bluuebunny/crossref_metadata_2025 huggingface dataset:
Non‐invasive Flicker Neurostimulation Mitigates Stress Pathology in a Sex‐Dependent Manner
Authors: Franklin Tina Carla , Goodson Matthew , Zepeda Hector , Kye Nancy , Bitarafan Sara , Kraus Jacob , Braun Luke , Prichard Ashley , Wood Levi B , Singer Annabelle C
Published: January 2025

Background

Chronic stress promotes life‐long risk for neuropsychiatric decline by increasing neuroinflammation and disrupting synaptic health and plasticity. Our lab and others have recently demonstrated that non‐invasive gamma sensory stimulation (flicker) modulates immune signaling, restores microglial function, and improves cognitive performance in mouse models of Alzheimer’s disease (AD). However, no research to date has studied the effects of flicker in the context of stress. Accordingly, our goal for this study was to determine if flicker mitigates neuropsychiatric‐like behavioral deficits and rescues glial and synaptic pathology following chronic stress.

Method

Daily audiovisual flicker intervention was introduced concomitantly with daily stress exposure (28 days) at multiple frequencies in male and female C57BL6 mice (n = 6/group per sex). The mice were then tested for anxiety‐like behaviors and anhedonia using a range of behavioral tests. We quantified transcriptomic changes in cortical Thy1+ pyramidal neurons, microglia, and astrocytes to identify cell‐type specific genes modulated by flicker intervention in chronically stressed mice. To determine how flicker mitigates stress‐induced cellular changes in the prefrontal cortex, a region vulnerable to stress and AD pathology, we next quantified spine density changes in Thy1‐GFP mice and measured glial morphology changes as a proxy for microglial and astrocyte reactivity using the semi‐automated Imaris imaging software to determine synaptic health and inflammatory profile, respectively.

Result

We found that stress‐induced molecular changes in the prefrontal cortex are modulated in a sex‐, and frequency‐specific manner that coincides with behavioral resilience in stressed mice. Our findings indicates that audiovisual flicker protects against stress‐induced behavioral deficits and mitigates stress‐induced neuroimmune responses in a sex‐ and frequency‐specific manner.

Conclusion

Together, these findings show frequency optimized flicker intervention improves stress pathology and may prevent neuropsychiatric health decline in conditions with sex dimorphic symptoms and prevalence.
A unified framework for federated discovery, interrogation, and analysis using the GAAIN and AD Workbench platforms: A case study using the BLSA cohort
Authors: Pappas Ioannis , Xiao Cally , Griswold Michael E. , Phatak Mukta , Toga Arthur W.
Published: January 2025

Background

There is a consensus in the Alzheimer’s disease and related dementias (ADRD) community that data sharing can accelerate science leading to better biomarkers, treatments and preventative measures. However, the ADRD community faces extensive challenges when it comes to sharing of complex biomarker data due to heavy‐handed data sharing mandates and various types of restrictions.

Methods

The Global Alzheimer’s Association Interactive Network (GAAIN) and the Alzheimer’s Disease (AD) Data Initiative have pioneered methods in federated data sharing and learning methodologies by allowing data partners to share their data while protecting their data ownership rights. Users can access, interrogate, and analyze data in a way that is functionally equivalent to raw data access. These two platforms have made a strategic partnership to enhance data interoperability and analysis by using powerful data interrogation and analysis techniques that are provided to the users for free.

Results

For this presentation we will demonstrate data discovery, interrogation, and analysis using the GAAIN platform and the AD Workbench, which is the AD Data Initiative’s cloud‐based platform. We will showcase an example of data analysis using the Baltimore Longitudinal Study of Aging (BLSA), America’s longest‐running scientific study of human aging and related cognitive and physical changes. We will use GAAIN and the AD Workbench for data discovery and advanced statistical modeling for the purposes of understanding risk factors for dementia in the BLSA cohort.

Conclusions

We show an end‐to‐end pipeline of data discovery, interrogation, and analysis using the respective GAAIN and AD workbench tools. We are hoping that similar workflows can be incorporated by stakeholders thus increasing data and tool sharing among the ADRD community.
Orthogonal‐Group‐Controlled Site‐Selective I‐Branching of Poly‐N‐acetyllactosamine Chains Reveals Unique Binding Specificities of Proteins towards I‐Antigens
Authors: Bao Shumin , Shen Tangliang , Chen Congcong , Han Jinghua , Tajadura‐Ortega Virginia , Shabahang MohammadHossein , Du Zhenming , Feizi Ten , Chai Wengang , Li Lei
Published: January 2025

Poly‐N‐acetyllactosamine (poly‐LacNAc) is ubiquitously expressed on cell surface glycoconjugates, serving as the backbone of complex glycans and an extended scaffold that presents diverse glycan epitopes. The branching of poly‐LacNAc, where internal galactose (Gal) residues have β1‐6 linked N‐acetylglucosamine (GlcNAc) attached, forms the blood group I‐antigen, which is closely associated with various physiological and pathological processes including cancer progression. However, the underlying mechanisms remain unclear as many of the I‐antigen sequences are undefined and inaccessible. In this study, we developed a highly efficient orthogonal‐group‐controlled approach to access site‐selectively I‐branched poly‐LacNAc chains. The approach relies on three orthogonal protecting groups, each of them “caps” one internal Gal residue of poly‐LacNAc. These groups can be readily “decapped” by specific enzymes or chemical reduction to expose desired sites for GCNT2‐catalyzed I‐branching. This approach enabled the rapid preparation of a diverse library of 41 linear and branched poly‐LacNAc glycans from a single precursor. Glycan microarray analysis using these complex glycans revealed unique recognitions of I‐branches by lectins, anti‐I mAbs, and galectins. Surprisingly, oxidized forms of linear poly‐LacNAc strongly bound to several glycan‐binding proteins (GBPs). These findings help to bridge the gap in recognition of I‐branching and open new avenues for therapeutic development by targeting galectins.
Precise Manipulation on the Structural Defects of Poly (Triazine Imide) Single Crystals for Efficient Photocatalytic Overall Water Splitting
Authors: Zhuzhang Hangyu , Liang Xiaocong , Li Jiaxiang , Xue Sikang , Lin Yifan , Sa Baisheng , Wang Sibo , Zhang Guigang , Yu Zhiyang , Wang Xinchen
Published: January 2025

