In-Brain Multiphoton Imaging of Vaterite Cargoes Loaded with Carbon Dots.

Biocompatible fluorescent agents are key contributors to the theranostic paradigm by enabling real-time in vivo imaging. This study explores the optical properties of phenylenediamine carbon dots (CDs) and demonstrates their potential for fluorescence imaging in cells and brain blood vessels. The nonlinear absorption cross-section of the CDs was measured and achieved values near 50 Goeppert-Mayer (GM) units with efficient excitation in the 775-895 nm spectral range. Mesoporous vaterite nanoparticles were loaded with CDs to examine the possibility of a biocompatible imaging platform. Efficient one- and two-photon imaging of the CD-vaterite composites uptaken by diverse cells was demonstrated. For an in vivo scenario, CD-vaterite composites were injected into the bloodstream of a mouse, and their flow was monitored within the blood vessels of the brain through a cranial window. These results show the potential of the platform for high-brightness biocompatible imaging with the potential for both sensing and simultaneous drug delivery.

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.

Optically Controlled Dissolution Kinetics of Vaterite Microcapsules: Toward Novel Crystal Growth Strategies.

Controllable continuous release of functional materials from capsules is one of the unmet functions of theragnosis particles; on this way, understanding cargo-fluid interactions in vitro is an essential milestone. We develop a flexible platform to investigate single particle-fluid interactions utilizing a glass micropipette as a highly localized flow source around an optically trapped particle. In proof-of-concept experiments, this microparticle is sensitive to local microflow distribution, thus serving as a probe. The very same flows are capable of the particle rotating (i.e., vaterite drug cargo) at frequencies dependent on the mutual particle-pipette position. Platform flexibility comes from different interactions of a tweezer (optical forces) and a pipette (mechanical/hydrodynamical) with a microparticle, which makes this arrangement an ideal microtool. We studied the vaterite dissolution kinetics and demonstrated that it can be controlled on demand, providing a wide cargo release dynamic rate. Our results promote the use of inorganic mesoporous nanoparticles as a nanomedicine platform.

Thin-film conformal fluorescent SU8-phenylenediamine.

The SU8 polymer is a negative photoresist widely used to produce high-quality coatings, with controllable thicknesses ranging from nanometers to millimeters, depending on fabrication protocols. Apart from conventional use cases in microelectronics and fluidics, SU8 is quite an attractive platform in nanophotonics. This material, being straightforwardly processed by ultraviolet lithography, is transparent to wavelengths longer than 500 nm. However, introducing fluorescent agents within the SU8 matrix remains a challenge owing to its high hydrophobicity. Here, we develop a process, where colorful quantum dots co-participate in the polymerization process by epoxide amination and become a part of a new fluorescent material - SU8-phenylenediamine. Through comprehensive characterization methods, including XPS and 1H-NMR analyses, we demonstrate that m-PD covalently binds to SU8 epoxy sites with its molecular amine, virtually forming a new material and not just a mixture of two compounds. After characterizing the new strongly fluorescent platform, thin 300 nm films were created on several surfaces, including a conformal coverage of a nanofluidic capillary. This new process provides opportunities to incorporate various functional molecules into optoelectronic devices without the need for multistep deposition and surface functionalization.

Gilded vaterite optothermal transport in a bubble.

Laser beams, capable of controlling the mechanical motion of micron-scale objects, can serve as a tool, enabling investigations of numerous interaction scenarios under full control. Beyond pure electromagnetic interactions, giving rise to conventional gradient forces and radiation pressure, environment-induced thermal effects can play a role and, in certain cases, govern the dynamics. Here we explore a thermocapillary Marangoni effect, which is responsible for creating long-range few hundreds of nano-Newton forces, acting on a bubble around a 'gilded vaterite' nanoparticle. Decorating calcium carbonate spherulite (the vaterite) with gold nanoseeds allows tuning its optical absorption and, as a result, controlling its temperature in a solution. We demonstrate that keeping a balance between electromagnetic and thermal interactions allows creating of a stable micron-scale bubble around the particle and maintaining its size over time. The bubbles are shown to remain stable over minutes even after the light source is switched off. The bubbles were shown to swim toward a laser focus for over 400-µm distances across the sample. Optothermal effects, allowing for efficient transport, stable bubble creation, and particle-fluid interaction control, can grant nano-engineered drug delivery capsules with additional functions toward a theragnostic paradigm shift.

Organic Kainate Single Crystals for Second-Harmonic and Broadband THz Generation.

