School of Chemistry - Research Publications

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    An investigation of evanescent wave-induced fluorescence spectroscopy for exploring high refractive index media
    Chakraborty, S ; Xu, Y ; Roberts, A ; Goswami, D ; Smith, TA (IOP Publishing Ltd, 2023-01-01)
    Abstract Evanescent wave-induced fluorescence spectroscopy (EWIFS) is a widely used technique for probing the interfacial behavior of different complex media in investigations of samples in the physical, chemical, and biological sciences. This technique takes advantage of the sharply decaying evanescent field, established following total internal reflection (TIR) at the interface of two media, for spatially identifying the photoluminescence characteristics of the sample. The generation of the evanescent field requires the refractive index of the second medium to be lower than that of the first, so a major disadvantage of this increasingly widely used spectroscopic technique is the inability to exploit the advantages of EWIFS to image a sample with a higher refractive index than the incident substrate medium. A proposed configuration in which a thin, low refractive index intermediate layer is established between the TIR substrate and a high refractive index sample is investigated. We illustrate that this arrangement does not afford the desired advantages of evanescent field-induced fluorescence measurements for investigating high refractive index media.
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    Deconstructed beetles: Bilayered composite materials produce green coloration with remarkably high near-infrared reflectance
    Ospina-Rozo, L ; Priscilla, N ; Hutchison, J ; van de Meene, A ; Roberts, NW ; Stuart-Fox, D ; Roberts, A (ELSEVIER, 2023-06)
    Beetle elytra (hardened forewings) are a promising source of inspiration to develop or enhance the performance of human-fabricated composite materials. The structures responsible for optical properties in the ultra-violet to visible spectrum (300–700 nm) have been extensively characterised, but we have limited knowledge of optical properties and their physical origin in the near-infrared (NIR; 700–1700 nm). We examined the elytra of three species of green scarab beetles (Xylonichus eucalypti, Anoplognathus prasinus and Paraschizognathus olivaceus) with very high NIR reflectance. We manually separated layers in the elytra to disambiguate their contributions to the overall optical response. We show that unlike other scarabs, nanostructures within the cuticle layer do not produce notable reflectance. Instead, the cuticle resembles a pigment-based filter with 50% transmittance in the NIR and absorption in the visible spectrum contributing to the green appearance. Each species has a layer below the cuticle that appears white to the naked eye and produces broadband reflectance, particularly in the near-infrared; however, the structure of the white underlay differs markedly between the three species. In A. prasinus and P. olivaceus, the structure is disordered (no regular, repeated elements at optical length scales); whereas in Xylonichus eucalypti, the white underlay was notably thinner and comprised quasi-ordered hollow cylindrical structures embedded in a chitin matrix. We modelled the coherent scattering produced by this structure to demonstrate that it is responsible for broadband visible and NIR reflectance. We discuss biological implications and technological applications of the composite structure of beetle elytra.
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    A General Method for Direct Assembly of Single Nanocrystals
    Zhang, H ; Liu, Y ; Ashokan, A ; Gao, C ; Dong, Y ; Kinnear, C ; Kirkwood, N ; Zaman, S ; Maasoumi, F ; James, TD ; Widmer-Cooper, A ; Roberts, A ; Mulvaney, P (WILEY-V C H VERLAG GMBH, 2022-07)
    Abstract Controlled nanocrystal assembly is a pre‐requisite for incorporation of these materials into solid state devices. Many assembly methods have been investigated which target precise nanocrystal positioning, high process controllability, scalability, and universality. However, most methods are unable to achieve all of these goals. Here, surface templated electrophoretic deposition (STED) is presented as a potential assembly method for a wide variety of nanocrystals. Controlled positioning and deposition of a wide range of nanocrystals into arbitrary spatial arrangements − including gold nanocrystals of different shapes and sizes, magnetic nanocrystals, fluorescent organic nanoparticles, and semiconductor quantum dots − is demonstrated. Nanoparticles with diameters <10 nm are unable to be deposited due to their low surface charge and strong Brownian motion (low Péclet number). It is shown that this limit can be circumvented by forming clusters of nanocrystals or by silica coating nanocrystals to increase their effective size.
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    Direct Assembly of Vertically Oriented, Gold Nanorod Arrays
    Zhang, H ; Liu, Y ; Shahidan, MFS ; Kinnear, C ; Maasoumi, F ; Cadusch, J ; Akinoglu, EM ; James, TD ; Widmer-Cooper, A ; Roberts, A ; Mulvaney, P (WILEY-V C H VERLAG GMBH, 2021-02-03)
    Although many nanoscale materials such as quantum dots and metallic nanocrystals exhibit size dependent optical properties, it has been difficult to incorporate them into optical or electronic devices because there are currently no methods for precise, large‐scale deposition of single nanocrystals. Of particular interest is the need to control the orientation of single nanocrystals since the optical properties are usually strongly anisotropic. Here a method based on electrophoretic deposition (EPD) is reported to precisely assemble vertically oriented, single gold nanorods. It is demonstrated that the orientation of gold nanorods during deposition is controlled by the electric dipole moment induced along the rod by the electric field. Dissipative particle dynamics simulations indicate that the magnitude of this dipole moment is dominated by the polarizability of the solution phase electric double layer around the nanorod. The resulting vertical gold nanorod arrays exhibit reflected colors due to selective excitation of the transverse surface plasmon mode. The EPD method allows assembly of arrays with a density of over one million, visually resolvable, vertical nanorods per square millimeter.