bluuebunny/crossref_metadata_2025_split huggingface dataset:
Water‐Vapor Responsive Metallo‐Peptide Nanofibers
Authors: Dey Avishek , Naranjo Elma , Saha Ranajit , Zhang Sheng , Nair Maya Narayanan , Li Tai‐De , Chen Xi , Ulijn Rein V. 
Published: August 2024

AbstractShort peptides are versatile molecules for the construction of supramolecular materials. Most reported peptide materials are hydrophobic, stiff, and show limited response to environmental conditions in the solid‐state. Herein, we describe a design strategy for minimalistic supramolecular metallo‐peptide nanofibers that, depending on their sequence, change stiffness, or reversibly assemble in the solid‐state, in response to changes in relative humidity (RH). We tested a series of histidine (H) containing dipeptides with varying hydrophobicity, XH, where X is G, A, L, Y (glycine, alanine, leucine, and tyrosine). The one‐dimensional fiber formation is supported by metal coordination and dynamic H‐bonds. Solvent conditions were identified where GH/Zn and AH/Zn formed gels that upon air‐drying gave rise to nanofibers. Upon exposure of the nanofiber networks to increasing RH, a reduction in stiffness was observed with GH/Zn fibers reversibly (dis‐)assembled at 60–70 % RH driven by a rebalancing of hydrogen bonding interactions between peptides and water. When these metallo‐peptide nanofibers were deposited on the surface of polyimide films and exposed to varying RH, peptide/water‐vapor interactions in the solid‐state mechanically transferred to the polymer film, leading to the rapid and reversible folding‐unfolding of the films, thus demonstrating RH‐responsive actuation.
Triphasic Hydroxysilylation of Alkenes by Mechanically Piezoelectric Catalysis
Authors: Wang Xiaohong , Zhang Xuemei , He Xiaochun , Guo Guangqing , Huang Qian , You Fengzhi , Wang Qingqing , Qu Ruiling , Zhou Fei , Lian Zhong 
Published: August 2024

AbstractThe 1,2‐hydroxysilylation of alkenes is crucial for synthesizing organosilicon compounds which are key intermediates in material science, pharmaceuticals, and organic synthesis. The development of strategies employing hydrogen atom transfer pathways is currently hindered by the existence of various competing reactions. Herein, we reported a novel mechanochemical strategy for the triphasic 1,2‐hydroxysilylation of alkenes through a single‐electron‐transfer pathway. Our approach not only circumvents competitive reactions to enable the first‐ever 1,2‐hydroxysilylation of unactivated alkenes but also pioneers the research in mechanic force‐induced triphasic reactions under ambient conditions. This gentle method offers excellent compatibility with various functional groups, operates under simple and solvent‐free conditions, ensures rapid reaction time. Preliminary mechanistic investigations suggest that silylboronate can be transformed to a silicon radical by highly polarized Li2TiO3 particles and oxygen under ball‐milling condition.
Unveiling the Activity Origin of Electrochemical Oxygen Evolution on Heteroatom‐Decorated Carbon Matrix
Authors: Li Yang , Chen Cailing , Zhao Guoxiang , Huang Huawei , Ren Yuanfu , Zuo Shouwei , Wu Zhi‐Peng , Zheng Lirong , Lai Zhiping , Zhang Jian , Rueping Magnus , Han Yu , Zhang Huabin 
Published: August 2024

AbstractChemical modification via functional dopants in carbon materials holds great promise for elevating catalytic activity and stability. To gain comprehensive insights into the pivotal mechanisms and establish structure‐performance relationships, especially concerning the roles of dopants, remains a pressing need. Herein, we employ computational simulations to unravel the catalytic function of heteroatoms in the acidic oxygen evolution reaction (OER), focusing on a physical model of high‐electronegative F and N co‐doped carbon matrix. Theoretical and experimental findings elucidate that the enhanced activity originates from the F and pyridinic‐N (Py−N) species that achieve carbon activation. This activated carbon significantly lowers the conversion energy barrier from O* to OOH*, shifts the potential‐limiting step from OOH* formation to O* generation, and ultimately optimizes the energy barrier of the potential‐limiting step. This wok elucidates that the critical role of heteroatoms in catalyzing the reaction and unlocks the potential of carbon materials for acidic OER.
Photo‐BQCA: Postiv allostere Modulatoren ermöglichen die optische Kontrolle des M1‐Rezeptors
Authors: Gerwe Hubert , Schaller Eva , Sortino Rosalba , Opar Ekin , Martínez‐Tambella Joaquín , Bermudez Marcel , Lane J. Robert , Gorostiza Pau , Decker Michael 
Published: August 2024

