RESUMO
Biological photonic nanoarchitectures are capable of rapidly and chemically selectively sensing volatile organic compounds due to changing color when exposed to such vapors. Here, stability and the vapor sensing properties of butterfly and moth wings were investigated by optical spectroscopy in the presence of water vapor. It was shown that repeated 30 s vapor exposures over 50 min did not change the resulting optical response signal in a time-dependent manner, and after 5-min exposures the sensor preserved its initial properties. Time-dependent response signals were shown to be species-specific, and by using five test substances they were also shown to be substance-specific. The latter was also evaluated using principal component analysis, which showed that the time-dependent optical responses can be used for real-time analysis of the vapors. It was demonstrated that the capability to detect volatile organic compounds was preserved in the presence of water vapor: high-intensity color change signals with short response times were measured in 25% relative humidity, similar to the one-component case; therefore, our results can contribute to the development of biological photonic nanoarchitecture-based vapor detectors for real-world applications, like living and working environments.
Assuntos
Borboletas , Gases , Umidade , Mariposas , Asas de Animais/fisiologia , Animais , Óptica e FotônicaRESUMO
Photonic nanoarchitectures in the wing scales of butterflies and moths are capable of fast and chemically selective vapor sensing due to changing color when volatile vapors are introduced to the surrounding atmosphere. This process is based on the capillary condensation of the vapors, which results in the conformal change of the chitin-air nanoarchitectures and leads to a vapor-specific optical response. Here, we investigated the optical responses of the wing scales of several butterfly and moth species when mixtures of different volatile vapors were applied to the surrounding atmosphere. We found that the optical responses for the different vapor mixtures fell between the optical responses of the two pure solvents in all the investigated specimens. The detailed evaluation, using principal component analysis, showed that the butterfly-wing-based sensor material is capable of differentiating between vapor mixtures as the structural color response was found to be characteristic for each of them.
Assuntos
Borboletas , Mariposas , Compostos Orgânicos Voláteis , Asas de Animais/química , Asas de Animais/fisiologia , Ácido Acético/análise , Ácido Acético/química , Animais , Borboletas/fisiologia , Etanol , Masculino , Mariposas/fisiologia , Óptica e Fotônica , Pigmentação , Análise de Componente Principal , Espectrofotometria/instrumentação , Compostos Orgânicos Voláteis/análise , Compostos Orgânicos Voláteis/química , Asas de Animais/anatomia & histologiaRESUMO
The butterfly Mimeresia neavei (Joicey & Talbot, 1921) is the only species in the exclusively African subtribal clade Mimacraeina (Lipteninae: Lycaenidae: Lepidoptera) having sexual dimorphism expressed by structurally blue-colored male and pigmentary colored orange-red female phenotypes. We investigated the optical mechanism generating the male blue color by various microscopic and experimental methods. It was found that the blue color is produced by the lower lamina of the scale acting as a thin film. This kind of color production is not rare in day-flying Lepidoptera, or in other insect orders. The biological role of the blue color of M. neavei is not yet well understood, as all the other species in the clade lack structural coloration, and have less pronounced sexual dimorphism, and are involved in mimicry-rings.
Assuntos
Borboletas/ultraestrutura , Pigmentação , Asas de Animais/ultraestrutura , Animais , Feminino , Masculino , Fenômenos ÓpticosRESUMO
Fast, chemically-selective sensing of vapors using an optical readout can be achieved with the photonic nanoarchitectures occurring in the wing scales of butterflies possessing structural color. These nanoarchitectures are built of chitin and air. The Albulina metallica butterfly is remarkable as both the dorsal (blue) and ventral (gold-green) cover scales are colored by the same type (pepper-pot) of photonic nanoarchitecture, exhibiting only a short-range order. The vapors of ten different volatiles were tested for sensing on whole wing pieces and some of the volatiles were tested on single scales as well, both in reflected and transmitted light. Chemically-selective responses were obtained showing that selectivity can be increased by using arrays of sensors. The sensing behavior is similar in single scales and on whole wing pieces, and is similar in reflected and transmitted light. By immersing single scales in an index-matching fluid for chitin, both the light scattering and the photonic nanoarchitecture were switched off, and the differences in pigment content were revealed. By artificially stacking several layers of blue scales on top of each other, both the intensity of the characteristic photonic signal in air and the magnitude of the vapor sensing response for 50% ethanol vapor in artificial air were increased.
