bluuebunny/crossref_metadata_2025_split huggingface dataset:
Reconstructing the Coordination Environment of Fe/Co Dual‐atom Sites towards Efficient Oxygen Electrocatalysis for Zn–Air Batteries
Authors: Liu Hengqi , Huang Jinzhen , Feng Kun , Xiong Rui , Ma Shengyu , Wang Ran , Fu Qiang , Rafique Moniba , Liu Zhiguo , Han Jiecai , Hua Daxing , Li Jiajie , Zhong Jun , Wang Xianjie , Zhao Zhonglong , Yao Tai , Jiang Sida , Xu Ping , Zhang Zhihua , Song Bo 
Published: November 2024

AbstractDual‐atom catalysts with nitrogen‐coordinated metal sites embedded in carbon can drive the oxygen reduction and evolution reactions (ORR/OER) in rechargeable zinc–air batteries (ZABs), and the further improvement is limited by the linear scaling relationship of intermediate binding energies in the absorbate evolution mechanism (AEM). Triggering the lattice oxygen mechanism (LOM) is promising to overcome this challenge, but has yet been verified since the lacking of bridge oxygen (O) in the rigid coordination environment of the metal centers. Here, we demonstrate that suitably tailored dual‐atom catalysts of FeCo−N−C can undergo out‐plane and in‐plane reconstruction to form the both axial O and bridge O at the metal centers, and thus activate the LOM pathway. The tailored FeCo−N−C with shortened Fe−N bonds also favors the ORR process, therefore is a promising dual‐atom oxygen catalyst. The assembled rechargeable ZABs demonstrate a peak power density of 332 mW cm−2, and exhibit no notable decline after ~720 h of continuous cycling.
Stereoselective Radical Acylfluoroalkylation of Bicyclobutanes via N‐Heterocyclic Carbene Catalysis
Authors: Xiao Chuyu , Shan Jing‐Ran , Liu Wen‐Deng , Gao Xingyuan , Dai Jingwei , Wang Zuwei , Wang Wentao , Houk K. N. , Zhao Jiannan 
Published: November 2024

AbstractCyclobutanes are prominent structural components in natural products and drug molecules. With the advent of strain‐release‐driven synthesis, ring‐opening reactions of bicyclo[1.1.0]butanes (BCBs) provide an attractive pathway to construct these three‐dimensional structures. However, the stereoselective difunctionalization of the central C−C σ‐bonds remains challenging. Reported herein is a covalent‐based organocatalytic strategy that exploits radical NHC catalysis to achieve diastereoselective acylfluoroalkylation of BCBs under mild conditions. The Breslow enolate acts as a single electron donor and provides an NHC‐bound ketyl radical with appropriate steric hindrance, which effectively distinguishes between the two faces of transient cyclobutyl radicals. This operationally simple method tolerates various fluoroalkyl reagents and common functional groups, providing a straightforward access to polysubstituted cyclobutanes (75 examples, up to >19 : 1 d.r.). The combined experimental and theoretical investigations of this organocatalytic system confirm the formation of the NHC‐derived radical and provide an understanding of how stereoselective radical‐radical coupling occurs.
Catalytic Asymmetric Synthesis of Inherently Chiral Eight‐Membered O‐Heterocycles through Cross‐[4+4] Cycloaddition of Quinone Methides
Authors: Xu Da , Zhou Guojie , Liu Bangli , Jia Shiqi , Liu Yidong , Yan Hailong 
Published: November 2024

AbstractInherently chiral eight‐membered rings embedded in tetraphenylene derivatives and hetero‐analogues exhibit unique properties and allow diverse applications. A conceptually viable and straightforward approach to these frameworks is [4+4] cycloaddition, which still remains elusive. Herein, we describe the stereoselective cross‐[4+4] cycloaddition of quinone methides (QMs), leading to the formation of oxa‐analogues of tetraphenylene with exceptional chemo‐, diastereo‐, and enantioselectivity. The structures of these novel rigid eight‐membered O‐heterocycles were explored by single‐crystal X‐ray diffraction, and their stereochemical stability was elaborated through both density functional theory (DFT) calculations and thermal racemization experiments. The developed methodology exhibited broad substrate scope and the resulting cross‐[4+4] cycloadducts could be readily transformed into valuable chiral building blocks. Our findings expand the library of inherently chiral medium‐sized rings and also contribute to the advancement of asymmetric cross‐[4+4] cycloadditions of quinone methides.
Optimizing Propylene/Propane Sieving Separation through Gate‐Pressure Control within a Flexible Organic Framework
Authors: Li Lu , Xiang Fahui , Li Yunbin , Yang Yisi , Yuan Zhen , Chen Yanting , Yuan Furong , He Lei , Xiang Shengchang , Chen Banglin , Zhang Zhangjing 
Published: November 2024

