bluuebunny/crossref_metadata_2025_split huggingface dataset:
Scalable and Precise Synthesis of Structurally Colored Bottlebrush Block Copolymers: Enabling Refined Color Calibration for Sustainable Photonic Pigments
Authors: Wang Bangbang , Zhang Kunyu , Pan Li , Li Yuesheng , Song Dong‐Po 
Published: January 2025

AbstractSelf‐assembled bottlebrush block copolymers (BBCPs) offer a vibrant, eco‐friendly alternative to traditional toxic pigments and dyes, providing vivid structural colors with significantly reduced environmental impact. Scaling up the synthesis of these polymers for practical applications has been challenging with conventional batch methods, which suffer from slow mass and heat transfer, inadequate mixing, and issues with reproducibility. Precise control over molecular weight and dispersity remains a significant challenge for achieving finely tuned color appearances. Here, we present an alternative strategy to overcome the challenges by integrating a rapid continuous flow technique with an in‐line self‐assembly procedure. This strategy enables the rapid, stable and large‐scale synthesis of narrow‐dispersed BBCPs, exceeding 2 kg/day, a significant improvement over conventional gram‐scale methods. Furthermore, precise control over the degree of polymerization is achieved with an unprecedented interval accuracy of four repeat units. This level of precision enables refined color calibration in the resulting photonic pigments, effectively eliminating the need for labor‐intensive and costly multiple batch syntheses.
Exceptional CO2 Hydrogenation to Ethanol via Precise Single‐Atom Ir Deposition on Functional P Islands
Authors: Liu Lingyue , Liu Jinjie , Li Guangchao , Shi Xiuwen , Yin Jun , Zheng Shourong , Yung Ka‐Fu , Yang Hong Bin , Lo Tsz Woon Benedict 
Published: January 2025

AbstractThe thermocatalytic hydrogenation of CO2 to ethanol has attracted significant interest because ethanol offers ease of transport and substantial value in chemical synthesis. Here, we present a state‐of‐the‐art catalyst for the CO2 hydrogenation to ethanol achieved by precisely depositing single‐atom Ir species on P cluster islands situated on the In2O3 nanosheets. The Ir1‐Px/In2O3 catalyst achieves an impressive ethanol yield of 3.33 mmol g−1 h−1 and a turnover frequency (TOF) of 914 h−1 under 1.0 MPa (H2/CO2=3 : 1) at 180 °C, nearly 8 times higher than that of the unmodified Ir1/In2O3 catalyst. Additionally, at a more industrially relevant pressure of 5.0 MPa, the TOF of the Ir1‐Px/In2O3 catalyst can reach up to 2108 h−1, surpassing previously reported catalysts. Combined in situ characterization and theoretical studies reveal that the hydrogenation process is significantly enhanced by the Ir1‐Px entities. Specifically, the Ir atom facilitates CO2 activation and C−C coupling, while the surrounding P island exhibits exceptional H2 dissociation ability. These three steps have been found crucial for the CO2 hydrogenation reaction. This discovery opens new opportunities for the regulation of the microenvironment of current catalysts by providing essential chemical functionalities that enhance intricate and complex reaction processes.
Stereochemistry‐Tuned Hydrogen‐Bonding Synergistic Covalent Adaptable Networks: Towards Recycled Elastomers with Excellent Creep‐Resistant Performance
Authors: Feng Zhenghuai , Xie Miao , Lai Jialiang , Wang Zhanhua , Xia Hesheng 
Published: January 2025

