Molecular Energy Transfer under the Strong Light-Matter Interaction Regime.

Research into strong light-matter interactions continues to fascinate, being spurred on by unforeseen and often spectacular experimental observations. Properties that were considered to depend exclusively on material composition have been found to be drastically altered when a material is placed inside a resonant optical cavity. This is nowhere more the case than in the field of intermolecular energy transfer, where polaritonic states formed as a result of strong light-matter interactions have been shown to promote energy transfer over distances vastly exceeding conventional limits. In this review, we provide the reader with a succinct account of the fundamental concepts of intermolecular energy transfer, and how they are modified by strong light-matter interactions. We also summarize recent experimental advances in the area, including in optoelectronic device contexts, and highlight both the potential and challenges that remain in this exciting field of research going forward.

Probing the Interaction between Individual Metal Nanocrystals and Two-Dimensional Metal Oxides via Electron Energy Loss Spectroscopy.

Metal nanoparticles can photosensitize two-dimensional metal oxides, facilitating their electrical connection to devices and enhancing their abilities in catalysis and sensing. In this study, we investigated how individual silver nanoparticles interact with two-dimensional tin oxide and antimony-doped indium oxide using electron energy loss spectroscopy (EELS). The measurement of the spectral line width of the longitudinal plasmon resonance of the nanoparticles in absence and presence of 2D materials allowed us to quantify the contribution of chemical interface damping to the line width. Our analysis reveals that a stronger interaction (damping) occurs with 2D antimony-doped indium oxide due to its highly homogeneous surface. The results of this study offer new insight into the interaction between metal nanoparticles and 2D materials.

Photoactive p-Type Spinel CuGa2O4 Nanocrystals.

Herein we report the synthesis and characterization of spinel copper gallate (CuGa2O4) nanocrystals (NCs) with an average size of 3.7 nm via a heat-up colloidal reaction. CuGa2O4 NCs have a band gap of ∼2.5 eV and marked p-type character, in agreement with ab initio simulations. These novel NCs are demonstrated to be photoactive, generating a clear and reproducible photocurrent under blue light irradiation when deposited as thin films. Crucially, the ability to adjust the Cu/Ga ratio within the NCs, and the effect of this on the optical and electronic properties of the NCs, was also demonstrated. These results position CuGa2O4 NCs as a novel material for optoelectronic applications, including hole transport and light harvesting.

A comparison of multiband and multiband multiecho gradient-echo EPI for task fMRI at 3 T.

A multiband (MB) echo-planar imaging (EPI) sequence is compared to a multiband multiecho (MBME) EPI protocol to investigate differences in sensitivity for task functional magnetic resonance imaging (fMRI) at 3 T. Multiecho sampling improves sensitivity in areas where single-echo-EPI suffers from dropouts. However, It requires in-plane acceleration to reduce the echo train length, limiting the slice acceleration factor and the temporal and spatial resolution Data were acquired for both protocols in two sessions 24 h apart using an adapted color-word interference Stroop task. Besides protocol comparison statistically, we performed test-retest reliability across sessions for different protocols and denoising methods. We evaluated the sensitivity of two different echo-combination strategies for MBME-EPI. We examined the performance of three different data denoising approaches: "Standard," "AROMA," and "FIX" for MB and MBME, and assessed whether a specific method is preferable. We consider using an appropriate autoregressive model order within the general linear model framework to correct TR differences between the protocols. The comparison between protocols and denoising methods showed at group level significantly higher mean z-scores and the number of active voxels for MBME in the motor, subcortical and medial frontal cortices. When comparing different echo combinations, our results suggest that a contrast-to-noise ratio weighted echo combination improves sensitivity in MBME compared to simple echo-summation. This study indicates that MBME can be a preferred protocol in task fMRI at spatial resolution (≥2 mm), primarily in medial prefrontal and subcortical areas.

Solution processed bismuth oxyiodide (BiOI) thin films and solar cells.

