bluuebunny/crossref_metadata_2025_split huggingface dataset:
Lewis Base Controlled (4+3) and (4+2) Annulations of MBH Carbonates with Benzofuran‐Derived Azadienes: Access to Highly Substituted Benzofuro[3,2‐b]Azepines and Spirotetrahydroquinolines
Authors: Wang Kai‐Kai , Li Ya‐Fei , Li Lan‐Xin , Yao Wei‐Wei , Li Yan‐Li , Bi Ran , Li Feng , He Xiao‐Long , Chen Rongxiang 
Published: August 2024

AbstractCatalyst‐controlled switchable (4+3) and (4+2) annulation reactions of Morita–Baylis–Hillman carbonates with benzofuran‐derived azadienes have been established. Employing PCy3 as the catalyst, the reaction could provide a variety of synthetically useful benzofuro[3,2‐b]azepines in good yields (80–92%) with excellent chemo‐ and regioselectivities via (4+3) cycloaddition reactions. Whereas changing the catalyst from PCy3 to DMAP, the chemo‐ and regioselectivities were switched to construct highly substituted spirotetrahydroquinoline scaffolds with three sequential stereocenters containing all‐carbon spiro‐quaternary stereocenters in excellent efficiency and diastereoselectivities (92–96% yields with all cases>25:1 dr) via (4+2) annulations. In addition, the synthetic utility of this method was further showcased by gram‐scale reactions and synthetic transformations of the product.
Unlocking the AhR Therapeutic Potential for Cystic Fibrosis With an Integrated Mucosal Platform for Drug Screening
Authors: Sardelli Lorenzo , Frasca Enrica , Garbero Valentina Olga , Butnarasu Cosmin , Affricano Alex , Medana Claudio , Visentin Sonja 
Published: August 2024

AbstractBacterial‐derived molecules are at the basis of bacteria–bacteria and bacteria–host communication. In the context of cystic fibrosis (CF), they are considered possible therapeutic molecules for their natural binding capability on the immunomodulatory cytoplasmic aryl hydrocarbon receptor (AhR). An exponentially growing number of bacteria‐derived molecules are identified as AhR activators, highlighting the need for systems to screen possible lead candidates. This challenge is addressed by applying an in vitro tool mimicking the two main barriers that potential AhR‐targeting drugs must overcome: the cytoplasmic membrane and the CF pathological mucus. A small dataset of AhR ligands with potential therapeutic applications is selected. The apparent permeability of bacterial‐derived molecules across a cellular membrane model is quantified and molecules capable of reaching the cytoplasmic target (AhR) are identified. In a second step, a CF in vitro mucus model is integrated with the phospholipid membrane and the impact of mucus on permeability is assessed. Overall, this study proposes an integrated mucosal platform as a suitable tool in the emerging field of postbiotics as a therapeutic strategy for CF. The mucosal platform can enable the rapid identification of molecules compatible with cytoplasmic targeting of AhR among candidate‐drug representatives.
Highly‐Sensitive and High Operating Range Fully‐Printed Humidity Sensors Based on BiFeO3/BiOCl Heterojunctions
Authors: Fourmont Paul , Vaussenat Fabrice , Gratuze Mathieu , Ross Caroline A. , Cloutier Sylvain G. 
Published: August 2024

AbstractFully‐printed humidity sensors based on BiFeO3/BiOCl heterojunctions fabricated using a two‐step process with serigraphic printing are reported. Most importantly, this unique sensor architecture provides a broader relative humidity sensing range compared to pristine BFO sensors due to a synergistic effect between dense networks of BiOCl nanosheets synthetized atop BFO powders. With surface‐to‐weight ratios reaching 7.75 m2 g−1, these heterostructures increase the sensitivity and operating range of BFO‐based humidity sensors. While previously reported BFO humidity sensors only detect relative humidities above 30%, The BFO/BiOCl heterojunctions can measure relative humidities as low as 15% due to their increased surface area. Optimal growth and packing of the BiOCl nanosheet/BFO powder heterostructure are achieved by tuning the loading of the BFO powder and simultaneously forming the BiOCl sheets by chemical etching and annealing of the BFO powder. Excellent performance of optimized sensors including tracking and monitoring different types of breathing are demonstrated while mounted on an oxygen mask.
Electrocatalytic Ammonia Oxidation to Nitrite and Nitrate with NiOOH‐Ni
Authors: Liu Hanwen , Yang Cheng‐Jie , Dong Chung‐Li , Wang Jiashu , Zhang Xin , Lyalin Andrey , Taketsugu Tetsuya , Chen Zhiqi , Guan Daqin , Xu Xiaomin , Shao Zongping , Huang Zhenguo 
Published: August 2024

