bluuebunny/crossref_metadata_2025 huggingface dataset:
Tailoring Tumor Cell Golgi Apparatus‐Targeting Self‐Assembled Peptide for Effective Immunotherapy via Reshaping MIF‐Mediated Immunosuppressive Network
Authors: Li Xiang , Wang Chengxinqiao , Liu Junhan , Deng Guifang , Deng Yongqiang , Hu Fang , Wang Yupeng , Zhou Dongfang
Published: February 2025

The immunosuppressive network formed by the enhanced crosstalk between tumor cells and various types of immune cells may ultimately lead to the formation of tumor immunosuppressive microenvironment (TIME). The Golgi apparatus (GA) of tumor cells is a key organelle in the formation of a tumor immunosuppressive network. However, there are no studies to show whether interfering with the GA of tumor cells can reshape the immunosuppressive network to enhance the effectiveness of immunotherapy. Therefore, the tumor cell GA‐targeting self‐assembled peptide (NF‐1) is tailored, and confirmed that NF‐1 treatment can achieve an effective immunotherapy and found that tumor cell‐derived GA‐dependent migration inhibitory factor (MIF) mediates the formation of immunosuppressive network in breast cancer (BRCA) through multi‐omics analysis, in vivo, and in vitro experiments. NF‐1 treatment‐induced MIF reduction can reshape the immunosuppressive network and convert a “cold” tumor into a “hot” tumor, thus enabling immunotherapy in BRCA and enhancing the ICB efficacy in colon adenocarcinoma (COAD). This study presents a general strategy for interfering with tumor GA for effective immunotherapy in BRCA, COAD, and other cancers characterized by a “cold” immune microenvironment.
Structure and Wiring Optimized TT/MT Double‐Helical Fiber Sensors: Fabrication and Applications in Human Motion Monitoring and Gesture Recognition
Authors: Chen Ziwei , Qian Daoxiong , Xie Dandan , Gao Chunxia , Shi Jian , Morikawa Hideaki , Zhu Chunhong
Published: February 2025

A fibrous flexible sensor, with its small size, minimally burdens the human body, ranking among the most user‐friendly flexible sensors. However, its application is often limited by damage caused by electrode movement, as flexible sensors are typically attached to joints, which can be greatly alleviated by placing the two electrodes on the same side. Inspired by the hydrogen bonds in the double‐helical structure of DNA, the double‐helical electrode design is commonly found and applied in fiber‐based batteries and supercapacitors into fibrous flexible sensors through coaxial wet‐spinning and further treatment. The double helical sensor exhibits high strength and maintains stable operation and is prepared under over 300% strain with gauge factors (GF) of 0.9, 39.5, and 349, respectively, in its working ranges. This unique single‐sided electrode structure also enabled applications such as water flow sensing. The sensor into a smart glove capable of real‐time is further integrated, five‐channel finger motion detection, and used a convolutional neural network (CNN)‐based machine learning algorithm to achieve 98.8% accuracy in recognizing six common gestures. This study provides a novel approach to optimize the electrode distribution in fiber‐based flexible sensors through an internally encapsulated double‐helical structure, making a significant contribution to the field of flexible sensing.
A Platinum Complex‐Based Dimerized Electron Acceptor for Efficient Organic Solar Cells
Authors: Cheng Yang , Jiang Dongcheng , Xiao Chengyi , Li Mengdi , Lin Yi , Zhao Chaowei , Tang Zheng , Yin Hang , Li Weiwei
Published: February 2025

Metal–organic complexes have demonstrated excellent performance in organic light‐emitting diodes, yet their potential in organic solar cells (OSCs) remains underexplored. In this study, a novel metal–organic complex, Pt‐Y, which features a platinum core connected to Y‐acceptor arms, for application in OSCs is designed and synthesized. The dimerized Pt‐Y acceptor is prepared through straightforward reactions, with the key precursor linking the platinum metal and Y‐acceptors synthesized through Sonogashira coupling. Steady‐state and transient photoluminescence measurements revealed that Pt‐Y exhibits distinct singlet and triplet states with microsecond lifetimes—significantly longer than the nanosecond lifetimes of Y‐acceptors without the metal. Incorporating Pt‐Y as a third component in ternary OSCs has resulted in a remarkable efficiency of 19.2%. Further morphological analysis and transient absorption measurements indicate that the dimerized Pt‐Y displays excellent miscibility with the Y‐acceptor, leading to minimal phase separation and the formation of fibrillar structures. These structures enhance charge separation and transport while reducing charge recombination. This work presents a facile approach to developing metal–organic complexes with exceptional photovoltaic performance in OSCs.
Circularly Polarized Luminescence Inversion in AIE‐Active Crystal Enabled by Solvent‐Induced Transition Dipole Moment Regulation
Authors: Niu Xiaofei , Ou Xinwen , Ren Shizhe , Wang Ke , Song Fengyan , Dong Xiaobin , Guo Wu‐Jie , Peng Hui‐Qing , Zhao Zujin , Lam Jacky W. Y. , Zhao Yong Sheng , Li Fei , Yu Shu‐Yan , Tang Ben Zhong
Published: February 2025

