bluuebunny/crossref_metadata_2025_split huggingface dataset:
On the Mechanism of Solvents Catalyzed Structural Transformation in Metal Halide Perovskites
Authors: Xi Jun , Jiang Junke , Duim Herman , Chen Lijun , You Jiaxue , Portale Giuseppe , Liu Shengzhong (Frank) , Tao Shuxia , Loi Maria Antonietta 
Published: June 2023

AbstractMetal halide perovskites show the capability of performing structural transformation, allowing the formation of functional heterostructures. Unfortunately, the elusive mechanism governing these transformations limits their technological application. Herein, the mechanism of 2D–3D structural transformation is unraveled as catalyzed by solvents. By combining a spatial‐temporal cation interdiffusivity simulation with experimental findings, it is validated that, protic solvents foster the dissociation degree of formadinium iodide (FAI) via dynamic hydrogen bond, then the stronger hydrogen bond of phenylethylamine (PEA) cation with selected solvents compared to dissociated FA cation facilitates 2D–3D transformation from (PEA)2PbI4 to FAPbI3. It is discovered that, the energy barrier of PEA out‐diffusion and the lateral transition barrier of inorganic slab are diminished. For 2D films the protic solvents catalyze grain centers (GCs) and grain boundaries (GBs) transforme into 3D phases and quasi‐2D phases, respectively. While in the solvent‐free case, GCs transform into 3D–2D heterostructures along the direction perpendicular to the substrate, and most GBs evolve into 3D phases. Finally, memristor devices fabricated using the transformed films uncover that, GBs composed of 3D phases are more prone to ion migration. This work elucidates the fundamental mechanism of structural transformation in metal halide perovskites, allowing their use to fabricate complex heterostructures.
Strategic Management of High‐Lying Triplet Excitons to Realize the Breakthrough in Efficiency of Blue Fluorescence OLEDs Based on AIE Emitter
Authors: Lin Chengwei , Han Pengbo , Qu Fenlan , Xiao Shu , Qiao Xianfeng , Yang Dezhi , Dai Yanfeng , Sun Qian , Qin Anjun , Tang Ben Zhong , Ma Dongge 
Published: June 2023

AbstractAggregation‐induced emission (AIE) materials are attractive for the fabrication of high‐efficiency organic light‐emitting diodes (OLEDs) owing to the “hot exciton” process by reverse intersystem crossing (hRISC) and high photoluminescence quantum yields (PLQY). However, the internal conversion (IC) from the high‐lying triplet excitation states (Tn, n≥2) to the lower excited triplet state (Tn‐1) is inevitable, resulting in severe exciton losses. Herein, an effective device structure is designed that reuses the lost triplet excitons caused by IC and realizes the breakthrough in the efficiency of blue fluorescence OLEDs based on AIE molecule as an emitter. The maximum external quantum efficiency reached as high as 14.8% and is kept at 14.4% at the luminance of 1000 cd m−2. In the designed device, a triplet–triplet annihilation (TTA) up‐conversion material 1‐[2,5‐dimethyl‐4‐(1‐pyrenyl)phenyl]pyrene (DMPPP) is introduced into the AIE emitter as a triplet sensitizer to receive the lost triplet excitons, and a thin TTA up‐conversion layer 9‐[4‐(10‐phenyl‐9‐anthryl)phenyl]‐9H‐carbazole (CzPA) is introduced in the middle of the doped layer to form the emissive layer (EML). It is found that the hRISC process of iTPB‐2AC greatly enhances the utilization efficiency of TTA intermediate state ([TT]*) excitons on CzPA to iTPB‐2AC so that the utilization of the lost excitons is maximized. This work establishes physical insights into the AIE emission materials and device fabrication of high‐efficiency blue fluorescence OLEDs.
Thiols as Powerful Atom Transfer Catalyst: Opportunities in Photoredox‐Mediated Reactions
Authors: Bao Xiaobo , Yu Wei , Wang Guoli 
Published: June 2023

