bluuebunny/crossref_metadata_2025 huggingface dataset:
Measuring walking impairment in patients with intermittent claudication: psychometric properties of the Walking Estimated-Limitation Calculated by History (WELCH) questionnaire
Authors: Rezvani Farhad , Härter Martin , Dirmaier Jörg
Published: August 2021

Objectives

Patient-reported outcome measures can facilitate the assessment of walking impairment in peripheral artery disease patients with intermittent claudication in clinical trials and practice. The aim of this study was to test the psychometric properties of the German version of the ‘Walking Estimated-Limitation Calculated by History’ (WELCH) questionnaire.

Methods

The assessed properties included feasibility, test-retest reliability, construct validity (i.e., convergent, divergent and known-groups validity) and responsiveness using classic psychometric methods. Psychometric properties were tested as part of a randomized controlled home-based exercise trial for patients with symptomatic peripheral artery disease at Fontaine stage IIA/B.

Results

Analyses were conducted in subgroups of 1,696 patients at baseline and 1,233 patients at 12-month follow-up (i.e., post-intervention) who completed the WELCH along with a battery of other self-report measures. The WELCH did not exhibit relevant floor or ceiling effects < 15% achieved lowest or highest possible scores), showed evidence for good test-retest reliability (ICC = .81, 95% CI [.71–.88]) and was found to be well suited for self-completion by patients (< 5% missing data per item). WELCH scores showed moderate to strong correlations with related measures of walking impairment at both time points (Walking Impairment Questionnaire: r = .56 − .74; VascuQoL-25 activity subscale: r = .61 − .66) and distinguished well among patients with poor and high quality of life when adjusting for confounders (t = 13.67, p < .001, d = .96). Adequate divergent validity was indicated by a weaker correlation between the WELCH and general anxiety at both time points (GAD-7: r =  − .14 to  − .22). The WELCH improved by 6.61 points (SD = 17.04, 95% CI [5.13–8.10], d = 0.39) in response to exercise treatment and was able to identify large clinically important improvements observed on the walking distance (AUC = .78, 95% CI [.71–.84]) and speed subscales (AUC = .77, 95% CI [.68–.86]) of the Walking Impairment Questionnaire.

Conclusions

The WELCH is considered a feasible, reliable and valid patient-reported outcome measure for the measurement of walking impairment in patients with peripheral artery disease. The WELCH showed evidence for responsiveness to changes in walking impairment, yet further studies are warranted to conclusively determine the WELCH’s ability to detect intervention effects.
The Implementation and Impact of Blockchain Technology in the Finance and Trade Sector of Economy of the Developing World
Authors: Abbasi Faizan Naseer , Sidhu Shazaf Masood
Published: August 2021

Blockchain technology is a diverse technology and one of the most advanced in the field of finance and trade sector and with each passing day it is showing magnanimous outcomes in developed countries, while we in our article have focused more on its implementation and impact in the developing part of the world and on the basis of evaluation via online format we concluded our findings.
Intangible Assets and Economic Growth in Nigeria: An Empirical Investigation
Authors: Pearce Okumoko Tubo , Friday Cookey Ibeinmo , Mcdonald Question Emomotimi
Published: August 2021

This work examines the impact of intangible assets on economic growth in Nigeria, using time series data from 1990 to 2019. Relevant theoretical and empirical literatures were reviewed. Government expenditure on research and development, intellectual capital proxied by human capital stock, intellectual property and service sector employment were regressed as independent variables against the real GDP (proxy for economic growth) as the dependent variable. Secondary data were used for this work. The ARDL bound test was adopted in estimating the model. We discovered that government expenditure on R&D, intellectual capital and intellectual property do not have significant relationship with economic growth proxied by RGDP; meanwhile service sector employment had a significant relationship with economic growth in Nigeria. Also, government expenditure on R&D; and service sector employment were rightly signed; while intellectual capital and intellectual property were not rightly signed. This implies that when government increases its expenditure on R&D, it will result to economic growth, so also service sector employment in the long-run. Meanwhile, an increase in intellectual capital and intellectual property will reduce RGDP. We therefore propose that government should upgrade its spending on R&D so as to boost intellectual capital and property. The government should also create employment for the stock of human capital. Finally, government institutions such as producers’ protection agencies should be empowered to protect intellectual properties in Nigeria.
Effect of Wi-Fi Radiation on Heart Rate Variability, Salivary Cortisol Level and Cognition
Authors: Mahila .
Published: August 2021

The study aims to analyse the effects of Wi-Fi radiations from mobile phone towers on the level of salivary cortisol , its effects on cardiovascular system , and on the cognitive levels of the subjects. on thirty six subjects exposed to Wi-Fi radiation from mobile phone tower (Group I) and thirty six subjects not exposed to Wi-Fi radiation from mobile phone tower (Group II). The frequency domain parameters of Heart rate variability, salivary cortisol level between both the groups was statistically significant. LF,LF/HF component was increased in Group I, HF component was increased in Group II which signifies parasympathetic withdrawal and sympathetic dominance in Group I. Cognition level was slightly increased in Group II but not statistically significant between both the Groups.
Highly Integrated Phase Change and Radiative Cooling Fiber Membrane for Adaptive Personal Thermal Regulation
Authors: Zhu Zhijun , Bashir Akbar , Wu Xiaohong , Liu Chen , Zhang Yichi , Chen Nanhao , Li Ziqi , Chen Yan , Ouyang Xing , Chen Da‐Zhu
Published: December 2024