Control of the dissymmetry of circularly polarized luminescence (CPL) is intriguing and has great potential for applications in the field of optics. The traditional control strategy involves using the opposite enantiomers to achieve reversal of CPL signs. However, regulating CPL reversal by controlling only the transition dipole moments without changing molecular or supramolecular chirality remains a challenge. Herein, we developed a couple of crystal materials based on axially chiral aggregation‐induced emission luminogens (AIEgens). These materials exhibit achiral solvent‐induced CPL sign inversion with identical helical structures and molecular chirality in their crystalline states. (R)‐BPAuCzT displays (+)‐CPL with a dissymmetry factor of luminescence (glum) value of +9.81 × 10−4 (560 nm), while (R)‐BPAuCzC exhibits (−)‐CPL with a glum value of −1.02 × 10−3 (560 nm). Time‐dependent density functional theory calculations show that the magnetic and electric transition dipole moments at S1 → S0 of the (R)‐BPAuCzC unit cell are considerably influenced by the cocrystallized solvent molecules, revealing a solvent‐induced CPL inversion mechanism. The nonbonding interactions between the solvent molecules (i.e., tetrahydrofuran or CDCl3) and AIEgens in the crystal play a crucial role in the manipulation of the transition dipole moment of these crystal materials. Moreover, microrods of (R)‐BPAuCzT, (R)‐BPAuCzC, and (R)‐BPAuCzDCE exhibit optical waveguide properties with relatively low optical‐loss coefficients of 187.3, 567.4, and 65.2 dB/cm, respectively. These findings can help in developing a new strategy toward controlling CPL signals and providing a potential application for future integrated photonic circuits.
An atomically economical and environmentally benign approach for the scalable synthesis of rare‐earth metal‐organic framework catalysts
Authors: Zhang Xin , Bai Xuefeng , Li Yi , Xie Yabo , Zhang Run‐Ji , Chen Da‐Yu , Zhang Jian‐Yu , Xing Na , Li Jian‐Rong
Published: February 2025

Metal–organic frameworks (MOFs), as an emerging class of porous materials, demonstrated substantial potential for applications in chemical engineering processes. However, their production often generates significant waste including ionic residues and organic solvents, posing considerable environmental concerns. Herein, we report the environmentally benign MOF synthesis with metal oxides precursors, yielding water as the exclusive by‐product. This approach not only enhances atom economy but also promotes solvent recycling by preventing anion accumulation, significantly reducing waste generation. The synthesis can be easily scaled up in a 10‐L reactor with an impressive space–time yield of 608 kg·m−3·day−1. Furthermore, MOF‐76(Y) was implemented in a reactor for catalytic cycloaddition reaction at kg‐scale. Through optimization of the interfacial contact between CO2 and the reaction liquid phase, a yield of 96.7% was achieved under mild conditions. This work demonstrates a rare example of scalable and sustainable synthesis of MOF materials coupled with catalysis implementation at kilogram scale.
Two‐Pot Synthesis of Indolizinoindole Derivatives via Lewis Acid‐Mediated Intramolecular Regioselective Cyclization of 3‐Acylpyrroles
Authors: Mamta  , Shah Imtiyaz Ahmad , Verma Mainika , Rangan Krishnan , Iype Eldhose , Khungar Bharti , Kumar Indresh
Published: February 2025

A two‐pot method has been developed to access indolizino[8,7‐b]indole derivatives through Lewis acid‐mediated regioselective C5‐cyclization of 3‐acylpyrrole prepared from the feedstock materials. The overall reaction proceeds through amine‐catalyzed direct aldol reaction/Paal‐Knorr reaction/oxidation between succinaldehyde, aromatic aldehyde, and tryptamine in a sequential multicomponent fashion for N‐alkyl pyrrole followed by dearomative cyclization. A series of substituted indolizino[8,7‐b]indoles have been prepared with good yields and excellent regioselectivity.
Use of Nonhuman Primates in Periodontal Disease Research: Contribution of the Caribbean Primate Research Center and Cayo Santiago Rhesus Colony
Authors: Ebersole Jeffrey L. , Novak M. J. , Cappelli D. , Dawson D. R. , Gonzalez O. A.
Published: February 2025

This review article provides a historical summary regarding the use, value, and validity of the nonhuman primate model of periodontal disease. The information provided cites results regarding the features of naturally occurring periodontitis in various nonhuman primate species, as well as the implementation of a model of experimental periodontitis. Clinical similarities to human disease are discussed, as well as the use of these models to document physiological and pathophysiological tissue changes in the periodontium related to the initiation and progression of the disease. Additionally, the use of these analytics in examination of the tissue characteristics of the disease, and the utility of nonhuman primates in testing and describing various therapeutic modalities are described. As periodontitis represents a disease of an oral microbiome dysbiosis, features of the altered microbiome in the disease in nonhuman primates are related to similar findings in the human condition. The review then provides a summary of the features of local and systemic host responses to a periodontal infection in an array of nonhuman primate species. This includes attributes of innate immunity, acute and chronic inflammation, and adaptive immune responses. Finally, extensive information is presented regarding the role of Macaca mulatta derived from the Cayo Santiago community in evaluating critical biologic details of disease initiation, progression, and resolution. This unique resource afforded the capacity to relate risk and expression of disease and traits of the responses to age, sex, and matriline derivation (e.g., heritability) of the animals. The Cayo Santiago colony continues to provide a critical preclinical model for assessment of molecular aspects of the disease process that can lead to both new targets for therapeutics and consideration of vaccine approaches to preventing and/or treating this global disease.
The Alzheimer's Association Global Biomarker Standardization Consortium (GBSC) plasma phospho‐tau Round Robin study
Authors: Ashton Nicholas J. , Keshavan Ashvini , Brum Wagner S. , Andreasson Ulf , Arslan Burak , Droescher Mathias , Barghorn Stefan , Vanbrabant Jeroen , Lambrechts Charlotte , Van Loo Maxime , Stoops Erik , Iyengar Shweta , Ji HaYeun , Xu Xiaomei , Forrest‐Hay Alex , Zhang Bingqing , Luo Yuling , Jeromin Andreas , Vandijck Manu , Bastard Nathalie Le , Kolb Hartmuth , Triana‐Baltzer Gallen , Bali Divya , Janelidze Shorena , Yang Shieh‐Yueh , Demos Catherine , Romero Daniel , Sigal George , Wohlstadter Jacob , Malyavantham Kishore , Khare Meenakshi , Jethwa Alexander , Stoeckl Laura , Gobom Johan , Kac Przemysław R. , Gonzalez‐Ortiz Fernando , Montoliu‐Gaya Laia , Hansson Oskar , Rissman Robert A. , Carrillo Maria C. , Shaw Leslie M. , Blennow Kaj , Schott Jonathan M. , Zetterberg Henrik
Published: February 2025

INTRODUCTION

The Alzheimer's Association Global Biomarker Standardization Consortium conducted a blinded case–control study to learn which phosphorylated tau (p‐tau) assays provide the largest fold‐changes in Alzheimer's disease (AD) versus non‐AD and show commutability in measuring patient samples and candidate certified reference materials (CRMs).

