bluuebunny/crossref_metadata_2025_split huggingface dataset:
Covalent Organic Framework (COF) Derived Ni‐N‐C Catalysts for Electrochemical CO2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites
Authors: Li Changxia , Ju Wen , Vijay Sudarshan , Timoshenko Janis , Mou Kaiwen , Cullen David A. , Yang Jin , Wang Xingli , Pachfule Pradip , Brückner Sven , Jeon Hyo Sang , Haase Felix T. , Tsang Sze‐Chun , Rettenmaier Clara , Chan Karen , Cuenya Beatriz Roldan , Thomas Arne , Strasser Peter 
Published: February 2022

AbstractElectrochemical CO2 reduction is a potential approach to convert CO2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel‐nitrogen‐doped carbon (Ni‐N‐C) is an efficient catalyst for CO2 reduction to CO, and the single‐site Ni−Nx motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)‐derived Ni‐N‐C catalysts, for which the Ni−Nx content could be adjusted by the pyrolysis temperature. The combination of high‐angle annular dark‐field scanning transmission electron microscopy and extended X‐ray absorption fine structure evidenced the presence of Ni single‐sites, and quantitative X‐ray photoemission addressed the relation between active site density and turnover frequency.
A TMEDA–Iron Adduct Reaction Manifold in Iron‐Catalyzed C(sp2)−C(sp3) Cross‐Coupling Reactions
Authors: Bakas Nikki J. , Sears Jeffrey D. , Brennessel William W. , Neidig Michael L. 
Published: February 2022

AbstractHerein, we expand the current molecular‐level understanding of one of the most important and effective additives in iron‐catalyzed cross‐coupling reactions, N,N,N′,N′‐tetramethylethylenediamine (TMEDA). Focusing on relevant phenyl and ethyl Grignard reagents and slow nucleophile addition protocols commonly used in effective catalytic systems, TMEDA‐iron(II)‐aryl intermediates are identified via in situ spectroscopy, X‐ray crystallography, and detailed reaction studies to be a part of an iron(II)/(III)/(I) reaction cycle where radical recombination with FePhBr(TMEDA) (2Ph) results in selective product formation in high yield. These results differ from prior studies with mesityl Grignard reagent, where poor product selectivity and low catalytic performance can be attributed to homoleptic iron–ate species. Overall, this study represents a critical advance in how amine additives such as TMEDA can modulate selectivity and reactivity of organoiron species in cross‐coupling.
Frustrated Lewis Pair in Zeolite Cages for Alkane Activations
Authors: Chen Wei , Han Jingfeng , Wei Yingxu , Zheng Anmin 
Published: February 2022

AbstractThe frustrated Lewis pair (FLP) concept in homogeneous catalysis was extended to heterogeneous catalysis via the supramolecular system of FLP between deprotonated zeolite framework oxygens and confined carbocations in methanol‐to‐olefin (MTO) reactions. In this FLP, the polymethylbenzenium (PMB+) functioned as the Lewis acid to accept an electron pair, and the deprotonated framework oxygen site acted as the Lewis base to donate an electron pair. This FLP theoretically demonstrated the ability to undergo H2heterolysis and alkanes dehydrogenation, and this was further confirmed by gas chromatography–mass spectrometer (GC‐MS) catalytic experiments inside FLP‐containing chabazite zeolites. All these findings not only bring new recognition to the carbocation chemistry in zeolite cages but also put forward a new reaction pathway as one part of MTO reactions.
Palladium‐Catalyzed Tail‐to‐Tail Reductive Dimerization of Terminal Alkynes to 2,3‐Dibranched Butadienes
Authors: Guo Hongyu , Zhang Sheng , Li Yang , Yu Xiaoqiang , Feng Xiujuan , Yamamoto Yoshinori , Bao Ming 
Published: February 2022

AbstractThe palladium‐catalyzed tail‐to‐tail reductive dimerization of terminal alkynes is described for the first time. Aromatic terminal alkynes bearing diverse and sensitive functional groups as well as aliphatic terminal alkynes are efficiently transformed to 2,3‐dibranched butadienes. The key to achieve a selective tail‐to‐tail reductive dimerization reaction is to control appropriately the acidity of the reaction solution, which is accomplished by a combined use of pivalic acid and para‐toluenesulfonic acid. The tail‐to‐tail reductive dimerization reaction is proposed to proceed via a cationic alkenyl palladium intermediate under acidic conditions.
Highly Efficient Asymmetric Multiple Resonance Thermally Activated Delayed Fluorescence Emitter with EQE of 32.8 % and Extremely Low Efficiency Roll‐Off
Authors: Liu Futong , Cheng Zhuang , Jiang Yixuan , Gao Lei , Liu Hanxuan , Liu Hui , Feng Zijun , Lu Ping , Yang Wensheng 
Published: February 2022

