bluuebunny/crossref_metadata_2025 huggingface dataset:
Conjugated Polymers with an Oxindole‐Terminated Quinoidal Unit: Energy Level Modulation Toward Air‐Stable n‐Doped Conductors
Authors: Wang Tianzuo , Xu Chenhui , Deng Yunfeng , Geng Yanhou
Published: October 2024

Developing n‐doped conjugated polymers (CPs) with good air stability remains a significant obstacle to the advancement of organic thermoelectrics. In this study, three CPs (designated PmQ2F, PsQ4F, and PsQ6F) containing an oxindole‐terminated quinoidal unit are synthesized. To obtain an isomeric purity quinoidal unit and tune the LUMO (lowest unoccupied molecular orbital) energies of the CPs, fluoride (F) atoms on the monomers are strategically installed. Compared to a polymer with isomeric quinoidal units (PmQ2F), polymers with an isomerically pure quinoidal unit (PsQ4F and PsQ6F) exhibited higher electron mobilities owing to their more‐ordered molecular packing structures. After n‐doping, PsQ4F and PsQ6F show higher electrical conductivities than PmQ2F. Moreover, the former demonstrated excellent air stability for over 2 months, which can be attributed to the synergistic effects of the quinoidal structure and the reduced LUMO energy. The work offers a novel molecular design strategy that can be expected to advance the development of n‐type CPs for air‐stable organic thermoelectrics.
Bi Cluster Engineering for Tunable Broadband NIR Optical Response
Authors: Chen Jingfei , Dong Quan , Liu Ziang , Zhang Ke , Wang Dazhao , Huang Yupeng , Yu Zhuoming , Lv Shichao , Feng Xu , Li Xueliang , Qiu Jianrong , Zhou Shifeng
Published: October 2024

Near‐infrared (NIR) broadband active photonic materials play a crucial role in various domains such as optical communication, phototherapy, and medical imaging. However, the construction of NIR photonic materials with tunable optical response still remains a great challenge. This manuscript proposes a topological structure engineering strategy in Bi‐activated glass for the realization of the controllable NIR emission. By manipulating the topological structure of glass, the Bi cluster configuration can be precisely control, with the cluster size from 2.78 to 1.64 nm. Correspondingly, various optical properties including broadband emission, excited state absorption (ESA), and even unsaturable loss (UL) can be rationally switched. Based on the above findings, Bi cluster‐activated bulk glasses, optical fibers, and the derived NIR active devices with notably improved performance can be successfully fabricated. Their application potentials in optical communication and NIR imaging are also demonstrated. The study highlights the promise of Bi cluster‐activated materials in advancing NIR photonic materials and devices. Furthermore, the topological‐mediated cluster regulation strategy may also provide new insights into the fundamental science and cutting technology of other cluster‐activated materials.
3D‐Printed‐Cryogel‐Impregnated Functionalized Scaffold Augments Bone Regeneration in Critical Tibia Fracture in Goat
Authors: Nikhil Aman , Gugjoo Mudasir B. , Das Ankita , Ahmad Syed M. , Kumar Ashok
Published: October 2024

Critical‐size bone trauma injuries present a significant clinical challenge because of the limited availability of autografts. In this study, a photocurable composite comprising of polycaprolactone, polypropylene fumarate, and nano‐hydroxyapatite (nHAP) (P─P─H) is printed, which shows good osteoconduction in a rat model. A cryogel composed of gelatin‐nHAP (GH) is developed to incorporate osteogenic components, specifically bone morphogenetic protein‐2 (BMP‐2) and zoledronic acid (ZA), termed as GH+B+Z, which is investigated for osteoinductive property in a rat model. Further, a 3D‐printed P─P─H scaffold impregnated with GH+B+Z is designed and implanted in a critical‐size defect (25 × 10 × 5 mm) in goat tibia. After 4 months, the scaffold is well‐integrated with adjacent native bone, with osteoinduction observed in the cryogel‐filled region and osteoconduction over the printed scaffold. X‐ray radiography and micro‐CT analysis showed bone in‐growth in the treatment group with 45 ± 1.4% bone volume/tissue volume (BV/TV), while the defect remained unhealed in the control group with BV/TV of 10.5 ± 0.5%. Histology showed significant cell infiltration and matrix deposition over the printed P─P─H scaffold and within the GH cryogel site in the treatment group. Immunohistochemical staining depicted significantly higher normalized collagen I intensity in the treatment group (34.45 ± 2.61%) compared to the control group (4.22 ± 0.78).
Piezoelectric‐Enhanced Nanocatalysts Trigger Neutrophil N1 Polarization against Bacterial Biofilm by Disrupting Redox Homeostasis
Authors: Ge Min , Zhu Wanbo , Mei Jiawei , Hu Tingting , Yang Chuang , Lin Han , Shi Jianlin
Published: October 2024

Strategies of manipulating redox signaling molecules to inhibit or activate immune signals have revolutionized therapeutics involving reactive oxygen species (ROS). However, certain diseases with dual resistance barriers to the attacks by both ROS and immune cells, such as bacterial biofilm infections of medical implants, are difficult to eradicate by a single exogenous oxidative stimulus due to the diversity and complexity of the redox species involved. Here, this work demonstrates that metal‐organic framework (MOF) nanoparticles capable of disrupting the bacterial ROS‐defense system can dismantle bacterial redox resistance and induce potent antimicrobial immune responses in a mouse model of surgical implant infection by simultaneously modulating redox homeostasis and initiating neutrophil N1 polarization in the infection microenvironment. Mechanistically, the piezoelectrically enhanced MOF triggers ROS production by tilting the band structure and acts synergistically with the aurintricarboxylic acid loaded within the MOF, which inhibits the activity of the cystathionine γ‐cleaving enzyme. This leads to biofilm structure disruption and antigen exposure through homeostatic imbalance and synergistic activation of neutrophil N1 polarization signals. Thus, this study provides an alternative but promising strategy for the treatment of antibiotic‐resistant biofilm infections.
Manganese‐Catalyzed Three‐Component Vinylation of Phosphines with Sulfones and Alcohols
Authors: Lin Qiongzhen , Sun Feixiang , Wang Tinghuai , Yang Jue , Tang Jun , Liu Weiping
Published: October 2024

