Thermo-optics of gilded hollow-core fibers.

Hollow core fibers, supporting waveguiding in a void, open a room of opportunities for numerous applications owing to an extended light-matter interaction distance and relatively high optical confinement. Decorating an inner capillary with functional materials allows tailoring the fiber's optical properties further and turns the structure into a functional device. Here, we functionalize an anti-resonant hollow-core fiber with 18 nm-size gold nanoparticles, approaching a uniform 45% surface coverage along 10 s of centimeters along its inner capillary. Owing to a moderately low overlap between the fundamental mode and the gold layer, the fiber maintains its high transmission properties; nevertheless, the entire structure experiences considerable heating, which is observed and quantified with the aid of a thermal camera. The hollow core and the surrounding capillary are subsequently filled with ethanol and thermo-optical heating is demonstrated. We also show that at moderate laser intensities, the liquid inside the fiber begins to boil and, as a result, the optical guiding is destroyed. The gilded hollow core fiber and its high thermal-optical responsivity suggest considering the structure as an efficient optically driven catalytic reactor in applications where either small reaction volumes or remote control over a process are demanded.

Hidden imaging in thin polymer films with embedded fluorescent peptide nanodots.

Fluorescent (FL) encrypting nanostructures, such as quantum dots, carbon dots, organic dyes, lanthanide nanocrystals, DNA, and more, are effective tools for advanced applications in high-resolution hidden imaging. These applications include tracking, labeling, security printing, and anti-counterfeiting drug technology. In this work, what we believe to be a new FL encoding nanostructures has been proposed, which consists of recently discovered nanometer-scale peptide dots. When refolded into a beta-sheet peptide secondary structure, these biocompatible nanoparticles exhibit a strong and tunable FL effect. The biophotonic FL covers the entire visible spectrum, making the peptide dots next-generation nanoscale light sources with a quantum yield of 30%. Our studies demonstrate that these FL bio-nanodots also exhibit a significant irreversible photo-bleaching effect associated with the light-induced destruction of noncovalent intermolecular hydrogen bonds of the peptide dots' highly stable beta-sheet secondary structure. We present what we believe is a new approach for achieving high-resolution long-term optical memory by tailoring various hidden images in the developed thin polyvinyl alcohol (PVA) polymer films with an embedded dense array of FL peptide nanodots. The technology enables recording photo-bleached patterns, barcodes, and high-resolution images.

Optothermal Needle-Free Injection of Vaterite Nanocapsules.

The propulsion and acceleration of nanoparticles with light have both fundamental and applied significance across many disciplines. Needle-free injection of biomedical nano cargoes into living tissues is among the examples. Here a new physical mechanism of laser-induced particle acceleration is explored, based on abnormal optothermal expansion of mesoporous vaterite cargoes. Vaterite nanoparticles, a metastable form of calcium carbonate, are placed on a substrate, underneath a target phantom, and accelerated toward it with the aid of a short femtosecond laser pulse. Light absorption followed by picosecond-scale thermal expansion is shown to elevate the particle's center of mass thus causing acceleration. It is shown that a 2 µm size vaterite particle, being illuminated with 0.5 W average power 100 fsec IR laser, is capable to overcome van der Waals attraction and acquire 15m sec-1 velocity. The demonstrated optothermal laser-driven needle-free injection into a phantom layer and Xenopus oocyte in vitro promotes the further development of light-responsive nanocapsules, which can be equipped with additional optical and biomedical functions for delivery, monitoring, and controllable biomedical dosage to name a few.

Biocompatibility characterization of vaterite with a bacterial whole-cell biosensor.

The growing biomedical challenges impose the continuous development of novel platforms. Ensuring the biocompatibility of drug delivery and implantable biomedical devices is an essential requirement. Calcium carbonate (CaCO3) in the form of vaterite nanoparticles is a promising platform, which has demonstrated distinctive optical and biochemical properties, including high porosity and metastability. In this study, the biocompatibility of differently shaped CaCO3 vaterite particles (toroids, ellipsoids, and spheroids) are evaluated by bacterial toxicity mode-of-action with a whole-cell biosensor. Different Escherichia coli (E. coli) strains were used in the bioluminescent assay, including cytotoxicity, genotoxicity and quorum-sensing. Firstly, both scanning electron microscopy (SEM) and fluorescence microscopy characterizations were conducted. Bacterial cell death and aggregates were observed only in the highest tested concentration of the vaterite particles, especially in toroids 15-25 µm. After, the bioluminescent bacterial panel was exposed to the vaterite particles, and their bioluminescent signal reflected their toxicity mode-of-action. The vaterite particles resulted in an induction factor (IF > 1) on the bacterial panel, which was higher after exposure to the toroids (1.557 ≤ IF ≤ 2.271) and ellipsoids particles (1.712 ≤ IF ≤ 2.018), as compared to the spheroids particles (1.134 ≤ IF ≤ 1.494), in all the tested bacterial strains. Furthermore, the vaterite particles did not affect the viability of the bacterial cells. The bacterial monitoring demonstrated the biofriendly nature of especially spheroids vaterite nanoparticles.