Post transition metal chalcohalides are an emerging class of semiconductor materials for optoelectronic applications. Within this class, bismuth oxyiodide (BiOI) is of particular interest due to its high environmental stability, low toxicity, and defect tolerance considered typical of 'ns2' materials. Here we fabricate BiOI thin films using a solution-processed method that affords pin-hole free highly pure films without any residual carbon or other contaminant species. Based on these films, solution processed all-inorganic solar cells with an architecture ITO/NiOx/BiOI/ZnO/Al are fabricated for the first time. Additional device improvements are realised by templating BiOI thin film growth to attain efficiencies that rival some of the best vacuum deposited devices. The BiOI thin films and devices outlined here are an excellent platform for the further development of solution processed bismuth chalcohalide optoelectronic devices.

Photoinitiated Energy Transfer in Porous-Cage-Stabilised Silver Nanoparticles.

We report a new composite material consisting of silver nanoparticles decorated with three-dimensional molecular organic cages based on light-absorbing porphyrins. The porphyrin cages serve to both stabilize the particles and allow diffusion and trapping of small molecules close to the metallic surface. Combining these two photoactive components results in a Fano-resonant interaction between the porphyrin Soret band and the nanoparticle-localised surface-plasmon resonance. Time-resolved spectroscopy revealed the silver nanoparticles transfer up to 37 % of their excited-state energy to the stabilising layer of porphyrin cages. These unusual photophysics cause a 2-fold current increase in photoelectrochemical water-splitting measurements. The composite structure provides a compelling proof of concept for advanced photosensitiser systems with intrinsic porosity for photocatalytic and sensing applications.

Reinterpreting the Fate of Iridium(III) Photocatalysts─Screening a Combinatorial Library to Explore Light-Driven Side-Reactions.

Photoredox catalysts are primarily selected based on ground and excited state properties, but their activity is also intrinsically tied to the nature of their reduced (or oxidized) intermediates. Catalyst reactivity often necessitates an inherent instability, thus these intermediates represent a mechanistic turning point that affords either product formation or side-reactions. In this work, we explore the scope of a previously demonstrated side-reaction that partially saturates one pyridine ring of the ancillary ligand in heteroleptic iridium(III) complexes. Using high-throughput synthesis and screening under photochemical conditions, we identified different chemical pathways, ultimately governed by ligand composition. The ancillary ligand was the key factor that determined photochemical stability. Following photoinitiated electron transfer from a sacrificial tertiary amine, the reduced intermediate of complexes containing 1,10-phenanthroline derivatives exhibited long-term stability. In contrast, complexes containing 2,2'-bipyridines were highly susceptible to hydrogen atom transfer and ancillary ligand modification. Detailed characterization of selected complexes before and after transformation showed differing effects on the ground and excited state reduction potentials dependent on the nature of the cyclometalating ligands and excited states. The implications of catalyst stability and reactivity in chemical synthesis was demonstrated in a model photoredox reaction.

New inhibitor targeting Acyl-CoA synthetase 4 reduces breast and prostate tumor growth, therapeutic resistance and steroidogenesis.

Acyl-CoA synthetase 4 (ACSL4) is an isoenzyme of the fatty acid ligase-coenzyme-A family taking part in arachidonic acid metabolism and steroidogenesis. ACSL4 is involved in the development of tumor aggressiveness in breast and prostate tumors through the regulation of various signal transduction pathways. Here, a bioinformatics analysis shows that the ACSL4 gene expression and proteomic signatures obtained using a cell model was also observed in tumor samples from breast and cancer patients. A well-validated ACSL4 inhibitor, however, has not been reported hindering the full exploration of this promising target and its therapeutic application on cancer and steroidogenesis inhibition. In this study, ACSL4 inhibitor PRGL493 was identified using a homology model for ACSL4 and docking based virtual screening. PRGL493 was then chemically characterized through nuclear magnetic resonance and mass spectroscopy. The inhibitory activity was demonstrated through the inhibition of arachidonic acid transformation into arachidonoyl-CoA using the recombinant enzyme and cellular models. The compound blocked cell proliferation and tumor growth in both breast and prostate cellular and animal models and sensitized tumor cells to chemotherapeutic and hormonal treatment. Moreover, PGRL493 inhibited de novo steroid synthesis in testis and adrenal cells, in a mouse model and in prostate tumor cells. This work provides proof of concept for the potential application of PGRL493 in clinical practice. Also, these findings may prove key to therapies aiming at the control of tumor growth and drug resistance in tumors which express ACSL4 and depend on steroid synthesis.

