bluuebunny/crossref_metadata_2025 huggingface dataset:
Correlations of Calcination Temperature with the Catalytic Properties of CuFe2O4 for the Synthesis of Green Fuels
Authors: Zander Judith , Daumann Florian , Loukrakpam Rameshwori , Roth Christina , Weber Birgit , Marschall Roland
Published: December 2024

Spinel oxides are promising multifunctional electrocatalysts based on earth‐abundant elements. While NiFe2O4 and CoFe2O4 have been widely studied for the oxygen evolution reaction (OER), CuFe2O4 has been less investigated. Herein, cubic CuFe2O4 nanoparticles are synthetic using a microwave‐assisted approach. The effect of post‐synthetic calcination on particle morphology, crystal structure, and inherent properties such as optical bandgap, magnetic moment, or degree of inversion is investigated. The influence of the post‐synthetic treatment on the electrochemical performance is then evaluated. It is found that higher calcination temperatures are beneficial for the OER, the hydrogen evolution reaction, and the oxygen reduction reaction (ORR), which can be explained by an improved crystallinity, removal of organic surface residues and changes in the dominant crystal phase—and relatedly the conductivity. Especially for the ORR activity, an increase in the electrochemical active surface area and a decrease in the charge transfer resistance upon calcination are important prerequisites. The activity of CuFe2O4 for the reduction of CO2 to CO, in contrast, is mainly determined by the local environment of Cu2+ and is best at a comparatively high degree of inversion and low amounts of organic residues and for particles with a cubic structure.
Synthesis of N‐,O‐,S‐Heterocyclic Spiroadamantanes by Condensation of Ketones with Bifunctional OH‐, NH‐, SH‐Acids under the Action of Copper‐Containing Catalysts
Authors: Gallyamova Leysan I. , Bayguzina Alfiya R. , Ramazanov Ilfir R.
Published: December 2024

Synthesis of adamantyl‐containing cyclic ketals, spirooxazolidines, spiroimidazolidines, spirooxathiolanes, spirodithiolanes, spirooxazines, spirobenzodioxoles with high yields was carried out by condensation of adamantyl‐containing ketones (adamantanone, kemantan, diamantanone) with diols, 1,2‐ethanedithiol and 2‐mercaptoethanol, 1,2‐diaminoethane and 2‐aminoethanol under the action of copper‐containing catalysts. In the case of multigram‐scale reaction of adamant‐2‐one with 1,2‐propanediol, the amount of catalyst can be reduced to 0.1 mol %.
Visible‐Light Mediated, Photocatalyst‐Free C−S Bond Formation via EDA Complex Formation
Authors: Shanthi. Markabandhu , Perumal Karuppaiah , Hemamalini Vijayakumar , Dandela Rambabu , Ramesh Subburethinam
Published: December 2024

The presence of sulphur groups in the structures of many natural products and therapeutic candidates makes sulfur‐containing molecules indispensable. In organic chemistry, the study of carbon‐sulfur (C−S) bond formation via electron donor‐acceptor (EDA) complexes is a dynamic and developing field. EDA complexes facilitate a variety of chemical transformations, including the production of C−S bonds, by interacting between an electron‐rich donor and an electron‐deficient acceptor. In this review, we focus on the literature reports on formation of electron donor‐acceptor complex (EDA) between appropriate starting materials. Some new research investigates the use of light to stimulate C−S bond formation using EDA complexes. Photo‐redox catalysis is a promising field in which substrates can be activated under gentler circumstances. In this review, we have highlighted the photoactivation of the EDA complex and an intermediate formed in the reaction itself. We classified the collection of the journal under the following headings such as one pot ring annulation and cyclization involving C−S bond formation, C−S bond formation by dehalogenation, C−S bond formation in multicomponent reaction, C−S bond formation by leaving group, C−S bond formation on alkene/alkyne and other miscellaneous.
A Practical Approach to Cyclopropanation of Masked o‐Benzoquinones with Applications in Tropolone Derivative Synthesis
Authors: Huang Kuan‐Hsun , Lo Yao‐Ping , Mukherjee Anupam , Devendar Badugu , Sharma Sandeep , Chiu I.‐Chen , Chang Yu‐Pei , Chang Yi‐Chuan , Wu Chi‐Phi , Liao Chun‐Chen , Chuang Gary Jing
Published: December 2024

The Corey–Chaykovsky cyclopropanation of readily available masked o‐benzoquinones (MOBs) has been investigated to generate functionalized bicyclo[4.1.0]heptane derivatives with regioselectivity. The resulting bicyclic products were subjected to a sequence of hydrolysis, BF₃ ⋅ Et₂O‐mediated ring‐opening, and then again hydrolysis to access various tropolone derivatives – a class of molecules with significant roles in synthetic, biological, and theoretical chemistry. Utilizing an improved approach based on established cyclopropanation and ring‐opening strategies, several bicyclo[4.1.0]heptanes, tropolone difluorides, and tropolones can be synthesized from readily available MOBs. Our efforts focused on modifying each step to make these reactions general and of considerable practical value.
Lewy body co‐pathology in Alzheimer's disease and primary age‐related tauopathy contributes to differential neuropathological, cognitive, and brain atrophy patterns
Authors: Almeida Francisco C. , Santos Alexandra , Jesus Tiago , Coelho Ana , Quintas‐Neves Miguel , Gauthreaux Kathryn , Mock Charles N. , Kukull Walter A. , Crary John F. , Oliveira Tiago Gil
Published: December 2024

INTRODUCTION

Alzheimer's disease (AD) co‐pathology with Lewy bodies (LB) is frequent and influences clinical manifestations and outcomes. Its significance in primary age‐related tauopathy (PART) is unknown. We investigated the influence of LB on cognition and brain atrophy in AD and PART.

METHODS

We performed a retrospective cohort study in a large sample of autopsied participants with AD neuropathological change (ADNC) with and without LB and PART with and without LB, with corresponding ante mortem magnetic resonance imaging (MRI) data from the National Alzheimer's Coordinating Center dataset.