AbstractDas Forschungsgebiet der G‐Protein‐gekoppelten Rezeptoren (GPCRs) hat stark vom Gewinn an räumlich‐zeitlicher Auflösung profitiert, der mit der Entwicklung licht‐kontrollierbarer und ‐schaltbarer Verbindungen einhergeht. Die meisten der synthetisierten molekularen Werkzeuge adressieren die Klasse A GPCRs (Rhodopsin‐ähnlich), die größte Subfamilie dieser Rezeptorklasse. All diese molekularen Werkzeuge wurden entworfen, um die orthosterische Bindungsstelle der GPCRs zu adressieren. In dieser Arbeit berichten wir über die ersten photoschaltbaren allosterischen Modulatoren an Klasse A GPCRs, die entwickelt wurden, um den muscarinischen Acetylcholinrezeptor Subtyp 1 (M1) zu aktivieren. Die dargestellten Derivate der Benzylchinoloncarbonsäure (BQCA), nämlich Photo‐BQCisA and Photo‐BQCtrAns, zeigen komplementäres photopharmakologisches Verhalten und erlauben die reversible Kontrolle über den M1R mittels Licht als externem Stimulus. Dieses Verhalten lässt diese Substanzen wertvoll erscheinen, etwa um das M1R‐Signalling zu untersuchen und zudem dient diese Arbeit als Machbarkeitsstudie für die Darstellung anderer photoschaltbarer Modulatoren für Klasse A‐Rezeptoren
Bioorthogonal Synthetic Chemistry Enabled by Visible‐Light Photocatalysis
Authors: Mato Mauro , Fernández‐González Xulián , D'Avino Cinzia , Tomás‐Gamasa María , Mascareñas José L. 
Published: August 2024

AbstractThe field of bioorthogonal chemistry has revolutionized our ability to interrogate and manipulate biological systems at the molecular level. However, the range of chemical reactions that can operate efficiently in biological environments without interfering with the native cellular machinery, remains limited. In this context, the rapidly growing area of photocatalysis offers a promising avenue for developing new type of bioorthogonal tools. The inherent mildness, tunability, chemoselectivity, and external controllability of photocatalytic transformations make them particularly well‐suited for applications in biological and living systems. This minireview summarizes recent advances in bioorthogonal photocatalytic technologies, with a particular focus on their potential to enable the selective generation of designed products within biologically relevant or living settings.
G‐Quadruplex RNA Based PROTAC Enables Targeted Degradation of RNA Binding Protein FMRP for Tumor Immunotherapy
Authors: Peng Ruixi , Huang Qian , Wang Li , Qiao Gongxi , Huang Xiangrong , Jiang Jianhui , Chu Xia 
Published: August 2024

