bluuebunny/crossref_metadata_2025 huggingface dataset:
Schwann Cell‐Specific Ablation of Beclin 1 Impairs Myelination and Leads to Motor and Sensory Neuropathy in Mice
Authors: Gambarotto Lisa , Russo Loris , Bresolin Silvia , Persano Luca , D'Amore Rachele , Ronchi Giulia , Zen Federica , Muratori Luisa , Cani Alice , Negro Samuele , Megighian Aram , Calabrò Sonia , Braghetta Paola , Bizzotto Dario , Cescon Matilde
Published: December 2024

The core component of the class III phosphatidylinositol 3‐kinase complex, Beclin 1, takes part in different protein networks, thus switching its role from inducing autophagy to regulating autophagosomal maturation and endosomal trafficking. While assessed in neurons, astrocytes, and microglia, its role is far less investigated in myelinating glia, including Schwann cells (SCs), responsible for peripheral nerve myelination. Remarkably, the dysregulation in endosomal trafficking is emerging as a pathophysiological mechanism underlying peripheral neuropathies, such as demyelinating Charcot‐Marie‐Tooth (CMT) diseases. By knocking out Beclin 1 in SCs here a novel mouse model (Becn1 cKO) is generated, developing a severe and progressive neuropathy, accompanied by involuntary tremors, body weight loss, and premature death. Ultrastructural analysis revealed abated myelination and SCs displaying enlarged cytoplasm with progressive accumulation of intracellular vesicles. Transcriptomic and histological analysis from sciatic nerves of 10‐day and 2‐month‐old mice revealed pro‐mitotic gene deregulation and increased SCs proliferation at both stages with axonal loss and increased immune infiltration in adults, well reflecting the progressive motor and sensory functional impairment that characterizes Becn1 cKO mice, compared to controls. The study establishes a further step in understanding key mechanisms in SC development and points to Beclin 1 and its regulated pathways as targets for demyelinating CMT forms.
Aberrant Chitinase 3‐Like 1 Expression in Basal Cells Contributes to Systemic Sclerosis Fibrosis
Authors: Wang Xiuyuan , Ye Tianbao , Huang Junxia , Hu Feifei , Huang Chengjie , Gu Bei , Xu Xinzhi , Yang Ji
Published: December 2024

Systemic sclerosis (SSc) is an autoimmune disease characterized by extensive skin and internal organ fibrosis. However, the mechanism underlying fibrosis remains unclear, and effective treatments for halting or reversing fibrosis are lacking. In this study, single‐cell RNA sequencing is used to obtain a comprehensive overview of skin cells from patients with SSc and healthy controls. A subset of basal cells with high chitinase 3‐like 1 (Chi3L1) expression, which potentially plays an important role in fibroblast activation, is identified in SSc. Subsequently, patients with SSc are present with increased expression of Chi3L1 in the skin and serum, and elevated serum levels are associated with skin induration and pulmonary function. Furthermore, Chi3L1 promoted the differentiation of SSc dermal fibroblasts into myofibroblasts, and Chi3L1‐deficient (Chi3L1‐/‐) mice showed amelioration of fibrosis in a bleomycin‐induced SSc (BLM‐SSc) model. Mechanistically, Chi3L1 mediates fibroblast activation primarily by interacting with interleukin‐17 receptor A (IL‐17RA), thereby initiating downstream nuclear factor kappa B and mitogen‐activated protein kinases signaling pathways. Moreover, the anti‐fibrotic effect of IL‐17RA antagonists in BLM‐SSc mice is demonstrated. In conclusion, Chi3L1 is a potential biomarker for the degree of fibrosis in SSc. Chi3L1 and its receptor, IL‐17RA, are promising therapeutic targets for patients with SSc.
Clostridium Scindens Protects Against Vancomycin‐Induced Cholestasis and Liver Fibrosis by Activating Intestinal FXR‐FGF15/19 Signaling
Authors: Xiao Jintao , Hou Yanliang , Luo Xingyang , Zhu Yuhao , Li Wenhu , Li Bingbing , Zhou LinXiang , Chen Xia , Guo Ying , Zhang Xiaomei , He Haiyue , Liu Xiaowei
Published: December 2024

Primary sclerosing cholangitis (PSC) is characterized by abnormal bile acid metabolites and altered gut microbiota, with no effective treatments available. Vancomycin, a glycopeptide antibiotic, has emerged as a promising candidate. However, the mechanism by which vancomycin impacts the progression of PSC remains unknown. Mice treated with vancomycin exhibit increased hepatic collagen deposition and injury, due to the inhibition of intestinal FXR‐FGF15/19 axis and the elevation of bile acid levels. These effects are associated with the reduction in Clostridia XIVa, especially Clostridium scindens (C. scindens). Gavage of C. scindens alleviates vancomycin‐induced bile acid accumulation and liver fibrosis via activating intestinal FXR‐FGF15/19 signaling. Similar effects are observed in mice treated with engineered Escherichia coli Nissle 1917 that are capable of expressing bile acid 7α‐dehydratas (BaiE) from C. scindens (EcN‐BaiE). Activating intestinal FXR‐FGF15/19 signaling by fexaramine (Fex) or recombinant protein FGF19 reverse vancomycin‐induced liver injury and fibrosis. These results demonstrate that long‐term oral vancomycin exacerbates cholestatic liver injury, while C. scindens mitigates this effect by activating the intestinal FXR‐FGF15/19 signaling pathway. This underscores the importance of monitoring bile acid levels in PSC patients receiving vancomycin treatment and suggests that C. scindens may serve as a potential therapeutic approach for PSC patients.
A Room‐Temperature Terahertz Photodetector Imaging with High Stability and Polarization‐Sensitive Based on Perovskite/Metasurface
Authors: Li Yifan , Jia Yiming , Yang He , Wu Yinghui , Cao Yajun , Zhang Xuyang , Lou Cunguang , Liu Xiuling , Huang Long‐Biao , Yao Jianquan
Published: December 2024

