bluuebunny/crossref_metadata_2025_split huggingface dataset:
Atomic Zincophilic Sites Regulating Microspace Electric Fields for Dendrite‐Free Zinc Anode
Authors: Fan Wenjie , Li Ping , Shi Jing , Chen Jingwei , Tian Weiqian , Wang Huanlei , Wu Jingyi , Yu Guihua 
Published: September 2023

AbstractAqueous Zn metal batteries are promising candidates for large‐scale energy storage due to their intrinsic advantages. However, Zn tends to deposit irregularly and forms dendrites driven by the uneven space electric field distribution near the Zn‐electrolyte interphase. Herein it is demonstrated that trace addition of Co single atom anchored carbon (denoted as CoSA/C) in the electrolyte regulates the microspace electric field at the Zn‐electrolyte interphase and unifies Zn deposition. Through preferential adsorption of CoSA/C on the Zn surface, the atomically dispersed Co‐N3 with strong charge polarization effect can redistribute the local space electric field and regulate ion flux. Moreover, the dynamic adsorption/desorption of CoSA/C upon plating/stripping offers sustainable long‐term regulation. Therefore, Zn||Zn symmetric cells with CoSA/C electrolyte additive deliver stable cycling up to 1600 h (corresponding to a cumulative plated capacity of 8 Ah cm−2) at a high current density of 10 mA cm−2, demonstrating the sustainable feature of microspace electric field regulation at high current density and capacity.
B(C6F5)3‐Catalyzed One‐Pot Tandem Diastereoselective Synthesis of cis‐2,3‐Disubstituted 1,2,3,4‐Tetrahydroquinoxalines and cis‐2,4‐Disubstituted 2,3,4,5‐Tetrahydro‐1H‐1,5‐benzodiazepines
Authors: Luo Zhenli , Yang Ji , Yao Zhen , Yang Jianbo , Xu Lijin , Shi Qian 
Published: September 2023

AbstractB(C6F5)3‐catalyzed one‐pot tandem cyclization/hydrosilylation of easily accessible 1,2‐diaminobenzenes and 1,2‐ and 1,3‐diketones with polymethylhydrosiloxane (PMHS) has been developed for step‐economic diastereoselective synthesis of cis‐2,3‐disubstituted 1,2,3,4‐tetrahydroquinoxalines and cis‐2,4‐disubstituted 2,3,4,5‐tetrahydro‐1H‐1,5‐benzodiazepines. This metal‐free catalytic protocol provides access to various differently substituted products in 53–95% yield and with diastereoselectivities ranging from 6:1 to 20:1. The diastereoselectivity strongly depends on the choice of hydrosilane, with PMHS being optimal. The reaction is operationally simple and readily scaled up, and proceeds without exclusion of air and moisture.
Bioengineered Hyaluronan Hydrogels for the Delivery of Molecular and Cellular Therapies
Authors: Silva Joana , Azevedo Helena S. 
Published: September 2023

AbstractHyaluronan (HA) is an extracellular matrix (ECM)‐based polymer with unique physicochemical properties including biocompatibility, biodegradability, viscoelasticity, and high‐water retention. However, its solubility in water drastically reduces its half‐life in vivo. Through judicious chemical modifications, its structure is easily crosslinked and can conjugate with numerous therapeutic molecules, extending their therapeutic function. Throughout this review, an overview of crosslinking methods to create HA hydrogels is provided, including covalent (permanent, transient/dynamic) and noncovalent chemistries, as well as the use of nonmodified HA in supramolecular hydrogels. HA‐based injectable hydrogels are very appealing as a three‐dimensional network for the delivery of therapeutic molecules (drugs and biomolecules) and stem cells. HA hydrogels are capable of mimicking important features of the native ECM and can provide spatiotemporal signals to regulate cell fate. The final part of the review also describes the application of HA hydrogels as vehicles for delivering stem cells and therapeutics, capable of modulating cell behavior.
Data‐Driven Virtual Material Analysis and Synthesis for Solid Electrolyte Interphases
Authors: Rajagopal Deepalaxmi , Koeppe Arnd , Esmaeilpour Meysam , Selzer Michael , Wenzel Wolfgang , Stein Helge , Nestler Britta 
Published: September 2023

