Structural characterization of biologically formed materials is essential for understanding biological phenomena and their enviro-nment, and for generating new bio-inspired engineering concepts. For example, nacre—the inner lining of some mollusk shells—encodes local environmental conditions throughout its formation and has exceptional strength due to its nanoscale brick-and-mortar structure. This layered structure, comprising alternating transparent aragonite (CaCO3) tablets and thinner organic polymer layers, also results in stunning interference colors. Existing methods of structural characterization of nacre rely on some form of cross-sectional analysis, such as scanning or transmission electron microscopy or polarization-dependent imaging contrast (PIC) mapping. However, these techniques are destructive and too time- and resource-intensive to analyze large sample areas. Here, we present an all-optical, rapid, and nondestructive imaging technique—hyperspectral interference tomography (HIT)—to spatially map the structural parameters of nacre and other disordered layered materials. We combined hyperspectral imaging with optical-interference modeling to infer the mean tablet thickness and its disorder in nacre across entire mollusk shells from red and rainbow abalone (Haliotis rufescens and Haliotis iris) at various stages of development. We observed that in red abalone, unexpectedly, nacre tablet thickness decreases with age of the mollusk, despite roughly similar appearance of nacre at all ages and positions in the shell. Our rapid, inexpensive, and nondestructive method can be readily applied to in-field studies.Complex optical phenomena can emerge from a variety of biological or bio-inspired processes, from arrays of colors in peacocks (1) and other birds (2), butterflies (3), and opals (4), to the metal-like sheen of herring (5) and unique polarization-dependent properties of jewel beetles (6) and Pollia fruit (7). Nacre, or mother-of-pearl, is a prominent biologically formed mineral structure found throughout our oceans. It lines the inside of the shells formed by many mollusks, including bivalves, cephalopods, and gastropods. It features brilliant iridescent colors (Fig. 1) and is studied and emulated in part because of its outstanding mechanical performance (8, 9). The striking, colorful appearance of nacre has been a source of scientific curiosity since the days of Brewster (10), Rayleigh (11), and Raman (12, 13), and is the product of optical interference resulting from multiple interface reflections as light propagates through its stratified structure comprising stacks of transparent polygonal aragonite tablets (CaCO3) interspersed with organic polymer (chitin and proteins) layers (14–16) (Fig. 1A). Nacre is one of seven mollusk shell structures (17). In the nacre structure, the aragonite tablets are typically 5 to 10 μm in diameter and hundreds of nanometers thick [200 to 1,100 nm across all shells, and 250 to 500 nm in red abalone (18)], while the organic sheets are an order of magnitude thinner (14, 16, 19). In columnar nacre formed by gastropods like abalone and snails (Fig. 1), co-oriented tablets are stacked on top of one another, while in sheet nacre formed by bivalves like pearl oysters and pen shells, co-oriented tablets are staggered diagonally (18) (see Movie S1 for an animation showing how co-oriented tablets are stacked in columnar nacre). Despite the significant structural and formation–mechanism differences, the thicknesses of tablets and organic layers are similar in columnar and sheet nacre, and so are the optical and mechanical behavior (20). The resulting palette of colors is primarily dependent on the nacre tablet thickness and the viewing angle, and the optical response that yields these colors can be understood as that of a Bragg reflector (21) with disorder in the layer thicknesses, where the optical band gaps are determined by the thicknesses of the transparent layers (5, 22, 23). Thus, the spectrum of light reflected from a nacre surface encodes information about its physical structure (Fig. 1 B–D).Open in a separate windowFig. 1.(A) Nacre, the colorful iridescent inner lining of some mollusk shells. Here, the red abalone, or H. rufescens, shell features columnar nacre, which comprises thousands of layers of polygonal aragonite tablets interspersed with organic sheets. (B) A close-up photograph of the nacre surface shows a variety of colors and nonuniformities. (C and D) Given a broadband white light source illuminating nacre at a fixed angle of incidence, variations in color are observed due to the difference in average thickness of aragonite tablets comprising nacre. (E) Hyperspectral interference tomography (HIT) setup: A hyperspectral camera collects predominantly specular reflectance data across a sample illuminated by a collimated source at a fixed angle of incidence from the normal to the sample . The reflected light is polarized using a wire-grid polarizer. (F) A color photograph of a region of nacre that was analyzed. (G) Map of the mean tablet thickness (MTT) obtained