METHODS

Thirty‐three different p‐tau assays measured paired plasma and cerebrospinal fluid (CSF) from 40 participants (25 with “AD pathology” and 15 with “non‐AD pathology” by CSF amyloid beta [Aβ]42/Aβ40 and p‐tau181 criteria). Four CRMs were assessed.

RESULTS

Plasma p‐tau217 demonstrated higher fold‐changes between AD and non‐AD than other p‐tau epitopes. Fujirebio LUMIPULSE G, UGOT IPMS, and Lilly MSD p‐tau217 provided the highest fold‐changes. Plasma p‐tau217 showed the strongest correlations between plasma assays (rho = 0.81–0.97). The CRMs were not commutable across assays.

DISCUSSION

Plasma p‐tau217 showed larger fold‐changes and better accuracy for detecting AD pathology in symptomatic individuals, with greater cross‐platform agreement than other p‐tau variants. Further work is needed to develop suitable CRMs facilitating cross‐assay standardization.

Highlights

Paired plasma and cerebrospinal fluid (CSF) samples from twenty‐five Alzheimer's disease (AD) and 15 non‐AD patients were measured blind.

Thirty‐three plasma assays were compared, for phosphorylated tau‐181 (p‐tau181), 205, 212, 217 and 231.

Plasma p‐tau217 consistently had the highest fold‐change and was best correlated between assays.

Plasma‐CSF correlations were weak to moderate.

There was lack of commutability for four candidate reference materials.
Pd‐Catalyzed Skeletal Rearrangement via C(sp3)−C(sp3) Activation to Access α,β‐Unsaturated δ/γ‐Lactone
Authors: Manna Kartic , Maji Suman , Sharma Akhilesh , Kumar Nikunj , Gupta Puneet , Maiti Debabrata
Published: February 2025

The activation of non‐polar aliphatic C−C bonds represents a significant challenge that remains to be addressed in the field of Pd(II) catalysis. In this study, we present a dual ligand approach as a means of addressing this issue. The process entails lactonization of cyclobutane and cyclopropane carboxylic acid via the activation of non‐polar C(sp3)−C(sp3) bond despite the high feasibility of both οrtho‐C(sp2)−H and β or γ ‐C(sp3)−H activation. Density Functional Theory (DFT) calculations were performed to reveal the mechanistic insights and elucidate the role of dual ligands in facilitating this challenging transformation.
Transient Dangling Active Sites of Fe(III)−N−C Single‐Atom Catalyst for Efficient Electrochemical CO2 Reduction Reaction
Authors: Qiu Yun‐Ze , Liu Xiao‐Meng , Li Wenying , Li Jun , Xiao Hai
Published: February 2025

The Fe single‐atom catalyst (SAC) with an oxidation state of III anchored on the N‐doped carbon substrate (Fe(III)−N−C) delivers superior activity for catalyzing the electrochemical CO2 reduction reaction (eCO2RR) to produce CO, but its mechanism remains contentious and the commonly adopted FeN4‐C model is not a conformant model for Fe(III)−N−C but for Fe(II)−N−C. Herein, employing the grand‐canonical ensemble modeling with the density functional theory method benchmarked against the high‐level wavefunction theory method, we first identify the conformant model for Fe(III)−N−C to be FeN1C3‐C, and we then unveil that the Fe(III)N1C3‐C SAC generates a novel type of dangling active site transiently under working conditions, in which the Fe single‐atom leaves from the anchoring site by breaking all the Fe−C bonds but retains a stable binding to the substrate by the Fe−N bond. Thus, we further elucidate that this flexible dangling active site of Fe(III)−N−C renders a convoluted reaction network with facile CO2 activation, which delivers superior activity for eCO2RR. Our findings provide a novel understanding of the structure–activity relationship for Fe−N−C and concrete insights into the design of highly active SACs.
Multifunctional Polymer Interphase with Fast Kinetics for Ultrahigh‐rate Zn Metal Anode
Authors: Xue Pan , Guo Can , Gong Wenbin , Chen Yuting , Chen Xiang , Li Xiaoge , Yang Jingyi , Zhang Qichong , Davey Kenneth , Zhu Kaiping , Mao Jianfeng , Guo Zaiping
Published: February 2025

Polymer interphase on Zn anodes obviates dendrite growth and significant side reactions including corrosion and hydrogen evolution in aqueous zinc ion batteries (AZIBs), however has drawbacks of slow kinetics and large overpotential for Zn plating/stripping that prevent practical application especially under high‐rate conditions. Here, a multifunctional polymer interphase with fast kineticsis reported, using poly(phenazine‐alt‐pyromellitic anhydride) (PPPA) as an electrolyte additive. PPPA, with linear π‐conjugated structure and enriched polar pyridine (conjugated cyclic −C=N−) and carbonyl (C=O) groups, preferentially adsorbs on the Zn anode to form a stable solid‐electrolyte interphase (SEI) layer in situ. The PPPA SEI is efficient to block direct contact between water molecules and Zn anode, and regulate the interfacial solvation structure and Zn depostion. Importantly, the expanding π‐conjugated structure of PPPA is shown to provide abundant 2D open channels for rapid Zn2+ transport, and the delocalized π electrons form a space electrostatic field to facilitate de‐solvation and diffusion of Zn2+. As a result, the Zn metal anode with PPPA/ZnSO4 electrolyte exhibits high Coulombic efficiency of 98.3 % at current density of 20 mA  cm−2, and excellent cycle lifespan for over 2000 cycles (400 h) at current density 50 mA cm−2 and plating/stripping capacity of 5 mAh cm−2. The Zn||MnO2 full battery exhibited a discharge capacity of 74.4 mAh g−1 after 5000 cycles at the current density of 2000 mA g−1, demonstrating practical feasibility. It is concluded that judicious engineering of polymer additives and interphase will benefit the development of commercial AZIBs with fast kinetics for high‐rate applications.
Divergent Total Syntheses of Six Crinipellin‐Type Diterpenoids through Tandem 4π‐Electrocyclization/Dicycloexpansion
Authors: Ke Tian , Hou Si‐Hua , Wang Yun‐Peng , Fang Kun , Hu Jing‐Han , Lu Ka , Tu Yong‐Qiang
Published: February 2025

