bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cross‐Scale Process Intensification of Spindle CuO Supported Tungsten Single‐Atom Catalysts toward Enhanced Electrochemical Hydrogen Production
Authors: Chang Chaoqun , Li Xiaodong , Wei Shizhong , Zhao Yang , Gong Lihua , Zhang Yonghui , Liu Jian , Gong Feilong 
Published: October 2024

AbstractProcess intensification engineering of electrocatalysts is crucial to facilitate electrocatalytic reaction, while its cross‐scale modulation is of great challenge. Herein, the spindle CuO supported tungsten single‐atom catalysts (W SACs) with tunable mesoscale electric field and atomic‐scale coordination structure are reported toward enhanced electrochemical hydrogen evolution process. Finite element analysis indicates the mesoscale electric field can be enhanced by tailoring the tip angle of spindle configuration from 74° to 27°, enhancing hydrogen production rate by 5 times. Based on the density functional theory calculations, the configuration regulation also triggers the increase of coordination number of W–O, which increases charge transfer and downshifts d‐band center, stabilizing W sites and optimizing hydrogen desorption process. The optimized WSA/CuO‐27 exhibits much better hydrogen evolution activity (η100 = 94 mV) and stability (200 mA cm−2 for 120 h) than as‐prepared WSA/CuO‐56 and WSA/CuO‐74 analogues. Impressively, the anion exchange membrane electrolyzer fabricated with the WSA/CuO‐27 presents excellent activity comparable to that of commercial electrocatalysts, and also delivers an ultra‐low attenuation of 0.085 mA cm−2 h−1 at 300 mA cm−2 after continuous electrocatalysis for 120 h. This work inspires the design of high‐efficiency supported metal catalysts for electrochemical synthesis via the cross‐scale process intensification engineering.
KIF11 Variants Associated With Novel Renal System Involvement—Two Cases That Expand the Phenotypic Spectrum of Microcephaly With or Without Chorioretinopathy, Lymphedema, or Impaired Intellectual Development
Authors: Gonzalez Tessa , Tyler Rebecca C. , Schilter Kala F. , McCarrier Julie , Muriello Michael , Basel Donald , Reddi Honey V. 
Published: October 2024

ABSTRACTPathogenic variants in KIF11 are linked to microcephaly with or without chorioretinopathy, lymphedema, or impaired intellectual development (MCLMR). To our knowledge, renal phenotypes have not been described in the literature in association with KIF11‐related disorders. This study is a case report of two probands with heterozygous pathogenic variants in KIF11 who presented with the common clinical features of MCLMR but also had additional renal involvement not previously reported as associated phenotypes of MCLMR, elucidating phenotypic expansion of this syndrome.
Evaluation and treatment of rhinosinusitis with primary antibody deficiency in children: Evidence‐based review with recommendations
Authors: Makary Chadi A. , Azar Antoine , Gudis David , Crawford Anna , Hannikainen Paavali , Kim Jean , Joe Stephanie , Kimple Adam J. , Lam Kent , Lee Jivianne T. , Luong Amber U. , Marcus Sonya , McArdle Erica , Mullings Warren , Peppers Brian P. , Lewandrowski Callum , Lin Sandra Y. , Ramadan Hassan H. , Rose Austin S. , Ryan Lindsey , Toskala Elina , Baroody Fuad M. 
Published: October 2024

