Single molecule Förster resonance energy transfer (smFRET) is widely used to monitor conformations and interactions dynamics at the molecular level. However, conventional smFRET measurements are ineffective at donor-acceptor distances exceeding 10 nm, impeding the studies on biomolecules of larger size. Here, we show that zero-mode waveguide (ZMW) apertures can be used to overcome the 10 nm barrier in smFRET. Using an optimized ZMW structure, we demonstrate smFRET between standard commercial fluorophores up to 13.6 nm distance with a significantly improved FRET efficiency. To further break into the classical FRET range limit, ZMWs are combined with molecular constructs featuring multiple acceptor dyes to achieve high FRET efficiencies together with high fluorescence count rates. As we discuss general guidelines for quantitative smFRET measurements inside ZMWs, the technique can be readily applied for monitoring conformations and interactions on large molecular complexes with enhanced brightness.

Ultraviolet (UV) plasmonics aims at combining the strong absorption bands of molecules in the UV range with the intense electromagnetic fields of plasmonic nanostructures to promote surfaceenhanced spectroscopy and catalysis. Currently, aluminum is the most widely used metal for UV plasmonics, and is generally assumed to be remarkably stable thanks to its natural alumina layer passivating the metal surface. However, we find here that under 266 nm UV illumination, aluminum can undergo a dramatic photocorrosion in water within a few tens of seconds and even at low average UV powers. This aluminum instability in water environments critically limits the UV plasmonics applications. We show that the aluminum photocorrosion is related to the nonlinear absorption by water in the UV range leading to the production of hydroxyl radicals. Different corrosion protection approaches are tested using scavengers for reactive oxygen species and polymer layers deposited on top of the aluminum structures. Using optimized protection, we achieve a ten-fold increase in the available UV power range leading to no visible photocorrosion effects. This technique is crucial to achieve stable use of aluminum nanostructures for UV plasmonics in aqueous solutions.