It is well known that the macroscopic physico-chemical properties of ionic liquids (ILs) are influenced by the presence of water that strongly interferes with the supramolecular organization of these fluids. However, little is known about the function of water traces within this confined space and restricted ionic environments, i.e. between cations and anions. Using specially designed ILs namely 1,2,3-trimethyl-1H-imidazol-3-ium imidazol-1-ide (MMMI·Im) and 3-n-butyl-1,2-dimethyl-1H-imidazol-3-ium imidazol-1-ide (BMMI·Im), the structure and function of water have been determined in condensed, solution and gas phases by X-ray diffraction studies, NMR, molecular dynamics simulations (MDS) and DFT calculations. In the solid state the water molecule is trapped inside the ionic network (constituted of contact ion pairs formed by π+–π− interaction) through strong H-bonds involving the water hydrogens and the nitrogens of two imidazolate anions forming a guest@host supramolecular structure. A similar structural arrangement was corroborated by DFT calculations and MDS. The presence of a guest@host species (H2O@ILpair) is maintained to a great extent even in solution as detected by 1H–1H NOESY-experiments of the ILs dissolved in solvents with low and high dielectric constants. This confined water catalyses the H/D exchange with other substrates containing acidic-H such as chloroform.
Several fabrication techniques are recently used to produce a nanopattern for sensing, as focused ion beam milling (FIB), e-beam lithography (EBL), nanoimprinting, and soft lithography. Here, interference lithography is explored for the fabrication of large area nanohole arrays in metal films as an efficient, flexible, and scalable production method. The transmission spectra in air of the 1 cm2 substrate were evaluated to study the substrate behavior when hole-size, periodicity, and film thickness are varied, in order to elucidate the best sample for the most effective sensing performance. The efficiency of the nanohole array was tested for bulk sensing and compared with other platforms found in the literature. The sensitivity of ~1000 nm/RIU, achieved with an array periodicity in the visible range, exceeds near infrared (NIR) performances previously reported, and demonstrates that interference lithography is one of the best alternative to other expensive and time-consuming nanofabrication methods.
An experimental investigation on how the bulk and surface sensitivities of gold nanohole arrays fabricated by interference lithography affect the degree of white light beam collimation is presented. The optical transmission response of nanohole arrays has been recorded by focused and collimated beam transmission spectra. The results show that both the bulk and surface sensitivities for the collimated case are much larger than for the focused case. In particular, the shape of the spectra was dependent on the degree of beam collimation. The results showed that improved sensing performance (around 3.5 times) and higher figure of merit (around 4.4 times) can be obtained by simply adjusting the incident/collection experimental conditions in transmission measurements.