The chiral structure of porous chitin within the wing-scales of Callophrys rubi

Schröder‐Turk, Gerd E.; Wickham, Shelley F. J.; Averdunk, Holger; Brink, F.; Gerald, John Fitz; Poladian, L.; Large, M. I.; Hyde, Stephen T.

doi:10.1016/j.jsb.2011.01.004

Cited by 135 publications

(105 citation statements)

References 39 publications

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“…For all investigated crystallites, the chitin volume fraction ranges from 0. 28 Table S1), which is agreement with values mentioned in the literature (8,21).…”

Section: Resultssupporting

confidence: 90%

“…Here, we investigate the chiral symmetry breaking of the singlegyroid structure, a complex network-like ordered nanostructure observed in the wing scales of various butterfly species, including Callophrys rubi (6)(7)(8)(9), and other arthropod species (10). The gyroid geometry, which serves as biophotonic crystals, has cubic symmetry (I4 1 32) and is characterized by the topologically particularly simple srs-net (the label for the chiral degree-three network modeled on SrSi2) (11).…”

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confidence: 99%

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Coexistence of both gyroid chiralities in individual butterfly wing scales of Callophrys rubi

Winter

Butz

Dieker

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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The wing scales of the Green Hairstreak butterfly Callophrys rubi consist of crystalline domains with sizes of a few micrometers, which exhibit a congenitally handed porous chitin microstructure identified as the chiral triply periodic single-gyroid structure. Here, the chirality and crystallographic texture of these domains are investigated by means of electron tomography. The tomograms unambiguously reveal the coexistence of the two enantiomeric forms of opposite handedness: the left-and right-handed gyroids. These two enantiomers appear with nonequal probabilities, implying that molecularly chiral constituents of the biological formation process presumably invoke a chiral symmetry break, resulting in a preferred enantiomeric form of the gyroid structure. Assuming validity of the formation model proposed by Ghiradella H (1989) J Morphol 202(1): 69-88 and Saranathan V, et al. (2010) Proc Natl Acad Sci USA 107(26):11676-11681, where the two enantiomeric labyrinthine domains of the gyroid are connected to the extracellular and intra-SER spaces, our findings imply that the structural chirality of the single gyroid is, however, not caused by the molecular chirality of chitin. Furthermore, the wing scales are found to be highly textured, with a substantial fraction of domains exhibiting the <001> directions of the gyroid crystal aligned parallel to the scale surface normal. Both findings are needed to completely understand the photonic purpose of the single gyroid in gyroid-forming butterflies. More importantly, they show the level of control that morphogenesis exerts over secondary features of biological nanostructures, such as chirality or crystallographic texture, providing inspiration for biomimetic replication strategies for synthetic self-assembly mechanisms.electron tomography | chirality | crystallographic texture | photonic crystal | butterfly wing scales A lthough the formation of chiral structures is fascinating, their occurrence can often be rationalized by simple energy or free energy considerations without a need to resort to their possible biological origin. For example, handed structures are observed in the simplest models of phyllotaxis (1) and self-assembly of biological fibers (2). In such models, there is no energetic distinction between and hence, a balance of the two enantiomers [that is, the right-handed (RH) and left-handed (LH) versions of the chiral structure]. Chiral symmetry breaking, the process by which one enantiomer occurs exclusively or with prevalence, is commonly observed in biological materials on a range of scales from molecular dimensions and the structure of DNA to the macroscopic size of snails (3). The dominance of one enantiomer is driven by the presence of a force or molecular building block that favors one enantiomer over the other; constituent chiral molecules (4), genetically controlled molecular pathways (3), and biological generation of torque (5) are possible causes.Here, we investigate the chiral symmetry breaking of the singlegyroid structure, a complex network-lik...

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“…For all investigated crystallites, the chitin volume fraction ranges from 0. 28 Table S1), which is agreement with values mentioned in the literature (8,21).…”

Section: Resultssupporting

confidence: 90%

mentioning

confidence: 99%

Coexistence of both gyroid chiralities in individual butterfly wing scales of Callophrys rubi

Winter

Butz

Dieker

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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“…[28][29][30][31][32][33][34] The gyroid-structured scales stack in a tiled manner on the ventral wings of C. rubi. Randomly oriented domains exist inside the scales, as shown in the optical image of a single gyroid scale ( Figure 2a) and also demonstrated in the SEM and TEM images (Figures 2b-d).…”

Section: Resultsmentioning

confidence: 99%

Highly sensitive, reproducible and uniform SERS substrates with a high density of three-dimensionally distributed hotspots: gyroid-structured Au periodic metallic materials