Herein, we report a manganese‐catalyzed three‐component vinylation strategy for the synthesis of vinylphosphines from readily available alcohols, sulfones, and phosphines via acceptorless dehydrogenative strategy. This multi‐component, four‐stage, one‐pot protocol offers a stereoselective approach, overcoming the challenges associated with achieving these products through the hydrophosphination of terminal alkynes. The reaction utilizes sulfones and common alcohols to access both (E)‐β‐substituted vinylphosphines (using methanol) and α‐substituted vinylphosphines (using primary alcohols) in yields ranging from 52% to 99%, with E:Z stereoselectivity of 95:5 to 99:1. Importantly, the synthesized branched‐substituted vinylphosphines exhibited superior ligand performance in the copper‐catalyzed cross‐coupling of aryl bromides with pyrazole compared to the commercially available PPh3 and diphenyl(vinyl)phosphane.
Ccl2‐Induced Regulatory T Cells Balance Inflammation Through Macrophage Polarization During Liver Reconstitution
Authors: Wang Rui , Liang Qing , Zhang Qian , Zhao Shuchao , Lin Yuxiang , Liu Bing , Ma Yinjiang , Mai Xiaoya , Fu Quanze , Bao Xiaorui , Wang Nan , Chen Binglin , Yan Peng , Zhu Yongsheng , Wang Kejia
Published: October 2024

Inflammation is highlighted as an initial factor that helps orchestrate liver reconstitution. However, the precise mechanisms controlling inflammation during liver reconstitution have not been fully elucidated. In this study, a clear immune response is demonstrated during hepatic reconstitution. Inhibition of the hepatic inflammatory response retards liver regeneration. During this process, Ccl2 is primarily produced by type 1 innate lymphoid cells (ILC1s), and ILC1‐derived Ccl2 recruits peripheral ILC1s and regulatory T cells (Tregs) to the liver. Deletion of Ccl2 or Tregs exacerbates hepatic injury and inflammatory cytokine release, accelerating liver proliferation and regeneration. The adoption of Tregs and IL‐10 injection reversed these effects on hepatocyte regenerative proliferation. Additionally, Treg‐derived IL‐10 can directly induce macrophage polarization from M1 to M2, which alleviated macrophage‐secreted IL‐6 and TNF‐α and balanced the intrahepatic inflammatory milieu during liver reconstitution. This study reveals the capacity of Tregs to modulate the intrahepatic inflammatory milieu and liver reconstitution through IL‐10‐mediated macrophage polarization, providing a potential opportunity to improve hepatic inflammation and maintain homeostasis.
Non‐Volatile Resistive Switching in Nanoscaled Elemental Tellurium by Vapor Transport Deposition on Gold
Authors: Ghomi Sara , Martella Christian , Lee Yoonseok , Chang Penny Hui‐Ping , Targa Paolo , Serafini Andrea , Codegoni Davide , Massetti Chiara , Gharedaghi Sepideh , Lamperti Alessio , Grazianetti Carlo , Akinwande Deji , Molle Alessandro
Published: October 2024

Two‐dimensional (2D) materials are promising for resistive switching in neuromorphic and in‐memory computing, as their atomic thickness substantially improve the energetic budget of the device and circuits. However, many 2D resistive switching materials struggle with complex growth methods or limited scalability. 2D tellurium exhibits striking characteristics such as simplicity in chemistry, structure, and synthesis making it suitable for various applications. This study reports the first memristor design based on nanoscaled tellurium synthesized by vapor transport deposition (VTD) at a temperature as low as 100 °C fully compatible with back‐end‐of‐line processing. The resistive switching behavior of tellurium nanosheets is studied by conductive atomic force microscopy, providing valuable insights into its memristive functionality, supported by microscale device measurements. Selecting gold as the substrate material enhances the memristive behavior of nanoscaled tellurium in terms of reduced values of set voltage and energy consumption. In addition, formation of conductive paths leading to resistive switching behavior on the gold substrate is driven by gold‐tellurium interface reconfiguration during the VTD process as revealed by energy electron loss spectroscopy analysis. These findings reveal the potential of nanoscaled tellurium as a versatile and scalable material for neuromorphic computing and underscore the influential role of gold electrodes in enhancing its memristive performance.
Smart Photovoltaic Windows for Next‐Generation Energy‐Saving Buildings
Authors: Wang Qian , Na Zongxu , Yu Li , Dai Songyuan , Nazeeruddin Mohammad Khaja , Yang Huai
Published: October 2024

The global energy system transforming from fossil fuels to renewable green energy through the adaption of innovative and dynamic green technologies. Energy‐saving buildings (ESBs) are attracting extensive attention as intelligent architectures capable of significantly reducing the energy consumption for heating, air‐conditioning, and lighting. They provide comfortable working and living environment by regulating and harnessing solar energy. Smart photovoltaic windows (SPWs) offer a promising platform for designing ESBs due to their unique feature. They can modulate solar energy based on dynamic color switching behavior under external stimuli and generate electrical power by harvesting solar energy. In this review, the‐state‐of‐art of strategies and technologies are summarized putting SPWs toward high‐efficiency ESBs. The SPWs are systematically categorized according to the working principle and functional component. For each type of SPWs, material and architecture engineering are focused on to optimize operation mode, optical modulation capability, photovoltaic performance and durability for giving ESBs flexible manipulation, extraordinary energy‐saving effect, and high electricity power. In addition, the challenges and opportunities in this cutting‐edge research area are discussed, with the aim of promoting the development of advanced multifunctional SPWs and their application in high efficiency ESBs.
Alkali‐Stable Metal–Organic Frameworks with Enhanced Electroconductivity for Black‐Brown Electrochromic Energy Storage Smart Window
Authors: Wang Xinyi , Liu Zhiqiang , Ma Heqi , Liu Yiwen , Sui Qing , Feng Jifei , Cai Guofa
Published: October 2024

