bluuebunny/crossref_metadata_2025 huggingface dataset:
Multifunctional Wood Composite Aerogel with Integrated Radiant Cooling and Fog–Water Harvesting for All‐Day Building Energy Conservation
Authors: Yu Yang , Wei Liyan , Pang Zhongwei , Wu Jianfei , Dong Youming , Pan Xiaohang , Hu Jundie , Qu Jiafu , Li Jianzhang , Tian Dan , Cai Yahui
Published: October 2024

Passive radiative cooling, as a cooling technique with no energy input, can continuously radiate heat into the supercooled universe. However, the continuous cooling effect tends to cause the problem of nighttime overcooling. Moreover, non‐renewable radiative cooling materials and energy‐intensive processing methods lead to increased carbon emissions and resource consumption. Therefore, there is an urgent need to develop a renewable and environmentally friendly self‐adaption radiative cooling thermal management material. In this paper, a high‐performance self‐adaption thermal management wood composite aerogel material is designed and prepared by in situ growth of multi‐scale silicon dioxide on wood. The constructed passive radiative cooling material has a sub‐ambient cooling effect of up to 13.5 °C and 20.2 °C  during daytime in winter and summer, respectively. Meanwhile, it has a certain thermal insulation performance (2.0 °C above ambient) due to low thermal conductivity (0.063370 ± 0.000329 W m−1 k−1) at night in winter. In addition, the material is also suitable for fog–water harvesting (fog–water harvesting rate of 59.27 ± 0.76 mg min−1) due to its hydrophobicity. This work can significantly promote the practical application of passive radiative cooling materials.
Positional Isomerism Toward Tunable Organic Afterglow and Reversible Photoactivation Behavior for Anti‐Counterfeiting and Encryption
Authors: Wu Zongyao , Xu Zixuan , Wang Deliang , Deng Guoqing , Lin Songwang , Zhao Zheng , Wang Dong , Xiong Yu , Tang Ben Zhong
Published: October 2024

Achieving amorphous polymers with ultralong room‐temperature phosphorescence (RTP), tunable organic afterglow, and reversible photoactivation behavior is highly desirable for practical applications but challenging. Herein, simple positional isomers with three carboxyl groups located in the ortho, meta, and para positions of the triphenylamine skeleton are designed and synthesized. By physically blending with the poly(vinyl alcohol) matrix, these isomers show ultralong RTP properties, among which the meta‐isomer has the longest RTP lifetime (620.1 ms). Theoretical calculations reveal that the more efficient intersystem crossing, the slower radiative decay rate of the lowest triplet excitons, and stronger intermolecular hydrogen‐bonding interactions should be responsible for the superior RTP property of meta‐isomer. Furthermore, the tunable organic afterglow is readily realized via a triplet‐to‐singlet energy transfer process. More impressively, the meta and para isomers exhibit reversible photoactivated ultralong RTP properties after embedding into the rigid poly(methyl methacrylate) matrix. Finally, amorphous and flexible polymer films prepared from these positional isomers show potential applications in advanced anti‐counterfeiting and multilevel encryption through subtly combining ultralong RTP lifetime, tunable organic afterglow, and reversible photoactivation behavior.
Engineered Multifunctional Artificial Dermis for Infected Burn Wound Healing
Authors: Wu Zhuoxia , Li Ming , Liu Qianqian , Sun Jing , Tao Chen , Jia Bo , Sun Xiaoyan , Zhang Hongjie , Liu Kai , Wang Fan
Published: October 2024

Burn wound healing is a dynamic and interconnected process, with the complex status of the extracellular matrix (ECM) potentially leading to bacterial infections, drug resistance, or even fatality. However, it remains a grand challenge to assemble a skin‐like material showing similar biological properties as healthy ECM to accelerate burn healing. In this study, the ECM composition is closely mimicked and adaptive multifunctional artificial dermis is developed by leveraging Ag─S bonds, supramolecular interactions among recombinant proteins, Ag+, and hyaluronic acid (HA). The artificial dermis exhibits long‐lasting broad‐spectrum antibacterial activity, achieved though controlled Ag+ release via Ag─S bonds, supramolecular interactions, and recombinant protein‐guided multi‐level assembly, reaching a steady plateau of 83.7% in the later stage. It is found that inflammation is reduced by downregulating IL‐6 and TGF‐β expression. Furthermore, the epidermal growth factor (EGF) within the recombinant proteins stimulates Col1α, ELN, and CD31 upregulation, facilitating ECM remodeling. These adaptive multifunctional artificial dermis effectively address wound infections, accelerate collagen deposition, promote re‐epithelialization, and enhance angiogenesis in infected wounds, highlighting their potential to revolutionize burn wound treatment and offering a promising avenue to holistic care.
In Situ Constructed Magnetic Core‐Shell Hydrogen‐Bonded Organic Framework‐on‐Metal–Organic Framework Structure: an Efficient Catalyst for Peroxymonosulfate Activation
Authors: Du Yingying , Ding Chenhui , Deng Chao , Banerjee Susanta , Agarwal Seema
Published: October 2024

Zeolite imidazole‐based framework (ZIF‐67), a notable class of metal–organic frameworks (MOFs), shows promise in activating peroxymonosulfate (PMS) for pollutant degradation due to its uniformly distributed cobalt ions. However, its nanoparticle form and the elution of cobalt ions during use cause challenges in recycling and the risk of secondary pollution. In this study, a magnetic core‐shell hydrogen‐bonded organic framework (HOF) on the MOF (HOF‐on‐Fe3O4/ZIF‐67) is successfully prepared. The porous HOF shell not only protects the active sites and mitigates cobalt ion leaching but also reduces mass transfer limitations, ensuring sustained catalytic performance. The magnetic Fe3O4 core enhances electron transfer between cobalt ions, boosts catalytic efficiency, and facilitates easy separation and recycling. This core‐shell structure effectively activates PMS, achieving 100% removal of Rhodamine B, a model wastewater dye, within 10 min (Rh B = 50 mg L−1, HFZ = 150 mg L−1, PMS = 1.5 mm, pH = 7, room temperature). Furthermore, under the protection of the HOF shell, cobalt ion leaching is minimized to a negligible value (0.14 mg L−1) after 5 cycles of use. The research provides fresh perspectives into the development of core‐shell composite materials with improved performance and recyclability in wastewater treatment.
Highly Reversible Zn Anode Design Through Oriented ZnO(002) Facets
Authors: Yang Chengwu , Woottapanit Pattaraporn , Geng Sining , Lolupiman Kittima , Zhang Xinyu , Zeng Zhiyuan , He Guanjie , Qin Jiaqian
Published: October 2024