AbstractThe employing visible light to drive organic transformations is the most promising choice to meet the needs for green synthesis, in which the reactions promoted by visible light may provide a more efficient and greener method. Currently, the most abundant methods for activation and functionalization of reaction substrates have relied on the direct single‐electron transfer (SET) between the excited photocatalyst and substrates, and these wonderful works were summarized and docoumented in many reviews. As a complement to the above reactions, the photoredox‐mediated atom transfer transformations (photocatalyst‐to‐HAT catalyst‐to‐substrates) to generate radical species are showing an explosively growing trend. In this review, we highlight recent significant developments in this rapidly growing area, mainly focusing on the photoinduced base‐to‐substrates charge transfer reactions.
Cation Disordered Anti‐Perovskite Cathode Materials with Enhanced Lithium Diffusion and Suppressed Phase Transition
Authors: Deng Zhi , Chen Diancheng , Ou Mingyang , Zhang Yuanpeng , Xu Jia , Ni Dixing , Ji Zhaoran , Han Jiantao , Sun Yang , Li Shuai , Ouyang Chuying , Wang Zhaoxiang 
Published: June 2023

AbstractRecently, a new family of anti‐perovskite Li2TMSO was discovered as promising cathode materials for Li‐ion batteries (LIBs) with superiorities in high specific capacity, low cost, and environmental friendliness. However, the applications of these anti‐perovskite materials meet severe challenges in the cyclability and rate performance. Herein, a cation‐disordered anti‐perovskite type solid solution Li2Fe1−xMnxSO (LFMSO, x = 0, 0.2, 0.5) with excellent electrochemical performance is reported. On the basis of comprehensive structural characterizations, the role of the cation disordering in LFMSO is clarified. In comparison with Li2FeSO (LFSO), the reduced Li‐ion diffusion barrier and the increased Li‐rich octahedral configurations in LFMSO with higher configurational entropy imply the facilitated long‐range Li‐ion diffusion and the suppressed phase transition, which favor the high‐rate capability and cycling stability. In addition, the large lattice distortion and Coulombic interaction between the anions and cations lead to the breathing of the unit cell during charge/discharge. The variation of the unit cell volume decreases to 2.5% upon Li‐ion delithiation. A superstructure is observed in LFMSO for the first time. These findings help to pave the way for the research and development of novel cathode materials for the next generation LIBs.
A Structurally Flexible Halide Solid Electrolyte with High Ionic Conductivity and Air Processability
Authors: Karkera Guruprakash , Soans Mervyn , Akbaş Ayça , Witter Raiker , Euchner Holger , Diemant Thomas , Cambaz Musa Ali , Meng Zhen , Dasari Bosubabu , Chandrappa Shivaraju Guddehalli , Menezes Prashanth W. , Fichtner Maximilian 
Published: June 2023

AbstractIn this work, a structurally revivable, chloride‐ion conducting solid electrolyte (SE), CsSn0.9In0.067Cl3, with a high ionic conductivity of 3.45 × 10−4 S cm−1 at 25 °C is investigated. The impedance spectroscopy, density functional theory, solid‐state 35Cl NMR, and electron paramagnetic resonance studies collectively reveal that the high Cl− ionic mobility originates in the flexibility of the structural building blocks, Sn/InCl6 octahedra. The vacancy‐dominated Cl− ion diffusion encompasses co‐ordinated Sn/In(Cl) site displacements that depend on the exact stoichiometry, and are accompanied by changes in the local magnetic moments. Owing to these promising properties, the suitability of the CsSn0.9In0.067Cl3, as an electrolyte is demonstrated by designing all‐solid‐state batteries, with different anodes and cathodes. The comparative investigation of interphases with Li, Li–In, Mg, and Ca anodes reveals different levels of reactivity and interphase formation. The CsSn0.9In0.067Cl3 demonstrates an excellent humidity tolerance (up to 50% relative humidity) in ambient air, maintaining high structural integrity without compromises in ionic conductivity, which stands in contrast to commercial halide‐based lithium conductors. The discovery of a halide perovskite conductor, with air processability and structure revival ability paves the way for the development of advanced air processable SEs, for next‐generation batteries.
Activating Amorphous Ru Metallenes Through Co Integration for Enhanced Water Electrolysis
Authors: Jose Vishal , Do Viet‐Hung , Prabhu P , Peng Chun‐Kuo , Chen San‐Yuan , Zhou Yingtang , Lin Yan‐Gu , Lee Jong‐Min 
Published: June 2023