Metal–organic frameworks (MOFs) deliver potential applications in electrochromism and energy storage. However, the poor intrinsic conductivity of MOFs in electrolytes seriously hampers the development of the above‐mentioned electrochemical applications, especially in one MOF electrode. Herein, a new Ni‐based MOF (denoted Ni‐DPNDI) is proposed with enhanced conductivity by π‐delocalized DPNDI connectors. Predictably, the obtained Ni‐DPNDI MOF achieves a conductivity of up to 4.63 S∙m−1 at 300 K. Profiting from its unique electronic structure, the Ni‐DPNDI MOF delivers excellent electrochromic and energy storage performance with a great optical modulation (60.8%), a fast switching speed (tc = 7.9 s and tb = 6.4 s), a moderate specific capacitance (25.3 mAh·g−1) and good cycle stability over 2000 times. Meanwhile, energy storage capacity is visual by the coloration states of Ni‐DPNDI film. As a proof of the potential application, a large‐area (100 cm2) electrochromic energy storage smart window is further designed and displayed. The strategy provides an interesting alternative to porous multifunctional materials for the new generation of electronic devices with diverse applications.
Cell‐Membrane‐Inspired Ultrathin Silica Nanochannels Coating for Long‐Term Stable Photoelectrocatalysis with Enhanced Performance
Authors: Yan Wenyan , Zhou Lin , Luo Zisheng , Ding Shenghua , Li Dong , Lin Xingyu
Published: October 2024

Photoelectrocatalysis has attracted significant attention for water splitting and contaminant degradation. However, the lifetime of photoelectrocatalysis devices is hampered by the severe instability and photocorrosion of the photo‐active nanomaterial on the photoelectrode, which is a key limitation to realizing industrialization. Typically, the conventional protection strategy of photoelectrodes usually suffers from the trade‐off between the photoelectrocatalytic activity and stability. Inspired by biological cell membrane with water channels, here a highly permeable and ultrathin silica coating with ultrasmall straight nanochannels is in situ grown that stabilizes the photoelectrode. These ultrasmall channels boost photoelectrocatalysis by accelerating water transport and reducing the reaction energy within the confined nanochannels. Specifically, the ultrathin coating imparts significant mechanical and structural stability to the photo‐active nanomaterial, thereby preventing its detachment, dissolution, and crystal damage without compromising performance. As a result, the protected photoelectrode exhibits enhanced water splitting activity and excellent stability over 120 h, whereas the photocurrent of the unprotected photoelectrode degrades rapidly. Meanwhile, the coated photoelectrode also exhibits superior photoelectrocatalytic degradation efficiency (>97%), even after the 10th cycle. This strategy is facile and universal and can be extended to construct other stable and high‐performance electrodes for promoting photoelectrocatalysis in practical applications.
Dual‐Interphase‐Stabilizing Sulfolane‐Based Electrolytes for High‐Voltage and High‐Safety Lithium Metal Batteries
Authors: Zhou Junhua , Zhang Chi , Wang Huimin , Guo Yanpeng , Xie Chuan , Luo Yufeng , Wang Chao , Wen Shujing , Cai Jiehua , Yu Wancheng , Chen Fan , Zhang Yufei , Huang Qiyao , Zheng Zijian
Published: October 2024

High‐voltage Li metal battery (HV‐LMB) is one of the most promising energy storage technologies to achieve ultrahigh energy density. Nevertheless, electrolytes reported to date are difficult to simultaneously stabilize the Li metal anode and high‐voltage cathode, especially without the assistance of expensive and corrosive high‐concentration Li salts. Herein, a dual‐interphase‐stabilizing (DIS) and safe electrolyte that bypasses the high‐concentration Li salt is reported. The electrolyte consists of high‐flash‐point sulfolane as solvent, molecular‐orbital‐engineered additives that enable stable B‐F rich cathodic interphase, and unique C‐F rich organic anodic interphase. The stable cycling of both Li metal anode and 4.75 V‐LiCoO2 cathode in the DIS electrolyte (> 500 cycles) is demonstrated. HV‐LMB pouch cells of a high energy density (435 Wh kg−1) can sustainably operate for more than 100 cycles. Moreover, the low cost and high thermal stability of the DIS electrolyte offer superior cost‐effectiveness and safety for large‐scale applications of HV‐LMBs in the future.
Are we measuring impact accurately? Identifying potential sources of bias in the evaluation of extension personnel and programs
Authors: Wright Andrew , Wright Jeffrey , McCorkle Dean , Hyde Jeffrey
Published: October 2024

Agricultural extension programs must demonstrate their value to compete for limited government funding. As extension professionals measure the value of their programs, the risk exists that the information they report will provide a biased or an inaccurate measure of value. We examine the evaluation process for extension programs and extension personnel to identify potential sources of bias or inaccuracies. We find that bias and inaccuracy in program evaluation often stems from a focus on short‐term outcomes, rather than long‐term impacts, while bias in personnel evaluation can result from information asymmetries that exist between extension personnel and their evaluators.
Sex Differences in Cortical Thickness and Neuropsychiatric Symptom Burden Based on APOE4 Homozygosity in Alzheimer's Disease
Authors: Khoury Marc A. , Valcic Mila , Churchill Nathan W. , Di Battista Alex , De Luca Vincenzo , Fornazzari Luis R. , Munoz David G. , Fischer Corinne E. , Schweizer Tom A.
Published: October 2024

