bluuebunny/crossref_metadata_2025_split huggingface dataset:
Enantioselective (3+2) Annulation of Donor‐Acceptor Cyclopropanes with Aldehydes and Ketones Catalyzed by Brønsted Bases
Authors: Obregón Erlaitz B. , Rost Louise G. , Kocemba Ida R. , Kristensen Anne , McLeod David A. , Jørgensen Karl Anker 
Published: July 2024

AbstractThe substituted tetrahydrofuran core is a structural motif in many biologically active and natural compounds. However, the scarcity of enantioselective methods developed towards its synthesis makes this field challenging and attractive to explore. Herein, the first Brønsted‐base catalyzed enantioselective (3+2) annulation of donor‐acceptor cyclopropanes with aldehydes and ketones affording enantioenriched 2,3,5‐substituted tetrahydrofurans is reported. The reaction concept is based on activation of racemic β‐cyclopropyl ketones by a chiral bifunctional Brønsted base which catalyzes the (3+2) annulation for a range of aldehydes and ketones. For aldehydes, the annulation furnished tetrahydrofurans in excellent yield, good diastereoselectivity and with excellent enantioselectivity up to >99 % ee. Surprisingly, aromatic aldehydes afforded the cis‐2,5‐substituted tetrahydrofurans as the major diastereoisomer, while for aliphatic aldehydes the trans‐cycloadduct was favored. The reaction also proceeds well for ketones affording spiro tetrahydrofurans in excellent yields and enantioselectivities (up to 99 % ee). Hammett studies have been conducted to elucidate the influence of the electronic nature of benzaldehydes on the stereoselectivity. Based on the diastereochemical outcome for the aldehydes, two reaction paths for aromatic and aliphatic aldehydes are proposed. Finally, two diastereoselective synthetic transformations have been conducted to demonstrate the synthetic potential of the obtained products.
Organic‐Inorganic Hybrid Cuprous‐Based Metal Halides with Unique Two‐Dimensional Crystal Structure for White Light‐Emitting Diodes
Authors: Meng Xuan , Jiang Junke , Yang Xinyu , Zhao Hongyuan , Meng Qichao , Bai Yunfei , Wang Qiujie , Song Jitao , Katan Claudine , Even Jacky , Yu William W. , Liu Feng 
Published: July 2024

AbstractTernary cuprous (Cu+)‐based metal halides, represented by cesium copper iodide (e.g., CsCu2I3 and Cs3Cu2I5), are garnering increasing interest for light‐emitting applications owing to their intrinsically high photoluminescence quantum yield and direct band gap. Toward electrically driven light‐emitting diodes (LEDs), it is highly desirable for the light emitters to have a high structural dimensionality as it may favor efficient electrical injection. However, unlike lead‐based halide perovskites whose light‐emitting units can be facilely arranged in three‐dimensional (3D) ways, to date, nearly all ternary Cu+‐based metal halides crystallize into 0D or 1D networks of Cu−X (X=Cl, Br, I) polyhedra, whereas 3D and even 2D structures remain mostly uncharted. Here, by employing a fluorinated organic cation, we report a new kind of ternary Cu+‐based metal halides, (DFPD)CuX2 (DFPD+=4,4‐difluoropiperidinium), which exhibits unique 2D layered crystal structure. Theoretical calculations reveal a highly dispersive conduction band of (DFPD)CuBr2, which is beneficial for charge carrier injection. It is also of particular significance to find that the 2D (DFPD)CuBr2 crystals show appealing properties, including improved ambient stability and an efficient warm white‐light emission, making it a promising candidate for single‐component lighting and display applications.
Molecular Editing of Pyrroles to Benzenes/Naphthalenes by N2O Deletion.
Authors: Xiao Wen‐jie , Li Cheng‐xin , Lv Jing‐yi , Xu Shan , Shi Wen‐xia , Su Xiao‐can , Xue Jia‐ying , Huang Bao‐qin , Zou Yong , Yan Ming , Zhang Xue‐jing 
Published: July 2024