RESULTS

LB co‐pathology worsened cognitive impairment in both PART and ADNC. On longitudinal follow‐up, LB impacted cognitive decline in multiple domains. Additionally, LB influenced brain atrophy on MRI across groups and LB regional staging was different in PART and ADNC, accompanying tauopathy progression.

DISCUSSION

These results suggest that LB co‐pathology is associated with divergent patterns of cognitive impairment, brain atrophy, and regional pathological distribution in PART and AD.

Highlights

Lewy body (LB) co‐pathology is frequent in Alzheimer's disease (AD) with important clinical implications.

LB co‐pathology is also present in primary age‐related tauopathy (PART), but its significance is still understudied.

In PART and AD, LB leads to higher cognitive impairment and brain regional atrophy.

In PART and AD, LB tends to accompany neurofibrillary tangle progression, suggesting amyloid pathology might be a trigger for regional pathology progression.
Differential associations of neighborhood disadvantage, race/ethnicity, and cognitive status with experiences of psychosocial distress in the HABS‐HD cohort
Authors: Rhoads Tasha , Wong Christina G. , Cobos Kimberly , O'Bryant Sid E. , Kind Amy J. H. , Miller Justin B. ,   Health and Aging Brain Study (HABS‐HD) Team
Published: December 2024

INTRODUCTION

Understanding how contextual socioeconomic factors are associated with psychosocial distress among different ethnoracial groups is important for addressing health disparities in individuals at risk for Alzheimer's disease.

METHODS

Using Health and Aging Brain Study–Health Disparities (HABS‐HD) data collected between 2017 and 2023, we examined the association of neighborhood disadvantage with psychosocial distress using demographically adjusted linear regression models, stratified by ethnoracial group and cognitive status.

RESULTS

We included 630 non‐Hispanic Black, 1109 Hispanic, and 1068 non‐Hispanic White older adults deemed cognitively normal (CN) or diagnosed with mild cognitive impairment (MCI). Residing in areas of greater neighborhood disadvantage was associated with increased chronic stress (CS) among CN White participants, but this relationship was attenuated among White participants with MCI. Regardless of cognitive status, severe levels of disadvantage were associated with increased CS and depression among Black participants.

DISCUSSION

Aging in more disadvantaged neighborhoods was associated with greater CS and depression for Black and White participants.

Highlights

Greater neighborhood disadvantage was associated with increased depression and chronic stress for White and Black individuals.

Individuals with mild cognitive impairment reported greater levels of psychosocial distress.

These findings are relevant for addressing mental health inequity in aging populations.
Association of APOE alleles and polygenic profiles comprising APOE‐TOMM40‐APOC1 variants with Alzheimer's disease neuroimaging markers
Authors: Kulminski Alexander M. , Jain‐Washburn Ethan , Nazarian Alireza , Wilkins Heather M. , Veatch Olivia , Swerdlow Russell H. , Honea Robyn A.
Published: December 2024

INTRODUCTION

TOMM40 and APOC1 variants can modulate the APOE‐ε4‐related Alzheimer's disease (AD) risk by up to fourfold. We aim to investigate whether the genetic modulation of ε4‐related AD risk is reflected in brain morphology.

METHODS

We tested whether 27 magnetic resonance imaging‐derived neuroimaging markers of neurodegeneration (volume and thickness in temporo‐limbic regions) are associated with APOE‐TOMM40‐APOC1 polygenic profiles using the National Alzheimer's Coordinating Center Uniform Data Set linked to the AD Genetic Consortium data.

RESULTS

All brain regions studied using structural phenotypes were smaller in individuals with AD. The ε4 allele was associated with smaller limbic (entorhinal, hippocampus, parahippocampus) brain volume and cortical thickness in AD cases than controls. There were significant differences in the associations for the higher‐risk and lower‐risk ε4‐bearing APOE‐TOMM40‐APOC1 profiles with temporo‐limbic region markers.

DISCUSSION

The APOE‐AD heterogeneity may be partly attributed to the modulating role of the TOMM40 and APOC1 genes in the APOE cluster.

Highlights

The ε4 allele is associated with smaller values of neuroimaging markers in AD cases.

Larger values of neuroimaging markers may protect against AD in the ε4 carriers.

TOMM40 and APOC1 variants differentiate AD risk in the ε4 carriers.

The same variants can differentiate the links between ε4 and neuroimaging markers.
Signatures of the Correlated‐Hopping Interaction in Non‐Linear Transport Through a Quantum Dot
Authors: Eckern Ulrich , Wysokiński Karol I.
Published: December 2024

In condensed matter systems with the Coulomb interaction playing an important role one expects, besides the on‐site (local) Hubbard‐type interaction, that also other (non‐local) terms depending on the site occupancy, known as correlated or assisted hopping, exist. Even though such terms in quantum dots tunnel coupled to external electrodes may have quite an appreciable amplitude, the interpretation of experiments on these systems—usually in the linear response regime—seems not to require their presence. However, since the correlated‐hopping term breaks the particle‐hole symmetry of the standard Anderson model and modifies all transport characteristics of the system, the detailed knowledge of its influence on measurable characteristics, especially in the non‐linear regime, is a prerequisite for its experimental detection. In this paper, the non‐linear transport properties of junctions composed of a quantum dot tunnel coupled to external electrodes are studied. The system is modeled by the single‐impurity Anderson Hamiltonian with Hubbard on‐site interaction and with a non‐local correlated‐hopping interaction. Using the previously found general expression for the spin‐dependent transport and spectral Green functions as well as general formulae for charge and heat transport, relevant transport characteristics are calculated in the strongly non‐linear regime.
Leistung und Stabilität eines Korund‐Typ‐In2O3‐Katalysators für die Kohlendioxidhydrierung zu Methanol
Authors: Gili Albert , Brösigke Georg , Javed Mudassar , Dal Molin Emiliano , Isbrücker Philipp , Repke Jens‐Uwe , Hess Franziska , Gurlo Aleksander , Schomäcker Reinhard , Bekheet Maged F.
Published: December 2024