Sex differences in patterns of cortical thickness and neuropsychiatric symptom (NPS) burden were examined among individuals with Alzheimer's disease (AD) and two copies (homozygote carriers) of the e4 allele of the apolipoprotein gene (APOE). A total of 752 participants with a clinical etiologic diagnosis of AD were selected from the National Alzheimer's Coordinating Center (NACC) database. Bayesian multilevel regression was used to examine both the within‐ and between‐sex differences in gray‐matter cortical thickness and total NPS burden associated with APOE homozygosity. Female homozygote carriers displayed a high probability of having reduced cortical thickness primarily in medial–lateral temporal regions and a greater burden of NPS, relative to both non‐homozygous females and homozygous males. These findings support the notion that APOE4 status affects cortical thickness and symptom burden in men and women with AD differentially, with females showing more pronounced effects in brain areas known to be vulnerable in early AD. Future investigations should attempt to elucidate the proposed pattern of decline longitudinally.
Klebsiella liver phlegmon mimicking a solid liver tumour
Authors: Necas Martin , Mitchell Jereme
Published: October 2024

Introduction

This case examines the sonographic and clinical challenge of diagnosing a Klebsiella pnumoniae pyogenic liver abscess with systemic metastatic infection.

Case Description

The patient in this case study is an 81‐year‐old man who presented with intermittent rigors. Following radiological and clinical assessments, a Klebsiella pnumoniae pyogenic liver abscess, with evidence of systemic metastatic infection, was diagnosed. Sonographic features of the liver abscess were atypical for a cystic lesion and instead appeared as a solid mass, raising the possibility of malignancy. Treatment of intravenous ceftriaxone infusions resulted in full resolution of the liver lesion.

Discussion

The discussion criticises the terminology when describing hepatic lesions, which result from a Klebsiella pnumoniae infection. The term hepatic phlegmon is appropriate when a liver lesion caused by bacterial infection demonstrates a solid appearance on radiologic imaging. The term hepatic abscess is appropriate in cases where liver lesions caused by bacterial infection demonstrate a fluid filled core on radiologic imaging. Differentiation of these terms is important when treating the underlying lesion as a phlegmon, in contrast to an abscess, cannot be drained because it contains no pus. The variable sonographic appearances of Klebsiella pnumoniae pyogenic abscesses were also examined. Despite reported sonographic appearances in the literature, none are sufficient to distinguish a pyogenic liver abscess from malignancy without further investigation.

Conclusion

Ultrasound operators should be aware of the variable sonographic appearances of a Klebsiella pnumoniae liver abscess and how these features, combined with non‐homogenous terminology, can obfuscate the correct diagnosis.
Recommendations for clinical implementation of blood‐based biomarkers for Alzheimer's disease
Authors: Mielke Michelle M. , Anderson Matthew , Ashford J. Wesson , Jeromin Andreas , Lin Pei‐Jung , Rosen Allyson , Tyrone Jamie , Vandevrede Lawren , Willis Deanna R. , Hansson Oskar , Khachaturian Ara S. , Schindler Suzanne E. , Weiss Joan , Batrla Richard , Bozeat Sasha , Dwyer John R. , Holzapfel Drew , Jones Daryl Rhys , Murray James F. , Partrick Katherine A. , Scholler Emily , Vradenburg George , Young Dylan , Braunstein Joel B. , Burnham Samantha C. , de Oliveira Fabricio Ferreira , Hu Yan Helen , Mattke Soeren , Merali Zul , Monane Mark , Sabbagh Marwan Noel , Shobin Eli , Weiner Michael , Udeh‐Momoh Chinedu T.
Published: October 2024

Blood‐based biomarkers (BBM) for Alzheimer's disease (AD) are being increasingly used in clinical practice to support an AD diagnosis. In contrast to traditional diagnostic modalities, such as amyloid positron emission tomography and cerebrospinal fluid biomarkers, BBMs offer a more accessible and lower cost alternative for AD biomarker testing. Their unique scalability addresses the anticipated surge in demand for biomarker testing with the emergence of disease‐modifying treatments (DMTs) that require confirmation of amyloid pathology. To facilitate the uptake of BBMs in clinical practice, The Global CEO Initiative on Alzheimer's Disease convened a BBM Workgroup to provide recommendations for two clinical implementational pathways for BBMs: one for current use for triaging and another for future use to confirm amyloid pathology. These pathways provide a standardized diagnostic approach with guidance on interpreting BBM test results. Integrating BBMs into clinical practice will simplify the diagnostic process and facilitate timely access to DMTs for eligible patients.
Psychological outcomes of dementia risk estimation in MCI patients: Results from the PreDADQoL project
Authors: Rostamzadeh Ayda , Kalthegener Franziska , Schwegler Carolin , Romotzky Vanessa , Gil‐Navarro Silvia , Rosende‐Roca Maitée , Ortega Gemma , Canabate Pilar , Moreno Mariola , Maier Franziska , Zeyen Philip , Schild Ann‐Katrin , Meiberth Dix , Sannemann Lena , Bohr Lara , Schmitz‐Luhn Björn , Boada Mercè , Woopen Christiane , Jessen Frank
Published: October 2024

INTRODUCTION

Understanding the impact of biomarker‐based dementia risk estimation in people with mild cognitive impairment (MCI) and their care partners is critical for patient care.

METHODS

MCI patients and study partners were counseled on Alzheimer's disease (AD) biomarker and dementia risk was disclosed. Data on mood, quality of life (QoL), and satisfaction with life (SwL) were obtained 1 week and 3 months after disclosure.

