Grip strength, working memory, and emotion perception in middle-aged males.

This study examined the association between grip strength and emotional working memory in middle-aged adults. Seventy-six males aged 40-60years (mean=48.5years, SD=5.4) participated in this cross-sectional study. They completed a muscular fitness assessment using a maximum grip strength test and emotional n-back tasks under two emotion conditions (fearful and neutral facial pictures) and two working memory loads (1-back and 2-back tasks). Hierarchical regression analyses indicated that greater muscular fitness was associated with superior working memory performance in the fearful condition in both the 1-back and 2-back tasks, after controlling for confounders. Greater muscular fitness was also associated with superior working memory performance in the neutral condition when the working memory load was high (2-back task) but not low (1-back task). These findings suggest a positive association between muscular fitness and emotional working memory and highlight the importance of maintaining muscular fitness for physical and cognitive-emotional well-being in middle-aged adults.

Hematite (α-Fe2O3) with Oxygen Defects: The Effect of Heating Rate for Photocatalytic Performance.

Hematite (α-Fe2O3) emerges as an enticing material for visible-light-driven photocatalysis owing to its remarkable stability, low toxicity, and abundance. However, its inherent shortcomings, such as a short hole diffusion length and high recombination rate, hinder its practical application. Recently, oxygen vacancies (Vo) within hematite have been demonstrated to modulate its photocatalytic attributes. The effects of Vo can be broadly categorized into two opposing aspects: (1) acting as electron donors, enhancing carrier conductivity, and improving photocatalytic performance and (2) acting as surface carrier traps, accelerating excited carrier recombination, and deteriorating performance. Critically, the generation rate, distribution, role, and behavior of Vo significantly differ for synthesis methods due to differences in formation mechanisms and oxygen diffusion. This complexity hampers simplified discussions of Vo, necessitating careful investigation and nuanced discussion tailored to the specific method and conditions employed. Among various approaches, hydrothermal synthesis offers a simple and cost-effective route. Here, we demonstrate a hydrothermal synthesis method for Vo introduction to hematite using a carbon source, where variations in the heating rate have not been previously explored in terms of their influence on Vo generation. The analyses revealed that the concentration of Vo was maximized at a heating rate of 16 °C/min, indicative of a high density of surface defects. With regard to photocatalytic performance, elevated heating rates (16 °C/min) fostered the formation of Vo primarily on the hematite surface. The photocatalytic activity was 7.1 times greater than that of the sample prepared at a low heating rate (2 °C/min). These findings highlight the crucial role of surface defects, as opposed to bulk defects, in promoting hematite photocatalysis. Furthermore, the facile control over Vo concentration achievable via manipulating the heating rate underscores the promising potential of this approach for optimizing hematite photocatalysts.

Coherent electronic coupling in quantum dot solids induces cooperative enhancement of nonlinear optoelectronic responses.

Synchronized dynamics of quantum dot (QD) ensembles are essential for generating ultrafast and giant optical responses beyond those of individual QDs. Increasing the strength of the direct electronic coupling between QDs is a key strategy for the realization of cooperative quantum phenomena. Here, we observe a quantum cooperative effect on nonlinear photocurrents caused by the coherent electronic coupling in semiconductor QD solids. We measure quantum interference signals cooperatively generated in QD solids. We control the inter-QD distance with atomic precision using bidentate ligands that strongly link the QDs. The harmonic quantum interference signals are strongly enhanced when shortening the molecular length of the ligand. Furthermore, we clarify that the coherence length of multiexcitons extends to neighbouring QDs. This finding is direct evidence that multiexciton coherent tunnelling assists the ultrafast exciton delocalization. Cooperative enhancement in QD solids may find application in advanced quantum optoelectronics.

Localised surface plasmon resonance inducing cooperative Jahn-Teller effect for crystal phase-change in a nanocrystal.

The Jahn-Teller effect, a phase transition phenomenon involving the spontaneous breakdown of symmetry in molecules and crystals, causes important physical and chemical changes that affect various fields of science. In this study, we discovered that localised surface plasmon resonance (LSPR) induced the cooperative Jahn-Teller effect in covellite CuS nanocrystals (NCs), causing metastable displacive ion movements. Electron diffraction measurements under photo illumination, ultrafast time-resolved electron diffraction analyses, and theoretical calculations of semiconductive plasmonic CuS NCs showed that metastable displacive ion movements due to the LSPR-induced cooperative Jahn-Teller effect delayed the relaxation of LSPR in the microsecond region. Furthermore, the displacive ion movements caused photo-switching of the conductivity in CuS NC films at room temperature (22 °C), such as in transparent variable resistance infrared sensors. This study pushes the limits of plasmonics from tentative control of collective oscillation to metastable crystal structure manipulation.

