A biophysically constrained brain connectivity model based on stimulation-evoked potentials.

BACKGROUND: Single-pulse electrical stimulation (SPES) is an established technique used to map functional effective connectivity networks in treatment-refractory epilepsy patients undergoing intracranial-electroencephalography monitoring. While the connectivity path between stimulation and recording sites has been explored through the integration of structural connectivity, there are substantial gaps, such that new modeling approaches may advance our understanding of connectivity derived from SPES studies. NEW METHOD: Using intracranial electrophysiology data recorded from a single patient undergoing stereo-electroencephalography (sEEG) evaluation, we employ an automated detection method to identify early response components, C1, from pulse-evoked potentials (PEPs) induced by SPES. C1 components were utilized for a novel topology optimization method, modeling 3D electrical conductivity to infer neural pathways from stimulation sites. Additionally, PEP features were compared with tractography metrics, and model results were analyzed with respect to anatomical features. RESULTS: The proposed optimization model resolved conductivity paths with low error. Specific electrode contacts displaying high error correlated with anatomical complexities. The C1 component strongly correlated with additional PEP features and displayed stable, weak correlations with tractography measures. COMPARISON WITH EXISTING METHOD: Existing methods for estimating neural signal pathways are imaging-based and thus rely on anatomical inferences. CONCLUSIONS: These results demonstrate that informing topology optimization methods with human intracranial SPES data is a feasible method for generating 3D conductivity maps linking electrical pathways with functional neural ensembles. PEP-estimated effective connectivity is correlated with but distinguished from structural connectivity. Modeled conductivity resolves connectivity pathways in the absence of anatomical priors.

Modified Carbon Nanotubes Favor Fibroblast Growth by Tuning the Cell Membrane Potential.

As is known, carbon nanotubes favor cell growth in vitro, although the underlying mechanisms are not yet fully elucidated. In this study, we explore the hypothesis that electrostatic fields generated at the interface between nonexcitable cells and appropriate scaffold might favor cell growth by tuning their membrane potential. We focused on primary human fibroblasts grown on electrospun polymer fibers (poly(lactic acid)─PLA) with embedded multiwall carbon nanotubes (MWCNTs). The MWCNTs were functionalized with either the p-methoxyphenyl (PhOME) or the p-acetylphenyl (PhCOMe) moiety, both of which allowed uniform dispersion in a solvent, good mixing with PLA and the consequent smooth and homogeneous electrospinning process. The inclusion of the electrically conductive MWCNTs in the insulating PLA matrix resulted in differences in the surface potential of the fibers. Both PLA and PLA/MWCNT fiber samples were found to be biocompatible. The main features of fibroblasts cultured on different substrates were characterized by scanning electron microscopy, immunocytochemistry, Rt-qPCR, and electrophysiology revealing that fibroblasts grown on PLA/MWCNT reached a healthier state as compared to pure PLA. In particular, we observed physiological spreading, attachment, and Vmem of fibroblasts on PLA/MWCNT. Interestingly, the electrical functionalization of the scaffold resulted in a more suitable extracellular environment for the correct biofunctionality of these nonexcitable cells. Finally, numerical simulations were also performed in order to understand the mechanism behind the different cell behavior when grown either on PLA or PLA/MWCNT samples. The results show a clear effect on the cell membrane potential, depending on the underlying substrate.

A Quasi-Bound States in the Continuum Dielectric Metasurface-Based Antenna-Reactor Photocatalyst.

Metasurfaces are a class of two-dimensional artificial resonators, creating new opportunities for strong light-matter interactions. One type of nonradiative optical metasurface that enables substantial light concentration is based on quasi-Bound States in the Continuum (quasi-BIC). Here we report the design and fabrication of a quasi-BIC dielectric metasurface that serves as an optical frequency antenna for photocatalysis. By depositing Ni nanoparticle reactors onto the metasurface, we create an antenna-reactor photocatalyst, where the virtually lossless metasurface funnels light to drive a chemical reaction. This quasi-BIC-Ni antenna-reactor drives H2 dissociation under resonant illumination, showing strong polarization, wavelength, and optical power dependencies. Both E-field-induced electronic and photothermal heating effects drive the reaction, supported by load-dependent reactivity studies and our theoretical model. This study unlocks new opportunities for photocatalysis that employ dielectric metasurfaces for light harvesting in an antenna-reactor format.

A biophysically constrained brain connectivity model based on stimulation-evoked potentials.