AbstractCovalent adaptable networks (CANs) offer innovative solutions for the reprocessing and recycling of thermoset polymers. However, achieving a balance between easy reprocessing and creep resistance remains a challenge. This study focuses on designing and synthesizing polyurethane (PU) materials with tailored properties by manipulating the stereochemistry of diamine chain extenders. By employing cis‐ and trans‐configurations of diamine extenders, we developed a series of PU materials with varying mechanical properties and creep resistance. The trans‐configured materials (R,R‐DAC‐PU or S,S‐DAC‐PU) exhibited superior creep resistance and mechanical strength due to dense hydrogen bonding networks. The cis‐configured materials (Cis‐DAC‐PU) exhibited enhanced processability and elasticity. Under 0.1 MPa stress, R,R‐DAC‐PU showed a mere 3.5 % strain change at 170 °C over 60 minutes, highlighting its superior creep resistance. Both configurations can be recycled via urea bond exchange reactions using hot pressing or solvothermal methods. Density Functional Theory (DFT) calculations indicate that both the (R,R‐DCA‐UB‐U)2 and (S,S‐DCA‐UB‐U)2 segments form six hydrogen bonds with shorter bond lengths, leading to stronger hydrogen‐bonding interactions. Conversely, the (Cis‐DCA‐UB‐U)2 segment forms four hydrogen bonds with longer bond lengths, resulting in weaker interactions. This work highlights the critical role of stereochemistry in designing high‐performance, recyclable polymer materials with tailored properties.
Super Strong Bonding at the Interface between ETL and Perovskite for Robust Flexible Optoelectronic Devices
Authors: Hui Jingjing , Zhan Jun , Zhang Jinxia , Gao Xiaowen , Wang Cong , Li Yiyi , Li Jin , Wang Kewei , He Zeyu , Li Qi , Wang Yi , Liang Yongqi , Chen Langxing , Zhang Yukui , Xu Dongsheng 
Published: January 2025

AbstractOrganic‐inorganic hybrid perovskites have demonstrated great potential for flexible optoelectronic devices due to their superior optoelectronic properties and structural flexibility. However, mechanical deformation‐induced cracks at the buried interface and delamination from the substrate severely constrain the optoelectronic performance and device lifespan. Here, we design a two‐site bonding strategy aiming to reinforce the mechanical stability of the SnO2/perovskite interface and perovskite layer using a multifunctional organic salt, 4‐(trifluoromethoxy)phenylhydrazine hydrochloride (TPH). This approach significantly enhances the bonding at the buried interface between the electron transport layer and perovskite layer, which is demonstrated by TPH‐modified SnO2/perovskite interface remaining intact after 10,000 bending cycles. Meanwhile, TPH mitigates void formation, enhances perovskite crystallinity at the buried interface, and inhibits ion migration inside the devices. Furthermore, incorporating TPH in perovskite bulk decreases the nucleation activation energy and accelerates nucleation, leading to high‐quality perovskite film. Consequently, power conversion efficiencies (PCEs) of 21.64 % and 23.61 % are achieved for target flexible and rigid perovskite solar cells, respectively. The target flexible device retained 92.3 % of its initial PCE after 25,000 bending cycles. This approach provides a robust solution for enhancing the mechanical durability of flexible perovskite optoelectronic devices.
Evaporation‐Assisted Synthesis of Olympic Gels
Authors: Xiong Xinhong , Xue Mingju , Xue Lulu , Zhang Luzhi , Zhang Zhongyan , Chen Jian , Zhang Guojie , Liu Hong , Cui Jiaxi 
Published: January 2025

AbstractCatenated networks exclusively composed of intertwining rings were first envisioned as “Olympic gels” by Pierre‐Gilles de Gennes four decades ago but have not been successfully prepared in artificial materials yet due to the challenge in synthesis. Herein, we present a bio‐inspired, evaporation‐assisted strategy to address this issue. In our design, the evaporation of liquid catalysts that induce ring‐chain equilibrium of polymer systems drives macrocycles to encounter and assists their catenation through reversible cyclization. Complete removal of liquid catalysts stabilizes the resulting ring‐interlocked networks by deactivating the catenation‐decatenation process. The strategy is demonstrated by the system of hydroxyethyl lipoate (LpHE) and dimethyl formamide (DMF). The results indicate that DMF evaporation leads to the formation of global LpHE polycatenane networks. This evaporation‐assisted strategy displays versatility in several tested cyclic monomers, highlighting its potential as a general approach to fabricate ring‐interlocked elastomers and topologically intricate materials.
Converting Fe−N−C Single‐atom Catalyst to a New FeNxSey Cluster Catalyst for Proton‐exchange Membrane Fuel Cells
Authors: Zhao Yang , Yin Pengfei , Yang Yuanyuan , Wang Ruguang , Gong Cairong , Li Jisi , Guo Jiaxin , Wang Quanlu , Ling Tao 
Published: January 2025