Environmental heat influx often limits the effectiveness of radiative cooling materials, particularly in wearable applications where thermal comfort is paramount. This study introduces an innovative solution for personal thermal management through radiative cooling phase change (RC‐PC) fiber membranes. Fabricated by coaxial electrospinning, these membranes combine a poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) and tetraethyl orthosilicate (TEOS) composite shell, encapsulating n‐octadecane as the core phase change material. The membranes demonstrate exceptional optical performance, with a solar reflectivity of 95.0% and an emissivity of 88.6% within the atmospheric window, effectively minimizing ambient heat absorption. The n‐octadecane‐infused fibers (0.3 mL h−1 C18@TEOS/PHBV) exhibit a phase change enthalpy of 88.3 J g−1, reducing heating rates and improving cooling by ≈1 °C at dawn. Under typical solar radiation (939.5 W m−2), the membranes provide an average cooling power of 89.0 W m−2, peaking at 95.3 W m−2. Notably, they achieve a cooling reduction of 5.1 °C under 550.2 W m−2, maintaining temperatures significantly lower than conventional fabrics, with a differential of 4.4 °C compared to medical protective clothing. These findings underscore the potential of RC‐PC fiber membranes for sustainable, efficient personal thermal management.
A Bone‐Targeting Hydrogen Sulfide Delivery System for Treatment of Osteoporotic Fracture via Macrophage Reprogramming and Osteoblast‐Osteoclast Coupling
Authors: Qin Yi , Zhang Zhen , Guo Xiaobin , Li Wenhao , Xia Wenyu , Ge Gaoran , Li Yanyue , Guan Min , Gao Ang , Mao Lu , Wang Huaiyu , Chu Paul K. , Geng Dechun
Published: December 2024

The demand for systemic treatment of osteoporotic fractures to reduce recurrence is increasing, but current anti‐osteoporosis medications exhibit unsatisfactory efficacy due to adverse events and limited effects on fracture healing. Herein, a bone‐targeting zeolitic imidazolate framework‐8 (ZIF)‐based hydrogen sulfide (H2S) delivery system (ZIF‐H2S‐SDSSD) is designed to simultaneously promote fracture healing and alleviate osteoporosis. With bone‐targeting peptide SDSSD grafted on the surface, ZIF‐H2S‐SDSSD nanoparticles release H2S in bone tissues without affecting the serum H2S level, thereby mitigating potential risks of systematic H2S delivery. Upon cellular uptake, the acidic environment in lysosomes drives the release of H2S from the encapsulated zinc sulfide in conjunction with the degradation of ZIF. The synergistic effects of released Zn2+ and H2S promote macrophage metabolic reprogramming by suppressing succinate accumulation and mitochondrial reactive oxygen species (mtROS) production, and further regulate osteoblast‐osteoclast coupling. Overall, this strategy holds great promise in the clinical treatment of osteoporotic fractures and broadens the application of nanomedicine therapy for orthopedic diseases.
Self‐Healing Hydrogel‐Based Triboelectric Nanogenerator in Smart Glove System for Integrated Drone Safety Protection and Motion Control
Authors: Wang Chengwen , Niu Hongsen , Shen Guozhen , Li Yang
Published: December 2024

Flexible sensing technology offers significant advantages in gesture recognition and human–machine interactions. However, existent smart gloves based on flexible sensors still have limitations in their security mechanisms; thus, they are unsuitable for high‐risk environments where identity verification and system protection are critical. This study proposes an innovative smart glove system in which person recognition and gesture control functionalities are integrated. The glove utilizes a triboelectric nanogenerator based on a polyvinyl‐alcohol–sodium‐alginate–conductive‐polyaniline (PSP) hydrogel electrode as the sensor and exhibits high sensitivity, fast response/recovery, and fatigue resistance. These properties are primarily attributed to the excellent stretchability, conductivity, and self‐healing ability of the PSP hydrogel. Because of the coordinated design of the hardware–software architecture, the smart glove enables precise control of drone flight postures via contact sensing. The glove also leverages non‐contact sensing to recognize personalized fingertip trajectories, enabling user recognition and unlocking the aforementioned drone control interface. This design improves not only the flexibility and portability of drone operation but also safety of weapon systems in future battlefield environments.
Kinetics‐Mediating Artificial Interphase for Ultrafast Zn Metal Anodes
Authors: Liu Qiaoyun , Jiao Long , Wang Jizhen , Bai Hongyuan , Yi Chao , Fu Yusen , Liu Jiajia , Wang Chuang , Lei Yechen , Zhang Tian , Yang Leixin , Shu Dengkun , Yang Shuo , Li Chenyang , Li Huan , Zhang Wenjun , Cheng Bowen
Published: December 2024

Achieving long‐term cycling stability of Zn metal anodes at high rates is crucial for the practical applications of aqueous Zn ion batteries. However, the sluggish kinetics of Zn deposition and uncontrollable dendrite growth at the electrolyte/electrode interface will inevitably lead to inferior energy efficiency and limited cycling lifespan. To address these challenges, a consecutive kinetics‐mediating mechanism is proposed through the development of an in situ crafted amorphous zinc pyrophosphate (ZPPO) artificial interphase on the Zn anode (ZPPO@Zn). Experimental and theoretical analyses indicate that the designed interphase can not only drive homogeneous ion diffusion and high Zn2+ enrichment at the reaction interface, but also simultaneously lower the Gibbs free energy of Zn2+ deposition, thus enabling dendrites‐free and kinetics‐boosted Zn electrodeposition under high current densities. Notably, the ZPPO@Zn electrode demonstrates exceptional long‐term lifespans, e.g., over 2800 and 750 h of stable cycling in symmetrical cells at high current densities of 20 and 40 mA cm−2, respectively, with low overpotential. Even under the challenging cycling condition of ultra‐high depth of discharge (DOD) of 80%, a steady cycling over 130 h is maintained. This study provides new insights into the design and optimization of interfacial engineering for fabricating high‐performance Zn metal anodes.
Magnetointeractive Cr2Te3‐Coated Liquid Metal Droplets for Flexible Memory Arrays and Wearable Sensors
Authors: Li Puyan , Feng Yixiong , Ding Chenchen , Zhong Ruirui , Yan Weiyu , Song Junjie , Hong Zhaoxi , Hu Bingtao , Tan Jianrong , Sun Jingyu , Song Xiuju
Published: December 2024