AbstractSolid electrolyte interphases (SEIs) form as reduction products at the electrodes and strongly affect battery performance and safety. Because SEI formation poses a highly nonlinear, complex multi‐physics problem over various lengths and time scales, traditional modeling approaches struggle to characterize SEI evolution solely with existing physical properties. To improve the characterization of SEIs, it proposes a data‐driven strategy for a virtual material design that learns to represent and characterize SEI formation with physical and data‐driven properties from kinetic Monte Carlo simulations. A Variational AutoEncoder with a property regressor learns data‐driven properties, which represent SEI configurations and correlate with physical target properties. This new neural network design encodes the high‐dimensional structural and reaction spaces into a lower‐dimensional latent space, while the property regressor orders the latent space by physical target properties. The model achieves high correlation scores between target and predicted properties from latent representations, thereby proving that the data‐driven properties enrich the expressiveness of SEI characterizations.
Identification of the first homozygous intragenic deletion in the YY1AP1 gene in a consanguineous family: New insights into the phenotypic variability associated with Grange syndrome
Authors: Viora‐Dupont E. , Denommé‐Pichon A. , Chevarin M. , Patat O. , Willems M. , Bourgon N. , Bruel A. , Aubert‐Mucca M. , Galinier M. , Itier R. , Decramer S. , Piton A. , Gerard B. , Billon C. , Jeunemaitre X. , Duffourd Y. , Callier P. , Thauvin C. , Philippe C. , Faivre L. , Albuisson J. , Vitobello A. 
Published: September 2023

AbstractGrange syndrome (GRNG—MIM#135580) is a rare recessive disorder associating variable features including diffuse vascular stenosis, brachysyndactyly, osteopenia with increased bone fragility, cardiac malformations, and variable developmental delay. Since its first description in 1998, only 15 individuals from 10 families have been reported, carrying homozygous or compound heterozygous frameshift or nonsense variants in YY1AP1. In a patient with cutaneous and bone syndactyly and a hemorrhagic stroke at the age of 16 months, consistent with a clinical diagnosis of GRNG, we performed exome sequencing after negative array‐CGH and congenital limb malformation panel results. Copy number variant analysis from exome data identified a homozygous intragenic out‐of‐frame deletion of 1.84 kb encompassing exons seven and eight of YY1AP1, confirming a molecular diagnosis of GRNG. Genetic counseling led to the identification of additional family members compatible with GRNG. Here, we provide new insights into the phenotypic variability associated with GRNG and highlight the utility of the detection of small copy number variants to identify the molecular causes of heterogeneous malformative genetic disorders.
Variable phenotype of a null PPP1R13L allele in children with dilated cardiomyopathy
Authors: Tulbah Sahar , Alruwaili Nadiah , Alhashem Amal , Aljohany Arwa , Alhadeq Faten , Brotons Dimpna C. Albert , Alwadai Abdullah , Al‐Hassnan Zuhair N. 
Published: September 2023

AbstractChildhood‐onset cardiomyopathy is a genetically heterogeneous group of conditions with several genes implicated. Recently, biallelic loss‐of‐function variants in PPP1R13L have been reported in association with a syndromic form of dilated cardiomyopathy (DCM). In addition, affected children manifest skin and hair abnormalities, cleft lip and palate (CLP), and eye findings. Here, we delineate the condition further by describing the phenotype associated with a homozygous frameshift variant (p.Arg330 ProfsTer76) in PPP1R13L detected in two sibships in a consanguineous family with six affected children. The index case had DCM and wooly hair, two of his siblings had DCM and CLP while three cousins had, in addition, glaucoma. Global developmental delay was observed in one child. All the children, except one, died during early childhood. Whole exome sequencing and whole genome sequencing did not reveal any other plausible variant. We provide further evidence that implicates PPP1R13L in a variable syndromic form of severe childhood‐onset DCM and suggests expanding the spectrum of this condition to include glaucoma. Given the variability of the phenotype associated with PPP1R13‐related DCM, a thorough evaluation of each case is highly recommended even in the presence of an apparently isolated DCM.
Photoredox‐Catalyzed Three‐Component Difluoroalkylation of Quinoxalin‐2(1H)‐ones with Unactivated Vinylarenes and [Ph3PCF2H]+Br−
Authors: Xu Yuandong , Qu Hongzhao , Yuan Jinwei , Guo Na , Yang Liangru , Yin Yanli , Qu Lingbo , Mao Jian 
Published: September 2023