Hot hole transfer at the plasmonic semiconductor/semiconductor interface.

Localized surface plasmon resonance (LSPR)-induced hot-carrier transfer provides an attractive alternative for light-harvesting using the full solar spectrum. This defect-mediated hot-carrier transfer is identical at the plasmonic semiconductor/semiconductor interface and can overcome the low efficiency of plasmonic energy conversion, thus boosting the efficiency of IR-light towards energy conversion. Here, using femtosecond transient absorption (TA) measurements, we directly observe the ultrafast non-radiative carrier dynamics of LSPR-driven hot holes created in CuS nanocrystals (NCs) and CuS/CdS hetero nanocrystals (HNCs). We demonstrate that in the CuS NCs, the relaxation dynamics follows multiple relaxation pathways. Two trap states are populated by the LSPR-induced hot holes in times (100-500 fs) that efficiently compete with the conventional LSPR mechanism (250 fs). The trapped hot holes intrinsically relax in 20-40 ps and then decay in 80 ns and 700 ns. In the CuS/CdS HNCs, once the CuS trap states have been populated by the LSPR-generated hot holes, the holes get transferred through plasmon induced transit hole transfer (PITCT) mechanism in 200-300 ps to the CdS acceptor phase and relax in 1-8 and 40-50 µs. The LSPR-recovery shows a weak excitation wavelength and fluence dependence, while the dynamics of the trap states remains largely unaffected. The direct observation of formation and decay processes of trap states and hole transfer from trap states provides important insight into controlling the LSPR-induced relaxation of degenerate semiconductors.

Fast, Economical, and Reproducible Sensing from a 2D Si Wire Array: Accurate Characterization by Single Wire Spectroscopy.

Silicon (Si) is promising as a field enhancement material because of its high abundance, low toxicity, and high refractive index. The field enhancement effect intensifies light-matter interactions, which improves photocatalysis, solar cell performance, and sensor sensitivity. To manufacture field enhancement materials on a production scale, the fabrication technique must be simple, cost-effective, fast, and highly reproducible and must produce a high enhancement factor (EF). Herein, we report on an economical and efficient fabrication method for a field enhancement substrate consisting of a two-dimensional Si wire array (2D-SiWA). This substrate was demonstrated as a fluorescence sensor with high sensitivity (EF > 200) and composed of a large area (6.0 mm2). In addition, single wire spectroscopy was used to identify very high reproducibility of the sensor sensitivity in regular regions (97%) and a mixture of regular and irregular regions (87%) of the 2D-SiWA. The large-area Si fluorescence sensor fabrication was cost-effective and rapid and was 50× less expensive, 20×faster, and 60,000×larger than the typical electron beam lithography method.

Experience-Dependent Modulation of Rubber Hand Illusion in Badminton Players.

Badminton players have a plastic modification of their arm representation in the brain due to the prolonged use of their racket. However, it is not known whether their arm representation can be altered through short-term visuotactile integration. The neural representation of the body is easily altered when multiple sensory signals are integrated in the brain. One of the most popular experimental paradigms for investigating this phenomenon is the "rubber hand illusion." This study was designed to investigate the effect of prolonged use of a racket on the modulation of arm representation during the rubber hand illusion in badminton players. When badminton players hold the racket, their badminton experience in years is negatively correlated with the magnitude of the rubber hand illusion. This finding suggests that tool embodiment obtained by the prolonged use of the badminton racket is less likely to be disturbed when holding the racket.

Near-Unity Singlet Fission on a Quantum Dot Initiated by Resonant Energy Transfer.