AbstractMolecular editing promises to facilitate the rapid diversification of complex molecular architectures by rapidly and conveniently altering core frameworks. This approach has the potential to accelerate both drug discovery and total synthesis. In this study, we present a novel protocol for the molecular editing of pyrroles. Initially, N‐Boc pyrroles and alkynes are converted into N‐bridged compounds through a Diels–Alder reaction. These compounds then undergo deprotection of the Boc group, nitrosylation, and cheletropic N2O extrusion to yield benzene or naphthalene products. By using benzyne as a substrate, this method can be conceptually viewed as a fusion of skeletal editing of the pyrrole ring and site‐selective peripheral editing of the benzene ring. Furthermore, this proof‐of‐concept protocol has demonstrated its potential to transform the (hetero)arene motif from commercially available drugs, offering the possibility of generating new biologically active compounds.
Non‐Isocyanate Synthesis of Covalent Adaptable Networks Based on Dynamic Hindered Urea Bonds: Sequential Polymerization and Chemical Recycling
Authors: Lyu Jihong , Lee Seulchan , Bae Hyoung Eun , Jung Hyocheol , Park Young Il , Jin Young‐Jae , Jeong Ji‐Eun , Kim Jin Chul 
Published: July 2024

AbstractThe development of environmentally sustainable processes for polymer recycling is of paramount importance in the polymer industry. In particular, the implementation of chemical recycling for thermoset polymers via covalent adaptable networks (CANs), particularly those based on the dynamic hindered urea bond (HUB), has garnered intensive attention from both the academic and industrial sectors. This interest stems from its straightforward chemical structure and reaction mechanism, which are well‐suited for commercial polyurethane and polyurea applications. However, a substantial drawback of these CANs is the requisite use of toxic isocyanate curing agents for their synthesis. Herein, we propose a new HUB synthesis pathway involving thiazolidin‐2‐one and a hindered amine. This ring‐opening reaction facilitates the isocyanate‐free formation of a HUB and enables sequential reactions with acrylate and epoxide monomers via thiol–Michael and thiol–epoxy click chemistry. The CANs synthesized using this methodology exhibit superior reprocessability, chemical recyclability, and reutilizability, facilitated by specific catalytic and solvent conditions, through the reversible HUB, thiol–Michael addition, and transesterification processes.
Butadiene Sulfone Based Binary Deep Eutectic Electrolyte for High Performance Lithium Metal Batteries
Authors: Zhou Tiankun , Lei Chengjun , Li Jinye , Wang Huijian , Liu Tingting , He Xin , Liang Xiao 
Published: July 2024

AbstractDeep eutectic electrolytes (DEEs) have attracted significant interest due to the unique physiochemical properties, yet challenges persist in achieving satisfactory Li anode compatibility through a binary DEE formula. In this study, we introduce a nonflammable binary DEE electrolyte comprising of lithium bis(trifluoro‐methane‐sulfonyl)imide (LiTFSI) and solid butadiene sulfone (BdS), which demonstrates enhanced Li metal compatibility while exhibiting high Li+ ion migration number (0.52), ionic conductivity (1.48 mS ⋅ cm−1), wide electrochemical window (~4.5 V vs. Li/Li+) at room temperature. Experimental and theoretical results indicate that the Li compatibility derives from the formation of a LiF‐rich SEI, attributed to the undesirable adsorption and deformation of BdS on Li surface that facilitates the preferential reactions between LiTFSI and Li metal. This stable SEI effectively suppresses dendrites growth and gas evolution reactions, ensuring a long lifespan and high coulombic efficiency in both the Li||Li symmetric cells, Li||LiCoO2 and Li||LiNi0.8Co0.1Mn0.1O2 full cells. Moreover, the BdS eutectic strategy exhibit universal applicability to other metal such as Na and Zn by pairing with the corresponding TFSI‐based salts.
First Main‐Group Element Lewis Acid Thionyl Chloride Adduct and its Chemistry
Authors: Tölke Katharina , Porath Sven , Neumann Beate , Stammler Hans‐Georg , Hoge Berthold 
Published: July 2024