Assuntos
Borboletas/anatomia & histologia , Imagem Óptica , Asas de Animais/anatomia & histologia , Animais , Masculino , Fenômenos Ópticos , Análise de Componente Principal , Volatilização , Asas de Animais/ultraestruturaRESUMO
Photonic nanoarchitectures occurring in the scales of Blue butterflies are responsible for their vivid blue wing coloration. These nanoarchitectures are quasi-ordered nanocomposites which are constituted from a chitin matrix with embedded air holes. Therefore, they can act as chemically selective sensors due to their color changes when mixing volatile vapors in the surrounding atmosphere which condensate into the nanoarchitecture through capillary condensation. Using a home-built vapor-mixing setup, the spectral changes caused by the different air + vapor mixtures were efficiently characterized. It was found that the spectral shift is vapor-specific and proportional with the vapor concentration. We showed that the conformal modification of the scale surface by atomic layer deposition and by ethanol pretreatment can significantly alter the optical response and chemical selectivity, which points the way to the efficient production of sensor arrays based on the knowledge obtained through the investigation of modified butterfly wings.
Assuntos
Borboletas/anatomia & histologia , Asas de Animais/anatomia & histologia , Animais , Pigmentação , Análise de Componente Principal , VolatilizaçãoRESUMO
Butterfly wing scales containing photonic nanoarchitectures act as chemically selective sensors due to their color change when mixing vapors in the atmosphere. Based on butterfly vision, we built a model for efficient characterization of the spectral changes in different atmospheres. The spectral shift is vapor specific and proportional with the vapor concentration. Results were compared to standard principal component analysis. The modification of the chemical properties of the scale surface by the deposition of 5 nm of Al(2)O(3) significantly alters the character of the optical response. This is proof of the possibility to purposefully tune the selectivity of such sensors.
Assuntos
Borboletas/fisiologia , Gases/análise , Fótons , Asas de Animais/química , Animais , Microscopia Eletrônica de Varredura , PigmentaçãoRESUMO
Beside the more than two thousand normal specimens of Polyommatus icarus (Rottemburg, 1775) yielded by rearing experiments, there was one perfectly bilateral dichromatic individual first considered to be gynandrous. On the basis of analysing genitalia traits, wing surface covering scale micromorphology, and the spectral characteristics of the blue colour generated by the cover scales, the gender of the specimen has been identified as female. This exemplar was investigated in comparison with gynandrous specimens from the collections of the Hungarian Natural History Museum exhibiting various degrees of intermixing of blue and brown coloration. Focus stacking microscopy for detailed scale morphology and UV-visible reflectance spectroscopy was used for the characterization of the optical properties. Inspecting literature references and the Lycaenidae collection of the museum, further examples have been found for female bilateral dichromatism in the closely related polyommatine lycaenid species Lysandra bellargus (Rottemburg, 1775) and Lysandra coridon (Poda, 1761) what suggests that polyommatine female dichromaticity may be displayed by the manner of bilaterality and mosaicism, phenomena hitherto solely connected to gynandromorphy.
Assuntos
Borboletas , Asas de Animais , Animais , Borboletas/anatomia & histologia , Feminino , Masculino , Asas de Animais/anatomia & histologia , Caracteres Sexuais , PigmentaçãoRESUMO
The iridescent structural colours of butterflies, generated by photonic nanoarchitectures, often function as species-specific sexual signals; therefore, they are reproduced precisely from generation to generation. The wing scales of oakblue hairstreak butterflies (genus Arhopala, Theclinae, Lycaenidae, Lepidoptera) contain multi-layer photonic nanoarchitectures, which can generate a wide range of structural colours, from violet to green. By scanning (SEM) and cross-sectional transmission electron microscopy (TEM) investigation, the colour tuning mechanism of the cover scales was explored. We revealed that the characteristic size change of structural elements in similar photonic nanoarchitectures led to different structural colours that were examined by various reflectance spectrophotometry techniques. The measured structural properties of the naturally tuned photonic nanoarchitectures were used to calculate wing reflectances, which were compared with the measurement results. We found that the simulated structural colours were systematically redshifted by 95-126 nm as compared with the measured normal-incidence reflectance results. This is attributed to the swelling of the chitinous multi-layer structures during the standard TEM sample preparation and the tilt of the cover scales, which both affect the apparent layer thicknesses in the TEM cross-sections. We proposed a simulation correction and compared the results with the layer thicknesses measured on cryogenically prepared non-embedded SEM cross-sections.
