bluuebunny/crossref_metadata_2025_split huggingface dataset:
Carbon‐based Flame Retardants for Polymers: A Bottom‐up Review
Authors: Yeoh Guan Heng , De Cachinho Cordeiro Ivan Miguel , Wang Wei , Wang Cheng , Yuen Anthony Chun Yin , Chen Timothy Bo Yuan , Vargas Juan Baena , Mao Guangzhao , Garbe Ulf , Chua Hui Tong 
Published: May 2024

AbstractThis state‐of‐the‐art review is geared toward elucidating the molecular understanding of the carbon‐based flame‐retardant mechanisms for polymers via holistic characterization combining detailed analytical assessments and computational material science. The use of carbon‐based flame retardants, which include graphite, graphene, carbon nanotubes (CNTs), carbon dots (CDs), and fullerenes, in their pure and functionalized forms are initially reviewed to evaluate their flame retardancy performance and to determine their elevation of the flammability resistance on various types of polymers. The early transition metal carbides such as MXenes, regarded as next‐generation carbon‐based flame retardants, are discussed with respect to their superior flame retardancy and multifunctional applications. At the core of this review is the utilization of cutting‐edge molecular dynamics (MD) simulations which sets a precedence of an alternative bottom‐up approach to fill the knowledge gap through insights into the thermal resisting process of the carbon‐based flame retardants, such as the formation of carbonaceous char and intermediate chemical reactions offered by the unique carbon bonding arrangements and microscopic in‐situ architectures. Combining MD simulations with detailed experimental assessments and characterization, a more targeted development as well as a systematic material synthesis framework can be realized for the future development of advanced flame‐retardant polymers.
Dual‐Adaptive Heterojunction Synaptic Transistors for Efficient Machine Vision in Harsh Lighting Conditions
Authors: Wang Yiru , Nie Shimiao , Liu Shanshuo , Hu Yunfei , Fu Jingwei , Ming Jianyu , Liu Jing , Li Yueqing , He Xiang , Wang Le , Li Wen , Yi Mingdong , Ling Haifeng , Xie Linghai , Huang Wei 
Published: May 2024

AbstractPhotoadaptive synaptic devices enable in‐sensor processing of complex illumination scenes, while second‐order adaptive synaptic plasticity improves learning efficiency by modifying the learning rate in a given environment. The integration of above adaptations in one phototransistor device will provide opportunities for developing high‐efficient machine vision system. Here, a dually adaptable organic heterojunction transistor as a working unit in the system, which facilitates precise contrast enhancement and improves convergence rate under harsh lighting conditions, is reported. The photoadaptive threshold sliding originates from the bidirectional photoconductivity caused by the light intensity‐dependent photogating effect. Metaplasticity is successfully implemented owing to the combination of ambipolar behavior and charge trapping effect. By utilizing the transistor array in a machine vision system, the details and edges can be highlighted in the 0.4% low‐contrast images, and a high recognition accuracy of 93.8% with a significantly promoted convergence rate by about 5 times are also achieved. These results open a strategy to fully implement metaplasticity in optoelectronic devices and suggest their vision processing applications in complex lighting scenes.
Diastereoselective Synthesis of CF3‐Pyrano[3,4‐c]quinolones from Hetero‐Dendralenes and Aldehydes
Authors: Nagababu Chavakula , Sainadh Srirangam , Desagoni Madhu , Nanubolu Jagadeesh Babu , Punna Nagender 
Published: May 2024

AbstractHerein, we demonstrate an Oxa‐Diels‐Alder reaction of 3‐trifluoroacetyl‐4‐methyl‐quinolin‐2(1H)‐one with aldehydes in the presence of a base to engineer the functionalized pyrano[3,4‐c]quinolones. This reaction proceeds through an in‐situ generated hetero dendralene intermediate and features perfect stereoselectivity on a wide range of substrates with excellent atom economy. The high electron‐withdrawing nature of CF3‐group is responsible for making the methyl group present in quinolone moiety more acidic to furnish the corresponding hetero dendralene intermediate.
Two Catalytic Protocols for the Synthesis of CF2‐Containing Quinazolinones via Domino Reaction
Authors: Wei Congyin , Yu Zhiyou , Shi Lei 
Published: May 2024