AbstractIron‐nitrogen‐carbon (Fe−N−C) single‐atom catalyst is the most promising alternative to platinum catalyst for proton‐exchange membrane fuel cells (PEMFCs), however its high performance cannot be maintained for a long enough time in device operation. The construction of a new Fe coordination environment that is completely different from the square‐planar Fe−N4 configuration in classic Fe−N−C catalyst is expected to break the current stability limits of Pt‐free catalysts, which however remains unexplored. Here, we report, for the first time, the conversion of Fe−N−C catalyst to a new FeNxSey cluster catalyst, where the active Fe sites are three‐dimensionally (3D) co‐coordinated by N and Se atoms. Due to this unique Fe coordination configuration, the FeNxSey catalyst exhibits much better 4e− ORR activity and selectivity than the state‐of‐the‐art Fe−N−C catalyst. Specifically, the yields of hydrogen peroxide (H2O2) and ⋅OH radicals on the FeNxSey catalyst are only one‐quarter and one‐third of that on the Fe−N−C counterpart, respectively. Therefore, the FeNxSey catalyst exhibits outstanding cyclic stability, losing only 10 mV in half‐wave potential E1/2 after 10,000 potential cycles, much smaller than that of the Fe−N−C catalyst (56 mV), representing the most stable Pt‐free catalysts ever reported for PEMFCs. More significantly, the 3D co‐coordination structure effectively inhibits the Fe demetallization of the FeNxSey catalyst in the presence of H2O2. As a result, the FeNxSey based PEMFC shows excellent durability, with the current density attenuation significantly lower than that of the Fe−N−C based device after accelerated durability testing. Our work provides guidance for the development of next‐generation Pt‐free catalysts for PEMFCs.
Controlled Introduction of sp3 Quantum Defects in Fluorescent Carbon Nanotubes by Mechanochemistry
Authors: Sander Miriam , Metternich Justus T. , Dippner Pascal , Kruss Sebastian , Borchardt Lars 
Published: January 2025

AbstractPrecise control over low‐dimensional materials holds an immense potential for their applications in sensing, imaging and information processing. The controlled introduction of sp3 quantum defects (color centers) can be used to tailor the optoelectronic properties of single‐walled carbon nanotubes (SWCNTs) in the tissue transparency (>800 nm) and the telecommunication window. However, an uncontrolled functionalization of SWCNTs with defects leads to a loss of the NIR fluorescence. Here, we use mechanochemistry with aryldiazonium salts to create quantum defects in SWCNTs. The reaction proceeds within 5 min without solvents or illumination and can be controlled by a varied mechanochemical energy impact. By working in the solid‐state, this method presents an alternative synthetic route and marks a crucial step for tailoring photophysics of SWCNTs.
Supramolecular Switching of Liquid‐Liquid Phase Separation for Orchestrating Enzyme Kinetics
Authors: Wang Deyi , Zhou Lingying , Zhang Xiaokun , Zhou Zixiang , Huang Zehuan , Gao Ning 
Published: January 2025