AbstractMultiple resonance thermally activated delayed fluorescence (MR‐TADF) emitters show great potentials for high color purity organic light‐emitting diodes (OLEDs). However, the simultaneous realization of high photoluminescence quantum yield (PLQY) and high reverse intersystem crossing rate (kRISC) is still a formidable challenge. Herein, a novel asymmetric MR‐TADF emitter (2Cz‐PTZ‐BN) is designed that fully inherits the high PLQY and largekRISCvalues of the properly selected parent molecules. The resonating extended π‐skeleton with peripheral protection can achieve a high PLQY of 96 % and a fastkRISCof above 1.0×105 s−1, and boost the performance of corresponding pure green devices with an outstanding external quantum efficiency (EQE) of up to 32.8 % without utilizing any sensitizing hosts. Remarkably, the device sufficiently maintains a high EQE exceeding 23 % at a high luminance of 1000 cd m−2, representing the highest value for reported green MR‐TADF materials at the same luminescence.
Highly Enhanced Aromatics Selectivity by Coupling of Chloromethane and Carbon Monoxide over H‐ZSM‐5
Authors: Fang Xudong , Liu Hongchao , Chen Zhiyang , Liu Zhaopeng , Ding Xiangnong , Ni Youming , Zhu Wenliang , Liu Zhongmin 
Published: February 2022

AbstractThe transformation of methane into high value‐added chemicals such as aromatics provides a more desired approach towards sustainable chemistry but remains a critical challenge due to the low selectivity of aromatics and poor stability. Herein, we first report a coupling reaction of CH3Cl and CO (CCTA) based on methane conversion, which achieves extremely high aromatics selectivity (82.2 %) with the selectivity of BTX up to ca. 60 % over HZSM‐5. The promoting effects have been demonstrated on other zeolites especially 10‐membered rings (10 MR) zeolites. Multiple characterizations show that 2,3‐dimethyl‐2‐cyclopentene‐1‐one (DMCPO) is generated from acetyl groups and olefins. Furthermore, isotopic labeling analysis confirms that CO is inserted into the DMCPO and aromatics rings. A new aromatization mechanism is proposed, including the formation of the above intermediates, which conspicuously weakens the hydrogen transfer reaction, leading to a considerable increase of aromatics selectivity and a dramatic drop in alkanes.
Leveraging Electron‐Deficient Iminium Intermediates in a General Synthesis of Valuable Amines
Authors: Hsu Che‐Sheng , Gonçalves Carlos R. , Tona Veronica , Pons Amandine , Kaiser Marcel , Maulide Nuno 
Published: February 2022

AbstractThe development of reactions converting alkenes and alkynes into valuable building blocks remains one of the main goals of synthetic chemistry. Herein, we present the leveraging of highly electron‐deficient iminium ions, rare and fleeting intermediates, into a general amine synthesis. This enables the preparation of amines bearing e.g. valuable α‐trifluoromethyl moieties under mild conditions. This broad concept is highlighted by the late‐stage amination of quinine into a biologically interesting new analogue.
CO2‐Induced Exposure of the Intrinsic Magnetic Surface of BaTiO3 to Give Room‐Temperature Ferromagnetism
Authors: Gao Bo , Xu Song , Xu Qun 
Published: February 2022

AbstractPreparation of low‐dimensional ferromagnetic nanomaterials and investigation of their magnetic origin is critical to the exploration of novel materials with various applications such as data storage. Herein, non‐van der Waals (non‐vdW) BaTiO3 was successfully stripped to a low‐dimensional structure by treating the materials with supercritical CO2 (SC CO2). Under different CO2 pressures, SC CO2 selectively cleaves the covalent bonds of the bulk BaTiO3, leading to the exposure of various surfaces. After SC CO2 treatments, the BaTiO3 exhibits room‐temperature ferromagnetism, which is significantly stronger than conventional treatments. According to the experimental and theoretical investigations, the enhanced ferromagnetic property is attributed to the exposure of the intrinsic surfaces of BaTiO3.
Flexible Soft‐Solid Metal–Organic Framework Composite Membranes for H2/CO2 Separation
Authors: Shu Lun , Peng Yuan , Yao Rui , Song Hongling , Zhu Chenyu , Yang Weishen 
Published: February 2022

