Challenges and Recent Analytical Advances in Micro/Nanoplastic Detection.

Despite growing ecological concerns, studies on microplastics and nanoplastics are still in their initial stages owing to technical hurdles in analytical techniques, especially for nanoplastics. We provide an overview of the general attributes of micro/nanoplastics in natural environments and analytical techniques commonly used for their analysis. After demonstrating the analytical challenges associated with the identification of nanoplastics due to their distinctive characteristics, we discuss recent technological advancements for detecting nanoplastics.

Advancements of Intense Terahertz Field Focusing on Metallic Nanoarchitectures for Monitoring Hidden Interatomic Gas-Matter Interactions.

With the advancements of nanotechnology, innovative photonic designs coupled with functional materials provide a unique way to acquire, share, and respond effectively to information. It is found that the simple deposition of a 30 nm-thick palladium nanofilm on a terahertz (THz) metasurface chip with a 14 nm-wide effective nanogap of asymmetric materials and geometries allows the tracking of both interatomic and interfacial gas-matter interactions, including gas adsorption, hydrogenation (or dehydrogenation), metal phase changes, and unique water-forming reactions. Combinatorial analyses by simulation and experimental measurements demonstrate the distinct nanostructures, which leads to significant light-matter interactions and corresponding THz absorption in a real-time, highly repeatable, and reliable manner. The complex lattice dynamics and intrinsic properties of metals influenced by hydrogen gas exposure are also thoroughly examined using systematically controlled ternary gas mixture devices that mimic normal temperature and pressure. Furthermore, the novel degrees of freedom are utilized to analyze various physical phenomena, and thus, analytical methods that enable the tracking of unknown hidden stages of water-forming reactions resulting in water growth are introduced. A single exposure of the wave spectrum emphasizes the robustness of the proposed THz nanoscopic probe, bridging the gap between fundamental laboratory research and industry.

Fabry-Perot Cavity Control for Tunable Raman Scattering.

The Fabry-Perot (FP) resonator is an intuitive and versatile optical structure owing to its uniqueness in light-matter interactions, yielding resonance with a wide range of wavelengths as it couples with photonic materials encapsulated in a dielectric cavity. Leveraging the FP resonator for molecular detection, a simple geometry of the metal-dielectric-metal structure is demonstrated to allow tuning of the enhancement factors (EFs) of surface-enhanced Raman scattering (SERS). The optimum near-field EF from randomly dispersed gold nano-gaps and dynamic modulation of the far-field SERS EF by varying the optical resonance of the FP etalon are systematically investigated by performing computational and experimental analyses. The proposed strategy of combining plasmonic nanostructures with FP etalons clearly reveals wavelength matching of FP resonance to excitation and scattering wavelengths plays a key role in determining the magnitude of the SERS EF. Finally, the optimum near-field generating optical structure with controlled dielectric cavity is suggested for a tunable SERS platform, and its dynamic SERS switching performance is confirmed by demonstrating information encryption through liquid immersion.

Real-Time Underwater Nanoplastic Detection beyond the Diffusion Limit and Low Raman Scattering Cross-Section via Electro-Photonic Tweezers.

Emerging as substantial concerns in the ecosystem, submicron plastics have attracted much attention for their considerable hazards. However, their effect and even amount in the environment remain unclear. Establishing a substantive analytic platform is essential to expand the understanding of nanoplastics. However, the issues of diffusion and detection limit that arise from ultradiluted concentration and extremely small scales of nanoplastics leave significant technical hurdles to analyze the nanoplastic pollutants. In this study, we obtain effective Raman signals in real time from underwater nanoplastics with ultralow concentrations via AC electro-osmotic flows and dielectrophoretic tweezing. This enables the field-induced active collection of nanoplastics toward the optical sensing area from remote areas in a rapid manner, integrating conventional technical skills of preconcentration, separation, and identification in a single process. A step further, synergetic combination with plasmonic nanorods, accomplishes the highest on-site detection performance so far.

In Vitro Membrane Platform for the Visualization of Water Impermeability across the Liquid-Ordered Phase under Hypertonic Conditions.