Crinipellins are a significant class of naturally occurring highly congested tetraquinane diterpenoids, with many members exhibiting bio‐important antibacterial and anticancer activities. However, their complex structures, particularly their dense 5/5/5/5 tetracyclic frameworks, have made efficient synthesis challenging, leading chemists to attempt to create highly efficient and divergent routes. This study presents a concise, divergent synthesis of six crinipellins, completed in just 9–11 steps using commercially available materials. Particular highlights include: (1) a vital one‐step 4π‐electrocyclization/dicycloexpansion cascade that rapidly constructs the angular/fused tetraquinane scaffold with two contiguous quaternary carbons, and (2) strategic functionalizations through iso‐propylation, methylation, and Wacker oxidation/dehydrogenation, enabling the divergent syntheses of the six crinipellin members without using protecting groups. This approach provides a versatile platform for accessing additional crinipellin derivatives, which we believe will benefit medicinal and biological research.
The Last Piece of the Puzzle: Access to 7‐Connected Zirconium Metal–Organic Frameworks for Hexane Separation
Authors: Tang Xianhui , Jia Lei , Wang Xiaoliang , Su Shengyi , Chen Yongwei , Kong Xiang‐Jing , Ye Zi‐Ming , Xie Haomiao , Gong Wei , Du Enping , Liu Yan , Kirlikovali Kent O. , Farha Omar K. , Cui Yong
Published: February 2025

Zirconium metal–organic frameworks (Zr‐MOFs) exhibit a wide range of Zr6 cluster connectivities, from 3‐connected to 12‐connected, enabling diverse structural designs. However, odd‐numbered connectivities, especially the 7‐connected Zr‐MOFs, are exceptionally rare due to geometric symmetry challenges. To address this, we developed a geometric pre‐assembly strategy to achieve targeted cluster connectivity. Using this approach, we synthesized NU‐5001 {[Zr6O4(OH)4(H4‐L)2]}, a Zr‐MOF featuring 7‐connected Zr6 clusters, derived from the precursor 6‐connected Zr‐MOF, NU‐5000 {[Zr6O4(OH)4(H3‐L)2]}. NU‐5000, constructed with a tritopic chiral linker H3‐L {(R)‐4,4’,4’’‐[6’‐chloro‐2,2’‐diethoxy‐(1,1’‐binaphthalene)‐4,4’,6‐triyl]tribenzoic acid}, forms a (3,6)‐connected ant topology. Introducing a tetratopic chiral linker, 1,1’‐bi‐2‐naphthol tetracarboxylic acid H4‐L {(R)‐4,4’,4’’,4’’’‐[2,2’‐diethoxy‐(1,1’‐binaphthalene)‐4,4’,6,6’‐tetrayl]tetrabenzoic acid}, enabled an additional connection, resulting in NU‐5001 with a (3,4,7)‐connected topology. The H4‐L linker acts as either fully 4‐connected or 3‐connected with one arm uncoordinated. Additionally, NU‐5001M {[Zr6O4(OH)4(H4‐L) (H3‐L)]}, an isostructural variant, was synthesized using a mix of H3‐L and H4‐L linkers. NU‐5001’s unique pore structure and slight flexibility enable distinct adsorption behaviors for hexane isomers, highlighting its potential for kinetic separations. This work completes the Zr6 cluster connectivity landscape and demonstrates the feasibility of tuning Zr‐MOF connectivities through rational linker design, paving the way for rare, low‐symmetry frameworks with tailored properties.
H‐Bonds in Carbon Quantum Dot‐anchored C3N5 to Boost Proton‐Coupled Electron Transfer for Piezoelectric‐Driven Hydrogen Peroxide Synthesis under Ambient Conditions
Authors: Li Zhi , Tong Kangbo , Dong Haojie , Li Yatai , Wang Kai , Ding Tengda , Yun Yang , Zhou Yingtang , Zhu Mingshan
Published: February 2025

Tuning proton‐coupled electron transfer (PCET) is a promising strategy to boost the oxygen reduction reaction (ORR) for hydrogen peroxide (H2O2) synthesis, but the slow transmission rate of protons and electrons to active sites remains a significant bottleneck. To address this, we developed an H‐bond‐driven PCET process based on carbon quantum dot‐anchored C3N5 (CQDs‐C3N5) for piezo‐catalytic H2O2 synthesis. CQDs‐C3N5 exhibited a remarkable piezo‐catalytic synthesis rate of 5025 μmol g−1 h−1 under ambient conditions, surpassing that of most reported piezoelectric materials. This efficiency is attributed to the intermolecular H‐bonds between CQDs and C3N5, which significantly accelerate PCET in the ORR. The piezoelectric‐generated charges, from the dipole field of the C3N5 plane, and protons in water, were rapidly transferred to the C rings of CQDs via H‐bond networks. This process facilitated the adsorption of oxygen onto the C2 sites adjacent to the carboxyl groups of CQDs, which in turn led to the formation of H2O2 through a rapidly protonated, indirect 2e− pathway. Additionally, a piezo‐self‐Fenton reaction system was constructed for oxytetracycline‐rich wastewater purification, with effectively effects on chemical oxygen demand, antibiotic‐resistant bacteria and antibiotic‐resistant genes degradation, etc. This study highlights the critical role of H‐bond networks for tuning PCET in the ORR and provides a comprehensive understanding for the precise control of catalytic reaction kinetics through molecular structural engineering.
Flexible and Recyclable Epoxy Vitrimer With Improved Thermal Conductivity for Thermal Management
Authors: Wang Dong liang , Zhan Lebin , Zheng Zhihong , Zhang Jingyun , Yang Songwei , Luo Fubin , Hu Ting
Published: February 2025