AbstractAmmonia electrooxidation in aqueous solutions can be a highly energy‐efficient process in producing nitrate and nitrite while generating hydrogen under ambient conditions. However, the kinetics of this reaction are slow and the role of catalyst in facilitating ammonia electrooxidation is not well understood. In this study, a high‐performance NiOOH‐Ni catalyst is introduced for converting ammonia into nitrite with Faraday efficiency of up to 90.4% and nitrate production rate of 1 mg h−1 cm−2. By employing Operando techniques, the role of NiOOH catalyst is elucidated in the dynamic electrooxidation of ammonia. Density functional theory (DFT) calculations support experimental observations and reveal the mechanism of the electrochemical oxidation of ammonia to nitrite and nitrate. Overall, this research contributes to the development of a cost‐effective and highly efficient catalyst for large‐scale ammonia electrolysis, while shedding light on the underlying mechanism of the NiOOH catalyst in ammonia electrooxidation.
Mass transfer to a nanoelectrocatalyst
Authors: Robinson Klaudia Mata , Jordan Matthew , Wiesner Theodore F. 
Published: August 2024

AbstractThere are few studies of mass transfer to nanospheres (1 nm ≤ dp ≤ 100 nm). We have experimentally investigated the electrocatalytic reduction of hexacyanoferrate (III) to hexacyanoferrate (II) on gold nanospheres. The surface flux is insensitive to particle sizes of dp ≥ 30 nm and is essentially identical to that for a diffusion‐limited system. However, the measured fluxes in the range 5 nm ≤ dp ≤ 30 nm were one to three orders of magnitude smaller than predicted by a purely diffusion‐limited model. Using mathematical modeling, we evaluated six mechanisms affecting mass transfer to a nanoparticle in our experimental system. Among potential acceleratory effects, the curvature effect sharply increased the surface flux by a factor of 20. Other acceleratory effects of Brownian advection and enhanced surface reactivity played negligible roles, the latter due to screening by a charged stabilizing layer. Deceleratory effects of increased tortuosity by stabilizing layers and particle aggregation also played negligible roles. Electrostatic repulsion dominated mass transfer for dp ≤ 30 nm. This finding suggests tuning the charge and the tortuosity of the stabilizer layer to potentiate the flux will be useful in engineering nanosuspensions.
Modeling and experimental study on a photochemical microscale continuous oscillatory baffled reactor
Authors: Liu Peiwen , Zhu Weiping , Zhao Fang 
Published: August 2024

AbstractHerein, the first photochemical microscale continuous oscillatory baffled reactor, that is, Photo‐μCOBR, was designed and evaluated. Computational fluid dynamics simulations were used to optimize the key structural parameter and operating conditions. Then, the mixing process was simulated and the μCOBR was shown to be more than 23 times faster than the straight channel both under oscillating conditions. Finally, a glass Photo‐μCOBR was fabricated by femtosecond laser internal engraving technology, and the photocatalytic gas–liquid oxidation of dihydroartemisinic acid was performed. A yield of 65.9% was achieved in a residence time of ~120 s and at a gas–liquid flow rate ratio of 1:3 (vs. 18.6% in the capillary photomicroreactor under identical conditions). The results in this work offer guidelines for the design and operation of microscale COBRs, and the as‐fabricated Photo‐μCOBR displays good potential for gas–liquid photochemical reactions.
Little evidence for homoeologous gene conversion and homoeologous exchange events in Gossypium allopolyploids
Authors: Conover Justin L. , Grover Corrinne E. , Sharbrough Joel , Sloan Daniel B. , Peterson Daniel G. , Wendel Jonathan F. 
Published: August 2024