Conjugated polymers, represented by polymeric carbon nitrides (PCNs), have risen to prominence as new‐generation photocatalysts for overall water splitting (OWS). Despite considerable efforts, achieving highly crystalline PCNs with minimal structural defects remains a great challenge, and it is also difficult to examine the exact impact of complex defect states on OWS process, which largely limits their quantum efficiency. Herein, we devise a ‘in‐situ salt flux’ assisted copolymerization protocol by using nitrogen‐rich and nitrogen‐deficient monomers to precisely manipulate the structural defects of poly (triazine imide) (PTI) single crystals. Stoichiometric control between two comonomers enables continuous tunning of carbon‐ and nitrogen‐vacancies within PTI, allowing the construction of a series of PTI crystals with different defect states. Theoretical and experimental results unveil the carbon vacancies are related with the radiative decay of excitons, while the nonradiative decay is mainly derived from the nitrogen vacancies. Owing to the effective suppression of both radiative and nonradiative losses, the as‐synthesized PTI achieves a record apparent quantum efficiency of 37.8 % by one‐step‐excitation OWS. This work highlights the significance of rational control of the structural defects and describes clear structure‐property‐activity relationships in PTI photocatalyst, offering guidance for the development of polymer photocatalysts for solar fuel production.
Competitive Coordination and Dual Interphase Regulation of MOF‐Modified Solid‐State Polymer Electrolytes for High‐Performance Sodium Metal Batteries
Authors: Tian Wenyue , Lin Guangliang , Yuan Shaohui , Jin Ting , Wang Qinglun , Jiao Lifang
Published: January 2025

Solid‐state polymer electrolytes (SPEs) have emerged as prominent candidates for solid‐state sodium metal batteries (SMBs) due to their enhanced flexibility and reduced interfacial resistance. However, their performance is limited by poor Na+ conductivity at room temperature, disordered ion transport properties and unstable interfaces. Herein, a three‐dimensional (3D) interconnected copper metal–organic framework (Cu‐MOF) on polyacrylonitrile (PAN) fibers is introduced into polyethylene oxide (PEO)‐based SPEs to construct a composite electrolyte (PPNM). The open metal sites (OMS) of the Cu‐MOF compete with Na+, effectively coordinating with TFSI− anions and oxygen atoms in PEO, thereby reducing concentration polarization, weakening the Na+−O binding strength and facilitating Na+ migration. By harnessing the multifunctional properties of Cu‐MOF and PAN, the PPNM electrolyte exhibits superior ionic conductivity (1.03×10−4 S cm−1) and a high Na+ transference number (0.58) at room temperature. The strong anchoring of TFSI− anions by Cu‐MOF promotes the formation of inorganic‐rich (NaF and Na3N) cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) layers, enhancing dual interfacial stability. The Na3V2(PO4)3@C/PPNM/Na full cells realize robust cycling performance for 2000 cycles at 200 mA g−1. This work provides a facile strategy for regulating the Na+ coordination state and interphase engineering in solid‐state SMBs.
Leveraging Multivalent Assembly towards High‐Temperature Liquid‐Phase Phosphorescence
Authors: Luo Wuzhen , Chen Liming , Yin Guangqiang , Yue Chaojun , Xie Shiye , Zhou Jiayin , Feng Weihao , Nie Yujing , Qiu Huakai , Li Feiming , Cai Shunyou , Li Yijiang , Cai Zhixiong , Chen Tao
Published: January 2025

High‐temperature phosphorescence (HTP) materials have attracted considerable attention owing to their expanded application prospects, whereas they still suffer from severe deactivation in polar media, limiting their reliability and utility. Here, we present an efficient multivalent assembly strategy to achieve high‐temperature liquid‐phase phosphorescence (HTLP). The supramolecular assembly of multivalent modules leads to extremely robust hydrogen‐bonding networks, which firmly immobilize the organic phosphors and protect triplet excitons from annihilation in high‐temperature polar media, resulting in excellent HTLP emission. Moreover, the photophysical properties of HTLP are significantly enhanced by boosting multivalent interactions using multitopic phosphors, demonstrating a visible afterglow of 5 s in boiling water, more than 2 s in dimethylsulfoxide at 460 K (187 °C), and a long lifetime of 70.3 ms in N‐methylpyrrolidone at 476 K (203 °C). Based on their fluidity and robust HTLP emission, in situ microcracks detection of high‐temperature operating instruments and spatial‐time‐temperature‐resolved anticounterfeiting are demonstrated.
Sym‐ and Asym‐Expanded Heterohelicene Isomers Featuring Extended Multi‐Resonance Skeleton for Narrowband Deep‐Blue Fluorescence
Authors: Zeng Xuan , Luo Xiaofeng , Meng Guoyun , Wang Xuewen , Zhang Dongdong , Duan Lian
Published: January 2025