AbstractDynamic liquid‐liquid phase separation (LLPS) of intrinsically disordered proteins (IDPs) and associated assembly and disassembly of biomolecular condensates play crucial roles in cellular organization and metabolic networks. These processes are often regulated by supramolecular interactions. However, the complex and disordered structures of IDPs, coupled with their rapid conformational fluctuations, pose significant challenges for reconstructing supramolecularly‐regulated dynamic LLPS systems and quantitatively illustrating variations in molecular interactions. Inspired by the structural feature of IDPs that facilitates LLPS, we designed a simplified phase‐separating molecule, Nap‐o‐Nap, consisting of two naphthalene moieties linked by an ethylene glycol derivative. This compound exhibits LLPS under physiological conditions, forming coacervate microdroplets that undergo multiple cycles of disassembly and reassembly upon stoichiometric addition of Cucurbit[7]uril and Adamantane, respectively, based upon competitive host–guest interactions. Importantly, such reversible control offers a unique route to quantify entropically dominant nature (ΔS=14.0 cal ⋅ mol−1 ⋅ K−1) within the LLPS process, in which the binding affinity of host–guest interactions (ΔG=−14.9 kcal ⋅ mol−1) surpass that of the LLPS of Nap‐o‐Nap (ΔG=−2.1 kcal ⋅ mol−1), enabling the supramolecular regulation process. The supramolecularly switched LLPS, along with selective client recruitment and exclusion by resultant coacervates, provides a promising platform for either boosting or retarding enzymatic reactions, thereby orchestrating biological enzyme kinetics.
The Interplay of Methylidyne and Carbido Species: Modeling a Fundamental Step in the Fischer–Tropsch Synthesis
Authors: Burt Liam K. , Hill Anthony F. 
Published: January 2025

AbstractHeterobimetallic μ‐methylidyne complexes [WPt(μ2‐CH)(CO)2L2(Tp*)], where L2=(PPh3)2, (PPh3)(CO), (dppe), (PPh3)(CNC6H2Me3), have been obtained via the intermediacy of transient hydrido‐μ‐carbido complexes that undergo carbido‐hydrido coupling to model a fundamental step in the proposed mechanism for Fischer–Tropsch synthesis.
Pd/C as a Heterogeneous Catalyst for Ligand‐Free Homocoupling Reaction of Halo Compounds in Water and Total Synthesis of Daclatasvir
Authors: Mhate Mouzma , Khanra Moumita , Saharia Nilotpal , Radhakrishnanand P. , Ravichandiran V. , Swain Sharada Prasanna 
Published: January 2025

ABSTRACTThe United Nations sustainable development goals 9 and 12 discuss about adoption of sustainable and green chemistry concept for manufacturing of pharmaceuticals and chemicals. Water is universally accepted as a green solvent for organic reactions, and solvent‐free reactions are considered as green, sustainable methods for synthesis of heterocyclic compounds. Pd/C is a heterogeneous, recyclable catalyst and has been used for several cross‐coupling reactions. A ligand‐free Pd/C‐catalyzed homocoupling reaction of haloarenes in water is reported. The reaction condition is mild (reaction temp. 40°C), and the desired products were isolated in moderate to good yield (56%–81%). Activation of phase transfer catalyst under microwave irradiation reduced the catalyst loading and reaction time (from 24 h to 30 min). The major advantages of this method over existing methods are (i) ligand‐free homocoupling reaction, (ii) lower Pd/C catalyst loading, and (iii) use of water as a green and sustainable solvent. This reaction along with continuous‐flow bromination, and amine deprotection reactions were successfully applied for synthesis of antiviral drug daclatasvir.
Activin β Is Critical for Larval‐Pupal Transition in the 28 Spotted Lady Beetle Henosepilachna vigintioctopunctata
Authors: Fu Kai‐Yun , Chen Feng , Jin Lin , Li Guo‐Qing 
Published: January 2025

