Faculty (United Kingdom)

Na4MnV(PO4)3 stands as a promising cathode material for sodium-ion batteries owing to its low cost and multiple redox potentials. However, challenges such as drastic local distortion, irreversible phase evolution, and transition metal dissolution in multielectron redox processes, coupled with intrinsic low electronic conductivity jointly trouble its practical deployment. Herein, the Ti4+ with a d0 arrangement is employed to customize the TM-O bonds to eliminate the structural distortion in Na4MnV(PO4)3. The coupling coordination effect of multiple transition metals activates the Mn4+/3+ redox while reinforcing structural stability in over two-electron redox processes, enabling the Na3.1(MnV)0.7Ti0.6(PO4)3 (MnVTi) cathode to realize a 2.4 e- reversible transfer and deliver a specific capacity of 138.4 mAh g-1. Experimental and theoretical calculations reveal that robust TM-O bonds with dynamic covalent chemistry, particularly the strong covalent Ti-O bonds, unlock ultrafast and durable cycling performance (78.4% capacity retention after 10,000 cycles at 20 C). Furthermore, the enhanced electronic conductivity and reaction kinetics contribute to the exceptional rate performance (74.2 mAh g-1 at 50 C), fast-charging capability (1.77 min to reach 80% SOC), and fabulous all-weather adaptability (-40 to 50 °C). This work establishes a universal design paradigm for high-performance Mn-based polyanion cathodes through d0-metal coupling mediated by dynamic covalent chemistry.

The continuous failure to account for biological sex is a key impediment to developing effective neuroprotective treatments for ischemic stroke. While epigenetic modulators such as HDAC inhibitors show promise, the mechanisms behind their sexually dimorphic effects are unknown. We present a unique, sex-specific mechanism in which HDAC2 suppression offers substantial resilience to ischemic brain injury by significantly increasing the endogenous oxytocin (OXT) signaling axis. Through integrated in vitro and in vivo models, we show that HDAC2 knockdown not only reduces infarct size and enhances functional recovery, but also does so more effectively in females. We attribute this improved protection to a strong, female-specific increase of OXT and its receptor (OTR). This increased OXT signaling, possibly mediated by estrogen, resulted in significant decreases in apoptosis, neuroinflammation, and oxidative stress. Our findings show that HDAC2 serves as a critical epigenetic brake on a built-in neuroprotective mechanism that, when activated, triggers a therapeutically potent, sex-divergent response. This study sheds light on chemical biology by identifying a druggable epigenetic target that modulates an important neurohormonal circuit. More broadly, it establishes a new paradigm for individualized stroke therapy, shifting away from a one-size-fits-all strategy and toward leveraging innate, sex-specific protective mechanisms to improve treatment efficacy.

Abstract This study presents a bespoke hardware platform for indoor navigation, featuring a quadrotor equipped with an FZ3 card incorporating the AMD (formerly Xilinx) Zynq UltraScale+ ZU3EG MPSoC as the onboard computer. A core component of this platform is a field programmable gate array (FPGA) module specifically designed to efficiently compute Delaunay triangulations, enabling enhanced spatial awareness and real-time surface reconstruction. The onboard computer communicates with the flight controller, inertial measurement unit (IMU), ultra-wideband (UWB) localisation system, stereo camera, light detection and ranging (LiDAR) and ultrasonic sensors via robotic operating system (ROS) 2. The primary objective is to develop a cost-effective, modular unmanned aerial vehicle (UAV) system that can be adapted for a range of indoor navigation applications. The modular design supports different onboard computer platforms and sensor configurations, allowing researchers to easily customise the system for various experiments. By providing a practical framework for precise indoor navigation, this platform addresses the limitations of simulated, simplified laboratory setups, accelerating prototyping and supporting the deployment of UAVs in complex real-world environments. This work explores the UAV’s hardware architecture, the implementation of the Delaunay triangulation core on the FPGA system-on-chip (SoC), the ROS 2-based communication system and includes a detailed mass analysis and power estimation.