The conversion of a high-energy photon into two excitons using singlet fission (SF) has stimulated a variety of studies in fields from fundamental physics to device applications. However, efficient SF has only been achieved in limited systems, such as solid crystals and covalent dimers. Here, we established a novel system by assembling 4-(6,13-bis(2-(triisopropylsilyl)ethynyl)pentacen-2-yl)benzoic acid (Pc) chromophores on nanosized CdTe quantum dots (QDs). A near-unity SF (198 ± 5.7%) initiated by interfacial resonant energy transfer from CdTe to surface Pc was obtained. The unique arrangement of Pc determined by the surface atomic configuration of QDs is the key factor realizing unity SF. The triplet-triplet annihilation was remarkably suppressed due to the rapid dissociation of triplet pairs, leading to long-lived free triplets. In addition, the low light-harvesting ability of Pc in the visible region was promoted by the efficient energy transfer (99 ± 5.8%) from the QDs to Pc. The synergistically enhanced light-harvesting ability, high triplet yield, and long-lived triplet lifetime of the SF system on nanointerfaces could pave the way for an unmatched advantage of SF.

Attenuation of sensory processing in the primary somatosensory cortex during rubber hand illusion.

The neural representation of the body is easily altered by the integration of multiple sensory signals in the brain. The "rubber hand illusion" (RHI) is one of the most popular experimental paradigms to investigate this phenomenon. During this illusion, a feeling of ownership of the rubber hand is created. Some studies have shown that somatosensory processing in the brain is attenuated when RHI occurs. However, it is unknown where attenuation of somatosensory processing occurs. Here, we show that somatosensory processing is attenuated in the primary somatosensory cortex. We found that the earliest response of somatosensory evoked potentials, which is thought to originate from the primary somatosensory cortex, was attenuated during RHI. Furthermore, this attenuation was observed before the occurrence of the illusion. Our results suggest that attenuation of sensory processing in the primary somatosensory cortex is one of the factors influencing the occurrence of the RHI.

Morphology-Dependent Coherent Acoustic Phonon Vibrations and Phonon Beat of Au Nanopolyhedrons.

Coherent acoustic phonon vibrations of Au nanopolyhedrons, including nanocubes, nano-octahedrons, and nanocuboctahedrons, in aqueous solutions and poly(vinyl alcohol) (PVA) films, were investigated using transient absorption (TA) spectroscopy combined with finite element analysis based on continuum elastic theory. In each type of nanopolyhedron, two vibrational modes with similar quality factors (Qs) and phases were observed, suggesting that both were induced by thermal expansion. The low-frequency vibrational mode represents a tip-to-tip displacement in each nanopolyhedron, whereas the high-frequency mode is the breathing vibration of the whole particle and reveals morphology dependence, displaying a face-to-face displacement in nanocuboctahedrons, an edge-to-edge displacement in nano-octahedrons, and a combination of face-to-face and edge-to-edge displacements in nanocubes. Moreover, a clear phonon beat was identified in the two vibrational modes of the nanocuboctahedrons. Our experimental results provide a possible application of morphology-controllable metal nanoresonators.

Large Field Enhancement of Nanocoral Structures on Porous Si Synthesized from Rice Husks.

Silicon (Si) is a highly abundant, environmentally benign, and durable material and is the most popular semiconductor material; and it is used for the field enhancement of dielectric materials. Porous Si (PSi) exhibits high functionality due to its specific structure. However, the field enhancement of PSi has not been clarified sufficiently. Herein, we present the field enhancement of PSi by the fluorescence intensity enhancement of a dye molecule. The raw material used for producing PSi was rice husk, a biomass material. A nanocoral structure, consisting of spheroidal structures on the surface of PSi, was observed when PSi was subjected to chemical processes and pulsed laser melting, and it demonstrated large field enhancement with an enhancement factor (EF) of up to 545. Confocal microscopy was used for EF mapping of samples before and after laser melting, and the maps were superimposed on nanoscale scanning electron microscope images to highlight the EF effect as a function of microstructure. Nanocoral Si with high EF values were also evaluated by analyzing the porosity from gas adsorption measurements. Nanocoral Si was responsible for the high EF, according to thermodynamic calculations and agreement between experimental and calculation results as determined by Mie scattering theory.

Nanogap-Rich TiO2 Film for 2000-Fold Field Enhancement with High Reproducibility.