AbstractThe development of a facile strategy to construct defect‐free and flexible metal–organic framework (MOF)‐based membranes with high selectivity and good scalability holds great appeal. Here we report the fabrication of soft‐solid MOF composite membranes on polyvinylidene fluoride substrates. A representative membrane comprised of quasi‐vertically grown lamellar Zn2(Bim)4 (Bim=benzimidazolate) and lateral ultrathin polyamide film adhering to the MOF side facets. The straight interlayer galleries within unwrapped Zn2(Bim)4 acted as predominant pathways, while the polyamide served the function of defect elimination, synergistically inducing an unprecedented H2/CO2 selectivity of 1084 which set a new record for MOF‐based membranes. Separation performance was held constant after membrane rolling up into a tube with a diameter of 3 mm or folding and unfolding at 90° for 50 times. ZIF‐67 and ZIF‐8 composite membranes based on this strategy also realized extremely high H2/CO2 separation accuracies. These results, which demonstrate the intrinsic molecular sieving capability of MOFs, will promote the development of MOF‐based membranes in practical separation applications.
Halogen Bonding: A New Platform for Achieving Multi‐Stimuli‐Responsive Persistent Phosphorescence
Authors: Dai Wenbo , Niu Xiaowei , Wu Xinghui , Ren Yue , Zhang Yongfeng , Li Gengchen , Su Han , Lei Yunxiang , Xiao Jiawen , Shi Jianbing , Tong Bin , Cai Zhengxu , Dong Yuping 
Published: February 2022

AbstractMonotonous luminescence has always been a major factor limiting the application of organic room‐temperature phosphorescence (RTP) materials. Enhancing and regulating the intermolecular interactions between the host and guest is an effective strategy to achieve excellent phosphorescence performance. In this study, intermolecular halogen bonding (CN⋅⋅⋅Br) was introduced into the host–guest RTP system. The interaction promoted intersystem crossing and stabilized the triplet excitons, thus helping to achieve strong phosphorescence emission. In addition, the weak intermolecular interaction of halogen bonding is sensitive to external stimuli such as heat, mechanical force, and X‐rays. Therefore, the triplet excitons were easily quenched and colorimetric multi‐stimuli responsive behaviors were realized, which greatly enriched the luminescence functionality of the RTP materials. This method provides a new platform for the future design of responsive RTP materials based on weak intermolecular interactions between the host and guest molecules.
The synthesis and characterization of a magnetic histidine Schiff base palladium complex and its efficiency investigation in the nitroarene pollutants reduction and dyes degradation
Authors: Rafiee Fatemeh , Shirzadi Faezeh 
Published: January 2022

AbstractAt first, we prepared the chloropropyl‐modified Fe3O4@SiO2 nanoparticles and functionalized it with imidazole‐2carbaldehyde to provide an aldehyde functional group for the Schiff base formation with histidine amino acid. The nitrogen atoms of imidazole cycles, –C=N bonds, and –COOH groups of histidine could act as proper coordination positions for palladium complex formation. The obtained magnetic histidine Schiff base palladium complex (Fe3O4@SiO2@Im‐His@Pd) was characterized by fourier transform infrared (FT‐IR), field‐emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray (EDX), X‐ray diffraction (XRD), vibrating sample magnetometer (VSM) and inductively coupled plasma‐optical emission spectrometry (ICP‐OES) analysis. The prepared nanocomposite has shown good efficiency in the reduction of nitroarenes and dyes degradation under mild conditions at room temperature in short reaction times.
Design strategies of ZnO heterojunction arrays towards effective photovoltaic applications
Authors: Qiao Fen , Sun Kaiyue , Chu Huaqiang , Wang Junfeng , Xie Yi , Chen Liping , Yan Tingting 
Published: January 2022

