bluuebunny/crossref_metadata_2025_split huggingface dataset:
Orthogonal‐Group‐Controlled Site‐Selective I‐Branching of Poly‐N‐acetyllactosamine Chains Reveals Unique Binding Specificities of Proteins towards I‐Antigens
Authors: Bao Shumin , Shen Tangliang , Chen Congcong , Han Jinghua , Tajadura‐Ortega Virginia , Shabahang MohammadHossein , Du Zhenming , Feizi Ten , Chai Wengang , Li Lei 
Published: January 2025

AbstractPoly‐N‐acetyllactosamine (poly‐LacNAc) is ubiquitously expressed on cell surface glycoconjugates, serving as the backbone of complex glycans and an extended scaffold that presents diverse glycan epitopes. The branching of poly‐LacNAc, where internal galactose (Gal) residues have β1‐6 linked N‐acetylglucosamine (GlcNAc) attached, forms the blood group I‐antigen, which is closely associated with various physiological and pathological processes including cancer progression. However, the underlying mechanisms remain unclear as many of the I‐antigen sequences are undefined and inaccessible. In this study, we developed a highly efficient orthogonal‐group‐controlled approach to access site‐selectively I‐branched poly‐LacNAc chains. The approach relies on three orthogonal protecting groups, each of them “caps” one internal Gal residue of poly‐LacNAc. These groups can be readily “decapped” by specific enzymes or chemical reduction to expose desired sites for GCNT2‐catalyzed I‐branching. This approach enabled the rapid preparation of a diverse library of 41 linear and branched poly‐LacNAc glycans from a single precursor. Glycan microarray analysis using these complex glycans revealed unique recognitions of I‐branches by lectins, anti‐I mAbs, and galectins. Surprisingly, oxidized forms of linear poly‐LacNAc strongly bound to several glycan‐binding proteins (GBPs). These findings help to bridge the gap in recognition of I‐branching and open new avenues for therapeutic development by targeting galectins.
Precise Manipulation on the Structural Defects of Poly (Triazine Imide) Single Crystals for Efficient Photocatalytic Overall Water Splitting
Authors: Zhuzhang Hangyu , Liang Xiaocong , Li Jiaxiang , Xue Sikang , Lin Yifan , Sa Baisheng , Wang Sibo , Zhang Guigang , Yu Zhiyang , Wang Xinchen 
Published: January 2025

AbstractConjugated polymers, represented by polymeric carbon nitrides (PCNs), have risen to prominence as new‐generation photocatalysts for overall water splitting (OWS). Despite considerable efforts, achieving highly crystalline PCNs with minimal structural defects remains a great challenge, and it is also difficult to examine the exact impact of complex defect states on OWS process, which largely limits their quantum efficiency. Herein, we devise a ‘in‐situ salt flux’ assisted copolymerization protocol by using nitrogen‐rich and nitrogen‐deficient monomers to precisely manipulate the structural defects of poly (triazine imide) (PTI) single crystals. Stoichiometric control between two comonomers enables continuous tunning of carbon‐ and nitrogen‐vacancies within PTI, allowing the construction of a series of PTI crystals with different defect states. Theoretical and experimental results unveil the carbon vacancies are related with the radiative decay of excitons, while the nonradiative decay is mainly derived from the nitrogen vacancies. Owing to the effective suppression of both radiative and nonradiative losses, the as‐synthesized PTI achieves a record apparent quantum efficiency of 37.8 % by one‐step‐excitation OWS. This work highlights the significance of rational control of the structural defects and describes clear structure‐property‐activity relationships in PTI photocatalyst, offering guidance for the development of polymer photocatalysts for solar fuel production.
Competitive Coordination and Dual Interphase Regulation of MOF‐Modified Solid‐State Polymer Electrolytes for High‐Performance Sodium Metal Batteries
Authors: Tian Wenyue , Lin Guangliang , Yuan Shaohui , Jin Ting , Wang Qinglun , Jiao Lifang 
Published: January 2025