Die Hydrierung von Kohlendioxid zu Methanol ist eine wichtige chemische Reaktion zur Speicherung von Energie in chemischen Bindungen, wobei Kohlendioxid als Energiesenke verwendet wird. Indiumoxid gehört zu den vielversprechendsten Kandidaten für den Ersatz des Kupfer‐ und Zinkoxid‐Katalysators, der industriell für Synthesegasgemische eingesetzt wird, aber aus Gründen der Instabilität weniger idonhaltig für Edukte mit Kohlendioxid ist. Das Polymorph des Indiumoxids und die Betriebsbedingungen müssen noch optimiert werden, um eine optimale und stabile Leistung zu erzielen. Indiumoxid‐Katalysatoren, die unterschiedliche rhomboedrische und kubische Phasenverhältnisse enthalten, wurden mit einem solvothermischen Verfahren synthetisiert und in einem idealerweise gemischten Gasphasenreaktor bewertet. Der reine rhomboedrische Katalysator zeigt die beste Leistung in Bezug auf die Ausbeute an Methanol, Selektivität und Stabilität. Die Phasenstabilität wurde mit Synchrotron in situ‐XRD und Rietveld‐Verfeinerung analysiert, um Aufschluss über die Stabilität der verschiedenen Phasen bei erweiterten Betriebsbedingungen zu geben. Abhängig von der Durchflussrate, der Temperatur und dem Wasserstoffpartialdruck kommt es zu einer Transformation des Kristallsystems von rhomboedrisch zu kubisch, bei dem schließlich inaktives metallisches Indium entsteht. Falls vorhanden, dient kubisches In2O3 als Ausgangszentrum, um den Übergang von kubisch zu rhomboedrisch zu induzieren, was die Leistung beeinträchtigt. Diese Ergebnisse ermöglichen ein sinnvolleres Katalysatordesign und eine Feinabstimmung der Betriebsbedingungen, um eine optimale und stabile Leistungfähigkeit zu gewährleisten.
How to Easily Depolymerize Polyurethane Foam Wastes by Superbase Catalysts in Ionic Liquids Below 100 °C
Authors: Villa Rocio , Salas Rebeca , Maciá María , Velasco Francisco , Altava Belén , García‐Verdugo Eduardo , Lozano Pedro
Published: December 2024

This study introduces a novel and sustainable approach using Ionic Liquids (ILs) as a non‐innocent solvent that enhances the performance of the basic catalysts to depolymerize polyurethane foam wastes (PUFWs) through hydrolysis, alcoholysis or aminolysis under mild conditions. The system is stable, fully recoverable, and reusable. Hydrolysis of PUFWs can occur in just 2 minutes at 95–98 °C, producing a white polyol that is easily separated and reused in new polyurethane synthesis. The method was successfully scaled up to depolymerize 200 g of PUFW per batch (1 kg overall depolymerization system). This scalability, combined with the medium‘s reusability without loss of effectiveness, highlights its strong potential for industrial applications.
Topotactic Transformation in Fe3O4 Induces Spontaneous Growth of Compositionally Diverse Nanostructures
Authors: Muhammad Faheem , Chen Xiwen , Sun Qi , Wang Yuting , Mo Dongze , Li Yuyang , Miao Leiying , Wei Hui
Published: December 2024

Topotactic transformation is an emerging strategy for synthesizing materials with exotic functional properties. In this report, instead of producing new crystals with related structures, we exploited the topotactic transformation phenomenon to spontaneously produce compositionally diverse nanostructures on the transforming substrate. The surface of magnetite nanoparticles (Fe3O4 NPs) is topotactically transformed into maghemite (γ‐Fe2O3). Benefiting from such oxidation susceptibility of ultrasmall Fe3O4 NPs, we achieved spontaneous growth of metals (Ag, Au, Pt, and Pd), a non‐metal (Se), and a metal oxide (MnO2) based nanostructures onto the surface of Fe3O4. No spontaneous growth of nanostructures was observed when the oxidized Fe3O4 NPs were tested, likely due to the loss of the Fe2+‐associated mobile electrons. The obtained nanostructures displayed appreciable antioxidant activities, which we utilized to effectively treat inflammation in the intestines. It is anticipated that this synthetic route, based on topotactic transformation, represents a significant advancement in synthesizing various chemically diverse hetero‐nanostructures.
Expanding Polycyclic Tetramate Macrolactam (PoTeM) Core Structure Diversity by Chemo‐Enzymatic Synthesis and Bioengineering
Authors: Schuler Sebastian , Einsiedler Manuel , Evers Julia K , Malay Mert , Uka Valdet , Schneider Sabine , Gulder Tobias Alexander Marius
Published: December 2024

Polycyclic tetramate macrolactams (PoTeMs) represent a growing class of bioactive natural products that are derived from a common tetramate polyene precursor, lysobacterene A, produced by an unusual bacterial iterative polyketide synthase (PKS) / non‐ribosomal peptide synthetase (NRPS). The structural and functional diversity of PoTeMs is biosynthetically elaborated from lysobacterene A by pathway‐specific cyclizing and modifying enzymes. This results in diverse core structure decoration and cyclization patterns. However, approaches to directly edit the PoTeM carbon skeleton are currently not existing. We thus set out to modify the PoTeM core structure by exchanging the natural L‐ornithine‐derived building block by L‐lysine, hence extending macrocycle size by an additional CH2 group. We developed streamlined synthetic access to lysobacterene A and the corresponding extended analog and achieved cyclization of both precursors by the cognate PoTeM cyclases IkaBC in vitro. This chemo‐enzymatic approach corroborated the catalytic competence of IkaBC to produce a larger macrolactam yielding homo‐ikarugamycin. We thus engineered the adenylation domain active site of IkaA to directly accept L‐lysine, which upon co‐expression with IkaBC delivered a recombinant bacterial homo‐ikarugamycin producer. Our work establishes an entirely new PoTeM structural framework and sets the stage for the biotechnological diversification of the PoTeM natural product class in general.
Visible‐Light Photocatalyzed Skeletal Rearrangement Enables the Synthesis of Highly Functionalized Xanthenes with Antitumor Activity
Authors: Lin Shi‐Lin , Zhao Fen , Wei Fen , Shi Ying‐Tong , Wen Jing‐Kai , Yang Chao , Zhang Hao‐Shuo , Li Chuang‐Chuang , Liu Chang , Ye Wen‐Cai , Cheng Min‐Jing , Wang Lei
Published: December 2024