Magnetic liquid metal droplets, featured by unique fluidity, metallic conductivity, and magnetic reactivity, are of growing significance for next‐generation flexible electronics. Conventional fabrication routes, which typically incorporate magnetic nanoparticles into liquid metals, otherwise encounter the pitfall pertaining to surface adhesivity and corrosivity over device modules. Here, an innovative approach of synergizing liquid metals with 2D magnetic materials is presented, accordingly creating chromium(III)‐telluride‐coated liquid metal (CT–LM) droplets via a simple self‐assembly process. The CT–LM droplets exhibit controllable deformation and locomotion under magnetic fields, demonstrate nonadherence to various surfaces, and enable cost‐effective recycling of components. The functionality of CT–LM droplets is validated through their use in magnetointeractive memory devices to enable sensing/storing 64 magnetic paths and in wearable sensors as the flexible vibrator for dynamic gesture recognition with machine learning assistance. This work opens new avenues for the functional droplet design and broadens the horizons of flexible electronics.
A Sustainable Route From Quartz to Bifunctional Material with Adsorbed Lanthanides for Enhanced Fluorescent Activation in Doxycycline Sensing
Authors: Semeshko Olha , Fizer Maksym , Sliesarenko Valeriia , Briancin Jaroslav , Bondarchuk Oleksandr , Lobnik Aleksandra , Melnyk Inna
Published: December 2024

A nanosized bifunctional adsorbent with diamino and phenyl groups on its surface is synthesized through the functionalization of silica derived from quartz. The composition, morphology, and particle size of the functionalized silica are characterized using various physicochemical methods. The material demonstrates high sorption properties for La(III) and Ce(III), both found in Ni‐MH batteries, as well as Eu(III). The synthesized functionalized silica, with adsorbed lanthanides, is employed for sensor‐based detection of doxycycline in aqueous solutions. After sorbing lanthanides, the bifunctional adsorbent shows a linear response to doxycycline in the concentration range of 0.005–10.0 µm, with a detection limit of 0.15 µm L−1 and a quantification limit of 0.44 µm L−1. The increase in photoluminescence signal upon the addition of doxycycline is explained using Judd–Ofelt theory. Experimental W2 and W4 parameters of the Eu‐doped nanomatrix are determined to be 1.44 × 10−20 cm2 and 8.55 × 10−20 cm2, respectively, with these values increasing to 73.40 × 10−20 cm2 and 35.58 × 10−20 cm2 upon the addition of doxycycline. A significant increase in the radiative emission rate from 196 s−1 to 1977 s−1 is observed with doxycycline addition. It is demonstrated that the system containing the three lanthanides exhibits unique sensor properties, attributed to the co‐luminescence of the Eu(III) ion.
Fabrication of Perovskite Solar Cells: A Focused Review on Manual Deposition Methods
Authors: Zarabinia Nazila , Brown Thomas M.
Published: December 2024

This study provides an overview of manual deposition methods in the fabrication of perovskite solar cells, including drop casting, blade coating, spray coating, soft applicator, and other innovative methods. These methods can easily be tested in all laboratories at a small cost without buying expensive deposition equipment and can be a point of entry for researching this exciting field. Furthermore, new ideas and methods are first mostly developed and tested manually, and then automation happens at a second stage where precision engineering takes over. The latter typically enables higher performance and large‐scale manufacturing. This underlies the importance of implementing and understanding manual fabrication and providing a comparison of manual vs automation modes, which is the objective of this review. The analysis will be of interest to all those researchers wanting to understand or implement conventional or innovative manual methods for fabricating perovskite solar cells and their benefits as well as performance limitations compared to their automated counterparts.
Revealing Self‐Driven Broadband Photodetection Using Heterojunction of Bi2Se3 and Low‐Temperature Laser Molecular Beam Epitaxy Grown GaN on SrTiO3 (100) Substrate
Authors: Aggarwal Vishnu , Kumar Rahul , Gautam Sudhanshu , Yadav Aditya , Pradhan Bipul Kumar , Ganesan Ramakrishnan , Gupta Govind , Kumar M. Senthil , Walia Sumeet , Kushvaha Sunil Singh
Published: December 2024

Optoelectronic properties of GaN are underexplored on good lattice matching SrTiO3 (STO) due to STO's instability at the high GaN growth temperatures (800–1100 °C) required by traditional techniques. Here, GaN is grown on STO (100) at lower temperatures (500, 600, and 700 °C) using the laser‐assisted molecular beam epitaxy (LMBE) technique, and their morphological, crystalline, optical, and photodetection properties are analyzed. Further, heterojunction of Bi2Se3 thin film (bandgap of 0.3 eV) is formed on the highest photo‐responsive LMBE‐GaN/STO to fabricate a self‐powered broadband photodetector. The fabricated self‐powered heterojunction photodetectors device exhibits a high responsivity of 2.93 × 102 mAW−1 in ultraviolet region and a notable responsivity of 2.3 and 12 mAW−1 in visible and near‐infrared spectral regions, respectively. In addition, photoresponse properties of fabricated devices on bare LMBE‐GaN and its heterojunction are compared under UV light illumination. The photoresponsivity of heterojunction in UV region is estimated to be 3.05 × 104 mAW−1, which is enhanced by 100% compared to bare LMBE‐GaN. Combining the unique optoelectronic properties of GaN and rigidity of STO, epitaxy of GaN on STO enables construction of robust photodetector devices. Further, Bi2Se3‐functionalized GaN can provide self‐sufficient and high‐quality futuristic optoelectronics devices.
Regiodivergent Reactions of 2‐Alkynyl Aziridines with Grignard Reagents
Authors: Ji Wen‐Tao , Ping A‐Nan , Yang Gaosheng , Chai Zhuo
Published: December 2024