Fabrication of Electronic Junctions between Oriented Multilayers of Photosystem I and the Electrodes of Optoelectronic Solid-State Devices.

The efficient optoelectronic properties of photosynthetic proteins were explored in the quest for the fabrication of novel solid biohybrid devices. As most optoelectronic devices function in a dry environment, an attempt was made to fabricate an efficient electronic junction by covalent binding of photosynthetic reaction center proteins to metals, transparent semiconductor polymers, and solid semiconductors that function in a dry environment. The primary stages of photosynthesis take place in nanometric-size protein-chlorophyll complexes. Such is photosystem I (PSI), which generates a photovoltage of 1 V. The isolated PSI generates an absorbed light-energy conversion efficiency of ∼47% (∼23% solar energy) and internal quantum efficiency of ∼100%. The robust cyanobacterial PSI was used in the fabrication of solid-state optoelectronic devices by forming oriented multilayers from genetically engineered cysteine mutants between metal and transparent conducting semiconductor electrodes. Current-voltage measurements of the cells generated diode- and photodiode-like responses in the dark and the light, respectively. The cells were stable for many months in a dry environment. The generation of photocurrent and Voc indicated the formation of good electronic coupling between PSI and the electrodes, which can serve in the fabrication of solid-state biohybrid optoelectronic devices.

Biological Kerker Effect Boosts Light Collection Efficiency in Plants.

Being the polymorphs of calcium carbonate (CaCO3), vaterite and calcite have attracted a great deal of attention as promising biomaterials for drug delivery and tissue engineering applications. Furthermore, they are important biogenic minerals, enabling living organisms to reach specific functions. In nature, vaterite and calcite monocrystals typically form self-assembled polycrystal micro- and nanoparticles, also referred to as spherulites. Here, we demonstrate that alpine plants belonging to the Saxifraga genus can tailor light scattering channels and utilize multipole interference effect to improve light collection efficiency via producing CaCO3 polycrystal nanoparticles on the margins of their leaves. To provide a clear physical background behind this concept, we study optical properties of artificially synthesized vaterite nanospherulites and reveal the phenomenon of directional light scattering. Dark-field spectroscopy measurements are supported by a comprehensive numerical analysis, accounting for the complex microstructure of particles. We demonstrate the appearance of generalized Kerker condition, where several higher order multipoles interfere constructively in the forward direction, governing the interaction phenomenon. As a result, highly directive forward light scattering from vaterite nanospherulites is observed in the entire visible range. Furthermore, ex vivo studies of microstructure and optical properties of leaves for the alpine plants Saxifraga "Southside Seedling" and Saxifraga Paniculata Ria are performed and underline the importance of the Kerker effect for these living organisms. Our results pave the way for a bioinspired strategy of efficient light collection by self-assembled polycrystal CaCO3 nanoparticles via tailoring light propagation directly to the photosynthetic tissue with minimal losses to undesired scattering channels.

Non-Mie optical resonances in anisotropic biomineral nanoparticles.

The optical properties of nanoparticles have attracted continuous attention owing to their high fundamental and applied importance across many disciplines. A recently emerged field of all-dielectric nanophotonics employs optically induced electric and magnetic Mie resonances in dielectric nanoparticles with a high refractive index. This property allows obtaining additional valuable degrees of freedom to control the optical responses of nanophotonic structures. Here we propose a conceptually distinct approach towards reaching optical resonances in dielectric nanoparticles. We show that, lacking conventional Mie resonances, low-index nanoparticles can exhibit a novel anisotropy-induced family of non-Mie eigenmodes. Specifically, we investigate light interactions with calcite and vaterite nanospheres and compare them with the Mie scattering by a fused silica sphere. Having close permittivities and the same dimensions, these particles exhibit significantly different scattering behavior owing to their internal structure. While a fused silica sphere does not demonstrate any spectral features, the uniaxial structure of the permittivity tensor for calcite and the non-diagonal permittivity tensor for vaterite result in a set of distinguishable peaks in scattering spectra. Multipole decomposition and eigenmode analysis reveal that these peaks are associated with a new family of electric and magnetic resonances. We identify magnetic dipole modes of ordinary, extraordinary and hybrid polarization as well as complex electric dipole resonances, featuring a significant toroidal electric dipole moment. As both vaterite and calcite are biominerals, naturally synthesized and exploited by a variety of living organisms, our results provide an indispensable toolbox for understanding and elucidating the mechanisms behind the optical functionalities of true biological systems.