Expanded heterohelicenes composed of alternating linearly and angularly fused multi‐resonance (MR) skeletons have gained wide interest owing to their promising narrowband emissions. Herein, a pair of sym‐ and asym‐expanded heterohelicene isomers was obtained by merging boron/oxygen (B/O)‐embedded MR triangulene and indolo[3,2,1‐jk]carbazole units via one‐pot synthesis. Owing to their fully resonating extended helical skeleton, the target heterohelicenes exhibit a significantly narrowed spectra bandwidth while emission red‐shifting, thus affording deep‐blue narrowband emission with a peak at approximately 460 nm, full‐width‐at‐half‐maximum (FWHM) of only 18 nm, and near‐unity photoluminescence quantum yields. In comparison to the symmetrical structure, the asym‐expanded heterohelicene displays suppressed aggregation within doped films, thereby showing superior narrowband electroluminescence in devices with CIE coordinates of (0.12, 0.18) and a high external quantum efficiency of up to 25 %, which retains 18.1 % even at a high luminance of 10,000 cd m−1. Overall, this work provides a novel paradigm for the development of narrowband expanded heterohelicenes.
A BODIPY‐Containing Covalent Organic Framework as a Highly Porous Photosensitizer for Environmental Remediation and Pollutants Adsorption
Authors: Sánchez‐Naya Roberto , Beuerle Florian
Published: January 2025

The direct incorporation of borondipyrromethene (BODIPY) subunits into the structural backbone of covalent organic frameworks (COFs) gives facile access to porous photosensitizers but is still a challenging task. Here, we introduce β‐ketoenamine‐linked BDP‐TFP‐COF, which crystallizes in AA‐stacking mode with hcb topology. A comprehensive characterization reveals high crystallinity and enhanced stability in a variety of solvents, excellent mesoporosity (SABET=1042 m2 g−1), broad light absorption in the visible region, and red emission upon the exfoliation of few‐layer COF nanosheets. The versatility of multifunctional BODIPY‐COFs is highlighted in various applications. Pollutants Bisphenol A (BPA, qmax=426 mg g−1) and Methylene Blue (MB, qmax=96 mg g−1) have been efficiently removed from H2O. Fluorescence quenching or enhancement of exfoliated BDP‐TFP‐COF nanosheets have been utilized for dual‐mode sensing of MB or NEt3, respectively. Ultimately, the photosensitizing effect of the BODIPY units is retained in the COF. Thus, BPD‐TFP‐COF was established as a metal‐free triplet photosensitizer, which efficiently oxidized a mustard gas simulant under visible light irradiation.
Machine Learning‐Assisted Prediction of Photothermal Metal‐Phenolic Networks
Authors: Fan Dongqi , Chen Xu , Wang Shan , Zhan Jinglei , Chen Yuan , Zhou Houqi , Li Dize , Tang Han , He Qingqing , Chen Tao
Published: January 2025

Photothermal therapy (PTT) demonstrates significant potential in cancer treatment, wound healing, and antibacterial therapy, with its efficacy largely depending on the performance of photothermal agents (PTAs). Metal‐phenolic network (MPN) materials are ideal PTA candidates due to their low cost, good biocompatibility and excellent ligand‐to‐metal charge transfer properties. However, not all MPNs exhibit significant photothermal properties, and the vast chemical space of MPNs (over 700,000 potential combinations) complicates the screening of high‐photothermal materials. To address this challenge, this study introduces machine learning (ML) methods for predicting the photothermal performance of MPNs. A database of photothermal properties of 80 modular MPNs was constructed, and the ML process was optimized through feature engineering and model training. The selected extreme gradient boosting model (XGBoost) successfully identified 1,654 high photothermal MPNs from a virtual database of 44,438. Subsequent experimental validation revealed a remarkable success rate of 70 % in predicting high photothermal MPNs. Additionally, several previously unreported high photothermal MPNs were discovered, demonstrating advantages in photothermal antibacterial applications. This study offers an innovative ML‐driven approach for the efficient screening of MPN materials, providing a solid foundation for PTA design in PTT and other biomedical applications.
Asymmetric gem‐Hydroboration and gem‐Hydrogenation of Ynamides: A New Gateway to Chiral Fischer Carbene Complexes and their Catalytic Transformations
Authors: Babón Molina Juan Carlos , Renken Luis , Leutzsch Markus , Molina Betancourt Ricardo , Fürstner Alois
Published: January 2025

Ynamides, when reacted with H2 or HBpin in the presence of [Cp*RuCl]4, convert into chiral‐at‐metal Fischer carbenes by regioselective gem‐hydrogenation or gem‐hydroboration of the polarized triple bond, respectively. gem‐Hydroboration concomitantly affords a carbogenic borylated stereocenter adjacent to the ruthenium carbene unit, the configuration of which can be controlled using an Evans auxiliary. These are the first examples of asymmetric gem‐addition reactions to alkynes known in the literature; representative pianostool ruthenium carbene complexes formed by this unconventional route were characterized by crystallographic and spectroscopic means. They undergo various stoichiometric reactions and can even entertain catalytic asymmetric transformations, such as hydrogenative cyclopropanations or a novel type of borylative cycloisomerization.
Vesicle‐Encapsulated Chemosensing Ensembles Allow Monitoring of Transmembrane Uptake Coupled with Enzymatic Reactions
Authors: Jiang Ruixue , Nilam Mohamed , Piselli Claudio , Winterhalter Mathias , Guo Dong‐Sheng , Yu Sin‐Yi , Hennig Andreas , Nau Werner M.
Published: January 2025