Background: Single-pulse electrical stimulation (SPES) is an established technique used to map functional effective connectivity networks in treatment-refractory epilepsy patients undergoing intracranial-electroencephalography monitoring. While the connectivity path between stimulation and recording sites has been explored through the integration of structural connectivity, there are substantial gaps, such that new modeling approaches may advance our understanding of connectivity derived from SPES studies. New Method: Using intracranial electrophysiology data recorded from a single patient undergoing sEEG evaluation, we employ an automated detection method to identify early response components, C1, from pulse-evoked potentials (PEPs) induced by SPES. C1 components were utilized for a novel topology optimization method, modeling 3D conductivity propagation from stimulation sites. Additionally, PEP features were compared with tractography metrics, and model results were analyzed with respect to anatomical features. Results: The proposed optimization model resolved conductivity paths with low error. Specific electrode contacts displaying high error correlated with anatomical complexities. The C1 component strongly correlates with additional PEP features and displayed stable, weak correlations with tractography measures. Comparison with existing methods: Existing methods for estimating conductivity propagation are imaging-based and thus rely on anatomical inferences. Conclusions: These results demonstrate that informing topology optimization methods with human intracranial SPES data is a feasible method for generating 3D conductivity maps linking electrical pathways with functional neural ensembles. PEP-estimated effective connectivity is correlated with but distinguished from structural connectivity. Modeled conductivity resolves connectivity pathways in the absence of anatomical priors.

Nanoporous Titanium Oxynitride Nanotube Metamaterials with Deep Subwavelength Heat Dissipation for Perfect Solar Absorption.

We report a quasi-unitary broadband absorption over the ultraviolet-visible-near-infrared range in spaced high aspect ratio, nanoporous titanium oxynitride nanotubes, an ideal platform for several photothermal applications. We explain such an efficient light-heat conversion in terms of localized field distribution and heat dissipation within the nanopores, whose sparsity can be controlled during fabrication. The extremely large heat dissipation could not be explained in terms of effective medium theories, which are typically used to describe small geometrical features associated with relatively large optical structures. A fabrication-process-inspired numerical model was developed to describe a realistic space-dependent electric permittivity distribution within the nanotubes. The resulting abrupt optical discontinuities favor electromagnetic dissipation in the deep sub-wavelength domains generated and can explain the large broadband absorption measured in samples with different porosities. The potential application of porous titanium oxynitride nanotubes as solar absorbers was explored by photothermal experiments under moderately concentrated white light (1-12 Suns). These findings suggest potential interest in realizing solar-thermal devices based on such simple and scalable metamaterials.

Quantifying Efficiency of Remote Excitation for Surface-Enhanced Raman Spectroscopy in Molecular Junctions.

Surface-enhanced Raman spectroscopy (SERS) is enabled by local surface plasmon resonances (LSPRs) in metallic nanogaps. When SERS is excited by direct illumination of the nanogap, the background heating of the lattice and electrons can prevent further manipulation of the molecules. To overcome this issue, we report SERS in electromigrated gold molecular junctions excited remotely: surface plasmon polaritons (SPPs) are excited at nearby gratings, propagate to the junction, and couple to the local nanogap plasmon modes. Like direct excitation, remote excitation of the nanogap can generate both SERS emission and an open-circuit photovoltage (OCPV). We compare the SERS intensity and the OCPV in both direct and remote illumination configurations. SERS spectra obtained by remote excitation are much more stable than those obtained through direct excitation when the photon count rates are comparable. By statistical analysis of 33 devices, the coupling efficiency of remote excitation is calculated to be around 10%, consistent with the simulated energy flow.

Chiral Plasmonic Pinwheels Exhibit Orientation-Independent Linear Differential Scattering under Asymmetric Illumination.

Plasmonic nanoantennas have considerably stronger polarization-dependent optical properties than their molecular counterparts, inspiring photonic platforms for enhancing molecular dichroism and providing fundamental insight into light-matter interactions. One such insight is that even achiral nanoparticles can yield strong optical activity when they are asymmetrically illuminated from a single oblique angle instead of evenly illuminated. This effect, called extrinsic chirality, results from the overall chirality of the experimental geometry and strongly depends on the orientation of the incident light. Although extrinsic chirality has been well-characterized, an analogous effect involving linear polarization sensitivity has not yet been discussed. In this study, we investigate the differential scattering of rotationally symmetric chiral plasmonic pinwheels when asymmetrically irradiated with linearly polarized light. Despite their high rotational symmetry, we observe substantial linear differential scattering that is maintained over all pinwheel orientations. We demonstrate that this orientation-independent linear differential scattering arises from the broken mirror and rotational symmetries of our overall experimental geometry. Our results underscore the necessity of considering both the rotational symmetry of the nanoantenna and the experimental setup, including illumination direction and angle, when performing plasmon-enhanced chiroptical characterizations. Our results demonstrate spectroscopic signatures of an effect analogous to extrinsic chirality for linear polarizations.