AbstractSolid‐state polymer electrolytes (SPEs) have emerged as prominent candidates for solid‐state sodium metal batteries (SMBs) due to their enhanced flexibility and reduced interfacial resistance. However, their performance is limited by poor Na+ conductivity at room temperature, disordered ion transport properties and unstable interfaces. Herein, a three‐dimensional (3D) interconnected copper metal–organic framework (Cu‐MOF) on polyacrylonitrile (PAN) fibers is introduced into polyethylene oxide (PEO)‐based SPEs to construct a composite electrolyte (PPNM). The open metal sites (OMS) of the Cu‐MOF compete with Na+, effectively coordinating with TFSI− anions and oxygen atoms in PEO, thereby reducing concentration polarization, weakening the Na+−O binding strength and facilitating Na+ migration. By harnessing the multifunctional properties of Cu‐MOF and PAN, the PPNM electrolyte exhibits superior ionic conductivity (1.03×10−4 S cm−1) and a high Na+ transference number (0.58) at room temperature. The strong anchoring of TFSI− anions by Cu‐MOF promotes the formation of inorganic‐rich (NaF and Na3N) cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) layers, enhancing dual interfacial stability. The Na3V2(PO4)3@C/PPNM/Na full cells realize robust cycling performance for 2000 cycles at 200 mA g−1. This work provides a facile strategy for regulating the Na+ coordination state and interphase engineering in solid‐state SMBs.
Leveraging Multivalent Assembly towards High‐Temperature Liquid‐Phase Phosphorescence
Authors: Luo Wuzhen , Chen Liming , Yin Guangqiang , Yue Chaojun , Xie Shiye , Zhou Jiayin , Feng Weihao , Nie Yujing , Qiu Huakai , Li Feiming , Cai Shunyou , Li Yijiang , Cai Zhixiong , Chen Tao 
Published: January 2025

AbstractHigh‐temperature phosphorescence (HTP) materials have attracted considerable attention owing to their expanded application prospects, whereas they still suffer from severe deactivation in polar media, limiting their reliability and utility. Here, we present an efficient multivalent assembly strategy to achieve high‐temperature liquid‐phase phosphorescence (HTLP). The supramolecular assembly of multivalent modules leads to extremely robust hydrogen‐bonding networks, which firmly immobilize the organic phosphors and protect triplet excitons from annihilation in high‐temperature polar media, resulting in excellent HTLP emission. Moreover, the photophysical properties of HTLP are significantly enhanced by boosting multivalent interactions using multitopic phosphors, demonstrating a visible afterglow of 5 s in boiling water, more than 2 s in dimethylsulfoxide at 460 K (187 °C), and a long lifetime of 70.3 ms in N‐methylpyrrolidone at 476 K (203 °C). Based on their fluidity and robust HTLP emission, in situ microcracks detection of high‐temperature operating instruments and spatial‐time‐temperature‐resolved anticounterfeiting are demonstrated.
Sym‐ and Asym‐Expanded Heterohelicene Isomers Featuring Extended Multi‐Resonance Skeleton for Narrowband Deep‐Blue Fluorescence
Authors: Zeng Xuan , Luo Xiaofeng , Meng Guoyun , Wang Xuewen , Zhang Dongdong , Duan Lian 
Published: January 2025

AbstractExpanded heterohelicenes composed of alternating linearly and angularly fused multi‐resonance (MR) skeletons have gained wide interest owing to their promising narrowband emissions. Herein, a pair of sym‐ and asym‐expanded heterohelicene isomers was obtained by merging boron/oxygen (B/O)‐embedded MR triangulene and indolo[3,2,1‐jk]carbazole units via one‐pot synthesis. Owing to their fully resonating extended helical skeleton, the target heterohelicenes exhibit a significantly narrowed spectra bandwidth while emission red‐shifting, thus affording deep‐blue narrowband emission with a peak at approximately 460 nm, full‐width‐at‐half‐maximum (FWHM) of only 18 nm, and near‐unity photoluminescence quantum yields. In comparison to the symmetrical structure, the asym‐expanded heterohelicene displays suppressed aggregation within doped films, thereby showing superior narrowband electroluminescence in devices with CIE coordinates of (0.12, 0.18) and a high external quantum efficiency of up to 25 %, which retains 18.1 % even at a high luminance of 10,000 cd m−1. Overall, this work provides a novel paradigm for the development of narrowband expanded heterohelicenes.
A BODIPY‐Containing Covalent Organic Framework as a Highly Porous Photosensitizer for Environmental Remediation and Pollutants Adsorption
Authors: Sánchez‐Naya Roberto , Beuerle Florian 
Published: January 2025