Terahertz (THz) polarization detection facilitates the capture of multidimensional data, including intensity, phase, and polarization state, with broad applicability in high‐resolution imaging, communication, and remote sensing. However, conventional semiconductor materials are limited by energy band limitations, rendering them unsuitable for THz detection. Overcoming this challenge, the realization of high‐stability, room‐temperature polarization‐sensitive THz photodetectors (PDs) leveraging the thermoelectric effect of Cs0.05(FA0.85MA0.15)0.95Pb(I0.85Br0.15)3 (CsFAMA)/metasurfaces is presented. Two different structures of (T‐shaped and I‐shaped) THz PDs are constructed. The incorporation of perovskite/metasurfaces forms enhanced local field thermoelectric effect and polarization response. Owning to THz surface plasmon polariton (SPP) resonance effect and more boundary effect, the I‐shaped PDs exhibit superior performance, achieving a response of up to 94 V/W, with a response time of 138 µs, a low noise‐equivalent power of 5.03 pW/Hz1/2 and an anisotropy ratio of 1.38 under 0.1THz laser irradiation. Furthermore, the PD's stability is verified with the anisotropy ratio decreased by only 2% and polarization imaging results after 240 days of storage in air condition. This research introduces a method for achieving high‐performance, stable THz polarization detection technology, with significant potential for advancements in materials science, communication technology, and medical imaging.
Chirality Evolution of Supramolecular Helices by Electron Transfer Assisted Secondary Nucleation
Authors: Gao Laiben , Dou Xiaoqiu , Xing Chao , Yang Kaikai , Zhao Changli , Feng Chuanliang
Published: December 2024

Chirality evolution is ubiquitous and important in nature, but achieving it in artificial systems is still challenging. Herein, the chirality evolution of supramolecular helices based on l‐phenylalanine derivative (LPF) and naphthylamide derivate (NDIAPY) is achieved by the strategy of electron transfer (ET) assisted secondary nucleation. ET from LPF to NDIAPY can be triggered by 5 s UV irradiation on left‐handed LPF‐NDIAPY co‐assemblies, leading to NDIAPY radical anions and partial disassembly of the helices. Meanwhile, spontaneous reversion of radical anions into monomers occurs upon removal of UV light, and the surface of residual co‐assemblies can accelerate the reversion process. This surface accelerated reversion of ET further facilitates the secondary nucleation‐elongation events, giving rise to the formation of scale‐amplified and g vale‐increased left‐handed helices. Meanwhile, chirality evolution controlled by ET assisted secondary nucleation process can be also realized by adding the prepared LPF‐NDIAPY co‐assemblies into the total ET system. This study may provide a useful approach to constructing and modulating diverse chiral structures by manipulating the secondary nucleation process.
Molecular Understanding of the Role of Catalyst Particle Arrangement in Local Mass Transport Resistance for Fuel Cells
Authors: Ran Aoxin , Fan Linhao , Tongsh Chasen , Wang Jiaqi , Qin Zhengguo , Du Qing , Ni Meng , Jiao Kui
Published: December 2024

Platinum (Pt) catalyst performance loss caused by a high local oxygen transport resistance is an urgent problem to be solved for proton exchange membrane fuel cells (PEMFCs). Rationally arranging Pt particles on carbon support is the primary approach for reducing mass transport resistance. Herein, using a unique method coupling Hybrid Reverse Monte Carlo, molecular dynamics simulations, and experimental measurements, a Pt particle arrangement strategy is proposed to reduce local oxygen transport resistance, based on a molecular‐level understanding of its impact. The densely arranged Pt particles with a small interparticle distance lead to the denser ionomer layer due to the co‐attraction effect, leading to a high local oxygen transport resistance. The nonuniformly arranged Pt particles with various interparticle distances cause the heterogeneous ionomer density, inducing the heterogeneous oxygen transport. Increasing the Pt‐Pt interparticle distance from 2 to 5 nm substantially reduces the local oxygen transport resistance by over 50%. The uniform arrangement of Pt particles makes the ionomer layer density more homogeneous, resulting in more uniform oxygen transport. Therefore, uniformly arranging Pt particles with an interparticle distance of >5 nm on carbon support is preferred for reducing local oxygen transport resistance and improving the homogeneity of oxygen transport.
Dietary Palmitic Acid Drives a Palmitoyltransferase ZDHHC15‐YAP Feedback Loop Promoting Tumor Metastasis
Authors: Wang Jianxin , Shen Dachuan , Jiang Jian , Hu Lulu , Fang Kun , Xie Chunrui , Shen Ning , Zhou Yuzhao , Wang Yifei , Du Sha , Meng Songshu
Published: December 2024

Elevated uptake of saturated fatty acid palmitic acid (PA) is associated with tumor metastasis; however, the precise mechanisms remain partially understood, hindering the development of therapy for PA‐driven tumor metastasis. The Hippo–Yes‐associated protein (Hippo/YAP) pathway is implicated in cancer progression. Here it is shown that a high‐palm oil diet potentiates tumor metastasis in murine xenografts in part through YAP. It is found that the palmitoyltransferase ZDHHC15 is a YAP‐regulated gene that forms a feedback loop with YAP. Notably, PA drives the ZDHHC15‐YAP feedback loop, thus enforces YAP signaling, and hence promotes tumor metastasis in murine xenografts. In addition, it is shown that ZDHHC15 associates with Kidney and brain protein (KIBRA, also known as WW‐ and C2 domain‐containing protein 1, WWC1), an upstream component of Hippo signaling, and mediates its palmitoylation. KIBRA palmitoylation leads to its degradation and regulates its subcellular localization and activity toward the Hippo/YAP pathway. Moreover, PA enhances KIBRA palmitoylation and degradation. It is further shown that combinatorial targeting of YAP and fatty acid synthesis exhibits augmented effects against metastasis formation in mice fed with a Palm diet. Collectively, these findings uncover a ZDHHC15‐YAP feedback loop as a previously unrecognized mechanism underlying PA‐promoted tumor metastasis and support targeting YAP and fatty acid synthesis as potential therapeutic targets in PA‐driven tumor metastasis.
A Hierarchical Metal–Organic Framework Intensifying ROS Catalytic Activity and Bacterial Entrapment for Engineering Self‐Antimicrobial Mask
Authors: Huang Wei , Yuan Haitao , Yang Huangsheng , Shen Yujian , Guo Lihong , Zhong Ningyi , Wu Tong , Shen Yong , Chen Guosheng , Huang Siming , Niu Li , Ouyang Gangfeng
Published: December 2024