AbstractCopper‐catalyzed and visible‐light catalytic difluoroalkylation reactions of N‐cyanamide alkenes have been developed. Various α‐bromodifluoromethyl substituted esters, amides and heterocycles were employed as the CF2 source. Both protocols are characterized by medium to high yields, good functional group compatibility, and applicable to gram‐scale synthesis. Comparable studies of copper catalysis and photoredox catalysis demonstrate minimal differences between the two protocols. Preliminary mechanism suggest that both transformations involve tandem radical cyclization process.
Characteristics of MAPbI3 Stacked on the GaN Nanowires‐On‐Glass
Authors: Lee Kwang Jae , Kim Yeong Jae , Min Jung‐Hong , Kang Chun Hong , Subedi Ram Chandra , Zhang Huafan , Al‐Maghrabi Latifah , Park Kwangwook , Ahn Dante , Pak Yusin , Ng Tien Khee , Song Young Min , Ooi Boon S. , Bakr Osman M. , Min Jungwook 
Published: May 2024

AbstractWhen implementing optoelectronic devices through the stacking of heterogeneous materials, considering the bandgap offset is crucial for achieving efficient carrier dynamics. In this study, the bandgap offset characteristics are investigated when n‐type gallium nitride nanowires (n‐GaN NWs) are used as electron transport layers in methylammonium lead iodide (MAPbI3)‐based optoelectronic devices. n‐GaN NWs are grown on indium‐tin‐oxide (ITO)‐coated glass via the plasma‐assisted molecular beam epitaxy (PA‐MBE) process to form the “GaN NWs‐on‐glass” platform. A MAPbI3 thin film is then spin‐coated on the GaN NWs‐on‐glass. X‐ray photoelectron spectroscopy (XPS) shows that the valence and conduction band offsets in the MAPbI3/n‐GaN heterostructure are 2.19 and 0.40 eV, respectively, indicating a type‐II band alignment ideal for optoelectronic applications. Prototype photovoltaic devices stacking perovskite on GaN NWs‐on‐glass show excellent interfacial charge‐transfer ability, photon recycling, and carrier extraction efficiency. As a pioneering step in exploiting the diverse potential of the GaN‐on‐glass, it is demonstrated that the junction characteristics of MAPbI3/n‐GaN NW heterostructures can lead to a variety of optoelectronic device applications.
Silver Single Atoms Combined with Clusters on Carbon Nanotubes Mediates Exclusive Electrochemical CO2‐to‐CO Conversion
Authors: Xu Yanzhi , Zhang Xu , Yang Chenyu , Gong Chen , Qin Xupeng , Sun Haixin , Chen Honglei , Soldatov Mikhail A. , Zheng Kun , Li Changli , Gan Tao , Li Jiong , He Jingfu , Liu Qinghua 
Published: May 2024