AbstractDesigning efficient bifunctional electrocatalysts with excellent activity and robust stability presents a central challenge for the large‐scale commercialization of water electrolysis. Herein, a facile approach is reported for the construct of atomically thin amorphous RuM (MCo, Fe, or Ni) bimetallenes as high‐performance electrocatalysts toward both electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The RuCo bimetallene manifests excellent bifunctional activity characterized by low required overpotentials, superior price activity, robust electrochemical durability as well as a low cell potential water splitting performance, outperforming Pt/C and RuO2 benchmark catalysts. Combined operando X‐ray absorption spectroscopy investigation and theoretical simulations reveal the synergism taking place between binary constituents, in which Co serves a promotive role along the HER/OER reaction pathway, contributing via optimal binding to *OH for facile water dissociation as well as modulating the Ru electronic structure favorably, hence rendering high activity catalytic centers for both the alkaline HER and OER.
Preoperative neoadjuvant chemoradiotherapy provides borderline resectable thoracic esophageal cancer with equivalent treatment results as clinically T3 thoracic esophageal cancer
Authors: Wakita Akiyuki , Motoyama Satoru , Sato Yusuke , Nagaki Yushi , Fujita Hiromu , Kemuriyama Kohei , Hayashi Kenjiro , Imai Kazuhiro , Nanjo Hiroshi , Minamiya Yoshihiro 
Published: June 2023

AbstractAimBecause the optimal treatment strategy for borderline resectable (cT3br) thoracic esophageal cancer patients remains unclear, it is of great interest whether preoperative neoadjuvant therapy for cT3br could achieve results comparable to those seen with resectable T3 cancer (cT3r). We speculated that preoperative neoadjuvant chemoradiotherapy (NACRT) would be particularly effective in cT3br thoracic esophageal cancer patients and compared to cT3br and cT3r.MethodsOf 186 cT3 thoracic esophageal cancer patients treated with intended NACRT, 162 received radical esophagectomy. More than 97% were squamous cell carcinomas. Patients were partitioned into two groups according to whether invasion of adjacent organs was suspected (cT3br and cT3r). Treatment outcomes and survival were analyzed.ResultsSixty‐eight patients (36.6%) were classified as cT3br and 118 (63.4%) as cT3r. The cT3br group had significantly more tumors in the upper and middle mediastinum (p < 0.0001) and more cases with cM1 (lymph node) (p = 0.0104) than the cT3r group. In addition, the cT3br patients receiving esophagectomy exhibited a significantly lower pathological complete response rate than the cT3r patients (p = 0.0374). However, the R0 resection rate did not differ between the cT3br and cT3r patients (p = 0.0978), and the two groups treated with intended NACRT had similar 5‐year overall (OS) and disease‐specific survival (DSS) (p = 0.3831 and p = 0.9020). In addition, the incidence and patterns of recurrence did not differ between the cT3br and cT3r patients receiving esophagectomy (p = 0.8109 and p = 0.3128).ConclusionsPreoperative neoadjuvant chemoradiotherapy appears to be a promising treatment for patients with borderline resectable thoracic esophageal squamous cell carcinoma.
Katalytische formale [2π+2σ]‐Cycloaddition von Aldehyden mit Bicyclobutanen: Zweckmäßiger Zugang zu polysubstituierten 2‐Oxabicyclo[2.1.1]hexanen
Authors: Liang Yujie , Paulus Fritz , Daniliuc Constantin G. , Glorius Frank 
Published: June 2023