Leveraging functional materials to develop advanced personal protective equipment is of significant importance for cutting off the propagation of infectious diseases, yet faces ongoing challenges owing to the unsatisfied antimicrobial efficiency. Herein a hierarchically porous cerium metal–organic framework (Ce‐MOF) boosting the antimicrobial performance by intensifying catalytic reactive oxygen species (ROS) generation and bacterial entrapment simultaneously is reported. This Ce‐MOF presents dendritic surface topography and hierarchical pore channels where the Lewis acid Ce sites are dispersedly anchored. Attributing to this sophisticated nanoarchitecture rendering the catalytic Ce sites highly accessible, it shows a ca. 1800‐fold activity enhancement for the catalytic conversion of atmospheric oxygen to highly toxic ROS compared to traditional CeO2. Additionally, the dendritic and negative‐charged surface engineered in this Ce‐MOF substantially enhances the binding affinity toward positive‐charged bacteria, enabling the spatial proximity between the bacteria and the short‐lived ROS and therefore maximizing the utilization of highly toxic ROS to inactivate bacteria. It is demonstrated that this Ce‐MOF‐integrated face mask displays almost 100% antimicrobial efficacy even in insufficient light and dark scenarios. This work provides important insights into the design of antibacterial MOF materials by a pore‐ and surface‐engineering strategy and sheds new light on the development of advanced self‐antimicrobial devices.
SYISL Knockout Promotes Embryonic Muscle Development of Offspring by Modulating Maternal Gut Microbiota and Fetal Myogenic Cell Dynamics
Authors: Zuo Hao , Jiang Wei , Gao Jianwei , Ma Zhibo , Li Chen , Peng Yaxin , Jin Jianjun , Zhan Xizhen , Lv Wei , Liu Xiao , Hu Jingjing , Zhang Mengdi , Jia Yiming , Xu Zaiyan , Tang Junming , Zheng Rong , Zuo Bo
Published: December 2024

Embryonic muscle fiber formation determines post‐birth muscle fiber totals. The previous research shows SYISL knockout significantly increases muscle fiber numbers and mass in mice, but the mechanism remains unclear. This study confirms that the SYISL gene, maternal gut microbiota, and their interaction significantly affect the number of muscle fibers in mouse embryos through distinct mechanisms, as SYISL knockout alters maternal gut microbiota composition and boosts butyrate levels in embryonic serum. Both fecal microbiota transplantation and butyrate feeding significantly increase muscle fiber numbers in offspring, with butyrate inhibiting histone deacetylases and increasing histone acetylation in embryonic muscle. Combined analysis of RNA‐seq between wild‐type and SYISL knockout mice with ChIP‐seq for H3K9ac and H3K27ac reveals that SYISL and maternal microbiota interaction regulates myogenesis via the butyrate‐HDAC‐H3K9ac/H3K27ac pathway. Furthermore, scRNA‐seq analysis shows that SYISL knockout alone significantly increases the number and proportion of myogenic cells and their dynamics, independently of regulating histone acetylation levels. Cell communication analysis suggests that this may be due to the downregulation of signaling pathways such as MSTN and TGFβ. Overall, multiple pathways are highlighted through which SYISL influences embryonic muscle development, offering valuable insights for treating muscle diseases and improving livestock production.
Electrochemical Control of the Ultrafast Lattice Response of a Layered Semimetal
Authors: de Quesada Felipe A. , Muscher Philipp K. , Krakovsky Eliana S. , Sood Aditya , Poletayev Andrey D. , Sie Edbert J. , Nyby Clara M. , Irvine Sara J. , Zajac Marc E. , Luo Duan , Shen Xiaozhe , Hoffmann Matthias C. , Kramer Patrick L. , England R. Joel , Reid Alexander H. , Weathersby Stephen P. , Dresselhaus‐Marais Leora E. , Rehn Daniel A. , Chueh William C. , Lindenberg Aaron M.
Published: December 2024

The unique layer‐stacking in two‐dimensional (2D) van der Waals materials facilitates the formation of nearly degenerate phases of matter and opens novel routes for the design of low‐power, reconfigurable functional materials. Electrochemical ion intercalation between stacked layers offers a promising approach to stabilize bulk metastable phases and to explore the effects of extreme carrier doping and strain. However, in situ characterization methods to study the structural evolution and dynamical functional properties of these intercalated materials remains limited. Here a novel experimental platform is presented capable of simultaneously performing electrochemical lithium‐ion intercalation and multimodal ultrafast characterization of the lattice using both electron diffraction and nonlinear optical techniques. Using the layered semimetal WTe2 as a model system, the interlayer shear phonon mode that modulates stacking between 2Dlayers is probed, showing that small amounts of lithiation enhance the amplitude and lifetime of the phonon, contrary to expectations. This results from the dynamically fluctuating and anharmonic structure between nearly degenerate phases at room temperature, which can be stabilized by electronic carriers accompanying the inserted lithium ions. At high lithiation, the Td’ structure emerges and quenches the phonon response. This work defines new approaches for using electrochemistry to engineer the dynamic structure of 2D materials.
Symmetry Breaking in Rationally Designed Copper Oxide Electrocatalyst Boosts the Oxygen Reduction Reaction
Authors: Peng Haoyu , Wang Weiyi , Gao Jiyuan , Jiang Fan , Li Bowei , Wang Yicheng , Wu Yiqian , Wang Yue , Li Jiuqiang , Peng Jing , Hu Wei , Wen Zhenhai , Wang Dingsheng , Zhang Erhuan , Zhai Maolin
Published: December 2024

