bluuebunny/crossref_metadata_2025_split huggingface dataset:
SF3B2 Haploinsufficiency Associated With Hirschprung Disease and Complex Cardiac Defect Without Craniofacial Microsomia
Authors: Del Viso Florencia , Zhou Dihong , Starling Susan , Fleming Emily , Saunders Carol 
Published: September 2024

ABSTRACTHaploinsufficiency of SF3B2 is associated with craniofacial microsomia, characterized by mandibular hypoplasia and microtia, often with preauricular tags or pits, epibulbar dermoids, and cleft palate. In addition, extracraniofacial anomalies may be present, such as skeletal, cardiac renal, and abnormalities of the central nervous system. Variants have been either de novo or inherited, and both inter‐ and intrafamilial variability has been observed. Here we describe a patient referred for exome sequencing for a complex congenital heart defect and Hirschsprung disease found by exome sequencing to be heterozygous for a loss of function variant, c.945dup (p.Val316SerfsTer5), in SF3B2. This variant was inherited from a parent with an isolated cardiac defect. Interestingly, neither have the defining craniofacial features or other dysmorphisms. This report further illustrates the degree of phenotypic variability seen in SF3B2‐related disease and expands the spectrum to include Hirschsprung disease.
Pongo's ecological diversity from dental macrowear analysis
Authors: Fiorenza Luca , Mitchell D. Rex , Kullmer Ottmar 
Published: September 2024

AbstractObjectivesOrangutans are found in tropical rainforests of Borneo (Pongo pygmaeus) and Sumatra (Pongo abelii and Pongo tapanuliensis), and they are primarily considered frugivorous species. However, ecological studies reported differences in feeding behavior between these species. P. pygmaeus spend more time feeding on low‐quality foods, such as bark and tough vegetation than do P. abelii. The aim of this study is to investigate if there is any geographic variation in molar macrowear pattern between the two species.MethodsWe analyzed the macrowear pattern of second mandibular molars of 58 orangutan specimens combining dental topographic measurements (occlusal relief index, percentage of dentine exposure, and percentage of enamel wear) with the occlusal fingerprint analysis method.ResultsThe molar macrowear patterns of P. abelii and P. pygmaeus show no significant differences in most of the variables examined in this study. While P. pygmaeus molars are generally characterized by flatter occlusal morphology with slightly larger crushing and grinding areas than those of P. abelii, these differences are not statistically significant. However, we do observe a more variable wear in P. pygmaeus.ConclusionsSimilarities in molar macrowear patterns between the two species could be linked to overlapping long‐term diets, primarily composed of ripe and pulpy fruits. Dental macrowear is a cumulative process that occurs during the individual's lifetime, and it may be difficult to detect seasonal changes through its examination. Future studies could integrate tooth micro‐ and macrowear data for a better understanding of primate dental ecology.
Beyond administrative burden: Activation and administrative harm
Authors: McGann Michael , Ball Sarah 
Published: September 2024

AbstractWithin recent public policy and administration scholarship, there has been a growing focus on the concept of “administrative burden” to describe the learning, compliance and psychological costs incurred by citizens when trying to access services and exercise social and political rights. Specifically, in the context of activation and welfare‐to‐work programmes, scholars have highlighted the effects of administrative burdens on claimants' autonomy, dignity and well‐being. We bring critical social policy scholarship on administrative harm into conversation with Adam and Balfour's concept of “administrative evil” to highlight the underlying dynamics of masking, moral inversion and dehumanisation that facilitate street‐level workers to adopt dispositions of enforcement of administrative burdens. To illustrate the applicability of Adam and Balfour's work to understanding how experiences of administrative burden can be intensified by the practices and dispositions of street‐level workers, we draw on examples of from an ethnographic study of the delivery of welfare‐to‐work in Australia.
Pentagon‐Rich Caged Carbon Catalyst for the Oxygen Reduction Reaction in Acidic Electrolytes
Authors: Chen Guoping , Isegawa Miho , Koide Taro , Yoshida Yasuo , Harano Koji , Hayashida Kenji , Fujita Shusaku , Takeyasu Kotaro , Ariga Katsuhiko , Nakamura Junji 
Published: September 2024