Compartmentalized models with coupled catalytic networks are considered as “protocells” in the context of research related to the origin of life. To model the kinetics of a simple cellular uptake‐metabolism process, we use a compartmentalized protocell system that combines liposome‐encapsulated intravesicular reporter pairs with co‐encapsulated enzymes to monitor the membrane transport of a substrate (analyte uptake) and its subsequent enzymatic reaction inside the vesicles (metabolism to the product). The intravesicular chemosensing ensembles consist of the macrocycles cucurbit[7]uril or p‐sulfonatocalix[4]arene and matching fluorescent dyes to set up suitable reporter pairs. When these macrocycle/dye reporter pairs are co‐encapsulated with enzymes (trypsin, protein kinase A, or butyrylcholinesterase), it is possible to monitor first the transport of different substrates (polylysine, protamine, H‐LRRWSLG‐OH, or butyrylcholine) through added pores (outer membrane proteins F and C), with synthetic carriers (amphiphilic calixarenes), or by direct permeation (only for butyrylcholine). The subsequent enzymatic conversions of the substrates after they have entered the corresponding protocells can be monitored as consecutive reactions. The new type of in vitro assays can be applied to different enzymes and analytes, affording a comprehensive chemosensing system of high chemical complexity.
g‐C3N4 S‐Scheme Homojunction through Van der Waals Interface Regulation by Intrinsic Polymerization Tailoring for Enhanced Photocatalytic H2 Evolution and CO2 Reduction
Authors: Zhu Xianglin , Zhou Enlong , Tai Xishi , Zong Huibin , Yi Jianjian , Yuan Zhimin , Zhao Xingling , Huang Peng , Xu Hui , Jiang Zaiyong
Published: January 2025

The effective S‐scheme homojunction relies on the precise regulation of band structure and construction of advantaged charge migration interfaces. Here, the electronic structural properties of g‐C3N4 were modulated through meticulous polymerization of self‐assembled supramolecular precursors. Experimental and DFT results indicate that both the intrinsic bandgap and surface electronic characteristics were adjusted, leading to the formation of an in‐situ reconstructed homojunction interface facilitated by intrinsic van der Waals forces. The homojunction catalyst, composed of g‐C3N4 nanodots and ultra‐thin g‐C3N4 nanoflakes, exhibited a significant S‐scheme carrier separation mechanism, which enhances the utilization of electrons and holes. Consequently, under AM 1.5 light irradiation (~100 mW/cm2), the g‐C3N4 homojunction photocatalyst achieved a remarkable hydrogen evolution rate of 580 μmol h−1. Furthermore, a reversed CH4 selectivity in CO2 reduction was observed, yielding 80.30 μmol g−1 h−1 with a selectivity of 96.86 %, in contrast to the performance of bulk g‐C3N4, which produced only 2.22 μmol g−1 h−1 with the 15.69 % CH4 selectivity. These findings not only highlight the significant potential of the g‐C3N4 homojunction photocatalyst for hydrogen production and CO2 reduction but also propose a superior and effective strategy for optimizing the structural properties of g‐C3N4, which are crucial for the design of photocatalytic reactions.
CO Cryo‐Sorption as a Surface‐Sensitive Spectroscopic Probe of the Active Site Density of Single‐Atom Catalysts
Authors: Jeong Beomgyun , Abbas Hafiz Ghulam , Klein Benedikt P. , Bae Geunsu , Velmurugan Adith Ramakrishnan , Choi Chang Hyuck , Kim Geonhwa , Kim Dongwoo , Kim Ki‐jeong , Cha Byeong Jun , Kim Young Dok , Jaouen Frédéric , Maurer Reinhard J. , Ringe Stefan
Published: January 2025

Quantifying the number of active sites is a crucial aspect in the performance evaluation of single metal‐atom electrocatalysts. A possible realization is using adsorbing gas molecules that selectively bind to the single‐atom transition metal and then probing their surface density using spectroscopic tools. Herein, using in situ X‐ray photoelectron spectroscopy (XPS) and near edge X‐ray absorption fine structure (NEXAFS) spectroscopy, we detect adsorbed CO gas molecules on a FeNC oxygen reduction single atom catalyst. Correlating XPS and NEXAFS, we develop a simple surface‐ and chemically‐sensitive protocol to accurately and quickly quantify the active site density. Density functional theory‐based X‐ray spectra simulations reaffirm the assignment of the spectroscopic fingerprints of the CO molecules adsorbed at Fe‐N4‐C sites, and provide additional unexpected structural insights about the active site needed to explain the low‐temperature CO adsorption. Our work represents an important step towards an accurate quantitative catalytic performance evaluation, and thus towards developing reliable material design principles and catalysts.
Porphyrin‐based Vinylene‐linked 3D Covalent Organic Framework with Unprecedented cya Topology for Photocatalytic H2O2 Production
Authors: Gong Zihan , Gao Ying , Li Jing , Cai Zichen , Liu Naifang , Jiang Jianzhuang
Published: January 2025

Designing and realizing new topologies represent one of the most important ways toward developing new structures and functionalities for molecule‐based frameworks including SOFs, MOFs, and COFs. Herein, Aldol condensation between 5,10,15,20‐tetrayl(tetrakis(([1,1′:3′,1′′‐terphenyl]‐4,4′′‐dicarbaldehyde)))‐porphyrin (TTEP) and 2,4,6‐trimethyl‐1,3,5‐triazine (TMT) affords the vinylene‐linked 3D covalent organic framework Por‐COF‐cya. Powder X‐ray diffraction (PXRD) in combination with structural simulation reveals its high crystalline structure with an unprecedented cya topology in the molecule‐based frameworks reported thus far. Por‐COF‐cya displayed polycrystallinity and possessed high permanent porosity. Especially, the incorporation of light‐harvesting porphyrin unit and vinylene linkages in Por‐COF‐cya enables a conjugation effect within the framework, endowing it with a photocatalytic H2O2 production rate of 2209 μmol g−1h−1 in pure aqueous solution under visible‐light irradiation (λ >420 nm). Inclusion of the guest molecules TTF into the pores of Por‐COF‐cya results in a donor‐acceptor system TTF@Por‐COF‐cya, enhancing the photocatalytic activity with H2O2 production rate of 6994 μmol g−1h−1. This work paves a new way for the development of new topological functional molecule‐based frameworks toward diverse application potentials.
Confining Phosphoric Acid in Quaternized COF Channels for Ultra‐Stable and Fast Anhydrous Proton Transport
Authors: Pang Xiao , Shi Benbing , Liu Yawei , Wu Hong , Shen Jianliang , Guan Jingyuan , Wang Xiaoyao , Fan Chunyang , Cao Li , Zhu Tianhao , Kong Yan , Jiang Zhongyi
Published: January 2025