AbstractDie Synthese von bicyclischen Gerüsten hat jüngst großes Interesse erregt, da diese als gesättigte Bioisostere von Benzoiden eine wichtige Rolle in der modernen Wirkstoffforschung spielen. In dieser Arbeit berichten wir über eine BF3‐katalysierte [2π+2σ]‐Cycloaddition von Aldehyden mit Bicyclo[1.1.0]butanen (BCBs), um polysubstituierte 2‐Oxabicyclo[2.1.1]hexane zu synthetisieren. Zu diesem Zweck wurde ein neuartiges BCB entwickelt, das eine Acylpyrazolgruppe enthält, die nicht nur die Reaktionen erheblich erleichtert, sondern auch als Ansatzpunkt für verschiedene nachfolgende Transformationen dienen kann. Darüber hinaus können auch Aryl‐ und Vinylepoxide als Substrate verwendet werden, die nach der in situ‐Umlagerung zu Aldehyden eine Cycloaddition mit BCBs durchlaufen. Wir erwarten, dass unsere Ergebnisse den Zugang zu herausfordernden sp3‐reichen bicyclischen Gerüsten erleichtern und die Erforschung der BCB‐basierten Cycloadditionschemie fördern werden.
Activation of Bulk Li2S as Cathode Material for Lithium‐Sulfur Batteries through Organochalcogenide‐Based Redox Mediation Chemistry
Authors: Fan Qianqian , Si Yubing , Zhu Fulong , Guo Wei , Fu Yongzhu 
Published: June 2023

AbstractLithium sulfide (Li2S) is considered as a promising cathode material for sulfur‐based batteries. However, its activation remains to be one of the key challenges against its commercialization. The extraction of Li+ from bulk Li2S has a high activation energy (Ea) barrier, which is fundamentally responsible for the initial large overpotential. Herein, a systematic investigation of accelerated bulk Li2S oxidation reaction kinetics was studied by using organochalcogenide‐based redox mediators, in which phenyl ditelluride (PDTe) can significantly reduce the Ea of Li2S and lower the initial charge potential. Simultaneously, it can alleviate the polysulfides shuttling effect by covalently anchoring the soluble polysulfides and converting them into insoluble lithium phenyl tellusulfides (PhTe‐SxLi, x>1). This alters the redox pathway and accelerates the reaction kinetics of Li2S cathode. Consequently, the Li||Li2S‐PDTe cell shows excellent rate capability and enhanced cycling stability. The Si||Li2S‐PDTe full cell delivers a considerable capacity of 953.5 mAh g−1 at 0.2 C.
Accelerated Multi‐step Sulfur Redox Reactions in Lithium‐Sulfur Batteries Enabled by Dual Defects in Metal‐Organic Framework‐based Catalysts
Authors: Wang Xin , Zhang Xiaomin , Zhao Yan , Luo Dan , Shui Lingling , Li Yebao , Ma Ge , Zhu Yaojie , Zhang Yongguang , Zhou Guofu , Yu Aiping , Chen Zhongwei 
Published: June 2023

AbstractThe sluggish sulfur redox kinetics and shuttle effect of lithium polysulfides (LiPSs) are recognized as the main obstacles to the practical applications of the lithium‐sulfur (Li−S) batteries. Accelerated conversion by catalysis can mitigate these issues, leading to enhanced Li−S performance. However, a catalyst with single active site cannot simultaneously accelerate multiple LiPSs conversion. Herein, we developed a novel dual‐defect (missing linker and missing cluster defects) metal–organic framework (MOF) as a new type of catalyst to achieve synergistic catalysis for the multi‐step conversion reaction of LiPSs. Electrochemical tests and first‐principle density functional theory (DFT) calculations revealed that different defects can realize targeted acceleration of stepwise reaction kinetics for LiPSs. Specifically, the missing linker defects can selectively accelerate the conversion of S8→Li2S4, while the missing cluster defects can catalyze the reaction of Li2S4→Li2S, so as to effectively inhibit the shuttle effect. Hence, the Li−S battery with an electrolyte to sulfur (E/S) ratio of 8.9 mL g−1 delivers a capacity of 1087 mAh g−1 at 0.2 C after 100 cycles. Even at high sulfur loading of 12.9 mg cm−2 and E/S=3.9 mL g−1, an areal capacity of 10.4 mAh cm−2 for 45 cycles can still be obtained.
Ruptene – Eine Familie von Terpenanaloga Erlaubt Einblicke in Cyclisierungsmechanismen durch Unterbrechung der Kaskade
Authors: Gu Binbin , Dickschat Jeroen S. 
Published: June 2023