Herein, we report regiodivergent nucleophilic attack of Grignard reagents to 2‐alkynyl aziridines. Under the catalysis of a Cu(I)‐diphosphine complex, benzylic Grignard reagents add to the carbon‐carbon triple bond of the aziridines to deliver α‐allenylamines in moderate to excellent yields; the direct addition of the Grignard reagents to the aziridines in the absence of catalyst provided homopropargylic amine derivatives. Both reactions could proceed in highly enantiospecific ways. Further synthetic manipulations of these products enable rapid access to diverse useful heterocyclic molecular scaffolds.
Impact of Transition Metals and Electrocatalyst Layer Thickness on the Pt‐Based Cathodes of Proton Exchange Membrane Fuel Cells – Do Multimetallic Electrocatalysts Necessarily Yield an Improved Performance?
Authors: Sgarbi Ricardo , Ait Idir William , Labarde Quentin , Jourdin Camille , Martin Vincent , Andreetta Daniele , Wu Peizhe , Negro Enrico , Bassetto Fabio , Mainka Julia , Dillet Jérôme , Marty Clémence , Micoud Fabrice , Noto Vito Di , Kulesza Pawel , Lottin Olivier , Chatenet Marian
Published: December 2024

The interplay between i) cathodic electrocatalytic layer (EC layer) features of proton exchange membrane fuel cell (PEMFC), focusing on the oxygen reduction reaction (ORR) electrocatalyst (EC) and the Pt loading; and ii) the PEMFC performance and durability is evaluated. An innovative hierarchical “core–shell” carbon nitride multimetallic ORR electrocatalyst (“PtCuNi/C” H‐EC) is compared with a conventional Pt/C benchmark. The various contributions to PEMFC performance at beginning of test (BOT) are isolated and correlated to the physicochemical features of the ORR EC and the cathodic EC layer. The PEMFC durability is investigated extensively via accelerated stress tests (ASTs) mimicking long‐term operation. Particular attention is dedicated to determine how ageing affects: i) PEMFC cell voltage; and ii) the cathode electrochemically active surface area (ECSA). “Post‐mortem” studies are carried out to probe how ageing influences the cathodic EC layer features, including: i) chemical composition; ii) elements distribution; iii) EC morphology; and iv) structure and crystal size of the Pt‐based metal nanoparticles bearing the active sites. Integrating the experimental results allows to identify both the positive and the detrimental effects triggered by the introduction of transition metals (TMs) in the ORR EC on the factors modulating PEMFC performance and long‐term operation.
Understanding Cathode–Electrolyte Interphase Formation in Solid State Li‐Ion Batteries via 4D‐STEM
Authors: Paranamana Nikhila C. , Werbrouck Andreas , Datta Amit K. , He Xiaoqing , Young Matthias J.
Published: December 2024

Interphase layers that form at contact points between the solid electrolyte (SE) and cathode active material in solid‐state lithium‐ion batteries (SS‐LIBs) increase cell impedance, but the mechanisms for this interphase formation are poorly understood. Here, we demonstrate a simple workflow to study cathode–electrolyte interphase (CEI) formation using 4D‐scanning transmission electron microscopy (4D‐STEM) that does not require SS‐LIB assembly. We show benefits of MoCl5:EtOH as a chemical delithiating agent, and prepare chemically delithiated cathode LiNi0.6Co0.2Mn0.2O2 (NMC) powder in contact with Li10GeP2S12 (LGPS) SE powder as a SS‐LIB CEI surrogate. We map the composition and structure of the CEI layers using 4D‐STEM, energy dispersive X‐ray spectroscopy (EDS), and electron pair distribution function analysis (ePDF). EDS indicates O migration from NMC into LGPS. ePDF analysis indicates sulfate and phosphate formation localized on the surface of LGPS, as well as Li2O formation within the LGPS phase, and self‐decomposition of NMC. These results are consistent with an electrochemical self‐discharge mechanism for interphase formation arising from coupled redox reactions of sulfur oxidation in LGPS and transition metal reduction in NMC. This suggests that coatings which stop anion transport but allow Li+ and e− transport may prevent interphase formation and reduce impedance in SS‐LIBs.
High Energy Density Non‐Contact Bidirectional Spinning Oscillating Float‐Type Triboelectric Nanogenerators for Energy Extraction From Irregular Waves
Authors: Chen Feng , Dai Xianggang , Wu Xiaobo , Ding Zhenxing , Gao Yidong , Pang Yaokun , Jiang Tao , Luo Jianjun , Hong Zhanyong , Wang Zhong Lin
Published: December 2024

The pursuit of sustainable and self‐sufficient energy solutions has become critical for the advancement of marine Internet of Things (IoT) technologies. While triboelectric nanogenerators (TENGs) have shown great potential in harnessing high‐entropy, low‐frequency wave energy, their practical applications are hindered by low power output and issues related to frictional wear. Hence, this research presents a novel non‐contact bidirectional spinning oscillating float‐type triboelectric nanogenerator (OF‐TENG) for efficient wave energy harvesting. Utilizing a planetary gear and bidirectional rotation structural design, low‐frequency vertical wave energy with random and multi‐directional conditions can be converted into high‐frequency rotational energy. At a frequency of 0.5 Hz, the OF‐TENG achieves a peak output power of 93.48 mW, and an average output volumetric power density of 31.3 W m⁻3. Furthermore, the non‐contact working mode ensures robust output stability, with no significant performance degradation observed after 5,680,000 working cycles. An intelligent self‐powered marine ranching system for automatic feeding and water quality monitoring is further developed based on the OF‐TENG. This work not only provides an effective solution for harvesting low‐frequency wave energy, but also promotes the development of smart marine IoT technologies and marine agriculture.
Synergistic Configurational Entropy and Iron Vacancy Engineering in Na4Fe3(PO4)2P2O7 Cathode for High‐Power‐Density and Ultralong‐Life Na‐Ion Full Batteries
Authors: Hu Xiaoping , Liang Shuquan , Lin Jiande , Ren Wen , Fu Shengqiao , Cao Zhitao , Zhang Ting , Zhang Lei , Cao Xinxin
Published: December 2024