AbstractBackgroundThere is clear evidence that prevalence of primary antibody deficiency (PAD) is higher in children with chronic rhinosinusitis (CRS) than in the general population. The purpose of this multi‐institutional and multidisciplinary evidence‐based review with recommendations (EBRR) is to thoroughly review the literature on rhinosinusitis with PAD, summarize the existing evidence, and provide recommendations on the evaluation and management of rhinosinusitis in children with PAD.MethodsThe PubMed, Embase, and Cochrane databases were systematically reviewed from inception through December 2023. Studies on the evaluation and management of rhinosinusitis in PAD patients were included. An iterative review process was utilized in accordance with EBRR guidelines. Levels of evidence and recommendations on the evaluation and management principles for PAD were generated.ResultsA total of 50 studies were included in this evidence‐based review. These studies were evaluated on the incidence of PAD in rhinosinusitis patients, the incidence of rhinosinusitis in PAD patients, and on the different treatment modalities used and their outcome. The aggregate quality of evidence varied across the reviewed domains.ConclusionBased on the currently available evidence, the incidence of PAD in children with recalcitrant CRS can be significantly elevated. Despite the presence of multiple studies addressing rhinosinusitis and PAD, the level of evidence supporting different treatment options continues to be lacking. Optimal management requires a multidisciplinary approach through collaboration with clinical immunology. There is need for higher level studies that compare different treatments in children with PAD and rhinosinusitis.
Transient transition from Stable to Dissipative Assemblies in Response to the Spatiotemporal Availability of a Chemical Fuel
Authors: Kar Haridas , Chen Rui , Das Krishnendu , Prins Leonard J. 
Published: October 2024

AbstractThe transition from inactive to active matter implies a transition from thermodynamically stable to energy‐dissipating structures. Here, we show how the spatiotemporal availability of a chemical fuel causes a thermodynamically stable self‐assembled structure to transiently pass to an energy‐dissipating state. The system relies on the local injection of a weak affinity phosphodiester substrate into an agarose hydrogel containing surfactant‐based structures templated by ATP. Injection of substrate leads to the inclusion of additional surfactant molecules in the assemblies leading to the formation of catalytic hotspots for substrate conversion. After the local disappearance of the substrate as a result of chemical conversion and diffusion the assemblies spontaneously return to the stable state, which can be reactivated upon the injection of a new batch of fuel. The study illustrates how a dissipating self‐assembled system can cope with the intermittent availability of chemical energy without compromising long‐term structural stability.
NHC‐Catalyzed Aldimine Umpolung/6π‐Electrocyclization Cascade to Access Tetracyclic Dihydrochromeno Indoles
Authors: Das Rohan Chandra , Gupta Priyanshu , Chakraborty Sukriyo , Jindal Garima , Biju Akkattu T. 
Published: October 2024

AbstractThe umpolung of aldimines using N‐heterocyclic carbenes (NHCs) is less explored compared to the established polarity reversal of aldehydes. Described herein is an NHC‐catalyzed imine umpolung /6π‐electrocyclization cascade, which leads to the atom‐ and pot‐economic synthesis of biologically important dihydrochromeno indoles. For the first time, the nucleophilic aza‐Breslow intermediates have been intercepted with unactivated alkynes. Preliminary mechanistic and DFT studies shed light on the role of the phenolic −OH moiety in promoting the addition of the aza‐Breslow intermediate to the unactivated alkyne via an intramolecular proton transfer in a stepwise manner. DFT studies also support the regioselectivity preference for the 5‐exo‐dig cyclization pathway, leading to the exclusive formation of the indole products. Moreover, a comparison of Gibbs free energies provides insight into a thermodynamically preferred 6π‐electrocyclization over a competing oxa‐Michael pathway. Further, this strategy is applied to the formal synthesis of a Hepatitis C Virus (HCV) NS5A inhibitor in a step‐economical method.
Interception of Alkynyl Tetracoordinate Borons with Sulfur Electrophiles beyond the Zweifel Pathway
Authors: Ma Xingxing , An Yuanbiao , Li Luo , Cai Meihui , Song Qiuling 
Published: October 2024