A palladium-catalyzed (3+2) cycloaddition between arylalkynes and norbornene derivatives via C-H bond cleavage is reported. This reaction enables the selective synthesis of benzo-fused five-membered cyclic products from a variety of arylalkynes, including electronically biased and alkyl(aryl)alkynes. Notably, the use of a bulky bidentate ligand leads to the (2+2) cycloaddition, giving four-membered cyclobutene derivatives from the same starting materials. Mechanistic studies indicate that both cycloadditions proceeds through hydropalladation of the arylalkynes by Pd(0) and AcOH to generate a vinyl-Pd intermediate. DFT calculations suggest a ligand-to-ligand hydrogen transfer (LLHT) mechanism for this step. The subsequent turnover-determining step is proposed to vary with the ligand environment, involving either the C-H bond cleavage or reductive elimination, thereby governing pathway selectivity.

Polycarbonate (PC) is widely used in impact-resistant transparent components due to its excellent toughness and optical properties. However, its mechanical behavior under high strain rate loading remains insufficiently understood, particularly from a microstructural perspective. In this study, the macro-micro deformation mechanisms of PC under high strain rate compression were systematically investigated through an integrated approach combining multiscale simulations and microstructural characterization. Two PC grades with different molecular weights were subjected to dynamic compression experiments using a split Hopkinson pressure bar at high strain rates (4500, 5500, and 7000 s–1) and temperatures of 233, 296, and 353 K. The results reveal pronounced strain rate and temperature dependence in yield stress, yield strain, strain hardening, and unloading strain. Two-dimensional wide-angle X-ray diffraction and polarized Fourier-transform infrared analyzes demonstrate that molecular chain orientation is significantly enhanced under high strain rate loading, with lower molecular weight PC exhibiting more pronounced strain hardening due to easier chain alignment. Molecular dynamics simulations further elucidate that higher molecular weight PC possesses greater conformational stability and resistance to compression. Additionally, the DSGZ model parameters of different PC was calibrated, and accurately predicting the high strain rate compressive response in finite element simulations. The findings provide deep insights into the microstructural origins of the macroscopic mechanical behavior of PC under high-strain-rate compression, offering valuable guidance for material design and engineering applications.

The Metaproteomics Initiative was officially launched in 2021 to strengthen collaboration, promote knowledge exchange, and support and lead standardization efforts within the growing metaproteomics community. Over the past five years, the Initiative has developed into a structured, global network of researchers. It has launched community-driven benchmark studies, helped shape emerging metadata and reporting standards, developed practical guidance and training materials, organized international symposia, and fostered connections across the microbiome research landscape (https://metaproteomics.org/). We outline the Initiative's organization, activities, achievements, and ongoing efforts, and reflect on how sustained, community-led coordination has shaped the development of metaproteomics as a field. We further position the Grand Metaproteome Challenges as a next step toward coordinated, community-scale biological research, aimed at advancing functional microbiome studies across clinical, industrial, and environmental application domains, and invite engagement from the wider microbiome and omics communities.

In this study, manufacturing and mechanical characterization are performed on halloysite nanotube (HNT)-reinforced epoxy composite, carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber-added epoxy composite, and both HNT- and CTBN-rubber-added epoxy composites. It is aimed to explore the effects of HNT and CTBN rubber inclusions individually and the synergistic effects of HNT and CTBN rubber inclusions on the epoxy-based composite material. To achieve this, the mechanical characterization of the epoxy matrix composite is performed numerically and experimentally. To investigate the viscoelastic behavior, the samples are subjected to tensile and three-point bending tests at different strain rates (%1, %5, and %10 strain per minute) and to Charpy impact tests. The internal structures of the samples are observed using a scanning electron microscope (SEM). Results demonstrate that 1% HNT reinforcement increases the elastic modulus by 15% (from 599 to 688 MPa in tensile tests), while 10% CTBN rubber reduces stiffness by 38% but increases elongation at break by 48%. Hybrid composites (H10R05) achieve balanced properties with 16% higher stiffness than pure rubber systems while maintaining 44% higher ductility than pure epoxy. Charpy impact tests show that 10% rubber increases fracture energy by approximately 85% compared to pure epoxy, while HNT provides modest improvements. All samples exhibit strain-rate-dependent behavior, with elastic modulus increasing 10-16% from quasi-static to dynamic loading rates. Numerical modeling using the Mori-Tanaka, Halpin-Tsai, and finite element homogenization (FEH) methods successfully predicts experimental trends, with FEH showing the highest accuracy (deviations <5%). This study provides valuable insights into designing composite materials with balanced mechanical properties through multireinforcement strategies.