AbstractThe interaction between electron spin and oxygen molecules in non‐platinum catalysts, particularly carbon catalysts, significantly influences the catalytic performance of the oxygen reduction reaction (ORR). A promising approach to developing high‐performance catalysts involves introducing five‐membered ring structures with spin into graphitic carbons. In this study, we present the successful synthesis of cage‐like cubic carbon catalysts enriched with pentagon structures using pentagon ring‐containing C60 and a NaCl template. The number of pentagons contained in the structure was increased by doping with nitrogen and annealing, and the number of electron spins also increased, thereby improving catalytic activity. The prepared catalyst exhibits remarkable activity in ORR under acidic electrolytes. Furthermore, we elucidate the correlation between the pentagon structure, the number of spin, and catalytic activity, demonstrating that enhanced activity is contingent upon the presence of spin. Density functional theory (DFT) calculations support the role of spin in improving activity. The concept of spin and the introduction of pentagon structures provide new design principles for carbon catalysts.
As Aggregation‐Induced Emission Meets with Noncovalent Conformational Locks: Subtly Regulating NIR‐II Molecules for Multimodal Imaging‐Navigated Synergistic Therapies
Authors: Li Jiangao , Niu Niu , Wang Deliang , Zhu Jun , Li Xue , Kong Qiyu , Zhong Tang Ben , Wang Dong 
Published: September 2024

AbstractPhototheranostics is growing into a sparking frontier in disease treatment. Developing single molecular species synchronously featured by powerful absorption capacity, superior second near‐infrared (NIR‐II) fluorescence and prominent photothermal conversion ability is highly desirable for phototheranostics, yet remains formidably challenging. In this work, we propose a molecular design philosophy that the integration of noncovalent conformational locks (NoCLs) with aggregation‐induced emission (AIE) in a single formulation is able to boost multiple photophysical properties for efficient phototheranostics. The introduction of NoCLs skeleton with conformation‐locking feature in the center of molecular architecture indeed elevates the structural planarity and rigidity, which simultaneously promotes the absorption capacity and bathochromic‐shifts the emission wavelength centered in NIR‐II region. Meanwhile, the AIE tendency mainly originated from flexibly propeller‐like geometry at the ends of molecular architecture eventually endows the molecule with satisfactory emission intensity and photothermal conversion in aggregates. Consequently, by utilizing the optimized molecule, unprecedented performance on NIR‐II fluorescence‐photoacoustic‐photothermal trimodal imaging‐guided photothermal‐chemo synergistic therapy is demonstrated by the precise tumor diagnosis and complete tumor ablation.
Disilicon‐Mediated Carbon Monoxide Activation: From a 1,2,3‐Trisila‐ to 1,3‐Disilacyclopentadienes with Hypercoordinate λ4Si‐λ3C Double Bonds
Authors: Yao Shenglai , Budde Markus Stefan , Yang Xing , Xiong Yun , Zhao Lili , Driess Matthias 
Published: September 2024

AbstractThe facile reaction of the SiPh2‐bridged bis‐silylene (LSi:)2SiPh2 (L=PhC(NBut)2) with diphenylacetylene affords the unprecedented 1,2,3‐trisilacyclopentadiene (LSi)2(PhC)2SiPh2 1 with a hypercoordinate λ4Si−λ3Si double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert N2O to form the bicyclic oxygenation product 2 through O‐atom insertion in the Si=Si and Si−Si bonds. Strikingly, 1 can completely split the C≡O bonds of carbon monoxide under ambient conditions (1 atm, room temperature), yielding the 1,3‐disilacyclopentadiene 3, representing the first hypercoordinate example of a cyclosilene with a λ4Si‐λ3C double bond. Likewise, reaction of Xyl‐NC (Xyl=2,6‐dimethylphenyl), an isocyanide isoelectronic with CO, with 1 furnishes the related 1,3‐disilacyclopentadiene 4 but with an amidinato silylene pendent attached to the Si=C carbon ring atom.
LiLnGeS4 (Ln=La−Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through “Band Reformation of AGS”
Authors: Liu Qian‐Qian , Liu Xin , Li Mei‐Ze , Wang Rui‐Xi , Li Bingxuan , Wu Li‐Ming , Chen Ling 
Published: September 2024