Organic crystals with unique nonlinear optical properties have been attracting attention owing to their capability to outperform their conventional nonorganic counterparts. Since nonlinear material responses are linked to a crystal's internal microscopic structure, molecular engineering of maximally unharmonic quantum potentials can boost macromolecular susceptibilities. Here, large-scale kainic acid (kainate) single crystals were synthesized, and their linear and nonlinear optical properties were studied in a broad spectral range, spanning the visible to THz spectral regions. The non-centrosymmetric zwitterionic crystallization, molecular structure, and intermolecular arrangement were found to act as additive donor-acceptor domains, enhancing the efficiency of the intrinsic second-order optical nonlinearity of this pure enantiomeric crystal. Molecular simulations and experimental analysis were performed to retrieve the crystals' properties. The crystals were predicted and found to have good transparency in a broad spectral range from the UV to the infrared (0.2-20 µm). Second-harmonic generation was measured for ultrashort pumping wavelengths between 800 and 2400 nm, showing an enhanced response around 600 nm. Broadband THz generation was demonstrated with a detection limited bandwidth of >8 THz along with emission efficiencies comparable to and prevailing those of commercial ZnTe crystals. The broadband nonlinear response and high transparency make kainate crystals extremely attractive for realizing a range of nonlinear optical devices.

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.

Simple low-cost 3D metal printing via plastic skeleton burning.

Additive manufacturing of complex volumetric structures opened new frontiers in many technological fields, turning previously inconceivable designs into a practical reality. Electromagnetic components, including antenna and waveguiding elements, can benefit from exploring the third dimension. While fused deposition modeling (FDM) polymer printers become widely accessible, they manufacture structures with moderately low electromagnetic permittivities, compared to metals. However, metal 3D printers, being capable of producing complex volumetric constructions, remain extremely expensive and hard to maintain apparatus, suitable for high-end market applications. Here we develop a new metal printing technique, based on a low-cost and simple FDM device and subsequent electrochemical deposition. For testing the new method, we fabricated several antenna devices and compared their performances to standard printed FeCl3 etched board-based counterparts, demonstrating clear advantages of the new technique. Our new metal printing can be applied to manufacture electromagnetic devices as well as metallic structures for other applications.

Extraordinary broadband impedance matching in highly dispersive media - the white light cavity approach.

Suppressing reflections from material boundaries has always been an objective, common to many disciplines, where wave phenomena play a role. While impedance difference between materials necessarily leads to a wave reflection, introducing matching elements can almost completely suppress this phenomenon. However, many impedance matching approaches are based on resonant conditions, which come at a price of narrow bandwidth operation. Although various impedance matching architectures have been developed in the past, many of them fail to produce a broadband and flat (ripple-free) transmission, particularly in the presence of strong chromatic dispersion. Here we propose and demonstrate an approach for designing an optimal matching stack capable of providing a flat broadband transmission even in the presence of significant group velocity dispersion. As an experimental example for the method verification, we used a strong modal dispersion in a rectangular waveguide, operating close to a mode cut-off. The waveguide core consists of alternating polymer sections with a variable filling factor, realized using additive manufacturing. As a result, a broadband matching in the range of 7-8GHz was demonstrated and proved to significantly outperform the standard binomial transformer solution. The proposed method can find use across different disciplines, including optics, acoustics and wireless communications, where undesired reflections can significantly degrade system's performances.

Self-aligning roly-poly RFID tag.

Radio frequency identification (RFID) is a mature technology that allows contactless data readout via a wireless communication link. While numerous passive RFID tags are available on the market, accurate alignment between tags and readers is required in a vast majority of cases to mitigate polarization mismatches. We show that enhancing electromagnetic designs with additional mechanical degrees of freedom allows bypassing fundamental limitations and approach ideal performances. Here, we demonstrate a new miniature tag, accessible from any direction and immune to rotations in space. Our tag is made of a high permittivity ceramic resonator, inductively coupled to a metal ring, which contains an RFID chip. The structure is placed inside a spherical plastic holder. In this architecture, the ceramic resonator serves several functions. First, it allows reducing the device footprint without significant bandwidth degradation. Second, it acts as a bob, aligning the electromagnetic structure parallel to the ground, regardless of its initial orientation in space. The bob is designed to slide inside the plastic holder. This roly-poly effect relaxes the constraint on a mutual tag-reader orientation, including the polarization mismatch, and provides next to perfect long-range operation. Being only 55 mm in diameter, our device can be interrogated from a 12 m distance, regardless of the tag's orientation in space. Introducing mechanical degrees of freedom into electromagnetic designs allows obtaining new functionalities, contributing to applications where a mutual orientation between transvers is required.