Highly functionalized xanthenes possess an impressive range of bioactivities and daunting synthetic challenge due to their unique ring systems and stereocenters. Here, we report an unprecedented ketyl radicals‐induced skeletal rearrangement reaction of spirodihydrobenzofurans, enabled by zero‐valent iron as reducing agents via photoredox catalysis, facilitating the facile preparation of various highly functionalized xanthenes. The features of this protocol include high chemo‐ and regioselectivity, exceptionally mild conditions, a broad substrate scope, scalability to gram‐scale quantities, and consistent delivery of good to excellent yields. Mechanistic studies rationalize the function of this zero‐valent iron‐based reactivity in radical generation. Notably, this reaction was applied to the first asymmetric total synthesis of the complex polycyclic xanthene ent‐myrtucomvalones E−F. Moreover, this work led to the discovery of an agent with highly effective antiosteosarcoma activity in vitro and in vivo, potentially paving the way for the development of new xanthene‐based candidates for osteosarcoma treatment.
Diverse Synthesis of Arene‐Fused [n.1.1]‐Bridged Molecules via Catalytic Cycloaddition and Rearrangement Reactions
Authors: Yu Tao , Zhao Xue , Nie Zaicheng , Qin Lulu , Ding Zhengwei , Xu Liang , Li Pengfei
Published: December 2024

Although great advancement has been made in synthesis of 3D bridged bicyclic[n.1.1]‐bioisosteres, facile construction of 2D/3D merged molecules incorporating bridged rings, as novel chemical space in drug discovery, remains a significant challenge. Herein a collective, selective, and diversity‐oriented approach for up to 6 types of 2D/3D polycyclic scaffolds featuring bicyclo[n.1.1] substructure is reported. A boronyl radical‐catalyzed [2σ+2π] cycloaddition between bicyclo[1.1.0]butanes and ortho‐quinone methides afforded spirocyclic compounds containing a bicyclo[2.1.1]hexanes unit, which were used as intermediates for synthesis of three types of 2D/3D scaffolds via judiciously controlled Lewis acid‐catalyzed rearrangements. The reaction and rearrangement of para‐quinone methides worked analogously and provided another two polycyclic scaffolds.
Rapid N2O Formation from N2 on Water Droplet Surfaces
Authors: Jiang Qi , Xia Deming , Li Xiaofan , Zhang Hong , Yin Rujing , Xie Huaijun , Xie Hong‐bin , Jiang Jie , Chen Jingwen , Francisco Joseph S.
Published: December 2024

Nitrogen (N2) has long been considered as stable atmospheric reservoir for N element and has a persistence time of hundreds of years. This study reveals that oxygen (O2) at typical tropospheric concentrations can rapidly activate N2, leading to substantial production of nitrous oxide (N2O), the third most impactful greenhouse gas, at rates approaching 2.83±0.41 ppmv hour−1 catalyzed by ubiquitous water droplets in experimental systems. Notably, ozone (O3), typically consumed by N2O in the stratosphere, can further accelerate N2O formation. In contrast, the produced N2O concentration is below detection limits in the absence of O2/O3 or water droplets. A novel reduction‐then‐oxidation (RTO) mechanism was proposed to account for the rapid formation of N2O on the water droplet surfaces facilitated by the cooperation of water droplets and O2/O3. Further extrapolation indicates that the RTO pathway contributes several Tg N N2O annually, far exceeding the most known sources of N2O. These findings have broad implications for tracing atmospheric N2O sources, enhancing understanding of climate‐O2/O3 interactions, and paving avenues for developing new methodologies for N2O synthesis.
A High‐Entropy Engineering on Sustainable Anionic Redox Mn‐Based Cathode with Retardant Stress for High‐Rate Sodium‐Ion Batteries
Authors: Liu Shiqi , Liu Fangzheng , Zhao Shu , Zhuo Zengqing , Xiao Dongdong , Cui Zhongyi , Wang Yulong , Wang Boya , Wu Tianhao , Li Yuming , Liang Lisi , Huang Houbing , Yang Wanli , Yu Haijun
Published: December 2024

Manganese‐based (Mn‐based) layered oxides have emerged as competitive cathode materials for sodium‐ion batteries (SIBs), primarily due to their high energy density, cost‐effectiveness, and potential for mass production. However, these materials often suffer from irreversible oxygen redox reactions, significant phase transitions, and microcrack formation, which lead to considerable internal stress and degradation of electrochemical performance. This study introduces a high‐entropy engineering strategy for P2‐type Mn‐based layered oxide cathodes (HE‐NMCO), wherein a multi‐ingredient cocktail effect strengthens the lattice framework by modulating the local environmental chemistry. This innovative approach fosters sustainable reversible oxygen activity, mitigates stress concentrations at grain boundaries, and accelerates Na+ transport kinetics. The resulting robust lattice framework with optimized elemental interactions significantly improves structural integrity and reduces the formation of intragranular fractures. Consequently, HE‐NMCO demonstrates remarkable cycling stability, retaining 93.5 % capacity after 100 deep (de)sodiation cycles, alongside an enhanced rate capability of 134.1 mAh g−1 at 5 C. Notably, comparative studies through multimodal characterization techniques highlight HE‐NMCO′s superior reversibility in oxygen anion redox (OAR) reactions over extensive cycling, contrasting sharply with conventional NMCO cathode. This work elucidates the potential for advancing high energy and power density Mn‐based cathodes for SIBs through local species diversity.
Synergistic Pathways in PLA Breakdown and PTMC Formation: A One‐Pot Eutectic‐Driven Recycling Mechanism
Authors: Moins Sébastien , Coulembier Olivier
Published: December 2024