Passive water penetration across the cell membrane by osmotic diffusion is essential for the homeostasis of cell volume, in addition to the protein-assisted active transportation of water. Since membrane components can regulate water permeability, controlling compositional variation during the volume regulatory process is a prerequisite for investigating the underlying mechanisms of water permeation and related membrane dynamics. However, the lack of a viable in vitro membrane platform in hypertonic solutions impedes advanced knowledge of cell volume regulation processes, especially cholesterol-enriched lipid domains called lipid rafts. By reconstituting the liquid-ordered (Lo) domain as a likeness of lipid rafts, we verified suppressed water permeation across the Lo domains, which had yet to be confirmed with experimental demonstrations despite a simulation approach. With the help of direct transfer of the Lo domains from vesicles to supported lipid membranes, the biological roles of lipid composition in suppressed water translocation were experimentally confirmed. Additionally, the improvement in membrane stability under hypertonic conditions was demonstrated based on molecular dynamics simulations.

Development of a Photonic Switch via Electro-Capillarity-Induced Water Penetration Across a 10-nm Gap.

With narrow and dense nanoarchitectures increasingly adopted to improve optical functionality, achieving the complete wetting of photonic devices is required when aiming at underwater molecule detection over the water-repellent optical materials. Despite continuous advances in photonic applications, real-time monitoring of nanoscale wetting transitions across nanostructures with 10-nm gaps, the distance at which photonic performance is maximized, remains a chronic hurdle when attempting to quantify the water influx and molecules therein. For this reason, the present study develops a photonic switch that transforms the wetting transition into perceivable color changes using a liquid-permeable Fabry-Perot resonator. Electro-capillary-induced Cassie-to-Wenzel transitions produce an optical memory effect in the photonic switch, as confirmed by surface-energy analysis, simulations, and an experimental demonstration. The results show that controlling the wetting behavior using the proposed photonic switch is a promising strategy for the integration of aqueous media with photonic hotspots in plasmonic nanostructures such as biochemical sensors.

Ionic contrast across a lipid membrane for Debye length extension: towards an ultimate bioelectronic transducer.

Despite technological advances in biomolecule detections, evaluation of molecular interactions via potentiometric devices under ion-enriched solutions has remained a long-standing problem. To avoid severe performance degradation of bioelectronics by ionic screening effects, we cover probe surfaces of field effect transistors with a single film of the supported lipid bilayer, and realize respectable potentiometric signals from receptor-ligand bindings irrespective of ionic strength of bulky solutions by placing an ion-free water layer underneath the supported lipid bilayer. High-energy X-ray reflectometry together with the circuit analysis and molecular dynamics simulation discovered biochemical findings that effective electrical signals dominantly originated from the sub-nanoscale conformational change of lipids in the course of receptor-ligand bindings. Beyond thorough analysis on the underlying mechanism at the molecular level, the proposed supported lipid bilayer-field effect transistor platform ensures the world-record level of sensitivity in molecular detection with excellent reproducibility regardless of molecular charges and environmental ionic conditions.

Nanoscale Terahertz Monitoring on Multiphase Dynamic Assembly of Nanoparticles under Aqueous Environment.

Probing the kinetic evolution of nanoparticle (NP) growth in liquids is essential for understanding complex nano-phases and their corresponding functions. Terahertz (THz) sensing, an emerging technology for next-generation laser photonics, has been developed with unique photonic features, including label-free, non-destructive, and molecular-specific spectral characteristics. Recently, metasurface-based sensing platforms have helped trace biomolecules by overcoming low THz absorption cross-sectional limits. However, the direct probing of THz signals in aqueous environments remains difficult. Here, the authors report that vertically aligned nanogap-hybridized metasurfaces can efficiently trap traveling NPs in the sensing region, thus enabling us to monitor the real-time kinetic evolution of NP assemblies in liquids. The THz photonics approach, together with an electric tweezing technique via spatially matching optical hotspots to particle trapping sites with a nanoscale spatial resolution, is highly promising for underwater THz analysis, forging a route toward unraveling the physicochemical events of nature within an ultra-broadband wavelength regime.

Autofluorescence-Raman Mapping Integration analysis for ultra-fast label-free monitoring of adipogenic differentiation of stem cells.

Stem cell-based therapies have recently emerged to treat various incurable diseases and disorders. Types of stem cell-derived cells and their functions should be intensively analyzed before therapy. However, current pre-treatment steps for biological analysis are mostly destructive. Here, we report a novel optical method that enables ultra-fast and label-free characterization of cells, eliminating invasive, destructive steps. The technique, referred to as "autofluorescence-Raman mapping integration (ARMI)" analysis uses cell autofluorescence (AF) to reveal cellular morphology and cytosolic microstructures, while Raman mapping allows site-specific intensive analysis of target molecules, which enables ultra-fast identification of cell types. We used human mesenchymal stem cells (MSCs) as a model and induced adipogenesis. Lipid droplets in cells appeared as "blanks" in three-dimensional AF images and site-specific Raman mapping guided by AF identified the structure and components of the CH2 stretch. Adipogenesis could be rapidly and precisely analyzed, not only for the same batch but also for different batches. Therefore, the developed tool is highly useful for the accurate screening of stem cell differentiation and implementation in biomedical and clinical applications.