Naked eye direction of arrival estimation with a Fresnel lens.

Direction of arrival (DoA) estimation is of primary importance in a broad range of wireless applications, where electromagnetic waves play a role. While a vast majority of existing techniques is based on phase lag comparison in antenna arrays, intensity-based approaches are valuable in a range of low budget applications. Here we demonstrate a direct visible to a naked eye DoA device, based on a Fresnel zone plate lens, aperture, and a light-emitting diode indicator. Being a low budget device, it still allows achieving up to 90° angle of view, 19° of angular resolution, and 11° of angular accuracy at 10 GHz operational frequency. The demonstrated approach provides fast DoA visualization and can be used to adjust point-to-point communication links, identify radio wave pollution sources at home conditions and several others.

Single GaP nanowire nonlinear characterization with the aid of an optical trap.

Semiconductor nanowires exhibit numerous capabilities to advance the development of future optoelectronic devices. Among the III-V material family, gallium phosphide (GaP) is an attractive platform with low optical absorption and high nonlinear susceptibility, making it especially promising for nanophotonic applications. However, investigation of single nanostructures and their waveguiding properties remains challenging owing to typically planar experimental arrangements. Here we study the linear and nonlinear waveguiding optical properties of a single GaP nanowire in a special experimental layout, where an optically trapped structure is aligned along its major axis. We demonstrate efficient second harmonic generation in individual nanowires and unravel phase matching conditions, linking between linear guiding properties of the structure and its nonlinear tensorial susceptibility. The capability to pick up single nanowires, sort them with the aid of optomechanical manipulation and accurately position pre-tested structures opens a new avenue for the generation of optoelectronic origami-type devices.

Multicolor Phenylenediamine Carbon Dots for Metal-Ion Detection with Picomolar Sensitivity.

Carbon dots keep attracting attention in multidisciplinary fields, motivating the development of new compounds. Phenylenediamine C6H4(NH2)2 dots are known to exhibit colorful emission, which depends on size, composition, and the functional surface groups, forming those structures. While quite a few fabrication protocols have been developed, the quantum yield of phenylenediamine dots still does not exceed 50% owing to undesired fragment formation during carbonization. Here, we demonstrate that an ethylene glycol-based environment allows obtaining multicolor high-quantum-yield phenylenediamine carbon dots. In particular, a kinetic realization of solvothermal synthesis in acidic environments enhances carbonization reaction yield for meta phenylenediamine compounds and leads to quantum yields, exciting 60%. Reaction yield after the product's purification approaches 90%. Furthermore, proximity of metal ions (Nd3+, Co3+, La3+) can either enhance or quench the emission, depending on the concentration. Optical monitoring of the solution allows performing an accurate detection of ions at picomolar concentrations. An atomistic model of carbon dots was developed to confirm that the functional surface group positioning within the molecular structure has a major impact on dots' physicochemical properties. The high performance of new carbon dots paves the way toward their integration in numerous applications, including imaging, sensing, and therapeutics.

Amplified spontaneous emission and gain in highly concentrated Rhodamine-doped peptide derivative.

Bioinspired fluorescence, being widely explored for imaging purposes, faces challenges in delivering bright biocompatible sources. While quite a few techniques have been developed to reach this goal, encapsulation of high-quantum yield fluorescent dyes in natural biological forms suggest achieving superior light-emitting characteristics, approaching amplified spontaneous emission and even lasing. Here we compare gain capabilities of highly concentrated Rhodamine B solutions with a newly synthesized biocompatible peptide derivative hybrid polymer/peptide material, RhoB-PEG1300-F6, which contains the fluorescent covalently bound dye. While concentration quenching effects limit the maximal achievable gain of dissolved Rhodamine B, biocompatible conjugation allows elevating amplification coefficients towards moderately high values. In particular, Rhodamine B, anchored to the peptide derivative material, demonstrates gain of 22-23 cm-1 for a 10-2 M solution, while a pure dye solution possesses 25% smaller values at the same concentration. New biocompatible fluorescent agents pave ways to demonstrate lasing in living organisms and can be further introduced to therapeutic applications, if proper solvents are found.

Golden Vaterite as a Mesoscopic Metamaterial for Biophotonic Applications.