using HIT, overlaid on a grayscale rendering of the photograph in F. Highlighted in red is a 5 × 5-mm region used to analyze the ontogeny of nacre in Fig. 4. The region around this area was masked off using opaque tape, which is highlighted with the dashed white box.Understanding and characterizing the structure of nacre and other biomaterials have deep and surprising implications. For example, the average thickness of the tablets comprising ancient nacre can be used as a proxy for local ocean temperatures at the time of nacre formation, enabling paleoclimatology spanning hundreds of millions of years (18, 24, 25). The structure of nacre is also an inspiration for engineered materials thousands of times stronger than the constituent materials (15, 26, 27). To that end, new techniques have been developed to probe and understand the structure of nacre, such as polarization-dependent imaging contrast (PIC) mapping using X-ray absorption near-edge structure spectroscopy combined with photoemission electron spectromicroscopy (18, 28, 29), or X-ray nanotomography (30). However, these characterization techniques such as cross-sectional electron microscopy result in the destruction of the sample and are time-consuming and costly.Here, we present a method for rapid, nondestructive, and large-scale structural characterization of disordered and nonuniform stratified thin-film materials and apply it to the analysis of nacre. Our all-optical method employs hyperspectral imaging combined with thin-film modeling to extract nacre mean tablet thicknesses (MTTs) and tablet degree of disorder —defined as the standard deviation of the thicknesses—across large areas (Fig. 1 E–G). This characterization method is designated as hyperspectral interference tomography (HIT). We used HIT to map the structure of mollusk shell nacre across many stages of development and identified a previously unexplored relationship between the age of the organism and the structure of the nacre layer. We investigated two particular species of nacre-forming mollusks, Haliotis rufescens (red abalone) and Haliotis iris (paua, or rainbow abalone; data only in SI Appendix), for which the aragonite tablet thicknesses lie within a range of 250 to 500 nm (18, 31); however, the method is applicable to any other transparent layered structure of animal, plant, geologic, or synthetic origin. 相似文献
Burn wound care today has a primary objective of temporary or permanent wound closure. Commercially available engineered alternative tissues have become a valuable adjunct to the treatment of burn injuries. Their constituents can be biological, alloplastic or a combination of both. Here the authors describe the aspects of the development of a siloxane epidermis for a collagen‐glycosaminoglycan and for nylon‐based artificial skin replacement products. A method to fabricate an ultra‐thin epidermal equivalent is described. Pores, to allow the escape of wound exudate, were punched and a tri‐filament nylon mesh or collagen scaffold was imbedded and silicone polymerisation followed at 120°C for 5 minutes. The ultra‐structure of these bilaminates was assessed through scanning electron microscopy. An ultra‐thin biomedical grade siloxane film was reliably created through precision coating on a pre‐treated polyethylene terephthalate carrier. 相似文献
A fused aromatic furan‐substituted diketopyrrolopyrrole and novel diphenylfumaronitrile conjugated building blocks are used for the synthesis of an alternating copolymer ( DPFN‐DPPF ) via Suzuki polycondensation. In this paper, the first attempt to use the diphenylfumaronitrile building block for the synthesis of conjugated polymer is described. The number‐average and weight‐average molecular weights calculated for DPFN‐DPPF are 20 661 and 66 346 g mol?1, respectively. The optical bandgap calculated for DPFN‐DPPF is 1.53 eV whereas the highest occupied molecular orbital (HOMO) value calculated by photoelectron spectroscopy in air (PESA) is 5.50 eV. The calculated HOMO value is lower, which is suitable for stable organic electronic devices. DPFN‐DPPF polymer is used as an active layer in bottom‐contact bottom‐gate organic thin‐film transistor devices and the thin film exhibits a hole mobility of 0.20 cm2 V?1 s?1 in air.
Nanostructured diamond (NSD) films were grown on silicon and Ti–6Al–4V alloy substrates by microwave plasma chemical vapor deposition (MPCVD). NSD Growth rates of 5 μm/h on silicon, and 4 μm/h on Ti–6Al–4V were achieved. In a chemistry of H2/CH4/N2, varying ratios of CH4/H2 and N2/CH4 were employed in this research and their effect on the resulting diamond films were studied by X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. As a result of modifying the stock cooling stage of CVD system, we were able to utilize plasma with high power densities in our NSD growth experiments, enabling us to achieve high growth rates. Substrate temperature and N2/CH4 ratio have been found to be key factors in determining the diamond film quality. NSD films grown as part of this study were shown to contain 85% to 90% sp3 bonded carbon. 相似文献