Na4Fe3(PO4)2P2O7 cathode exhibits extensive potential for high‐power applications, owing to its large sodium ion diffusion channels, low cost, and suitable operating voltage. However, it suffers significant capacity degradation due to the inevitable NaFePO4 impurity. Herein, a synergistic strategy is proposed that integrates high entropy doping with Fe vacancy engineering, which not only preserves the phase purity but also provides additional active sites and further stabilizes its crystal structure. A novel Na4Fe2.61(Ni, Co, Mn, Cu, Zn, Mg)0.05(PO4)2P2O7 cathode has been successfully synthesized by a simple sol‐gel method, which exhibits an ultralong cycle life (over 15000 cycles at 5 A g−1) and outstanding rate capability (61.1 mAh g⁻¹ at 10A g−1). Additionally, a combined solid‐solution and biphasic reaction mechanism in sodium storage process is thoroughly confirmed. Notably, benefiting from the rational design of N/P ratio and well‐matched capacitive contributions, the full cells assembled with hard carbon anodes exhibit superior cycling durability, sustaining over 1000 cycles at a high current density of 1 A g⁻¹ without severe capacity deterioration. Such highly durable full cells with low N/P ratioand common ester‐based electrolytes have never been reported before. The present work offers new perspectives to expedite the commercialization of low‐cost, high‐power‐density sodium‐ion batteries.
Carbon‐zero co‐production of hydrogen and chemicals boosted by directional hydrogen spillover via terminated interface
Authors: Guo Xuanlin , Wu Huifang , Zhao Yang , Zheng Lirong , Wang Qian , Li Dianqing , Feng Junting
Published: December 2024

Acceptorless dehydrogenation of biomass‐alcohol provides an appealing route for co‐producing green H2 and high‐value chemicals. However, the sluggish H species binding step severely inhibits reaction equilibrium and cause C‐C cleavage. Herein, we propose a unique directional H spillover strategy driven by controlling electron transport direction via constructing Au‐O‐Cu‐O‐Mg/Al interfacial structure, to allow H species transfer from O‐H dehydrogenation Cu2+ site to C‐H dehydrogenation Au site to promote H2 formation. The structure that each Cu precisely terminated by Mg/Al is inherited from layered double hydroxides with orderly dispersed atom arrangement. Comprehensive studies substantiate that the unreducible Mg2+/Al3+ blocks electron transfer toward support, whereas Au‐O‐Cu electronic interaction drives H spillover from the support to Au. The Au/CuMgAl catalyst demonstrated unprecedentedly high glycerol dehydrogenation activity, showing 3–10 times turnover frequency (1.18 × 104 h−1) than other biomass‐derived H2 formation system, co‐producing lactic acid with selectivity up to 98.8%.
Longitudinal cognitive performance of participants with sporadic early onset Alzheimer's disease from LEADS
Authors: Hammers Dustin B. , Eloyan Ani , Taurone Alexander , Thangarajah Maryanne , Gao Sujuan , Beckett Laurel , Polsinelli Angelina J. , Kirby Kala , Dage Jeffrey L. , Nudelman Kelly , Aisen Paul , Reman Rema , La Joie Renaud , Lagarde Julien , Atri Alireza , Clark David , Day Gregory S. , Duara Ranjan , Graff‐Radford Neill R. , Grant Ian , Honig Lawrence S. , Johnson Erik C. B. , Jones David T. , Masdeu Joseph C. , Mendez Mario F. , Womack Kyle , Musiek Erik , Onyike Chiadi U. , Riddle Meghan , Rogalski Emily , Salloway Steven , Sha Sharon J. , Turner Raymond Scott , Wingo Thomas S. , Wolk David A. , Carrillo Maria C. , Rabinovici Gil D. , Dickerson Bradford C. , Apostolova Liana G. ,   the LEADS Consortium
Published: December 2024

INTRODUCTION

Early‐onset Alzheimer's disease (EOAD) manifests prior to the age of 65, and affects 4%–8% of patients with Alzheimer's disease (AD). The current analyses sought to examine longitudinal cognitive trajectories of participants with early‐onset dementia.

METHODS

Data from 307 cognitively normal (CN) volunteer participants and those with amyloid‐positive EOAD or amyloid‐negative cognitive impairment (EOnonAD) were compared. Cognitive trajectories across a comprehensive cognitive battery spanning 42 months were examined using mixed‐effects modeling.

RESULTS

The EOAD group displayed worse cognition at baseline relative to EOnonAD and CN groups, and more aggressive declines in cognition over time. The largest effects were observed on measures of executive functioning domains, while memory declines were blunted in EOAD.

DISCUSSION

EOAD declined 2–4× faster than EOnonAD, and EOAD pathology is not restricted to memory networks. Early identification of deficits is critical to ensure that individuals with sporadic EOAD can be considered for treatment using disease‐modifying medications.

Highlights

Represents the most comprehensive longitudinal characterization of sporadic EOAD to date.

The trajectory of cognitive declines was steep for EOAD participants and worse than for other groups.

Executive functioning measures exhibited the greatest declines over time in EOAD.
Plasma Aβ42/Aβ40 is sensitive to early cerebral amyloid accumulation and predicts risk of cognitive decline across the Alzheimer's disease spectrum
Authors: Trelle Alexandra N. , Young Christina B. , Vossler Hillary , Ramos Benitez Javier , Cody Karly A. , Mendiola Justin H. , Swarovski Michelle S. , Guen Yann Le , Feinstein Igor , Butler Robert R. , Channappa Divya , Romero America , Park Jennifer , Shahid‐Besanti Marian , Corso Nicole K. , Chau Kelly , Smith Amanda N. , Skylar‐Scott Irina , Yutsis Maya V. , Fredericks Carolyn A. , Tian Lu , Younes Kyan , Kerchner Geoffrey A. , Deutsch Gayle K. , Davidzon Guido A. , Sha Sharon J. , Henderson Victor W. , Longo Frank M. , Greicius Michael D. , Wyss‐Coray Tony , Andreasson Katrin I. , Poston Kathleen L. , Wagner Anthony D. , Mormino Elizabeth C. , Wilson Edward N.
Published: December 2024

INTRODUCTION

The availability of amyloid beta (Aβ) targeting therapies for Alzheimer's disease (AD) is increasing the demand for scalable biomarkers that are sensitive to early cerebral Aβ accumulation.