AbstractPremiseA complicating factor in analyzing allopolyploid genomes is the possibility of physical interactions between homoeologous chromosomes during meiosis, resulting in either crossover (homoeologous exchanges) or non‐crossover products (homoeologous gene conversion). Homoeologous gene conversion was first described in cotton by comparing SNP patterns in sequences from two diploid progenitors with those from the allopolyploid subgenomes. These analyses, however, did not explicitly consider other evolutionary scenarios that may give rise to similar SNP patterns as homoeologous gene conversion, creating uncertainties about the reality of the inferred gene conversion events.MethodsHere, we use an expanded phylogenetic sampling of high‐quality genome assemblies from seven allopolyploid Gossypium species (all derived from the same polyploidy event), four diploid species (two closely related to each subgenome), and a diploid outgroup to derive a robust method for identifying potential genomic regions of gene conversion and homoeologous exchange.ResultsWe found little evidence for homoeologous gene conversion in allopolyploid cottons, and that only two of the 40 best‐supported events were shared by more than one species. We did, however, reveal a single, shared homoeologous exchange event at one end of chromosome 1, which occurred shortly after allopolyploidization but prior to divergence of the descendant species.ConclusionsOverall, our analyses demonstrated that homoeologous gene conversion and homoeologous exchanges are uncommon in Gossypium, affecting between zero and 24 genes per subgenome (0.0–0.065%) across the seven species. More generally, we highlighted the potential problems of using simple four‐taxon tests to investigate patterns of homoeologous gene conversion in established allopolyploids.
Post‐operative outcomes of primary benign orbital tumor resection are independent of tumor size and morphology
Authors: Zhu Angela S. , Bartholomew Ryan A. , Zhao Yan , Mitchell Margaret B. , Bleier Benjamin S. , Ringel Barak 
Published: August 2024

Key points
Using 3D modeling, we studied the influence of orbital tumor morphology on post‐operative outcomes.
Orbital tumor volume did not influence postoperative complication rates.
Less spherical tumors may be correlated with a more extensive surgical approach.
Interfacial Electronic Interactions Promoted Activation for Nitrate Electroreduction to Ammonia over Ag‐Modified Co3O4
Authors: Fan Zhenhai , Cao Chunmei , Yang Xingchuan , Yuan Wenchuang , Qin Feiyang , Hu Yating , Sun Xiaobo , Liu Guoji , Tian Yun , Xu Li 
Published: August 2024

AbstractElectrocatalytic nitrate (NO3−) reduction to ammonia (NRA) offers a promising pathway for ammonia synthesis. The interfacial electronic interactions (IEIs) can regulate the physicochemical capabilities of catalysts in electrochemical applications, while the impact of IEIs on electrocatalytic NRA remains largely unexplored in current literature. In this study, the high‐efficiency electrode Ag‐modified Co3O4 (Ag1.5Co/CC) is prepared for NRA in neutral media, exhibiting an impressive nitrate conversion rate of 96.86 %, ammonia Faradaic efficiency of 96.11 %, and ammonia selectivity of ~100 %. Notably, the intrinsic activity of Ag1.5Co/CC is ~81 times that of Ag nanoparticles (Ag/CC). Multiple characterizations and theoretical computations confirm the presence of IEIs between Ag and Co3O4, which stabilize the CoO6 octahedrons within Co3O4 and significantly promote the adsorption of reactants (NO3−) as well as intermediates (NO2− and NO), while suppressing the Heyrovsky step, thereby improving nitrate electroreduction efficiency. Furthermore, our findings reveal a synergistic effect between different active sites that enables tandem catalysis for NRA: NO3− reduction to NO2− predominantly occurs at Ag sites while NO2− tends to hydrogenate to ammonia at Co sites. This study offers valuable insights for the development of high‐performance NRA electrocatalysts.
[19]Starphene: Combined In‐Solution and On‐Surface Synthesis Towards the Largest Starphene
Authors: Besteiro‐Sáez Javier , Mateo Luis M. , Salaverría Sergio , Wang Tao , Angulo‐Portugal Paula , Calupitan Jan Patrick , Rodríguez‐Fernández Jonathan , García‐Fuente Amador , Ferrer Jaime , Pérez Dolores , Corso Martina , de Oteyza Dimas G. , Peña Diego 
Published: August 2024

AbstractStarphenes are structurally appealing three‐fold symmetric polycyclic aromatic compounds with potential interesting applications in molecular electronics and nanotechnology. This family of star‐shaped polyarenes can be regarded as three acenes that are connected through a single benzene ring. In fact, just like acenes, unsubstituted large starphenes are poorly soluble and highly reactive molecules under ambient conditions making their synthesis difficult to achieve. Herein, we report two different synthetic strategies to obtain a starphene formed by 19 cata‐fused benzene rings distributed within three hexacene branches. This molecule, which is the largest starphene that has been obtained to date, was prepared by combining solution‐phase and on‐surface synthesis. [19]Starphene was characterized by high‐resolution scanning tunneling microscopy (STM) and spectroscopy (STS) showing a remarkable small HOMO‐LUMO transport gap (0.9 eV).
Catalytic Enantioselective Friedel–Crafts Allenylation
Authors: Das Priyotosh , Ghosh Debangshu , Mukherjee Santanu 
Published: August 2024