This study introduces a novel one‐pot strategy for the chemical valorization of poly(lactic acid) (PLA), coupling its base‐catalyzed depolymerization with the ring‐opening polymerization (ROP) of trimethylene carbonate (TMC). The process exploits an eutectic mixture of lactide (LA) and TMC, which lowers the thermal input required for PLA degradation. Using potassium aryloxide (KOArtBu) as a bifunctional catalyst, the PLA is first quickly hydrolyzed into oligomers or lactic acid, which subsequently initiate the slower polymerization of TMC. Notably, this transformation operates in the presence of residual water, eliminating the need for tedious drying steps. The method achieves selective PLA breakdown conversion and produces (oligo)lactic acid end‐capped poly(trimethylene carbonate) (PTMC) with tunable molar mass, depending on water content.
Propane Activation on Pt Electrodes at Room Temperature: Quantification of Adsorbate Identity and Coverage
Authors: Bhadouria Ashutosh , Heil Joseph N. , Parab Durvesh E. , Greeley Jeffrey P. , Tackett Brian M.
Published: December 2024

C−H bond activation is the first step in manufacturing chemical products from readily available light alkane feedstock and typically proceeds via carbon‐intensive thermal processes. The ongoing emphasis on decarbonization via electrification motivates low‐temperature electrochemical alternatives that could lead to sustainable chemicals production. Platinum (Pt) electrocatalysts have shown activity towards reacting alkanes; however, little is known about propane electrocatalytic activation and conditions suitable for enabling selective oxidation to valuable products. Herein, we utilize a combination of electrochemical mass spectrometry (ECMS) and density functional theory (DFT) calculations to elucidate the potential dependence of propane activation on Pt electrocatalysts. Results show a strong dependence of adsorption on the applied potential in room‐temperature aqueous acidic electrolyte, with a maximum coverage of propane‐derived adsorbates at 0.30 V vs RHE. Using charge deconvolution and deuterated experiments, the mechanism of adsorption was elucidated, and C3H2* was determined as the average dehydrogenated propane‐derived adsorbate species. DFT calculations further corroborate these results, showing that the formation of deeply dehydrogenated species is energetically accessible at room temperature. The combined theoretical and experimental findings yield insights for selective activation of paraffinic C−H bonds at room temperature, aqueous conditions—a critical step towards decarbonized chemical manufacturing.
Hour‐Long Afterglow in Flexible Polymeric Materials through the Introduction of Electron Donor/Acceptor Exciplexes
Authors: Shi Jiaju , Zhang Peng , Gao Haiyang , Zhu Fangming , Liang Guodong
Published: December 2024

The development of organic afterglow materials has garnered significant attention due to their diverse applications in smart devices, optoelectronics, and bioimaging. However, polymeric afterglow materials often suffer from short emission lifetimes, typically ranging from milliseconds to seconds, posing a significant challenge for achieving hour‐long afterglow (HLA) polymers. This study presents the successful fabrication of transparent HLA polymers by introducing electron donor/acceptor exciplexes. Employing aromatic polyesters as the polymer electron acceptor and charge reservoirs, the resulting HLA polymers exhibited a remarkable green afterglow that persisted for 12 hours under ambient conditions, representing the longest duration achieved for polymeric afterglow materials to date. Intriguingly, these HLA polymers could be activated solely by sunlight, maintaining a green afterglow for over 6 hours at room temperature in air, which outperformed all previously reported afterglow polymers. The doped polymers exhibited superior flexibility and transparency, making them ideal candidates for flexible display applications. Furthermore, successfully spinning these doped polymers into fibers while retaining their HLA properties opens up exciting possibilities for their use in wearable smart devices.
Stimuli‐Responsive DNA Nanomachines for Intracellular Targeted Electrochemiluminescence Imaging in Single Cells
Authors: Li Binxiao , Lu Yanwei , Huang Xuedong , Sojic Neso , Jiang Dechen , Liu Baohong
Published: December 2024

Electrochemiluminescence (ECL) microscopy has emerged as a powerful technique for single‐cell imaging owing to its unparalleled background‐free imaging advantages. However, controlled intracellular ECL imaging remains challenging. Here, we developed a stimuli‐responsive self‐assembled DNA nanomachine that enables the ECL imaging of intracellular target biomolecules in single cells. The ECL nanoprobe consists of an ECL nanoemitter constructed from Ru(bpy)32+‐doped metal–organic framework as the nanoreactor core, with a DNA polymer hydrogel (DNAgel) shell acting as the stimuli‐gated layer. The outer functionalized DNAgel of the ECL nanoprobe was specifically designed to block ECL generation and to dissociate by ATP molecules, thereby enabling selective recovery of ECL emission capability. Such an engineered stimuli‐responsive nanomachine successfully achieved the targeted ECL imaging of intracellular ATP distribution with spatial resolution. In addition, ECL imaging of various intracellular biomolecules should be generalizable by simply changing the switching DNA sequence of the probe. Our research provided a reliable strategy for ECL microscopy within cells, which will broaden the application of ECL in single‐cell and single‐molecule profiling.
Flexible Fiber Sensors for Real‐Time Monitoring of Redox Signaling Molecules in Exercise‐Mimicking Engineered Skeletal Muscle
Authors: Li Jia‐Xin , Fan Wen‐Ting , Sun Meng‐Yuan , Zhao Yi , Lu Yi‐Fei , Yang Yan‐Bing , Huang Wei‐Hua , Liu Yan‐Ling
Published: December 2024

