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Abstract Plasmonic nanostructures can both drive and interrogate light-driven catalytic reactions. Sensitive detection of reaction pathways is achieved by confining optical fields near the active surface. However, effective control of the reaction kinetics remains a challenge to utilize nanostructure constructs as efficient chemical reactors. Here we present a nanoreactor construct exhibiting high catalytic and optical efficiencies, based on a nanoparticle-on-mirror (NPoM) platform. We observe and track pathways of the Pd-catalysed C-C coupling reaction of molecules within a set of nanogaps presenting different chemical surfaces. Atomic monolayer coatings of Pd on the different Au facets enable tuning of the reaction kinetics of surface-bound molecules. Systematic analysis shows the catalytic efficiency of NPoM-based nanoreactors greatly improves on platforms based on aggregated nanoparticles. More importantly, we show Pd monolayers on the nanoparticle or on the mirror play significantly different roles in the surface reaction kinetics. Our data provides clear evidence for catalytic dependencies on molecular configuration in well-defined nanostructures. Such nanoreactor constructs therefore yield clearer design rules for plasmonic catalysis.

We often talk about our narrative experiences with others. For example, we might talk about the latest TV show or book in a series with friends. How does the media of a narrative (text, picture story) affect how we talk about it? Despite the fact that narratives can be experienced across different media, few studies have addressed the impacts of varied media. This study explored similarities and differences in how narratives are experienced across text and sequential picture stories. Picture and text versions were used for the same stories. Participants (n = 132) engaged in a think-aloud task at specific story units and provided ongoing think-aloud responses while reading or viewing. Natural language processing analyses were then conducted on the think-aloud responses. Results indicated that participants produced more words reflecting the internal states of characters and causality when reading than when viewing picture stories. Conversely, they produced more place words when viewing picture stories than reading text. Implications for theory and future directions are discussed.

Abstract Strong coupling between a single quantum emitter and an optical cavity (at rate Ω) accesses fundamental quantum optics and provides an essential building block for photonic quantum technologies. However, the minimum mode volume of conventional dielectric cavities restricts their operation to cryogenic temperature for strong coupling. Here we harness surface self-assembly to make deterministic strong coupling at room temperature using CdSe/CdS quantum dots (QDs) in nanoparticle-on-mirror (NPoM) plasmonic nanocavities. We achieve a fabrication yield of ~70% for single QD strong coupling by optimizing their size and nano-assembly. A clear and reliable Rabi splitting is observed both in the scattering of each nanocavity and their photoluminescence, which are however not equal. Integrating these quantum elements with electrical pumping allows demonstration of strong coupling in their electroluminescence. This advance provides a straightforward way to achieve practical quantum devices at room temperature, and opens up exploration of their nonlinear, electrical, and quantum correlation properties.

Abstract The molecule-metal interface is of paramount importance for many devices and processes, and directly involved in photocatalysis, molecular electronics, nanophotonics, and molecular (bio-)sensing. Here the photostability of this interface is shown to be sensitive even to room light levels for specific molecules and metals. Optical spectroscopy is used to track photoinduced migration of gold atoms when functionalised with different thiolated molecules that form uniform monolayers on Au. Nucleation and growth of characteristic surface metal nanostructures is observed from the light-driven adatoms. By watching the spectral shifts of optical modes from nanoparticles used to precoat these surfaces, we identify processes involved in the photo-migration mechanism and the chemical groups that facilitate it. This photosensitivity of the molecule-metal interface highlights the significance of optically induced surface reconstruction. In some catalytic contexts this can enhance activity, especially utilising atomically dispersed gold. Conversely, in electronic device applications such reconstructions introduce problematic aging effects.

Abstract Conjugated polymers are promising material candidates for many future applications in flexible displays, organic circuits, and sensors. Their performance is strongly affected by their structural conformation including both electrical and optical anisotropy. Particularly for thin layers or close to crucial interfaces, there are few methods to track their organization and functional behaviors. Here we present a platform based on plasmonic nanogaps that can assess the chemical structure and orientation of conjugated polymers down to sub-10 nm thickness using light. We focus on a representative conjugated polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), of varying thickness (2-20 nm) while it undergoes redox in situ. This allows dynamic switching of the plasmonic gap spacer through a metal-insulator transition. Both dark-field (DF) and surface-enhanced Raman scattering (SERS) spectra track the optical anisotropy and orientation of polymer chains close to a metallic interface. Moreover, we demonstrate how this influences both optical and redox switching for nanothick PEDOT devices.