METHODS

We evaluated fully‐automated Lumipulse plasma Aβ42/Aβ40 immunoassays for detecting cerebral Aβ in 457 clinically unimpaired (CU) and clinically impaired (CI) Stanford Alzheimer's Disease Research Center (Stanford ADRC) participants and 186 CU in the Stanford Aging and Memory Study (SAMS). Longitudinal change in ADRC plasma Aβ42/Aβ40 and cognition and cross‐sectional associations with SAMS memory and tau positron emission tomography (PET) were examined.

RESULTS

Plasma Aβ42/Aβ40 exhibited high performance in detecting amyloid positivity defined by PET (area under the curve [AUC]: 0.885, 95% confidence interval [CI]: 0.816–0.955). Once abnomal, plasma Aβ42/Aβ40 remained low and predicted cognitive decline in both CU and CI individuals. Among SAMS CU, plasma Aβ42/Aβ40 was associated with poorer hippocampal‐dependent memory and elevated tau accumulation.

DISCUSSION

Lumipulse plasma Aβ42/Aβ40 is a scalable assay for detection of cerebral Aβ and prediction of risk for cognitive decline across the AD continuum.

Highlights

Lumipulse plasma amyloid beta (Aβ)42/Aβ40 exhibited high accuracy in detecting amyloid positivity.

Plasma amyloid‐positive (Aβ+) individuals exhibited stability of Aβ42/Aβ40 over time.

Plasma Aβ42/Aβ40 predicted future cognitive decline across the Alzheimer's disease (AD) spectrum.

Plasma Aβ42/Aβ40 was sensitive to memory and tau burden in clinically unimpaired older adults.
Accelerated ovarian failure results in brain alterations related to Alzheimer's disease that are not recovered by high‐intensity interval training in mice
Authors: Mohammad Ahmad , Finch Michael S. , Rouhana Sarah , Mashouri Parastoo , Barry Ciara , Hubbard Emma F. , Sze Newman , Beaudette Shawn M. , Pyle W. Glen , Power Geoffrey A. , MacPherson Rebecca E. K.
Published: December 2024

INTRODUCTION

The menopausal decline in ovarian estrogen production is thought to increase the risk of Alzheimer's disease; however, this link requires further investigation. The chronological development of this connection is not well defined because of the lack of animal models that recapitulate the time course of menopause. This study characterized the cognitive and neuronal effects of the 4‐vinylcyclohexene diepoxide (VCD) model of ovarian failure in female mice and assessed whether high‐intensity interval training (HIIT) would attenuate impairments.

METHODS

Female mice were injected with VCD for 15 days. Novel object recognition tests (NORT) were conducted during (perimenopause) and after (menopause) ovarian failure (n = 7). HIIT was initiated in menopause and mice underwent NORT testing after 2 and 8 weeks of HIIT (n = 5).

RESULTS

VCD mice had a lower discrimination index, and lower SNAP25 and NeuN expression in perimenopause. HIIT did not recover memory in VCD mice.

DISCUSSION

Neuronal changes arise early in the perimenopausal transition and HIIT did not improve recognition memory when initiated in menopause.

Highlights

The menopausal decline in ovarian estrogen production increases the risk of Alzheimer's disease (AD).

The chronological development of this connection is not well defined because of the lack of animal models that recapitulate the time course of menopause.

4‐vinylcyclohexene diepoxide (VCD)–induced ovarian failure provides a model that simulates the average human experience in the transition from perimenopause to menopause.

We demonstrate that cognitive and biochemical effects related to AD pathology are present from the earliest available timepoint in perimenopause in VCD mice.

This work highlights the importance of examining the time course in the progression to menopause and the use of VCD as a model to investigate changes in the brain.
Performance of study partner reports in a non‐demented at‐risk sample
Authors: Huang Qi , Bolt Daniel , Jonaitis Erin , Hermann Bruce , Studer Rachel , Du Lianlian , Ryther Brenda , Sparks Lia , Galvin James E. , Johnson Sterling , Langhough Rebecca
Published: December 2024

INTRODUCTION

The Clinical Dementia Rating (CDR) Scale is a gold standard for staging impairment in Alzheimer's disease and other dementias (ADRD). The Quick Dementia Rating System (QDRS) offers similar results in 3 to 5 minutes without a trained clinician. This study aimed to (1) investigate concordance between comparably derived QDRS and CDR global scores, (2) examine item‐level QDRS/CDR agreement, and (3) compare sample characteristics and cognitive performance across QDRS/CDR global concordant/discordant groups.

METHODS

The study included 351 QDRS/CDR pairs from 297 participants in the Wisconsin Registry for Alzheimer's Prevention (WRAP). Analyses included descriptive indices of QDRS/CDR agreement, lasso logistic regression, tetrachoric correlations, and linear mixed models.

RESULTS

The QDRS global/CDR global concordance rate is 70.66%. Memory item discrepancies were primarily responsible for QDRS/CDR global rating discordance. Average cognitive scores were highest in concordant‐normal QDRS/CDR and lowest in concordant‐abnormal QDRS/CDR.

DISCUSSION

The QDRS effectively screened for impairment in this sample. Future analyses will investigate QDRS relations to ADRD biomarkers.

Highlights

The Quick Dementia Rating System (QDRS) effectively screened for impairment in Alzheimer's disease and other dementias (ADRD) in a non‐demented sample.