AbstractAlthough the adduct of aluminum trichloride with thionyl chloride has been reported, no thionyl chloride adduct of a main group element Lewis acid or organometallic compound has been structurally characterized. In this communication we present the synthesis and reactivity of the structurally ascertained adduct of thionyl chloride with tris(pentafluoroethyl)gallane as a representative of a main group element Lewis acid. Gallium and indium compounds with electron withdrawing groups, e.g. the pentafluoroethyl ligand, display versatile properties. While gallates and indates, [MR4]−, behave as weakly coordinating anions, neutral gallanes and indanes, MR3, are strong Lewis acids. Salts with the tetrakis(pentafluoroethyl)gallate and ‐indate, [M(C2F5)4]− (M=Ga, In), have recently been studied in detail. In contrast to this, work on the syntheses of the free Lewis superacids M(C2F5)3 (M=Ga, In) is scarce and underdeveloped. The hydrates [M(C2F5)3(OH2)2] proved to be suitable starting materials, particularly due to their thermal stability. Herein we report on synthesis and characterization of reactive adducts, [M(C2F5)3D], with the weak donor molecules (D) SOCl2 and Me3SiF. The effective Lewis acidities of Ga(C2F5)3 and In(C2F5)3 were experimentally determined by the (modified) Gutmann‐Beckett method and their catalytic potential is showcased.
An Organic Molecular Mimetic Metal‐Free Heterogeneous Catalyst for Electrocatalytic Alkyne Semihydrogenation
Authors: Song Ziyang , Yang Rong , Liu Xinyu , Zhang Bin , Wu Yongmeng 
Published: July 2024

AbstractThe direct construction of metal‐free catalysts on conductive substrates for electrocatalytic organic hydrogenation reactions is significant but still unexplored. Here, learning from the homogeneous molecular catalysts, an organic molecular mimetic metal‐free heterogeneous catalyst is designed and constructed in situ on a graphite flake electrode via a mild electrochemical oxidation‐reduction relay strategy. The as‐prepared −COOH‐ and −OH‐functionalized metal‐free catalyst exhibits an electrocatalytic alkyne semihydrogenation performance with a 72 % Faradaic efficiency, 99 % selectivity and 96 % yield of the alkene product, which is comparable to that of noble metal catalysts. The removal of these oxygen‐containing groups leads to negligible activity. The experimental and calculation results reveal that the origin of the high activity can be assigned to the −COOH and −OH groups on graphite. A flow electrolytic cell delivers ten grams of hydrogenated products with 81 % Faradaic efficiency. This metal‐free catalyst is also suitable for gas‐phase acetylene semihydrogenation and other electrocatalytic hydrogenation reactions.
Subsurface Single‐Atom Catalyst Enabled by Mechanochemical Synthesis for Oxidation Chemistry
Authors: Guan Xuze , Han Rong , Asakura Hiroyuki , Wang Bolun , Chen Lu , Yan Jay Hon Cheung , Guan Shaoliang , Keenan Luke , Hayama Shusaku , van Spronsen Matthijs A. , Held Georg , Zhang Jie , Gu Hao , Ren Yifei , Zhang Lun , Yao Zhangyi , Zhu Yujiang , Regoutz Anna , Tanaka Tsunehiro , Guo Yuzheng , Wang Feng Ryan 
Published: July 2024

AbstractSingle‐atom catalysts have garnered significant attention due to their exceptional atom utilization and unique properties. However, the practical application of these catalysts is often impeded by challenges such as sintering‐induced instability and poisoning of isolated atoms due to strong gas adsorption. In this study, we employed the mechanochemical method to insert single Cu atoms into the subsurface of Fe2O3 support. By manipulating the location of single atoms at the surface or subsurface, catalysts with distinct adsorption properties and reaction mechanisms can be achieved. It was observed that the subsurface Cu single atoms in Fe2O3 remained isolated under both oxidation and reduction environments, whereas surface Cu single atoms on Fe2O3 experienced sintering under reduction conditions. The unique properties of these subsurface single‐atom catalysts call for innovations and new understandings in catalyst design.
Correction of the cracking mechanism ratio in catalytic cracking process to characterize the thermal cracking reaction and realize highly sensitive identification of catalysts
Authors: Li Di , Dai Xiaojun , Shi Baozhen 
Published: July 2024

AbstractIn this work, we have specially carried out the catalytic cracking experiments of heavy distillate oil in the high temperature range of 500~700°C. The composition of dry gas generated in the catalytic cracking process was analyzed, with emphasis on the variation of yield of C1 and C2 products. Two cracking mechanism ratios (CMRs) were redefined by replacing the (C1 + C2) products in the traditional definition of CMR with CH4, and the feasibility of using them to characterize the thermal cracking reaction in the catalytic cracking process in the high temperature range was investigated. The results showed that CH4 was more sensitive to temperature than (C1 + C2) and it was feasible and more accurate to use CH4 instead of (C1 + C2) corrected R3 to characterize the thermal cracking reaction in the catalytic cracking process in the high temperature range. In addition, it was found that the corrected R3 had the effect of distinguishing and identifying catalysts.
Advanced, high‐performance thermo‐insulating plaster
Authors: Athanasiadi A. , Andrikopoulou M. , Smyrnioti M. , Georgiou Y. , Zamparas M. , Dracopoulos V. , Ioannides T. 
Published: July 2024