AbstractThe electrochemical reduction of CO2 (eCO2RR) that exclusively produces one product at industrial current density is crucial for the substantial storage of renewable energy. Modulating the electronic structure of atomically dispersed catalysts can effectively regulate the adsorption of rate‐determining‐step intermediates to achieve the desired products. Here, the study constructs a hybrid catalyst consisting of single Ag atoms and Ag atomic clusters supported on nitrogen‐doped multi‐walled carbon nanotubes that can effectively regulate the important intermediate structure of *COOH. The X‐ray photoelectron and X‐ray absorption near‐edge spectroscopies demonstrate that turning Ag single atoms into Ag clusters can weaken the electron transfer between Ag–N and present a relatively rich electron state. Thus, the rate‐determining step of *COOH massive formation is significantly accelerated, as proven by in situ synchrotron infrared spectroscopy and density functional theory calculations. Using this strategy, a CO Faradaic efficiency outperforming 99% from −0.3 to −0.8 V (vs reversible hydrogen electrode) with current densities above 200 mA cm−2 and a half‐cell energetic efficiency of 86% is achieved. This work highlights a promising approach to advancing synergistic catalysts for achieving more controllable and efficient eCO2RR.
Oxide‐Encapsulated Silver Electrocatalysts for Selective and Stable Syngas Production from Reactive Carbon Capture Solutions
Authors: Lin Zhexi , Blake Nathaniel , Pang Xueqi , He Zhirui , Mirshekari Gholamreza , Romiluyi Oyinkansola , Son Yoon Jun , Kabra Suryansh , Esposito Daniel V. 
Published: May 2024

AbstractElectrolysis of bicarbonate‐containing CO2 capture solutions is a promising approach towards achieving low‐cost carbon‐neutral chemicals production. However, the parasitic bicarbonate‐mediated hydrogen evolution reaction (HER) and electrode instability in the presence of trace impurities remain major obstacles to overcome. This work demonstrates that the combined use of titanium dioxide (TiO2) overlayers with the chelating agent ethylene diamine tetra‐acetic acid (EDTA) significantly enhances the selectivity and stability of Ag‐based electrocatalysts for bicarbonate electrolysis. The amorphous TiO2 overlayers suppress the HER by over 50 % at potentials more negative than −0.7 V vs. RHE, increasing the CO faradaic efficiency (FE) by 33 % (relative). In situ surface‐enhanced Raman spectroscopy (SERS) measurements reveal the absence of near‐surface bicarbonate species and an abundance of CO2 reduction intermediates at the Ag|TiO2 buried interface, suggesting that the overlayers suppress HER by blocking bicarbonate ions from reaching the buried active sites. In accelerated degradation tests with 5 ppm of Fe(III) impurity, the addition of EDTA allows stable CO production with >47 % FE, while the electrodes rapidly deactivate in the absence of EDTA. This work highlights the use of TiO2 overlayers for enhancing the CO : H2 ratio while simultaneously protecting electrocatalysts from impurities likely to be present in “open” carbon capture systems.
Chiral Teropyrenes: Synthesis, Structure, and Spectroscopic Studies
Authors: Bam Radha , Yang Wenlong , Longhi Giovanna , Abbate Sergio , Lucotti Andrea , Tommasini Matteo , Franzini Roberta , Villani Claudio , Catalano Vincent J. , Olmstead Marilyn M. , Chalifoux Wesley A. 
Published: May 2024

AbstractWe present the inaugural synthesis of a chiral teropyrene achieved through a four‐fold alkyne benzannulation catalyzed by InCl3, resulting in good yields. The product underwent thorough characterization using FT‐Raman and FT‐IR spectroscopies, demonstrating a close agreement with calculated spectra. X‐ray crystallographic analysis unveiled a notable twist in the molecule‘s backbone, with an end‐to‐end twist angle of 51°, consistent with computational predictions. Experimentally determined enantiomeric inversion barriers revealed a significant energy barrier of 23 kcal/mol, facilitating the isolation of enantiomers for analysis by circular dichroism (CD) and circularly polarized luminescence (CPL) spectroscopies. These findings mark significant strides in the synthesis and characterization of chiral teropyrenes, offering insights into their structural and spectroscopic properties.
Force Transduction Through Distant Force‐Bearing Regioisomeric Linkages Affects the Mechanochemical Reactivity of Cyclobutane
Authors: Flear Erica J. , Horst Matías , Yang Jinghui , Xia Yan 
Published: May 2024