The accelerated evolution of electronic devices has resulted in an increased demand for thermal management materials. In this study, methoxy polyethylene glycol (MPEG) was introduced into a covalent adaptable epoxy network. It is demonstrated that the epoxy material becomes softer as the amount of MPEG content is increased, specifically exhibiting excellent flexibility with an impressive elongation at break of 444.68%. The thermal conductivity of the epoxy resin was enhanced by the incorporation of boron nitride (BN) filler, and the findings demonstrated that the thermal conductivity of the composites was markedly elevated to 3.34 Wm−1 K−1 when the proportion of BN filler reached 50%. The potential use of such composites as thermal management materials is demonstrated in their application for heat dissipation in LED chips. In addition, the covalent adaptive network enables the decomposition of the composites prepared in this study under chemical conditions, with the fillers subsequently being separated by physical filtration. This approach offers a potential pathway toward the sustainable development of thermal management materials.
Electrochemical Hydrogen Evolution with Metal–Organic Framework‐Derived Catalysts: Strategies for d‐Band Modulation by Electronic Structure Modification
Authors: Singh Baghendra , Ansari Toufik , Indra Arindam
Published: February 2025

The effective use of metal‐organic framework (MOF)‐based materials in the electrocatalytic hydrogen evolution reaction (HER) relies on the understanding of their structural and electronic properties. While the structure and morphology of MOF‐derived catalysts significantly impact HER activity, tuning the d‐band structure through electronic structure modulation has emerged as a key factor in optimizing catalytic performance. Techniques such as composition tuning, heteroatom doping, surface modification, and interface engineering were found to be effective methods for manipulating the electronic configuration and, in turn, modulating the d‐band. This review systematically explores the design strategies for MOF‐derived catalysts by focusing on electronic structure modulation. It provides a detailed discussion of the various methods – used to modulate the electronic structure. Furthermore, the review establishes the relationship between d‐band tuning, Gibbs free energy, and electronic structure modulation, supported by both spectroscopic and theoretical evidences.
Twists and Loops: Exploring Lemniscular Vinylogous Benzioctaphyrin(2.0.1.0.2.0.1.0)
Authors: Vishwakarma Rampal , Jana Narayan Ch. , Das Mainak , Srinivasan A.
Published: February 2025

Octaphyrins, offer unparalleled opportunities for designing complex molecular architectures with distinct physical and chemical properties. However, lemniscate‐shaped benzioctaphyrins remain scantily explored, leaving a gap in understanding how this unconventional geometry/shape influences macrocyclic behaviour. In this study, we explore the design, synthesis, and structural properties of benzioctaphyrin by incorporating the bis‐E‐stilbene unit, where a vinylene π‐bridge connects phenylene rings. The benzioctaphyrin(2.0.1.0.2.0.1.0) adopts a lemniscate topology to alleviate steric strain, with protonation inducing conformational desymmetrization. The presence of a meta‐phenylene unit thwarts the global π‐conjugation, rendering the macrocycle nonaromatic. Notably, this work represents the first exploration of the oligomeric vinylene group in benzioctaphyrin framework. It offers new insights into how structural modifications influence topology, π‐electron delocalization, and macrocyclic flexibility, setting the stage for future advancements in topologically unique porphyrinoid systems.
Oxidation‐Condensation Tandem Catalysis via a Multifunctional Cu‐Based Metal‐Organic Framework
Authors: Kim Hyeonsu , Son Younghu , Hwang Dogyeong , Rao Purna Chandra , Kim Younghoon , Yoon Minyoung
Published: February 2025

The development of heterogeneous catalysts for tandem reactions remains a significant challenge for practical applications, primarily due to the need for multiple isolated catalytic sites. This study presents a novel metal‐organic framework (MOF), Cu‐AIPA, formulated as Cu(AIPA)(DMF)2 (AIPA: 2‐amino isophthalic acid, DMF: N, N‐dimethylformamide). The Cu‐AIPA framework integrates three distinct catalytic mechanisms: redox activity, Brønsted basicity, and Lewis acidity. The structure of Cu‐AIPA features redox‐active Cu(II) centers and Brønsted basic sites, enabling the sequential transformation of alcohols to aldehydes and their subsequent condensation into imines. The close spatial arrangement of these redox‐active/Lewis acidic and basic sites within the confined pores of Cu‐AIPA facilitates efficient tandem catalysis. This process involves oxidizing benzyl alcohol to benzaldehyde using TEMPO without requiring an external base, followed by amine condensation. Compared with HKUST‐1, another Cu‐based MOF with a high surface area, Cu‐AIPA demonstrated superior catalytic performance at room temperature. Recyclability tests revealed that Cu‐AIPA retained over 90 % conversion efficiency across at least three catalytic cycles. This study highlights the potential of MOFs incorporating multiple catalytic sites and confined pore structures for tandem reactions, emphasizing their potential for scalable and sustainable industrial applications.
A generalized extreme value approach for the analysis of stationary climatic covariate in a Mediterranean city
Authors: Cherif Semia
Published: February 2025