AbstractThe direct incorporation of borondipyrromethene (BODIPY) subunits into the structural backbone of covalent organic frameworks (COFs) gives facile access to porous photosensitizers but is still a challenging task. Here, we introduce β‐ketoenamine‐linked BDP‐TFP‐COF, which crystallizes in AA‐stacking mode with hcb topology. A comprehensive characterization reveals high crystallinity and enhanced stability in a variety of solvents, excellent mesoporosity (SABET=1042 m2 g−1), broad light absorption in the visible region, and red emission upon the exfoliation of few‐layer COF nanosheets. The versatility of multifunctional BODIPY‐COFs is highlighted in various applications. Pollutants Bisphenol A (BPA, qmax=426 mg g−1) and Methylene Blue (MB, qmax=96 mg g−1) have been efficiently removed from H2O. Fluorescence quenching or enhancement of exfoliated BDP‐TFP‐COF nanosheets have been utilized for dual‐mode sensing of MB or NEt3, respectively. Ultimately, the photosensitizing effect of the BODIPY units is retained in the COF. Thus, BPD‐TFP‐COF was established as a metal‐free triplet photosensitizer, which efficiently oxidized a mustard gas simulant under visible light irradiation.
Machine Learning‐Assisted Prediction of Photothermal Metal‐Phenolic Networks
Authors: Fan Dongqi , Chen Xu , Wang Shan , Zhan Jinglei , Chen Yuan , Zhou Houqi , Li Dize , Tang Han , He Qingqing , Chen Tao 
Published: January 2025

AbstractPhotothermal therapy (PTT) demonstrates significant potential in cancer treatment, wound healing, and antibacterial therapy, with its efficacy largely depending on the performance of photothermal agents (PTAs). Metal‐phenolic network (MPN) materials are ideal PTA candidates due to their low cost, good biocompatibility and excellent ligand‐to‐metal charge transfer properties. However, not all MPNs exhibit significant photothermal properties, and the vast chemical space of MPNs (over 700,000 potential combinations) complicates the screening of high‐photothermal materials. To address this challenge, this study introduces machine learning (ML) methods for predicting the photothermal performance of MPNs. A database of photothermal properties of 80 modular MPNs was constructed, and the ML process was optimized through feature engineering and model training. The selected extreme gradient boosting model (XGBoost) successfully identified 1,654 high photothermal MPNs from a virtual database of 44,438. Subsequent experimental validation revealed a remarkable success rate of 70 % in predicting high photothermal MPNs. Additionally, several previously unreported high photothermal MPNs were discovered, demonstrating advantages in photothermal antibacterial applications. This study offers an innovative ML‐driven approach for the efficient screening of MPN materials, providing a solid foundation for PTA design in PTT and other biomedical applications.
Asymmetric gem‐Hydroboration and gem‐Hydrogenation of Ynamides: A New Gateway to Chiral Fischer Carbene Complexes and their Catalytic Transformations
Authors: Babón Molina Juan Carlos , Renken Luis , Leutzsch Markus , Molina Betancourt Ricardo , Fürstner Alois 
Published: January 2025