AbstractThe main purpose of many current studies regarding energy efficiency is the improvement of the thermal resistance of buildings. To fulfill this goal, the development of advanced insulating materials, to be incorporated in the building envelopes, is imperative. Aerogels are ultralight porous materials typically produced via the sol‐gel process followed by supercritical drying of the wet gel. They exhibit very high porosities and a mesoporous‐macroporous structure which endows aerogels with extremely low thermal conductivity. This makes them ideal candidates for ambient thermal insulation applications. However, the cost for aerogel insulation is considerably higher than the one of standard insulation products. In the present work, highly porous aerogel‐like materials based on silica and commercial novolac resin were developed and added to common mortars. The prepared materials were dried under ambient pressure to minimize the manufacturing cost. The bulk density of silica quasi‐aerogels was 0.03 g/cm3–0.09 g/cm3 and that of the novolac resin samples 0.09 g/cm3–0.21 g/cm3. The aerogels were incorporated in mortars and cured for 28 days before measurement of thermal conductivity. The values of the thermal conductivity coefficient of the measured samples were 0.047 W/m K–0.058 W/m K for the silica reinforced mortars and 0.036 W/m K–0.044 W/m K for the novolac reinforced ones.
Isolation management to protect threatened native galaxiid fish species: Lessons from Aotearoa New Zealand
Authors: Jolly Martha E. , Warburton Helen J. , Bowie Sjaan , Challies Edward , Jellyman Phillip G. , McIntosh Angus R. 
Published: July 2024

Abstract
The use of barriers in freshwater systems to mitigate invasions, known as isolation management, has been increasingly implemented as a protection strategy for native fish. Barriers are crucial for securing vulnerable populations, but much remains to be learnt about the drivers of success and the implications of deliberate fragmentation.
In Aotearoa‐New Zealand, henceforth Aotearoa, native non‐migratory galaxiid (NMG) fishes are characterized by a disproportionate number of threatened species with introduced salmonids (trout) identified as a key driver of NMG declines.
We conducted a qualitative review of barriers protecting NMG in Aotearoa, illustrating varying outcomes and current knowledge gaps with case studies. Barrier types ranged from natural bedrock waterfalls, shallow velocity chutes and drying reaches to deliberately engineered structures (known commonly as exclusion barriers). Barriers were typically located in headwater streams or spring systems. NMG species secured by fragmentation often have high conservation value and barriers are essential for their protection.
Despite the critical role of these barriers, the isolated NMG populations above them are at risk of stochastic extirpation, invasion, or re‐invasion. Exclusion barriers may restrict access to habitat for native migratory fish species and can sometimes alter or remove ideal mesohabitat from protected populations.
Overall, when using exclusion barriers, managers must assess extinction risk for individual populations by isolation or invasion, balancing benefits and consequences. However, these assessments are frequently based on incomplete data and hindered by lack of general understanding of the underpinning processes. Despite well‐documented benefits to NMG population survival, key knowledge gaps such as long‐term viability of isolated populations, combinations of physical barrier parameters conferring exclusion under all flow regimes and extent of habitat loss to other native species still exist.
Design, synthesis, and biological evaluation of naphthalene imidazo[1,2‐b]pyridazine hybrid derivatives as VEGFR selective inhibitors
Authors: Wang Shuang , Gan LinLing , Han Lei , Deng Ping , Li Yihao , He Dongxiao , Chi Haoze , Zhu Liwei , Li Yuehui , Long Rui , Gan Zongjie 
Published: July 2024