Oxygen reduction reaction (ORR) kinetics is critically dependent on the precise modulation of the interactions between the key oxygen intermediates and catalytic active sites. Herein, a novel electrocatalyst is reported, featuring nitrogen‐doped carbon‐supported ultra‐small copper oxide nanoparticles with the broken‐symmetry C4v coordination filed sites, achieved by a mild γ‐ray radiation‐induced method. The as‐synthesized catalyst exhibits an excellent ORR activity with a half‐wave potential of 0.873 V and shows no obvious decay over 50 h durability in alkaline solution. This superior catalytic activity is further corroborated by the high‐performance in both primary and rechargeable Zn–air batteries with an ultrahigh‐peak‐power density (255.4 mW cm−2) and robust cycling stability. The experimental characterizations and density functional theory calculations show that the surface Cu atoms are configured in a compressed octahedron coordination. This geometric arrangement interacts with the key intermediate OH*, facilitating localized charge transfer and thereby weakening the Cu─O bond, which promotes the efficient transformation of OH* to OH− and the subsequent desorption, and markedly accelerates kinetics of the rate‐determining step in the reaction. This study provides new insights for developing the utilization of γ‐ray radiation chemistry to construct high‐performance metal oxide‐based catalysts with broken symmetry toward ORR.
Fish Fin‐Derived Non‐Invasive Flexible Bioinspired Contact Lens for Continuous Ophthalmic Drug Delivery
Authors: Li Xu , Li Hui , Wang Zihao , Wang Xianda , Zhang Jinlong , Bin Fengjiao , Chen Wei , Li Hongyang , Huo Dongmei , Xiao Dengbao
Published: December 2024

Efficient drug delivery is crucial for glaucoma patients. Flexible biomedical devices that enable sustained ocular drug delivery and can regulate the drug release rate according to physiological conditions are highly desirable for glaucoma treatments, addressing both low drug bioavailability and poor patient compliance from manual drug administration, and improving treatment outcomes. Inspired by the structure and reciprocating motion of fish dorsal fins, a drug‐eluting contact lens based on deformable microstructures for non‐invasive ocular surface drug delivery is developed. Liquid drugs are stored within the interstices of the deformable microstructural units, allowing for continuous drug release through diffusion upon contact with the ocular surface. Finite element analysis is utilized to study the intraocular drug transport dynamics of glaucoma and optimize the overall layout of the device. Microstructural units undergo deformation under loading, altering the interstitial spaces and modulating the drug release rate. This device can adaptively adjust its drug release rate based on changes in intraocular pressure (IOP) and can be proactively regulated in response to cyclic eye loads, accommodating elevated IOP caused by varying body postures and activities. As a flexible, non‐invasive, highly dynamic, and adaptive drug delivery platform, it holds significant potential for future biomedical applications.
Optimizing Interfacial Charge Dynamics and Quantum Effects in Heterodimensional Superlattices for Efficient Hydrogen Production
Authors: Li Jinpeng , Dong Weikang , Zhu Zibo , Yang Yang , Zhou Jiadong , Wang Sufan , Zhou Yao , Song Erhong , Liu Jianjun
Published: December 2024

Superlattice materials have emerged as promising candidates for water electrocatalysis due to their tunable crystal structures, electronic properties, and potential for interface engineering. However, the catalytic activity of transition metal‐based superlattice materials for the hydrogen evolution reaction (HER) is often constrained by their intrinsic electronic band structures, which can limit charge carrier mobility and active site availability. Herein, a highly efficient electrocatalyst based on a VS2‐VS heterodimensional (2D‐1D) superlattice with sulfur vacancies is designed addressing the limitations posed by the intrinsic electronic structure. The enhanced catalytic performance of the VS2‐VS superlattice is primarily attributed to the engineered heterojunction, where the work function difference between the VS2 layer and VS chain induces a charge separation field that promotes efficient electron‐hole separation. Introducing sulfur vacancies further amplifies this effect by inducing quantum localization of the separated electrons, thereby significantly boosting HER activity. Both theoretical and experimental results demonstrate that the superlattice achieves a ΔGH* of −0.06 eV and an impressively low overpotential of 46 mV at 10 mA·cm−2 in acidic media, surpassing the performance of commercial Pt/C while maintaining exceptional stability over 15 000 cycles. This work underscores the pivotal role of advanced material engineering in designing catalysts for sustainable energy applications.
Fully Printable Manufacturing of Miniaturized, Highly Integrated, Flexible Evaporation‐Driven Electricity Generator Arrays
Authors: Liu Qun , Guo Panwang , Zhang Xinyu , Ren Hehe , Liang Jing , Li Quancai , Tang Weinan , Wu Wei
Published: December 2024

Harvesting sustainable clean energy from natural water evaporation holds great promise to provide continuous power for portable and wearable electronics. However, poor portability and complex fabrication processes hinder the low‐cost and large‐scale integration of flexible evaporation‐driven electricity generators (FEEGs). Herein, a fully‐printed flexible evaporation‐driven generator (PFEEG) is developed. Utilizing custom‐formulated functional inks, the asymmetric structures, current collectors, and hygroscopic water storage units can be manufactured by a patternable, scalable, and layer‐by‐layer deposition technique of screen printing. Thus, a PFEEG unit (0.5 cm × 1 cm × 38 µm) can generate a voltage of ≈0.8 V over a wide relative humidity (RH) range from 20% to 90%, and a maximum power density of 1.55 µW cm−2 at 70% RH. An array of 200 PFEEGs connected in series or parallel can produce voltages up to 152.41 V or a current up to 1.02 mA. Furthermore, the scalable PFEEG array can not only be seamlessly connected with the printed flexible circuit but can also be integrated with a humidity sensor and display arrays to form a self‐powered printed flexible sensing system. This work presents a practical strategy for continuous power supply of portable and wearable electronics.
DRD4 Interacts with TGF‐β Receptors to Drive Colorectal Cancer Metastasis Independently of Dopamine Signaling Pathway
Authors: Zhou Yuan , Tang Jinlong , Weng Menghan , Zhang Honghe , Lai Maode
Published: December 2024