AbstractThe separation of propylene (C3H6) and propane (C3H8) is of great significance in the chemical industry, which poses a challenge due to their almost identical kinetic diameters and similar physical properties. In this work, we synthesized an ultramicroporous flexible hydrogen‐bonded organic framework (named HOF‐FJU‐106) by using molecule 2,3,6,7‐tetra (4‐cyanophenyl) tetrathiafulvalene (TTF‐4CN). The formation of the dimer causes the TTF‐4CN molecular to bend and weaken π‐stacked interactions, coupled with the flexibility of C≡N
H−C hydrogen bonds, which leads to reversible conversion between open and closed frameworks through the mutual slip of adjacent layers/columns under activation and stimulation of gas molecules. Through gas adsorption isotherms and adsorption enthalpy, HOF‐FJU‐106a exhibited adaptive adsorption and stronger binding affinity for C3H6, and presented a recorded gas uptake ratio of C3H6/C3H8 (23.77) among presentative HOF materials at room temperature to date. Importantly, the flexible HOF‐FJU‐106a shows an interesting phenomenon about the reversible gate pressure control under variable temperature, which realized the gas adsorption and separation performance enhancement for the binary C3H6/C3H8 mixtures. This strategy through designing HOFs with thermoregulatory gating effect is a powerful way to maximize the performance of materials.
Synthesis of 4‐Cyclobutene‐Isoquinolines From Aryl Imidates by Ru(II)‐Catalyzed Domino C–H Activation/Cyclization
Authors: Wang Min , Gao Lei , Miao Maozhong , Zong Qianshou , Ling Fei , Yao Jinzhong , Zhou Hongwei 
Published: November 2024

ABSTRACTA highly regioselective approach for constructing 4‐cyclobutene‐isoquinoline derivatives through ruthenium‐catalyzed domino C–H activation/cyclization of aryl imidates has been demonstrated. This new transformation tolerates various substituted functional groups on imidates and propargylic monofluoroalkynes, resulting in the corresponding products being delivered in moderate yields.
Inner experiences, mental health, and well‐being in autistic and non‐autistic adults
Authors: Mazurek Micah O. , Pappagianopoulos Jessica , Brunt Sophie , Nevill Rose , Menezes Michelle , Burroughs Christina , Sadikova Eleonora , Smith Jessica V. , Howard Mya 
Published: November 2024

AbstractThe nature of autistic adults' everyday inner experiences has been largely unstudied. The purpose of this study was to examine patterns of inner experiences and how they relate to mental health and wellness among autistic and non‐autistic adults. Autistic (n = 303) and non‐autistic (n = 289) adults (ages 21–82) completed online surveys assessing their anxiety, depression, happiness, life satisfaction, and inner thinking patterns, (inner speaking [i.e., verbal thinking], inner seeing [i.e., visual thinking], unsymbolized thinking, feelings, sensory awareness, self‐talk). Group differences in inner thinking were examined using Mann–Whitney U and chi‐square tests. Correlations and multiple linear regressions examined associations between inner experiences, mental health, and well‐being. Autistic adults had greater use of inner speaking and sensory awareness, compared to non‐autistic adults. The most common primary mode of inner experience for both groups was inner speaking, while fewer autistic adults reported that experiencing thoughts as feelings was their primary modality. Autistic adults reported greater use of self‐talk for social assessment, self‐criticism, and self‐management purposes, compared to non‐autistic adults. Experiencing thoughts as inner speech and as feelings were associated with anxiety in both groups. Using self‐talk for social assessment and self‐criticism purposes was correlated with anxiety and depression in both groups, while using self‐talk for self‐management was associated with depression and anxiety only among autistic adults. The results suggest that autistic and non‐autistic adults have similarities in overall patterns of inner thinking, yet autistic adults may be more likely to engage in self‐talk as a strategy to manage challenging day‐to‐day experiences.
Mitigating ibrutinib‐induced ventricular arrhythmia and cardiac dysfunction with metformin
Authors: Li Pengsha , Liu Daiqi , Gao Pan , Yuan Ming , Zhao Zhiqiang , Zhang Yue , Zhou Zandong , Zhang Qingling , Yuan Meng , Liu Xing , Tse Gary , Li Guangping , Bao Qiankun , Liu Tong 
Published: November 2024