RESUMO
The nymphalid butterfly Euphaedra neophron (Hopffer, 1855) is the only structurally coloured species representing the genus along the Indian Ocean coast in East Africa and Southern Africa, with a distribution from southern Somalia to the Kwa-Zulu-Natal region of South Africa. The range of E. neophron is subdivided to several, geographically distinct populations, currently recognised as subspecies by taxonomists on the basis of violet, blue, and green-coloured morphs. We investigated the optical mechanism of all these morphs by various materials science techniques. We found that the structural colour is generated by the lower lamina of the cover scales and the different colours are tuned according to their thickness, which was also proved by modelling. The colour tuning of the different subspecies does not reflect any clinal pattern, be it geographical or altitudinal.
RESUMO
The colour of the butterfly wing serves as an important sexual and species-specific signal. Some species produce structural colouration by developing wing scales with photonic nanoarchitectures. These nanostructures are highly conservative, allowing only a ±10 nm peak wavelength deviation in the reflectance spectra of the blue structural colour in natural Common Blue (Polyommatus icarus) populations. They are promising templates of future artificial photonic materials and can be used in potential applications, too. In this work, we present methodology and infrastructure for breeding laboratory populations of Common Blue as a cost-effective and environmentally friendly source of nanostructures. Our technology enables the production of approximately 7500 wing samples, equivalent to 0.5-1 m2 of photonic nanoarchitecture surface within a year in a single custom-made insectarium. To ascertain the reliability of this method, we compared reflectance properties between different populations from distant geographic locations. We also provide genetic background of these populations using microsatellite genotyping. The laboratory population showed genetic erosion, but even after four generations of inbreeding, only minimal shifts in the structural colouration were observed, indicating that wild Common Blue populations may be a reliable source of raw material for photonic surfaces.
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Photonic nanoarchitectures of butterfly wings can serve as biotemplates to prepare semiconductor thin films of ZnO by atomic layer deposition. The resulting biotemplated ZnO nanoarchitecture preserves the structural and optical properties of the natural system, while it will also have the features of the functional material. The ZnO-coated wings can be used directly in heterogeneous photocatalysis to decompose pollutants dissolved in water upon visible light illumination. We used the photonic nanoarchitectures of different Morpho butterflies with different structural colors as biotemplates and examined the dependence of decomposition rates of methyl orange and rhodamine B dyes on the structural color of the biotemplates and the thickness of the ZnO coating. Using methyl orange, we measured a ten-fold increase in photodegradation rate when the 20 nm ZnO-coated wings were compared to similarly coated glass substrates. Using rhodamine B, a saturating relationship was found between the degradation rate and the thickness of the deposited ZnO on butterfly wings. We concluded that the enhancement of the catalytic efficiency can be attributed to the slow light effect due to a spectral overlap between the ZnO-coated Morpho butterfly wings reflectance with the absorption band of dyes, thus the photocatalytic performance could be changed by the tuning of the structural color of the butterfly biotemplates. The photodegradation mechanism of the dyes was investigated by liquid chromatography-mass spectroscopy.
RESUMO
Graphene-covered silver nanoparticles were prepared directly on highly oriented pyrolytic graphite substrates and characterized by atomic force microscopy. UV-Vis reflectance spectroscopy was used to measure the shift in the local surface plasmon resonance (LSPR) upon exposure to acetone, ethanol, 2-propanol, toluene, and water vapor. The optical responses were found to be substance-specific, as also demonstrated by principal component analysis. Point defects were introduced in the structure of the graphene overlayer by O2 plasma. The LSPR was affected by the plasma treatment, but it was completely recovered using subsequent annealing. It was found that the presence of defects increased the response for toluene and water while decreasing it for acetone.
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The photocatalytic activity of a flat surface can be increased by micro- and nanostructuring the interface to increase the area of the contact surface between the photocatalyst and the solute, and moreover, to optimize charge carrier transfer. Further enhancement can be achieved by using photonic nanostructures, which exhibit photonic band gap (PBG). Structurally coloured butterfly wings offer a rich 'library' of PBGs in the visible spectral range which can be used as naturally tuned sample sets for biotemplating. We used conformal atomic layer deposition of ZnO on the wings of various butterfly species (Arhopala asopia, Hypochrysops polycletus, Morpho sulkowskyi, Polyommatus icarus) possessing structural colour extending from the near UV to the blue wavelength range, to test the effects arising from the nanostructured surfaces and from the presence of different types of PBGs. Aqueous solutions of rhodamine B were used to test the enhancement of photocatalytic activity that was found for all ZnO-coated butterfly wings. The best reaction rate of decomposing rhodamine B when illuminated with visible light was found in 15 nm ZnO coated M. sulkowskyi wing, the reflectance of which had the highest overlap with the absorption band of the dye and had the highest reflectance intensity.