The practical implementation of aqueous Zn‐ion batteries presents formidable hurdles, including uncontrolled dendrite growth, water‐induced side reactions, suboptimal Zn metal utilization, and intricate Zn anode manufacturing. Here, large‐scale construction of a highly oriented ZnO(002) lattice plane on Zn anode (ZnO(002)@Zn) with thermodynamic inertia and kinetic zincophilicity is designed to address such problems. Both theoretical calculations and experiment results elucidate that the ZnO(002)@Zn possesses high Zn chemical affinity, hydrogen evolution reaction suppression, and dendrite‐free deposition ability due to the abundant lattice oxygen species in ZnO(002) and its low lattice mismatch with Zn(002). These features synergistically promote ion transport and enable homogeneous Zn deposition. Consequently, the ZnO(002)@Zn anode displays a stable and prolonged cycling lifespan exceeding 500 h even under a larger depth of discharge (85.6%) and realizes an impressive average Coulombic efficiency of 99.7%. Moreover, its efficacy is also evident in V2O5‐cathode coin cells and pouch cells with not only high discharge capacity but also exceptional cycling stability. This integrated approach presents a promising avenue for addressing the challenges associated with Zn metal anodes, thereby advancing the prospects of aqueous Zn‐ion battery technologies.
Van der Waals Heterojunction Based Self‐Powered Biomimetic Dual‐Mode Sensor for Precise Object Identification
Authors: He Xu , Zhu Xinxu , Hong Zhaoan , Wang Bicheng , Hong Wenting , Yao Yu , Sun Fapeng , Cai Qian , Xu Gang , Liu Wei
Published: October 2024

The design and fabrication of materials that can concurrently respond to light and gas within the dual‐modal recognition domain present a significant challenge due to contradictory structural requirements. This innovative strategy introduces a type‐I heterojunction, combining the properties of Sb2Te3 and WSe2 nanosheets, to overcome these obstacles. The heterojunction is prepared through a precise stacking approach to create a single‐side barrier on the valence band and a near‐zero offset on the conduction band. The resulting Sb2Te3/WSe2 heterojunction demonstrates unparalleled performance, showcasing the best integrated photoelectric and gas sensing performance in a single device to date. Based on the above features, the heterojunction successfully integrates visual and olfactory sensing performance, achieving the first biomimetic visual‐olfactory dual‐mode recognition in a single device. This simulation increased the accuracy of distinguishing electric and fuel‐powered cars from ≈50% to ≈96%. This work introduces a novel approach to creating efficient, self‐powered sensing materials, paving the way for next‐generation biomimetic dual‐model devices with broad applications in environmental protection, medical care, and other fields.
Functional Carbon Springs Enabled Dynamic Tunable Microwave Absorption and Thermal Insulation
Authors: Wang Ze‐Yu , Li Zhao‐Chen , Li Bo , Shi An‐Feng , Zhang Long , Zhu Yin‐Bo , Ye Fang , Yu Shu‐Hong
Published: October 2024

Electromagnetic (EM) wave pollution and thermal damage pose serious hazards to delicate instruments. Functional aerogels offer a promising solution by mitigating EM interference and isolating heat. However, most of these materials struggle to balance thermal protection with microwave absorption (MA) efficiency due to a previously unidentified conflict between the optimizing strategies of the two properties. Herein, this study reports a solution involving the design of a carbon‐based aerogel called functional carbon spring (FCS). Its unique long‐range lamellar multi‐arch microstructure enables tunable MA performance and excellent thermal insulation capability. Adjusting compression strain from 0% to 50%, the adjustable effective absorption bandwidth (EAB) spans up to 13.4 GHz, covering 84% of the measured frequency spectrum. Notably, at 75% strain, the EAB drops to 0 GHz, demonstrating a novel “on‐off” switchability for MA performance. Its ultralow vertical thermal conductivity (12.7 mW m−1 K−1) and unique anisotropic heat transfer mechanism endow FCS with superior thermal protection effectiveness. Numerical simulations demonstrate that FCS outperforms common honeycomb structures and isotropic porous aerogels in thermal management. Furthermore, an “electromagnetic‐thermal” dual‐protection material database is established, which intuitively demonstrates the superiority of the solution. This work contributes to the advancement of multifunctional MA materials with significant potential for practical applications.
Azatriangulene‐Based Conductive C═C Linked Covalent Organic Frameworks with Near‐Infrared Emission
Authors: Hamzehpoor Ehsan , Ghamari Pegah , Tao Yuze , Rafique Muhammad Ghufran , Zhang Zhenzhe , Salehi Mahdi , Stein Robin S. , Ramos‐Sanchez Jorge , Laramée Arnaud W. , Cosa Gonzalo , Pellerin Christian , Seifitokaldani Ali , Khaliullin Rustam Z. , Perepichka Dmytro F.
Published: October 2024