AbstractBackgroundIbrutinib is a first‐line drug that targets Bruton's tyrosine kinase for the treatment of B cell cancer. However, cardiotoxicity induced by ibrutinib is a major side effect that limits its clinical use. This study aimed to investigate the mechanism of ibrutinib‐induced cardiotoxicity and evaluate the protective role of metformin.MethodsThe study utilized male C57BL/6 J mice, which were administered ibrutinib at a dosage of 30 mg/kg/day via oral gavage for 4 weeks to induce cardiotoxicity. Metformin was administered orally at 200 mg/kg/day for 5 weeks, starting 1 week before ibrutinib treatment. Cardiac function was assessed using echocardiography and electrophysiological studies, including surface electrocardiography and epicardial electrical mapping. Blood pressure was measured using a tail‐cuff system. Western blot analysis was conducted to evaluate the activity of the PI3K‐AKT and AMPK pathways, along with apoptosis markers.ResultsC57BL/6 J mice were treated with ibrutinib for 4 weeks to assess its effect on cardiac function. We observed that ibrutinib induced ventricular arrhythmia and abnormal conduction while reducing the left ventricular ejection fraction. Furthermore, pretreatment with metformin reversed ibrutinib‐induced cardiotoxicity. Mechanistically, ibrutinib decreased PI3K‐AKT activity, resulting in apoptosis of cardiomyocytes. Administration of metformin upregulated AMPK and PI3K‐AKT activity, which contributed to the improvement of cardiac function.ConclusionThe study concludes that metformin effectively mitigates ibrutinib‐induced cardiotoxicity, including ventricular arrhythmia and cardiac dysfunction, by enhancing AMPK and PI3K‐AKT pathway activity. These findings suggest that metformin holds potential as a therapeutic strategy to protect against the adverse cardiac effects associated with ibrutinib treatment, offering a promising approach for improving the cardiovascular safety of patients undergoing therapy for B cell cancers.
A Novel Prognostic Nomogram Based on TIGIT and NKG2A Can Predict Relapse‐Free Survival of Hepatocellular Carcinoma After Hepatectomy
Authors: Wang Junqi , Cao Yuqing , Tian Yu , Dai Chaoliu , Jin Tianqiang , Xu Feng 
Published: November 2024

ABSTRACTBackground and ObjectivesHepatocellular carcinoma (HCC) is a major global health concern, and emerging evidence suggests that TIGIT and NKG2A are potential immune checkpoints with implications for HCC progression. This study aimed to evaluate the prognostic significance of TIGIT and NKG2A expression in HCC patients who underwent radical liver resection.MethodsWe conducted a retrospective analysis of 144 HCC patients who underwent radical liver resection. TIGIT and NKG2A expression levels were assessed using the immunoreactive score. Cox proportional hazards models were utilized to analyze the association between TIGIT/NKG2A expression and clinical characteristics, relapse‐free survival (RFS), and overall survival (OS). Prognostic models for OS and RFS was developed and validated using concordance index and calibration curves. Additionally, the random forest algorithm was employed to identify independent risk factors for OS and RFS and their correlation with predicted survival.ResultsTIGIT and NKG2A expression were identified as independent risk factors for RFS, while TIGIT expression alone significantly impacted OS. The prognostic models showed good discriminative ability, with concordance indices exceeding 0.7 for predicting 1‐, 3‐, and 5‐year OS or RFS. Calibration curves confirmed the reliability of the nomograms for OS and RFS prediction. The areas under the ROC curve consistently exceeded 0.7 for predicting OS and RFS. Elevated levels of TIGIT and NKG2A expression were associated with diminished RFS, highlighting their importance as prognostic factors.ConclusionsOur study establishes the prognostic significance of TIGIT and NKG2A expression in predicting OS and RFS following radical liver resection for HCC patients. The developed prognostic models incorporating TIGIT and NKG2A expression hold promise for improving risk stratification and clinical management of HCC patients.
Periodontal phenotype modification in surgically facilitated orthodontics: A case report
Authors: Tironi Francesco , Sofos Stavros , Wong Jason , Leyva Megan , Contasti Gisella , Nevins Myron , Vardar‐Sengul Saynur 
Published: November 2024