AbstractAgGaS2 (AGS) is the most commonly used commercial infrared nonlinear optical (IR NLO) material. However, AGS has a narrow band gap (Eg=2.58 eV) and a low laser‐induced damage threshold (LIDT), primarily attributed to its mobile liquid‐like Ag+ constituent and the unstable Ag−S chemical bond. Herein, we propose a “band reformation of AGS” strategy, which leads to the successful syntheses of four lanthanide sulfides, LiLnGeS4 (Ln=La−Nd), crystalizing in an asymmetric Ama2 structure. LiLaGeS4 demonstrates that eliminating the presence of Ag‐4d band increases the Eg to 3.32 eV and enhances the LIDT (14–29×AGS, measured by both powder and single crystal); while increasing the nonbonding density of states of the S‐3p band enhances the 2nd‐nonlinear optical coefficient (1.06×AGS). Besides, the bond length discrepancy between [LiS4], [GeS4] and [LaS8] units leads to a moderate birefringence (Δn=0.052). Such a unique structure further results in extremely small thermal expansion with αL=0.41–1.74×10−5 K−1, along different crystallographic axes. Our theoretical studies indicate that the synergy of the structure building units contribute to the second harmonic generation performance. These results suggest that the “band reformation of AGS” strategy provides effective guidance to discover new NLO crystals with optimized performance.
Solution‐processing induced H‐aggregate of Perylene‐Diimide Zwitterion Exhibiting Compact Molecular Stacking toward Efficient Cathode Modification in Organic Solar Cells
Authors: Li Zhe , Xiang Yanhe , Li Jiayu , Feng Luxin , Zhang Ming , Zhang Zhiguo , Yan Shouke , Xu Bowei 
Published: September 2024

AbstractHigh‐performance organic cathode interlayers (CILs) play a crucial role in the advance of organic solar cells (OSCs). However, organic CILs have exhibited inferior performances to their inorganic counterparts over a long time, due to the inherent shortcoming of poor charge transporting capability. Here, we designed and synthesized a perylene‐diimide (PDI) zwitterion PDI‐B as high‐performance organic CIL for OSCs. We revealed that an obvious H‐aggregate of PDI‐B was formed during the solution processing, thereby significantly enhancing the charge transporting capability of the CIL. Compared to the classic PDINN, the π–π stacking distance of PDI‐B was reduced from 4.2 Å to 3.9 Å, which further facilitated the charge transport. Consequently, PDI‐B showed a high conductivity of 1.81×10−3S/m; this is comparable to that of inorganic CILs. The binary OSC showed an elevated PCE of 19.23 %, which is among the highest PCE values for binary OSCs. Benefitting from improved solvent resistance and good compatibility with large‐area processing method of PDI‐B, the photovoltaic performances of inverted and 1‐cm2 OSC were significantly improved. The results from this work provide a new approach of optimizing the condensed structure of PDI film to boost the charge conductivity, opening an avenue to develop high‐performance PDI‐based CILs.
Concise and Modular Chemoenzymatic Total Synthesis of Bisbenzylisoquinoline Alkaloids
Authors: Wang Jin , Zhao Jianxiong , Yu Zhenyang , Wang Siyuan , Guo Fusheng , Yang Jun , Gao Lei , Lei Xiaoguang 
Published: September 2024

AbstractThe bisbenzylisoquinoline alkaloids (bisBIAs) have attracted tremendous attention from the synthetic community due to their diverse and intriguing biological activities. Herein, we report the convergent and modular chemoenzymatic syntheses of eight bisBIAs bearing various substitutes and linkages in 5–7 steps. The gram‐scale synthesis of various well‐designed enantiopure benzylisoquinoline monomers was accomplished through an enzymatic stereoselective Pictet–Spengler reaction, followed by regioselective enzymatic methylation or chemical functionalization in a sequential one‐pot process. A modified intermolecular copper‐mediated Ullmann coupling enabled the concise and efficient total synthesis of five different linear bisBIAs with either head‐to‐tail or tail‐to‐tail linkage. A biomimetic oxidative phenol dimerization selectively formed the sterically hindered, electron‐rich diaryl ether bond, and subsequent intramolecular Suzuki–Miyaura domino reaction or Ullmann coupling facilitated the first enantioselective total synthesis of three macrocyclic bisBIAs, including ent‐isogranjine, tetrandrine and O‐methylrepandine. This study highlights the great potential of chemoenzymatic strategies in the total synthesis of diverse bisBIAs and paves the way to further explore the biological functions of these natural products.
Flavin‐Catalyzed, Photochemical Conversion of Dehydroalanine into 4,5‐Dihydroxynorvaline
Authors: Langschwager Tim , Storch Golo 
Published: September 2024