AbstractFragile X mental retardation protein (FMRP), an RNA binding protein (RBP), is aberrantly hyper‐expressed in human tumors and plays an essential role in tumor invasion, metastasis and immune evasion. However, there is no small‐molecule inhibitor for FMRP so far. In this study, we developed the first FMRP‐targeting degrader based on PROteolysis TArgeting Chimera (PROTAC) technology and constructed a heterobifunctional PROTAC through linking a FMRP‐targeting G‐quadruplex RNA (sc1) to a von Hippel‐Lindau (VHL)‐targeting ligand peptide (named as sc1‐VHLL). Sc1‐VHLL specifically degraded endogenous FMRP via ubiquitination pathway in both mouse and human cancer cells. The FMRP degradation significantly changed the secretion pattern of cancer cells, resulting in higher expression of pro‐inflammatory cytokine and smaller amounts of immunomodulatory contents. Furthermore, sc1‐VHLL, when encapsulated into ionizable liposome nanoparticles (LNP), efficiently targeted tumor site and degraded FMRP in cancer cells. In CT26 tumor‐bearing mouse model, FMRP degradation within tumors substantially promoted the infiltration of lymphocytes and CD8 T cells and reduced the proportion of Treg cells, reshaping the proinflammatory tumor microenvironment and accordingly transforming cold tumor into hot tumor. When combined with immune checkpoint blockade (ICB) therapy, sc1‐VHLL based treatment remarkably inhibited the tumor growth.
Radical Isomerization Homopolymerization of Linear α‐Olefins to Access C5, C6 or C7 Polymers
Authors: An Bang , Yue Chaowei , Liu Shuai , Sun Lixing , Sun Tingting , Liu Jian‐Biao , Li Yifan 
Published: August 2024

AbstractNon‐activated linear α‐olefins are valuable building blocks for organic transformation or olefin (co)polymerization, but they are recognized as textbook knowledge for non‐homopolymerizable monomers under radical conditions. In this article, we disclose our effort to achieve an unprecedented library of all carbon‐bonded sequence‐regulated polymers via radical isomerization homopolymerization of α‐olefin derivatives. The success of this distinctive polymerization is attributed to the remarkable efficiency and selectivity exhibited during the cyano group migration or hydrogen atom transfer, which is greatly enhanced by the precise engineering of their monomer structures. This polymerization process enables the elongation of polymer chains by five, six, or seven carbon atoms at each propagation step. These polymers, obtained through the cyano group migration or hydrogen atom transfer involved radical isomerization polymerization processes, emerge as promising candidates resembling polyethylene or polyacrylonitrile copolymers.
In situ Construction of Single‐Atom Electronic Bridge on COF to Enhance Photocatalytic H2 Production
Authors: Li Jie , Zhou Jie , Wang Xiao‐Han , Guo Can , Li Run‐Han , Zhuang Huifen , Feng Wenhai , Hua Yingjie , Lan Ya‐Qian 
Published: August 2024

AbstractPhotocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal‐covalent organic frameworks (MCOFs) with both small‐sized metal clusters and nitrogen‐rich ligands, named COF‐Cu3TG. Based on our design, small‐sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen‐rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single‐atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N2‐Ru‐N2 electron bridge (Ru‐SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g−1 h−1. Through theoretical calculation and EXAFS, the existence position and action mechanism of Ru‐SAEB were reasonably inferred, further confirming the rationality of the Ru‐SAEB configuration. A sufficiently proximity between the small‐sized Cu3 cluster and the Ru‐SAEB was found to expedite electron transfer. This work demonstrated the synergistic impact of small molecular clusters with Ru‐SAEB for efficient photocatalytic hydrogen production.
Construction of Highly Porous and Robust Hydrogen‐Bonded Organic Framework for High‐Capacity Clean Energy Gas Storage
Authors: Wang Jia‐Xin , Zhang Xu , Jiang Chenghao , Zhang Teng‐Fei , Pei Jiyan , Zhou Wei , Yildirim Taner , Chen Banglin , Qian Guodong , Li Bin 
Published: August 2024