Extreme value theory (EVT) is used as univariate extreme value analysis (EVA) in order to analyze and model the covariates temperature, relative humidity (RH) and the thermal comfort index (humidex) issued from a dataset of 38 years in Tunis. It is a South Mediterranean area known as a hotspot for climate change. The best approach is to reduce the data considerably by taking annual block maxima from mean monthly data. It will converge to a generalized extreme value distribution in order to estimate the return levels of the studied parameters. The stationarity of the series are checked by augmented Dickey‐Fuller test. The modeling of the three parameters shows a Weibull distribution pattern. The extreme/maximum monthly means temperature of 30.2°C and humidex of 39.4 have a common return level between 300 and 350 years. The highest mean monthly RH of 86.0% is expected to be exceeded every 50 years. For the next 38 years, the maxima monthly mean temperatures are expected to be stable, and the maxima monthly mean RH values, as well as the humidex monthly mean maxima are expected to decrease. The percentile air temperature hot day (TX90p) and night (TN90p) indices show globally linear upward trends and the ones of cold days (TX10p) and cold nights (TN10p) have a downward trend. The diurnal yearly temperature range shows an almost flat trend for its evolution through the years of study.
Suicidality in Autistic Adolescents and Adults: Sleep the Unexplored Connection?
Authors: Richdale Amanda L. , Morris Eric M. J. , Lawson Lauren P.
Published: February 2025

Despite substantial evidence linking insomnia with increased suicidality in non‐autistic populations, its role in autism remains under‐explored. Poor sleep, most commonly insomnia symptoms (hereafter insomnia), is a significant issue in autism, affecting up to 80% of autistic children and adults, compared with 30%–50% of children and about 45% of adults in the general population. Sleep, along with quality of life, anxiety, depression, and social well‐being, is a top mental health research priority for autistic adults. These factors are all significantly associated with insomnia in both autistic and non‐autistic individuals. Current findings highlight the association between depression, psychosocial factors, and suicidality in autistic individuals. Key factors in suicidality for autistic people include increased autistic traits, loneliness, lack of social support, and experiences such as camouflaging and burnout. What is under‐explored is the role of sleep in suicidality and mental health in autism. Effective psychological interventions for insomnia in autistic individuals are lacking, and there is limited understanding of whether treating insomnia can reduce suicidality. Only two pilot studies have investigated insomnia treatments for autistic adults. In this commentary, we argue that, given the high rate of suicidality in autism and the potential role of insomnia, it is crucial to investigate whether insomnia contributes to suicidality in autistic people and if addressing sleep through prevention strategies, supports, and interventions improves outcomes. Collaboration with the autistic community is essential for addressing this knowledge gap and developing effective interventions.
Multifunctional Surface Enhanced Raman Scattering Substrate Fe 3O4 @AgNPs@MIL‐101 for Pretreatment and Rapid Detection of Pesticide Residues on the Surface of Fruit Peels
Authors: Zhang Mingyu , Tian Yizhuo , Liu Sijia , Wang Yu , Li Haiyan , Chen Yafei , Gao Qing , Wang Xinli , Chen Mingli
Published: February 2025

A multifunctional surface‐enhanced Raman scattering substrate Fe3O4@AgNPs@MIL‐101 was prepared. Rapid SERS detection of pesticide residues was realized by direct pre‐enrichment and separation on the peel surface. MIL‐101 has an ortho‐octahedral framework and large pore size, which endowed Fe3O4@AgNPs@MIL‐101 with the ability to rapidly adsorb and separate positively charged targets. The introduction of tannic acid realized the in situ growth of AgNPs on the backbone, to modulate the electromagnetic enhancement. Pesticide molecules were adsorbed onto the surface of AgNPs mediated by central S atoms, accompanied by the interaction between pesticide molecules and AgNPs, the corresponding SERS signals of different pesticides were observed. Together with the introduction of magnetic coating Fe3O4, the molecules were enriched in the hotspot and separated to further enhance the SERS performance. Magnet instead of centrifugation was used to simultaneously perform surface extraction and sample separation for a noninvasive, rapid, immediate, and portable assay. The method was accomplished in measurement of thiram and thiabendazole on apple and tangerine epidermis, and the limits of detection (LODs) were 20 ng/cm2 and 4 μg/cm2, respectively. The recovery was reasonable, and it showed that the procedure is valuable for the rapid and nondestructive surface analysis of residual chemicals.
Breaking barriers: Smart vaccine platforms for cancer immunomodulation
Authors: Gomari Mohammad Mahmoudi , Ghantabpour Taha , Pourgholam Nima , Rostami Neda , Hatfield Stephen M. , Namazifar Farzaneh , Abkhiz Shadi , Eslami Seyed Sadegh , Ramezanpour Mahsa , Darestanifarahani Mahsa , Astsaturov Igor , Bencherif Sidi A.
Published: February 2025

Despite significant advancements in cancer treatment, current therapies often fail to completely eradicate malignant cells. This shortfall underscores the urgent need to explore alternative approaches such as cancer vaccines. Leveraging the immune system's natural ability to target and kill cancer cells holds great therapeutic potential. However, the development of cancer vaccines is hindered by several challenges, including low stability, inadequate immune response activation, and the immunosuppressive tumor microenvironment, which limit their efficacy. Recent progress in various fields, such as click chemistry, nanotechnology, exosome engineering, and neoantigen design, offer innovative solutions to these challenges. These achievements have led to the emergence of smart vaccine platforms (SVPs), which integrate protective carriers for messenger ribonucleic acid (mRNA) with functionalization strategies to optimize targeted delivery. Click chemistry further enhances SVP performance by improving the encapsulation of mRNA antigens and facilitating their precise delivery to target cells. This review highlights the latest developments in SVP technologies for cancer therapy, exploring both their opportunities and challenges in advancing these transformative approaches.
Genetic Characterization of the Immortalized Human Nasopharyngeal Carcinoma Cell Line NPC/HK1
Authors: Makowska Anna , Kontny Udo , van Helden Josef , Hildebrandt Barbara , Schüler Herdit M. , Weiskirchen Ralf
Published: February 2025

Background

Human nasopharyngeal carcinoma (NPC) cell lines are in vitro model systems that are widely available, easy to handle, and provide an unlimited supply of material. They also bypass ethical concerns associated with the use of primary human cells or tissue. However, many of these cell lines including 5‐8F, 6‐10B, CNE‐1, CNE‐2, HNE‐1, HONE‐1, SUNE1, SUNE2, and NPC‐TW01 have been shown to be misidentified or cross‐contaminated. While simple molecular genotyping techniques such as short tandem repeat profiling of human cell lines are available to confirm cell line identity, scientists often do not implement strategies to avoid misidentification. This has resulted in a large volume of publications containing incorrect information.