The functional and pharmacological significance of dopamine receptor D4 (DRD4) in psychiatric and neurological disorders is well elucidated. However, the roles of DRD4 in colorectal cancer (CRC) remain unclear. This study observes a significant upregulation of DRD4 expression in clinical samples, which is negatively correlated with patient prognosis. In vitro, overexpression of DRD4 causes a constitutive activation of β‐Arrestin2/PP2A/AKT independent of dopamine. Interestingly, this classical signaling pathway is not associated with the phenotype of DRD4‐promoted migration and invasion in CRC cells. Instead, DRD4 interacts with transforming growth factor beta receptors (TGFBR1 and TGFBR2) to activate Smad2 phosphorylation and promote Smad2/Smad4 complex nucleus translocation. Then, SNAI1 and JAG1 are transcriptionally activated to induce epithelial‐mesenchymal transition and enhance the metastatic potential of CRC. Notably, the COOH‐terminal domain is identified as the key intracellular region for the pro‐metastatic roles of DRD4. Furthermore, treatment with a TGFBR1 inhibitor combined with a BMP inhibitor effectively counteracts the pro‐metastatic effects induced by DRD4 both in vitro and in vivo. In conclusion, these findings uncover an unconventional role for DRD4 beyond its classic function as a neurotransmitter receptor. The intracellular signaling of DRD4 interacting with TGFBR1 can be targeted pharmacologically for CRC therapy.
Photocatalytic Cascade Alkylation/Cyclization of N‐Arylacrylamides with Simple Alkanes: A Convenient Approach to Quaternary C3 Alkylated Oxindoles
Authors: Ye Liang , Xu Haibin , Yu Jiong , Yan Han , Wang Min , Li Pinhua
Published: December 2024

A convenient and efficient protocol for the synthesis of 3,3‐dialkylated oxindoles through photocatalytic aerobic radical‐cascade alkylation/cyclization of N‐arylacrylamides with the alkyl radicals generated from simple alkanes is described. This method features a broad substrate scope, inexpensive alkyl radical precursors, simple conditions and good yields.
Program‐Modulated Kinetics of Perovskite‐Film Growth by Molecular “Thruster” for High‐Efficiency and Stable Perovskite Solar Cells
Authors: Han Chuanshuai , Wu Yeyong , Xu Guiying , Wu Xiaoxiao , Xu Jiacheng , Xu Tingting , Huang Shihao , Shen Yunxiu , Cao Zhiyun , Chen Weijie , Xu Xiaoping , Li Yaowen
Published: December 2024

The rapid reaction between lead iodide (PbI2) and formamidinium iodide (FAI) complicates the fabrication of high‐quality formamidinium lead iodide (FAPbI3) films. Conventional methods, such as using nonvolatile small molecular additives to slow the reaction, often result in buried interfacial voids and molecule diffusion, compromising the devices’ operational stability. In this study, we introduced a molecular “thruster”—a hypervalent iodine (III) compound with three carbonyl groups and a C−−I+ bond—that possesses coordination and dissociation abilities, enabling programed modulation of perovskite‐film growth kinetics. Initially, the three carbonyl groups coordinate with PbI2 to slow the reaction between FAI and PbI2, preventing δ‐phase formation. As temperature rises, the C−−I+ bond dissociates, promoting perovskite growth and the dissociated product iodobenzene will promote solvent volatilization, thus avoiding buried interfacial voids. Another product, a carbene compound with eight lone pair electrons sufficiently passivate the undercoordinated Pb2+ defects and anchors at grain boundaries without diffusion. Consequently, the resultant FAPbI3 film displays high‐quality with enhanced phase purity, compact morphology, and reduced defects. Evidently, 0.062‐ and 1.004‐cm2 pero‐SCs achieve power conversion efficiencies (PCEs) of up to 26.06 % (25.79 % certified) and 24.65 %, respectively. This approach also controls perovskite‐film growth on plastic substrates, resulting in flexible pero‐SCs with an impressive PCE of 25.12 %.
Erzeugung von HO−Zn−N2‐aktiven Zentren in Zeolithischen‐Imidazolat‐Gerüsten für Verbesserte (Foto−)elektrokatalytische Wasserstoffentwicklung
Authors: Huang Zheao , Wang Zhouzhou , Zhou Qiancheng , Rabl Hannah , Naghdi Shaghayegh , Yang Ze , Eder Dominik
Published: December 2024

Erzeugung und Charakterisierung wohldefinierter aktiver Zentren in zeolithischen Imidazolat‐basierten Gerüststrukturen (engl. zeolitic imidazolate frameworks ZIFs) ist zetral um ein grundlegendes Verständnis hinsichtlich der mechanistischen Details der (foto‐)elektrokatalytischen Wasserstoffentwicklungsreaktion (engl. hydrogen evolution reaction, HER) in diesen Hybridmaterialien zu erhalten. In dieser Arbeit erzeugen wirungesättigte, offene Metallzentren (engl. open metal sites) in ZIFs durch eine selektive Ligandenentfernungsstrategie (engl. selective ligand removal SeLiRe), charakterisieren diese umfassend hinsichtlich deren strukturelle und elektronische Eigenschaften und untersuchen deren Auswirkungen auf die HER Aktivität. In situ‐elektrochemische Analysen und Röntgenabsorptionsspektroskopie zeigen die Bildung von HO−Zn−N2 Zentren mit hoher Wertigkeit durch die Bindung von Zn−N2 mit Hydroxidionen des Elektrolyten. Das optimale OMS‐ZIF weist eine niedrige Überspannung von 0,41 V auf, um eine Stromdichte von 1,0 A cm−2 mit einer Stabilität von 120 Stunden zu erreichen. Theoretische Simulationen zeigen, dass diese aktiven Zentren die Aktivierungskinetik von Wassermolekülen beschleunigen und somit die Effizienz des Volmer‐Schrittes verbessern. Diese Arbeit zeigt eine vielseitige Strategie zur Einführung katalytisch aktiver Zentren in ZIFs und liefert neue Erkenntnisse über den elektrokatalytischen Mechanismus in alkalischen Medien.
Anionic Doping in Layered Transition Metal Chalcogenides for Robust Lithium‐Sulfur Batteries
Authors: Huang Chen , Yu Jing , Yue Zhang Chao , Cui Zhibiao , He Ren , Yang Linlin , Nan Bingfei , Li Canhuang , Qi Xuede , Qi Xueqiang , Li Junshan , Yuan Zhou Jin , Usoltsev Oleg , Simonelli Laura , Arbiol Jordi , Lei Yao‐Jie , Sun Qing , Wang Guoxiu , Cabot Andreu
Published: December 2024