Objective: Osteoarthritis (OA), which involves total joint damage and dysfunction, is a leading cause of disability worldwide. However, its exact pathogenesis remains unclear. Here, we identified TCF12 as an important regulator of the progression of OA. Methods: qRT-PCR, immunoblotting and immunohistochemistry (IHC) were used to detect the expression level of TCF12. The interaction of TCF12 with its downstream factor CXCR4 was assessed by Western blotting, immunofluorescence, qRT-PCR and luciferase assays. A mouse model was generated to examine the functions and mechanism of TCF12 in vivo. Result: TCF12 expression was upregulated in chondrocytes stimulated with IL-1β and osteoarthritic chondrocytes. TCF12 upregulates the expression of CXCR4 and leads to dysfunction of the TGF-β signaling pathway. Furthermore, knockdown of TCF12 alleviated cartilage damage in a mouse model generated by destabilization of the medial meniscus (DMM). Conclusion: TCF12 aggravates the progression of OA by targeting CXCR4 and then activating the TGF-β signaling pathway, suggesting that TCF12 may be a new target for the treatment of OA. The translational potential of this article: Transcription Factor 12(TCF12), is known to regulate cell development and differentiation, It has been widely studied in various organs and diseases, but its role in OA remains unclear. Here, we identified Transcription Factor 12(TCF12) as an important regulator mediating chondrocyte senescence and cartilage extracellular matrix degradation indicating its role in OA. We found that TCF12 expression was upregulated both locally and systemically as OA advanced in patients with OA, and in mice after DMM surgery to induce OA. TCF12 expression caused striking progressive articular cartilage damage, synovial hyperplasia in OA mice, and remarkably, it was relieved by intra-articular administration of mutant mouse TCF12 lentiviral vector (shTCF12). Furthermore, TCF12 upregulated the expression of CXCR4, leading to exacerbation of experimental OA partially through activation of TGF-β signaling in chondrocytes. TCF12 expression was upregulated in chondrocytes treated with IL-1β and osteoarthritic chondrocytes. Our findings established an essential role of TCF12 in chondrocyte senescence and cartilage extracellular matrix degradation during OA, and identified intra-articular injection of TCF12 as a potential therapeutic strategy for OA prevention and treatment.

Morchella spp. (true morels) are precious edible mushrooms consumed around the world, with a delicious taste, rich nutritional value, and unique healthcare effects. Various fungi and bacteria have been reported to colonize the ascocarps of Morchella, damaging their fruiting bodies and leading to serious economic losses in cultivation. The species identification of these colonizing organisms is crucial for understanding their colonization mechanisms on morels. Slime molds, which have characteristics of both “fungi” and “animals”, can occasionally colonize crops and edible fungi. However, there have been no reports of dictyostelid cellular slime molds (dictyostelids) colonizing plants and fungi to date. In this study, we discovered that dictyostelids colonized the surface of one wild ascoma of Morchella in the forest of Chongqing, China, with the tissues being black and rotten. Macro- and micro-morphological observations, along with molecular phylogenetic analyses, identified the specimens investigated in this study as Dictyostelium implicatum and Morchella sp. Mel-21. The results provide new knowledge of dictyostelid colonization on organisms and contribute to the diversity of species colonizing true morels. Moreover, this is also the first report of dictyostelids distributed in Chongqing, China. This study enhances our insights into the life history and potential ecological significance of dictyostelids and updates their distribution area in China. Further research will be conducted to uncover the mechanisms behind the colonization observed in this study.

Abstract Ceramic membranes are a promising alternative to polymeric membranes for selective separations, given their ability to operate under harsh chemical conditions. However, current fabrication technologies fail to construct ceramic membranes suitable for selective molecular separations. Herein, we demonstrate a molecular-level design of ceramic thin-film composite membranes with tunable subnanometer pores for precise molecular sieving. Through burning off the distributed carbonaceous species of varied dimensions within hybrid aluminum oxide films, we created membranes with tunable molecular sieving. Specifically, the membranes created with methanol showed exceptional selectivity toward monovalent and divalent salts. We attribute this observed selectivity to the dehydration of the large divalent ions within the subnanometer pores. As a comparison, smaller monovalent ions can rapidly permeate with an intact hydration shell. Lastly, the flux of neutral solutes through each fabricated aluminum oxide membrane was measured for the demonstration of tunable separation capability. Overall, our work provides the scientific basis for the design of ceramic membranes with subnanometer pores for molecular sieving using atomic layer deposition.

Abstract Anti-Stokes photoluminescence (PL) is light emission at a higher photon energy than the excitation, with applications in optical cooling, bioimaging, lasing, and quantum optics. Here, we show how plasmonic nano-cavities activate anti-Stokes PL in WSe2 monolayers through resonant excitation of a dark exciton at room temperature. The optical near-fields of the plasmonic cavities excite the out-of-plane transition dipole of the dark exciton, leading to light emission from the bright exciton at higher energy. Through statistical measurements on hundreds of plasmonic cavities, we show that coupling to the dark exciton leads to a near hundred-fold enhancement of the upconverted PL intensity. This is further corroborated by experiments in which the laser excitation wavelength is tuned across the dark exciton. We show that a precise nanoparticle geometry is key for a consistent enhancement, with decahedral nanoparticle shapes providing an efficient PL upconversion. Finally, we demonstrate a selective and reversible switching of the upconverted PL via electrochemical gating. Our work introduces the dark exciton as an excitation channel for anti-Stokes PL in WSe2 and paves the way for large-area substrates providing nanoscale optical cooling, anti-Stokes lasing, and radiative engineering of excitons.