AbstractDevelopment of highly porous and robust hydrogen‐bonded organic frameworks (HOFs) for high‐pressure methane and hydrogen storage remains a grand challenge due to the fragile nature of hydrogen bonds. Herein, we report a strategy of constructing the double‐walled framework to target highly porous and robust HOF (ZJU‐HOF‐5a) for extraordinary CH4 and H2 storage. ZJU‐HOF‐5a features a minimized twofold interpenetration with double‐walled structure, in which multiple supramolecular interactions are existed between the interpenetrated walls. This structural configuration can notably enhance the framework robustness while maintaining its high porosity, affording one of the highest gravimetric and volumetric surface areas of 3102 m2 g−1 and 1976 m2 cm−3 among the reported HOFs so far. ZJU‐HOF‐5a thus exhibits an extremely high volumetric H2 uptake of 43.6 g L−1 at 77 K/100 bar and working capacity of 41.3 g L−1 under combined swing conditions (77 K/100 bar→160 K/5 bar), and also impressive methane storage performance with a 5–100 bar working capacity of 187 (or 159) cm3 (STP) cm−3 at 270 K (or 296 K), outperforming most of the reported porous organic materials. Single‐crystal X‐ray diffraction studies on CH4‐loaded ZJU‐HOF‐5a reveal that abundant supramolecular binding sites combined with ultrahigh porosities account for its high CH4 storage capacities. Combined with high stability, super‐hydrophobicity, and easy recovery, ZJU‐HOF‐5a is placed among the most promising materials for H2 and CH4 storage applications.
Electrochemiluminescence Enhanced by a Non‐Emissive Dual Redox Mediator
Authors: Adamson Natasha S. , Blom Steven J. , Doeven Egan H. , Connell Timothy U. , Hadden Callum , Knežević Sara , Sojic Neso , Fracassa Alessandro , Valenti Giovanni , Paolucci Francesco , Ding Jialian , Wang Yafeng , Su Bin , Hua Carol , Francis Paul S. 
Published: August 2024

AbstractA sulfonated tris(1‐phenylpyrazolato)iridium(III) complex ([Ir(sppz)3]3−) serves as a proof‐of‐concept non‐emissive enhancer of the widely used ECL detection system of tris(2,2′‐bipyridine)ruthenium(II) ([Ru(bpy)3]2+) with tri‐n‐propylamine (TPrA) co‐reactant, acting through electrocatalysis of TPrA oxidation and efficient chemi‐excitation of the luminophore. Using self‐interference ECL spectroscopy, we show that the enhancer extends diffusion of the required electrogenerated precursors from the electrode surface. Previously reported enhancement through these pathways has been confounded by the inherent ECL of the enhancer, but the increase in [Ru(bpy)3]2+ ECL intensity using [Ir(sppz)3]3− was obtained without its concomitant emission. The most prominent enhancement (11‐fold) occurred at low potentials associated with the ‘indirect’ co‐reactant ECL pathway, which translated to between 2‐ and 6‐fold enhancement when the luminophore was immobilised on microbeads as a general model for enhanced ECL assays.
Interface Synergy of Exposed Oxygen Vacancy and Pd Lewis Acid Sites Enabling Superior Cooperative Photoredox Synthesis
Authors: Huang Zhi‐Sang , Wang Yin‐Feng , Qi Ming‐Yu , Conte Marco , Tang Zi‐Rong , Xu Yi‐Jun 
Published: August 2024

AbstractPhoto‐driven cross‐coupling of o‐arylenediamines and alcohols has emerged as an alternative for the synthesis of bio‐active benzimidazoles. However, tackling the key problem related to efficient adsorption and activation of both coupling partners over photocatalysts towards activity enhancement remains a challenge. Here, we demonstrate an efficient interface synergy strategy by coupling exposed oxygen vacancies (VO) and Pd Lewis acid sites for benzimidazole and hydrogen (H2) coproduction over Pd‐loaded TiO2 nanospheres with the highest photoredox activity compared to previous works so far. The results show that the introduction of VO optimizes the energy band structure and supplies coordinatively unsaturated sites for adsorbing and activating ethanol molecules, affording acetaldehyde active intermediates. Pd acts as a Lewis acid site, enhancing the adsorption of alkaline amine molecules via Lewis acid‐base pair interactions and driving the condensation process. Furthermore, VO and Pd synergistically promote interfacial charge transfer and separation. This work offers new insightful guidance for the rational design of semiconductor‐based photocatalysts with interface synergy at the molecular level towards the high‐performance coproduction of renewable fuels and value‐added feedstocks.
Vertically Fluorinated Graphene Encapsulated SiOx Anode for Enhanced Li+ Transport and Interfacial Stability in High‐Energy‐Density Lithium Batteries
Authors: Huang Lin‐Bo , Zhao Lu , Ma Zhi‐Feng , Zhang Xing , Zhang Xu‐Sheng , Lu Zhuo‐Ya , Li Ge , Luo Xiao‐Xi , Wen Rui , Xin Sen , Meng Qinghai , Guo Yu‐Guo 
Published: August 2024

