine zwitterionic moieties were combined and incorporated into a highly bio-based polyurethane (BPU). The long-lasting active-killing property for this antibacterial BPU coating was enabled through the extended release of the bounded carvacrol via hydrolysis in an aqueous environment and compared to unbound carvacrol by liquid infusion. Also, the release of carvacrol generates zwitterionic moieties to prevent further bacterial attachment at the release site, resulting in a "kill and defend" synergistic antibacterial function in the BPU. The kinetics of the extended-release property were investigated and compared with unbound carvacrol BPU coatings; unbound carvacrol infused into BPU was quickly exhausted after 2 days of immersion in water, while the extended-release surface exhibited a nearly constant release rate of ∼128 ng cm-2 h-1 even after 45 days. The in vitro antibacterial efficiency of the BPUs was quantitatively evaluated using the modified ISO standard for cross-laboratory comparison. As a result, approximately 98.9 and 98.7% of Escherichia coli and Staphylococcus aureus were eliminated from the coating surfaces, and only a negligible variance in the antibacterial efficiency was observed after 5 cycles of test. The feasibility for practical application was also demonstrated by challenging the BPU coatings in everyday settings. This "built-to-last" design theory provided insights for future development of greener antibacterial coatings with long-term performance.

Fracture-controlled surfaces as extremely durable ice-shedding materials.

Icing imposes a significant burden on those living in cold climates, with negative impacts on infrastructure, transportation, and energy systems. Over the past few decades, a wide range of materials with ice-shedding characteristics have been developed, including surfaces that are non-wetting/hydrophobic, liquid-infused, stress-localized, and those with low interfacial toughness. Although many of these materials have demonstrated low ice adhesion in a laboratory setting, none have achieved widespread practical adoption. This is primarily a result of the fact that they tend to have very low durability, limiting their applicability. Thus, the primary challenge in developing ice-shedding materials is finding materials with both low ice adhesion AND good durability. Here, we introduce the concept of a so-called "fracture-controlled surface." Through coordinated mechanical and chemical heterogeneity in the material structure, we affect the interfacial crack nucleation and growth on these surfaces. Through this controlled process, fracture-controlled surfaces exhibit both low ice adhesion and very high mechanical durability. Measurements of the durability of these surfaces indicate performance that is three orders of magnitude greater than other state-of-the-art ice-shedding materials. Physically, via mechanical heterogeneity of the material, we pre-specified the crack nucleation coordinates at the interface and guided the crack growth in an interfacial plane, with no kinking in other directions. This helps to maximize the energy that goes towards crack nucleation and growth. A detailed mathematical model is developed to predict adhesion of external solid objects on these materials. The model suggests that an elastic matching criterion is required to achieve minimal adhesion of solid objects on these materials. Fracture-controlled surfaces provide a rich material platform to guide future innovation of materials with minimal adhesion while having very high durability.

Freezing of few nanometers water droplets.

Water-ice transformation of few nm nanodroplets plays a critical role in nature including climate change, microphysics of clouds, survival mechanism of animals in cold environments, and a broad spectrum of technologies. In most of these scenarios, water-ice transformation occurs in a heterogenous mode where nanodroplets are in contact with another medium. Despite computational efforts, experimental probing of this transformation at few nm scales remains unresolved. Here, we report direct probing of water-ice transformation down to 2 nm scale and the length-scale dependence of transformation temperature through two independent metrologies. The transformation temperature shows a sharp length dependence in nanodroplets smaller than 10 nm and for 2 nm droplet, this temperature falls below the homogenous bulk nucleation limit. Contrary to nucleation on curved rigid solid surfaces, ice formation on soft interfaces (omnipresent in nature) can deform the interface leading to suppression of ice nucleation. For soft interfaces, ice nucleation temperature depends on surface modulus. Considering the interfacial deformation, the findings are in good agreement with predictions of classical nucleation theory. This understanding contributes to a greater knowledge of natural phenomena and rational design of anti-icing systems for aviation, wind energy and infrastructures and even cryopreservation systems.

Dynamic Intermolecular Interactions Control Adsorption from Mixtures of Natural Organic Matter and Protein onto Titanium Dioxide Nanoparticles.

Engineered nanoparticles (NPs) will obtain macromolecular coatings in environmental systems, changing their subsequent interactions. The matrix complexity inherent in natural waters and wastewaters greatly complicates prediction of the corona formation. Here, we investigate corona formation on titanium dioxide (TiO2) NPs from mixtures of natural organic matter (NOM) and a protein, bovine serum albumin (BSA), to thoroughly probe the role of mixture interactions in the adsorption process. Fundamentally different coronas were observed under different NP exposure conditions and time scales. In mixtures of NOM and protein, the corona composition was kinetically determined, and the species initially coadsorbed but were ultimately limited to monolayers. On the contrary, sequential exposure of the NPs to pure solutions of NOM and protein resulted in extensive multilayer formation. The intermolecular complexation between NOM and BSA in solution and at the NP surface was the key mechanism controlling these distinctive adsorption behaviors, as determined by size exclusion chromatography (SEC) and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. Overall, this study demonstrates that dynamic intermolecular interactions and the history of the NP surface must be considered together to predict corona formation on NPs in complex environmental media.