Lithium‐sulfur batteries (LSBs) are among the most promising next‐generation energy storage technologies. However, a slow Li−S reaction kinetics at the LSB cathode limit their energy and power densities. To address these challenges, this study introduces an anionic‐doped transition metal chalcogenide as an effective catalyst to accelerate the Li−S reaction. Specifically, a tellurium‐doped, carbon‐supported bismuth selenide with Se vacancies (Te−Bi2Se3–x@C) is prepared and tested as a sulfur host in LSB cathodes. X‐ray absorption and in situ X‐ray diffraction analyses reveal that Te doping induces lattice distortions and modulates the local coordination environment and electronic structure of Bi atoms to promote the catalytic activity toward the conversion of polysulfides. Additionally, the generated Se vacancies alter the electronic structure around atomic defect sites, increase the carrier concentration, and activate unpaired cations to effectively trap polysulfides. As a result, LSBs based on Te−Bi2Se3–x@C/S cathodes demonstrate outstanding specific capacities of 1508 mAh ⋅ g−1 at 0.1 C, excellent rate performance with 655 mAh ⋅ g−1 at 5 C, and near‐integral cycle stability over 1000 cycles. Furthermore, under high sulfur loading of 6.4 mg ⋅ cm−2, a cathode capacity exceeding 8 mAh ⋅ cm−2 is sustained at 0.1 C current rate, with 6.4 mAh ⋅ cm−2 retained after 300 cycles under lean electrolyte conditions (6.8 μL ⋅ mg−1).
High‐Valent Cobalt‐Difluoride in Oxidative Fluorination of Saturated Hydrocarbons
Authors: Das Agnideep , Twamley Brendan , Kelly Oscar R. , Panda Chakadola , Richardson Paul , McDonald Aidan R.
Published: December 2024

The heme paradigm where Fe=O acts as the C−H oxidant and Fe−OH rebounds with the formed carbon‐centered radical guides the design of the prototypical synthetic hydroxylation catalyst. We are exploring methods to evolve beyond the metal‐oxo oxidant and hydroxide rebound, to incorporate a wider array of functional group. We have demonstrated the application of CoII(OTf)2 (10 mol% catalyst; OTf=trimfluoromethanesulfonate) in combination with polydentate N‐donor ligands (e. g. BPMEN=N,N′‐dimethyl‐N,N′‐bis(pyrid‐2‐ylmethyl)ethane‐1,2‐diamine) and Selectfluor in the oxidative fluorination of saturated hydrocarbons in high yields. The addition of CsF to the reaction mixture induced near‐quantitative yields of fluorinated saturated hydrocarbons (>90 % yield of fluorinated product). For 1‐hydroxy, 1‐acetyl, 1‐carboxy‐, and 1‐acetamido‐adamantane, we demonstrated selective fluorination at the 3‐position. We propose two mechanisms for the CoII‐catalyzed reaction: either (i) an N‐radical, derived from Selectfluor, acted as the C−H oxidant followed by radical rebound with CoIII−F; or (ii) a CoIV−(F)2 species was the C−H oxidant followed by radical rebound with CoIII−F. Our combined spectroscopic, kinetic, and chemical trapping evidence suggested that an N‐radical was not the active oxidant. We concluded that a CoIV−(F)2 species was the likely active oxidant and CoIII−F was the likely F‐atom donor to a carbon centered radical producing a C−F bond.
Porous Halogen‐Bonded Frameworks Assembled through Hetero‐polytopic Ion Pair Templation
Authors: Smith Jordan N. , Hunter Callum I. , Doan Huan V. , Ting Valeska P. , White Nicholas G.
Published: December 2024

Halogen‐bonding (XB) interactions have been extensively studied in the preparation of crystalline frameworks, yet porous 3D framework materials built on XBs remain elusive. The donor‐acceptor interactions are strengthened by use of anionic XB acceptors; however, the requisite charge‐balancing cations typically disrupt the framework and occupy potential void space. In this work, we prepare a tetratopic XB donor bearing a crown ether moiety for sodium cation sequestration. We show that when this ionpair receptor is crystallised with NaCl it gives a 3D framework that is porous to solvent and vapour, and undergoes single‐crystal‐to‐single‐crystal reactions.
Fragment Discovery by X‐Ray Crystallographic Screening Targeting the CTP Binding Site of Pseudomonas Aeruginosa IspD
Authors: Willocx Daan , D'Auria Lucia , Walsh Danica , Scherer Hugo , Alhayek Alaa , Hamed Mostafa M. , Borel Franck , Diamanti Eleonora , Hirsch Anna K. H.
Published: December 2024