ABSTRACTThe activin cascade is activated when a pair of extracellular ligand (Myoglianin, Myo; Activin β, Actβ; Dawdle, Daw) binds to two pairs of transforming growth factor β (TGF) serine‐threonine receptor kinases, TGF‐β type I (Baboon, Babo) and II receptors. However, the roles of activin way have not well been explored in non‐Drosophilid insects. In the present paper, we compared the functions of Activin β (Actβ) ligand and receptor isoform BaboB in post‐embryonic development in a defoliating ladybird Henosepilachna vigintioctopunctata. RNA interference (RNAi) for Hvactβ but not Hvbabob upregulated juvenile hormone signal, reduced ecdysone pathway and impaired larval‐pupal transformation. The arresting Hvactβ RNAi larvae formed pupa‐specific black markings below the larval exuviae. Thus, the impairment of metamorphosis may be caused by failing to complete ecdysis behavior due to nonfunctional muscles. Consistently, larval body sizes were smaller and adult appendages were shorter in the Hvactβ RNAi larvae, in contrast to those in the Hvbabob depleted beetles. Conversely, knockdown of Hvbabob but not Hvactβ changed the pigmentation of adult elytra. Our results suggest that Actβ exerts regulative roles in JH production, ecdysteroidogenesis and organ remodeling, thus contributing to modulate the larva‐pupa‐adult transformation, through a BaboB independent way in H. vigintioctopunctata.
Fabrication of Stable Ru‐Doped Ni0.95Se Nanostructures for Photovoltaic Coupled Electrochemical Water Splitting in Alkaline Medium
Authors: Boruah Anakshi , Priyadarshi Shubham , Ghosh Swarup , Kumar Rajneesh , Chowdhury Joydeep , Pande Surojit 
Published: January 2025

AbstractDevelopment of a competent and stable electrocatalyst coupled with photovoltaic system for the generation of green hydrogen, can be a plausible answer to the existing energy crisis. Herein, we have developed Ru doped Ni0.95Se via hydrothermal method as a bifunctional catalyst for overall water splitting coupled with photovoltaic system. The developed pristine and doped samples were thoroughly characterized by various techniques. The pristine Ni0.95Se and the optimized Ru0.1Ni0.95Se system required a potential of −0.470 and −0.318 V vs. RHE, respectively to acquire a current density of 50 mA cm−2 for HER. The rapid kinetics of the optimized Ru0.1Ni0.95Se is illustrated by the Tafel slope wherein the pristine Ni0.95Se has a Tafel slope value of 172.2 mV/dec, and the Ru0.1Ni0.95Se catalyst has 102 mV/dec. The bifunctional electrocatalyst of Ru0.1Ni0.95Se exhibits very high stability (7 days) in an alkaline medium. Density functional calculations show Ru0.1Ni0.95Se has −0.69
value indicating its remarkable stability. To improve the overall activity and stability of the electrocatalyst Ru dopant is introduced as it tunes the electronic environment by generating a synergistic effect between the metal ions and Se2− anions. This work provides an approach for the generation of green hydrogen through water electrolysis coupled with PV.
Photophysical and Chiroptical Properties of Pyrazino‐Phenanthroline‐Helicene Derivative and its Rhenium(I) Complex
Authors: Kundu Debsouri , Jelonek Dominika , Del Rio Natalia , Vanthuyne Nicolas , Srebro‐Hooper Monika , Crassous Jeanne 
Published: January 2025

AbstractA novel coordination motif comprising [4]helicene fused with pyrazino‐phenanthroline (H4PP) has been synthesized and reacted with ReCl(CO)5 to yield its rhenium(I) complex (Re‐H4PP). Absorption and emission spectroscopic analysis conducted in dichloromethane and 2‐methyltetrahydrofuran reveals that combining pyrazino‐phenanthroline with helicene visibly affects the photophysical attributes of both the resulting ligand and its Re(I) complex as compared to their non‐helicene analogues, and even more importantly leads to relatively high photoluminescence quantum yield values, especially in the case of H4PP (29 %). Chiroptical studies through electronic circular dichroism and circularly polarized luminescence performed on enantiomerically enriched samples of Re‐H4PP show the chiral nature of low‐energy excited states affording notable glum values that amplify at cryogenic temperatures. Insights into experimental results are provided via first‐principles quantum‐chemical calculations showing important role of intra‐ligand charge‐transfer (ILCT) and metal‐to‐ligand CT (MLCT) states in determining photophysical features of these systems.
Influence of Cu2O Precursor Surface Orientation on Catalytic Performance and Product Selectivity in Nitrate Reduction Reactions
Authors: Takashima Toshihiro , Mochida Takumi , Sugamata Kaito , Yamagishi Tetsuya , Irie Hiroshi 
Published: January 2025