Two near‐infrared (NIR) emissive π‐conjugated covalent organic frameworks (COFs) pTANG1 and pTANG2 are synthesized using Knoevenagel condensation of trioxaazatriangulenetricarbaldehyde (TATANG) with benzene‐ and biphenyldiacetonitriles, respectively. The morphology of the COFs is affected by the size of TATANG precursor crystals. Donor–acceptor interactions in these COFs result in small bandgaps (≈1.6 eV) and NIR emission (λmax = 789 nm for pTANG1). pTANG1 can absorb up to 9 molecules of water per unit cell, which is accompanied by a marked quenching of the NIR emission, suggesting applications as humidity sensors. p‐Doping with magic blue significantly increases the electrical conductivities of the COFs by up to 8 orders of magnitude, with the room temperature conductivity of pTANG1 reaching 0.65 S cm−1, the highest among reported C═C linked COFs. 1H NMR relaxometry, temperature‐dependent fluorescence spectroscopy, and DFT calculations reveal that the higher rigidity of the shorter phenylene linker is responsible for the more extended conjugation (red‐shifted emission, higher electrical conductivity) of pTANG1 compared to pTANG2.
Advancing Anticancer Drug Discovery: Leveraging Metabolomics and Machine Learning for Mode of Action Prediction by Pattern Recognition
Authors: Saoud Mohamad , Grau Jan , Rennert Robert , Mueller Thomas , Yousefi Mohammad , Davari Mehdi D. , Hause Bettina , Csuk René , Rashan Luay , Grosse Ivo , Tissier Alain , Wessjohann Ludger A. , Balcke Gerd U.
Published: October 2024

A bottleneck in the development of new anti‐cancer drugs is the recognition of their mode of action (MoA). Metabolomics combined with machine learning allowed to predict MoAs of novel anti‐proliferative drug candidates, focusing on human prostate cancer cells (PC‐3). As proof of concept, 38 drugs are studied with known effects on 16 key processes of cancer metabolism, profiling low molecular weight intermediates of the central carbon and cellular energy metabolism (CCEM) by LC‐MS/MS. These metabolic patterns unveiled distinct MoAs, enabling accurate MoA predictions for novel agents by machine learning. The transferability of MoA predictions based on PC‐3 cell treatments is validated with two other cancer cell models, i.e., breast cancer and Ewing's sarcoma, and show that correct MoA predictions for alternative cancer cells are possible, but still at some expense of prediction quality. Furthermore, metabolic profiles of treated cells yield insights into intracellular processes, exemplified for drugs inducing different types of mitochondrial dysfunction. Specifically, it is predicted that pentacyclic triterpenes inhibit oxidative phosphorylation and affect phospholipid biosynthesis, as confirmed by respiration parameters, lipidomics, and molecular docking. Using biochemical insights from individual drug treatments, this approach offers new opportunities, including the optimization of combinatorial drug applications.
Hydroxypropyl Cellulose‐Based Meter‐Long Structurally Colored Fibers for Advanced Fabrics
Authors: Qin Qinan , Xu Yan
Published: October 2024

Structurally colored fibers are attractive alternatives to chemically colored fibers due to their rich optical properties, color stability, and environmental friendliness. However, the fabrication of structurally colored fibers using cost‐effective raw materials with the possibility to scale up remains challenging. Here, a simple and scalable approach is developed to fabricate continuous meter‐long structurally colored fibers exhibiting brilliant structural colors across the visible spectrum and helix orientation‐dependent polarization states. The fibers are fabricated by extrusion of concentrated aqueous solutions of chemically crosslinked hydroxypropyl cellulose (HPC). The wavelengths and polarization states can be tuned by solution concentration, relaxation time, and collector's surface energy. The HPC‐based structurally colored fibers display excellent optical stability to mechanical straining, repeated drying/water impregnation, and prolonged heating at 150 °C. It is demonstrated that the HPC‐based structurally colored fibers can be woven into structurally colored fabrics with wavelength‐ and polarization‐coded optical patterns. The current work presents a strategy to tune the chiral nematic order, which constitutes an important step toward mass production of structurally colored fibers with stable and rich optical properties using easily available raw materials.
The MICOS Complex Subunit Mic60 is Hijacked by Intracellular Bacteria to Manipulate Mitochondrial Dynamics and Promote Bacterial Pathogenicity
Authors: Cheng Changyong , Chen Mianmian , Sun Jing , Xu Jiali , Deng Simin , Xia Jing , Han Yue , Zhang Xian , Wang Jing , Lei Lei , Zhai Ruidong , Wu Qin , Fang Weihuan , Song Houhui
Published: October 2024

Host mitochondria undergo fission and fusion, which bacteria often exploit for their infections. In this study, the underlying molecular mechanisms are aimed to clarify through which Listeria monocytogenes (L. monocytogenes), a human bacterial pathogen, manipulates mitochondrial dynamics to enhance its pathogenicity. It is demonstrated that L. monocytogenes triggers transient mitochondrial fission through its virulence factor listeriolysin O (LLO), driven by LLO's interaction with Mic60, a core component of the mitochondrial contact site and the cristae organizing system (MICOS). Specifically, Phe251 within LLO is identify as a crucial residue for binding to Mic60, crucial for LLO‐induced mitochondrial fragmentation and bacterial pathogenicity. Importantly, it is that Mic60 affect the formation of F‐actin tails recruited by L. monocytogenes, thereby contributing to intracellular bacterial infection. Mic60 plays a critical role in mediating changes in mitochondrial morphology, membrane potential, and reactive oxidative species (ROS) production, and L. monocytogenes infection exacerbates these changes by affecting Mic60 expression. These findings unveil a novel mechanism through which intracellular bacteria exploit host mitochondria, shedding light on the complex interplay between hosts and microbes during infections. This knowledge holds promise for developing innovative strategies to combat bacterial infections.
Enhanced Performance of Close‐Spaced Sublimation Processed Antimony Sulfide Solar Cells via Seed‐Mediated Growth
Authors: Wu Wentao , Tang Bo , Wan Lei , Mao Xiaoli , Wang Haolin , Tong Guoqing , Chen Tao , Zhou Ru
Published: October 2024