With antimicrobial resistance (AMR) reaching alarming levels, new anti‐infectives with unprecedented mechanisms of action are urgently needed. The 2‐C‐methylerythritol‐D‐erythritol‐4‐phosphate (MEP) pathway represents an attractive source of drug targets due to its essential role in numerous pathogenic Gram‐negative bacteria and Mycobacterium tuberculosis (Mt), whilst being absent in human cells. Here, we solved the first crystal structure of Pseudomonas aeruginosa (Pa) IspD, the third enzyme in the MEP pathway and present the discovery of a fragment‐based compound class identified through crystallographic screening of PaIspD. The initial fragment occupies the CTP binding cavity within the active site. Confirmation of fragment–protein interactions was achieved through 1H saturation–transfer difference nuclear magnetic resonance (1H‐STD NMR spectroscopy). Building upon these findings and insights from the co‐crystal structures, we identified two growth vectors for fragment growing. We synthesized derivatives addressing both growth vectors, which showed improved affinities for PaIspD. Our new fragment class targets PaIspD, displays promising affinity and favorable growth vectors for further optimization.
Calcium Chemistry as A New Member of Post‐Lithium Battery Family: What Can We Learn from Sodium and Magnesium Systems
Authors: Li Zhenyou , Cui Shuangshuang , Häcker Joachim , Nojabaee Maryam , Fichtner Maximilian , Cui Guanglei , Zhao‐Karger Zhirong
Published: December 2024

The development of next‐generation battery technologies needs to consider their environmental impact throughout the whole cycle life, which has brought new chemistries based on earth‐abundant elements into the spotlight. Rechargeable calcium batteries are such an emerging technology, which shows the potential to provide high cell voltage and high energy density close to lithium‐ion batteries. Additionally, the use of Ca2+ as a charge carrier renders significant sustainable values. Although pioneering work on the electrochemistry of Ca has been carried out for more than half a century, demonstration of reversible Ca0/Ca2+ redox chemistry in non‐aqueous media was only achieved within the past decade. In this review, we will present recent development of rechargeable calcium batteries, focusing on mainly the similarities but also differences between Ca chemistry and other post‐lithium chemistry. According to the periodic nature of elements, magnesium (an alkaline earth element as Ca) and sodium (a diagonally adjacent element to Ca) have similar chemical properties to Ca in various aspects. We shall elaborate on how the solution chemistry, metal behaviors and transport mechanisms of Ca‐ions can be better understood in light of the established principles in the respective Mg/Na systems. We hope the discussion will inspire synergetic development between Ca batteries and other post‐lithium systems.
Genetic Incorporation of a Thioxanthone‐Containing Amino Acid for the Design of Artificial Photoenzymes
Authors: Chen Kai‐Yue , Ming Hui , Wang He‐Xiang , Wang Hua‐Qi , Xiang Zheng
Published: December 2024

Genetically encodable photosensitizers allow the design of artificial photoenzymes to expand the scope of abiological reactions. Herein, we report the genetic incorporation of a thioxanthone‐containing amino acid into a protein scaffold via an engineered pyrrolysyl‐tRNA/pyrrolysyl‐tRNA synthetase pair. The designer enzyme was engineered to catalyze a dearomative [2+2] cycloaddition reaction in high yields (up to>99 % yield) with excellent enantioselectivity (up to 98 : 2 e.r.). This work provides a robust and facile method for photoenzyme design and lays the foundation for the development of further photoenzymatic reactions.
Engineering of HO−Zn−N2 Active Sites in Zeolitic Imidazolate Frameworks for Enhanced (Photo)Electrocatalytic Hydrogen Evolution
Authors: Huang Zheao , Wang Zhouzhou , Zhou Qiancheng , Rabl Hannah , Naghdi Shaghayegh , Yang Ze , Eder Dominik
Published: December 2024

Currently, lack of ways to engineer specific and well‐defined active sites in zeolitic imidazolate frameworks (ZIFs) limits our fundamental knowledge with respect to the mechanistic details for (photo)electrocatalytic hydrogen evolution reaction (HER). Here, we introduce the open metal sites into ZIFs through the selective ligand removal (SeLiRe) strategy, comprehensively characterize the altered structural and electronic features, and evaluate their role in HER. In situ electrochemical analysis and X‐ray absorption spectroscopy reveal the formation of high‐valence HO−Zn−N2 sites through the binding of Zn−N2 with electrolyte hydroxide. The optimal OMS‐ZIF exhibits a low overpotential of 0.41 V to achieve an ampere‐level 1.0 A cm−2 with 120‐hour stability. Theoretical simulations indicate that these active sites accelerate the water molecules activation kinetics, consequently enhancing the efficiency of the Volmer step. This work demonstrates a versatile strategy to introduce highly active catalytic sites in ZIFs, providing new insights into the electrocatalytic mechanism in alkaline media.
Epiglottic injury and airway management – a challenging and unexpected diagnosis
Authors: Gutierres M. , Guedes F. , Rosa F. , Oliveira F. , Castro R. , Fernandes V.
Published: December 2024

Patients with facial trauma are complex; difficult airway management is often anticipated and challenging for the anaesthetist. Awake tracheal intubation is the gold standard in the management of predicted difficult airway because of its high success rate and safety profile. We present the case of a patient with facial trauma who underwent orotracheal intubation with combined videolaryngoscopy and flexible bronchoscopy, under conscious sedation with intermittent boluses of ketamine and dexmedetomidine. Videolaryngoscopy showed significant oedema and epiglottic laceration, not diagnosed by the computed tomography scan, with visualisation of a false passage that could have led to a failed intubation and further trauma. Airway management in patients with facial trauma is challenging and should be planned and discussed by a multidisciplinary team. A technique combining videolaryngoscopy and flexible bronchoscopy during awake intubation has previously been described and, when used in this case, was successful.
Deep Eutectic Solvent Engineered Dendritic Fibrous Nano‐Silica Catalyst for Sustainable Fixation of CO2 Into Value‐Added Product at Atmospheric Condition
Authors: Alla Sarat Chandra , Sudhakaran Allwin , Bembalge Omkar B. , Samal Akshaya K. , Torrejos Rey Eliseo , Norrrahim Mohd Nor Faiz , Jadhav Arvind H.
Published: December 2024

