Evolutionary pressure has pushed many extant species to develop micro/nanostructures that can significantly affect wettability and enable functionalities such as droplet jumping, self-cleaning, antifogging, antimicrobial, and antireflectivity. In particular, significant effort is underway to understand the insect wing surface structure to establish rational design tools for the development of novel engineered materials. Most studies, however, have focused on superhydrophobic wings obtained from a single insect species, in particular, the Psaltoda claripennis cicada. Here, we investigate the relationship between the spatially dependent wing wettability, topology, and droplet jumping behavior of multiple cicada species and their habitat, lifecycle, and interspecies relatedness. We focus on cicada wings of four different species: Neotibicen pruinosus, N. tibicen, Megatibicen dorsatus, and Magicicada septendecim and take a comparative approach. Using spatially resolved microgoniometry, scanning electron microscopy, atomic force microscopy, and high speed optical microscopy, we show that within cicada species, the wettability of wings is spatially homogeneous across wing cells. All four species were shown to have truncated conical pillars with widely varying length scales ranging from 50 to 400 nm in height. Comparison of the wettability revealed three cicada species with wings that are superhydrophobic (>150°) with low contact angle hysteresis (<5°), resulting in stable droplet jumping behavior. The fourth, more distantly related species (Ma. septendecim) showed only moderate hydrophobic behavior, eliminating some of the beneficial surface functional aspects for this cicada. Correlation between cicada habitat and wing wettability yielded little connection as wetter, swampy environments do not necessarily equate to higher measured wing hydrophobicity. The results, however, do point to species relatedness and reproductive strategy as a closer proxy for predicting wettability and surface structure and resultant enhanced wing surface functionality. This work not only elucidates the differences between inter- and intraspecies cicada wing topology, wettability, and water shedding behavior but also enables the development of rational design tools for the manufacture of artificial surfaces for energy and water applications.
Numerous natural surfaces have micro/nanostructures that result in extraordinary functionality, such as superhydrophobicity, self‐cleaning, antifogging, and antimicrobial properties. One such example is the cicada wing, where differences in nanopillar geometry and composition among species can impact and influence the degree of exhibited properties. To understand the relationships between surface topography and chemical composition with multifunctionality, the wing properties of Neotibicen pruinosus (superhydrophobic) and Magicicada cassinii (hydrophobic) cicadas are investigated at time points after microwave‐assisted extraction of surface molecules to characterize the chemical contribution to nanopillar functionality. Electron microscopy of the wings throughout the extraction process illustrates nanoscale topographical changes, while concomitant changes in hydrophobicity, bacterial fouling, and bactericidal properties are also measured. Extract analysis reveals the major components of the nanostructures to be fatty acids and saturated hydrocarbons ranging from C17 to C44. Effects on the antimicrobial character of a wing surface with respect to the extracted chemicals suggest that the molecular composition of the nanopillars plays both a direct and an indirect role in concert with nanopillar geometry. The data presented not only correlates the nanopillar molecular organization to macroscale functional properties, but it also presents design guidelines to consider during the replication of natural nanostructures onto engineered substrates to induce desired properties.
Biofouling disrupts the surface functionality and integrity of engineered substrates. A variety of natural materials such as plant leaves and insect wings have evolved sophisticated physical mechanisms capable of preventing biofouling. Over the past decade, several reports have pinpointed nanoscale surface topography as an important regulator of surface adhesion and growth of bacteria. Although artificial nanoengineered features have been used to create bactericidal materials that kill adhered bacteria, functional surfaces capable of synergistically providing antiadhesion and bactericidal properties remain to be developed. Furthermore, fundamental questions pertaining to the need for intrinsic hydrophobicity to achieve bactericidal performance and the role of structure length scale (nano vs micro) are still being explored. Here, we demonstrate highly scalable, cost-effective, and efficient nanoengineered multifunctional surfaces that possess both antiadhesion and bactericidal properties on industrially relevant copper (Cu) and aluminum (Al) substrates. We characterize antiadhesion and bactericidal performance using a combination of scanning electron microscopy (SEM), atomic force microscopy (AFM), live/dead bacterial staining and imaging, as well as solution-phase and Petrifilm measurements of bacterial viability. Our results showed that nanostructures created on both Cu and Al were capable of physical deformation of adhered Escherichia coli bacteria. Bacterial viability measurements on both Cu and Al indicated a complex interaction between the antiadhesion and bactericidal nature of these materials and their surface topography, chemistry, and structure. Increased superhydrophobicity greatly decreased bacterial adhesion while not significantly influencing surface bactericidal performance. Furthermore, we observed that more densely packed nanoscale structures improved antiadhesion properties when compared to larger features, even over extended time scales of up to 24 h. Our data suggests that the superhydrophobic Al substrate possesses superior antiadhesion and bactericidal effects, even over long time courses. The techniques and insights presented here will inform future work on antiadhesion and bactericidal multifunctional surfaces and enable their rational design.