AbstractAchieving high energy density has always been the goal of lithium‐ion batteries (LIBs). SiOx has emerged as a compelling candidate for use as a negative electrode material due to its remarkable capacity. However, the huge volume expansion and the unstable electrode interface during (de)lithiation, hinder its further development. Herein, we report a facile strategy for the synthesis of surface fluorinated SiOx (SiOx@vG−F), and investigate their influences on battery performance. Systematic experiments investigations indicate that the reaction between Li+ and fluorine groups promotes the in situ formation of stable LiF‐rich solid electrolyte interface (SEI) on the surface of SiOx@vG−F anode, which effectively suppresses the pulverization of microsized SiOx particles during the charge and discharge cycle. As a result, the SiOx@vG−F enabled a higher capacity retention of 86.4 % over 200 cycles at 1.0 C in the SiOx@vG−F||LiNi0.8Co0.1Mn0.1O2 full cell. This approach will provide insights for the advancement of alternative electrode materials in diverse energy conversion and storage systems.
Spiro‐Buckybowls: Synthesis and Selective Transformations Toward Chiral and Nonlinear Optical Polycycles
Authors: Shang Jihai , Wang Zhihua , Sun Chunlin , Wang Renjie , Hua Xinqiang , Feng Lijun , Yuan Chengshan , Liu Zitong , Zhang Hao‐Li , Xu Jialiang , Shao Xiangfeng 
Published: August 2024

AbstractIntegration of spirocycles with buckybowls is a promising strategy to construct three‐dimensional (3D) curved π‐systems and to endow distinctive physicochemical features arising from buckybowls. Herein, a series of carbon‐bridged spiro‐type heterosumanenes (spiro‐HSEs) were synthesized by combining 9,9′‐spirobifluorene and dichalcogenasumanenes (DCSs). It is found that spiro‐conjugation plays an important role in the geometric and electronic structures of spiro‐HSEs. The bowl depth of DCSs moiety becomes larger in the spiro‐HSEs. Owing to the Jahn‐Teller (J‐T) effect, two DCSs segments of spiro‐HSEs have different bowl depths accompanied with the unequal distribution of charge in radical cation state. Taking advantage of the typical reactions of DCSs, selective transformations of spiro‐HSEs have been adopted in accordance to the nature of chalcogen atoms (S, Se, Te) to bestow the value‐added functionalities. The emissive property is enhanced by converting the thiophene rings of S‐doped spiro‐HSE into thiophene S,S‐dioxides. A chiroptical polycycle could be produced by ring‐opening of the edge benzene of Se‐doped spiro‐HSE. The covalent adduct of Te‐doped spiro‐HSE with Br2 forms non‐centrosymmetric halogen‐bonded networks, resulting in the high performance second‐order nonlinear optics (NLO).
Simultaneous Structural and Electronic Engineering on Bi‐ and Rh‐co‐doped SrTiO3 for Promoting Photocatalytic Water Splitting
Authors: Pan Zhenhua , Vequizo Junie Jhon M. , Yoshida Hiroaki , Li Jianuo , Zheng Xiaoshan , Chu Chiheng , Wang Qian , Cai Mengdie , Sun Song , Katayama Kenji , Yamakata Akira , Domen Kazunari 
Published: August 2024