AbstractThe vascular endothelial growth factor receptor (VEGFR) is a receptor tyrosine kinase that is regarded as an emerging target for abnormal angiogenesis diseases. In this study, novel naphthalene imidazo[1,2‐b]pyridazine hybrids as VEGFR selective inhibitors were designed and synthesized using a scaffold hopping strategy based on ponatinib, a multitarget kinase inhibitor. Among the evaluated compounds, derivative 9k (WS‐011) demonstrated the most potent inhibitory potency against VEGFR‐2 (IC50 = 8.4 nM) and displayed superior VEGFR selectivity over a panel of 70 kinases compared with ponatinib. Furthermore, 9k possessed good cytotoxic effects on various cancer cell lines, especially the colon cancer HT‐29 cells, with an acceptable oral bioavailability. Moreover, 9k significantly inhibited the migration and invasion of human umbilical vein endothelial cells (HUVEC) cells and induced apoptosis through the upregulation of apoptotic proteins in HT‐29 cells. 9k also effectively suppressed the activation of VEGFR‐2 signaling pathways, which in turn inhibited the growth of HT‐29 cells and the tube formation of HUVECs in vitro. All of the findings revealed that 9k could be considered a promising antiangiogenesis lead that merits further investigation.
Soft drug inhibitors for the epigenetic targets lysine‐specific demethylase 1 and histone deacetylases
Authors: Seitz Johannes , Auth Marina , Prinz Tony , Hau Mirjam , Tzortzoglou Pavlos , Schulz‐Fincke Johannes , Schmidtkunz Karin , Baniahmad Adina A. , Willmann Dominica , Metzger Eric , Hein Lutz , Preissl Sebastian , Schüle Roland , Jung Manfred 
Published: July 2024

AbstractEpigenetic modulators such as lysine‐specific demethylase 1 (LSD1) and histone deacetylases (HDACs) are drug targets for cancer, neuropsychiatric disease, or inflammation, but inhibitors of these enzymes exhibit considerable side effects. For a potential local treatment with reduced systemic toxicity, we present here soft drug candidates as new LSD1 and HDAC inhibitors. A soft drug is a compound that is degraded in vivo to less active metabolites after having achieved its therapeutic function. This has been successfully applied for corticosteroids in the clinic, but soft drugs targeting epigenetic enzymes are scarce, with the HDAC inhibitor remetinostat being the only example. We have developed new methyl ester‐containing inhibitors targeting LSD1 or HDACs and compared the biological activities of these to their respective carboxylic acid cleavage products. In vitro activity assays, cellular experiments, and a stability assay identified potent HDAC and LSD1 soft drug candidates that are superior to their corresponding carboxylic acids in cellular models.
A new extended δ‐shock model with the consideration of shock magnitude
Authors: Lorvand Hamed , Eryilmaz Serkan 
Published: July 2024

AbstractIn this article, a new ‐shock model that takes into account the magnitude of shocks is introduced and studied from reliability perspective. According to the new model, the system breaks down if either a shock after non‐critical shock occurs in a time length less than or a shock after a critical shock occurs in a time length less than where . The distribution of the system's lifetime is studied for both discrete and continuous intershock time distributions. It is shown that a new model is useful to describe a certain cold standby repairable system.
Influences on androgen deprivation therapy prescribing before surgery in high‐risk prostate cancer
Authors: Dunsmore Jennifer , Duncan Eilidh , MacLennan Sara J. , N'Dow James , Cornford Philip , Esperto Francesco , Pavan Nicola , Ribal María J. , Roobol Monique J. , Skolarus Ted A. , MacLennan Steven 
Published: July 2024

AbstractObjectivesTo understand how best to further reduce the inappropriate use of pre‐surgical androgen deprivation therapy (ADT), we investigated the determinants (influences) of ADT prescribing in urologists in two European countries using an established behavioural science approach. Additionally, we sought to understand how resource limitations caused by COVID‐19 influenced this practice. Identification of key determinants, of undistributed and disrupted practice, will aid development of future strategies to reduce inappropriate ADT prescribing in current and future resource‐limited settings.Participants and MethodsWe conducted semi‐structured qualitative interviews with urologists practicing in Italy and the UK from February to July 2022. Interviews focussed on undisrupted (usual) practice and disrupted practice (changes made during COVID‐19 restrictions). Codes were generated inductively and were mapped to the 14 domains of the Theoretical Domains Framework. Relevant domains of influence were identified, and the similarities and differences between the UK and Italy were distinguished.ResultsWe identified 10 domains that were influential to ADT prescribing in the UK and eight in Italy. The role of guidance and evidence, the cancer care setting, the patients and the urologist's beliefs and experiences were identified as areas that were influential to ADT prescribing before surgery. Twenty‐one similarities and 22 differences between the UK and Italy, for usual and COVID‐19 practice, were identified across these 10 domains.ConclusionSimilarities and differences influencing ADT prescribing prior to surgery should be considered in behavioural strategy development and tailoring to reduce inappropriate ADT use. We gained an understanding of usual, undistributed care and resource‐limited or disrupted care due to COVID‐19 in two European countries. This gives an indication of how influences on ADT prescribing may change in future resource‐limited circumstances and where efforts can be focused now and in future.