Titanium dioxide (TiO2) is a crucial semiconductor for photocatalysts, solar cells, hydrogen evolution reactions, and antivirus agents. The properties and performances of these applications can improve significantly if the integrated TiO2 acts as a light harvester through a large field enhancement. This study investigates the electromagnetic field enhancement of a nanogap-rich TiO2 film with a large area, prepared by a facile dry process at room temperature. Herein, the loading pressure is applied to the TiO2 particles for closely packing them in the film. The field enhancement, as a function of the loading pressure, is explored from the fluorescence intensity enhancement of a dye molecule. An average enhancement factor >2000 is achieved, which is a remarkable record for semiconductors. Furthermore, the reproducibility is significant; the relative standard deviation value is small (∼4%). Calculations were performed using the finite-difference-time-domain method. A nanogap of 5 nm yields the highest EF for triangular-prism TiO2 particles.

1% defect enriches MoS2 quantum dot: catalysis and blue luminescence.

Defects in solids are typically recognized as unfavorable, leading to degradation of the structure and properties of the material. However, defects occasionally provide extraordinary benefits as the active sites of catalysts and chemical reactions, and can result in the creation of new electronic states. In particular, a low-dimensional material can become a defect-rich material due to the unique ratio of surface area to volume, giving many dangling bonds. Herein, we report the rapid (20 min) synthesis of MoS2 quantum dots (QDs) with a diameter of 4 nm at room temperature using nanosecond pulsed laser ablation in a binary solvent. The MoS2 QDs are crystalline particles composed of 3-5 layers and contain sulfur vacancies at an atomic concentration of 1% acting as a functional defect. The MoS2 QDs exhibit excellent electrocatalytic performance (Tafel slope = 49 mV dec-1) for the hydrogen evolution reaction and high quantum yield blue photoluminescence with a large Stokes shift.

Hard X-ray excited optical luminescence from protein-directed Au∼20 clusters.

Hard X-ray excited optical luminescence is a unique property of materials, which makes them promising for biological imaging applications. However, the preparation of biocompatible contrast agents for hard X-ray excited optical luminescence remains a considerable challenge that has, to date, not been overcome. In this study, we investigated the luminescence properties of protein-directed Au∼20 clusters upon hard X-ray irradiation, both in solution and when embedded in films.

Anomalous Photoinduced Hole Transport in Type I Core/Mesoporous-Shell Nanocrystals for Efficient Photocatalytic H2 Evolution.

Controlling the carrier dynamics in a semiconductor nanoparticulate photocatalyst is the key to developing catalytic activity. Generally, type I band alignment is unsuitable for photocatalysts because the photoinduced carriers accumulate in the narrow bandgap semiconductor. To avoid the termination of reactions and/or photocorrosion of materials caused by carrier accumulation, it is common to employ type II band alignment for photoenergy conversion systems instead of type I. However, CdS/ZnS core/mesoporous-shell heterostructures show superior photocatalytic activity despite having type I band alignment that is generally unfavorable for photocatalytic reactions. Transient absorption spectroscopy and time-resolved microwave conductivity revealed efficient photoinduced hole transfer from the CdS phase to the ZnS phase. The defect-mediated hole transfer from the CdS to the ZnS phase resulted in long-lived charge separation (>2.4 ms) leading to high photocatalytic performance. This study provides insight into defect-mediated carrier transfer in nanoparticulate photocatalysts, which could be used as a guideline for the design of highly active and stable nanoparticulate photocatalysts.

Walking and finger tapping can be done with independent rhythms.

Rhythmic movements occur in many aspects of daily life. Examples include clapping the hands and walking. The production of two independent rhythms with multiple limbs is considered to be extremely difficult. In the present study we evaluated whether two different, independent rhythms that involved finger tapping and walking could be produced. In Experiment I, twenty subjects that had no experience of musical instrument training performed rhythmic finger tapping with the right index finger and one of four different lower limb movements; (1) self-paced walking, (2) given-paced walking, (3) alternative bilateral heel tapping from a sitting position, and (4) unilateral heel tapping with the leg ipsilateral to the tapping finger from a sitting position. The target intervals of finger tapping and heel strikes for walking step/heel tapping were set at 375 ms and 600 ms, respectively. The even distribution of relative phases between instantaneous finger tapping and heel strike was taken as the criteria of independency for the two rhythms. In the self-paced walking and given-paced walking tasks, 16 out of 20 subjects successfully performed finger tapping and walking with independent rhythms without any special practice. On the other hand, in the bipedal heels striking and unipedal heel striking tasks 19 subjects failed to perform the two movements independently, falling into interrelated rhythms with the ratio mostly being 2:1. In Experiment II, a similar independency of finger tapping and walking at a given pace was observed for heel strike intervals of 400, 600, and 800 ms, as well as at the constant 375 ms for finger tapping. These results suggest that finger tapping and walking are controlled by separate neural control mechanisms, presumably with a supra-spinal locus for finger tapping, and a spinal location for walking.