AbstractFundamental understanding of mechanochemical reactivity is important for designing new mechanophores. Besides the core structure of mechanophores, substituents on a mechanophore can affect its mechanochemical reactivity through electronic stabilization of the intermediate or effectiveness of force transduction from the polymer backbone to the mechanophore. The latter factor represents a unique mechanical effect in considering polymer mechanochemistry. Here, we show that regioisomeric linkage that is not directly adjacent to the first cleaving bond in cyclobutane can still significantly affect the mechanochemical reactivity of the mechanophore. We synthesized three non‐scissile 1,2‐diphenyl cyclobutanes, varying their linkage to the polymer backbone via the o, m, or p‐position of the diphenyl substituents. Even though the regioisomers share the same substituted cyclobutane core structure and similar electronic stabilization of the diradical intermediate from cleaving the first C−C bond, the p isomer exhibited significantly higher mechanochemical reactivity than the o and m isomers. The observed difference in reactivity can be rationalized as the much more effective force transduction to the scissile bond through the p‐position than the other two substitution positions. These findings point to the importance of considering force‐bearing linkages that are more distant from the bond to be cleaved when incorporating mechanophores into polymer backbones.
SERS Detection of Trace Carcinogenic Aromatic Amines Based on Amorphous MoO3 Monolayers
Authors: Meng Xiangyu , Yu Jian , Shi Wenxiong , Qiu Lin , Qiu Keliang , Li Anran , Liu Zhen , Wang Yuening , Wu Jingjing , Lin Jie , Wang Xiaotian , Guo Lin 
Published: May 2024

AbstractAromatic amines are important commercial chemicals, but their carcinogenicity poses a threat to humans and other organisms, making their rapid quantitative detection increasingly urgent. Here, amorphous MoO3 (a‐MoO3) monolayers with localized surface plasmon resonance (LSPR) effect in the visible region are designed for the trace detection of carcinogenic aromatic amine molecules. The hot‐electron fast decay component of a‐MoO3 decreases from 301 fs to 150 fs after absorption with methyl orange (MO) molecules, indicating the plasmon‐induced hot‐electron transfer (PIHET) process from a‐MoO3 to MO. Therefore, a‐MoO3 monolayers present high SERS performance due to the synergistic effect of electromagnetic enhancement (EM) and PIHET, proposing the EM‐PIHET synergistic mechanism in a‐MoO3. In addition, a‐MoO3 possesses higher electron delocalization and electronic state density than crystal MoO3 (c‐MoO3), which is conducive to the PIHET. The limit of detection (LOD) for o‐aminoazotoluene (o‐AAT) is 10−9 M with good uniformity, acid resistance, and thermal stability. In this work, trace detection and identification of various carcinogenic aromatic amines based on a‐MoO3 monolayers is realized, which is of great significance for reducing cancer infection rates.
Synthesis, structural investigations, in vitro cytotoxicity, apoptotic activity, cell cycle analysis, and molecular modeling studies of nano‐sized Zn(II) Schiff base complex
Authors: Amri Nasser , Alaghaz Abdel‐Nasser M. A. 
Published: May 2024