Near-Perfect Absorption of Light by Coherent Plasmon-Exciton States.

We experimentally demonstrate and theoretically study the formation of coherent plasmon-exciton states which exhibit absorption of >90% of the incident light (at resonance) and cancellation of absorption. These coherent states result from the interaction between a material supporting an electronic excitation and a plasmonic structure capable of (near) perfect absorption of light. We illustrate the potential implications of these coherent states by measuring the charge separation attainable after photoexcitation. Our study opens the prospect for realizing devices that exploit coherent effects in applications.

Orientation-Dependent Soft Plasmonics of Gold Nanobipyramid Plasmene Nanosheets.

In parallel to the burgeoning field of soft electronics, soft plasmonics focuses on the design and fabrication of plasmonic structures supported on elastomers and to understand how their properties respond to mechanical deformations. Here, we report on a partial ligand-stripping strategy to fabricate elastomer-supported gold nanobipyramid (NBP) plasmene nanosheets. Unlike spherelike building blocks, NBP-building blocks display complex orientation-dependent plasmonic responses to external strains. By collecting polarized plasmonic resonance spectra in conjunction with electrostatic eigenmode modeling, we reveal simultaneous changes in interparticle spacing and spatial orientations of NBP building blocks under mechanical strains. Such changes are directly related to initial NBP packing orders. Further analysis of strain sensitivities for various NBP plasmenes indicated that plasmonic spectra of ∼45° oriented samples are mostly susceptible to strain at acute polarized angles. The results presented may enable novel applications in future soft optoelectronic devices in sensing, encryption, and data storage.

Single-subject Single-session Temporally-Independent Functional Modes of Brain Activity.

Temporally independent functional modes (TFMs) are functional brain networks identified based on their temporal independence. The rationale behind identifying TFMs is that different functional networks may share a common anatomical infrastructure yet display distinct temporal dynamics. Extracting TFMs usually require a larger number of samples than acquired in standard fMRI experiments, and thus have therefore previously only been performed at the group level. Here, using an ultra-fast fMRI sequence, MESH-EPI, with a volume repetition time of 158 â€‹ms, we conducted an exploratory study with n â€‹= â€‹6 subjects and computed TFMs at the single subject level on both task and resting-state datasets. We identified 6 common temporal modes of activity in our participants, including a temporal default mode showing patterns of anti-correlation between the default mode and the task-positive networks, a lateralised motor mode and a visual mode integrating the visual cortex and the visual streams. In alignment with other findings reported recently, we also showed that independent time-series are largely free from confound contamination. In particular for ultra-fast fMRI, TFMs can separate the cardiac signal from other fluctuations. Using a non-linear dimensionality reduction technique, UMAP, we obtained preliminary evidence that combinations of spatial networks as described by the TFM model are highly individual. Our results show that it is feasible to measure reproducible TFMs at the single-subject level, opening new possibilities for investigating functional networks and their integration. Finally, we provide a python toolbox for generating TFMs and comment on possible applications of the technique and avenues for further investigation.

A Tunable Polymer-Metal Based Anti-Reflective Metasurface.

