Photo-responsive antibacterial surfaces combining both on-demand photo-switchable activity and sustained biocidal release were prepared using sequential chemical grafting of nano-objects with different geometries and functions. The multi-layered coating developed incorporates a monolayer of near-infrared active silica-coated gold nanostars (GNS) decorated by silver nanoparticles (AgNP). This modular approach also enables us to unravel static and photo-activated contributions to the overall antibacterial performance of the surfaces, demonstrating a remarkable synergy between these two mechanisms. Complementary microbiological and imaging evaluations on both planktonic and surface-attached bacteria provided new insights on these distinct but cooperative effects.

The ability of nitric oxide (NO)-releasing polymer coatings to prevent biofilm formation is described. NO-releasing coatings on (poly(ethylene terephthalate) (PET) and silicone elastomer (SE)) were fabricated using aminosilane precursors. Pristine PET and SE were oxygen plasma treated, followed by immobilisation of two aminosilane molecules: N-(3-(trimethoxysilyl)propyl)diethylenetriamine (DET3) and N-(3-trimethoxysilyl)propyl)aniline (PTMSPA). N-diazeniumdiolate nitric oxide donors were formed at the secondary amine sites on the aminosilane molecules producing NO-releasing polymeric coatings. The NO payload and release were controlled by the aminosilane precursor, as DET3 has two secondary amine sites and PTMSPA only one. The antibacterial efficacy of these coatings was tested using a clinical isolate of Pseudomonas aeruginosa (PA14). All NO-releasing coatings in this study were shown to significantly reduce P. aeruginosa adhesion over 24 h with the efficacy being a function of the aminosilane modification and the underlying substrate. These NO-releasing polymers demonstrate the potential and utility of this facile coating technique for preventing biofilms for indwelling medical devices.

Molecules provide versatile building blocks, with a vast palette of functionalities and an ability to assemble via supramolecular and covalent bonding to generate remarkably diverse macromolecular systems. This is abundantly displayed by natural systems that have evolved on Earth, which exploit both supramolecular and covalent protocols to create the machinery of life. Importantly, these molecular assemblies deliver functions that are reproducible, adaptable, finessed and responsive. There is now a real need to translate complex molecular systems to surfaces and interfaces in order to engineer 21st century nanotechnology. ‘Top-down’ and ‘bottom-up’ approaches, and utilisation of supramolecular and covalent assembly, are currently being used to create a range of molecular architectures and functionalities at surfaces. In parallel, advanced tools developed for interrogating surfaces and interfaces have been deployed to capture the complexities of molecular behaviour at interfaces from the nanoscale to the macroscale, while advances in theoretical modelling are delivering insights into the balance of interactions that determine system behaviour. A few examples are provided here that outline molecular behaviour at surfaces, and the level of complexity that is inherent in such systems.

Bitartrate, a strongly bound chiral modifier, is able to restructure its adsorption footprint on Cu(110) in response to local adsorbates.

We have studied CO coordinated to ruthenium tetraphenylporphyrin (RuTPP)/Cu(110) and directly adsorbed to Cu(110), using femtosecond pump-sum frequency probe spectroscopy, to alter the degree of electron-vibration coupling between the metal substrate and CO. We observe the facile femtosecond laser-induced desorption of CO from RuTPP/Cu(110), but not from Cu(110). A change in the vibrational transients, in the first few picoseconds, from a red- to blue-shift of the C–O stretching vibration under photodesorption conditions, was also observed. This drastic change can be explained, if the cause of the C–O frequency redshift of Cu(110) is not the usually-assumed anharmonic coupling to low frequency vibrational modes, but a charge transfer from hot electrons to the CO 2π* state. This antibonding state shifts to higher energies on RuTPP, removing the C–O redshift and, instead, reveals a blueshift, predicted to arise from electron-mediated coupling between the coherently excited internal stretch and low frequency modes in the system.