Real‐time monitoring of reactive oxygen and nitrogen species (RONS) in skeletal muscle provides crucial insights into the cause‐and‐effect relationships between physical activity and health benefits. However, the dynamic production of exercise‐induced RONS remains poorly explored, due to the lack of sensing tools that can conform to soft skeletal muscle while monitor RONS release during exercise. Here we introduce dual flexible sensors via twisting carbon nanotubes into helical bundles of fibers and subsequent assembling electrochemical sensing components. These flexible sensors exhibit low bending stiffness, excellent H2O2 and NO sensing abilities, outstanding biocompatibility and compliance with engineered skeletal muscle tissue. This allows real‐time and simultaneous monitoring of H2O2 and NO release from engineered skeletal muscle in response to different exercise‐mimicking stretches, which reveals that warm‐up activities before high‐intensity exercise may enhance adaptive responses by down‐regulating H2O2 and up‐regulating NO production. The proposed sensing strategy demonstrates great versatility in monitoring multiple biomarkers of soft tissue and organs.
Isomerization‐Controlled Aggregation in Photoactive Layer: An Additive Strategy for Organic Solar Cells with Over 19.5 % Efficiency
Authors: Xia Zihao , Gao Chuanlin , Xie Zhixiang , Wu Miaoxuan , Chen Hansheng , Li Tongzi , Zhou Jiang , Cai Ting , Hu Huawei , Shuai Jing , Xie Chen , Zhang Guangye , Chen Wenduo , Liu Shenghua
Published: December 2024

Morphology control of the photoactive layer is crucial for achieving high‐performance organic solar cells (OSCs), yet it remains a significant challenge in this field. One effective approach is the additive strategy, which fine‐tunes the morphology of the photoactive layer. However, the underlying mechanisms governing the impact of different types of additives from liquid, solid, to volatile solid, on the bulk heterojunction morphology and device performance are not fully understood. Herein, we present an aggregation regulation strategy for acceptor molecules by incorporating three novel isomeric additives: 4‐bromo‐1,2‐dichlorobenzene (LCB), 1‐bromo‐2,4‐dichlorobenzene (SCB), and 2‐bromo‐1,4‐dichlorobenzene (VCB) into the blend active layer. This approach optimizes the bulk heterojunction morphology and enhances the photovoltaic performance of OSCs. Our results reveal that these additives induce stepwise regulation of acceptor molecule aggregation during film formation. The liquid additive LCB primarily extends solvent evaporation time, effectively preventing excessive aggregation, while the solid additive SCB significantly shortens the aggregation period during the film evolution, resulting in the most compact molecular π–π stacking. Furthermore, the volatile solid additive VCB fine‐tunes the intermolecular interactions and crystallization within the active layer, promoting optimal molecular self‐assembly and aggregation for ideal molecular stacking. Consequently, the power conversion efficiencies of 19.33 % and 19.51 % were achieved for the VCB‐processed D18 : L8‐BO‐ and PM6 : L8‐BO‐based OSCs, respectively, outperforming the LCB‐processed and SCB‐processed devices.
Through Space π‐Electrons Communication in [2,2]‐Paracyclophanes: Unprecendented Stabilization of Radicals
Authors: Fauvel Eléa , Moussounda Moussounda Koumba Tataye , El Kadiry Firas , Maria Sébastien , Rollet Marion , Maresca Marc , Siri Didier , Clément Jean‐Louis , Gigmes Didier , Nechab Malek
Published: December 2024

Efforts to understand radical stability have led to considerable progress in radical chemistry. In this article, we investigated a novel approach to enhancing the radical stability of carbon‐centered radicals through space electron delocalization within [2,2]‐paracyclophanes. Alkoxyamines possessing a paracyclophane scaffold exploit face‐to‐face π‐π‐interactions between the aromatic rings to effectively lower bond dissociation energy (BDE) for NO−C bond homolysis. Electron spin resonance (ESR) experiments and computational modeling have confirmed a better stability compared to the analogues without the paracyclophane core. Theoretical analyses further elucidate the role of through‐space electron communication in enhancing radical stability. This study highlights promising applications in fields such as organic synthesis, material science, and drug design. By achieving a low BDE for homolysis, the alkoxyamines efficiently release radicals, enabling successful application in nitroxide‐mediated polymerization (NMP) of styrene, which provides high control over polymer architecture. Additionally, preliminary anti‐proliferative assays reveal that the alkoxyamines exhibit promising anti‐cancer activities against lung, breast, and prostate cells, which is correlated to their ability to release radicals upon homolysis.
Mit Hybriden Enzym‐Elektrokatalysator‐Kaskaden Modifizierte Gasdiffusionselektroden für die Methanolerzeugung aus Kohlendioxid
Authors: Wang Panpan , Wang Xin , Chandra Shubhadeep , Lielpetere Anna , Quast Thomas , Conzuelo Felipe , Schuhmann Wolfgang
Published: December 2024

Wir schlagen eine hybride elektrokatalytisch‐bioelektrokatalytische Reaktionskaskade vor, die auf einer Gasdiffusionselektrode zur CO2‐Reduktion unter selektiver Bildung von Methanol integriert ist. Ag‐Bi2O3 reduziert gasförmiges CO2 bei neutralem pH‐Wert selektiv zu Formiat. Eine nachfolgende enzymatische Kaskade aus Formaldehyd‐Dehydrogenase und Alkohol‐Dehydrogenase, die beide von Nikotinamid‐Adenin‐Dinukleotid (NADH) abhängig sind, reduziert Formiat weiter sequentiell zu Formaldehyd und Methanol. Der enzymatisch oxidierte Redoxkofaktor NAD+ wird durch das Enzym Diaphorase regeneriert, das elektrochemisch an die Elektrode gekoppelt ist, indem es in ein Redoxpolymer auf Cobaltocen‐Basis eingebettet ist. Die Methanolbildung wird mithilfe eines hochselektiven Biosensors nachgewiesen, der auf Alkoholoxidase in Kombination mit Meerrettichperoxidase basiert, die in ein speziell angepasstes Redoxpolymer integriert sind. Die vorgeschlagene hybride elektrokatalytisch‐bioelektrokatalytische Kaskade ist ein Beispiel für eine allgemeine Strategie zur Verbesserung der Selektivität elektrokatalytischer Reaktionen und/oder zum Ersatz bioelektrochemisch anspruchsvoller Schritte wie der Synthese von Formiat aus CO2 unter Verwendung sauerstoffempfindlicher Formiatdehydrogenasen durch robustere anorganische Elektrokatalysatoren.
Molecular Micellar Aggregate Electrolytes Enable Durable Electrochemical Proton Storage
Authors: Dong Xiaoyu , Li Zhiwei , Wu Zhiyuan , Meng Fanhao , Xiao Hong , Xu Hai , Zhang Xiaogang , Lin Zhiqun , Dou Hui
Published: December 2024