AbstractBackgroundOrthodontic treatment in adults with thin periodontal phenotype presents challenges such as lengthy treatment time and increased risk for gingival recessions. In this case, surgically facilitated orthodontic treatment (SFOT) was proposed to accelerate orthodontic tooth movement while modifying the periodontal phenotype.MethodsAn orthodontic patient was referred for periodontal evaluation of lower anterior teeth, which presented a thin gingival phenotype and bone dehiscence. SFOT was performed on the mandible using particulate allograft combined with platelet rich fibrin (PRF) and collagen membrane to augment soft and hard tissue, thereby preventing future recessions, while accelerating the treatment times.ResultsSix‐month and 3‐year follow‐ups confirmed radiographic bone fill, absence of gingival recession and thick band of keratinized gingiva. SFOT also resulted in a shorter treatment time where desired tooth movements were achieved within 6 months with periodontal stability.ConclusionsSFOT provided clinical benefits by accelerating orthodontic movement, improving periodontal phenotype, preventing the displacement of teeth beyond the alveolar housing and minimizing the risk for development of dehiscences and gingival recessions.Key points
Orthodontic movements can create recessions and dehiscence in thin periodontal phenotypes.
SFOT can help prevent bone dehiscence and creates a thicker gingival phenotype while accelerating treatment time.
Plain Language SummaryAdults who face lengthy orthodontic treatments and have thin gums have risks of gum problems. Surgically facilitated orthodontic treatment (SFOT) can help by speeding up tooth movements and improving gum health and thickness.A patient with thin gums and lack of bone in the lower front teeth was evaluated. The SFOT procedure involved using a bone graft, healing factors, and a collagen membrane to strengthen the gums and bones. This approach aimed to prevent future gum problems and speed up orthodontic treatment.Follow‐ups at 6 months and 3 years after treatment showed good healing of the gums and bones, with no signs of gum recession and healthier, thicker gums. The desired tooth movements were achieved within 6 months, resulting in a shorter treatment time. The patient's gums remained stable throughout this period.SFOT offered significant clinical benefits, including faster tooth movement and improved gum health. It also helped prevent teeth from moving out of place and minimized the risk of gum recession and bone issues. This approach can be a valuable option for adults with thin gums undergoing orthodontic treatment.
Proactive and reactive sibling aggression and their mediating effects on the relationship between exposure to parental violence and adulthood intimate partner violence perpetration
Authors: Flores Ayleen , Charak Ruby 
Published: November 2024

AbstractIt is generally understood that individuals who experience exposure to parental violence (EPV) during childhood may come to perpetrate violence, but not all will. Research has shown that individuals who experience EPV can model maladaptive modes of problem‐solving that can later be seen in sibling relationships as aggression. This can lead to a heightened risk of adulthood intimate partner violence perpetration (IPV). This study aimed to examine the mediating role of proactive and reactive sibling aggression in the associations of three forms of childhood EPV—violence directed from mother‐to‐father, father‐to‐mother, bidirectional—and perpetration of sexual and physical IPV types during adulthood. Participants were 322 emerging adults in the age range 18–29 years (M = 24.69, SD = 2.91; 182 female) recruited online via Amazon's Mechanical Turk. Findings indicated that our sample endorsed bidirectional EPV (41.3%), proactive sibling aggression (87.2%) and reactive sibling aggression (94.7%) in childhood. In adulthood, they endorsed physical IPV (20.8%) and sexual IPV (22.7%). The mediation model indicated that those who had bidirectional EPV were more likely to engage in proactive aggression, which was associated with engagement in physical perpetration of IPV, and sexual perpetration of IPV. Findings suggest the need for intervention programs during childhood in those with exposure to parental violence and sibling proactive aggression.
Electrocatalytic Urea Synthesis via C─N Coupling Over Fe‐Based Catalyst
Authors: Waghela Santosh R , Adalder Ashadul , Mitra Koushik , Ghorai Uttam Kumar 
Published: November 2024

AbstractElectrochemical urea synthesis under ambient conditions offers a promising alternative to traditional methods, yet suffers from inefficient production due to poor binding of reactants to the catalyst surface, leading to competitive pathways. In this study, we report an electrochemical route for urea synthesis by dual reduction of CO2 and N2 gases using iron phthalocyanine (FePc) catalyst. The FePc electrocatalyst showed a urea yield rate of 357 µmol h−1 gcat−1 with a Faradaic efficiency (FE) of 14.36% at −0.4 V versus RHE. This work offers an awareness into the development of an electrochemical route for the efficient electrosynthesis of urea via C─N coupling.
Forensic Comparison of Amphetamine Chemical Profiles by Bayesian Predictive Modelling
Authors: Korpinsalo Tuomas , Rautavirta Juhana , Huhtala Sami , Reinikainen Tapani , Corander Jukka 
Published: November 2024