AbstractZweifel reaction is a powerful strategy to construct olefins from alkenyl tetracoordinate borons in organoboron chemistry, however, it usually only involves one functional group migration and then undergoes an elimination process affording alkenes or alkynes exclusively. Herein, we disclose several intriguing interception of alkynyl tetracoordinate borons with sulfur electrophiles. Wherein, the substituted benzothiophenes are accessed by consecutive 1,2‐migrations and intramolecular electrophilic substitution, meanwhile, the challenging and elusive five/four‐membered boracycles are easily assembled, and an approach to alkenyl sulfides with good stereoselectivity was developed as well. Moreover, by adding readily available deuterium sources, the tetrasubstituted deuterated alkenyl sulfides with high deuteration rates are constructed. These protocols not only improve atom economy by prohibiting the elimination of Zweifel intermediate, but also enrich the reaction modes of alkynyl tetracoordinate borons achieving versatile value‐added sulfur‐containing molecules. Mechanistic investigations illustrate that dichlorosulfoxide (SOCl2) and dialkylaminosulfur trifluoride‐type reagents (DAST‐type) as surfur sources could promote dual 1,2‐aryl migration of alkynyl tetracoordinate borons, which are distinct from traditional Zweifel reaction, and the regulation of steric hindrance could also make four‐membered boracycles and alkenyl sulfides feasible. And these transformations feature novel reaction modes and unusual reaction mechanisms with valuable products in high efficiency.
A Tricyclic Framework with Integrated B←N and Cyano Dual Functionalization for Superior n‐Type Organic Electronics
Authors: Jiang Zhen , Liu Di , Wang Yang , Song Wei , Yan Dongsheng , Ge Ziyi , Liu Yunqi 
Published: October 2024

Abstractn‐Type conjugated polymers featuring low‐lying lowest unoccupied molecular orbital (LUMO) energy levels are essential for achieving high‐performance n‐type organic thin‐film transistors (OTFTs) and organic thermoelectrics (OTEs). However, the synthesis of acceptors with strong electron‐withdrawing characteristics presents a significant challenge. Herein, a peripheral functionalization strategy is employed on the tricyclic framework anthracene by introducing dual N,O‐bidentate BF2/B(CN)2 groups to enhance its electron‐withdrawing capability. This approach successfully navigates synthetic challenges, leading to the development of two novel acceptor building blocks: DBNF and DBNCN. Compared to the counterparts with a single N,O‐bidentate BF2/B(CN)2 moiety, DBNF and DBNCN exhibit an extended π‐backbone, enhanced molecular packing, and improved electron‐withdrawing properties. Utilizing these innovative acceptor monomers, copolymers, PDBNF and PDBNCN, are synthesized, which exhibit considerably suppressed LUMO ≈−4.0 eV. The deep LUMO of PDBNF together with its favourable bimodal packing orientation leads to remarkable electron mobility of 3.04 cm2 V−1 s−1 with improved stability in OTFTs. Importantly, efficient n‐doping in OTEs is achieved with PDBNCN, exhibiting exceptional conductivity of 95.5 S cm−1 and a maximum power factor of 147.8 μW m−1 K−2—among the highest reported for solution‐processed n‐type polymers. This work underscores the effectiveness of introducing dual B←N and cyano functionalities in attaining high‐performance n‐type plastic electronics.
A Fluorinated Imide‐Functionalized Arene Enabling a Wide Bandgap Polymer Donor for Record‐Efficiency All‐Polymer Solar Cells
Authors: An Mingwei , Liu Qian , Jeong Sang Young , Liu Bin , Huang Enmin , Liang Qiming , Li Henan , Zhang Guangye , Woo Han Young , Niu Li , Guo Xugang , Sun Huiliang 
Published: October 2024