Proton electrochemistry holds eminent potential for developing high capacity and rate energy storage devices in the post‐lithium era. However, the decomposition of water in acidic aqueous electrolytes causes electrode corrosion, leading to capacity fading. Herein, we report a judicious design of molecular micellar aggregates as non‐aqueous electrolytes for stable and high‐voltage electrochemical proton storage. The key to our strategy lies in introducing cetyltrimethylammonium bromide (CTAB), forming micelles to improve the miscibility of acetonitrile (ACN) and H3PO4, afford channel for proton transport, and electrostatically interact with phosphate ions of H3PO4 to further promote proton transport. Such aggregates impart rapid and stable electrochemical proton storage with a widened operating voltage (1.8 V vs. 1.5 V in aqueous electrolyte). By optimizing CTAB content, proton transport can be enhanced. Asymmetric full proton battery using the optimal CTAB electrolyte achieves a maximum energy density of 102.8 Wh kg−1 and a maximum power density of 10.1 kW kg−1. Our simple yet robust route to micellar aggregate electrolytes enables stable proton storage, underscoring its potential for grid‐scale energy storage, emergency power supplies, and portable electronics.
Ion Hydration Enables Generality in Asymmetric Catalysis: Desymmetrization to P‐Stereogenic Triarylphosphine Derivatives
Authors: Liu Chi , Yang Yang , Hong Wenyang , Ma Jun‐An , Zhu Ye
Published: December 2024

Asymmetric synthesis relies on seamless transmission of stereochemical information from a chiral reagent/catalyst to a prochiral substrate. The disruption by substrates’ structural changes presents a hurdle in innovating generality‐oriented asymmetric catalysis. Here, we report a strategy for substrate adaptability by exploiting a fundamental physicochemical phenomenon—ion hydration, in developing remote desymmetrization to access P‐stereogenic triarylphosphine oxides and sulfides. Compared to existing methods, this approach does not require pre‐installed ortho substituents and avoids the use of Grignard/organolithium reagents. Simply tuning the water/ion ratio in the reaction media tailors the water‐mediated ionic substrate–catalyst preorganization to counterbalance the structural changes in the substrates, thus further increasing the diversity of enantioenriched P‐stereogenic compounds. This study shows that it is viable and practical to precisely manipulate ionic interactions through tuning the dynamic ion hydration in situ, thereby adding a distinctive dimension to catalyst engineering in the pursuit of substrate generality in asymmetric catalysis.
Towards Highly Stable Sn2+ Electrolyte for Aqueous Tin Batteries Using Hydroquinone Antioxidant
Authors: Wang Qiong , Zhang Fengyi , Shu Yu , Xiao Hongjie , Zhang Xi , Ma Xiaohui , Liu Jinlong , Wang Yonggang , Huang Jianhang , Xia Yongyao
Published: December 2024

Sn redox chemistry in aqueous acidic electrolyte was characterized with high reversibility and kinetics, which is considered as competitive anode material for aqueous batteries. Unfortunately, divalent Sn2+ is unstable in aqueous electrolyte. It was revealed that Sn2+ is easy to be oxidized to tetravalent Sn4+ by dissolved oxygen and then forms precipitate through hydrolysis process, leading to serious performance decay. Here, hydroquinone (HQ) was employed as antioxidant to prevent Sn2+ oxidation. With addition of HQ, Sn2+ electrolyte can maintain transparent and colorless after long‐time exposure under air atmosphere, while large amounts of sediment were observed in the electrolyte without HQ. Moreover, HQ can adsorb on electrode surface to regulate Sn deposition and suppress Sn dendrite formation. With the difunctional HQ additive, Sn anode shows a stable cycling performance more than 1500 cycles with a high average coulombic efficiency (CE) of 99.9 %. And the organic||Sn cell shows high cycling stability for 10,000 cycles with 71 % capacity retention. The hydroquinone antioxidant strategy provides a facile and cost‐effective way to develop highly stable Sn2+‐based electrolyte.
Dynamic Co‐Clustering and Self‐Sorting in Interactive Protocell Populations
Authors: Mishra Ananya , Taylor Hannah , Patil Avinash J. , Mann Stephen
Published: December 2024

The design and implementation of collective actions in model protocell communities is an on‐going challenge in synthetic protobiology. Herein, we covalently graft alginate or chitosan onto the outer surface of semipermeable enzyme‐containing silica colloidosomes to produce hairy catalytic protocells with pH‐switchable membrane surface charge. Binary populations of the enzymatically active protocells exhibit self‐initiated stimulus‐responsive changes in spatial organization such that the mixed community undergoes alternative modes of electrostatically induced self‐sorting and reversible co‐clustering. We demonstrate that co‐clustering, but not self‐sorting, mitigates signal attenuation in a binary community of enzyme‐containing sender and receiver protocells due to increased proximity effects. The level of signal attenuation is correlated with a time‐dependent pH‐mediated switch in the spatial organization of the sender and receiver populations. Our results pave the way towards the development of programmable networks of adaptive life‐like objects and could have implications for the development of interactive cytomimetic materials and agent‐based robotics.
A Lithiophilic Donor–Acceptor Polymer Modified Separator for High‐Performance Lithium Metal Batteries
Authors: Yang Tao , Xu Xijun , Chen Suping , Yang Yan , Li Fangkun , Fan Weizhen , Wu Yanxue , Zhao Jingwei , Liu Jun , Huo Yanping
Published: December 2024