RESULTS

Seventy‐five dyads were enrolled, and two‐thirds of the patients opted for biomarker testing. None of the participants experienced clinically relevant depression or anxiety after disclosure. All dyads reported moderate to high QoL and SwL throughout the study. Patients reported more subthreshold depressive symptoms 1 week and lower QoL and SwL 3 months after disclosure. In patients, depression (odds ratio [OR]: 0.76) and anxiety (OR: 0.81) were significant predictors for the decision against biomarker testing.

DISCUSSION

No major psychological harm is to be expected in MCI patients and care partners after dementia risk disclosure.

TRIAL REGISTRATION

This study is registered in the German clinical trials register (Deutsches Register Klinischer Studien, DRKS): http://www.drks.de/DRKS00011155, DRKS registration number: DRKS00011155, date of registration: 18.08.2017.

Highlights

Patients with mild cognitive impairment (MCI) and study partners were counseled on Alzheimer's disease (AD) biomarker‐based dementia risk estimation.

About two‐thirds of patients opted for biomarker testing and received their dementia risk based on their AD biomarker status.

Patients who decided in favor or against CSF biomarker testing differed in psychological features.

We did not observe major psychological harm after the dementia risk disclosure.

Coping strategies were associated with better subsequent mood and well‐being in all participants.
Examination of plasma biomarkers of amyloid, tau, neurodegeneration, and neuroinflammation in former elite American football players
Authors: Miner Annalise E. , Groh Jenna R. , Tripodis Yorghos , Adler Charles H. , Balcer Laura J. , Bernick Charles , Zetterberg Henrik , Blennow Kaj , Peskind Elaine , Ashton Nicholas J. , Gaudet Charles E. , Martin Brett , Palmisano Joseph N. , Banks Sarah J. , Barr William B. , Wethe Jennifer V. , Cantu Robert C. , Dodick David W. , Katz Douglas I. , Mez Jesse , van Amerongen Suzan , Cummings Jeffrey L. , Shenton Martha E. , Reiman Eric M. , Stern Robert A. , Alosco Michael L. ,   for the DIAGNOSE CTE Research Project
Published: October 2024

INTRODUCTION

Blood‐based biomarkers offer a promising approach for the detection of neuropathologies from repetitive head impacts (RHI). We evaluated plasma biomarkers of amyloid, tau, neurodegeneration, and inflammation in former football players.

METHODS

The sample included 180 former football players and 60 asymptomatic, unexposed male participants (aged 45–74). Plasma assays were conducted for beta‐amyloid (Aβ) 40, Aβ42, hyper‐phosphorylated tau (p‐tau) 181+231, total tau (t‐tau), neurofilament light (NfL), glial fibrillary acidic protein (GFAP), interleukin‐6 (IL‐6), Aβ42/p‐tau181 and Aβ42/Aβ40 ratios. We evaluated their ability to differentiate the groups and associations with RHI proxies and traumatic encephalopathy syndrome (TES).

RESULTS

P‐tau181 and p‐tau231(padj = 0.016) were higher and Aβ42/p‐tau181 was lower(padj = 0.004) in football players compared to controls. Discrimination accuracy for p‐tau was modest (area under the curve [AUC] = 0.742). Effects were not attributable to AD‐related pathology. Younger age of first exposure (AFE) correlated with higher NfL (padj = 0.03) and GFAP (padj = 0.033). Plasma GFAP was higher in TES‐chronic traumatic encephalopathy (TES‐CTE) Possible/Probable (padj = 0.008).

DISCUSSION

Plasma p‐tau181 and p‐tau231, GFAP, and NfL may offer some usefulness for the characterization of RHI‐related neuropathologies.

Highlights

Former football players had higher plasma p‐tau181 and p‐tau231 and lower Aβ42/ptau‐181 compared to asymptomatic, unexposed men.

Younger age of first exposure was associated with increased plasma NfL and GFAP in older but not younger participants.

Plasma GFAP was higher in participants with TES‐CTE possible/probable compared to TES‐CTE no/suggestive.
Pro‐Ictal EEG Scheduling Improves the Yield of Epilepsy Monitoring: Validating the Use of Multiday Seizure Cycles to Optimize Video‐EEG Timing
Authors: Naim‐Feil Jodie , Stirling Rachel E. , Karoly Philippa J. , Payne Daniel , Winterling Nicholas , Eden Dominique , Cook Mark J. , Grayden David B. , Maturana Matias , Freestone Dean R. , Nurse Ewan S.
Published: October 2024

Objective

A significant challenge of video‐electroencephalography (vEEG) in epilepsy diagnosis is timing monitoring sessions to capture epileptiform activity. In this study, we introduce and validate “pro‐ictal EEG scheduling”, a method to schedule vEEG monitoring to coincide with periods of increased seizure likelihood as a low‐risk approach to enhance the diagnostic yield.

Methods

A database of long‐term ambulatory vEEG monitoring sessions (n = 5,038) of adults and children was examined. Data from linked electronic seizure diaries were extracted (minimum 10 self‐reported events) to generate cycle‐based estimates of seizure risk. In adults, vEEG monitoring sessions coinciding with periods of estimated high‐risk were allocated to the high‐risk group (n = 305) and compared to remaining studies (baseline: n = 3,586). Test of proportions and risk‐ratios (RR) were applied to index differences in proportions and likelihood of capturing outcome measures (abnormal report, confirmed seizure, and diary event) during monitoring. The impact of clinical and demographic factors (age, sex, epilepsy‐type, and medication) was also explored.