Developing efficient carbon dioxide (CO2) capture and conversion methods is vital for climate change mitigation. Cycloaddition of CO2 with epoxides to form cyclic carbonates is a promising utilization method. In this study, a deep eutectic solvent‐modified dendritic fibrous nano‐silica (DES@DFNS) catalyst was synthesized by functionalizing DFNS with DES. This catalyst was used for the cycloaddition of CO2 with styrene oxide to produce styrene carbonate. The material's morphology and properties were characterized using various analytical techniques, revealing a high surface area, good porosity, and significant concentrations of Lewis acidic and basic sites. Rietveld refinement analysis provided insights into its phase composition, crystallite size, microstrain, stress, and other microstructural properties. Despite a lower surface area, DES@DFNS demonstrated superior catalytic activity. The interaction between DES and DFNS showed that DES was physically adsorbed onto the DFNS surface, contributing to its enhanced performance. Factors such as smaller crystallite size, higher microstrain, increased dislocation density, and improved elastic properties provided more active sites and greater mechanical stability, boosting overall efficiency and durability. The DES@DFNS catalyst achieved 99% conversion of styrene oxide with 96% selectivity and 95% yield of styrene carbonate at 120 °C for 10 h under solvent‐free, atmospheric conditions. The synergistic effect of Lewis acidic and basic sites on DES@DFNS supported catalytic activity under moderate conditions. Additionally, the catalyst demonstrated reusability, maintaining performance for up to six cycles without significant loss of activity, making it a promising candidate for sustainable CO2 fixation and valorization processes.
Mn (III)‐Porphyrin Complex as an Efficient and Recyclable Homogeneous Catalyst for Convenient Synthesis of Thioxo‐4,5‐Dihydro‐3H‐thiazolo Pyrimidin‐2‐One Derivatives in Aqueous Media via a One‐Pot Multicomponent Reaction
Authors: Alzahrani Abdullah Yahya Abdullah , Eskander Thomas Nady A. , Soliman Ahmed M.M. , Alraih Alhafez M. , Ali El‐Remaily Mahmoud Abd El Aleem Ali
Published: December 2024

This study successfully utilized the Mn (III)–porphyrin complex (Mn (PT)Cl) as an efficient and recyclable catalyst for a one‐pot, three‐component reaction involving aromatic aldehydes, 2,4‐thiazolidinedione, and thiourea. The reaction yielded thioxo‐4,5‐dihydro‐3H‐thiazolo pyrimidin‐2‐one derivatives under eco‐friendly conditions. Elemental and spectral analyses confirmed the structures of the synthesized compounds, validating the successful formation of the target products. The reactions were conducted in a sustainable environment using a green solvent mixture of H₂O and EtOH. The results showcased the excellent catalytic activity and selectivity of the complexes, resulting in good yields of the desired products. This research provides valuable insights into the synthetic applications of the Mn (PT)Cl complex and emphasizes the potential of such catalysts for various organic transformations. The method's simplicity, safety, commercial availability, stability, rapid reaction times, and high yields indicate promising future applications in industry.
Utilization of a One‐Pot Prepared Cobalt Selenide Embedded Carbon Matrix Electrode From ZIF‐12 for High‐Performance Asymmetric Supercapacitors
Authors: Siyahjani Gultekin Sirin , Bugday Nesrin , Sahin Damla , Ocakoglu Kasim , Gultekin Burak , Yaşar Sedat
Published: December 2024

It is becoming increasingly important to create novel energy storage devices with excellent cycle stability, high power density and high energy density due to the fast advancement in technology. Rechargeable batteries and electrochemical supercapacitors (SCs) are developed as energy storage devices to meet these energy requirements. In this work, a cobalt selenide embedded in a carbon matrix (Co6.8Se8@C) produced from ZIF‐12 via a one‐pot method by our group for the first time was used as an asymmetric SC electrode. In this work, a cobalt selenide embedded in a carbon matrix (Co6.8Se8@C) produced from ZIF‐12 as a precursor by our group previously has been used as an asymmetric SC electrode. The effects of the structural and morphological properties of this composite material on its electrochemical behaviour and capacitive performance were examined both in a three‐electrode system as a single electrode and in an asymmetric SC. The superior electrochemical storage performance with a specific capacitance of 77.06 Fg−1 at 1 Ag−1 and energy density of 27.09 Wh kg−1 at a power density of 441.90 W kg−1 were obtained with high stability and cycle life via the prepared electrode in asymmetric SC device.
Improved Electromagnetic Interference Shielding in Lightweight Polyvinylidene Fluoride‐Carbon Nanotube Composite Films
Authors: Dani Santhoshkumar , Hasamkal Arshad Ayub , Patil Praveen , Arun B. , Raju K. C. James , Udaykumar Khadke
Published: December 2024

As electronic devices become smaller and more common, the problem of electromagnetic interference (EMI) becomes more serious, requiring better shielding solutions. In this study, lightweight polyvinylidene fluoride (PVDF) composite films mixed with multiwalled carbon nanotubes (MWCNT) were developed to improve EMI shielding. A solution casting method and a thin film applicator ensured uniform thickness and flexibility in PVDF‐MWCNT films with varying MWCNT concentrations (0, 0.1, 1, and 2 wt%). Structural and surface properties were analyzed using X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and energy dispersive X‐ray spectroscopy (EDS). Dielectric response, AC conductivity, and EMI shielding effectiveness (EMI‐SE) in the Ku band (12–18 GHz) were measured. The PVDF film with 2 wt% MWCNT, at a thickness of 190 ± 10 μm, showed the highest complex permittivity and a record EMI‐SE value of 53.08 dB. This high EMI‐SE is attributed to increased multiple internal reflections within the thin film, enhancing attenuation and reducing reflection losses. These polymer nanocomposites offer a promising and lightweight option for advanced EMI shielding in the growing number of electronic devices.