As traditional lithium‐ion batteries near their theoretical limits, the advancement of lithium‐metal batteries (LMBs) becomes crucial for achieving higher energy densities. However, uncontrolled ion transport and unstable solid electrolyte interface (SEI) layer are key factors inducing lithium dendrite growth, hindering the development of LMBs. Separator modification is an effective strategy to address the challenges of LMBs. To tackle the issues, a donor–acceptor polymer (ArMT) consisting of benzene rings and triazine was successfully synthesized and modified onto commercial polypropylene (ArMT@PP) as separators for LMBs. Benefitting from the highly lithiophilic triazine organic units, this ArMT exhibits affinity towards Li+ and simplifies the solvation structure of Li+ during the diffusion process, thus decreasing the ion diffusion activation energy, thereby accelerating the migration of Li+. Furthermore, triazine organic units with appropriate pore size regulate the plating/stripping behavior of lithium metal anodes, thereby facilitating the formation of a stable solid electrolyte interface (SEI) layer. As a result, the assembled Li|ArMT@PP|Li symmetric cells exhibit stable plating/stripping over 800 h. Moreover, the LiFePO4|ArMT@PP|Li cells achieved excellent cycling stability with 127.3 mAh g−1 after 1200 cycles at 1 C and a high capacity retention of 90.58 %. This design strategy ensures a durable and dendrite‐free anode and paves the way for the development of high‐energy‐density LMBs.
Rapid N2O Formation from N2 on Water Droplet Surfaces
Authors: Jiang Qi , Xia Deming , Li Xiaofan , Zhang Hong , Yin Rujing , Xie Huaijun , Xie Hong-bin , Jiang Jie , Chen Jingwen , Francisco Joseph S.
Published: December 2024

Nitrogen (N2) has long been considered as stable atmospheric reservoir for N element and has a persistence time of hundreds of years. This study reveals that oxygen (O2) at typical tropospheric concentrations can rapidly activate N2, leading to substantial production of nitrous oxide (N2O), the third most impactful greenhouse gas, at rates approaching 2.83 ± 0.41 ppmv hour‐1 catalyzed by ubiquitous water droplets in experimental systems. Notably, ozone (O3), typically consumed by N2O in the stratosphere, can further accelerate N2O formation. In contrast, the produced N2O concentration is below detection limits in the absence of O2/O3 or water droplets. A novel reduction‐then‐oxidation (RTO) mechanism was proposed to account for the rapid formation of N2O on the water droplet surfaces facilitated by the cooperation of water droplets and O2/O3. Further extrapolation indicates that the RTO pathway contributes several Tg N N2O annually, far exceeding the most known sources of N2O. These findings have broad implications for tracing atmospheric N2O sources, enhancing understanding of climate‐O2/O3 interactions, and paving avenues for developing new methodologies for N2O synthesis.
In Vivo Self‐Assembly of PROTACs by Bioorthogonal Chemistry for Precision Cancer Therapy
Authors: Xie Shaowen , Zhu Jingjie , Peng Yihan , Zhan Fangyi , Zhan Feiyan , He Chen , Feng Dazhi , Xie Jia , Liu Jingyu , Zhu Huajian , Yao Hong , Xu Jinyi , Su Zhigui , Xu Shengtao
Published: December 2024

Proteolysis targeting chimeras (PROTACs) hold immense promise for targeted protein degradation; however, challenges such as off‐target effects, poor drug‐likeness properties, and the “hook effect” remain. This study introduces Nano‐Click‐formed PROTACs (Nano‐CLIPTACs) for precise tumor protein degradation in vivo. Traditional PROTACs with high molecular weight were first divided into two smaller druglike precursors capable of self‐assembling to form functional PROTACs through a bioorthogonal reaction. Then, optimal CLIPTACs precursors (W4 and Z2) were encapsulated individually into cyclic RGDfC‐peptide‐modified liposomes to prepare Nano‐CLIPTACs, enabling tumor‐targeted delivery and subsequent in situ self‐assembly to form PROTACs WZ42 within tumor cells. The degradation abilities of Nano‐CLIPTACs in vitro and in vivo were further verified using a key oncology target, anaplastic lymphoma kinase (ALK), validating the safety, efficacy and “anti‐hook effect” of this strategy. Overall, Nano‐CLIPTACs represent a critical step towards the clinical translation of PROTACs technology for precise targeted anti‐cancer therapies.
Zeolite Encapsulation to Enhance Interfacial Gas Availability for Photocatalytic Hydrogen Peroxide Production
Authors: Cao Bei , Liu Yifeng , Zhao Yue , Qu Jiangshan , Zhou Qin , Xiao Fengshou , Li Can , Wang Liang , Li Rengui
Published: December 2024

The photocatalytic oxidation of water with gaseous oxygen is environmentally benign for the synthesis of hydrogen peroxide (H2O2), but it is currently constrained by the inadequate supply of gaseous oxygen at the catalyst surface in a solid–liquid–gas triple‐phase reaction system. Herein, we address this challenge by employing the zeolite encapsulated catalysts that efficiently enrich gaseous oxygen and accelerate the H2O2 synthesis in aqueous conditions. We focus on the classical titania photocatalyst, encapsulating it within siliceous MFI zeolite crystals. This encapsulation results in a significant enhancement in H2O2 synthesis efficiency, achieving a yield that is ten times greater than that with unencapsulated TiO2. Mechanism study reveals that gaseous oxygen is notably concentrated within the microporous structure of the zeolite under aqueous conditions, thereby facilitating its interaction with the titania surface at the liquid‐solid interface. In addition, the H2O2 product could swiftly transfer through the micropores, thereby reducing the side reaction of decomposition. This design provides an alternative pathway to address the poor gas solubility of gaseous reactants in water, and paves the way for advancements in various other photocatalytic processes.