Direct comparison with terahertz metamaterials and surface-enhanced Raman scattering in a molecular-specific sensing performance.

Signal enhancement of spectroscopies including terahertz time-domain spectroscopy (THz-TDS) and surface-enhanced Raman scattering (SERS) is a critical issue for effective molecular detection and identification. In this study, the sensing performance between THz-TDS and SERS individually accompanied by the proper plasmonic subwavelength structures was compared. For the precisely quantitative study on the optical properties of rhodamine 6G (R6G) dyes, SERS incorporates with the non-linearly enhanced Raman emissions at the molecular characteristic peaks while THz-TDS refers to the transmittance change and the shift of the spectral resonance. The local molecular density-dependent trade-off relationship between limit-of-detection and quenching was observed from both measurements. The specificity for two samples, R6G and methylene blue, is determined by the discriminations in spectral features such as the intensity ratio of assigned peaks in SERS and transmittance difference in THz-TDS. The comprehension of field enhancement by the specific nanostructures was supported by the finite-element method-based numerical computations. As a result, both spectroscopic techniques with the well-tailored nanostructures show great potential for highly sensitive, reproducible, label-free, and cost-effective diagnosis tools in the biomedical fields.

Label-free brain tissue imaging using large-area terahertz metamaterials.

Terahertz (THz) imaging technology has shown significant potential for use in biomedical imaging owing to its non-ionizing characteristics by its low photon energy and its ultrabroadband spectral comparability with many molecular vibrational resonances. However, despite the significant advantage of being able to identify bio-materials in label-free configurations, most meaningful signals are buried by huge water absorption, thus it is very difficult to distinguish them using the small differences in optical constants at THz regime, limiting the practical application of this technology. Here, we demonstrate advanced THz imaging with enhanced color contrast by the use of THz field that is localized and enhanced by a nanometer-scale slot array. THz images of a biological specimen, such as mouse brain tissue and fingerprint, on a nano-slot array-based metamaterial sensing chip, which is elaborately fabricated in large-area, show a higher contrast and clearer boundary information in reflectance without any labeling. A reliable numerical solution to find accurate optical constants using THz nano-slot resonance for the quantitative analysis of target bio-specimens is also introduced. Finally, the precise optical properties of real bio-samples and atlas information are provided for specific areas where amyloid beta proteins, known to cause dementia, have accumulated in a mouse brain.

Asymmetric optical camouflage: tuneable reflective colour accompanied by the optical Janus effect.

Going beyond an improved colour gamut, an asymmetric colour contrast, which depends on the viewing direction, and its ability to readily deliver information could create opportunities for a wide range of applications, such as next-generation optical switches, colour displays, and security features in anti-counterfeiting devices. Here, we propose a simple Fabry-Perot etalon architecture capable of generating viewing-direction-sensitive colour contrasts and encrypting pre-inscribed information upon immersion in particular solvents (optical camouflage). Based on the experimental verification of the theoretical modelling, we have discovered a completely new and exotic optical phenomenon involving a tuneable colour switch for viewing-direction-dependent information delivery, which we define as asymmetric optical camouflage.

Time-Dependent Wetting Scenarios of a Water Droplet on Surface-Energy-Controlled Microcavity Structures with Functional Nanocoatings.

We report the surface-energy-dependent wetting transition characteristics of an evaporating water droplet on surface-energy-controlled microcavity structures with functional nanocoatings. The droplet wetting scenarios were categorized into four types depending on the synergistic effect of surface energy and pattern size. The silicon (Si) microcavity surfaces (γSi = 69.8 mJ/m2) and the polytetrafluoroethylene (PTFE)-coated microcavity surfaces (γPTFE = 15.0 mJ/m2) displayed stable Wenzel and Cassie wetting states, respectively, irrespective of time. In contrast, diamond-like carbon (DLC)-coated (γDLC = 55.5 mJ/m2) and fluorinated diamond-like carbon (FDLC)-coated (γFDLC = 36.2 mJ/m2) surfaces demonstrated a time-dependent transition of wetting states. In particular, the DLC-coated surface showed random filling of microcavities at the earlier time point, while the FDLC-coated surface displayed directional filling of microcavities at the late stage of drop evaporation. Such dynamic wetting scenarios based on surface energy, in particular, the random and directional wetting transitions related to surface energy of nanocoatings have not been explored previously. Furthermore, the microscopic role of nanocoating in the wetting scenarios was analyzed by monitoring the time-dependent deformation and movement of the air-water interface (AWI) at individual cavities using the fluorescence interference-contrast (FLIC) technique. A coating-dependent depinning mechanism of the AWI was responsible for variable filling of cavities leading to time-dependent wetting scenarios. A capillary wetting model was used to relate this depinning event to the evaporation-induced internal flow within the droplet. Interestingly, FLIC analysis revealed that a hydrophilic nanocoating can induce microscopic hydrophobicity near the cavity edges leading to delayed and variable cavity filling. The surface energy-dependent classification of the wetting scenarios may help the design of novel evaporation-assisted thermodynamic and mass-transfer processes.