AbstractOxide‐derived copper (OD−Cu) has attracted considerable attention due to its exceptional electrocatalytic performance toward various reactions, including the reduction of nitrate (NO3−) to ammonia (NH3). Furthermore, numerous techniques have been developed to synthesize copper oxides with well‐defined surface orientations. However, the relationship between the surface orientation of the precursor and the NO3− reduction performance of the resulting OD−Cu catalyst remains unclear. In this study, two types of OD−Cu electrodes, prepared by reducing copper oxide (Cu2O) with exposed (100) and (111) facets grown on Cu substrates, were employed for NO3− reduction. The OD−Cu catalyst derived from Cu2O(111) exhibited a lower overpotential for initiating NO3− reduction and achieved a higher current density compared to the catalyst derived from Cu2O(100). Conversely, the catalyst prepared from Cu2O(100) demonstrated superior Faradaic efficiency for NH3 production. These differences are attributed to variations in the preferential reaction steps of NO3− reduction on each catalyst.
Manganese‐Catalyzed Electrochemical Amination of Activated Alkenes
Authors: Karan Avijit , Ghosh Sumit , Hajra Alakananda 
Published: January 2025

AbstractWe have unveiled a new manganese‐catalyzed electrochemical amination method to transform activated alkenes into a diverse array of vinyl amines harnessing sodium azide as the aminating reagent. The strategy claims notable versatility by accommodating a broad spectrum of substrates, demonstrating good compatibility with diverse functional groups, as well as delivering a moderate to good range of yields. The successful late‐stage functionalization further underscores its practical utility. A radical mechanism is proposed based on experimental mechanistic studies.
A Novel Microfluidic‐Based Fluorescence Detection Method Reveals Heavy Atom Effects on Photophysics of Fluorophores With High Triplet Quantum Yield: A Numerical Simulation Study
Authors: Dirican Selim Can , Demirbay Barış 
Published: January 2025

ABSTRACTThe present study introduces the idea of a novel fluorescence‐based imaging technique combined with a microfluidic platform that enables a precise control of dark transient state populations of fluorescent probes flowing over a uniform, top flat supergaussian excitation field with a constant flow rate. To demonstrate the imaging capability of the proposed detection method, numerical simulations have been performed by considering laser, microscope and flow parameters of experimental setup together with photophysical model and electronic transition rates of fluorescent dyes. As an output data to be assessed, fluorescence image data is simulated numerically for bromine‐free carboxyfluorescein and its brominated derivatives having different numbers of bromine atoms. Based on the magnitudes of applied excitation irradiances and flow rates, which can be manually controlled by user during experiments, the presence of dark state populations can appear as broadening, shifts and decays in normalized fluorescence intensity signals that are computed from simulated fluorescence images. As such changes in signals become more pronounced upon an increase in the degree of bromination, it is elicited that heavy atom effect can be resolved by properly tuning excitation powers of laser and flow rates. Proposed imaging method has potential to provide invaluable means to conventional fluorescence methods and can open up new perspectives in biomedical research.
Novel Nitrogen Hybrid F− Sensors Based on ESIPT Mechanism Achieving Super Low Detection Limits
Authors: Zhu Zeyang , Xu Zixuan , Li Xuemei , Wang Hui , Cao Xinghui , Li Shouzhu , Su Linhan , Wu Shasha 
Published: January 2025

ABSTRACTTwo novel nitrogen hybrid fluorescent sensors based on the ESIPT mechanism were successfully synthesized for the detection of fluoride ions (F−), and they exhibit high sensitivity and selectivity with a fast response. The detection limits even reach the parts per billion level. With the addition of F−, both sensors showed a ratiometric fluorescence change with a large Stokes shift. According to the hydrogen‐1 (1H) NMR titration, it was confirmed that the desilication reaction occurred between the sensors and F−. This work provides guidance for the subsequent development of F− fluorescence sensors.