AbstractThe chemical synthesis of unnatural amino acids (UAA) is a key strategy for preparing designed peptides, including pharmaceutically active compounds. Alterations of existing amino acid residues such as dehydroalanine (Dha) are particularly important since selected positions can be addressed without the necessity of a complete de novo synthesis. The intriguing UAA 4,5‐dihydroxynorvaline (Dnv) is found in a variety of naturally occurring peptides and biologically active compounds. However, no method is currently available to modify an existing peptide with this residue. We report the use of flavin catalysts and visible light irradiation for this challenge, which serves as a versatile strategy for converting Dha into Dnv. Our study shows that excited flavins are competent hydrogen atom abstraction catalysts for ethers and acetals, which allows masked 1,2‐dihydroxyethylene functionalization from 2,2‐dimethyl‐1,3‐dioxolane. The masked diol was successfully coupled to Dha residues, and a series of Dnv‐containing products is reported. A mild and orthogonal protocol for deprotection of the acetal group was also identified, allowing free Dnv‐modified peptides to be obtained. This method provides a straightforward strategy for Dnv functionalization, which is envisioned to be crucial for accessing natural products and synthetic analogues with pharmaceutical activity.
Metal‐N Coordination in Lithium‐Sulfur Batteries: Inhibiting Catalyst Passivation
Authors: Ao Xin , Kong Yang , Zhao Shangquan , Chen Zhongxin , Li Yong , Liao Xingyu , Tian Bingbing 
Published: September 2024

AbstractLithium‐sulfur (Li−S) batteries exhibit great potential as the next‐generation energy storage techniques. Application of catalyst is widely adopted to accelerate the redox kinetics of polysulfide conversion reactions and improve battery performance. Although significant attention has been devoted to seeking new catalysts, the problem of catalyst passivation remains underexplored. Herein, we find that metal‐N coordination has a previously overlooked role in preventing the catalyst passivation. In the case of nickel, the Ni catalyst reacts with S8 to produce NiSx compounds on the surface, leading to catalyst passivation and slow the kinetics of LiPSs conversion. In contrast, when Ni is coordinated with N (typically Ni−N4), S8 remains stable on the surface. The Ni−N4 exhibits excellent resistance to passivation and rapid kinetics of LiPSs conversion. Consequently, the sulfur cathode with Ni−N4 exhibits a high rate capability of 604.11 mAh g−1 at 3 C and maintains a low capacity decay rate of 0.046 % per cycle over 1000 cycles at 2 C. Furthermore, preventing S passivation in M−N coordination applies not only to Ni−N4 but also to various coordination numbers and transition metals. This study reveals a new aspect of metal‐N coordination in inhibiting catalyst passivation, improving our understanding of catalysts in Li−S batteries.
Non‐Fused Star‐Shape Giant Trimer Electron Acceptors for Organic Solar Cells with Efficiency over 19 %
Authors: Zhou Wen , Liu Jiabin , Xie Jiaping , You Shiyong , Deng Jiawei , Yu Fan , Jeong Sang Young , Woo Han Young , Wu Feiyan , Chen Lie 
Published: September 2024

AbstractOrganic solar cells (OSCs) based on giant molecular acceptors (GMAs) have attracted extensive attention due to their excellent power conversion efficiency (PCE) and operation stability. However, the large conjugated plane of GMAs poses great challenges in regulating the solubility, over‐size aggregation and yield, which in turn further constrains their development in commercial products. Herein, we employ a non‐fused skeleton strategy to develop novel non‐fused star‐shape trimers (3BTT6F and 3BTT6Cl) for improving device performance. Single‐bond linkage can break the rigid planarity to form a 3D architecture, generating multidimensional charge transfer pathways. Importantly, the non‐fused skeleton strategy can not only significantly improve solubility and synthesis yield, but also effectively suppress molecular excessive aggregation. Consequently, due to the optimized film‐forming process and charge dynamics, 3BTT6F‐based binary device obtains a high PCE of 17.52 %, which is significantly higher than the reported fully fused trimers. Excitingly, 3BTT6F‐based ternary device even obtains a top‐level PCE of 19.26 %. Furthermore, the non‐fused star‐shape configuration also endows these acceptors with enhanced intermolecular interaction in the active layer, demonstrating excellent operational stability. Our work emphasizes the potential of non‐fused star‐shape trimers, providing a new pathway for achieving highly efficient and stable OSCs.
Exploring Cu(triNHC) as a Bifunctional Catalyst for Carbonate Synthesis From CO2 and Epoxy Amines/Sulfides/Ethers
Authors: Ha Changsu , Lee Jong Hyeok , Sokolova Ekaterina , Sung Kihyuk , Jang Hye‐Young 
Published: September 2024