Antimony sulfide (Sb2S3) has attracted much attention due to its great prospect to construct highly efficient, cost‐effective, and environment‐friendly solar cells. The scalable close‐spaced sublimation (CSS) is a well‐developed physical deposition method to fabricate thin films for photovoltaics. However, the CSS‐processed absorber films typically involve small grain size with high‐density grain boundaries (GBs), resulting in severe defects‐induced charge‐carrier nonradiative recombination and further large open‐circuit voltage (VOC) losses. In this work, it is demonstrated that a chemical bath deposited‐Sb2S3 seed layer can serve as crystal nuclei and mediate the growth of large‐grained, highly compact CSS‐processed Sb2S3 films. This seed‐mediated Sb2S3 film affords reduced defect density and enhanced charge‐carrier transport, which yields an improved power conversion efficiency (PCE) of 4.78% for planar Sb2S3 solar cells. Moreover, the VOC of 0.755 V that is obtained is the highest reported thus far for vacuum‐based evaporation and sublimation processed Sb2S3 devices. This work demonstrates an effective strategy to deposit high‐quality low‐defect‐density Sb2S3 films via vacuum‐based physical methods for optoelectronic applications.
Enhancing CO2 Electroreduction Precision to Ethylene and Ethanol: The Role of Additional Boron Catalytic Sites in Cu‐Based Tandem Catalysts
Authors: Yu Fuqing , Shu Minxing , Zhang Guangyao , Yu Qiming , Wang Hongming
Published: October 2024

The electrocatalytic conversion of carbon dioxide (CO2) into valuable multicarbon (C2+) compounds offers a promising approach to mitigate CO2 emissions and harness renewable energy. However, achieving precise selectivity for specific C2+ products, such as ethylene and ethanol, remains a formidable challenge. This study shows that incorporating elemental boron (B) into copper (Cu) catalysts provides additional adsorption sites for *CO intermediates, enhancing the selectivity of desirable C2+ products. Additionally, using a nickel single‐atom catalyst (Ni‐SAC) as a *CO source increases local *CO concentration and reduces the hydrogen evolution reaction. In situ experiments and density functional theory (DFT) calculations reveal that surface‐bound boron units adsorb and convert *CO more efficiently, promoting ethylene production, while boron within the bulk phase of copper influences charge transfer, facilitating ethanol generation. In a neutral electrolyte, the bias current density for ethylene production using the B‐O‐Cu2@Ni‐SAC0.05 hybrid catalyst exceeded 300 mA cm−2, and that for ethanol production with B‐O‐Cu5@Ni‐SAC0.2 surpassed 250 mA cm−2. This study underscores that elemental doping in Cu‐based catalysts not only alters charge and crystalline phase arrangements at Cu sites but also provides additional reduction sites for coupling reactions, enabling the efficient synthesis of distinct C2+ products.
Dual Cocatalytic Sites Synergize NiFe Layered Double Hydroxide to Boost Oxygen Evolution Reaction in Anion Exchange Membrane Water Electrolyzer
Authors: Shi Yue , Song Lumin , Liu Yan , Wang Tiantian , Li Caixia , Lai Jianping , Wang Lei
Published: October 2024

Nickel‐iron layered double hydroxide (LDH) is a promising cost‐efficient catalyst to replace noble metals for alkaline oxygen evolution reaction (OER), yet its intrinsic activity under high current density conditions is not satisfactory, which greatly constrains the industrial application of NiFe LDH catalysts. Herein, a new class of integrated Co and W co‐doped NiFe LDH catalysts is reported with dual cocatalytic sites for alkaline OER catalysis. The optimized Co2.8, W3.8‐NiFe LDH integrated catalyst has superior alkaline OER activity (255 mV@1000 mA cm−2) and excellent catalytic stability (200 h@500 mA cm−2). The turnover frequency value of Co2.8, W3.8‐NiFe LDH can reach 4.02 s−1 at 1.49 V versus RHE, which is 9.6 times higher than that of NiFe LDH and superior to the noble metal catalysts. Moreover, it can achieve 1.0 A cm−2 at 1.86 V and maintain 300‐h stable operation in anion exchange membrane water electrolyzer. Theoretical and experimental studies indicate that W sites promote the *OH adsorption and Co sites favor protons desorption of OH*. These dual cocatalytic sites jointly promote *O coverage, effectively accelerating alkaline OER kinetic.
Homogeneous Complexation Strategy to Manage Bromine for High‐Capacity Zinc–Bromine Flow Battery
Authors: Xiong Qinghua , Huang Mingbao , Ren Tianlu , Wu Shixi , Wang Wenfeng , Xiang Zhipeng , Wan Kai , Fu Zhiyong , Liang Zhenxing
Published: October 2024

Zinc–bromine flow batteries (ZBFBs) have received widespread attention as a transformative energy storage technology with a high theoretical energy density (430 Wh kg−1). However, its efficiency and stability have been long threatened as the positive active species of polybromide anions (Br2n+1−) are subject to severe crossover across the membrane at a high concentration. Herein, a novel highly hydrophilic complexing agent, N‐methyl‐N, N‐bis(2‐hydroxyethyl)‐1‐propanaminium bromide (PMDA), is developed to effectively manage bromine in a homogeneous posolyte, which realizes a low bromine crossover at a high operating concentration in ZBFBs. Both theoretical and experimental results suggest that the PMDA interacts with Br2n+1− and forms a larger‐size complex PMDABr2n+1. When adding 0.40 m PMDA, the bromine stays homogeneous at a high concentration up to 1.20 m, and its permeability is remarkably decreased by 74%. For demonstration, the ZBFB achieves a operating capacity record of 57.2 Ah L−1 in a homogeneous bromine posolyte with a high Coulombic efficiency of ≈90.0% and superior cycling stability (capacity retention rate of 100.0% per cycle). This work provides one innovative bromine management strategy to realize a high capacity and superior stability in ZBFBs.
Comprehensive Understanding of Steric‐Hindrance Effect on the Trade‐Off Between Zinc Ions Transfer and Reduction Kinetics to Enable Highly Reversible and Stable Zn Anodes
Authors: Hu Nan , Tao Jin , Tan Yi , Song Huawei , Huang Dan , Liu Penggao , Chen Zhengjun , Yin Xucai , Zhu Jinliang , Xu Jing , He Huibing
Published: October 2024