AbstractAll‐polymer solar cells (all‐PSCs) present compelling advantages for commercial applications, including mechanical durability and optical and thermal stability. However, progress in developing high‐performance polymer donors has trailed behind the emergence of excellent polymer acceptors. In this study, we report a new electron‐deficient arene, fluorinated bithiophene imide (F‐BTI) and its polymer donor SA1, in which two fluorine atoms are introduced at the outer β‐positions in the thiophene rings of BTI to fine‐tune the energy levels and aggregation of the resulting polymers. SA1 exhibits a deep HOMO level of −5.51 eV, a wide bandgap of 1.81 eV and suitable miscibility with the polymer acceptor. Polymer chains incorporating F‐BTI result in a highly ordered π–π stacking and favorable phase‐separated morphology within the all‐polymer active layer. Thus, SA1 : PY‐IT‐based all‐PSCs exhibit an efficiency of 16.31 % with excellent stability, which is further enhanced to a record value of 19.33 % (certified: 19.17 %) by constructing ternary device. This work demonstrates that F‐BTI offers an effective route for developing new polymer materials with improved optoelectronic properties, and the emergence of F‐BTI will change the scenario in terms of developing polymer donor for high‐performance and stable all‐PSCs.
The Trifluorooxygenate Anion [OF3]−: Spectroscopic Evidence for a Binary, Hypervalent Oxygen Species
Authors: Meyer Deniz F. , Medel Robert , Riedel Sebastian 
Published: October 2024

AbstractExperimental evidence for hypervalent compounds of second‐row elements is still scarce in literature. Here, we present the first report of the long‐sought binary, hypervalent trifluorooxygenate anion [OF3]−. It was isolated in solid Ne matrices under cryogenic conditions after reacting oxygen difluoride with free fluoride ions from laser ablation of alkali metal fluorides MF (M=Li−Cs). VSEPR theory and calculations at the CCSD(T) level predict a C2v‐symmetric T‐shape structure with one short and two long O−F bond lengths in [OF3]−. This is confirmed experimentally by FTIR spectroscopy in combination with isotopic labeling. Analysis of the natural local molecular orbitals shows the presence of one 2c–2e and one 3c–4e bond each. Natural resonance theory indicates the importance of the stability of [OF2]⋅− for the stability of [OF3]−. Although free [OF2]⋅− was not detected, the species MOF2 (M=Na−Cs) could be observed in the same experiments, which are best described as contact ion pairs of M+[OF2]⋅−.
Benzylic C−H Radical Sulfation by Persulfates
Authors: Xia Zhen , Ye Zhongyao , Deng Ting , Tan Ze , Song Chunlang , Li Jiakun 
Published: October 2024

AbstractSulfation is a highly valuable pathological and physiological process, yet it is often underappreciated considering the rather difficult accessibility of organosulfates. O‐sulfonation (O−SO3), a conventional and still common way to make organosulfates, restricts its applicability to hydroxyl compounds and therein lies a major challenge of library construction. Here, we describe a benzylic C−H radical sulfation with persulfates via C−O bond formation. This strategy leverages modular control over the reactivity of persulfates and the stability of sulfate radicals by coutercations. K+/NH4+ stabilized sulfate radicals act as the oxidant to generate carbon‐centered radicals from substrates, and activation of persulfates by n‐NBu4+ provides O−O resource pool to facilitate C−OSO3− bond formation via a bimolecular homolytic substitution (SH2) process.
Organocatalytic Asymmetric Construction of 2,6‐Diazabicyclo‐[2.2.2]octanes by Harnessing the Potential of an 3‐Oxindolium Ion Intermediate
Authors: Yadav Jyothi , Patel Arun , Dolas Atul Jankiram , Iype Eldhose , Rangan Krishnan , Kumar Indresh 
Published: October 2024

AbstractDue to its structural complexity and intrinsic sensitivity of bridged aminal junction, 2,6‐diazabicyclo[2.2.2]octane (2,6‐DABCO) has remained a highly desirable target in synthetic chemistry. However, the asymmetric access to this unit is still insufficient and hampered by the need for meticulously created functionalities for intricate double aza‐cyclizations. Herein, we have developed a novel enantio‐ and diastereoselective protocol to access polycyclic chiral 2,6‐DABCOs under metal‐free conditions. This domino process involves the amine‐catalyzed [4+2] annulation between glutaraldehyde and 2‐arylindol‐3‐ones, followed by an acid‐mediated Pictet–Spengler reaction/intramolecular aza‐cyclization cascade sequence with tryptamine by trapping of in situ generated 3‐oxindolium ion intermediate for the first time. Overall, 2,6‐DABCOs fused with medicinally relevant scaffolds were isolated with good yield and excellent stereoselectivity by constructing five new bonds and four stereocenters in a one‐pot operation.
Impact of cellulose enrichment on castor oil polyurethane sheets: A path to greener materials
Authors: Mangal Mangal , Rao Chebrolu Venkateswara , Das Nipu Kumar , Bose Suryasarathi , Banerjee Tamal 
Published: October 2024