Concordance rate between QDRSCDR global and Clinical Dementia Rating (CDR) Scale global scores is 70.66%.

Memory item discrepancies primarily cause QDRS/CDR global score discordance.

Cognitive scores are associated with QDRS/CDR concordances/discordances.

Future analyses will explore QDRS relations to ADRD biomarkers.
One‐Step Process for the Regiodivergent Double Hydrocyanation of 1,3‐Butadiene
Authors: Long Jinguo , Wang Ting , Zhong Hongyu , Jiao Mingdong , Morandi Bill , He Lin , Cheng Gui‐Juan , Fang Xianjie
Published: December 2024

In industry, the two important nitrile starting materials, adiponitrile and 2‐methylglutaronitrile, are primarily manufactured through the well‐known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel‐catalyzed divergent, one‐step double hydrocyanation of 1,3‐butadiene to produce either adiponitrile or 2‐methylglutaronitrile in high regioselectivity. The key to this success lies in the highly tunable binding pockets of the bidentate phosphite ligands, which creates a geometrically defined coordination space around the nickel center. The first hydrocyanation that produces either the linear or branched alkenyl nitrile was identified as the selectivity‐determining step. Organometallic studies confirm the formation of well‐defined diphosphite nickel diene complexes in solution, and the role of ligands in dictating regioselectivity was further rationalized by DFT computations. This result provides the first example of a highly selective nickel‐catalyzed synthesis of adiponitrile and 2‐methylglutaronitrile from butadiene, and it also represents a high‐level of catalyst‐controlled regioselectivity via the fine‐tuning of ligand pocket geometry.
One‐Step Process for the Regiodivergent Double Hydrocyanation of 1,3‐Butadiene
Authors: Long Jinguo , Wang Ting , Zhong Hongyu , Jiao Mingdong , Morandi Bill , He Lin , Cheng Gui-Juan , Fang Xianjie
Published: December 2024

In industry, the two important nitrile starting materials, adiponitrile and 2‐methylglutaronitrile, are primarily manufactured through the well‐known DuPont process, which consists of a tandem sequence including first hydrocyanation, isomerization and second hydrocyanation. However, this mature process has the intrinsic defects of step efficiency and regioselectivity. Herein, we report a nickel‐catalyzed divergent, one‐step double hydrocyanation of 1,3‐butadiene to produce either adiponitrile or 2‐methylglutaronitrile in high regioselectivity. The key to this success lies in the highly tunable binding pockets of the bidentate phosphite ligands, which creates a geometrically defined coordination space around the nickel center. The first hydrocyanation that produces either the linear or branched alkenyl nitrile was identified as the selectivity‐determining step. Organometallic studies confirm the formation of well‐defined diphosphite nickel diene complexes in solution, and the role of ligands in dictating regioselectivity was further rationalized by DFT computations. This result provides the first example of a highly selective nickel‐catalyzed synthesis of adiponitrile and 2‐methylglutaronitrile from butadiene, and it also represents a high‐level of catalyst‐controlled regioselectivity via the fine‐tuning of ligand pocket geometry.
Decoding regulatory programs underlying placode and dermal condensate cell fate commitment during hair follicle induction via single‐cell multi‐omics analysis
Authors: Li Fang , Li Minghao , Zhang Tongtong , Sui Menghua , Khatib Hasan , Wang Xin
Published: December 2024

Understanding differences in chromatin state and changes in gene regulatory landscape of placode (Pc) and dermal condensate are crucial for decoding hair follicle (HF) morphogenesis programs. To identify cell‐type‐specific chromatin accessibility patterns in the developing HF, we integrated chromatin accessibility and transcriptome profiles at single‐cell resolution during the murine HF induction stage. We applied unbiased analyses to identify seven major HF cell types and reclustered dermal (Der) and epithelium (Epi) subtypes to trace their cell fate specification. Our analysis showed that gene regulation in Der and Epi lineages is largely determined by cis‐regulatory elements that direct gene expression in response to specific developmental cues. The chromatin accessibility of Twist2, Enpp2, Dkk1, and Sox2 varied from fibroblasts (Fb) to pre‐DC lineage, while that of Edar, Lhx2, and Wnt10b varied from Epi to Pc lineage. Cell‐type‐specific enrichment of transcription factor binding motifs implicated Twist2 and Nfatc4 as key regulators in Fb to pre‐DC fate specification, and Fos, Bach1, and Klf1 in Epi to Pc niche fate specification. Additionally, alignment of cell‐type‐specific peaks to super‐enhancer databases identified key regulatory elements in both lineages. We identified and validated the critical cis‐regulatory elements in pre‐DC and Pc fate specifications through embryonic dorsal skin culture in vitro, suggesting that these elements may regulate critical genes essential for HF induction. Overall, our results provide a foundation for a comprehensive analysis of gene regulatory programs that initiate HF development, offering insights into the molecular mechanism of HF morphogenesis and clinical treatments of alopecia by skin grafts.
Photothermal Miniemulsion Polymerization by Amphiphilic Gold Nanoclusters
Authors: Yang Ning , Kang Yuetong , Liu Jiaren , Wang Jiaxi , Zan Yonghui , Zhao Xuan , Wang Xiaoyu , Li Lidong
Published: December 2024