AbstractDie terpenoiden Substratanaloga (7R)‐6,7‐Dihydrogeranylgeranyldiphosphat (6,7‐Dihydro‐GGPP) und (7R)‐6,7‐Dihydrogeranylfarnesyldiphosphat (6,7‐Dihydro‐GFPP) wurden ausgehend von (S)‐Citronellol synthetisiert und enzymatisch mit neun Diterpen‐ bzw. zwei Sesterterpen‐Synthasen umgewandelt. In zwei Fällen wurden die Substratanaloga in Cyclisierungsreaktionen, die denen des nativen Substrats GGPP entsprachen, zu Diterpenen umgesetzt, während in den anderen neun Fällen die Cyclisierungskaskade unterbrochen oder umgelenkt wurde, was zu Produkten führte, die als Ruptene bezeichnet wurden. Mehrere der isolierten Ruptene stellen Deprotonierungsprodukte kationischer Intermediate dar, die Analoga der Intermediate sind, die entlang der Cyclisierungskaskaden für die nativen Substrate GGPP oder GFPP vorgeschlagen werden, und geben so Einblicke in die komplexen Reaktionsmechanismen der durch Terpensynthasen vermittelten Biosynthese.
Catalytic Formal [2π+2σ] Cycloaddition of Aldehydes with Bicyclobutanes: Expedient Access to Polysubstituted 2‐Oxabicyclo[2.1.1]hexanes
Authors: Liang Yujie , Paulus Fritz , Daniliuc Constantin G. , Glorius Frank 
Published: June 2023

AbstractSynthesis of bicyclic scaffolds has attracted tremendous attention because they are playing an important role as saturated bioisosteres of benzenoids in modern drug discovery. Here, we report a BF3‐catalyzed [2π+2σ] cycloaddition of aldehydes with bicyclo[1.1.0]butanes (BCBs) to access polysubstituted 2‐oxabicyclo[2.1.1]hexanes. A new kind of BCB containing an acyl pyrazole group was invented, which not only significantly facilitates the reactions, but can also serve as a handle for diverse downstream transformations. Furthermore, aryl and vinyl epoxides can also be utilized as substrates which undergo cycloaddition with BCBs after in situ rearrangement to aldehydes. We anticipate that our results will promote access to challenging sp3‐rich bicyclic frameworks and the exploration of BCB‐based cycloaddition chemistry.
Fabrication and performance of phase change microcapsules with fatty acid monoglyceride based waterborne polyurethane as the shell
Authors: Ning Xin , Li Jian , Wang Chenyi , Ren Qiang 
Published: June 2023

AbstractPolyurethane phase change microcapsules (PU‐PCMs) with high encapsulation efficiency are fabricated with ethyl palmitate as the phase change material and fatty acid monoglyceride based waterborne polyurethane as the shell. The compositions and morphologies of microcapsules are characterized by Fourier transform infrared spectrometer (FT‐IR), field scanning electron microscope (FSEM) and laser particle size analyzer. The encapsulation efficiency and phase change performances of microcapsules are investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results show that PU‐PCMs have smooth surface and spherical shape and the size of about 300 nm. TGA and DSC results show that the encapsulation efficiency of ethyl palmitate in PU‐PCMs prepared with fatty acid monoglyceride is up to 92.3%, which is much higher than that of PU‐PCMs prepared with other diols. The fatty acid monoglyceride based polyurethane prepolymer has better affinity with ethyl palmite than polyurethane prepolymer prepared with other diols, which causes the high encapsulation efficiency of phase change materials. The result of DSC show that the melting enthalpy of fatty acid monoglyceride based PU‐PCMs is 81.6 J g−1and the phase change temperature is 26.75°C. After 200 heating/cooling cycle test, the phase change temperatures and shapes of microcapsules remain unchanged, which show that the microcapsules have good phase change stability. The temperature‐regulating performance and application of the PU‐PCMs in fabricating semi‐transparent temperature‐regulating glass are conducted and investigated. Results of these investigations indicate that PU‐PCMs fabricated from fatty acid monoglyceride show promising applications in heat‐energy storage and temperature‐regulation fields.
A metabarcoding protocol targeting two DNA regions to analyze root‐associated fungal communities in ferns and lycophytes
Authors: Guillen‐Otero Thais , Lee Soon‐Jae , Chen Cheng‐Wei , Szoevenyi Peter , Kessler Michael 
Published: June 2023