AbstractActivating metal ion‐doped oxides as visible‐light‐responsive photocatalysts requires intricate structural and electronic engineering, a task with inherent challenges. In this study, we employed a solid (template)‐molten (dopants) reaction to synthesize Bi‐ and Rh‐codoped SrTiO3 (SrTiO3 : Bi,Rh) particles. Our investigation reveals that SrTiO3 : Bi,Rh manifests as single‐crystalline particles in a core (undoped)/shell (doped) structure. Furthermore, it exhibits a well‐stabilized Rh3+ energy state for visible‐light response without introducing undesirable trapping states. This precisely engineered structure and electronic configuration promoted the generation of high‐concentration and long‐lived free electrons, as well as facilitated their transfer to cocatalysts for H2 evolution. Impressively, SrTiO3 : Bi,Rh achieved an exceptional apparent quantum yield (AQY) of 18.9 % at 420 nm, setting a new benchmark among Rh‐doped‐based SrTiO3 materials. Furthermore, when integrated into an all‐solid‐state Z‐Scheme system with Mo‐doped BiVO4 and reduced graphene oxide, SrTiO3 : Bi,Rh enabled water splitting with an AQY of 7.1 % at 420 nm. This work underscores the significance of simultaneous structural and electronic engineering and introduces the solid‐molten reaction as a viable approach for this purpose.
Electrical conductivity enhancement in polyaniline films via mixed ion‐electron conductive fillers
Authors: Abdalla Sahar , Telfah Ahmad , Ferjani Hela , Tavares Carlos J. , Etzkorn Johannes 
Published: August 2024

AbstractThe influence of mixed ion‐electronic conductive fillers on the physical characteristics of protonated polyaniline (P‐PANI) nanocomposite films is investigated by incorporating titanium nanoparticles (TiNPs) and lithium trifluoromethanesulfonate () at various concentrations. The introduction of into the P‐PANI matrix results in the appearance of additional X‐ray diffraction peaks ascribed to a titanium phase, confirming the presence of TiNPs. The incorporation of leads to changes in intensities, linewidths, and diffraction angles, indicating interactions between ions and nitrogen atoms in the matrix. The bandgap energy for the pristine P‐PANI film is 3.40 eV, being reduced to 3.29 eV upon incorporating in the P‐PANI matrix. An increase in the concentration of in the P‐PANI/TiNPs composite films with decreasing TiNPs concentration leads to a continuous increase in bandgap energy to 3.59 eV. The electrical conductivity of pristine P‐PANI is 0.49 mS/cm. The addition of TiNPs increases the conductivity to 2.16 mS/cm, while the addition of LiOTf increases it to 1.72 mS/cm. Notably, (P‐PANI)/TiNPs nanocomposite films with 7:3 and 5:5 wt.% ratios exhibit superior electrical conductivity compared with individual (P‐PANI)/TiNPs and (P‐PANI)/LiOTf films, attributed to effective ionic‐electronic coupling at phase‐separated region interfaces. This study reveals impact of and on the structural, optical, and electrical properties of P‐PANI nanocomposite films, thereby enhancing their potential for integration into advanced electronic and optoelectronic devices.
Impact of hydrolysis on the quantification of sulfonated acrylamide copolymers by size exclusion chromatography with UV detection
Authors: Gonçalves Cecília C. R. , Duncke Angela C. P. , Maqueira Luis , Creatto Eduardo J. , Limberger Jones , Pérez‐Gramatges Aurora 
Published: August 2024

AbstractSize exclusion chromatography with UV detection (SEC‐UV) is a precise method for quantifying polyacrylamides in water. However, its accuracy can be compromised in complex matrices due to chemical degradation of the polymer. This study focuses on the impact of hydrolysis on quantifying sulfonated polyacrylamide copolymers (PAM‐AMPS) via SEC‐UV, analyzing key influencing factors. Using controlled hydrolysis, hydrolyzed copolymer (HPAM‐AMPS) standards with varying hydrolysis degree (HD) (HD = 7%–33%) were prepared without significant changes in polymer chain size. SEC‐UV analysis revealed that quantification accuracy is highly dependent on hydrolysis extent. Errors are minimal for HD up to 10%, but significantly higher for HDs of 22%–33%. Furthermore, this effect is modulated by polymer concentration. Our findings indicate that there are two compensating factors for the decrease in molar absorptivity due to amide‐to‐carboxylate substitution: the sulfonate group acting as an additional chromophore, and a redshift in absorption spectra due to hydrogen bonding at higher concentrations. This interplay between HD and concentration in this type of sulfonated polyacrylamide can help reduce quantification errors in complex aqueous samples prone to chemical degradation, like those found in environmental and subsurface applications.