The electrode interface concentration polarization attributed to the contradiction between sluggish mass transfer process and rapid electrochemical reduction kinetics significantly restricts the practical application of Zn anode. Creating a moderate Zn ions transfer and reduction chemistry is essential for durable zinc‐ion batteries. In this work, this trade‐off effect is realized by selecting large‐size 4‐Aminomethyl cyclohexanecarboxylic acid (AMCA) molecule as the electrolyte additive. Intriguingly, AMCA molecules reorganize the Zn2+ solvation structure via the robust coordination with Zn2+ and reconstruct H‐bond networks, giving a pulled desolvation process. Meanwhile, AMCA enlarges the Zn2+ solvation size with a push force, confining the rapid electrochemical reduction kinetics. The balanced chemical environment is maintained via the moderate pull‐push interplay. Besides, AMCA can anchor on zinc surface to create a water‐poor microenvironment, fostering homogeneous Zn (002) deposition and effectively restricting water‐induced side‐reactions. Notably, the Zn||Zn symmetric cell with AMCA operates stably over 167 days at 20 mA cm−2. Moreover, the Zn||VOX full cell employed AMCA ensures outstanding capacity retention of 99.15% after 590 cycles at 2 A g−1, even with low N/P (4.3), lean electrolyte (50 µL mAh−1) and ultrathin Zn foil of 10 µm. This work reveals unique insights into the balanced interfacial chemistry design toward high‐performance zinc batteries.
A combination of covalent and noncovalent restricted‐intramolecular‐rotation strategy for supramolecular AIE‐type photosensitizer toward photodynamic therapy
Authors: Li Qingfang , Zhang Peijuan , Wang Pingxia , Yan Chaochao , Wang Kaige , Yang Wanni , Dang Dongfeng , Cao Liping
Published: October 2024

Photodynamic therapy (PDT) is a promising noninvasive method for targeted cancer cell destruction. Still, its effectiveness is often hindered by the aggregation‐caused quenching effect of organic photosensitizer (PS) in aqueous environments. Here, we have employed a combination of covalent and noncovalent restricted‐intramolecular‐rotation strategies to develop supramolecular PSs with aggregation‐induced emission (AIE) characteristics. Firstly, a water‐soluble octacationic molecular cage (1) with a bilayer tetraphenylethene (TPE) structure has been designed and synthesized, which minimizes intramolecular rotation of TPE moieties and achieves the single‐molecule‐level aggregation by the covalent restriction of intramolecular rotation (RIR) via molecular engineering synthesis. Compared with its single‐layer TPE analog, 1 exhibits superior efficiency in generating reactive oxygen species (ROS) including superoxide radical (O2−•) and singlet oxygen (1O2) upon white‐light irradiation. Subsequently, by forming a 1:4 host–guest complex (1@CB[8]4) between 1 and cucurbit[8]uril (CB[8]), O2−• generation can be further enhanced by the noncovalent RIR via the host–guest assembly. Additionally, 1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide (NADH) in water. Given its Type‐I ROS generation and catalytic activity for NADH oxidation, 1@CB[8]4 acts as a supramolecular AIE‐type PS to exhibit strong photo‐induced cytotoxicity upon white‐light irradiation under hypoxic conditions, showcasing its potential for synergistic PDT.
Heritability in the Rhesus Macaque (Macaca mulatta) Vertebral Column
Authors: Villamil Catalina I. , Negrón Jeziel J. , Middleton Emily R.
Published: October 2024

The vertebral column plays a central role in primate locomotion and positional behavior. Understanding its evolution, therefore, has the potential to clarify evolutionary processes that have occurred in the primate lineage as well as the specific behaviors of extinct primates. However, to understand primate vertebral anatomy, it is important to determine how much of this anatomy is heritable and how much develops as a response to environmental factors during life. We estimated heritability for vertebral counts as well as typical cervical, thoracic, and lumbar elements from 210 individuals from the pedigreed Cayo Santiago Macaca mulatta skeletal collection. We found moderate heritability of vertebral counts (h2 = 0.216–0.326), but with strong heritability of the type of variation (e.g., a tendency to meristic or homeotic change) in the vertebral count (h2 = 0.599), suggesting a possible explanation for high variability in vertebral numbers among the hominoids in particular. The moderate heritability of vertebral count also suggests that vertebral count is an unsuitable metric for estimating the ancestral state for some taxa. We found strong heritability in the morphology of cervical and upper lumbar zygapophyseal facets (h2 = 0.548–0.550) and the thoracic spinous processes (h2 = 0.609–0.761), including high heritability of the spinous process angle in the upper thoracic and upper lumbar elements (h2 = 0.649–0.752). We suggest these are related to maintaining stability in the cervical and lumbar regions, and reducing motion in the thoracic region, respectively. We propose that spinous processes may contain greater phylogenetic information, whereas transverse processes may contain greater information of function ‘in life’. We also found important size effects, suggesting that size is the most heritable component of overall form and largely responsible for intertrait differences. This suggests that it is inappropriate to indiscriminately remove size effects from morphological comparisons.
Dementia risk scores, apolipoprotein E, and risk of Alzheimer's disease: One size does not fit all
Authors: Andrews Shea J. , Boeriu Ana I. , Belloy Michael E. , Renton Alan E. , Fulton‐Howard Brian , Brenowitz Willa D. , Yaffe Kristine ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: October 2024

INTRODUCTION

Evaluating the generalizability of dementia risk scores, primarily developed in non‐Latinx White (NLW) participants, and interactions with genetic risk factors in diverse populations is crucial for addressing health disparities.