Phosphoric acid (H3PO4) doping is a widely employed strategy to facilitate anhydrous proton transport in high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs). However, significant H3PO4 leaching during long‐term operation poses critical challenges to maintaining membrane stability and proton conductivity. Herein, H3PO4 is incorporated into positively charged nanochannels of quaternized covalent organic framework membranes (QACOFMs), leveraging strong electrostatic interactions and confinement effects to achieve exceptional H3PO4 retention under hydration conditions. Moreover, the shortened hydrogen bond length between H3PO4 (O−H…O <2.7 Å) and the highly interconnected hydrogen bond network in the H3PO4@QACOFMs facilitate ultra‐fast anhydrous proton transport. As a result, the H3PO4@QACOFMs exhibit superior anhydrous proton transport in a broader temperature range (60 °C–200 °C) and the highest proton conductivity reaches about 379.7 mS cm−1 at 200 °C.
Cobalt‐Catalyzed Enantioselective Reductive Coupling of Imines and Internal Alkynes
Authors: Maji Kakoli , Palai Angshuman , Mallick Dibyendu , Maji Biplab
Published: January 2025

Chiral allylamines are important structural components in natural products, pharmaceuticals, and chiral catalysts. Herein, we report a cobalt‐catalyzed enantioselective reductive coupling of imines with internal alkynes to synthesize chiral allylamines. The reaction is catalyzed by a cobalt complex derived from commercially available bisphosphine ligand utilizing zinc as the electron donor. The substrate scope is extensive. Symmetric and unsymmetric alkyl and aryl alkynes have been successfully coupled with various imines derived from aryl and alkyl aldehydes. Tri‐ and tetra‐substituted allyl amines were isolated in high yields, with enantiomeric excess surpassing >99.9 % and regioselectivities exceeding >20 : 1. These chiral allyl amines can serve as versatile platforms for subsequent transformations while preserving their stereochemical integrity. Extensive experimental and computational mechanistic studies were performed to elucidate the mechanism. These investigations have indicated that an in situ cobalt(I) catalyst enables the oxidative cyclization of alkynes and imines, and a spin crossover occurs during the enantio‐determining step. Zinc plays a pivotal role in facilitating the transmetallation of the resulting azacobaltacycle. The observed enantioselectivity was interpreted by the stabilization of the transition state through higher stabilizing interaction energy from high negative polarization, dispersion, and C−H⋅⋅⋅π interactions.
Electronic Substitution Effect on ESIPT‐Driven pH and Amine Sensing: Exploring Mechanism
Authors: Kaushik Bharat , Agarwal Annu , Singh Ajeet , Rahaman Laskar Inamur
Published: January 2025

It is required to have a more straightforward and easier way to check the quality of food to ensure the safety of the public health. The decomposition of meat protein results in ammonia and biogenic amines (BAs). Consequently, to evaluate the safety and quality of meat products throughout the storage, transit, and consumption depends on the sensitive detection of the released BAs. Here, we have designed and synthesized three luminescent‐based probe molecules, which originated from 2‐(2‐hydroxyphenyl) benzothiazole (HBT) derivatives and showed the excited state‐induced proton transfer (ESIPT) phenomenon. The two substituents (OMe and NO2) were used rationally at the para position of HBT, and the electronic properties were evaluated using Hammett substituent constants. The proton donating ability of the O−H to the acceptor is largely facilitated by the presence of a strong electron‐withdrawing group, which in this case is NO2. The proton transfer rate can be controlled, and in this case, to a slower rate with the influence of the electron donating group OMe. The controllability of proton transfer led us to use it in pH sensing. A prominent and multi‐color change with pH variation was observed in the case of the OMe substituted compound. These probes were further employed for amine sensing, and the limit of detection (LOD) was determined to be 28.6 μM and 61.34 nM for ammonia and hydrazine, respectively. In addition, strip‐based detection of spoilage of chicken meat was studied for real‐world applications via both contact and non‐contact modes.
Regioselective Difluoroalkylation of 2‐Pyridones with Fluoroalkyl Bromides Enabled by a Nickel(II) Catalyst
Authors: Pradhan Chandini , Khandelwal Disha , Punji Benudhar
Published: January 2025

Regioselective C−H difluoroalkylation of diverse 2‐pyridones with ethyl bromodifluoroacetates and bromodifluoroacetamides is accomplished by using a (dppf)NiCl2 catalyst under mild conditions. This efficient protocol could deliver a variety of C‐3 difluoroalkylated pyridones with the tolerance of a range of highly susceptible functionalities, such as −Cl, −Br, −I, −COMe, −CN, −NMe2 and −NO2, including heteroarenes like pyridinyl, furanyl, thiophenyl and carbazolyl moieties. A preliminary mechanistic study suggests the radical pathway for the reaction involving fluoroalkyl radical intermediate.
Comparison of Blocked Versus Mixed Trialing When Teaching Foundational Skills to Early Learners
Authors: McKeown Ciobha A. , Walker Stephen F. , Peters Kerri P.
Published: January 2025