ABSTRACTForensic chemists frequently employ statistical profiling approaches to assess the degree of similarity between samples of illicit drugs. Such profiling information can help reveal connections between nodes in distribution networks and manufacturing laboratories. For amphetamine, the routine method of comparing a pair of samples includes the use of a dissimilarity measure based on the Pearson correlation coefficient calculated between their chemical profiles obtained through gas chromatography–mass spectrometry. This simple measure of (dis)similarity has been shown distinguish pairs sharing a common origin (e.g., same production batch) to a reasonable level of accuracy. However, Pearson correlation fails to capture all the relevant notions of similarity between chemical profiles of amphetamine. We present a new statistical method for forensic drug comparison that uses a more sophisticated statistical modelling approach to determine similarity between samples. We show that this leads to improved performance over the correlation‐based approach. The proposed method is easily extendable and has an intuitive interpretation both from chemistry and forensic perspectives, which supports wide applicability to illicit drug profiling in practice.
Competitive Heavy‐Atom Tunneling Reactions Controlled Through Electronic Effects
Authors: Roque José P. L. , Nunes Cláudio M. , Saito Fumito , Bernhardt Bastian , Fausto Rui , Schreiner Peter R. 
Published: November 2024

AbstractControlling QMT reactivity remains exceptionally challenging and largely unexplored, as it requires rationales distinctly different from those used for classical chemical reactivity. Herein, we investigated how QMT reactivity can be controlled using electronic substituent effects. Benzazirines, which have the exceptional feature to react via two competitive QMT pathways, were used as model compounds. Three novel derivatives with increasingly stronger electron‐donating substituents at C4 [R = OH, N(CH3)2, and N(CH2)4] were generated in argon matrices at 3 K. Remarkably, different QMT selectivities were observed in all benzazirines. As the electron‐donating strength of the substituent increases, the QMT ring‐opening to nitrene starts to compete with the QMT ring‐expansion to ketenimine, becoming the dominant process for the strongest electron‐donating substituent [N(CH2)4]. A theoretical analysis of the substituent effects on the QMT reactivity of benzazirines was performed and compared with the experimental data for these and other C4 derivatives. Overall, the results compellingly demonstrate how subtle changes in electronic effects can be used to fine‐tune QMT selectivity.
Substitution of the Axial Type 1 Cu Ligand Affords Binding of a Water Molecule in Axial Position Affecting Kinetics, Spectral, and Structural Properties of the Small Laccase Ssl1
Authors: Olbrich Anna C. , Mielenbrink Steffen , Willers Vivian P. , Koschorreck Katja , Birrell James A. , Span Ingrid , Urlacher Vlada B. 
Published: November 2024

AbstractMulticopper oxidases use Cu ions as cofactors to oxidize various substrates. High reduction potential at Type 1 Cu is considered as crucial for effective catalysis. Previous studies have shown that replacing the axial methionine ligand of the Type 1 Cu with leucine or phenylalanine leads to an increased reduction potential, but not always to higher enzyme activity. Here we present a study on six variants of the small laccase Ssl1 from Streptomyces sviceus, where the axial methionine ligand was substituted, and the effect of the axial ligand on reduction potential, activity, spectral properties and structure was investigated. Absorption, electronic circular dichroism and EPR spectra revealed the presence of a stronger coordinating axial ligand like oxygen, which influences the electronic and catalytic properties more than the nature of the amino acid side chain. The crystal structures of the Ssl1 variants were solved, which show that none of the amino acid side chains coordinate to the Cu. Instead, a water molecule is found in the axial coordination site, which support the spectroscopic data. Our findings highlight the importance of combining structural and spectroscopic methods to investigate the effect of amino acid exchange on multicopper oxidases.
Synthesis and Photophysical Properties of 4’‐5’ Disubstituted CinNapht Dyes Accessible through Double SNAr Late‐Stage Functionalization
Authors: Tacke Eléonore , Estaque Lilian , Hoang Minh‐Duc , Durand Philippe , Clavier Gilles , Pieters Grégory , Chevalier Arnaud 
Published: November 2024

AbstractThis article describes the synthesis of a difluorinated CinNapht derivative in the 4′ and 5′ positions allowing the easy access to two new families of fluorophores by late‐stage functionalization using SNAr. The first one comprises derivatives incorporating hindered aromatic amines in the 4′ and 5′ positions, which show red‐emission in apolar solvents. The second one is obtained through the use of dinucleophiles. Among them, Tetrahydroquinoxaline (THQ) and tetrahydrobenzodiazepine (THB) compounds show strongly redshifted emission. The photophysical properties of all the fluorophores in these two families are studied and rationalized by DFT and TDDFT calculations. The most promising compounds have been used to image living cells by confocal microscopy.