Wang

Zhang

et al. 2018

NPG Asia Mater

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Surface-enhanced Raman spectroscopy (SERS) is an important tool for the analytical, trace detection of many inorganic and organic materials, especially for materials involved in medical care, food safety and environmental pollution. Numerous efforts have been dedicated to exploring periodic metallic materials with a high density of hotspots. However, for most periodic metallic materials fabricated by top-down and bottom-up approaches, the distribution of hotspots is restricted to one or two dimensions. Here, for the first time, we report the successful fabrication of a bio-inspired bicontinuous gyroid-structured Au SERS substrate with a high density of three-dimensionally (3D) distributed hotspots. The as-required gyroid-structured substrates were demonstrated to be highly sensitive, reproducible and uniform, with an enhancement factor of up to 10 9 . Finite-difference time domain (FDTD) simulations were conducted to reveal the mechanism leading to the high enhancement and we found that the interconnected helices in the gyroid structure not only increase the hotspot density but also contribute to increasing the scattering cross-section of the incident laser. The substrate was then adopted for the SERS detection of bis(2-ethylhexyl) phthalate, the most frequently used plasticizer in food, paints, house-hold items, perfumes and so on, and reached a detection limit of 1 fM, which is among the best results ever reported. Moreover, the mechanism deduced here will provide insight into the future design and selection of novel surface plasmonic resonance substrates, as many other bicontinuous interconnected systems are available. NPG Asia Materials (2018) 10, e462; doi:10.1038/am.2017.230; published online 12 January 2018 INTRODUCTIONThe fabrication of surface plasmonic resonance (SPR) materials with ultra-high plasmonic enhancement has long been a critical research area due to their broad applications as chemical sensors, biological sensors, plasmonic solar cells, photocatalysts and other environmentally friendly devices. 1-3 Among these applications, the most famous is the surface-enhanced Raman spectroscopy (SERS) detection of trace analytes, especially for analytes involved in medical care, food safety and environmental pollution. Various nanoparticle systems with novel nanomorphologies and their assemblies have been fabricated and reported to show excellent SPR performance. 2-5 However, SERS nanostructures composed of nanoparticles face significant challenges in achieving a reproducible and uniform Raman response due to the difficulty in fabricating uniform SERS active sites. Periodic metallic materials could provide hotspots with high density, reproducibility and uniformity, which completely meet the requirement of valid SERS substrates, and therefore numerous efforts have been dedicated to engineering periodic metallic materials with novel nanomorphologies,

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“…There may be other possible structures causing the polarization phenomena. This includes molecular chirality like in liquid crystals and chiral photonic crystals as has been observed in beetles as well as in butterflies [3,14,15].…”

Section: MMmentioning

confidence: 98%

Cuticle structure of the scarab beetle Cetonia aurata analyzed by regression analysis of Mueller-matrix ellipsometric data

Arwin¹,

Berlind²,

Johs³

et al. 2013

Opt. Express

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Abstract:Since one hundred years it is known that some scarab beetles reflect elliptically and near-circular polarized light as demonstrated by Michelson for the beetle Chrysina resplendens. The handedness of the polarization is in a majority of cases left-handed but also right-handed polarization has been found. In addition, brilliant colors with metallic shine are observed. The polarization and color effects are generated in the beetle exoskeleton, the so-called cuticle. The objective of this work is to demonstrate that structural parameters and materials optical functions of these photonic structures can be extracted by advanced modeling of spectral multi-angle Mueller-matrix data recorded from beetle cuticles. A dual-rotating compensator ellipsometer is used to record normalized Mueller-matrix data in the spectral range 400 -800 nm at angles of incidence in the range 25-75 • . Analysis of data measured on the scarab beetle Cetonia aurata are presented in detail. The model used in the analysis mimics a chiral nanostructure and is based on a twisted layered structure. Given the complexity of the nanostructure, an excellent fit between experimental and model data is achieved. The obtained model parameters are the spectral variation of the refractive indices of the cuticle layers and structural parameters of the chiral structure.

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The chiral structure of porous chitin within the wing-scales of Callophrys rubi

Cited by 135 publications

References 39 publications

Coexistence of both gyroid chiralities in individual butterfly wing scales of Callophrys rubi

Coexistence of both gyroid chiralities in individual butterfly wing scales of Callophrys rubi

Highly sensitive, reproducible and uniform SERS substrates with a high density of three-dimensionally distributed hotspots: gyroid-structured Au periodic metallic materials

Cuticle structure of the scarab beetle Cetonia aurata analyzed by regression analysis of Mueller-matrix ellipsometric data

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