AbstractYnamides, when reacted with H2 or HBpin in the presence of [Cp*RuCl]4, convert into chiral‐at‐metal Fischer carbenes by regioselective gem‐hydrogenation or gem‐hydroboration of the polarized triple bond, respectively. gem‐Hydroboration concomitantly affords a carbogenic borylated stereocenter adjacent to the ruthenium carbene unit, the configuration of which can be controlled using an Evans auxiliary. These are the first examples of asymmetric gem‐addition reactions to alkynes known in the literature; representative pianostool ruthenium carbene complexes formed by this unconventional route were characterized by crystallographic and spectroscopic means. They undergo various stoichiometric reactions and can even entertain catalytic asymmetric transformations, such as hydrogenative cyclopropanations or a novel type of borylative cycloisomerization.
Vesicle‐Encapsulated Chemosensing Ensembles Allow Monitoring of Transmembrane Uptake Coupled with Enzymatic Reactions
Authors: Jiang Ruixue , Nilam Mohamed , Piselli Claudio , Winterhalter Mathias , Guo Dong‐Sheng , Yu Sin‐Yi , Hennig Andreas , Nau Werner M. 
Published: January 2025

AbstractCompartmentalized models with coupled catalytic networks are considered as “protocells” in the context of research related to the origin of life. To model the kinetics of a simple cellular uptake‐metabolism process, we use a compartmentalized protocell system that combines liposome‐encapsulated intravesicular reporter pairs with co‐encapsulated enzymes to monitor the membrane transport of a substrate (analyte uptake) and its subsequent enzymatic reaction inside the vesicles (metabolism to the product). The intravesicular chemosensing ensembles consist of the macrocycles cucurbit[7]uril or p‐sulfonatocalix[4]arene and matching fluorescent dyes to set up suitable reporter pairs. When these macrocycle/dye reporter pairs are co‐encapsulated with enzymes (trypsin, protein kinase A, or butyrylcholinesterase), it is possible to monitor first the transport of different substrates (polylysine, protamine, H‐LRRWSLG‐OH, or butyrylcholine) through added pores (outer membrane proteins F and C), with synthetic carriers (amphiphilic calixarenes), or by direct permeation (only for butyrylcholine). The subsequent enzymatic conversions of the substrates after they have entered the corresponding protocells can be monitored as consecutive reactions. The new type of in vitro assays can be applied to different enzymes and analytes, affording a comprehensive chemosensing system of high chemical complexity.
g‐C3N4 S‐Scheme Homojunction through Van der Waals Interface Regulation by Intrinsic Polymerization Tailoring for Enhanced Photocatalytic H2 Evolution and CO2 Reduction
Authors: Zhu Xianglin , Zhou Enlong , Tai Xishi , Zong Huibin , Yi Jianjian , Yuan Zhimin , Zhao Xingling , Huang Peng , Xu Hui , Jiang Zaiyong 
Published: January 2025

AbstractThe effective S‐scheme homojunction relies on the precise regulation of band structure and construction of advantaged charge migration interfaces. Here, the electronic structural properties of g‐C3N4 were modulated through meticulous polymerization of self‐assembled supramolecular precursors. Experimental and DFT results indicate that both the intrinsic bandgap and surface electronic characteristics were adjusted, leading to the formation of an in‐situ reconstructed homojunction interface facilitated by intrinsic van der Waals forces. The homojunction catalyst, composed of g‐C3N4 nanodots and ultra‐thin g‐C3N4 nanoflakes, exhibited a significant S‐scheme carrier separation mechanism, which enhances the utilization of electrons and holes. Consequently, under AM 1.5 light irradiation (~100 mW/cm2), the g‐C3N4 homojunction photocatalyst achieved a remarkable hydrogen evolution rate of 580 μmol h−1. Furthermore, a reversed CH4 selectivity in CO2 reduction was observed, yielding 80.30 μmol g−1 h−1 with a selectivity of 96.86 %, in contrast to the performance of bulk g‐C3N4, which produced only 2.22 μmol g−1 h−1 with the 15.69 % CH4 selectivity. These findings not only highlight the significant potential of the g‐C3N4 homojunction photocatalyst for hydrogen production and CO2 reduction but also propose a superior and effective strategy for optimizing the structural properties of g‐C3N4, which are crucial for the design of photocatalytic reactions.
CO Cryo‐Sorption as a Surface‐Sensitive Spectroscopic Probe of the Active Site Density of Single‐Atom Catalysts
Authors: Jeong Beomgyun , Abbas Hafiz Ghulam , Klein Benedikt P. , Bae Geunsu , Velmurugan Adith Ramakrishnan , Choi Chang Hyuck , Kim Geonhwa , Kim Dongwoo , Kim Ki‐jeong , Cha Byeong Jun , Kim Young Dok , Jaouen Frédéric , Maurer Reinhard J. , Ringe Stefan 
Published: January 2025