Carrier-Selective Blocking Layer Synergistically Improves the Plasmonic Enhancement Effect.

Plasmonic enhancement is a versatile and convenient way to enhance the conversion efficiency of various photoenergy conversion systems, such as photocatalysts and solar cells. We refine a plasmonic enhancement system by focusing on a carrier blocking layer (between a plasmonic metal and a photoactive layer), which is commonly used to prevent a major quenching channel in a plasmonic enhancement system. The hydrogen evolution reaction (HER) activity is enhanced by 33 times from the introduction of a carrier-selective blocking layer (CSBL) in Ag-CdS nanoparticles. The Ag2S layer, a typical example of a CSBL, synergistically improves the plasmonic enhancement effect of Ag on the photocatalytic HER activity of CdS by both the selective blocking of photoexcited electrons and the effective transfer of holes, which extends the lifetime of the active species (electrons in the conduction band) in the semiconductor photocatalyst (CdS) to accelerate the photocatalytic HER. We propose a new strategy for a further improvement of plasmonic enhancement systems.

Author Correction: Clear and transparent nanocrystals for infrared-responsive carrier transfer.

The original version of this Article omitted the fourth author Taizo Yoshinaga, who is from the 'Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Japan'. Consequently, the third sentence of the Author Contributions, 'M.S. and M.K. synthesized the ITO NCs and ITO/semiconductor oxides' was revised to 'M.S., M.K. and T.Y. synthesized the ITO NCs and ITO/semiconductor oxides'. This has been corrected in both the PDF and HTML versions of the Article.

Clear and transparent nanocrystals for infrared-responsive carrier transfer.

Infrared-light-induced carrier transfer is a key technology for 'invisible' optical devices for information communication systems and energy devices. However, clear and colourless photo-induced carrier transfer has not yet been demonstrated in the field of photochemistry, to the best of our knowledge. Here, we resolve this problem by employing short-wavelength-infrared (1400-4000 nm) localized surface plasmon resonance-induced electron injection from indium tin oxide nanocrystals to transparent metal oxides. The time-resolved infrared measurements visualize the dynamics of the carrier in this invisible system. Selective excitation of localized surface plasmon resonances causes hot electron injection with high efficiency (33%) and long-lived charge separation (~ 2-200 µs). We anticipate our study not only provides a breakthrough for plasmonic carrier transfer systems but may also stimulate the invention of state-of-the-art invisible optical devices.

Phase segregated Cu2-x Se/Ni3Se4 bimetallic selenide nanocrystals formed through the cation exchange reaction for active water oxidation precatalysts.

Control over the composition and nanostructure of solid electrocatalysts is quite important for drastic improvement of their performance. The cation exchange reaction of nanocrystals (NCs) has been reported as the way to provide metastable crystal structures and complicated functional nanostructures that are not accessible by conventional synthetic methods. Herein we demonstrate the cation exchange-derived formation of metastable spinel Ni3Se4 NCs (sp-Ni3Se4) and phase segregated berzelianite Cu2-x Se (ber-Cu2-x Se)/sp-Ni3Se4 heterostructured NCs as active oxygen evolution reaction (OER) catalysts. A rare sp-Ni3Se4 phase was formed by cation exchange of ber-Cu2-x Se NCs with Ni2+ ions, because both phases have the face-centered cubic (fcc) Se anion sublattice. Tuning the Ni : Cu molar ratio leads to the formation of Janus-type ber-Cu2-x Se/sp-Ni3Se4 heterostructured NCs. The NCs of sp-Ni3Se4 and ber-Cu2-x Se/sp-Ni3Se4 heterostructures exhibited high catalytic activities in the OER with small overpotentials of 250 and 230 mV at 10 mA cm-2 in 0.1 M KOH, respectively. They were electrochemically oxidized during the OER to give hydroxides as the real active species. We anticipate that the cation exchange reaction could have enormous potential for the creation of novel heterostructured NCs showing superior catalytic performance.