Abstract Molecular vibrations couple to visible light only weakly, have small mutual interactions, and hence are often ignored for non-linear optics. Here we show the extreme confinement provided by plasmonic nano- and pico-cavities can sufficiently enhance optomechanical coupling so that intense laser illumination drastically softens the molecular bonds. This optomechanical pumping regime produces strong distortions of the Raman vibrational spectrum related to giant vibrational frequency shifts from an optical spring effect which is hundred-fold larger than in traditional cavities. The theoretical simulations accounting for the multimodal nanocavity response and near-field-induced collective phonon interactions are consistent with the experimentally-observed non-linear behavior exhibited in the Raman spectra of nanoparticle-on-mirror constructs illuminated by ultrafast laser pulses. Further, we show indications that plasmonic picocavities allow us to access the optical spring effect in single molecules with continuous illumination. Driving the collective phonon in the nanocavity paves the way to control reversible bond softening, as well as irreversible chemistry.

Blue-emission (∼480 ​nm) CsPbBr3 nanoparticles with ultra-small size (∼2.1 ​nm) are synthesized using the liquid nitrogen freezing with the ligand of dodecylbenzene sulfonic acid (DBSA). Asymmetric narrow emissions at the low energy side, with the full width at half-maximum of ∼20 ​nm, are observed in solution and film at room temperature. The spectral asymmetry is mainly ascribed to phonon vibronic replica with averaged phonon energy of ∼40 ​meV. Moreover, exciting this CsPbBr3 nanoparticles solution using linearly polarized 6 ns pulsed laser at 355 ​nm, we observe polarized emission with polarization degree (PPL) of ∼7%, and PPL decreases more than 20% in the vibronic progression. However, the PPL goes to zero in frozen solutions as well as in films. Thus we speculate the polarized emission is due to the photoinduced re-alignment of nanoparticles, and the diminished PPL at the phonon side band may be due to the non-adiabatic electronic-to-vibronic transitions. The novel phenomena from the ultra-small CsPbBr3 nanoparticle demonstrated in this work may provide fundamental insights into its photophysics with direct implications for optoelectronics.

Aims: This study aimed to investigate the role and mechanism of meniscal cell lysate (MCL) in fibroblast-like synoviocytes (FLSs) and osteoarthritis (OA). Methods: Meniscus and synovial tissue were collected from 14 patients with and without OA. MCL and FLS proteins were extracted and analyzed by liquid chromatography‒mass spectrometry (LC‒MS). The roles of MCL and adenine nucleotide translocase 3 (ANT3) in FLSs were examined by enzyme-linked immunosorbent assay (ELISA), flow cytometry, immunofluorescence, and transmission electron microscopy. Histological analysis was performed to determine ANT3 expression levels in a male mouse model. Results: We discovered for the first time that MCL was substantially enriched in the synovial fluid of OA patients and promoted the release of inflammatory cytokines from FLSs through MCL phagocytosis. Through LC‒MS, ANT3 was identified and determined to be significantly upregulated in MCL and OA-FLSs, corresponding to impaired mitochondrial function and cell viability in OA-FLSs. Mitochondrial homeostasis was restored by ANT3 suppression, thereby alleviating synovial inflammation. Furthermore, elevated ANT3 levels inhibited ERK phosphorylation. Specifically, silencing ANT3 prevented inhibition of ERK phosphorylation and significantly reduced the elevation of reactive oxygen species (ROS) and JC1 membrane potential in MCL-induced synovial inflammation. Conclusion: This study revealed the important roles of MCL and ANT3 in FLS mitochondria. Silencing ANT3 rescued ERK phosphorylation, thereby restoring mitochondrial homeostasis in FLSs and alleviating synovitis and OA development, offering a potential target for treating synovitis and preventing early-stage OA. Cite this article: Bone Joint Res 2023;12(4):274–284.

Learning-based image registration approaches typically learn to map from input images to a transformation matrix. Regarding the current deep-learning-based image rigid registration approaches learn a transformation matrix in a one-shot way. Our purpose is to present a deep reinforcement learning (DRL) based method for image registration to explicitly model the step-wise nature of the human registration process. We cast an image registration process as a Markov Decision Process (MDP) where actions are defined as global image adjustment operations. Then we train our proxy to learn the optimal action sequences to achieve a good registration. More specifically, we propose a DRL proxy incorporating an attention mechanism to address the challenge of large differences in appearance between images from different modalities. Registration experiments on 3D CT-MR image pairs of patients with nasopharyngeal carcinoma and on publicly available 3D PET-MR image pairs show that our approach significantly outperforms other methods, and achieves state-of-the-art performance in multi-m-modal medical image registration.

While renewable H2O2 is promising industrially relevant regent, it remains a challenge to modulate materials’ photocatalytic and electronic properties for effect light-harvesting. Here, authors examine core-shell Ag/Pd co-catalysts on BiVO4 for photocatalytic H2O2 synthesis.