AbstractQuantifying the number of active sites is a crucial aspect in the performance evaluation of single metal‐atom electrocatalysts. A possible realization is using adsorbing gas molecules that selectively bind to the single‐atom transition metal and then probing their surface density using spectroscopic tools. Herein, using in situ X‐ray photoelectron spectroscopy (XPS) and near edge X‐ray absorption fine structure (NEXAFS) spectroscopy, we detect adsorbed CO gas molecules on a FeNC oxygen reduction single atom catalyst. Correlating XPS and NEXAFS, we develop a simple surface‐ and chemically‐sensitive protocol to accurately and quickly quantify the active site density. Density functional theory‐based X‐ray spectra simulations reaffirm the assignment of the spectroscopic fingerprints of the CO molecules adsorbed at Fe‐N4‐C sites, and provide additional unexpected structural insights about the active site needed to explain the low‐temperature CO adsorption. Our work represents an important step towards an accurate quantitative catalytic performance evaluation, and thus towards developing reliable material design principles and catalysts.
Porphyrin‐based Vinylene‐linked 3D Covalent Organic Framework with Unprecedented cya Topology for Photocatalytic H2O2 Production
Authors: Gong Zihan , Gao Ying , Li Jing , Cai Zichen , Liu Naifang , Jiang Jianzhuang 
Published: January 2025

AbstractDesigning and realizing new topologies represent one of the most important ways toward developing new structures and functionalities for molecule‐based frameworks including SOFs, MOFs, and COFs. Herein, Aldol condensation between 5,10,15,20‐tetrayl(tetrakis(([1,1′:3′,1′′‐terphenyl]‐4,4′′‐dicarbaldehyde)))‐porphyrin (TTEP) and 2,4,6‐trimethyl‐1,3,5‐triazine (TMT) affords the vinylene‐linked 3D covalent organic framework Por‐COF‐cya. Powder X‐ray diffraction (PXRD) in combination with structural simulation reveals its high crystalline structure with an unprecedented cya topology in the molecule‐based frameworks reported thus far. Por‐COF‐cya displayed polycrystallinity and possessed high permanent porosity. Especially, the incorporation of light‐harvesting porphyrin unit and vinylene linkages in Por‐COF‐cya enables a conjugation effect within the framework, endowing it with a photocatalytic H2O2 production rate of 2209 μmol g−1h−1 in pure aqueous solution under visible‐light irradiation (λ >420 nm). Inclusion of the guest molecules TTF into the pores of Por‐COF‐cya results in a donor‐acceptor system TTF@Por‐COF‐cya, enhancing the photocatalytic activity with H2O2 production rate of 6994 μmol g−1h−1. This work paves a new way for the development of new topological functional molecule‐based frameworks toward diverse application potentials.
Confining Phosphoric Acid in Quaternized COF Channels for Ultra‐Stable and Fast Anhydrous Proton Transport
Authors: Pang Xiao , Shi Benbing , Liu Yawei , Wu Hong , Shen Jianliang , Guan Jingyuan , Wang Xiaoyao , Fan Chunyang , Cao Li , Zhu Tianhao , Kong Yan , Jiang Zhongyi 
Published: January 2025