AbstractAn efficient synthesis of a variety of 3‐difluoroalkyl quinoxalin‐2(1H)‐ones via a photoredox‐catalyzed three‐component reaction between quinoxalin‐2(1H)‐ones, vinylarenes, with inexpensive and easily accessible difluoromethyltriphenyl phosphonium bromide salt as the difluoromethylated reagent is described. This protocol shows excellent reactivity, providing a wide range of difluoroalkyl‐substituted quinoxalin‐2(1H)‐ones in moderate to excellent yields under mild conditions. A difluoroalkyl radical intermediate was involved in this three‐component transformation.
Molecular Stacking and Aggregation Optimization of Photoactive Layer through Solid Additive Enables High‐Performance Organic Solar Cells
Authors: Zhang Wenjing , Wu Yue , Ma Ruijie , Fan Hongyu , Li Xiaoxiao , Yang Hang , Cui Chaohua , Li Yongfang 
Published: September 2023

AbstractRegulating molecular packing and aggregation of photoactive layer is a critical but challenging issue in developing high‐performance organic solar cells. Herein, two structurally similar analogues of anthra[2,3‐b : 6,7‐b′]dithiophene (ADT) and naphtho[1,2‐b : 5,6‐b′]dithiophene (NDT) are developed as solid additive to exploit their effect in regulating the molecular aggregation and π‐stacking of photoactive layer. We clarify that the perpendicular arrangements of NDT can enlarge the molecular packing space and improve the face‐on stacking of Y6 during the film formation, favoring a more compact and ordered long‐range π‐π stacking in the out‐of‐plane direction after the removal of NDT under thermal annealing. The edge‐to‐face stacked herringbone‐arrangement of ADT along with its non‐volatilization under thermal annealing can induce the coexistence of face‐on and edge‐on stacking of blend film. As a result, the NDT treatment shows encouraging effect in improving the photovoltaic performance of devices based on various systems. Particularly, a remarkable PCE of 18.85 % is achieved in the PM6 : L8‐BO‐based device treated by NDT additive, which is a significant improvement with regard to the PCE of 16.41 % for the control device. This work offers a promising strategy to regulate the molecular packing and aggregation of photoactive layer towards significantly improved performance and stability of organic solar cells.
Heavy‐Atom Tunneling in Bicyclo[4.1.0]hepta‐2,4,6‐trienes
Authors: Prado Merini Melania , Schleif Tim , Sander Wolfram 
Published: September 2023

AbstractHeavy‐atom tunneling limits the lifetime and observability of bicyclo[4.1.0]hepta‐2,4,6‐triene, a key intermediate in the rearrangement of phenylcarbene. Bicyclo[4.1.0]hepta‐2,4,6‐triene had been proposed as the primary intermediate of the rearrangement of phenylcarbene, but despite many efforts evaded its characterization even in cryogenic matrices. By introducing fluorine substituents into theortho‐positions of the phenyl ring of phenylcarbene, the highly strained cyclopropene 1,5‐difluorobicyclo[4.1.0]hepta‐2,4,6‐triene becomes stable enough to be characterized in argon matrices. However, even at 3 K this cyclopropene is only metastable and rearranges via heavy‐atom tunneling to the corresponding cycloheptatetraene. Calculations suggest that fluorination is necessary to slow down the tunneling rearrangement of the bicycloheptatriene. The parent bicycloheptatriene rapidly rearranges via heavy‐atom tunneling and therefore cannot be detected under matrix isolation conditions.
Adaptive Supramolecular Networks: Emergent Sensing from Complex Systems
Authors: Selinger Allison J. , Hof Fraser 
Published: September 2023

AbstractMolecular differentiation by supramolecular sensors is typically achieved through sensor arrays, relying on the pattern recognition responses of large panels of isolated sensing elements. Here we report a new one‐pot systems chemistry approach to differential sensing in biological solutions. We constructed an adaptive network of three cross‐assembling sensor elements with diverse analyte‐binding and photophysical properties. This robust sensing approach exploits complex interconnected sensor‐sensor and sensor‐analyte equilibria, producing emergent supramolecular and photophysical responses unique to each analyte. We characterize the basic mechanisms by which an adaptive network responds to analytes. The inherently data‐rich responses of an adaptive network discriminate among very closely related proteins and protein mixtures without relying on designed protein recognition elements. We show that a single adaptive sensing solution provides better analyte discrimination using fewer response observations than a sensor array built from the same components. We also show the network's ability to adapt and respond to changing biological solutions over time.
Selective Oxidative Dehydrogenation of Ethane and Propane over Copper‐Containing Mordenite: Insights into Reaction Mechanism and Product Protection
Authors: Artsiusheuski Mikalai A. , Verel René , van Bokhoven Jeroen A. , Sushkevich Vitaly L. 
Published: September 2023