AbstractPremiseDetailed studies of the fungi associated with lycophytes and ferns provide crucial insights into the early evolution of land plants. However, most investigations to date have assessed fern–fungus interactions based only on visual root inspection. In the present research, we establish and evaluate a metabarcoding protocol to analyze the fungal communities associated with fern and lycophyte roots.MethodsWe used two primer pairs focused on the ITS rRNA region to screen the general fungal communities, and the 18S rRNA to target Glomeromycota fungi (i.e., arbuscular mycorrhizal fungi). To test these approaches, we collected and processed roots from 12 phylogenetically distant fern and lycophyte species.ResultsWe found marked compositional differences between the ITS and 18S data sets. While the ITS data set demonstrated the dominance of orders Glomerales (phylum Glomeromycota), Pleosporales, and Helotiales (both in phylum Ascomycota), the 18S data set revealed the greatest diversity of Glomeromycota. Non‐metric multidimensional scaling (NMDS) ordination suggested an important geographical effect in sample similarities.DiscussionThe ITS‐based approach is a reliable and effective method to analyze the fungal communities associated with fern and lycophyte roots. The 18S approach is more appropriate for studies focused on the detailed screening of arbuscular mycorrhizal fungi.
Using a health observance event to raise awareness: An assessment of World Birth Defects Day
Authors: Kleven Danielle L. , Mai Cara T. , Bermejo‐Sánchez Eva , Groisman Boris , Walani Salimah , Peck Jessica , Cosentino Viviana , Botto Lorenzo D. , Zezza Simonetta , Romitti Paul A. , Mastroiacovo Pierpaolo 
Published: June 2023

AbstractWorld Birth Defects Day (WorldBDDay), observed annually on March 3, was launched in 2015 to advocate for public health surveillance, research, and prevention of birth defects, along with improved care and treatment for affected individuals. Following its fifth observance in 2019, we assessed WorldBDDay by analyzing: (a) engagement and content of over 2000 WorldBDDay posts on Facebook, Twitter, and Instagram; (b) interview responses from 9 WorldBDDay charter (founding) organizations on their perceptions of strengths and areas for improvement for WorldBDDay; (c) survey responses from 61 WorldBDDay 2019 partner (participating) organizations on their WorldBDDay 2019 activities; and (d) post‐2019 social media engagement. Most social media posts (60%) occurred from organizations using Twitter (80% vs. 14% for Instagram and 6% for Facebook), although posts from individuals had higher levels of engagement (e.g., likes and comments). The highest engagement occurred for posts focused on general awareness, prevention, or events. Charter organizations reported the need for existing and new partner engagement, including a designated WorldBDDay contact for regular communication and coordination of activities and prepared prevention‐focused messaging. Partner organizations reported using the WorldBDDay toolkit, especially key messages and social media tips, and suggested expanding the toolkit with relevant resources. Post‐2019 Twitter engagement was lower than 2019 WorldBDDay (peak event) but showed similar reach to WorldBDDay events prior to 2019. Our assessment identified WorldBDDay health observance events as an important tool to support knowledge dissemination and global community engagement around birth defects. Moving forward, engagement with more individuals and organizations may improve the reach of WorldBDDay.