AbstractPhosphoric acid (H3PO4) doping is a widely employed strategy to facilitate anhydrous proton transport in high‐temperature proton exchange membrane fuel cells (HT‐PEMFCs). However, significant H3PO4 leaching during long‐term operation poses critical challenges to maintaining membrane stability and proton conductivity. Herein, H3PO4 is incorporated into positively charged nanochannels of quaternized covalent organic framework membranes (QACOFMs), leveraging strong electrostatic interactions and confinement effects to achieve exceptional H3PO4 retention under hydration conditions. Moreover, the shortened hydrogen bond length between H3PO4 (O−H…O <2.7 Å) and the highly interconnected hydrogen bond network in the H3PO4@QACOFMs facilitate ultra‐fast anhydrous proton transport. As a result, the H3PO4@QACOFMs exhibit superior anhydrous proton transport in a broader temperature range (60 °C–200 °C) and the highest proton conductivity reaches about 379.7 mS cm−1 at 200 °C.
Cobalt‐Catalyzed Enantioselective Reductive Coupling of Imines and Internal Alkynes
Authors: Maji Kakoli , Palai Angshuman , Mallick Dibyendu , Maji Biplab 
Published: January 2025

AbstractChiral allylamines are important structural components in natural products, pharmaceuticals, and chiral catalysts. Herein, we report a cobalt‐catalyzed enantioselective reductive coupling of imines with internal alkynes to synthesize chiral allylamines. The reaction is catalyzed by a cobalt complex derived from commercially available bisphosphine ligand utilizing zinc as the electron donor. The substrate scope is extensive. Symmetric and unsymmetric alkyl and aryl alkynes have been successfully coupled with various imines derived from aryl and alkyl aldehydes. Tri‐ and tetra‐substituted allyl amines were isolated in high yields, with enantiomeric excess surpassing >99.9 % and regioselectivities exceeding >20 : 1. These chiral allyl amines can serve as versatile platforms for subsequent transformations while preserving their stereochemical integrity. Extensive experimental and computational mechanistic studies were performed to elucidate the mechanism. These investigations have indicated that an in situ cobalt(I) catalyst enables the oxidative cyclization of alkynes and imines, and a spin crossover occurs during the enantio‐determining step. Zinc plays a pivotal role in facilitating the transmetallation of the resulting azacobaltacycle. The observed enantioselectivity was interpreted by the stabilization of the transition state through higher stabilizing interaction energy from high negative polarization, dispersion, and C−H⋅⋅⋅π interactions.
Electronic Substitution Effect on ESIPT‐Driven pH and Amine Sensing: Exploring Mechanism
Authors: Kaushik Bharat , Agarwal Annu , Singh Ajeet , Rahaman Laskar Inamur 
Published: January 2025

AbstractIt is required to have a more straightforward and easier way to check the quality of food to ensure the safety of the public health. The decomposition of meat protein results in ammonia and biogenic amines (BAs). Consequently, to evaluate the safety and quality of meat products throughout the storage, transit, and consumption depends on the sensitive detection of the released BAs. Here, we have designed and synthesized three luminescent‐based probe molecules, which originated from 2‐(2‐hydroxyphenyl) benzothiazole (HBT) derivatives and showed the excited state‐induced proton transfer (ESIPT) phenomenon. The two substituents (OMe and NO2) were used rationally at the para position of HBT, and the electronic properties were evaluated using Hammett substituent constants. The proton donating ability of the O−H to the acceptor is largely facilitated by the presence of a strong electron‐withdrawing group, which in this case is NO2. The proton transfer rate can be controlled, and in this case, to a slower rate with the influence of the electron donating group OMe. The controllability of proton transfer led us to use it in pH sensing. A prominent and multi‐color change with pH variation was observed in the case of the OMe substituted compound. These probes were further employed for amine sensing, and the limit of detection (LOD) was determined to be 28.6 μM and 61.34 nM for ammonia and hydrazine, respectively. In addition, strip‐based detection of spoilage of chicken meat was studied for real‐world applications via both contact and non‐contact modes.