AbstractCopper(II)‐containing mordenite (CuMOR) is capable of activation of C−H bonds in C1‐C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time‐resolved Cu K‐edge X‐ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π‐complexes of olefins with CuI sites, formed upon reduction of CuII‐oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.
An Unlocked Two‐Dimensional Conductive Zn‐MOF on Polymeric Carbon Nitride for Photocatalytic H2O2 Production
Authors: Li Yunxiang , Guo Yan , Luan Deyan , Gu Xiaojun , Lou Xiong Wen (David) 
Published: September 2023

AbstractDeveloping highly efficient catalytic sites for O2 reduction to H2O2, while ensuring the fast injection of energetic electrons into these sites, is crucial for artificial H2O2 photosynthesis but remains challenging. Herein, we report a strongly coupled hybrid photocatalyst comprising polymeric carbon nitride (CN) and a two‐dimensional conductive Zn‐containing metal–organic framework (Zn‐MOF) (denoted as CN/Zn‐MOF(lc)/400; lc, low crystallinity; 400, annealing temperature in °C), in which the catalytic capability of Zn‐MOF(lc) for H2O2 production is unlocked by the annealing‐induced effects. As revealed by experimental and theoretical calculation results, the Zn sites coordinated to four O (Zn‐O4) in Zn‐MOF(lc) are thermally activated to a relatively electron‐rich state due to the annealing‐induced local structure shrinkage, which favors the formation of a key *OOH intermediate of 2e− O2 reduction on these sites. Moreover, the annealing treatment facilitates the photoelectron migration from the CN photocatalyst to the Zn‐MOF(lc) catalytic unit. As a result, the optimized catalyst exhibits dramatically enhanced H2O2 production activity and excellent stability under visible light irradiation.
Sabatier Relations in Electrocatalysts Based on High‐entropy Alloys with Wide‐distributed d‐band Centers for Li‐O2 Batteries
Authors: Tian Jiaming , Rao Yuan , Shi Wenhui , Yang Jiawei , Ning Wenjie , Li Haoyu , Yao Yonggang , Zhou Haoshen , Guo Shaohua 
Published: September 2023

AbstractLi‐O2 battery (LOB) is a promising “beyond Li‐ion” technology with ultrahigh theoretical energy density (3457 Wh kg−1), while currently impeded by the sluggish cathodic kinetics of the reversible gas‐solid reaction between O2 and Li2O2. Despite many catalysts are developed for accelerating the conversion process, the lack of design guidance for achieving high performance makes catalysts exploring aleatory. The Sabatier principle is an acknowledged theory connecting the scaling relationship with heterogeneous catalytic activity, providing a tradeoff strategy for the topmost performance. Herein, a series of catalysts with wide‐distributed d‐band centers (i.e., wide range of adsorption strength) are elaborately constructed via high‐entropy strategy, enabling an in‐depth study of the Sabatier relations in electrocatalysts for LOBs. A volcano‐type correlation of d‐band center and catalytic activity emerges. Both theoretical and experimental results indicate that a moderate d‐band center with appropriate adsorption strength propels the catalysts up to the top. As a demonstration of concept, the LOB using FeCoNiMnPtIr as catalyst provides an exceptional energy conversion efficiency of over 80 %, and works steadily for 2000 h with a high fixed specific capacity of 4000 mAh g−1. This work certifies the applicability of Sabatier principle as a guidance for designing advanced heterogeneous catalysts assembled in LOBs.
Taming of Furfurylidenes by Chiral Bismuth‐Rhodium Paddlewheel Catalysts. Preparation and Functionalization of Optically Active 1,1‐Disubstituted (Trifluoromethyl)cyclopropanes
Authors: Peeters Matthias , Decaens Jonathan , Fürstner Alois 
Published: September 2023