When teaching discriminations, clinicians may choose to teach one target at a time, repeatedly, until mastery (blocked‐trial instruction), or they may choose to teach multiple targets, interspersed, simultaneously (mixed‐trial instruction). Historically, it was recommended clinicians use mixed‐trial instruction at the onset of teaching as blocked‐trial instruction may produce faulty stimulus control. However, a recent study demonstrated that a modified blocked‐trial instructional arrangement was more efficient than mixed‐trial instruction and block‐size fading was unnecessary to maintain discriminated performance in adults with intellectual and developmental disabilities. The generality of these results to early learners is unknown. This study extended the aforementioned research to early learners diagnosed with autism spectrum disorder. Using an adapted alternating treatment design, we compared the rate of acquisition with both instructional formats across two foundational early learner skills. Comparable learning across both formats for all four early learners was observed.
Predictive Value of Machine Learning Models for Cerebral Edema Risk in Stroke Patients: A Meta‐Analysis
Authors: Deng Qi , Yang Yu , Bai Hongyu , Li Fei , Zhang Wenluo , He Rong , Li Yuming
Published: January 2025

Introduction

Stroke patients are at high risk of developing cerebral edema, which can have severe consequences. However, there are currently few effective tools for early identification or prediction of this risk. As machine learning (ML) is increasingly used in clinical practice, its effectiveness in predicting cerebral edema risk in stroke patients has been explored. Nonetheless, the lack of systematic evidence on its predictive value challenges the update of simple and user‐friendly risk assessment tools. Therefore, we conducted a systematic review to evaluate the predictive utility of ML for cerebral edema in stroke patients.

Methods

We searched PubMed, Embase, Web of Science, and the Cochrane Database up to February 21, 2024. The risk of bias in selected studies was assessed using a bias assessment tool for predictive models. Meta‐analysis synthesized results from validation sets.

Results

We included 22 studies with 25,096 stroke patients and 25 models, which were constructed using common and interpretable clinical features. In the validation cohort, the models achieved a concordance index (c‐index) of 0.840 (95% CI: 0.810–0.871) for predicting poststroke cerebral edema, with a sensitivity of 0.76 (95% CI: 0.72–0.79) and a specificity of 0.87 (95% CI: 0.83–0.90).

Conclusion

ML models are significant in predicting poststroke cerebral edema, providing clinicians with a powerful prognostic tool. However, radiomics‐based research was not included. We anticipate advancements in radiomics research to enhance the predictive power of ML for poststroke cerebral edema.
Quantitative Assessment of Deep Gray Matter Susceptibility and Correlation With Cognition in Patients With Liver Cirrhosis
Authors: Wu Wenjun , Su Yu , Qin Ziji , Kang Jiamin , Xiang Dongqiao , Liu Dingxi , Zheng Chuansheng , Haacke E. Mark , Wang Lixia
Published: January 2025

Background and Objectives

Accumulation of metals quantified by quantitative susceptibility mapping (QSM) in deep gray matter (DGM) and their impact on cognition have not been studied in patients with liver cirrhosis. This study aims to use QSM to investigate the association between DGM susceptibility and cognition in cirrhotic patients.

Methods

Thirty cirrhotic patients and 30 age‐, gender‐, and education‐matched controls were imaged using a multiecho gradient‐echo sequence for QSM analysis in a 3T scanner. The susceptibility values were determined for the caudate nucleus (CN), putamen (PU), globus pallidus (GP), thalamus (TH), red nucleus (RN), substantia nigra (SN), and dentate nucleus (DN). All subjects underwent number connection test A (NCT‐A), digit substitution test (DST), and Montreal Cognitive Assessment (MoCA). Comparisons between the two groups and the correlation between the susceptibility values and neuropsychological scores were analyzed.

Results

The susceptibility values of bilateral CN, TH, and RN were significantly lower in cirrhotic patients. Cirrhotic patients exhibited significantly prolonged NCT‐A time and decreased DST and MoCA scores. The NCT‐A, DST, MoCA, and sub‐domain scores were correlated with susceptibility values of RN, DN, SN, and CN, respectively. The susceptibility value of the left RN was a predictor variable for the DST, MoCA, and visuospatial–executive scores; those of the right CN and left RN were predictor variables for the naming score, and that of the left SN was an independent predictor variable for the language score.

Conclusions

Altered susceptibility values of DGM measured by QSM are potential quantitative indicators of cognitive impairment in cirrhotic patients.
The Role of Atrial Fibrillation and Oral Anticoagulation Status in Health‐Related Quality of Life 12 Months After Ischemic Stroke or TIA
Authors: Olma Manuel C. , Steindorf‐Sabath Lena , Tütüncü Serdar , Kunze Claudia , Fiessler Cornelia , Kirchhof Paulus , Dietzel Joanna , Schurig Johannes , Oschmann Patrick , Niehaus Ludwig , Urbanek Christian , Thomalla Götz , Nabavi Darius G. , Röther Joachim , Laufs Ulrich , Veltkamp Roland , Heuschmann Peter U. , Haeusler Karl Georg , Endres Matthias ,   for the MonDAFIS Investigators
Published: January 2025

Aims

Atrial fibrillation (AF) accounts for about 20% of all ischemic strokes worldwide. It is known that AF impairs health‐related quality of life (HRQOL) in the general population, but data on HRQOL in stroke patients with newly diagnosed AF are sparse.

Methods

Post hoc analysis of the prospective, investigator‐initiated, multicenter MonDAFIS study (NCT02204267) to analyze whether AF‐related oral anticoagulation (OAC), and/or AF‐symptom severity are associated with HRQOL after ischemic stroke or transient ischemic attack (TIA). HRQOL was measured using the EQ‐5D‐3L‐questionnaire (including EQ‐index/EQ‐VAS) at baseline and after 12 months using multivariable linear mixed models. AF symptom severity was assessed using the European Heart Rhythm Association classification and symptom severity score (EHRA score) categorizing patients with no/mild/severe/disabling AF‐related symptoms.