A new novel tetradentate ligand, [(1E,1′E)‐N,N′‐(1,2‐phenylene)bis(1‐(5‐(2‐fluorophenyl)furan‐2‐yl)methanimine) (PFPFMI), and its nano‐sized [Zn(PFPFMI)Cl2].3H2O complex were synthesized. The geometry of PFPFMI and its Zn(II) complex was described through CHN analyses, Fourier‐transform infrared spectroscopy (FTIR), UV–visible, X‐ray diffraction (XRD), thermal gravimetric analysis (TGA), and mass spectral data tests. The spectral data of the nano‐sized [Zn(PFPFMI)Cl2].3H2O complex indicates that the PFPFMI ligand functions as a tetradentate (N2O2) coordination through two azomethine nitrogen groups (N) and two furan ring oxygen (O) atoms. Density functional theory (DFT) calculations were performed using the molecular studio software to investigate the optimal geometry of PFPFMI and its [Zn(PFPFMI)Cl2].3H2O complex. The SEM, TEM, XRD, AFM, and energy dispersive X‐ray analysis (EDX) analyses of the studied complex unveil distinct and strong diffraction peaks, indicating its crystalline nature and providing evidence of its nano‐sized particle sizes. Additionally, the inhibition zone diameter was used to assess the in vitro antimicrobial action of PFPFMI and the particular complex against Gram‐positive bacteria Streptococcus pneumonia and Bacillus subtilis, Gram‐negative bacteria Pseudomonas aeruginosa, Salmonella typhi, and Escherichia coli, as well as fungi Aspergillus fumigatus, Geotricum candidum, Syncephalastrum racemosum, and Candida tropicalis. The [Zn(PFPFMI)Cl2].3H2O complex exhibits higher activity than the ligand PFPFMI. In vitro cytotoxicity of the synthesized [Zn(PFPFMI)Cl2].3H2O complex was explored using MCF7 (breast cancer), HCT116 (colon cancer), A549 (lung cancer), HePG‐2 (liver cancer), A375 (melanoma cancer), and normal lung fibroblast (WI38) cell lines. Based on IC50 and selective index (SI) values, it was shown that the complex exhibited higher potency against MCF7 cell lines. Moreover, the Zn(II) complex exhibited the ability to induce DNA damage in MCF7 cells, resulting in dose‐dependent cell apoptosis. Subsequent investigations revealed that complex 2 also induced cell cycle arrest in the G2 and S phases.
Progress and Prospect of Sn‐based Metal‐organic Framework Derived Anode Materials for Metal‐ion Batteries
Authors: Zhang Weitao , Qi Yongyu , Fang Jie , Mai Wanxin , Lin Xiaoming , Yang Huachao , Wu Yongbo 
Published: May 2024

AbstractIn order to realize the growing demand for superior energy storage devices and electric vehicles, commercial anode candidates for next‐generation rechargeable batteries need to meet the characteristics of low cost, high energy density, high capacity, and stable performance. The emerging tin‐based anodes show great potential for high performance metal‐ion battery anodes due to their high theoretical capacity, low cost, green harmless and high safety. Tin based anode materials include tin gold based materials, tin alloy materials, tin based oxides, tin based phosphide, tin based sulfides, multi‐component composite materials, etc. However, the change in volume and structure of tin‐based anode materials during the cycle has become the biggest obstacle to its development. Metal‐organic frameworks (MOFs) provide a wide range of possibilities for achieving high rate capacity and excellent cycle stability by finely regulating the structure and composition of tin‐based materials at the molecular level. The latest progress of tin‐based materials derived from MOFs as anode materials for metal‐ion batteries (including lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries) was reviewed in this paper. Firstly, the preparation method and morphology control of tin‐based MOF are briefly introduced, and the structural characteristics, storage mechanism and modification of tin‐based MOF derived materials are emphatically discussed. Finally, we summarized the existing modification measures and challenges of these anode materials, and put forward the prospect of the future.
The effects of an online positive psychology intervention on pre‐service teachers' efficacy, ability to cope and emotional regulation
Authors: Hoferichter Frances , Jentsch Armin 
Published: May 2024

AbstractPre‐service teachers have been identified as a risk group for developing burnout syndromes over the course of their careers due to increased perceived psychological distress and, in particular, if there is a lack of coping strategies. To provide pre‐service teachers with appropriate techniques and concepts that can be successfully applied in educational and work contexts, an online positive psychology intervention was designed to improve participants' resilience, in particular their self‐efficacy, emotion regulation and ability to cope. Linear mixed models that simultaneously analyse variability between subjects and over time revealed that pre‐service teachers who participated in the intervention benefited from the programme with respect to an increase of their emotion regulation strategies, self‐efficacy and ability to cope compared to the control group—although at baseline, they exhibited less beneficial emotion regulation, self‐efficacy and ability to cope. The findings suggest that such positive psychology interventions could help pre‐service teachers build their resilience.
Using the Performance Diagnostic Checklist‐Human Services to assess and increase teacher token delivery
Authors: Hoffmann Audrey N. , Pastina Colleen 
Published: May 2024