AbstractThe first enantioselective Friedel‐Crafts (FC) allenylation reaction for the creation of central chirality is developed under cooperative Ir(I)/(phosphoramidite,olefin) and Lewis acid catalysis. This enantioconvergent reaction utilizes racemic allenylic alcohol as the electrophile and shows compatibility with a variety of electron‐rich arenes and heteroarenes. The resulting highly enantioenriched (up to >99.5 : 0.5 e.r.) 1,1‐disubstituted allenylic methanes, bearing a benzylic carbon stereocenter, are obtained with complete regiocontrol – both on (hetero)arenes as well as on the allenylic fragment. This protocol allows for the enantioselective formal introduction of a 4‐carbon alkyl chain into (hetero)arenes, along with the creation of a benzylic stereocenter. Judicious synthetic elaborations not only lead to formal enantioselective FC alkylation products of less electron‐rich arenes but also of substituted arenes in ortho‐ and even meta‐selective fashion. An intramolecular version of this FC allenylation is shown to proceed with promising enantioselectivity under the same catalytic conditions. Mechanistic studies revealed the involvement of dynamic kinetic asymmetric transformation (DyKAT) of racemic allenylic alcohols in this reaction.
Development of Macrocyclic Neurotensin Receptor Type 2 (NTS2) Opioid‐Free Analgesics
Authors: Desgagné Michael , Chartier Magali , Lagard Camille , Ferková Sára , Choquette Mathieu , Longpré Jean‐Michel , Côté Jérôme , Boudreault Pierre‐Luc , Sarret Philippe 
Published: August 2024

AbstractThe opioid crisis has highlighted the urgent need to develop non‐opioid alternatives for managing pain, with an effective, safe, and non‐addictive pharmacotherapeutic profile. Using an extensive structure–activity relationship approach, here we have identified a new series of highly selective neurotensin receptor type 2 (NTS2) macrocyclic compounds that exert potent, opioid‐independent analgesia in various experimental pain models. To our knowledge, the constrained macrocycle in which the Ile12 residue of NT(7–12) was substituted by cyclopentylalanine, Pro7 and Pro10 were replaced by allyl‐glycine followed by side‐chain to side‐chain cyclization is the most selective analog targeting NTS2 identified to date (Ki 2.9 nM), showing 30,000‐fold selectivity over NTS1. Of particular importance, this macrocyclic analog is also able to potentiate the analgesic effects of morphine in a dose‐ and time‐dependent manner. Exerting complementary analgesic actions via distinct mechanisms of nociceptive transmission, NTS2‐selective macrocycles can therefore be exploited as opioid‐free analgesics or as opioid‐sparing therapeutics, offering superior pain relief with reduced adverse effects to pain patients.
Organocatalyzed Carbonylation of Alkyl Halides Driven by Visible Light
Authors: Liu Xin , Portela Brandon S. , Wiedenbeck Analiese , Chrisman Cameron H. , Paton Robert S. , Miyake Garret M. 
Published: August 2024

AbstractHerein, we describe a new strategy for the carbonylation of alkyl halides with different nucleophiles to generate valuable carbonyl derivatives under visible light irradiation. This method is mild, robust, highly selective, and proceeds under metal‐free conditions to prepare a range of structurally diverse esters and amides in good to excellent yields. In addition, we highlight the application of this activation strategy for 13C isotopic incorporation. We propose that the reaction proceeds by a photoinduced reduction to afford carbon‐centered radicals from alkyl halides, which undergo subsequent single electron‐oxidation to form a carbocationic intermediate. Carbon monoxide is trapped by the carbocation to generate an acylium cation, which can be attacked by a series of nucleophiles to give a range of carbonyl products.
Stereoselective Hydroxyallylation of Cyclopropenes with Cyclopropanols via NHC Catalysis of Transient Organozinc Species
Authors: Tsukiji Kento , Matsumoto Arimasa , Kanemoto Kazuya , Yoshikai Naohiko 
Published: August 2024