Electrostatic polarization fields trigger glioblastoma stem cell differentiation.

Over the last few years it has been understood that the interface between living cells and the underlying materials can be a powerful tool to manipulate cell functions. In this study, we explore the hypothesis that the electrical cell/material interface can regulate the differentiation of cancer stem-like cells (CSCs). Electrospun polymer fibres, either polyamide 66 or poly(lactic acid), with embedded graphene nanoplatelets (GnPs), have been fabricated as CSC scaffolds, providing both the 3D microenvironment and a suitable electrical environment favorable for CSCs adhesion, growth and differentiation. We have investigated the impact of these scaffolds on the morphological, immunostaining and electrophysiological properties of CSCs extracted from human glioblastoma multiform (GBM) tumor cell line. Our data provide evidence in favor of the ability of GnP-incorporating scaffolds to promote CSC differentiation to the glial phenotype. Numerical simulations support the hypothesis that the electrical interface promotes the hyperpolarization of the cell membrane potential, thus triggering the CSC differentiation. We propose that the electrical cell/material interface can regulate endogenous bioelectrical cues, through the membrane potential manipulation, resulting in the differentiation of CSCs. Material-induced differentiation of stem cells and particularly of CSCs, can open new horizons in tissue engineering and new approaches to cancer treatment, especially GBM.

Detection of Strong Light-Matter Interaction in a Single Nanocavity with a Thermal Transducer.

The concept of strong light-matter coupling has been demonstrated in semiconductor structures, and it is poised to revolutionize the design and implementation of components, including solid state lasers and detectors. We demonstrate an original nanospectroscopy technique that permits the study of the light-matter interaction in single subwavelength-sized nanocavities where far-field spectroscopy is not possible using conventional techniques. We inserted a thin (∼150 nm) polymer layer with negligible absorption in the mid-infrared range (5 µm < λ < 12 µm) inside a metal-insulator-metal resonant cavity, where a photonic mode and the intersubband transition of a semiconductor quantum well are strongly coupled. The intersubband transition peaks at λ = 8.3 µm, and the nanocavity is overall 270 nm thick. Acting as a nonperturbative transducer, the polymer layer introduces only a limited alteration of the optical response while allowing to reveal the optical power absorbed inside the concealed cavity. Spectroscopy of the cavity losses is enabled by the polymer thermal expansion due to heat dissipation in the active part of the cavity, and performed using atomic force microscopy (AFM). This innovative approach allows the typical anticrossing characteristic of the polaritonic dispersion to be identified in the cavity loss spectra at the single nanoresonator level. Results also suggest that near-field coupling of the external drive field to the top metal patch mediated by a metal-coated AFM probe tip is possible, and it enables the near-field mapping of the cavity mode symmetry including in the presence of a strong light-matter interaction.

Fast Topology Optimization for Near-Field Focusing All-Dielectric Metasurfaces Using the Discrete Dipole Approximation.

Using an efficient implementation of the discrete dipole approximation and topology optimization, we design all-dielectric metasurfaces capable of focusing light into intense deep subwavelength hotspots. The light focusing of these metasurfaces far outweighs conventional lenses and can provide dramatic enhancements of processes that depend superlinearly on light intensity, such as light-powered membrane distillation and photocatalysis. Our approach can easily be generalized to optimize metasurfaces for other functionalities, such as nonlinear optics or photothermal conversion.

Utilizing the Broad Electromagnetic Spectrum and Unique Nanoscale Properties for Chemical-Free Water Treatment.

Clean water is critical for drinking, industrial processes, and aquatic organisms. Existing water treatment and infrastructure are chemically-intensive and based on nearly century-old technologies that fail to meet modern large and decentralized communities. The next-generation of water processes can transition from outdated technologies by utilizing nanomaterials to harness energy from across the electromagnetic spectrum, enabling electrified and solar-based technologies. The last decade was marked by tremendous improvements in nanomaterial design, synthesis, characterization, and assessment of material properties. Realizing the benefits of these advances requires placing greater attention on embedding nanomaterials onto and into surfaces within reactors and applying external energy sources. This will allow nanomaterial-based processes to replace Victorian-aged, chemical intensive water treatment technologies.