METHODS

We analyzed the association of the Cardiovascular Risk Factors, Aging, and Incidence of Dementia (CAIDE) and modified CAIDE (mCAIDE) scores with dementia risk using logistic regression models stratified by race/ethnicity in National Alzheimer's Coordinating Center (NACC) and Alzheimer's Disease Neuroimaging Initiative (ADNI), and assessed their interaction with apolipoprotein E (APOE).

RESULTS

Higher CAIDE scores were associated with an increased risk of dementia in Asian, Latinx, and NLW participants but not in Black participants. In contrast, higher mCAIDE scores were also associated with an increased risk of dementia in Black participants. Unfavorable mCAIDE risk profiles exacerbated the apolipoprotein E*ε4 (APOE*ε4) risk effect and attenuated the APOE*ε2 protective effect.

DISCUSSION

Our findings underscore the importance of evaluating the validity of dementia risk scores in diverse populations for their use in personalized medicine approaches to promote brain health.

Highlights

Dementia risk scores demonstrate race/ethnic‐specific effects on dementia risk.

Unfavorable modifiable risk profiles moderate the effect of APOE on dementia risk.

Dementia risk scores need to be validated in diverse populations.
Arterial spin labeling perfusion MRI in the Alzheimer's Disease Neuroimaging Initiative: Past, present, and future
Authors: Thropp Pamela , Phillips Eliana , Jung Youngkyoo , Thomas David L. , Tosun Duygu ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: October 2024

On the 20th anniversary of the Alzheimer's Disease Neuroimaging Initiative (ADNI), this paper provides a comprehensive overview of the role of arterial spin labeling (ASL) magnetic resonance imaging (MRI) in understanding perfusion changes in the aging brain and the relationship with Alzheimer's disease (AD) pathophysiology and its comorbid conditions. We summarize previously used acquisition protocols, available data, and the motivation for adopting a multi‐post‐labeling delay (PLD) acquisition scheme in the latest ADNI MRI protocol (ADNI 4). We also detail the process of setting up this scheme on different scanners, emphasizing the potential of ASL imaging in future AD research.

Highlights

The Alzheimer's Disease Neuroimaging Initiative (ADNI) adopted multimodal arterial spin labeling magnetic resonance imaging (ASL MRI) to meet evolving biomarker requirements.

The ADNI provides one of the largest multisite, multi‐vendor ASL data collections.

The ADNI 4 incorporates multi‐post‐labeling delay ASL techniques to jointly quantify cerebral blood flow and arterial transit time.

ADNI 4 ASL MRI protocol is apt for detecting early Alzheimer's disease with cerebrovascular pathology.
Obesity and Multiple Sclerosis Severity: A Mendelian Randomization Study
Authors: Alzamanan Fatema , Ding Yuan , Harroud Adil
Published: October 2024

Obesity is implicated in the development of multiple sclerosis (MS), but its effect on disability is less well‐established. This study examined the effects of various obesity measures on MS severity in 12,584 MS cases, using Mendelian randomization to mitigate confounding. Results showed a significant association between higher genetically‐determined body mass index (N = 806,834) and increased MS severity (P = 0.02). This finding was supported by additional measures of general obesity but not adiposity distribution. The convergence of this genetic evidence with prior observational studies strengthens the association between obesity and adverse long‐term disability in MS, suggesting weight management as a potential therapeutic strategy. ANN NEUROL 2025;97:90–94
A Proteomics Pipeline for Generating Clinical Grade Biomarker Candidates from Data‐Independent Acquisition Mass Spectrometry (DIA‐MS) Discovery
Authors: Fu Qin , Vegesna Manasa , Sundararaman Niveda , Damoc Eugen , Arrey Tabiwang N. , Pashkova Anna , Mengesha Emebet , Debbas Philip , Joung Sandy , Li Dalin , Cheng Susan , Braun Jonathan , McGovern Dermot P. B. , Murray Christopher I. , Xuan Yue , Van Eyk Jennifer E.
Published: October 2024

Clinical biomarker development has been stymied by inaccurate protein quantification from mass spectrometry (MS) discovery data and a prolonged validation process. To mitigate these issues, we created the Targeted Extraction Assessment of Quantification (TEAQ) software package that uses data‐independent acquisition analysis from a discovery cohort to select precursors, peptides, and proteins that adhere to analytical criteria required for established targeted assays. TEAQ was applied to DIA‐MS data from plasma samples acquired on a new high resolution accurate mass (HRAM) mass spectrometry platform where precursors were evaluated for linearity, specificity, repeatability, reproducibility, and intra‐protein correlation based on 8‐ or 11‐point loading curves at three throughputs. This data can be used as a general resource for developing other targeted assays. TEAQ analysis of data from a case and control cohort for inflammatory bowel disease (n=492) identified 1110 signature peptides for 326 quantifiable proteins from the 1179 identified proteins. Applying TEAQ analysis to discovery data will streamline targeted assay development and the transition to validation and clinical studies.
Synthesis and Structure Determination by 3D Electron Diffraction of the Extra‐large Pore Zeolite ITQ‐70
Authors: Tirado Juan I. , Sala Andrés , Bordes Antonio , Pratim Das Partha , Palatinus Lukáš , Nicolopoulos Stavros , Jordá Jose L. , Vidal‐Moya Alejandro , Blasco Teresa , Sastre German , Valencia Susana , Rey Fernando
Published: October 2024