Results

During vEEG monitoring, the high‐risk group was significantly more likely to have an abnormal vEEG report (190/305:62% vs 1,790/3,586:50% [%change = 12%], RR = 1.25, 95% confidence interval [CI] = [1.137–1.370], p < 0.001), present with a confirmed seizure (56/305:18% vs 424/3,586:11% [%change = 7%], RR = 1.63, 95% CI = [1.265–2.101], p < 0.001) and report an event (153/305:50% vs 1,267/3,586:35% (%change = 15%), RR = 1.420, 95% CI = [1.259:1.602], p < 0.001). Similar effects were observed across clinical and demographic features.

Interpretation

This study provides the first large‐scale validation of pro‐ictal EEG scheduling in improving the yield of vEEG. This innovative approach offers a pragmatic and low‐risk strategy to enhance the diagnostic capabilities of vEEG monitoring, significantly impacting epilepsy management. ANN NEUROL 2024;96:1148–1159
Integrated Design of Homogeneous/Heterogeneous Copper Complex Catalysts to Enable Synergistic Effects on Sulfur and Lithium Evolution Reactions
Authors: Yang Qin , Wang Chensheng , Song Lixian , Zhang Yunfeng , Shen Zhaoyang , Cai Wenlong , Song Yingze
Published: October 2024

Fatal polysulfide shuttling, sluggish sulfur redox kinetics and detrimental lithium dendrites have curtailed the real discharge capacity, working lifespan and safety of lithium−sulfur (Li−S) batteries. Organic small molecule promotors as one type of emerging active catalysts can fulfil the management of the electrochemical species evolution behaviors. Herein, an integrated engineering is organized by synthesizing dual chlorine‐bridge enabled binuclear copper complex (Cu2(phen)2Cl2) and its derivative generated in electrolyte (Cu‐ETL) as the heterogeneous and homogeneous catalyst, respectively. The well‐designed Cu‐ETL with a optimized concentration of 0.25 wt% as a homogeneous enabler offers highly utilized Cu centers and the sufficient interface contact for guiding the Li2S nucleation/decomposition reactions. The Cu2(phen)2Cl2 loaded on carbon spheres as an interlayer (Cu‐INT) can break through the catalytic limitation resulting from the saturated concentration of Cu‐ETL and thus offers an extended manipulation effect. Benefiting from the synergistic effect, the Li−S battery shows stable cycling at 3 C upon 500 cycles with a capacity degradation rate as low as 0.029 % per cycle. Of specific note, an actual cell energy density of 372.1 Wh kg−1 is harvested by a 1.2 Ah‐level soft‐packaged pouch cell, implying a chance for requiring the demand of high‐energy batteries.
Bright Nanocomposites based on Quantum Dot‐Initiated Photocatalysis
Authors: Hu Zhuang , Gao Feng , Qin Haiyan , Cui Xin , Wang Linqin , Yang Wenxing , Lu Chunyuan , Zhang Biaobiao , Sun Licheng
Published: October 2024

Integrating quantum dots (QDs) into polymer matrix to form nanocomposites without compromising the QD photoluminescence (PL) is crucial to emerging QD light‐emitting and solar energy conversion fields. However, the most widely‐used bulk polymerization technique, where monomers serve as the QD solvent, usually leads to QD PL quenching caused by radical initiators. Here we demonstrate high‐brightness nanocomposites with near‐unity PL quantum yield (QY), through a novel QDs‐catalyzed (‐initiated) bulk polymerization without using any radical initiators. Different from previous reports where QDs were designed as photo‐sensitizers/catalysts (always with cocatalysts) and hence non‐emissive in catalytic conditions, our QDs combine high brightness with highly effective catalysis, a combination that was previously considered to be hardly possible. In our case, apart from emitting light (at a large probability), the photoexcited QDs act as ‘overall reaction’ catalysts by simultaneously employing photoexcited electrons and holes to produce active radicals without the need of any sacrificial agents. These active radicals, though with a small amount, are sufficient to initiate effective chain reaction‐dominated bulk polymerization, eliminating the requirement of extra radical initiators. This study provides new insights for understanding and development of QDs for energy applications.
The utilization of Industry 4.0 technologies to enhance the circular economy through the engagement of stakeholders in Brazilian food technology companies
Authors: da Silva Tiago Hennemann Hilario , Sehnem Simone
Published: October 2024

Sustainable business models tend to have greater potential for the transition to the circular economy. The present study aims to investigate how Brazilian startups in the food segment foodtech are integrating Industry 4.0 technologies to boost the circular economy, emphasizing the importance of stakeholder engagement in the process. The choice of this unit of analysis is associated with companies that were born recently, with a high chance of having sustainable and circular business models. The research involved eight food technology startups, using questionnaires, interviews, and content analysis to collect data on circular supply chain practices, Industry 4.0 technologies adopted, and the level of stakeholder engagement. The results indicate that foodtech startups are progressively incorporating technologies such as automation, big data, biotechnology, and the Internet of Things, to promote circular economy initiatives. The active participation of stakeholders has been fundamental, contributing to innovation and efficiency in processes. However, the complete transition to the circular economy and the full adoption of Industry 4.0 technologies are challenged by obstacles, including high costs and regulatory barriers. The study found that startups play a crucial role in this transition, due to their agility and capacity for innovation, which can serve as an example for larger companies. Collaboration between businesses, regulators, academic institutions, and society is essential to overcome these challenges and facilitate effective transformation. This work offers valuable practical insights for foodtech startups looking to adopt circular practices, highlighting technologies, and practices that can result in economic and environmental benefits. Startups emerge not only as adopters of new technologies but also as agents of change in industrial practices, shaping a more sustainable future for the food sector. It is recommended that future research explore the impact of regulatory policies and incentives on accelerating the adoption of these technologies by startups, in addition to evaluating the long‐term economic viability of these technological innovations in promoting a more circular economy.
α‐Glucosidase Inhibiting Chromene Derivatives from Ageratum conyzoides L. Essential Oil Extracted via NADES‐Assisted Hydrodistillation
Authors: Parmar Kusum , Aggarwal Gaurav , Sharma Upendra
Published: October 2024