AbstractDue to the growing concern over the depletion of the global crude oil stock and environmental issues, the replacement of petroleum‐based polymers with environmentally benign alternatives derived from renewable resource has attracted great attention. In the current study, four different polyurethane (PU) sheets were synthesized from unmodified castor oil (CO) and hexamethylene diisocyanate (HDI), incorporating cellulose nanofibers (CNF) as a filler. The mixture consisting molar ratio of CO, HDI, and CNF in a ratio of 1:5:0.8 yielded the best results. This formulation achieved a tensile strength of 22.55 MPa and an elongation at break of 55.9%. Additionally, the resulting PU sheets exhibited excellent thermal properties, with a glass transition temperature (Tg) and melting temperature (Tm) that were notably enhanced, further highlighting the effectiveness of this specific mixture in producing high‐performance, bio‐based PUs. Fourier‐transform infrared spectroscopy (FTIR), thermal, and mechanical characterizations indicated that both reinforced and unreinforced PU exhibited properties within acceptable ranges. Given the bio‐based origins of CO and cellulose, the synthesized polymers are biodegradable and suitable for biomaterial applications. The study confirms that the bio‐based origins of CO and cellulose render synthesized polymers biodegradable, suitable for various biomaterial applications.
Controllability of nonlinear stochastic impulsive switched systems in Hilbert spaces
Authors: Ansari Shahin , Malik Muslim 
Published: October 2024

AbstractIn this paper, nonlinear first order stochastic switched control systems with non‐instantaneous impulses (NIIs) in infinite‐dimensional spaces are considered. Semigroup theory of linear operators and a fixed‐point approach are used to develop the main results. First, we present the mild solution for the proposed system. Then, we derive sufficient conditions to ensure the total controllability and trajectory controllability results. Further, to validate the study, we provide examples.
Characterising core body temperature response of free‐moving C57BL/6 mice to 1.95 GHz whole‐body radiofrequency‐electromagnetic fields
Authors: Sylvester Emma , Deng Chao , McIntosh Robert , Iskra Steve , Frankland John , McKenzie Raymond , Croft Rodney J. 
Published: October 2024

AbstractThe present study investigated the core body temperature (CBT) response of free‐moving adult male and female C57BL/6 mice, during and following a 2‐h exposure to 1.95 GHz RF‐EMF within custom‐built reverberation chambers, using temperature capsules implanted within the intraperitoneal cavity and data continuously logged and transmitted via radiotelemetry postexposure. Comparing RF‐EMF exposures (WBA‐SAR of 1.25, 2.5, 3.75, and 5 W/kg) to the sham‐exposed condition, we identified a peak in CBT within the first 16 min of RF‐EMF exposure (+0.15, +0.31, +0.24, +0.37°C at 1.25, 2.5, 3.75, and 5 W/kg respectively; statistically significant at WBA‐SAR ≥ 2.5 W/kg only), which largely dissipated for the remainder of the exposure period. Immediately before the end of exposure, only the CBT of the 5 W/kg condition was statistically differentiable from sham. Based on our findings, it is apparent that mice are able to effectively compensate for the increased thermal load at RF‐EMF strengths up to 5 W/kg. In addition, the elevated CBT at the end of the exposure period in the 5 W/kg condition was statistically significantly reduced compared to the sham condition immediately after RF‐EMF exposure ceased. This would indicate that measures of CBT following the end of an RF‐EMF exposure period may not reflect the actual change in the CBT of mice caused by RF‐EMF exposure in mice.
A High‐Throughput Drug Repurposing Strategy to Treat TBX2 and/or TBX3 Dependent Cancers
Authors: Bleloch Jenna S. , Lu Sizhu , Khan Saif Feroz , Serala Karabo , Seraia Elena , Millar Val , Ebner Daniel , Goding Colin , Prince Sharon 
Published: October 2024