In this study, we present the synthesis, characterization, and structural analysis of a novel zeolite, ITQ‐70, using 3D electron diffraction. This unique material was synthesized under alkaline conditions, employing tetrakis(diethylamino)phosphonium as an organic structure‐directing agent, leading to the formation of a pure silica zeolite. ITQ‐70 is distinguished by its extra‐large pore apertures, which extend along all three axes and intersect one to the other. A notable feature of this zeolite is the presence of structurally ordered defects in very high concentrations (38 % of the silicon atoms). As a result, ITQ‐70 exhibits the lowest framework density (10.0 T/1000 Å3) ever reported for any zeolite except RWY (7.6 T/1000 Å3), which contains sulfur instead of oxygen connecting T‐atoms.
De(sulfon)amidative Cyclization: The Synthesis of Dibenzolactams and Dibenzosultams for Organic Light Emitting Diode Materials
Authors: Luo Anping , Li Zhijie , Chen Haohua , Wang Ya , Liu Xiaoyu , Bin Zhengyang , Yang Yudong , You Jingsong
Published: October 2024

This study addresses a challenge in organic synthetic chemistry: the direct cleavage of amide bonds, which is typically hampered by the thermodynamic stability of the C(Ar)−C(acyl) bond. Previous methods often rely on “CO” extrusion‐jointing transition metal‐catalyzed process and require activated tertiary amides, limiting their applicability due to incompatibility with reactive functional groups such as halogens. Herein, we report a transition metal‐free approach for the deamidative cyclization of biaryl diamides via a radical process, yielding dibenzolactam derivatives. Along this line, we have developed the desulfonamidative cyclization of biaryl disulfonamides to produce dibenzosultams through direct nucleophilic aromatic substitution, demonstrating high selectivity for unsymmetrical structures. Additionally, unsymmetrical sulfamoyl biaryl amides, containing both amide and sulfonamide functionalities, can selectively undergo desulfonamidative coupling with the amide to form dibenzolactams, which offers a complementary synthetic pathway to unsymmetric dibenzolactams. These protocols exhibit excellent compatibility with reactive functional groups, including halogens, providing an innovative synthetic toolbox for the development of thermally activated delayed fluorescence (TADF) materials used in organic light emitting diodes (OLEDs). DMAC‐PDO, incorporating a dibenzolactam as the acceptor unit, serves as an efficient blue TADF emitter with a maximum external quantum efficiency (EQEmax) of 23.4 %.
Formamidinium Incorporates into Rb‐based Non‐Perovskite Phases in Solar Cell Formulations
Authors: Gunes Ummugulsum , Hope Michael A. , Zhang Yuxuan , Zheng Likai , Pfeifer Lukas , Grätzel Michael , Emsley Lyndon
Published: October 2024

Organic‐inorganic hybrid perovskite materials, such as formamidinium lead iodide (FAPbI3), are among the most promising emerging photovoltaic materials. However, the spontaneous phase transition from the photoactive perovskite phase to an inactive non‐perovskite phase complicates the application of FAPbI3 in solar cells. To remedy this, alkali metal cations, most often Cs+, Rb+ or K+, are included during perovskite synthesis to stabilize the photoactive phase. The atomic‐level mechanisms of stabilization are complex. While Cs+ dopes directly into the perovskite lattice, Rb+ does not, but instead forms an additional non‐perovskite phase, and the mechanism by which Rb confers increased stability remains unclear. Here, we use 1H−87Rb double resonance NMR experiments to show that FA+ incorporates into the Rb‐based non‐perovskite phases (FAyRb1‐yPb2Br5 and δ‐FAyRb1‐yPbI3) for both bromide and iodide perovskite formulations. This is demonstrated by changes in the 1H and 87Rb chemical shifts, 1H−87Rb heteronuclear correlation spectra, and 87Rb{1H} REDOR spectra. Simulation of the REDOR dephasing curves suggests up to ~60 % FA+ incorporation into the inorganic Rb‐based phase for the bromide system. In light of these results, we hypothesize that the substitution of FA+ into the non‐perovskite phase may contribute to the greater stability conferred by Rb salts in the synthesis of FA‐based perovskites.
Integrated Monomer Synthesis and Framework Assembly: Achieving Isoreticular Modulation of Hydrogen‐Bonded Organic Frameworks
Authors: Shang Yanxue , Ma Lishuang , Kang Zixi , Wu Yanfang , Fan Weidong , Wang Rongming , Yan Zifeng , Sun Daofeng , Zeng Jingbin
Published: October 2024

Systematic construction of isoreticular hydrogen‐bonded organic frameworks (HOFs) promises tailored material properties crucial for diverse applications, yet is challenging due to the weak, flexible, and non‐directional nature of hydrogen bonds. Herein, we develop an “integrated monomer synthesis‐framework assembly” (ISA) methodology for constructing a series of isoreticular HOFs. Unlike traditional methods where monomers are first synthesized and then assembled into HOFs, the ISA system employs dicyandiamide rigid hydrogen‐bonded hexameric clusters as connecting nodes to covalently react with planarized C3‐symmetric cyano‐precursors (C3‐CPs) to generate diaminotriazine (DAT) monomers, while simultaneously inducing the directional assembly into isoreticular (6,3)‐net hcb topological DAT‐C6‐HOFs. The pore sizes and microenvironments of the resulting DAT‐C6‐HOFs can be precisely tuned by varying the structural modulation (length and steric hindrance) of the π‐bridge on C3‐CPs, enabling highly selective sensing towards perfluorooctanoic acid over other homologous molecules, that are difficult to be separated and detected by chromatography. Overall, the ISA methodology facilitates the scalable creation of families of isostructural HOFs and provides a customized structural platform for investigating factors beyond topology that impact the capturing, releasing, and responding to guest molecules.
Triflic Acid‐Catalyzed Dehydrative Amination of 2‐Arylethanols with Weak N‐Nucleophiles in Hexafluoroisopropanol
Authors: Van Hoof Max , Mayer Robert J. , Moran Joseph , Lebœuf David
Published: October 2024