This work employed a green approach utilizing natural deep eutectic solvent (NADES)‐assisted hydrodistillation for EO extraction from the aerial part of Ageratum conyzoides. Out of seven deep eutectic combinations used, glycerol‐lactic acid (GLY:LA) (1 : 1) mixture significantly enhanced the yield from 0.78 mg/g (water as extraction media) to 1.00 mg/g. GC and GC‐MS analysis revealed that EOs mainly contain (E)‐β‐caryophyllene (15.2–25.3 %), (E)‐β‐farnesene (2.7–8.2 %), and notably, precocene‐I (8.2–18.0 %) and precocene‐II (31.8–51.4 %), which varied significantly across different extraction media. Further column chromatography‐based purification of EO led to the isolation of two known chromene derivatives precocene‐I (1) and precocene‐II (2). Precocene‐I exhibited potent anti‐diabetic activity (IC50 0.26 mg/mL) compared to the standard drug acarbose. Among the EO samples, USK−N7, which had the highest percentage of precocene‐I, showed the highest activity. The present study demonstrated the potential use of this weed plant as an anti‐diabetic agent.
Phytotoxic and Cytogenetic Assessment of Glycerol Triazole Derivatives in Model Plants and Weeds
Authors: de Assis Alves Thayllon , de Assis Alves Thammyres , Gazolla Poliana Aparecida Rodrigues , Lima Ângela Maria Almeida , Belizario de Oliveira Mariana , Aniceto da Silva Danilo , Tebaldi de Queiroz Vagner , Ricardo Teixeira Róbson , Vidal Costa Adilson , Miranda Praça‐Fontes Milene
Published: October 2024

Weed invasion represents a challenge for farmers, who typically manage it with herbicides. However, this approach raises concerns about environmental and human health, as well as increasing resistance in these plants with continued use. Therefore, exploring alternative methods, such as heterocyclic compounds, triazoles, is essential due to their biological and environmental relevance. This study aimed to evaluate the effects of twelve 1,2,3‐triazoles on the germination and early development of Lactuca sativa, Bidens pilosa, and Lolium multiflorum, as well as their impact on cell division in the cells of L. sativa. Triazole derivatives 4a, 4b, 4c, 4g, 4h, 4i, 4k, and 4l exhibited phytotoxicity, showing varying levels of inhibition in germination, germination speed index, and root growth. Chlorinated compounds were the most detrimental to lettuce development. B. pilosa was notably affected by compounds 4h, 4i, 4k, and 4l, while L. multiflorum responded most to triazoles 4c and 4l, with effectiveness comparable to that of the herbicide glyphosate. All derivatives, except 4l, exhibited aneugenic mechanisms of action, and 4a, 4b, 4c, 4e, 4f, and 4g showed clastogenic effects. This study demonstrated the potential of triazoles as effective agents against weed growth, with mechanisms that warrant further investigation for agricultural applications.
A New Isoflavone Xylopyranoside and Isoflavone Derivatives from the Roots of Ochna integerrima and Their DPPH Radical Scavenging Activity
Authors: Wongpakham Sirilug , Samsee Thanatcha , Wongpakam Komgrit , Promden Worrawat , Thima Kanthinich , Khulmanee Tachin , Patrapuvich Rapatbhorn , Sangdee Aphidech , Kijjoa Anake , Seephonkai Prapairat
Published: October 2024

Ochna integerrima (Louri) Merr. is one of the two species of the genus Ochna (family Ochnaceae) found in Thailand. Its bark is used in traditional Thai medicine to treat digestive disorders. Phytochemical investigation of the crude MeOH extract of the root woods of O. integerrima furnished an unreported isoflavone glycoside, gerontoisoflavone A‐4′‐O‐β‐D‐xylopyranoside (1), together with the previously described irisolone methyl ether (2), iriskumaonin methyl ether (3), iriskumaonin (4), gerontoisoflavone A (5), isoprunetin (6), a flavone glycoside, vitexin (7), and a chromone derivative, lophilone A (8). The structure of 1 was elucidated by 1D and 2D NMR spectral analysis as well as HRMS data. Compounds 1–7 were evaluated for their 2,2‐diphenyl‐1‐picrylhydrazil radical (DPPH⋅) scavenging activity and antiplasmodial activity against a chloroquine‐ and pyrimethamine‐resistant strain of Plasmodium falciparum (K1). Compounds 5 exhibited strongest scavenging activity, with a scavenging concentration at 50 % (SC50) of 137.7 μM, while 4 and 6 displayed weak scavenging activity, with SC50 values of 4 and 5 times higher than that of 5. None of the tested compounds showed antiplasmodial activity against P. falciparum (K1) at a concentration of 5 μg/mL.
Computational Exploration of Limonin as a Potential Inhibitor of DapB in Klebsiella pneumoniae
Authors: Mahur Pragati , Sharma Abhishek , Singh Amit Kumar , Muthukumaran Jayaraman , Jain Monika
Published: October 2024