AbstractZnO nanorods (NRs) heterojunction arrays have been widely used in photovoltaic cells owing to the outstanding photoelectrical chracteristics, high stability and low cost. The NRs arrays structure can integrate multiple functional components, so that it can exhibit more excellent physical and chemical properties that even independent components do not possess. The design of heterojunction nanostructures can effectively solve the problems of light absorption and carrier transport. First, the synthesis methods of ZnO NRs and their heterojunction arrays were systematically introduced, including traditional chemical vapor deposition (CVD), electrodeposition, hydrothermal method, and so on, the different structures and properties of ZnO NRs heterojunctions were analyzed. Then, the selected materials could be further processed and assembled into NRs array heterojunction with integrated functions were discussed. The strategies of maximizing energy conversion performance (structure optimization, heterojunction, surface plasmon resonance, and doping) were emphatically summarized. In addition, the research progress of ZnO NRs and their heterojunctions in photoelectric energy conversion system were summarized, and the application potential of combining nanostructure design with solar cells was summarized. Finally, the challenges and future development prospects of ZnO NRs and their heterojunction arrays in photovoltaic conversion were pointed out.
How carbon coating or continuous carbon pitch matrix influence the silicon electrode/electrolyte interfaces and the performance in Li‐ion batteries
Authors: Roland Aude , Fullenwarth Julien , Ledeuil Jean‐Bernard , Martinez Hervé , Louvain Nicolas , Monconduit Laure 
Published: January 2022

AbstractThe Si surface coating by carbon is an appealing strategy to improve both the electronic conductivity and to stabilize the solid electrolyte interphase (SEI). In the present study, the electrochemical performance comparison of three nanocrystalline silicon‐based electrodes confirms the advantage brought by the carbon presence either as coating or in a composite, to improve their performance in Li‐ion batteries (LIBs). To rationalize this behavior, a full study of the electrode/electrolyte interface was achieved through the analysis of the cumulated relative irreversible capacity and the impedance and X‐ray photoelectron spectroscopies measurements. The study highlighted that the carbon coating leads to more efficient and less resistive SEI than that formed on silicon or on the native oxide surface. The pitch carbon matrix offers the same advantages and avoids moreover the isolation of particles. The control of the Si/electrolyte interface has a crucial role in the performance of Si‐based electrodes as negative electrodes for LIB.
Investigation of the effect of group counselling based on schema therapy on academic expectation stress in high school students
Authors: Koçak Lokman , Çelik Eyüp 
Published: January 2022

AbstractThis research is a preliminary evaluation study to determine whether group counselling based on schema therapy has an effect on academic expectation stress in high school students. In this study, a 2 × 3 split‐plot design was used. The Academic Expectation Stress Inventory was applied for data collection purposes. The effect of group counselling based on schema therapy on academic expectation stress was tested using a two‐factor ANOVA for mixed measurements. As a result of the analysis, the intervention*time effect was found to be significant with regard to academic expectation stress. The findings obtained in the study reveal that group counselling based on schema therapy creates a significant decrease in adolescents' academic expectation stress level, and this decline continues, as shown in the follow‐up test. As a result, it can be said that the group counselling programme based on schema therapy, which was developed as a preliminary evaluation study, has the potential to reduce the academic expectation stress level of high school students.
Self‐expanding transcatheter aortic valve replacement in patients with extremely horizontal aortas
Authors: Zhou Dao , Chen Jun , Fan Jiaqi , Yidilisi Abuduwufuer , Dai Hanyi , Xu Yeming , Zhu Gangjie , Guo Yuchao , Wang Jian'an , Liu Xianbao 
Published: January 2022

AbstractObjectivesTo evaluate the feasibility of self‐expanding transcatheter aortic valve replacement (TAVR) in patients with aortic stenosis and extremely horizontal aortas (aortic angulation ≥70°).BackgroundAs TAVR using a self‐expanding prosthesis is an off‐label treatment for patients with extremely horizontal aortas, these patients are often excluded from randomized controlled trials involving self‐expanding TAVR.MethodsThis study enrolled 27 consecutive patients with extremely horizontal aortas who underwent self‐expanding TAVR for severe aortic stenosis.ResultsThe patients' average age was 76.4 years, with a median Society of Thoracic Surgeons score of 4.53%. The device success and 30‐day mortality rates were 66.7% and 7.4%, respectively. The sinotubular junction (STJ) was significantly smaller in the device success group (p = 0.001). The receiver operating characteristic curve analysis found that the area under the curve was 0.907 (95% confidence interval: 0.790–1.000, p = 0.001), validating the association between STJ diameter and device success. An optimal cutoff of 33.6 mm was determined using the Youden index, with a sensitivity and specificity of 88.9% and 77.8%, respectively. The device success rate was significantly higher (93.3% vs. 33.3%, p = 0.003) in patients with STJ diameters ≤33.6 mm (n = 15). In the subgroup analyses, severe valve calcification (n = 9) was associated with a higher incidence of moderate or severe paravalvular leakage (44.0% vs. 0%, p = 0.008), while a higher rate of second valve implantation (60.0% vs. 9.1%, p = 0.030) was found in patients with less than moderate valve calcification (n = 5).ConclusionSelf‐expanding TAVR could be suitable for patients with extremely horizontal aortas after careful preoperative evaluation.
Complication during robotic‐PCI: Iatrogenic guiding catheter dissection
Authors: Khokhar Arif A. , Zelias Aleksander , Zlahoda‐Huzior Adriana , Dudek Dariusz 
Published: January 2022

