bluuebunny/crossref_metadata_2025 huggingface dataset:
Decoupling Nucleation and Growth of Crystal for DMSO‐Free Self‐Assembly Tin Perovskite Films and Their Optoelectronic Application
Authors: Dong He , Huang Rui , Gao Weiyin , Li Wangyue , Ran Xueqin , Chao Lingfeng , Wang Xiaobo , Zhou Yipeng , Wu Zhongbin , Chen Yonghua , Ran Chenxin
Published: January 2025

Tin (Sn)‐based perovskites show significant potential in lead‐free perovskite optoelectronics. Currently, the spin‐coating method combining DMSO co‐solvent and antisolvent‐dropping has been adopted to produce Sn‐based perovskite films. However, DMSO intrinsically oxidizes Sn2+ while fast antisolvent‐dropping causes serious coupling between crystal nucleation and growth, leading to the easy formation of defects and poor stability of Sn‐based perovskite films. Herein, hydrazine acetate (HAAc) ionic salt, possessing strong coordination ability with Sn2+, is developed to stabilize Sn2+ and decouple the crystallization by promoting pre‐formed crystals (PFCs) in precursor solution and enabling the self‐assembly of PFCs during spin‐coating. The HAxFA1‐xSnI3 films fabricated by this PFCs self‐assembly technique show tunable bandgap, low defect density, and oriented crystals, producing optoelectronic devices with decent photovoltaic and electroluminescence performance. The DMSO‐free one‐step film‐forming enabled by HAAc‐assisted crystallization decoupling can open up new avenues for facile and low‐cost manufacturing of efficient and stable optoelectronic devices adopting Sn‐based perovskite films.
In@Mn3O4 with Rich Interface Low‐Coordination Mn Active Sites for Boosting Electrocatalytic Nitrogen Reduction
Authors: Wu Tingkai , Du Yue , Zuo Zhi‐Jun , Li Shaoquan , Wu Jinting , Gao Jian , Mu Tiansheng , Zhang Yong‐Chao , Zhu Xiao‐Dong
Published: January 2025

Electrocatalytic nitrogen reduction reaction (NRR) is a potential strategy for green synthesis of ammonia. However, the lack of efficient catalysts with both high activity and high selectivity restricts the development of electrocatalytic NRR. In this study, a simple water‐based redox method is used to synthesize the core–shell nanoparticle catalyst with 2D Mn3O4 nanoparticle as shell and In as core. The Mn3O4 nanoparticle shell with rich interface low‐coordination Mn helps to provide more active sites for electrocatalytic NRR. At the same time, the In nucleus gives electrons to the Mn3O4 nanoparticle shell, jointly promotes the adsorption and activation of nitrogen, as well as the enhancement of NRR activity. Moreover, the designed Mn3O4 shell is hydrophobicity, which effectively reduces the side reaction of hydrogen evolution of H proton generated from water dissociation, and the selectivity of NRR is improved. In 0.1 m Na2SO4, the ammonia yield of In@Mn3O4 is 89.44 µg h−1 mgcat−1 (−0.9 V vs RHE) and the maximum Faradaic efficiency is 27.01% at −0.7 V (vs RHE), superior to most reported catalysts. The unique core–shell structure and the design of low Mn coordination provide unique insights for the regulation of the nitrogen–water interface environment and rational design of advanced NRR electrocatalysts.
Enzyme‐Mediated In Situ Self‐Assembly AIE Probes: Mapping the Distribution of Acetylcholinesterase in Aging Mice Brain
Authors: Zhu Zhirong , Hu Shanshan , Zhang Youheng , Liu Shichang , Cai Chuandong , Wang Yu , Yu Qianqian , Liang Jiahui , Shi Yiqi , Yang Haojian , Zhao Xiaolei , Cao Lu , Wang Qi , Zhu Wei‐Hong
Published: January 2025

Acetylcholinesterase (AChE) exhibits profound association with the underlying pathological mechanisms of aging‐related disorders. However, revealing the spatial distribution of AChE among whole‐brain remains an uncharted territory, posing a substantial challenge. Herein, a dual regulation strategy to obtain an aggregation‐induced emission (AIE)‐activable probe for high‐fidility mapping of AChE in the brain is proposed. The well‐tailored probe (AChE‐QM‐2) consists of four components: AChE‐specific cleavage unit (dimethylcarbamate), self‐immolative linker (p‐hydroxybenzyl alcohol), AIE framework (Py‐QM), and electron‐donor group (EDG). The hydrophilic pyridine salt of AChE‐QM‐2 improves its dispersity, collaborating with EDG to lower its ΔES1‐T1 and HOMO‐LUMO energy gap, resulting reduced fluorescence quantum yield (Φf) and initial off‐fluorescence state. Moreover, optimizing EDGs further enhance the probe's responsive performance and extend its wavelength. Upon AChE‐activization, AChE‐QM‐2 undergoes deionization, resulting in molecule aggregation and increased Φf, further triggering amplified AIE signal. AChE‐QM‐2 has successfully realized monitoring of endogenous AChE in PC12 cells, tissues and living mice. Furthermore, utilizing light‐sheet microscopy, spatial mapping of the intracranial AChE, providing a highly specialized visualization of its localization within the brain, is achieved for the first time. This study satisfactorily demonstrates a valuable strategy for designing ultra‐sensitive AIE enzymatic probes, highlighting their potential for precise analysis in fundamental life science research.
Colon‐Targeted Ginseng Polysaccharides‐Based Microspheres for Improving Ulcerative Colitis via Anti‐Inflammation and Gut Microbiota Modulation
Authors: Huo De‐yang , Li Yan‐fei , Song Ling‐jie , Zhang Wen‐xin , Li Xin‐dian , Zhang Jing , Ren Shen , Wang Zi , Li Wei
Published: January 2025