We demonstrate a novel nanofluidic diode that produces rectification factors in excess of 1000. The nanofluidic diode consists of ion permselective nanopores that connect two reservoirs of different diameters- a micropore reservoir and a macropore reservoir. On the application of +100 V to the micropore, a low OFF state current is observed. The OFF state is caused by formation of the ion depleted zone in the micropore because the anions are prevented from entering the nanopores from the micropore and the cations are depleted in this region to maintain charge neutrality. On the application of −100 V, we observe a high ON state current. The ON state is caused by formation of the ion enriched zone in the microchannel because the anions cannot pass through the nanopores and accumulate in the microchannel. To maintain charge neutrality the cations also become enriched in the microchannel. The ratio of ON state current to the OFF state current gives the rectification of current. Here, plasma oxidation is used to achieve a nanopore with a large wall surface charge density of σn = −55 mC/m2 which yields a rectification of current on the order of 3500 that is nearly two orders of magnitude higher than those reported thus far. In contrast to the other nanofluidic diodes, this nanofluidic diode does not introduce asymmetry to the nanopore, but asymmetry is produced by having the nanopores join a micropore and a macropore. Introduction of asymmetry into the fluidic reservoirs which the nanopores connect is quite simple. Hence, the nanofluidic diode is easy to scale up to industrial level.
Laser-ablation electrospray ionization (LAESI) imaging mass spectrometry (IMS) is an emerging bioanalytical tool for direct imaging and analysis of biological tissues. Performing ionization in an ambient environment, this technique requires little sample preparation and no additional matrix, and can be performed on natural, uneven surfaces. When combined with optical microscopy, the investigation of biological samples by LAESI allows for spatially resolved compositional analysis. We demonstrate here the applicability of LAESI-IMS for the chemical analysis of thin, desiccated biological samples, specifically Neotibicen pruinosus cicada wings. Positive-ion LAESI-IMS accurate ion-map data was acquired from several wing cells and superimposed onto optical images allowing for compositional comparisons across areas of the wing. Various putative chemical identifications were made indicating the presence of hydrocarbons, lipids/esters, amines/amides, and sulfonated/phosphorylated compounds. With the spatial resolution capability, surprising chemical distribution patterns were observed across the cicada wing, which may assist in correlating trends in surface properties with chemical distribution. Observed ions were either (1) equally dispersed across the wing, (2) more concentrated closer to the body of the insect (proximal end), or (3) more concentrated toward the tip of the wing (distal end). These findings demonstrate LAESI-IMS as a tool for the acquisition of spatially resolved chemical information from fragile, dried insect wings. This LAESI-IMS technique has important implications for the study of functional biomaterials, where understanding the correlation between chemical composition, physical structure, and biological function is critical. Graphical abstract Positive-ion laser-ablation electrospray ionization mass spectrometry coupled with optical imaging provides a powerful tool for the spatially resolved chemical analysis of cicada wings.
Nanoimprinting lithography (NIL) is a nextgeneration nanofabrication method, capable of replicating nanostructures from original master surfaces. Here, we develop highly scalable, simple, and nondestructive NIL using a dissolvable template. Termed dissolvable template nanoimprinting lithography (DT-NIL), our method utilizes an economic thermoplastic resin to fabricate nanoimprinting templates, which can be easily dissolved in simple organic solvents. We used the DT-NIL method to replicate cicada wings which have surface nanofeatures of ∼100 nm in height. The master, template, and replica surfaces showed a >∼94% similarity based on the measured diameter and height of the nanofeatures. The versatility of DT-NIL was also demonstrated with the replication of re-entrant, multiscale, and hierarchical features on fly wings, as well as hard silicon wafer-based artificial nanostructures. The DT-NIL method can be performed under ambient conditions with inexpensive materials and equipment. Our work opens the door to opportunities for economical and highthroughput nanofabrication processes.
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