Chiral molecules are shown to induce circular dichroism (CD) at surface plasmon resonances of gold nanostructures when in proximity to the metal surface without direct bonding to the metal. By changing the molecule-Au separation, we were able to learn about the mechanism of plasmonic CD induction for such nanostructures. It was found that even two monolayers of chiral molecules can induce observable plasmonic CD, while without the presence of the plasmonic nanostructures their own CD signal is unmeasurable. Hence, plasmonic arrays could offer a route to enhanced sensitivity for chirality detection.
Formation of unwanted deposits on steels during their interaction with liquids is an inherent problem that often leads to corrosion, biofouling and results in reduction in durability and function. Here we report a new route to form anti-fouling steel surfaces by electrodeposition of nanoporous tungsten oxide (TO) films. TO-modified steels are as mechanically durable as bare steel and highly tolerant to compressive and tensile stresses due to chemical bonding to the substrate and island-like morphology. When inherently superhydrophilic TO coatings are converted to superhydrophobic, they remain non-wetting even after impingement with yttria-stabilized-zirconia particles, or exposure to ultraviolet light and extreme temperatures. Upon lubrication, these surfaces display omniphobicity against highly contaminating media retaining hitherto unseen mechanical durability. To illustrate the applicability of such a durable coating in biofouling conditions, we modified naval construction steels and surgical instruments and demonstrated significantly reduced marine algal film adhesion, Escherichia coli attachment and blood staining.
Gold nanoisland films displaying localized surface plasmon resonance optical response were constructed by evaporation on glass and annealing. The surface plasmon distance sensitivity and refractive index sensitivity (RIS) for island films of different nominal thicknesses and morphologies were investigated using layer-by-layer polyelectrolyte multilayer assembly. Since the polymer forms a conformal coating on the Au islands and the glass substrate between islands, the relative sensitivity of the optical response to adsorption on and between islands was evaluated. The RIS was also determined independently using a series of solvents. An apparent discrepancy between the behavior of the RIS for wavelength shift and intensity change is resolved by considering the different physical nature of the two quantities, leading to the use of a new variable, that is, RIS (for intensity change) normalized to the surface density of islands. In the present system the surface plasmon decay length and RIS are shown to be directly correlated; both parameters increase with increasing average island size. This result implies that a higher RIS is not always beneficial for sensing; maximizing the transducer optical response requires the interrelated RIS and decay length to be optimized with respect to the dimensions of the studied analyte-receptor system. It is shown that, as a rule, transducers comprising larger islands furnish better overall sensitivity for thicker adlayers, whereas thinner adlayers produce a larger response when sensed using transducers comprising smaller islands, despite the lower RIS of the latter.
Strongly bound and highly stable gold island films on glass are obtained by a simple, one‐step preparation procedure (see figure) based on high‐temperature annealing and partial embedding of gold nanostructures evaporated on glass, providing stable and effective localized plasmon transducers.
Gold island films displaying localized plasmon properties were prepared by evaporation of just-percolated Au films onto glass substrates followed by annealing at g550 °C. Annealing induces depercolation and formation of large, singlecrystalline, well-separated islands, partially embedded in the glass. Two dewetting mechanisms were identified, depending on the initial film morphology. The variability of island sizes and shapes provides effective means of tuning the position of the localized surface plasmon resonance (LSPR) band in a wide wavelength range. With an increase in the Au nominal thickness a transition occurs from transducers dominated by absorbance to ones dominated by scattering. Numerical simulations taking into account the shape and size distribution in actual island samples are in agreement with the experimental spectra. Refractive index sensitivity (RIS) measurements at a constant wavelength or at a constant extinction, tailored to the specific transducer, provide superior sensitivity to refractive index change, up to ca. 600 nm RIU À1 in wavelength shift.
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