Anti-reflective surfaces are of great interest for optical devices, sensing, photovoltaics, and photocatalysis. However, most of the anti-reflective surfaces lack in situ tunability of the extinction with respect to wavelength. This communication demonstrates a tunable anti-reflective surface based on colloidal particles comprising a metal core with an electrochromic polymer shell. Random deposition of these particles on a reflective surface results in a decrease in the reflectance of up to 99.8% at the localized surface plasmon resonance frequency. This narrow band feature can be tuned by varying the pH or by application of an electric potential, resulting in wavelength shifts of up to 30 nm. Electrophoretic particle deposition is shown to be an efficient method for controlling the interparticle distance and thereby further optimizing the overall efficiency of the anti-reflective metasurface.

Mapping Local Surface Plasmon Modes in a Nanoplasmonic Trimer Using Cathodoluminescence in the Scanning Electron Microscope.

The excitability of local surface plasmon modes in radial trimers composed of gold nanorods was mapped using hyperspectral cathodoluminescence (CL) in the scanning electron microscope. In symmetric trimers, the local plasmon resonances could be excited most effectively at the ends of individual rods. Introducing asymmetry into the structure breaks the degeneracy of the dipole modes and changes the excitability of transverse dipole modes in different directions. CL in the scanning electron microscope has great potential to interrogate individual nanophotonic structures and is a complement to electron energy loss spectroscopy and optical microscopy.

The Tandem Photoredox Catalysis Mechanism of [Ir(ppy)2(dtb-bpy)]+ Enabling Access to Energy Demanding Organic Substrates.

We report the discovery of a tandem catalytic process to reduce energy demanding substrates, using the [Ir(ppy)2(dtb-bpy)]+ (1+) photocatalyst. The immediate products of photoinitiated electron transfer (PET) between 1+ and triethylamine (TEA) undergo subsequent reactions to generate a previously unknown, highly reducing species (2). Formation of 2 occurs via reduction and semisaturation of the ancillary dtb-bpy ligand, where the TEA radical cation serves as an effective hydrogen atom donor, confirmed by nuclear magnetic resonance, mass spectrometry, and deuterium labeling experiments. Steady-state and time-resolved luminescence and absorption studies reveal that upon irradiation, 2 undergoes electron transfer or proton-coupled electron transfer (PCET) with a representative acceptor (N-(diphenylmethylene)-1-phenylmethanamine; S). Turnover of this new photocatalytic cycle occurs along with the reformation of 1+. We rationalize our observations by proposing the first example of a mechanistic pathway where two distinct yet interconnected photoredox cycles provide access to an extended reduction potential window capable of engaging a wide range of energy demanding and synthetically relevant organic substrates including aryl halides.

Broadband High-Efficiency Chiral Splitters and Holograms from Dielectric Nanoarc Metasurfaces.

Simultaneous broadband and high efficiency merits of designer metasurfaces are currently attracting widespread attention in the field of nanophotonics. However, contemporary metasurfaces rarely achieve both advantages simultaneously. For the category of transmissive metadevices, plasmonic or conventional dielectric metasurfaces are viable for either broadband operation with relatively low efficiency or high efficiency at only a selection of wavelengths. To overcome this limitation, dielectric nanoarcs are proposed as a means to accomplish two advantages. Continuous nanoarcs support different electromagnetic resonant modes at localized areas for generating phase retardation. Meanwhile, the geometric nature of nanoarc curvature endows the nanoarcs with full phase coverage of 0-2π due to the Pancharatnam-Berry phase principle. Experimentally incorporated with the chiral-detour phase principle, a few compelling functionalities are demonstrated, such as chiral beamsplitting, broadband holography, and helicity-selective holography. The continuous nanoarc metasurfaces prevail over plasmonic or dielectric discretized building block strategies and the findings lead to novel designs of spin-controllable metadevices.

Telomeropathies: Etiology, diagnosis, treatment and follow-up. Ethical and legal considerations.