Methods

In this paper, we have established a cell line karyogram that contains several marker chromosomes and a set of typical aberrations characteristic of NPC/HK1.

Results and Conclusions

Combined with the typical multiloci short tandem repeat signature of NPC/HK1, the cytogenetic analysis provides an effective means to avoid unreliable experimental outcomes and scientific misinterpretation.
Lanthanides Gd and Tm Can Inhibit Carnitine/Acylcarnitine Transporter: Insights from All‐Atoms Simulations
Authors: Prejanò Mario , Tonazzi Annamaria , Giangregorio Nicola , Indiveri Cesare , Marino Tiziana
Published: February 2025

Recent experimental evidence highlighted the inhibition of carnitine/acylcarnitine carrier (CAC), an important mitochondrial transmembrane protein for living organisms, by the early lanthanide Pr3+. A possible explanation of such a behaviour was found in the preference of the cation for amino acids like aspartate and glutamate containing a carboxylate in the side chain, laying in the inter‐membrane space. Interaction of the cation with these residues can cause halt the transfer of the protein‘s substrates between the matrix and cytoplasm thus opening to new scenarios concerning the CAC‐metal interactions and its relative inhibition. In the present work, the panel of metals binding the CAC protein is predictively expanded including Gd3+ and Tm3+, selected as representative species of middle and late lanthanides, respectively. A more realistic membrane‐containing model of the protein was built and the comparative analysis of the molecular dynamics (MD) simulations of CAC apo‐form with its complexed systems, named CAC−Pr, CAC−Gd and CAC−Tm, was performed. The analysis of the trajectories revealed that the inhibition is caused by the coordination of D132 and E179 to the cations and that such interactions generate a reorganization of important salt‐bridges inside the framework of CAC. In detail, MD simulations highlighted that a spontaneous conformational change from cytoplasmatic‐state (c‐state) to matrix‐state (m‐state) induced by cations and that, in this condition, the protein channel is occluded, thus explaining the inhibition.
Importance of childhood vaccines: Saving lives
Authors: Knopf Alison
Published: February 2025

It's almost unbelievable that there is still argument from some parties against vaccination. For children and adolescents 6 months through 17 years, rates of vaccination are less than 40% for the seasonal flu vaccine and less than 10% for the updated COVID‐19 vaccine, the American Academy of Pediatrics (AAP) reports. This is worrying for pediatricians.
Insights into Segregation and Aggregation in Dilute Atom Alloy Catalysts using DFT and Machine Learning
Authors: Sison Arnold D. , Quaynor Michael M.N.A. , Navodye S. A. Keishana , Gunasooriya G. T. Kasun Kalhara
Published: February 2025

Dilute atom alloys (DAAs) are an important class of heterogeneous catalysts due to their ability to precisely tune the activity and selectivity of reactions. DAA catalysts typically consist of a small quantity of metal solute in a metal host. Key considerations in the stability of DAA catalysts are the segregation and aggregation energy. In this work, we report a systematic theoretical study of segregation and aggregation energies of DAA catalysts composed of 3d, 4d, and 5d transition metals. To investigate the nature of DAAs, we analyzed both Bader charge and density of states, as well as formation energies to identify the most stable DAA configuration for a given alloy. We further applied regression‐based, tree‐based, and neural network machine learning (ML) models to gain physics‐based insights in predicting segregation and aggregation energies based on readily available atomic and bulk features. We found that the d‐band filling of the solute and host, nearest neighbor distance of the host and d‐band width of the solute determine the segregation energy while the Pauling electronegativity of the host and solute, nearest neighbor distance of the host, and cohesive energy of host determine aggregation energy. Our findings provide crucial insights for DAA catalyst design.
Development of Multipurpose Supported Asymmetric Salen Catalysts by Cu(0)‐Mediated Reversible Deactivation Radical Copolymerization
Authors: Schulz Emmanuelle , Bechara Rafaela , Mellah Mohamed , Barroca-Aubry Nadine , Ozanam François , Gouget-Laemmel Anne-Chantal , Aureau Damien , Dragoé Diana , Roger Philippe
Published: February 2025

Designing heterogeneous catalysts that ensure efficient recycling and reuse of the catalyst in a wide range of transformations remains a real challenge. In this contribution, targeted copolymers are used as supports for the development of heterogeneous asymmetric catalysts. They are made up of two methacrylate monomers, 3‐azidopropylmethacrylate (AZMA), and 2‐methoxyethyl methacrylate (MEMA) used as a diluting agent. Polymerization was carried out using Cu(0)‐mediated reversible deactivation radical polymerization (RDRP), yielding two copolymers with controlled MEMA/AZMA compositions of 70/30 and 30/70 with moderate dispersity control (Ð = 1.32‐1.54), targeting polymers with a similar molar mass, which is important to achieve precise control of the catalyst loading to implement asymmetric catalysis. The copolymers were post‐functionalized using click chemistry with two salen complexes containing a chromium or a cobalt center, these species being recognized for their broad range of applications. The supported catalysts were evaluated in two reactions and recovered by precipitation and filtration techniques. The first reaction involved the asymmetric ring opening (ARO) of cyclohexene oxide with trimethylsilylazide, catalyzed by the chromium sites, the second reaction was the dynamic kinetic resolution (DKR) of epibromohydrin with water, promoted by the cobalt sites. The recycling was effective, demonstrating the robustness and viability of the procedure.
Visible‐Light Photoredox Catalytic Direct N‐(Het)Arylation of Lactams
Authors: Boselli Monica Fiorenza , Ghosh Indrajit , Intini Niccolò , Fattalini Marco , Puglisi Alessandra , König Burkhard , Benaglia Maurizio
Published: February 2025