The catalytic deoxyamination of readily available 2‐arylethanols offers an appealing, simple, and straightforward means of accessing β‐(hetero)arylethylamines of biological interest. Yet, it currently represents a great challenge to synthetic chemistry. In most cases, the alcohol has to be either pre‐activated in situ or converted into a reactive carbonyl intermediate, limiting the substrate scope for some methods. Examples of direct dehydrative amination of 2‐arylethanols are thus still scarce. Here, we describe a catalytic protocol based on the synergy of triflic acid and hexafluoroisopropanol, which enables the direct and stereospecific amination of a broad array of 2‐arylethanols, and does not require any pre‐activation of the alcohol. This approach yields high value‐added products incorporating sulfonamide, amide, urea, and aniline functionalities. In addition, this approach was applied to the sulfidation of 2‐arylethanols. Mechanistic experiments and DFT computations indicate the formation of phenonium ions as key intermediates in the reaction.
Fuel‐Driven π‐Conjugated Superstructures to Form Transient Conductive Hydrogels
Authors: Tsironi Ifigeneia , Maleszka Jarek A. , Kriebisch Brigitte A. K. , Wilson‐Kovacs Robert S. , Acevedo Orlando , O'Leary Shamus L. , Watt John , Boekhoven Job , Olivier Jean‐Hubert
Published: October 2024

Despite advances in creating dissipative materials with transient properties, such as hydrogels and active droplets, their application remains confined to temporal changes in structural properties. Developing out‐of‐equilibrium materials whose electronic functions are parameterized by a chemical reaction cycle is challenging. Yet, this class of materials is required to construct biomimetic materials. In contrast to traditional chemical reaction cycles that exploit molecularly dissolved building blocks at thermodynamic equilibrium, we show that fiber structures derived from reactive naphthalene diimide (NDI) building blocks can be used as resting states to form far‐from‐equilibrium conductive hydrogels after the addition of chemical fuels. Upon fueling the NDI‐derived fibers, a dual‐component activation and deactivation pathway is deduced by kinetic analysis and is absent when using a molecularly dissolved resting state. Investigating the solid‐state morphologies of the structures formed throughout the fuel‐driven reaction cycle using cryo‐EM reveals that the resting thermodynamic fibers evolve to transient thicker fibrils and layered superstructures. We show that the transient redox‐active hydrogels exhibit a nearly threefold increase in electrical conductivity upon fuel consumption before reverting to their original value over hours. These far‐from‐equilibrium materials are potential candidates in applications such as programmable biorobotics and chemical computing.
Das tödliche Pilzgift Muscarin wird bei Zellverletzung aus einem harmlosen phosphorylierten Vorläufer freigesetzt
Authors: Dörner Sebastian , Trottmann Felix , Jordan Paul M. , Rogge Kai , Bartels Benjamin , Werz Oliver , Hertweck Christian , Hoffmeister Dirk
Published: October 2024

l‐(+)‐Muscarin (1)‐produzierende Pilze stellen eine ernste Gefahr für die menschliche Gesundheit dar, da deren Aufnahme zu Kreislaufversagen oder sogar zum Tod führen kann. Jedoch ist deren Inhaltsstoff‐Profil erstaunlich wenig verstanden, ebenso fehlt Wissen zur Freisetzung dieses Giftes und zu potentiell giftigen verwandten Stoffen. Wir identifizierten im Mycel des 1‐produzierenden Rinnigbereiften Trichterlings Clitocybe rivulosa 4’‐Phosphomuscarin (2) als hauptsächlichen Inhaltsstoff. Dessen Struktur wurde durch hochauflösende Massenspektrometrie, Kernresonanzspektroskopie, und durch Vergleich mit einem synthetisierten Standard aufgeklärt. Diese bislang übersehene phosphorylierte Verbindung detektierten wir ebenfalls in den Risspilzen Pseudosperma spectrale und Inocybe nitidiuscula. Studien zur Aktivierung des muscarinischen Acetylcholinrezeptors M3 zeigten nur geringe Affinität von 2 am Wirkort. Außerdem präsentieren wir biologische Beweise, dass Muscaridin (3), ein mit 1 verwandtes und mit diesem zusammen vorkommendes quaternäres Amin den muscarinischen Acetylcholinrezeptor M3 menschlicher embryonaler Nierenzellen nicht aktiviert. Unsere Arbeit gewährt wichtige Einblicke in das Inhaltsstoffprofil und die Pharmakologie einiger der wichtigsten Giftpilze. Da das harmlose 2 durch unspezifische enzymatische Esterspaltung das potentiell tödliche 1 freisetzen kann, sind diese Ergebnisse für die Notfallmedizin sehr relevant, um die wahre Toxizität dieser Pilze einzuschätzen.
Near‐Infrared Room‐Temperature Phosphorescence from Monocyclic Luminophores
Authors: Yan Zi‐Ang , Yin Chenjia , Tian He , Ma Xiang
Published: October 2024

Compact luminophores with long emission wavelengths have aroused considerable theoretical and practical interest. Organics with room‐temperature phosphorescence (RTP) are also desirable for their longer lifetimes and larger Stokes shifts than fluorescence. Utilizing the low electronic transition energy intrinsic to thiocarbonyl compounds, electron‐withdrawing groups were attached to the 4H‐pyran‐4‐thione core to further lower the excited state energies. The resulting mini‐phosphors were doped into suitable polymer matrices. These purely organic, amorphous materials emitted near‐infrared (NIR) RTP. Having a molar mass of only 162 g mol−1, one of the phosphors emitted RTP that peaked at 750 nm, with a very large Stokes shift of 15485 cm−1 (403 nm). Thanks to the good processability of the polymer film, light‐emitting diodes (LEDs) with NIR emission were easily fabricated by coating doped polymer on ultraviolet LEDs. This work provides an intriguing strategy to achieve NIR RTP using compact luminophores.