Telomeropathies involve a wide variety of infrequent genetic diseases caused by mutations in the telomerase maintenance mechanism or the DNA damage response (DDR) system. They are considered a family of rare diseases that often share causes, molecular mechanisms and symptoms. Generally, these diseases are not diagnosed until the symptoms are advanced, diminishing the survival time of patients. Although several related syndromes may still be unrecognized this work describes those that are known, highlighting that because they are rare diseases, physicians should be trained in their early diagnosis. The etiology and diagnosis are discussed for each telomeropathy and the treatments when available, along with a new classification of this group of diseases. Ethical and legal issues related to this group of diseases are also considered.

Optical image processing with metasurface dark modes.

Here we consider image processing using the optical modes of metasurfaces with an angle-dependent excitation. These spatially dispersive modes can be used to directly manipulate the spatial frequency content of an incident field, suggesting their use as ultra-compact alternatives for analog optical information processing. A general framework for describing the filtering process in terms of the optical transfer functions is provided. In the case where the relevant mode cannot be excited with a normally incident plane wave (a dark mode), high-pass filtering is obtained. We provide examples demonstrating filtering of both amplitude and pure phase objects.

Luminescence of a Transition Metal Complex Inside a Metamaterial Nanocavity.

Modification of the local density of optical states using metallic nanostructures leads to enhancement in the number of emitted quanta and photocatalytic turnover of luminescent materials. In this work, the fabrication of a metamaterial is presented that consists of a nanowire separated from a metallic mirror by a polymer thin film doped with a luminescent organometallic iridium(III) complex. The large spin-orbit coupling of the heavy metal atom results in an excited state with significant magnetic-dipole character. The nanostructured architecture supports two distinct optical modes and their assignment achieved with the assistance of numerical simulations. The simulations show that one mode is characterized by strong confinement of the electric field and the other by strong confinement of the magnetic field. These modes elicit drastic changes in the emitter's photophysical properties, including dominant nanocavity-derived modes observable in the emission spectra along with significant increases in emission intensity and the total decay rate. A combination of simulations and momentum-resolved spectroscopy helps explain the mechanism of the different interactions of each optical mode supported by the metamaterial with the excited state of the emitter.

Photoinduced Electron Transfer in the Strong Coupling Regime: Waveguide-Plasmon Polaritons.

Reversible exchange of photons between a material and an optical cavity can lead to the formation of hybrid light-matter states where material properties such as the work function [ Hutchison et al. Adv. Mater. 2013 , 25 , 2481 - 2485 ], chemical reactivity [ Hutchison et al. Angew. Chem., Int. Ed. 2012 , 51 , 1592 - 1596 ], ultrafast energy relaxation [ Salomon et al. Angew. Chem., Int. Ed. 2009 , 48 , 8748 - 8751 ; Gomez et al. J. Phys. Chem. B 2013 , 117 , 4340 - 4346 ], and electrical conductivity [ Orgiu et al. Nat. Mater. 2015 , 14 , 1123 - 1129 ] of matter differ significantly to those of the same material in the absence of strong interactions with the electromagnetic fields. Here we show that strong light-matter coupling between confined photons on a semiconductor waveguide and localized plasmon resonances on metal nanowires modifies the efficiency of the photoinduced charge-transfer rate of plasmonic derived (hot) electrons into accepting states in the semiconductor material. Ultrafast spectroscopy measurements reveal a strong correlation between the amplitude of the transient signals, attributed to electrons residing in the semiconductor and the hybridization of waveguide and plasmon excitations.

[Rho GTPases as molecular targets in cancer. Strategies and therapeutic opportunities]. / Rho GTPasas como blancos moleculares en cáncer. Estrategias y oportunidades terapéuticas.

Rho GTPases are molecular switches that control the different cellular processes. Deregulation of these proteins is associated to transformation and malignant progression in several cancer types. Given the evidence available of the role of Rho GTPases in cancer it is suggested that these proteins can serve as potential therapeutic targets. This review focuses on the strategies used to develop Rho GTPases modulators and their potential use in therapeutic settings.