Precise capture and dynamic relocation of nanoparticulate biomolecules through dielectrophoretic enhancement by vertical nanogap architectures.

Toward the development of surface-sensitive analytical techniques for biosensors and diagnostic biochip assays, a local integration of low-concentration target materials into the sensing region of interest is essential to improve the sensitivity and reliability of the devices. As a result, the dynamic process of sorting and accurate positioning the nanoparticulate biomolecules within pre-defined micro/nanostructures is critical, however, it remains a huge hurdle for the realization of practical surface-sensitive biosensors and biochips. A scalable, massive, and non-destructive trapping methodology based on dielectrophoretic forces is highly demanded for assembling nanoparticles and biosensing tools. Herein, we propose a vertical nanogap architecture with an electrode-insulator-electrode stack structure, facilitating the generation of strong dielectrophoretic forces at low voltages, to precisely capture and spatiotemporally manipulate nanoparticles and molecular assemblies, including lipid vesicles and amyloid-beta protofibrils/oligomers. Our vertical nanogap platform, allowing low-voltage nanoparticle captures on optical metasurface designs, provides new opportunities for constructing advanced surface-sensitive optoelectronic sensors.

Compensation of spin-orbit interaction using the geometric phase of distributed nanoslits for polarization-independent plasmonic vortex generation.

A metasurface is a planar optical device that controls the phase, amplitude, and polarization of light through subwavelength-scale unit elements, called meta-atom. The tunability of plasmonic vortex lens (PVL) which generates surface plasmon polaritons (SPPs) carrying orbital angular momentum can be improved by using meta-atom. However, conventional PVLs exhibit nonuniform field profiles according to the incident polarization states owing to the spin-orbital interaction (SOI) effect observed during SPP excitation. This paper describes a method of compensating for SOI of PVL by using the geometric phase of distributed nanoslits in a gold film. By designing the orientation angles of slit pairs, the anti-phase of the SOI effect can be generated for compensatory effect. In addition, polarization-independent PVLs are designed by applying a detour phase based on the position of the slit pairs. PVLs for center-, off-center-, and multiple-focus cases are demonstrated and measured via a near-field scanning microscope.

Kinetics of lipid raft formation at lipid monolayer-bilayer junction probed by surface plasmon resonance.

A label-free, non-dispruptive, and real-time analytical device to monitor the dynamic features of biomolecules and their interactions with neighboring molecules is an essential prerequisite for biochip- and diagonostic assays. To explore one of the central questions on the lipid-lipid interactions in the course of the liquid-ordered (lo) domain formation, called rafts, we developed a method of reconstituting continuous but spatially heterogeneous lipid membrane platforms with molayer-bilayer juntions (MBJs) that enable to form the lo domains in a spatiotemporally controlled manner. This allows us to detect the time-lapse dynamics of the lipid-lipid interactions during raft formation and resultant membrane phase changes together with the raft-associated receptor-ligand binding through the surface plasmon resonance (SPR). For cross-validation, using epifluorescence microscopy, we demonstrated the underlying mechanisms for raft formations that the infiltration of cholesterols into the sphingolipid-enriched domains plays a crucial roles in the membrane phase-separation. Our membrane platform, being capable of monitoring dynamic interactions among lipids and performing the systematic optical analysis, will unveil physiological roles of cholesterols in a variety of biological events.

Surface Correlation-Based Fingerprinting Method Using LTE Signal for Localization in Urban Canyon.