Nanoporous Metals: From Plasmonic Properties to Applications in Enhanced Spectroscopy and Photocatalysis.

The field of plasmonics is capable of enabling interesting applications in different wavelength ranges, spanning from the ultraviolet up to the infrared. The choice of plasmonic material and how the material is nanostructured has significant implications for ultimate performance of any plasmonic device. Artificially designed nanoporous metals (NPMs) have interesting material properties including large specific surface area, distinctive optical properties, high electrical conductivity, and reduced stiffness, implying their potentials for many applications. This paper reviews the wide range of available nanoporous metals (such as Au, Ag, Cu, Al, Mg, and Pt), mainly focusing on their properties as plasmonic materials. While extensive reports on the use and characterization of NPMs exist, a detailed discussion on their connection with surface plasmons and enhanced spectroscopies as well as photocatalysis is missing. Here, we report on different metals investigated, from the most used nanoporous gold to mixed metal compounds, and discuss each of these plasmonic materials' suitability for a range of structural design and applications. Finally, we discuss the potentials and limitations of the traditional and alternative plasmonic materials for applications in enhanced spectroscopy and photocatalysis.

A 3D Plasmonic Antenna-Reactor for Nanoscale Thermal Hotspots and Gradients.

Plasmonic nanoantennas focus light below the diffraction limit, creating strong field enhancements, typically within a nanoscale junction. Placing a nanostructure within the junction can greatly enhance the nanostructure's innate optical absorption, resulting in intense photothermal heating that could ultimately compromise both the nanostructure and the nanoantenna. Here, we demonstrate a three-dimensional "antenna-reactor" geometry that results in large nanoscale thermal gradients, inducing large local temperature increases in the confined nanostructure reactor while minimizing the temperature increase of the surrounding antenna. The nanostructure is supported on an insulating substrate within the antenna gap, while the antenna maintains direct contact with an underlying thermal conductor. Elevated local temperatures are quantified, and high local temperature gradients that thermally reshape only the internal reactor element within each antenna-reactor structure are observed. We also show that high local temperature increases of nominally 200 °C are achievable within antenna-reactors patterned into large extended arrays. This simple strategy can facilitate standoff optical generation of high-temperature hotspots, which may be useful in applications such as small-volume, high-throughput chemical processes, where reaction efficiencies depend exponentially on local temperature.

All-Optically Reconfigurable Plasmonic Metagrating for Ultrafast Diffraction Management.

Hot-electron dynamics taking place in nanostructured materials upon irradiation with fs-laser pulses has been the subject of intensive research, leading to the emerging field of ultrafast nanophotonics. However, the most common description of nonlinear interaction with ultrashort laser pulses assumes a homogeneous spatial distribution for the photogenerated carriers. Here we theoretically show that the inhomogeneous evolution of the hot carriers at the nanoscale can disclose unprecedented opportunities for ultrafast diffraction management. In particular, we design a highly symmetric plasmonic metagrating capable of a transient symmetry breaking driven by hot electrons. The subsequent power imbalance between symmetrical diffraction orders is calculated to exceed 20% under moderate (∼2 mJ/cm2) laser fluence. Our theoretical investigation also indicates that the recovery time of the symmetric configuration can be controlled by tuning the geometry of the metaatom, and can be as fast as 2 ps for electrically connected configurations.

Challenges in Plasmonic Catalysis.

The use of nanoplasmonics to control light and heat close to the thermodynamic limit enables exciting opportunities in the field of plasmonic catalysis. The decay of plasmonic excitations creates highly nonequilibrium distributions of hot carriers that can initiate or catalyze reactions through both thermal and nonthermal pathways. In this Perspective, we present the current understanding in the field of plasmonic catalysis, capturing vibrant debates in the literature, and discuss future avenues of exploration to overcome critical bottlenecks. Our Perspective spans first-principles theory and computation of correlated and far-from-equilibrium light-matter interactions, synthesis of new nanoplasmonic hybrids, and new steady-state and ultrafast spectroscopic probes of interactions in plasmonic catalysis, recognizing the key contributions of each discipline in realizing the promise of plasmonic catalysis. We conclude with our vision for fundamental and technological advances in the field of plasmon-driven chemical reactions in the coming years.

Tuning temperature gradients in subwavelength plasmonic nanocones with tilted illumination.