Gold nanoclusters (AuNCs), which are approximately 2 nm in size, exhibit distinctive photophysical and catalytic properties, but their performance is often compromised by environmental factors. To mitigate these challenges, attempts have been made to incorporate AuNCs into polymer matrices to enhance their stability. Miniemulsion polymerization has proven to be an effective method for fabricating organic‐inorganic composites. Here, we present a facile photothermal‐assisted method for miniemulsion polymerization utilizing AuNCs, which serve as co‐stabilizers of the emulsion and photothermal conversion agents. By grafting tryptamine onto hydrophilic AuNCs, the amphiphilic AuNCs were spontaneously adsorbed at the styrene/water interfaces, resulting in stable nanoemulsions. Taking advantage of the photothermal properties of surface‐bounded AuNCs, rapid polymerization of styrene within the nanoemulsion was successfully initiated by external laser irradiation. The prepared nanocomposites inherited the photothermal activity of AuNCs and exhibited good photothermal stability and repeatability. This approach not only facilitates remote control of chemical reactions, but also optimizes the distribution of AuNCs within the final polymer matrix, thereby enabling the efficient synthesis of nanocomposites while exploiting the unique photofunctionality of AuNCs.
Single‐Atom Based Metal‐Organic Frameworks for Efficient C−S Cross‐Coupling
Authors: Sai Kumar Gobbilla , Kumar Deepak , Thakur Aditya , Gupta Mukul , Kumar Velpula Praveen , Lo Rabindranath , Jayaramulu Kolleboyina
Published: December 2024

Single‐atom‐based Metal‐Organic Frameworks (MOFs) hold great promising candidates for heterogeneous catalysis, demonstrating outstanding catalytic activity and exceptional product selectivity. This is attributed to their optimal atom utilization, high surface energy, and the presence of unsaturated coordination environments. Here in, we have developed a nickel single‐atom catalyst (SAC) featuring Ni single atoms covalently attached to defect‐engineered Zr‐oxide clusters within the stable UiO‐66 (Universitetet i Oslo) framework, synthesized via a straightforward solution impregnation method (denoted as UiO‐66/Ni now onwards). The resulting UiO‐66/Ni catalyst, with a uniform distribution of nickel single atoms, exhibits remarkable stability and demonstrates exceptional performance in C−S coupling reactions of various aryl thiols and aryl halides, yielding desired products with outstanding catalytic activity and selectivity, regardless of electron‐donating or withdrawing substituents at room temperature and maintains robust stability even after six cycles. Advanced density functional theory calculations have been exploited to clarify the mechanism of C−S cross‐coupling for examining the influence of substituents on the aromatic ring of aryl thiols through free energy profiles. The collaborative action of nickel single atoms and the defects of UiO‐66 during the oxidative addition and reductive elimination steps facilitated the formation of energetically favorable C−S cross‐coupling products. This study offers valuable insights for the development of enhanced single atom‐based hybrid catalytic systems for heterogeneous coupling reactions.
Broadband Excited YAlO3:Cr3+, Er3+ Phosphors for Enhancing the Spectral Response of GaSb Solar Cell
Authors: Tawalare P. K. , Nafdey R. A. , Tumram Priya V. , Krupadam R. J. , Moharil S. V.
Published: December 2024

We report Er3+ emission in YAlO3 host, sensitized by Cr3+. The excitation bands of Cr3+ at 416 and 555 nm are broad and effectively cover the region 400–600 nm. The phosphor can be useful for converting 400–600 nm radiations to infrared (IR) light around 1521 nm. This property can be useful for enhancing the spectral response of some solar cells such as GaSb to wavelengths below 600 nm down to 400 nm for which the photovoltaic conversion is poor.
Anatomical etiology of bunny lines based on cadaveric dissection and ultrasonographic evaluation
Authors: Ahn Haeryun , Hu Hyewon , Kim Soo‐Bin , Lee Ji‐Hyun , Choi You‐Jin , Hu Kyung‐Seok , Shah‐Desai Sabrina , Abe Shinichi , Kim Hee‐Jin
Published: December 2024

Bunny lines are vertical and diagonal wrinkles attributed to contractions of the nasalis muscle. Common management involves botulinum toxin (BoNT) injections into wrinkles immediately below the nasal bridge. Here, we investigated the anatomical structures underneath bunny lines and their relationships with adjacent muscular structures. The area between the medial canthus and nasal dorsum was examined by ultrasonography in 13 adult volunteers (mean age, 29.4 years) and dissected in 39 cadavers. The findings consistently showed a non‐muscular area (bunny triangle) between the borders of the procerus, nasalis, orbicularis oculi (OOc), and levator labii superioris alaeque nasi (LLSAN) muscles. The size and shape of the bunny triangle vary according to the width of the procerus and nasalis muscles. The muscles neighboring the bunny lines affect the thinning of the thin skin between the medial canthus and nasal dorsum. Our results indicate that conventional BoNT injection into bunny line wrinkles is likely to target connective tissue rather than a muscle, potentially producing suboptimal results. Therefore, the BoNT injection points probably need to target the borders of the procerus, nasalis, OOc, and LLSAN muscles to be most efficient.
Norcrohalane A, an Unusual C15nor‐Halimane‐Type Diterpenoid from Croton crassifolius
Authors: Tang Qing , Tang Yu‐Jun , Wu Tian‐Yuan , Zheng Wei‐Xuan , Zhu Hui‐Hui , Situ Qian‐Yi , Ou Hui‐Lin , Li Can‐Jie , Zhang Yu‐Bo , Wang Guo‐Cai
Published: December 2024

An unusual C15 nor‐halimane‐type diterpenoid, norcrohalane A (1), a new nor‐lasserane‐type sesquiterpenoid, norcrolasane A (2), along with four known compounds (3–6) were isolated from the roots of Croton crassifolius. Compound 1 represents the first example of a C15 nor‐halimane‐type diterpenoid, which features a rare 6/6/6 tricyclic ring system, and the A ring is aromatic. Compound 2 is a rare nor‐lasserane‐type sesquiterpenoid. Their structures and absolute configurations were established by a combination of mass spectrometry, nuclear magnetic resonance, electronic circular dichroism calculation, and single‐crystal X‐ray diffraction analyses. The anti‐neuroinflammatory activities of 1–6 were evaluated for their inhibitory effects on nitric oxide (NO) production in lipopolysaccharide‐induced BV2 cells, and compounds 1 and 2 showed moderate inhibition on NO production with IC50 values of 26.82 ± 0.61 and 17.35 ± 0.78 µM, respectively.