Results

A first episode of AF was detected in 261/2927 (8.9%) patients within 12 months after the index stroke and 227/2920 (7.8%) patients had AF and were anticoagulated at 12 months. HRQOL (measured by EQ‐index, n = 2495 patients) was higher in AF patients on OAC compared to AF patients without OAC at 12 months after stroke (mean difference: MD: –16.8, 95% CI: 5.6 to 28.0), and similar in AF patients under OAC compared with patients without AF (MD: 2.0, 95% CI: –2.2 to 6.3). AF‐related symptoms were negatively associated with HRQOL (measured by EQ‐index) indicating that stroke patients with AF‐related symptoms had a lower HRQOL compared to asymptomatic AF patients (mild vs. asymptomatic: MD: –9.0, 95% CI: –17.7 to –0.3; severe/disabling vs. asymptomatic: MD: –19.1, 95% CI: –34.7 to –3.4).

Discussion

Stroke patients with newly diagnosed AF are at risk of lower quality of life at 12 months, depending on OAC status and AF symptom severity.
Optimizing Sustainable Resource Efficiency: A Fuzzy‐Set Qualitative Comparative Analysis of Sustainable Practices in SMEs
Authors: Edu Abeeku S. , Ofosuhene Eunice , Agozie Divine Q. , Gyamfi Bright Akwasi , Asongu Simplice A.
Published: January 2025

This study examines the influence of sustainability practices on resource efficiency in Ghana's small and medium‐sized enterprises (SMEs), utilizing a comprehensive framework that integrates environmental and social dimensions, enabling conditions, innovative practices, and technological advancements. Through a survey of 462 manufacturing SMEs, the research uncovers the complex interrelationships between sustainability practices and their impact on resource efficiency. The findings reveal four distinct sustainability pathways: the first underscores the critical importance of environmental dimensions and enabling conditions without robust social dimensions and innovative practices. The second highlights the significance of environmental and enabling conditions, even when technological innovativeness is limited. The third and fourth pathways emphasize the pivotal role of social dimensions and technological innovation, with innovative practices as supportive elements. Additionally, two typologies emerge, illustrating the integration of environmental and social dimensions with enabling conditions and the synergy between technological innovation, social dimensions, and innovative practices. This research advances the discourse on sustainability within SMEs, emphasizing the necessity for reduced resource consumption, conservation, efficient production, circular economy principles, and waste minimization. The findings suggest that achieving SDG 8.4 by 2030, which targets global resource efficiency, hinges on adopting these sustainable pathways with emphasis on Ghanaian SMEs. This study provides a deeper understanding of sustainability practices among developing economy SMEs, shedding light on the intricate dynamics that enhance resource management. It offers critical insights for policymakers and practitioners seeking to promote sustainability in local SMEs, particularly in Ghana, advocating for a holistic approach that considers the multifaceted nature of sustainability.
Empowering Engineering Students Through Artificial Intelligence (AI): Blended Human–AI Creative Ideation Processes With ChatGPT
Authors: Baltà‐Salvador Rosó , El‐Madafri Ismail , Brasó‐Vives Enric , Peña Marta
Published: January 2025

The integration of artificial intelligence (AI) into education has the potential to revolutionize how students engage in academic activities and tasks. This research empirically analyses the influence of AI on creative ideation within educational settings to validate AI's role in enhancing human creativity since creative tasks, which inherently rely on human intuition, emotion and divergent thinking, may be stifled by systematic AI tools. The study explores whether ChatGPT can aid the creative process or inadvertently limit human creativity with a mixed‐method approach consisting of a randomized controlled experiment with third‐year engineering students in which a total of 728 ideas were obtained, along with a structured survey. The results revealed a predominantly positive perception towards AI‐assisted ideation; nevertheless, concerns were raised about AI's influence on creativity and innovation. While no significant differences in ideation outcomes were observed between the groups that used AI and those that did not, significant differences emerged between students who had prior experience with ChatGPT and those who did not. Qualitative insights provided a nuanced view of student experiences on blended human–AI ideation processes, shedding light on its advantages and disadvantages in educational practices. This research also underscores critical considerations and potential risks associated with the adoption of AI, suggesting that while AI has a place in educational settings, its role should be carefully calibrated to support rather than stifle student creativity and innovation. From the findings, the study provides practical recommendations and best practices regarding the integration of AI tools in education.
Prognostic factors in patients with localized and metastatic alveolar rhabdomyosarcoma. A report from two studies and two registries of the Cooperative Weichteilsarkom Studiengruppe CWS
Authors: Koscielniak Ewa , Stegmaier Sabine , Ljungman Gustaf , Kazanowska Bernarda , Niggli Felix , Ladenstein Ruth , Blank Bernd , Hallmen Erika , Vokuhl Christian , Blattmann Claudia , Sparber‐Sauer Monika , Klingebiel Thomas
Published: January 2025

Background

The histologic classification of rhabdomyosarcoma (RMS) as alveolar (aRMS) or embryonal (eRMS) is of prognostic importance, with the aRMS being associated with a worse outcome. Specific gene fusions (PAX3/7::FOXO1) found in the majority of aRMS have been recognized as markers associated with poor prognosis and are included in current risk stratification instead of histologic subtypes in localized disease. In metastatic disease, the independent prognostic significance of fusion status has not been definitively established. The objective of this analysis was to evaluate survival outcomes of patients with localized and metastatic aRMS and its association with fusion status and subtype (PAX3/7::FOXO1, FOXO1 break), and clinical prognostic factors.