Inducing and controlling temperature gradients in illuminated subwavelength plasmonic structures is a challenging task. Here, we present a strategy to remotely induce and tune temperature gradients in a subwavelength metallic nanocone by adjusting the angle of incidence of linearly polarized continuous-wave illumination. We demonstrate, through rigorous three-dimensional numerical simulations, that properly tilting the incident illumination angle can increase or decrease the photoinduced temperature gradients within the nanostructure. We analyze the apex-base photoinduced temperature gradient for different illumination directions, resembling typical illumination schemes utilized in surface or tip-enhanced Raman spectroscopy.

Giant photothermoelectric effect in silicon nanoribbon photodetectors.

The photothermoelectric (PTE) effect enables efficient harvesting of the energy of photogenerated hot carriers and is a promising choice for high-efficiency photoelectric energy conversion and photodetection. Recently, the PTE effect was reported in low-dimensional nanomaterials, suggesting the possibility of optimizing their energy conversion efficiency. Unfortunately, the PTE effect becomes extremely inefficient in low-dimensional nanomaterials, owing to intrinsic disadvantages, such as low optical absorption and immature fabrication methods. In this study, a giant PTE effect was observed in lightly doped p-type silicon nanoribbons caused by photogenerated hot carriers. The open-circuit photovoltage responsivity of the device was 3-4 orders of magnitude higher than those of previously reported PTE devices. The measured photovoltage responses fit very well with the proposed photothermoelectric multiphysics models. This research proposes an application of the PTE effect and a possible method for utilizing hot carriers in semiconductors to significantly improve their photoelectric conversion efficiency.

Polarized evanescent waves reveal trochoidal dichroism.

Matter's sensitivity to light polarization is characterized by linear and circular polarization effects, corresponding to the system's anisotropy and handedness, respectively. Recent investigations into the near-field properties of evanescent waves have revealed polarization states with out-of-phase transverse and longitudinal oscillations, resulting in trochoidal, or cartwheeling, field motion. Here, we demonstrate matter's inherent sensitivity to the direction of the trochoidal field and name this property trochoidal dichroism. We observe trochoidal dichroism in the differential excitation of bonding and antibonding plasmon modes for a system composed of two coupled dipole scatterers. Trochoidal dichroism constitutes the observation of a geometric basis for polarization sensitivity that fundamentally differs from linear and circular dichroism. It could also be used to characterize molecular systems, such as certain light-harvesting antennas, with cartwheeling charge motion upon excitation.

Galvanic Replacement Reaction as a Route to Prepare Nanoporous Aluminum for UV Plasmonics.

There is a growing interest in extending plasmonics applications into the ultraviolet region of the electromagnetic spectrum. Noble metals are commonly used in plasmonic, but their intrinsic optical properties limit their use above 350 nm. Aluminum is probably the most suitable material for UV plasmonics, and in this work we fabricated substrates of nanoporous aluminum starting from an alloy of Al2Mg3. The porous metal is obtained by means of a galvanic replacement reaction. Such nanoporous metal can be exploited to achieve a plasmonic material suitable for enhanced UV Raman spectroscopy and fluorescence. Thanks to the large surface to volume ratio, this material represents a powerful platform for promoting interaction between plasmonic substrates and molecules in the UV.

Solar thermal desalination as a nonlinear optical process.

The ever-increasing global need for potable water requires practical, sustainable approaches for purifying abundant alternative sources such as seawater, high-salinity processed water, or underground reservoirs. Evaporation-based solutions are of particular interest for treating high salinity water, since conventional methods such as reverse osmosis have increasing energy requirements for higher concentrations of dissolved minerals. Demonstration of efficient water evaporation with heat localization in nanoparticle solutions under solar illumination has led to the recent rapid development of sustainable, solar-driven distillation methods. Given the amount of solar energy available per square meter at the Earth's surface, however, it is important to utilize these incident photons as efficiently as possible to maximize clean water output. Here we show that merely focusing incident sunlight into small "hot spots" on a photothermally active desalination membrane dramatically increases--by more than 50%--the flux of distilled water. This large boost in efficiency results from the nearly exponential dependence of water vapor saturation pressure on temperature, and therefore on incident light intensity. Exploiting this inherent but previously unrecognized optical nonlinearity should enable the design of substantially higher-throughput solar thermal desalination methods. This property provides a mechanism capable of enhancing a far wider range of photothermally driven processes with supralinear intensity dependence, such as light-driven chemical reactions and separation methods.