Mesoscopic photonic systems with tailored optical responses have great potential to open new frontiers in implantable biomedical devices. However, biocompatibility is typically a problem, as engineering of optical properties often calls for using toxic compounds and chemicals, unsuitable for in vivo applications. Here, a unique approach to biofriendly delivery of optical resonances is demonstrated. It is shown that the controllable infusion of gold nanoseeds into polycrystalline sub-micrometer vaterite spherulites gives rise to a variety of electric and magnetic Mie resonances, producing a tuneable mesoscopic optical metamaterial. The 3D reconstruction of the spherulites demonstrates the capability of controllable gold loading with volumetric filling factors exceeding 28%. Owing to the biocompatibility of the constitutive elements, "golden vaterite" paves the way to introduce designer-made Mie resonances to cutting-edge biophotonic applications. This concept is exemplified by showing efficient laser heating of gold-filled vaterite spherulites at red and near-infrared wavelengths, highly desirable in photothermal therapy, and photoacoustic tomography.

Efficient radiational outcoupling of electromagnetic energy from hyperbolic metamaterial resonators.

Hyperbolic metamaterials were initially proposed in optics to boost radiation efficiencies of quantum emitters. Adopting this concept for antenna design allows approaching long-standing contests in radio physics. For example, broadband impedance matching, accompanied with moderately high antenna gain, is among the existent challenges. Here we propose employing hyperbolic metamaterials for a broadband impedance matching, while a structured layer on top of a metamaterials slab ensures an efficient and directive energy outcoupling to a free space. In particular, a subwavelength loop antenna, placed underneath the matching layer, efficiently excites bulk metamaterial modes, which have well-resolved spatial-temporal separation owing to the hypebolicity of effective permeability tensor. Interplaying chromatic and modal dispersions enable to map different frequencies into non overlapping spatial locations within a compact subwavelength hyperbolic slab. The outcoupling of energy to the free space is obtained by patterning the slab with additional resonant elements, e.g. high index dielectric spheres. As the result, two-order of magnitude improvement in linear gain of the device is predicted. The proposed new architecture can find a use in applications, where multiband or broadband compact devices are required.

Multispectral sensing of biological liquids with hollow-core microstructured optical fibres.

The state of the art in optical biosensing is focused on reaching high sensitivity at a single wavelength by using any type of optical resonance. This common strategy, however, disregards the promising possibility of simultaneous measurements of a bioanalyte's refractive index over a broadband spectral domain. Here, we address this issue by introducing the approach of in-fibre multispectral optical sensing (IMOS). The operating principle relies on detecting changes in the transmission of a hollow-core microstructured optical fibre when a bioanalyte is streamed through it via liquid cells. IMOS offers a unique opportunity to measure the refractive index at 42 wavelengths, with a sensitivity up to ~3000 nm per refractive index unit (RIU) and a figure of merit reaching 99 RIU-1 in the visible and near-infra-red spectral ranges. We apply this technique to determine the concentration and refractive index dispersion for bovine serum albumin and show that the accuracy meets clinical needs.

Auxiliary Optomechanical Tools for 3D Cell Manipulation.

Advances in laser and optoelectronic technologies have brought the general concept of optomechanical manipulation to the level of standard biophysical tools, paving the way towards controlled experiments and measurements of tiny mechanical forces. Recent developments in direct laser writing (DLW) have enabled the realization of new types of micron-scale optomechanical tools, capable of performing designated functions. Here we further develop the concept of DLW-fabricated optomechanically-driven tools and demonstrate full-3D manipulation capabilities over biological objects. In particular, we resolved the long-standing problem of out-of-plane rotation in a pure liquid, which was demonstrated on a living cell, clamped between a pair of forks, designed for efficient manipulation with holographic optical tweezers. The demonstrated concept paves the way for the realization of flexible tools for performing on-demand functions over biological objects, such as cell tomography and surgery to name just few.

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.

Microstructured Optical Waveguide-Based Endoscopic Probe Coated with Silica Submicron Particles.

Microstructured optical waveguides (MOW) are of great interest for chemical and biological sensing. Due to the high overlap between a guiding light mode and an analyte filling of one or several fiber capillaries, such systems are able to provide strong sensitivity with respect to variations in the refractive index and the thickness of filling materials. Here, we introduce a novel type of functionalized MOWs whose capillaries are coated by a layer-by-layer (LBL) approach, enabling the alternate deposition of silica particles (SiO2) at different diameters-300 nm, 420 nm, and 900 nm-and layers of poly(diallyldimethylammonium chloride) (PDDA). We demonstrate up to three covering bilayers consisting of 300-nm silica particles. Modifications in the MOW transmission spectrum induced by coating are measured and analyzed. The proposed technique of MOW functionalization allows one to reach novel sensing capabilities, including an increase in the effective sensing area and the provision of a convenient scaffold for the attachment of long molecules such as proteins.