Methods

A total of 470 patients with aRMS ≤21 years of age enrolled in two CWS‐trials and two registries was eligible for the analysis.

Results

The 5‐year event‐free survival (EFS) and overall survival (OS) rates for all patients with localized vs. metastatic tumors were: 56% and 65% vs. 18% and 22%, respectively. Of the 368 (78%) tumors tested, specific fusion was found in 330 (90%), considered “fusion positive” FP (PAX3::FOXO1 in 280, PAX7::FOXO1 in 49, FOXO1 break in 59 tumors). In patients with localized tumors, univariate analysis revealed that clinical group, tumor invasiveness (T1 vs.T2), regional lymph node involvement (N0 vs. N1) and FOXO1 fusion were significantly associated with EFS and OS, tumor size and PAX variant with OS only. In patients with metastatic aRMS, age, bone/marrow (B/BM) metastases, FOXO1 fusion and PAX variant were associated with EFS and OS, T status with OS only. Multivariate analysis identified PAX3::FOXO1 fusion as an independent adverse prognostic factor for EFS in patients with localized disease and for EFS and OS in patients with metastatic disease, B/BM metastases for EFS.

Conclusion

PAX3::FOXO1 fusion should replace FOXO1 fusion as an adverse prognostic factor in risk stratification. The prognostic relevance of PAX7::FOXO1‐positive and FOXO1 fusion negative aRMS, along with the clinical factors described in this report, allows further refinement of risk assessment of patients with localized and metastatic aRMS.
Cancer Incidence Among People With a Prior Hospital Record of Depression in Scotland, 1991–2019: A Cohort Study
Authors: Ashcroft Thulani , Fleetwood Kelly , Campbell Christine , Jackson Caroline A.
Published: January 2025

Objective

Current evidence on the association between depression and cancer risk is conflicting, with little understanding of how associations vary by time period or sociodemographic factors. We aimed to compare cancer incidence in people with versus without a previous hospital admission record for depression, by sociodemographic factors and over time.

Methods

We conducted a cohort study using national linked data in Scotland from 1991 to 2019. We calculated sex‐stratified age standardised incidence rates for all cancers, lung, female breast, colorectal and prostate cancer, and used quasi‐Poisson regression models to obtain sex‐specific estimates of cancer incidence and relative risks of cancer in those with versus without a prior hospital admission record of depression.

Results

There were 128,654 people with a hospital record of depression with 12,802 incident cancers and 847,656 cancers among those without depression. Age‐standardised cancer incidence rates were higher in both males and females with versus without depression. Depression was associated with a 20%–30% increased risk of all cancers combined, a difference that did not vary by sex, age or deprivation and persisted over three decades. Depression was associated with higher risks of lung (RR 1.79, 95% CI 1.70–1.88) and colorectal cancer (RR 1.12, 95% CI 1.05–1.19), but not breast or prostate cancer.

Conclusions

We identified an entrenched disparity in cancer incidence by depression status. Further research should identify underlying mechanisms and inform cancer prevention strategies in this vulnerable group. Meanwhile, health care professionals have a key role to play in optimising physical health care for people with depression.
FXYD3 Is Frequently Expressed in Pancreatic Ductal Adenocarcinoma but Does Not Predict Survival
Authors: Rasko Nathalie B. , Nahm Christopher B. , Turchini John , Teh Rachel , Rasmussen Helge , Byeon Sooin , Sahni Sumit , Samra Jaswinder S. , Gill Anthony J. , Mittal Anubhav
Published: January 2025

Background

FXYD3 is a Na/K‐ATPase modulator which is upregulated in pancreatic ductal adenocarcinoma (PDAC), but its prognostic role is unknown. This study evaluated FXYD3 expression in chemo‐naive patients with surgically‐resected PDAC at a single centre (1993–2014).

Method

FXYD3 expression was assessed in tumour specimens using immunohistochemistry.

Results

145 of 180 PDAC tumour specimens were FXYD3‐immunopositive (80.5%). There was no difference in median overall survival between the FXYD3 negative (27.60 months) and positive groups (25.00 months) (log‐rank p = 0.9718). FXYD3 expression correlated positively with late‐stage disease (OR 3.041, 95% CI 1.190–7.455, p = 0.0175). There was no significant association with T stage, positive lymph nodes, perineural invasion, lymphovascular invasion or histological grade.

Conclusion

Immunohistochemical FXYD3 expression does not predict survival in chemo‐naive PDAC patients, but is associated with late‐stage disease. The high rate of FXYD3 overexpression warrants therapeutic evaluation.
DNA Methylation in Prostate Cancer: Clinical Implications and Potential Applications
Authors: Muletier Romane , Bourgne Céline , Guy Laurent , Dougé Aurore
Published: January 2025

Background

Prostate cancer is a common cancer with a variable prognosis. Its management is currently guided by histological and biological markers such as the Gleason score and PSA. Developments in molecular biology are now making it possible to identify new targets for better classification of prostate cancer. Among emerging biomarker, DNA methylation, an epigenetic process, is increasingly being studied in carcinogenesis. Techniques for analyzing DNA methylation are constantly improving, and digital PCR now allows absolute methylation quantification with high sensitivity. These techniques can be performed on circulating tumor DNA.

Materials & Methods

We conducted a literature review of scientific articles addressing the topic of DNA methylation in prostate cancer.

Results & discussion

This review summarizes the different genes whose methylation is involved in carcinogenesis and their clinical implications, both diagnostic and prognostic. Methylation monitoring could also be useful for the prediction of treatment response. However, most studies are retrospective, and prospective studies are needed to validate these data.