AbstractAlthough 2‐furyl‐carbenes (furfurylidenes) are prone to instantaneous electrocyclic ring opening, chiral [BiRh]‐paddlewheel complexes empowered by London dispersion allow (trifluoromethyl)furfurylidene metal complexes to be generated from a bench‐stable triftosylhydrazone precursor. These reactive intermediates engage in asymmetric [2+1] cycloadditions and hence open entry into valuable trifluoromethylated cyclopropane or ‐cyclopropene derivatives in optically active form, which are important building blocks for medicinal chemistry but difficult to make otherwise.
Effects of branched‐chain fatty acid triacylglycerols on the crystallization of palm oil‐based blends
Authors: Han Junze , Yang Dongying , Zhang Hong , Bi Yanlan , Xu Xuebing 
Published: September 2023

AbstractThe aim of this study was to assess how branched‐chain fatty acid triacylglycerols (BCFA‐TAG) at different concentrations (1–10 g/100 g) affect palm oil‐based blend PO‐PS (palm olein/palm stearin = 7/3, wt/wt) crystallization and other related performance. The addition of BCFA‐TAG significantly affected the crystallization of PO‐PS by accelerating the onset of PO‐PS crystallization through promoting the nucleation of PO‐PS crystals while delaying the growth of the crystals as a whole. The reduction in t1/2 provided good evidence of the delay, with the effect of high concentrations (10 g/100 g) being the most pronounced. Adding BCFA‐TAG to PO‐PS reduced its solid fat content (SFC), with a more significant effect at higher concentrations (5, 8, and 10 g/100 g). After 48 h of crystallization at 25°C, BCFA‐TAG induced a more compact and orderly crystalline network of PO‐PS with an increase in space‐filling, resulting in an increase in hardness. The crystal density of the higher concentration samples (PO‐PS + 10% BCFA‐TAG) decreased over storage time, suggesting a crystal dilution effect of high concentrations of BCFA‐TAG. The PO‐PS + 10% BCFA‐TAG sample maintained the β′ crystalline form throughout the 30 days of storage without conversion to the β crystalline form, thus showing a positive effect of BCFA‐TAG in alleviating the post‐hardness of the palm oil.
Combining NIR spectroscopy with DD‐SIMCA for authentication and iSPA‐PLS‐DA for discrimination of ethyl route and oil feedstocks of biodiesels in biodiesel/diesel blends
Authors: da Costa Gean Bezerra , de Fernandes David Douglas Sousa , Véras Germano , Diniz Paulo Henrique Gonçalves Dias , Gondim Amanda Duarte 
Published: September 2023

AbstractThe main biofuels produced on an industrial large scale are biodiesel and ethanol, which are the most economically viable and widely implemented solutions to replace conventional fossil fuels from a greener and more sustainable perspective. In such a scenario, there is an opportunity to produce fully renewable biodiesel using ethanol instead of methanol, which is mainly derived from fossil resources. In this paper, near‐infrared (NIR) spectroscopy was used to discriminate biodiesel/diesel (B7) blends regarding the synthesis route and oil feedstock of biodiesels simultaneously. Data‐Driven Soft Independent Modeling of Class Analogy (DD‐SIMCA) authenticated correctly all ethyl B7 (target) samples into the acceptance area, while rejected all non‐target samples, implying in an efficiency of 100%. Additionally, Partial Least Squares‐Discriminant Analysis coupled with interval selection by the Successive Projections Algorithm (iSPA‐PLS‐DA) discriminated all ethyl B7 samples correctly, considering cottonseed, sunflower, and soybean as oil feedstocks. Moreover, only one ethyl cottonseed B7 sample was incorrectly discriminated when methyl B7 samples from the same three oil feedstocks were included in the model. As advantages, the proposed analytical methodology contributes to the United Nations' Sustainable Development Goal (SDG) #7 (affordable and clean energy) as well as aligns with the principles of Green Analytical Chemistry.
Stochastic comparisons of coherent systems with active redundancy at the component or system levels and component lifetimes following the accelerated life model
Authors: Panja Arindam , Kundu Pradip , Pradhan Biswabrata 
Published: September 2023

AbstractAn effective way to increase system reliability is to use redundancies (spares) into the systems either in component level or in system level. In this prospect, it is a significant issue that which set of available spares providing better system reliability in some stochastic sense. In this paper, we derive sufficient conditions under which a coherent system with a set of active redundancy at the component level or the system level provide better system reliability than that of the system with another set of redundancy, with respect some stochastic orders. We have derived the results for the component lifetimes following accelerated life (AL) model. The results obtained help us to design more reliable systems by allocating appropriate redundant components from the set of available options for the same. Various examples satisfying the sufficient conditions of the theoretical results are provided. Some results are illustrated with real‐world data.