Circular Dichroism in Biological Photonic Crystals and Cubic Chiral Nets

Saba, Matthias; Thiel, Michael; Turner, Mark D.; Hyde, Stephen T.; Gu, Miṅ; Große-Brauckmann, Karsten; Neshev, Dragomir N.; Mecke, Klaus; Schröder‐Turk, Gerd E.

doi:10.1103/physrevlett.106.103902

Cited by 145 publications

(169 citation statements)

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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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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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“…1D). The network exhibiting an LH screw along <111> is defined as LH srs-network, and the one with an RH screw along <111> is named RH srs-net (13,22). All reconstructed crystallites contain several unit cells of the expected cubic gyroid structure, from which the chirality of each crystallite is determined.…”

Section: Resultsmentioning

confidence: 99%

“…The single-gyroid material (of a given fixed handedness) has been clearly shown to discriminate between LH and RH circular polarized light (13,14,38,41,42). Given the prevalence of the LH enantiomer of the single gyroid and the frequent occurrence of the <001> inclination [being the sole direction with strong circular dichroism (12,23)], the wing scales of C. rubi fulfill the prerequisites for the existence of an optical circular polarization signal.…”

Section: Discussionmentioning

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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“…The presence of diamond-type photonic crystals in weevil scales may have distinct evolutionary advantages that can range from differences in reflectance properties to enhancement of mating chances [5]. Light reflected by gyroid photonic crystals can be highly polarized [28], whereas diamond photonic crystals show hardly any polarization dependency (figure 3; [10,22,26]). Whether or not, this difference in polarization properties has a biological function has yet to be investigated.…”

Section: Discussion (A) Biophotonic Structures In Weevils and Beetlesmentioning

confidence: 99%

Brilliant camouflage : photonic crystals in the diamond weevil, Entimus imperialis

et al. 2012

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The neotropical diamond weevil, Entimus imperialis, is marked by rows of brilliant spots on the overall black elytra. The spots are concave pits with intricate patterns of structural-coloured scales, consisting of large domains of three-dimensional photonic crystals that have a diamond-type structure. Reflectance spectra measured from individual scale domains perfectly match model spectra, calculated with anatomical data and finite-difference time-domain methods. The reflections of single domains are extremely directional (observed with a point source less than 58), but the special arrangement of the scales in the concave pits significantly broadens the angular distribution of the reflections. The resulting virtually angle-independent green coloration of the weevil closely approximates the colour of a foliaceous background. While the closedistance colourful shininess of E. imperialis may facilitate intersexual recognition, the diffuse green reflectance of the elytra when seen at long-distance provides cryptic camouflage.

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Circular Dichroism in Biological Photonic Crystals and Cubic Chiral Nets

Cited by 145 publications

References 32 publications

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

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

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

Brilliant camouflage : photonic crystals in the diamond weevil, Entimus imperialis

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