ABSTRACTBackgroundThe highly homologous T‐box transcription factors TBX2 and TBX3 are critical for embryonic development, and their overexpression in postnatal tissues contributes to a wide range of malignancies, including melanoma and rhabdomyosarcoma. Importantly, when TBX2 and TBX3 are depleted in cancers where they are overexpressed, the malignant phenotype is inhibited, and they have therefore been regarded as druggable targets. However, the time and costs associated with de novo drug development are challenging and result in drugs that are costly, especially for patients in low‐ and middle‐income countries. In the current study, we therefore combined a targeted and drug repurposing approach to identify drugs that are expected to be more efficacious and cost‐effective with significantly reduced side effects.MethodsA high‐throughput cell‐based immunofluorescence screen was performed to identify drugs in the Pharmakon 1600 drug library that can negatively regulate TBX2 and/or TBX3 levels. “Hit” drugs were validated for their effect on TBX2/TBX3 levels and cytotoxicity in TBX2/TBX3‐dependent melanoma and rhabdomyosarcoma cells. To this end, immunofluorescence, western blotting, quantitative real‐time PCR, and MTT cell viability assays were performed.ResultsNiclosamide, piroctone olamine, and pyrvinium pamoate, were identified as TBX2 and/or TBX3‐targeting drugs, and they exhibited cytotoxicity in a TBX2/TBX3‐dependent manner. Furthermore, these “Hit” drugs were shown to induce senescence and/or apoptosis.ConclusionsNiclosamide, piroctone olamine, and pyrvinium pamoate are promising, cost‐effective therapeutic agents for the treatment of TBX2/TBX3‐dependent cancers.
Exploring the Potential of Enhanced Prognostic Performance of NCCN‐IPI in Diffuse Large B‐Cell Lymphoma by Integrating Tumor Microenvironment Markers: Stromal FOXC1 and Tumor pERK1/2 Expression
Authors: Kim Ji‐Ye , Kahttana Ibadullah , Yoon Hyonok , Chang Sunhee , Yoon Sun Och 
Published: October 2024

ABSTRACTBackgroundFOXC1 and ERK1‐2 are proteins implicated in aggressive biological behavior of various malignancies including lymphomas.Material and MethodsWe investigate the additive prognostic value of stromal FOXC1 expression and tumor phosphorylated ERK1‐2 (pERK1‐2) expression to the established National Comprehensive Cancer Network International Prognostic Index (NCCN‐IPI), in 92 diffuse large B‐cell lymphoma (DLBCL) cases. Multidimensional analysis using statistics and machine learning (ML) models assessed prognostic value of established clinicopathologic variables with stromal FOXC1 and tumor pERK1‐2 expressions.ResultsBoth high FOXC1 stroma group and high pERK1‐2 tumor group were significantly associated with shorter progression‐free survival (PFS) and overall survival (OS) compared with low group (p = 0.015, 0.034 and p = 0.025, 0.025 each respectively). In multivariable analysis, high FOXC1 stromal expression was an independent prognostic factor of OS (p = 0.037). The addition of stromal FOXC1 and tumor pERK1‐2 to the NCCN‐IPI score significantly improved prediction of time to death compared with NCCN‐IPI score alone (Harrell's C‐index = 0.801 vs. 0.764; p = 0.030). ML models reconfirmed the addition of stromal FOXC1 expression and tumor pERK1‐2 to NCCN‐IPI score had the highest C‐index (0.952) among combinations. Stromal FOXC1 and tumor pERK1‐2 were determinants of DLBCL prognosis, whose addition significantly improved prognostic performance of the NCCN‐IPI.