AbstractStaff implementation fidelity of behavioral interventions is an ongoing challenge in many educational settings. The Performance Diagnostic Checklist‐Human Services (PDC‐HS) is one tool that may be effective in identifying effective solutions to identified staff performance issues. This study examined the use of the PDC‐HS to assess and identify interventions for increasing staff delivery of token reinforcers within a Positive Behavior Interventions and Supports (PBIS) school‐wide system. Participants included five classroom teachers, ranging from 2 to 22 years of teaching experience. A concurrent multiple baseline design across participants was used including a baseline condition, implementation of a non‐indicated intervention based on the PDC‐HS, and implementation of a PDC‐HS indicated intervention. The number of teacher‐delivered tokens per school day was measured across the study. Results indicated participants' daily number of delivered tokens increased following implementation of the PDC‐HS indicated intervention.
A dynamic nomogram for predicting pathologic complete response to neoadjuvant chemotherapy in locally advanced rectal cancer
Authors: Wang Guancong , Li Jiasen , Huang Ying , Guo Yincong 
Published: May 2024

AbstractAimTo explore the clinical factors associated with pathologic complete response (pCR) for locally advanced rectal cancer (LARC) patients treated with neoadjuvant chemoradiotherapy (nCRT) and develop a web‐based dynamic nomogram.MethodsRetrospective analysis of patients with examination confirmed LARC from 2011 to 2022. Patients from the Union Hospital of Fujian Medical University were included as the training cohort (n = 1579) and Zhangzhou Hospital of Fujian Medical University as the external validation cohort (n = 246).ResultsIn the training cohort, after nCRT, 350 (22.2%) patients achieved pCR. More stomas were avoided in pCR patients (73.9% vs. 69.7%, p = 0.043). After a median follow‐up time of 47.7 months (IQR 2–145) shown OS (5‐year: 93.7% vs. 81.0%, HR = 0.310, 95%CI: 0.189–0.510, p < 0.001) and DFS (5‐year: 91.2% vs. 75.0%, HR = 0.204, 95%CI: 0.216–0.484, p < 0.001) were significantly better among patients with pCR than non‐pCR. Multivariable Logistic analysis shown pCR was significantly associated with Pre‐CRT CEA (HR = 0.944, 95%CI: 0.921–0.968; p < 0.001), histopathology (HR = 4.608, 95%CI: 2.625–8.089; p < 0.001), Pre‐CRT T stage (HR = 0.793, 95%CI: 0.634–0.993; p = 0.043), Pre‐CRT N stage (HR = 0.727, 95%CI: 0.606–0.873; p = 0.001), Pre‐CRT MRI EMVI (HR = 0.352, 95%CI: 0.262–0.473; p < 0.001), total neoadjuvant therapy (HR = 2.264, 95%CI: 1.280–4.004; p = 0.005). Meanwhile, the online version of the nomogram established in this study was publicized on an open‐access website (URL: https://pcrpredict.shinyapps.io/LARC2/). The model predicted accuracy with a C‐index of 0.73 (95% CI: 0.70–0.75), with an average C‐index of 0.73 for the internal cross validation and 0.78 (95% CI: 0.72–0.83) for the external validation cohort, showing excellent model accuracy. Delong test results showed the model has an important gain value for clinical characteristics to predict pCR in rectal cancer.ConclusionsPatients with pCR had a better prognosis, including OS and DFS, and were independently associated with Pre‐CRT CEA, histopathology, Pre‐CRT T/N stage, Pre‐CRT MRI EMVI, and TNT. A web‐based dynamic nomogram was successfully established for clinical use at any time.