AbstractA stereoselective hydroxyallylation reaction of cyclopropenes with cyclopropanols is achieved under zinc‐mediated conditions, affording densely functionalized cyclopropanes with excellent diastereocontrol over three contiguous stereocenters within and outside the cyclopropane ring. A racemic variant of the reaction is synergistically promoted by catalytic N‐heterocyclic carbene (NHC) and organic base, whereas chiral amino alcohol‐derived bifunctional NHC enables a catalytic enantioselective variant. The reaction likely involves the generation of enolized zinc homoenolate via ring‐opening of zinc cyclopropoxide and enolization of the resulting homoenolate, followed by its addition to the cyclopropene as a prochiral allylzinc nucleophile. Our mechanistic investigations highlighted the transient nature of enolized homoenolate, which, once generated from thermodynamically predominant cyclopropoxide, immediately proceeds to allylzincation with cyclopropene. The NHC not only promotes the rate‐determining generation of enolized homoenolate but also engages in the allylzincation process. The resulting cyclopropylzinc species undergoes partial in situ protonation while partially remaining intact, thereby leaving an opportunity for trapping with an external electrophile.
A Metal–Sulfur–Carbon Catalyst Mimicking the Two‐Component Architecture of Nitrogenase
Authors: Xia Junkai , Xu Jiawei , Yu Bing , Liang Xiao , Qiu Zhen , Li Hao , Feng Huajun , Li Yongfu , Cai Yanjiang , Wei Haiyan , Li Haitao , Xiang Hai , Zhuang Zechao , Wang Dingsheng 
Published: August 2024

AbstractThe production of ammonia (NH3) from nitrogen sources involves competitive adsorption of different intermediates and multiple electron and proton transfers, presenting grand challenges in catalyst design. In nature nitrogenases reduce dinitrogen to NH3 using two component proteins, in which electrons and protons are delivered from Fe protein to the active site in MoFe protein for transfer to the bound N2. We draw inspiration from this structural enzymology, and design a two‐component metal–sulfur–carbon (M−S−C) catalyst composed of sulfur‐doped carbon‐supported ruthenium (Ru) single atoms (SAs) and nanoparticles (NPs) for the electrochemical reduction of nitrate (NO3−) to NH3. The catalyst demonstrates a remarkable NH3 yield rate of ~37 mg L−1 h−1 and a Faradaic efficiency of ~97 % for over 200 hours, outperforming those consisting solely of SAs or NPs, and even surpassing most reported electrocatalysts. Our experimental and theoretical investigations reveal the critical role of Ru SAs with the coordination of S in promoting the formation of the HONO intermediate and the subsequent reduction reaction over the NP‐surface nearby. Such process results in a more energetically accessible pathway for NO3− reduction on Ru NPs co‐existing with SAs. This study proves a better understanding of how M−S−Cs act as a synthetic nitrogenase mimic during ammonia synthesis, and contributes to the future mechanism‐based catalyst design.
Thiopentone‐based total intravenous anaesthesia for a patient with carnitine palmitoyltransferase II deficiency and malignant hyperthermia susceptibility
Authors: Essackjee Z. , Sloan G. 
Published: August 2024

SummaryIn this case report, we discuss the use of a thiopentone infusion for the maintenance of anaesthesia in a patient with confirmed malignant hyperthermia susceptibility and carnitine palmitoyltransferase 2 deficiency. The concurrence of both diagnoses precluded the use of both propofol‐based total intravenous anaesthesia and volatile inhalational anaesthesia. This patient had been anaesthetised previously with a triple infusion regimen of thiopentone, midazolam and remifentanil and this was a unique opportunity to compare the two instances. Electroencephalogram‐based depth of anaesthesia monitoring was in routine use by the time of the second anaesthetic, and thus, the thiopentone infusion could be adjusted accordingly, resulting in a more rapid emergence time. We hope that this case may serve as an example of suitable anaesthetic alternative should both propofol infusion and inhalational anaesthesia not be an option.
Research methods and the use of visual representation in library and information science research
Authors: Matusiak Krystyna K. , Osinska Veslava , Organisciak Peter , Thomas Pitts Robyn 
Published: August 2024

AbstractThe increasing variety of research strategies and data collection techniques in information science, the access to large secondary data sets, and the ubiquity of information visualization call for expanding the classification of research methods and exploring how research is communicated visually. This study examined the relationship between types of data used in empirical research, visualizations, and research methods applied in information science studies. It analyzed 751 research articles published in the Journal of the Association for Information Science and Technology (JASIST) using content analysis and machine learning techniques. The study finds that most empirical studies adopted a quantitative design with data mining, bibliometrics, experiments, and surveys as dominant strategies. The substantial use of secondary data points to the shift in how data are collected in empirical research. The JASIST articles used a variety of visualizations to present research designs and findings, with quantitative and mixed methods studies employing primarily tables and charts and qualitative studies relying more on tables and diagrams. This study uniquely explores the relationship between research methods and visualization. It contributes to the classification of the methods in information science by expanding the range of strategies within the quantitative, qualitative, and mixed methods designs.