Developmental, cellular and biochemical basis of transparency in clearwing butterflies.

The wings of butterflies and moths (Lepidoptera) are typically covered with thousands of flat, overlapping scales that endow the wings with colorful patterns. Yet, numerous species of Lepidoptera have evolved highly transparent wings, which often possess scales of altered morphology and reduced size, and the presence of membrane surface nanostructures that dramatically reduce reflection. Optical properties and anti-reflective nanostructures have been characterized for several 'clearwing' Lepidoptera, but the developmental processes underlying wing transparency are unknown. Here, we applied confocal and electron microscopy to create a developmental time series in the glasswing butterfly, Greta oto, comparing transparent and non-transparent wing regions. We found that during early wing development, scale precursor cell density was reduced in transparent regions, and cytoskeletal organization during scale growth differed between thin, bristle-like scale morphologies within transparent regions and flat, round scale morphologies within opaque regions. We also show that nanostructures on the wing membrane surface are composed of two layers: a lower layer of regularly arranged nipple-like nanostructures, and an upper layer of irregularly arranged wax-based nanopillars composed predominantly of long-chain n-alkanes. By chemically removing wax-based nanopillars, along with optical spectroscopy and analytical simulations, we demonstrate their role in generating anti-reflective properties. These findings provide insight into morphogenesis and composition of naturally organized microstructures and nanostructures, and may provide bioinspiration for new anti-reflective materials.

Phase-Separated Nanophotonic Structures by Inkjet Printing.

The spontaneous phase separation of two or more polymers is a thermodynamic process that can take place in both biological and synthetic materials and which results in the structuring of the matter from the micro- to the nanoscale. For photonic applications, it allows forming quasi-periodic or disordered assemblies of light scatterers at high throughput and low cost. The wet process methods currently used to fabricate phase-separated nanostructures (PSNs) limit the design possibilities, which in turn hinders the deployment of PSNs in commercialized products. To tackle this shortcoming, we introduce a versatile and industrially scalable deposition method based on the inkjet printing of a polymer blend, leading to PSNs with a feature size that is tuned from a few micrometers down to sub-100 nm. Consequently, PSNs can be rapidly processed into the desired macroscopic design. We demonstrate that these printed PSNs can improve light management in manifold photonic applications, exemplified here by exploiting them as a light extraction layer and a metasurface for light-emitting devices and point-of-care biosensors, respectively.

Processing Effects on the Self-Assembly of Brush Block Polymer Photonic Crystals.

The self-assembly of poly(dimethylsiloxane)-b-poly(trimethylene carbonate) (PDMS-b-PTMC) bottlebrush block polymers was investigated under different processing conditions. Small-angle X-ray scattering (SAXS) and UV/Visible spectroscopy provided insight into the self-assembly and structure in response to heating and applied pressure. In the absence of applied pressure (i.e., before annealing), the PDMS-b-PTMC bottlebrush block polymers are white solids and adopt small, randomly oriented lamellar grains. Heating the materials to 140 °C in the absence of applied pressure appears to "lock in" the isotropic, short-range-ordered state, preventing the formation of the long-range-ordered lamellar structure responsible for photonic properties. Applying modest anisotropic pressure (3 psi) between parallel plates at ambient temperature orients the short-range lamellar grains; however, applied pressure alone does not produce long-range order. Only when the bottlebrush block polymers were heated (>100 °C) under modest pressure (3 psi) were long-range-ordered photonic crystals formed. Analysis of the SAXS data motivated analogies to liquid crystals and revealed the potential self-assembly pathway. These results provide insight into the structure and self-assembly of bottlebrush block polymers with low glass transition temperature side chains in response to different processing conditions.

Overcoming evanescent field decay using 3D-tapered nanocavities for on-chip targeted molecular analysis.

Enhancement of optical emission on plasmonic nanostructures is intrinsically limited by the distance between the emitter and nanostructure surface, owing to a tightly-confined and exponentially-decaying electromagnetic field. This fundamental limitation prevents efficient application of plasmonic fluorescence enhancement for diversely-sized molecular assemblies. We demonstrate a three-dimensionally-tapered gap plasmon nanocavity that overcomes this fundamental limitation through near-homogeneous yet powerful volumetric confinement of electromagnetic field inside an open-access nanotip. The 3D-tapered device provides fluorescence enhancement factors close to 2200 uniformly for various molecular assemblies ranging from few angstroms to 20 nanometers in size. Furthermore, our nanostructure allows detection of low concentration (10 pM) biomarkers as well as specific capture of single antibody molecules at the nanocavity tip for high resolution molecular binding analysis. Overcoming molecule position-derived large variations in plasmonic enhancement can propel widespread application of this technique for sensitive detection and analysis of complex molecular assemblies at or near single molecule resolution.

Glucose Sensing Using Surface-Enhanced Raman-Mode Constraining.

Diabetes mellitus is a chronic disease, and its management focuses on monitoring and lowering a patient's glucose level to prevent further complications. By tracking the glucose-induced shift in the surface-enhanced Raman-scattering (SERS) emission of mercaptophenylboronic acid (MPBA), we have demonstrated fast and continuous glucose sensing in the physiologically relevant range from 0.1 to 30 mM and verified the underlying mechanism using numerical simulations. Bonding of glucose to MPBA suppresses the "breathing" mode of MPBA at 1071 cm-1 and energizes the constrained-bending mode at 1084 cm-1, causing the dominant peak to shift from 1071 to 1084 cm-1. MPBA-glucose bonding is also reversible, allowing continuous tracking of ambient glucose concentrations, and the MPBA-coated substrates showed very stable performance over a 30 day period, making the approach promising for long-term continuous glucose monitoring. Using Raman-mode-constrained, miniaturized SERS implants, we also successfully demonstrated intraocular glucose measurements in six ex vivo rabbit eyes within ±0.5 mM of readings obtained using a commercial glucose sensor.

Bioinspired phase-separated disordered nanostructures for thin photovoltaic absorbers.

The wings of the black butterfly, Pachliopta aristolochiae, are covered by micro- and nanostructured scales that harvest sunlight over a wide spectral and angular range. Considering that these properties are particularly attractive for photovoltaic applications, we analyze the contribution of these micro- and nanostructures, focusing on the structural disorder observed in the wing scales. In addition to microspectroscopy experiments, we conduct three-dimensional optical simulations of the exact scale structure. On the basis of these results, we design nanostructured thin photovoltaic absorbers of disordered nanoholes, which combine efficient light in-coupling and light-trapping properties together with a high angular robustness. Finally, inspired by the phase separation mechanism of self-assembled biophotonic nanostructures, we fabricate these bioinspired absorbers using a scalable, self-assembly patterning technique based on the phase separation of binary polymer mixture. The nanopatterned absorbers achieve a relative integrated absorption increase of 90% at a normal incident angle of light to as high as 200% at large incident angles, demonstrating the potential of black butterfly structures for light-harvesting purposes in thin-film solar cells.