Mass spectral MS/MS libraries are essential in non-targeted metabolomics as they facilitate metabolite annotation and provide the basis for in silico annotation tools and fragmentation rules. While significant progress has been made towards more comprehensive MS/MS libraries, those efforts have focused mainly on collision-induced dissociation (CID) and higher-energy collisional dissociation (HCD) based approaches. In this work, we introduce a flow injection MRM HR-based acquisition strategy that acquires electron-activated dissociation (EAD) and CID across a wide range of fragmentation energies within a single injection. The workflow supports both nontargeted and targeted analysis, through efficient library generation and MRM HR-parameter optimization, respectively. We apply the workflow via a set of 40 steroid standards, known for their important role in human health, disease, and doping, expanding the coverage of public libraries for both CID and EAD. Finally, we utilize public MS/MS libraries and raw data to reveal that EAD MS/MS spectra can, to some extent, be annotated via existing MS/MS libraries, governed by CID and HCD, and show that the acquired CID library enables novel annotations in publicly available clinical data, demonstrating its utility for biological studies.

Academic pressure could increase the risk of adolescent depression and self-harm. However, there are few longitudinal studies of this association, and those that exist have limitations. We aimed to investigate associations between perceived levels of academic pressure and subsequent depressive symptoms and self-harm from adolescence to early adulthood. Our hypothesis was that higher levels of academic pressure would be associated with higher levels of depressive symptoms and self-harm. In this longitudinal study, we used data from the Avon Longitudinal Study of Parents and Children (Avon, UK) that includes adolescents born in 1991-92. Our primary exposure of interest was academic pressure measured at age 15 years, using items from a school experiences questionnaire (total scores 0-9). Outcomes were depressive symptoms assessed with the Short Mood and Feelings Questionnaire at five timepoints between age 16 years and 22 years (total scores 0-26), and a self-harm questionnaire at four timepoints between age 16 years and 24 years. Analyses were linear (depressive symptoms) and logistic (self-harm in the previous year) multilevel models in samples with multiply imputed data, before and after adjustments. We included 4714 adolescents (2725 [57·8%] female, 1989 [42·2%] male). In fully adjusted models, a 1-point increase in academic pressure at age 15 years was associated with a 0·43 (95% CI 0·36-0·51) point increase in depressive symptoms. This association was largest when depressive symptoms were assessed at age 16 years (0·53, 0·42-0·64), but remained at age 22 years (0·35, 0·23-0·47). For self-harm, in fully adjusted models, each 1-point increase in academic pressure was associated with an 8% higher odds of self-harm (adjusted odds ratio 1·08, 1·01-1·16), with no differences over time. Our findings support the hypothesis that academic pressure is a potential modifiable risk factor for adolescent depressive symptoms, and possibly self-harm. Interventions to reduce academic pressure could be developed and evaluated. Sir Henry Dale Fellowship, Wellcome Trust, and Royal Society.

We investigate the coupled evolution of heterogeneous strain, crystallinity, and stress fields in natural rubber (NR) sheets containing a circular hole during uniaxial stretching, with a focus on how strain-induced crystallization (SIC) influences local stress concentration at structural discontinuities. By high-resolution digital image correlation, an empirical strain-crystallinity relationship and a hyperelasticity analysis firmly grounded in stress–strain data obtained under diverse deformation modes, we quantitatvely map the spatial distributions of strain, SIC, and stress in the extreme vicinity (≈0.2 mm) of the defect. Local strain concentration at the lateral hole edges triggers pronounced SIC, resulting in strong stiffening and a stress concentration factor (Kt*) as high as 4.5─significantly exceeding classical elastic predictions. Upon further stretching, Kt* plateaus, eventually as SIC develops in the far-field region, promoting a more homogeneous stress distribution. The SIC-induced stiffening also generates a highly anisotropic stress field near the hole edges due to preferential reinforcement along the crystalline orientation. The localized SIC causes characteristic hole-shape evolution, where the hole becomes increasingly elongated along the stretching axis compared with the fully amorphous state. These findings elucidate the fundamental interplay between SIC and local stress concentration in elastomers with structural discontinuities and provide mechanistic insights for designing defect-tolerant, high-toughness rubber materials.