ABSTRACTThis study highlights the synergistic interplay between a Lewis acidic copper ion and a dissociated ligand from Cu(triNHC) complexes in the synthesis of cyclic carbonates from CO2 and epoxy compounds. The reactions were found to proceed efficiently under Cu(triNHC)‐catalyzed conditions, yielding significant quantities of cyclic carbonates across various epoxy substrates encompassing amine, sulfide, and ether functionalities. Stereochemical analyses underscore a pronounced propensity for retaining the stereochemistry of epoxy compounds in the resultant carbonates. This suggests a mechanism involving double inversion of stereochemistry during the reaction, which comprises catalyst‐mediated epoxide ring opening, subsequent CO2 addition, and carbonate ring closing. These findings align with established mechanisms for CO2 fixation reactions, shedding light on the intricate pathways underlying this catalytic process.
A new Co‐based cathode with high performance for intermediate‐temperature solid oxide fuel cells
Authors: Zhou Chaoran , Liang Zhixian , Qiu Hao , Jiang Shanshan , Wang Wei , Su Chao 
Published: September 2024

AbstractSolid oxide fuel cells (SOFCs) as highly effective energy conversation devices have gained substantial recognition and research interest. The electrochemical properties of the traditional SOFCs are restricted by the sluggish reaction kinetics for the cathode material when lowering the operation temperature to below 600°C. In addition, the stability of the cathode at reduced temperatures is also a big challenge for the widely popularization of SOFC technology. Achieving high activities and stable ORR in the cathode is crucial for the development of SOFCs. The doping active metal method has been demonstrated as an effective approach to optimize the phase structure and improve the ORR activity of the cathode. Herein, we successfully develop an Ir‐doped SrCoO3 − δ (SrCo0.98Ir0.02O3 − δ, SCI) cathode for SOFCs. SCI exhibits a low area‐specific resistance (ASR) of 0.057 Ω cm2 at 650°C, ~ 44% lower than 0.102 Ω cm2 of Ir‐free SrCoO3 − δ. The Ni–Sm0.2Ce0.8O1.90 (SDC) anode‐supported fuel cell with SDC electrolyte and SCI cathode obtains an excellent output performance (e.g., 1,128 mW cm−2 at 650°C). The desired results underscore the feasibility of the Ir‐doping strategy as an optimized method for the exploitation of advancing cathode in SOFCs.
Plasma treatment and annealing conditions on mechanical and electrical properties of thermoplastic composites
Authors: Keerthiveettil Ramakrishnan Sumesh , Vackova Tatana , Jenikova Zdenka , Krum Stanislav , Spatenka Petr 
Published: September 2024

AbstractIn this research carbon fibers (CFs) with plasma polyethylene (PPE) was utilized for enhancing the properties. The 10 wt% CF with PPE (CF/PPE) exhibited favorable electrical conductivity (34 Ω cm), with better tensile strength (22.7 MPa), flexural strength (26.89 MPa) compared with the other CF combinations. In the positive temperature coefficient (PTC) test, after the initial trial, the CF/PPE combination exhibited a change in path at higher temperatures (125 and 128°C) due to temperature fluctuations, which altered the properties of composites. It is evident that the resistivity (R) ratio exhibits higher values (CF/PPE) for annealing samples (90°C for 5 h). The annealing process resulted in a PTC intensity of 2.53, which was higher than nonannealing (1.94). Scanning electron microscopy (SEM) analysis without annealing procedure revealed a greater number of deformations in the combination, which resulted in decrease in repeatability. The majority of combinations exhibited enthalpy of melting between 114.3 and 116.4 J/g. The annealed combination, which was heated to 128°C, exhibited an increase in enthalpy up to 122.4 J/g. The melting point of both the annealing and nonannealing samples increased from 131 to 134.1°C following the R–T test, while the crystallization temperature remained unaffected.