Lactam rings are essential structural motifs in organic chemistry, widely present in natural products and clinically important drugs, such as antibiotics and antiepileptics. Existing methods for synthesizing N‐functionalized lactams often require harsh conditions, toxic reagents, or complex catalytic systems. Here, we report a mild and efficient photochemical approach for generating N‐centered radicals, enabling straightforward N‐heteroarylation of lactams. This versatile method enables the synthesis of a range of N‐(het)arylated lactams and is effective even in aqueous media, facilitating the functionalization of biomolecules. Furthermore, the photochemical reaction is easily scalable under continuous flow conditions, making it highly suitable for large‐scale applications.
Regulating the Cytotoxicity of Anticancer Drugs by Pillar[6]arene‐based Host‐Guest Complex
Authors: Jia Xinyu , Wei Haoyu , Huang Yan , Duan Wengui , Liu Luzhi
Published: February 2025

Creating molecular‐level host‐guest complexes with properties responsive to endogenous substance stimuli‐responsive as drug delivery systems, is critical for improving drug stability, reducing side effects, and amplifying therapeutic efficacy. Herein, a delivery system for the chemotherapeutic drug chlorambucil (CLB) was developed using the host‐guest interaction with amino‐pillar[6]arene (NP6). NP6 exhibits a high affinity for CLB (Ka=3.5×103 M−1), resulting in a 1 : 1 host‐guest complex NP6@CLB. This complex not only effectively prevents premature drug leakage and improves drug stability but also significantly reduces the cytotoxicity of CLB on L‐02 cells. Notably, NP6 also demonstrated superior complexation (Ka=3.6×103 M−1) with ATP, an endogenous substance in cells. During NP6@CLB delivery, ATP can compete with CLB to form a host‐guest complex with NP6. This process blocks drug efflux while releasing CLB, thereby synergistically enhancing the antitumor effects on HeLa cells. This “one stone, two birds” design strategy—where host‐guest complexes facilitate both direct drug delivery and synergistic enhancement of antitumor properties via ATP binding, opens a new perspective for constructing multifunctional supramolecular chemotherapeutic platforms based on pillar[n]arene.
Continuous Flow Synthesis of β‐Aminoketones as Masked Vinyl Ketone Equivalents
Authors: Bannon Ruairi , Smyth Megan , Moody Thomas S. , Wharry Scott , Roth Philippe M. C. , Gauron Guillaume , Baumann Marcus
Published: February 2025

Herein we report the efficient synthesis of β‐aminoketones via addition of a vinyl Grignard reagent into amides followed by trapping of the vinyl ketone intermediate with the magnesium‐amide by‐product. The reaction was successfully translated from a batch process into continuous flow mode to increase its efficiency, safety and scalability. Different set‐ups were evaluated to minimize/overcome clogging issues arising from magnesium salt precipitates. Ultimately, the resulting β‐aminoketones were obtained in high yields and productivities with residence times of less than 90 seconds at elevated temperatures of 50 °C. Importantly, the β‐aminoketone products are valuable building blocks that can be unmasked to reactive vinyl ketones via a Cope elimination process.
Protonation of Nitrogen‐Containing Covalent Organic Frameworks for Enhanced Catalysis
Authors: Gu Yu‐Hao , Xu Xinyu , Yuan Shuai
Published: February 2025

Covalent organic frameworks (COFs) are a class of porous crystalline materials with ordered structures and tunable properties, which have been widely explored in catalysis, sensing, gas storage, and separation. Among various post‐synthetic modifications, protonation emerges as a simple yet effective strategy to fine‐tune the properties of nitrogen‐containing COFs, thereby enhancing their catalytic performance. This concept article highlights the contribution of protonation on the mass transfer kinetics, charge distribution, photo‐response, charge transfer, and other properties related to photocatalysis and electrocatalysis. The applications of protonated COFs are explored in catalytic processes including hydrogen evolution, CO2 reduction, H2O2 synthesis, and singlet oxygen generation. We also emphasize the necessity of considering the protonation process when nitrogen‐containing COFs are applied in acidic environments to accurately reveal the structure‐activity relationship. By analyzing recent advancements in protonated COFs, this article underscores the potential and challenges of protonation as a powerful tool for advancing COF‐based catalytic systems.
The Diverse Reactivity of an Al(I) Carbenoid Towards Phosphorus‐Based Ylides. The Crucial Role of Co‐Crystallised Lithium Halide
Authors: Dmitrienko Anton , Pilkington Melanie , Nikonov Georgii I.
Published: February 2025

Attempts to generate NacNacAl‐based (NacNac=[ArNC(Me)CHC(Me)NAr]−; Ar=2,6‐iPr2C6H3) alkylidenes via reactions with trimethyl(methylidene), triphenyl(methylidene) and triethyl(ethylidene) phosphiranes led to new and unexpected reactivity patterns. Reaction with Me3P=CH2 resulted in the intermolecular deprotonation of the NacNac −CCH3 backbone. Reaction with Ph3P=CH2*LiI afforded an equimolar mixture of NacNacAlH2 and the ortho‐metalated adduct, NacNac'Al(η(C,C)2−CH2=PPh2(o‐C6H4)) (NacNac’=[ArNC(Me)CHC(=CH2)NAr]2−). Finally, the use of Et3P=CHMe*LiBr resulted in the fragmentation of the NacNac moiety.