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Quantum confinement of the charge carriers of graphene is an effective way to engineer its properties. This is commonly realized through physical edges that are associated with the deterioration of mobility and strong suppression of plasmon resonances. Here, we demonstrate a simple, large-area, edge-free nanostructuring technique, based on amplifying random nanoscale structural corrugations to a level where they efficiently confine charge carriers, without inducing significant inter-valley scattering. This soft confinement allows the low-loss lateral ultra-confinement of graphene plasmons, scaling up their resonance frequency from the native terahertz to the commercially relevant visible range. Visible graphene plasmons localized into nanocorrugations mediate much stronger light-matter interactions (Raman enhancement) than previously achieved with graphene, enabling the detection of specific molecules from femtomolar solutions or ambient air. Moreover, nanocorrugated graphene sheets also support propagating visible plasmon modes, as revealed by scanning near-field optical microscopy observation of their interference patterns.
RESUMO
Solar radiation is a cheap and abundant energy for water remediation, hydrogen generation by water splitting, and CO2 reduction. Supported photocatalysts have to be tuned to the pollutants to be eliminated. Spectral engineering may be a handy tool to increase the efficiency or the selectivity of these. Photonic nanoarchitectures of biological origin with hierarchical organization from nanometers to centimeters are candidates for such applications. We used the blue wing surface of laboratory-reared male Polyommatus icarus butterflies in combination with atomic layer deposition (ALD) of conformal ZnO coating and octahedral Cu2O nanoparticles (NP) to explore the possibilities of engineering the optical and catalytic properties of hybrid photonic nanoarchitectures. The samples were characterized by UV-Vis spectroscopy and optical and scanning electron microscopy. Their photocatalytic performance was benchmarked by comparing the initial decomposition rates of rhodamine B. Cu2O NPs alone or on the butterfly wings, covered by a 5 nm thick layer of ZnO, showed poor performance. Butterfly wings, or ZnO coated butterfly wings with 15 nm ALD layer showed a 3 to 3.5 times enhancement as compared to bare glass. The best performance of almost 4.3 times increase was obtained for the wings conformally coated with 15 nm ZnO, deposited with Cu2O NPs, followed by conformal coating with an additional 5 nm of ZnO by ALD. This enhanced efficiency is associated with slow light effects on the red edge of the reflectance maximum of the photonic nanoarchitectures and with enhanced carrier separation through the n-type ZnO and the p-type Cu2O heterojunction. Properly chosen biologic photonic nanoarchitectures in combination with carefully selected photocatalyst(s) can significantly increase the photodegradation of pollutants in water under visible light illumination.
RESUMO
The males of more than 80% of the Lycaenidae species belonging to the tribe Polyommatini exhibit structural coloration on their dorsal wing surfaces. These colors have a role in reinforcement in prezygotic reproductive isolation. The species-specific colors are produced by the cellular self-assembly of chitin/air nanocomposites. The spectral position of the reflectance maximum of such photonic nanoarchitectures depends on the nanoscale geometric dimensions of the elements building up the nanostructure. Previous work showed that the coloration of male Polyommatus icarus butterflies in the Western and Eastern Palearctic exhibits a characteristic spectral difference (20 nm). We investigated the coloration and the de novo developed DNA microsatellites of 80 P. icarus specimens from Europe from four sampling locations, spanning a distance of 1621 km. Remarkably good concordance was found between the spectral properties of the blue sexual signaling color (coincident within 5 nm) and the population genetic structure as revealed by 10 microsatellites for the P. icarus species.