The Global Satellite Navigation System (GNSS) used in various location-based services is accurate and stable in outdoor environments. However, it cannot be utilized in an indoor environment because of low signal availability and degradation of accuracy due to the multipath distortion of satellite signals in urban areas. On the contrary, LTE signals are available almost everywhere in urban areas and are quite stable without much variation throughout the year. This is because of the fixed location of base stations and the well-maintained policy of mobile communication service providers. Its varied stability and reliability make LTE signals a more viable method for localization. However, there are some complexities in utilizing LTE signals including signal interference distortion phenomena during propagation multipath fading, and various types of noise. In this paper, we propose a surface correlation-based fingerprinting method to utilize LTE signals for localization in urban areas. The surface correlation converts timely measured signal strength into spatial pattern using the walking distance from a Pedestrian Dead-Reckoning (PDR). The surface correlation is carried out by comparing the spatial signal strength pattern of a pedestrian`s movement trajectory with a fingerprinting database to estimate the location. A reference trajectory of the moving pedestrian is chosen to have a greater correlation among the multiple trajectory candidates generated from a link-based fingerprinting database. By comparing spatial signal strength patterns, the proposed method can improve robustness in localization overcoming the accuracy degradation problem due to RF multipath and noise that are dominant in the conventional RSS measurement-based LTE localization scheme. The test results in urban areas demonstrate that the proposed surface correlation-based fingerprinting method has improved performance compared to the other conventional methods, thus proving to be a useful complementary method to the GNSS in urban areas.

Highly Sensitive Color Tunablility by Scalable Nanomorphology of a Dielectric Layer in Liquid-Permeable Metal-Insulator-Metal Structure.

A liquid-permeable concept in a metal-insulator-metal (MIM) structure is proposed to achieve highly sensitive color-tuning property through the change of the effective refractive index of the dielectric insulator layer. A semicontinuous top metal film with nanoapertures, adopted as a transreflective layer for MIM resonator, allows to tailor the nanomorphology of a dielectric layer through selective etching of the underneath insulator layer, resulting in nanopillars and hollow voids in the insulator layer. By allowing outer mediums to enter into the hollow voids of the dielectric layer, such liquid-permeable MIM architecture enables to achieve the wavelength shift as large as 323.5 nm/RIU in the visible range, which is the largest wavelength shift reported so far. Our liquid-permeable approaches indeed provide dramatic color tunablility, a real-time sensing scheme, long-term durability, and reproducibility in a simple and scalable manner.

Artificial Rod and Cone Photoreceptors with Human-Like Spectral Sensitivities.

Photosensitive materials contain biologically engineered elements and are constructed using delicate techniques, with special attention devoted to efficiency, stability, and biocompatibility. However, to date, no photosensitive material has been developed to replace damaged visual-systems to detect light and transmit the signal to a neuron in the human body. In the current study, artificial nanovesicle-based photosensitive materials are observed to possess the characteristics of photoreceptors similar to the human eye. The materials exhibit considerably effective spectral characteristics according to each pigment. Four photoreceptors originating from the human eye with color-distinguishability are produced in human embryonic kidney (HEK)-293 cells and partially purified in the form of nanovesicles. Under various wavelengths of visible light, electrochemical measurements are performed to analyze the physiological behavior and kinetics of the photoreceptors, with graphene, performing as an electrode, playing an important role in the lipid bilayer deposition and oxygen reduction processes. Four nanovesicles with different photoreceptors, namely, rhodopsin (Rho), short-, medium-, and longwave sensitive opsin 1 (1SW, 1MW, 1LW), show remarkable color-dependent characteristics, consistent with those of natural human retina. With four different light-emitting diodes for functional verification, the photoreceptors embedded in nanovesicles show remarkably specific color sensitivity. This study demonstrates the potential applications of light-activated platforms in biological optoelectronic industries.

Ultrasensitive terahertz sensing of gold nanoparticles inside nano slot antennas.

We introduce a robust control method of terahertz (THz) transmission by tuning filling factors of Au nanoparticles (AuNPs) inside nano slot antennas. AuNPs in sub-100 nm diameters were spread over the nano slot antennas, followed by sweeping them into the slots. AuNPs can be efficiently localized and inserted into nano slots where the THz fields are greatly enhanced, by a "squeegee" made of the polydimethylsiloxane (PDMS). The sweeping of the AuNPs results in further dramatic reduction of THz transmission by suppressing the fundamental resonance mode of the nano slot, as compared to a typical random dropping case. It definitely works for an accurate THz transmission control, as well as the removal of unwanted ions that occasionally confuse signal accuracy from the target signals. Our approach provides a complete reinterpretation of sample deposition for further steady demands in developing ultrasensitive terahertz (THz) molecule sensors.