Klebsiella pneumoniae has emerged as a significant multidrug‐resistant pathogen, classified as a critical priority by the World Health Organization. The rising rates of antibiotic resistance have led to increased therapeutic failures, diminishing the effectiveness of existing antibiotics. Consequently, there is an urgent need for alternative treatments to effectively inhibit the growth of K. pneumoniae and mitigate associated diseases. Phytochemicals have demonstrated potential advantages over traditional antibiotics, prompting their exploration as innovative therapeutic agents. This study aimed to identify phytochemicals that can inhibit dapB, a vital enzyme in the lysine biosynthesis pathway of K. pneumoniae, which is essential for protein synthesis and the cross‐linking of the bacterial peptidoglycan cell wall. We screened 17,934 phytochemicals based on Lipinski's Rule of Five, along with their Absorption, Distribution, Metabolism, Excretion properties and toxicological parameters. Next, we conducted triplicate docking studies against dapB to evaluate the library further. The most promising molecules then underwent 100 ns Molecular Dynamics simulations in triplicate, followed by MM/PBSA based binding free energy calculations to identify potential dapB inhibitors. This in silico analysis highlighted limonin as a promising inhibitor of dapB in K. pneumoniae. Further experimental validation is crucial to enhance limonin's potential as a novel therapeutic agent against K. pneumoniae‐associated diseases.
Covalent Labeling of Matrix Metalloproteases with Affinity‐Based Probes Containing Tuned Reactive N‐Acyl‐N‐Alkyl Sulfonamide Cleavable Linkers
Authors: Devel Laurent , Malgorn Carole , Tohon Regis‐William , Launay Marie , Patiniotis Konstantinos , Sejalon‐Cipolla Mylene , Beau Fabrice , Thai Robert , Bruyat Pierrick , Bonino Annabelle , Bregant Sarah , Subra Gilles , Cantel Sonia , Georgiadis Dimitris
Published: October 2024

Original covalent probes with an N‐acyl‐N‐alkyl sulfonamide cleavable linker were developed to target a broad set of human Matrix Metalloproteases (MMPs). The electrophilicity of this cleavable linker was modulated to improve the selectivity of the probes as well as reduce their unspecific reactivity in complex biological matrices. We first demonstrated that targeting the S3 subsite of MMPs enables access to broad‐spectrum affinity‐based probes that exclusively react with the active version of these proteases. The probes were further assessed in proteomes of varying complexity, where human MMP‐13 was artificially introduced at known concentration and the resulting labeled MMP was imaged by in‐gel fluorescence imaging. We showed that the less reactive probe was still able to covalently modify MMP‐13 while exhibiting reduced off‐target unspecific reactivity. This study clearly demonstrated the importance of finely controlling the reactivity of the NASA warhead to improve the selectivity of covalent probes in complex biological systems.
Protein–Polymer Conjugates: Advancing Enzyme Catalysis in Synthetic Chemistry
Authors: Ouyang Jingping , Li Jian , Wu Changzhu
Published: October 2024

Enzyme catalysis is prominent in chemical synthesis due to its specificity, selectivity, and efficiency. However, enzymes often face challenges, such as inactivation and inhibition in practical applications, and they are also limited by narrow reaction scopes in complex catalytic scenarios like cascade reactions. These persistent issues have driven the development of chemical modifications of enzymes, aiming to enhance enzyme catalysis with external chemical entities. Polymers are particularly notable among these entities for their functional moieties and protective effects on biomolecules, enhancing enzyme properties, and even creating new‐to‐nature catalysis by harnessing catalytic promiscuity. This concept aims to introduce the field of protein–polymer conjugates for diverse emerging applications across emulsion biocatalysis, artificial enzymes, and supramolecular enzyme catalysis.
Organolanthanide‐Mediated Tandem Insertion/Cyclisation of Alkynylbenzonitriles with Secondary Amines Elucidated Through a Computational Approach
Authors: Tobisch Sven
Published: October 2024

A detailed mechanistic probe of the organolanthanide‐mediated tandem insertion/annulation of alkynylbenzonitriles with secondary amines by an archetypical homoleptic lanthanum silylamide starting material is presented. An in‐depth computational scrutiny of alternatively plausible pathways for relevant productive steps and also performance‐degrading pathways identified the pathway likely traversed in productive catalysis. It entails the transformation of the starting material into various of silylamide/amide compounds, of which the lanthanum bis‐silylamide/amide is thermodynamically prevalent, capable of promoting the process. Benzonitrile insertion is irreversible to readily afford the lanthanum amidinate, which can adopt various easily interconvertible ligation pattern. The rather rapid protonolysis of the La─N imine linkage would lead to undesirable aminoamidines, but its net endergonicity renders this performance‐degrading avenue nonviable. Instead, the lanthanum amidinate is converted back into catalytically competent lanthanum bis‐silylamide/amide with the release of the observed aminoisoindole product. This transformation favors a stepwise insertative cyclisation/La─C alkenyl protonolysis sequence over an otherwise kinetically noncompetitive proton‐triggered stepwise N─C/C─H bond forming process. The operative insertative pathway comprises turnover‐limiting and irreversible insertion of the alkyne C≡C tether into the La─N amidinate linkage followed by La─C alkenyl aminolysis at the intervening lanthanum alkenylisoindinyl intermediate. The DFT‐assessed barrier for turnover‐limiting insertative N─C ring closure favorably compares with reported performance data.
Photoredox Radical‐Polar Crossover Reaction of gem‐Difluoroalkenes: A Facile Access to Diverse Difluoroalkyl Sulfides
Authors: Liang Rong‐Bin , Wang Ying‐Jie , Miao Ting‐Ting , Wang Yao‐Jun , Wang Si‐Wei , Wang Qin , Guo Yi‐Fei , Li Sanliang , Zhong Jian‐Ji
Published: October 2024

Difluoroalkyl sulfide (‐CF2S‐) moieties are an important class of skeletons in medicinal chemistry. Herein, a photoredox radical‐polar crossover reaction is reported for the three‐component thiofluorination, thiohydroxylation, thioalkoxylation, thioaminolation, and thiochlorination of gem‐difluoroalkenes towards diverse α‐functionalized difluoroalkyl sulfides. Such an approach features mild conditions, operational simplicity, and good substrate scope.