AbstractRobotic‐assisted percutaneous interventions (R‐PCI) is a revolutionary technology designed to improve operator safety and procedural precision. The second‐generation CorPath GRX (Corindus) R‐PCI platform allows operators to manipulate the guiding catheter using robotic joystick controls. We report a case where robotic guide catheter manipulation caused a dramatic left main stem dissection. We highlight important concepts learned following this complication.
Social deprivation index and ischemic events after percutaneous coronary intervention in patients with diabetes mellitus
Authors: Torabi Asad J. , Mshelbwala Fakilahyel S. , Hugenberg Daniel , Kovacs Richard J. , Kreutz Rolf P. 
Published: January 2022

AbstractThe aim of this study was to assess neighborhood‐based differences in outcomes of diabetics versus non‐diabetics undergoing percutaneous coronary interventions. Disparities in healthcare access impact long‐term outcomes in safety net populations. Diabetes mellitus (DM) is associated with worse clinical outcomes in patients with coronary artery disease (CAD) and may disproportionately impact patients with CAD from underserved populations. We created a geocoded retrospective cohort of patients who underwent percutaneous coronary intervention (PCI) at an urban safety net hospital in this single‐center cohort analysis. We evaluated long‐term ischemic events in diabetics versus nondiabetics through review of electronic medical records. Social deprivation index (SDI) was calculated based on US‐census tract level and stratified according to quintiles. Among 1002 patients, 46% (n = 463) were diabetic and among those 48% (n = 222) were in the highest quintile of SDI. Baseline and angiographic characteristics were similar among diabetic and nondiabetic subjects. Among diabetic patients, those in the highest SDI quintile had significantly higher risk of cardiovascular death and myocardial infarction as compared to those in the remaining quintiles (log rank: p = 0.029) (adjusted hazard's ratio: 1.72 [95% CI: 1.01–2.92], p = 0.04). There was no association of the SDI with outcomes in nondiabetic patients (log rank: p = 0.39). In an underserved population, patients with diabetes and high SDI demonstrate higher rates of adverse ischemic events and cardiovascular death during long‐term follow up after PCI. Further research examining the impact of disparities in healthcare access on outcomes after PCI in patients with diabetes is warranted.
Paving the Way for Reliable Alzheimer's Disease Blood Diagnosis by Quadruple Electrochemical Immunosensing
Authors: Valverde Alejandro , Gordón Pidal José M. , Montero‐Calle Ana , Arévalo Beatriz , Serafín Verónica , Calero Miguel , Moreno‐Guzmán María , López Miguel Ángel , Escarpa Alberto , Yáñez‐Sedeño Paloma , Barderas Rodrigo , Campuzano Susana , Pingarrón José M. 
Published: February 2022

AbstractAlzheimer's disease (AD), the most common neurodegenerative disorder, demands new cost‐effective and easy‐to‐use strategies for its reliable detection, mainly in the preclinical stages. Here, we report the first immunoplatform for the electrochemical multidetermination of four candidate protein biomarkers in blood, neurofilament light chain (NfL), Tau, phosphorylated Tau (p‐Tau) and TAR DNA‐Binding Protein 43 (TDP‐43). It involves implementation of sandwich‐type immunoassays and enzymatic labelling with horseradish peroxidase (HRP) on the surface of magnetic microbeads (MBs). Amperometric detection is performed after depositing the magnetic immunoconjugates on disposable quadruple transduction platforms by monitoring the enzymatic reduction of H2O2 mediated by hydroquinone (HQ). The immunoplatform achieved LOD values smaller than the content of target biomarkers in plasma of healthy subjects, with RSD values<5 %, and lower cost and shorter assay time (60–90 min) than other available methodologies and was applied to the analysis of plasma from healthy controls and AD patients.