Assuntos
Escamas de Animais/anatomia & histologia , Borboletas/genética , Asas de Animais/anatomia & histologia , Animais , Borboletas/anatomia & histologia , Cor , DNA/genética , Europa (Continente) , Masculino , Repetições de Microssatélites/genética , Filogeografia , EspectrofotometriaRESUMO
Color is an important communication channel for day-flying butterflies. Chemical (pigmentary) coloration is often supplemented by physical color generated by photonic nanostructures. These nanoarchitectures - which are characteristic for a given species - exhibit wavelength ranges in which light propagation is forbidden. The photonic nanoarchitectures are located in the lumen of the wing scales and are developed individually by each scale during metamorphosis. This self-assembly process is governed by the genes in the nucleus of the scale producing cell. It is crucial to establish well-defined measurement methods for the unambiguous characterization and comparison of colors generated in such a complex manner. Owing to the intricate architecture ordered at multiple levels (from centimeters to tens of nanometers), the precise quantitative determination of butterfly wing coloration is not trivial. In this paper, we present an overview of several optical spectroscopy measurement methods and illustrate techniques for processing the obtained data, using the species Polyommatus bellargus as a test case, the males of which exhibit a variation in their blue structural color that is easily recognizable to the naked eye. The benefits and drawbacks of these optical methods are discussed and compared. Furthermore, the origin of the color differences is explained in relation to differences in the wing scale nanomorphology revealed by electron microscopy. This in turn is tentatively associated with the unusually large genetic drift reported for this species in the literature.
Assuntos
Borboletas , Entomologia , Pigmentos Biológicos , Animais , Borboletas/anatomia & histologia , Entomologia/instrumentação , Entomologia/métodos , Masculino , Nanoestruturas/análise , Nanoestruturas/química , Pigmentação/fisiologia , Pigmentos Biológicos/análise , Análise Espectral , Asas de Animais/anatomia & histologiaRESUMO
A large fraction of dorsal wing surface ground scales show an unusual granulated nature, composed of material apparently extruded from the scale lumen in male individuals of both Trichonis Hewitson, 1865 species in the tribe Eumaeini, a rare Guyanian-Amazonian genus. Only a few not-granulated male specimens are known, females are not granulated. The granulated scales are investigated by various microscopic (optical, scanning and transmission electron microscopy, focused ion beam lamella cutting) and spectroscopic (optical reflectance, energy-dispersive X-ray (EDS), Raman) techniques. The characteristic blue colour unique in the South American representatives of the tribe is documented and analysed. EDS spectra show that the granules contain additional calcium and oxygen as compared with the un-granulated regions of the same scale. Electron diffraction (inside the TEM) did not reveal any crystalline component in the granules. The granulated wing surfaces of the males exhibit a UV absorption band at 280 nm, characteristic for biogenic CaCO3; therefore, the material of the granules is tentatively identified as CaCO3. It is shown that the granules influence the optical properties of the dorsal wing surface resulting in a characteristic spectrum.
Assuntos
Borboletas , Animais , Cor , Feminino , Masculino , Microscopia Eletrônica de Transmissão , Caracteres Sexuais , Asas de AnimaisRESUMO
Silver nanoparticles (Ag NPs) play important roles in the development of plasmonic applications. Combining these nanoparticles with graphene can yield hybrid materials with enhanced light-matter interaction. Here, we report a simple method for the synthesis of graphene-silver nanoparticle hybrids on highly oriented pyrolytic graphite (HOPG) substrates. We demonstrate by scanning tunneling microscopy and local tunneling spectroscopy measurements the electrostatic n-type doping of graphene by contact with silver. We show by UV-Vis reflectance investigations that the local surface plasmon resonance (LSPR) of Ag NPs partially covered with graphene is preserved for at least three months, i.e., three times longer than the LSPR of bare Ag NPs. The gradual loss of LSPR is due to the spontaneous sulfurization of non-covered Ag NPs, as revealed by scanning electron microscopy and energy-dispersive X-ray spectroscopy. We show that the Ag NPs completely sandwiched between graphene and HOPG do not sulfurize, even after one year.
RESUMO
Color is a widely used communication channel in the living world for a variety of functions ranging from sexual communication to warning colors. A particularly rich spectrum of colors appears on the wings of many butterflies. The males of lycaenid butterflies often exhibit a conspicuous blue coloration generated by photonic nanoarchitectures on their dorsal wing surfaces. Using UV-VIS spectroscopy, we investigated the spatio-temporal variations of this coloration for Polyommatus icarus butterflies, considering an interval of more than 100 years and a geographical range spanning Europe (west) and Asia (east). The blue coloration in Hungary is very stable both within a year (three broods typical in Hungary) and within the period of 100 years (more than 300 generations). East-west geographic variation was investigated among 314 male P. icarus butterflies. In agreement with earlier genetic and morphometric studies, it was found that the western males are not divided in distinct lineages. Clear differences in coloration were found between the eastern and western groups, with a transition in the region of Turkey. These differences are tentatively attributed to bottleneck effects during past glaciations.