Natural plant‐derived polysaccharides exhibit substantial potential for treating ulcerative colitis (UC) owing to their anti‐inflammatory and antioxidant properties and favorable safety profiles. However, their practical application faces several challenges, including structural instability in gastric acid, imprecise targeting of inflamed regions, and limited intestinal retention times. To address these limitations, pH‐responsive, colon‐targeting microspheres (pWGPAC MSs) are developed for delivering phosphorylated wild ginseng polysaccharides (pWGP) to alleviate UC. These pWGPAC MSs are fabricated by incorporating pWGP into calcium‐crosslinked alginate microspheres with subsequent chitosan surface modification to enhance mucosal adhesion. These pWGPAC MSs demonstrated exceptional stability under acidic conditions while enabling targeted release in the colon. In a mouse model of UC, the pWGPAC MSs effectively mitigated mucosal injury, attenuated inflammation, and restored intestinal barrier function. Further mechanistic investigations revealed that these pWGPAC MSs modulated the TLR4/MYD88 signaling pathway and promoted M2 macrophage polarization. Integrated microbiome and metabolome analyses demonstrated that these pWGPAC MSs regulated the gut microbiota composition and decreased pro‐inflammatory metabolite levels. In addition, these microspheres demonstrated promising safety profiles. Collectively, these findings establish pWGPAC MSs as a promising therapeutic strategy for the treatment of UC and provide a solid foundation for future clinical applications.
Transferrin‐Based Bismuth Nanoparticles for Radiotherapy with Immunomodulation Against Orthotopic Glioma
Authors: Huang Xiaoyu , Ge Wei , Li Shuxian , Huang Ruofan , Wang Fu
Published: January 2025

Modern radiotherapy frequently employs radiosensitizers for radiation dose deposition and triggers an immunomodulatory effect to enhance tumor destruction. However, developing glioma‐targeted sensitizers remains challenging due to the blood–brain barrier (BBB) and multicomponent instability. This study aims to green‐synthesize transferrin–bismuth nanoparticles (TBNPs) as biosafe radiosensitizers to enhance X‐ray absorption by tumors and stimulate the immune response for glioma therapy. The proposed protein‐based strategy provides TBNPs with BBB‐crossing ability and prevents off‐target toxicity. Cellular experiments following 4 Gy of X‐ray irradiation reveal that TBNPs increase DNA damage in glioma cells and trigger immunomodulation, thereby inducing immunogenic cell death. Furthermore, TBNPs effectively inhibit tumor growth through synergistic radiotherapy and immunotherapy in an orthotopic glioma mouse model. The findings highlight TBNPs as promising radiosensitizers for effective and biosafe radiotherapy with immunomodulation.
Self‐Sustained Biophotocatalytic Nano‐Organelle Reactors with Programmable DNA Switches for Combating Tumor Metastasis
Authors: Han Wenshuai , Ding Jiayi , Qiao Bo , Yu Yingjie , Sun Hao , Crespy Daniel , Landfester Katharina , Mao Xiangzhao , Jiang Shuai
Published: January 2025

Metastasis, the leading cause of mortality in cancer patients, presents challenges for conventional photodynamic therapy (PDT) due to its reliance on localized light and oxygen application to tumors. To overcome these limitations, a self‐sustained organelle‐mimicking nanoreactor is developed here with programmable DNA switches that enables bio‐chem‐photocatalytic cascade‐driven starvation‐photodynamic synergistic therapy against tumor metastasis. Emulating the compartmentalization and positional assembly strategies found in living cells, this nano‐organelle reactor allows quantitative co‐compartmentalization of multiple functional modules for the designed self‐illuminating chemiexcited PDT system. Within the space‐confined nanoreactor, biofuel glucose is converted to hydrogen peroxide (H2O2) which enhances luminol‐based chemiluminescence (CL), consequently driving the generation of photochemical singlet oxygen (1O2) via chemiluminescence resonance energy transfer. Meanwhile, hemoglobin functions as a synchronized oxygen supplier for both glucose oxidation and PDT, while also exhibiting peroxidase‐like activity to produce hydroxyl radicals (·OH). Crucially, the nanoreactor keeps switching off in normal tissues, with on‐demand activation in tumors through toehold‐mediated strand displacement. These findings demonstrate that this nanoreactor, which is self‐sufficient in light and oxygen and precise in striking tumors, presents a promising paradigm for managing highly metastatic cancers.
Alignment, Rising, Sticking, and Phototaxis: Modulating the Behavior of Hematite Micropeanuts
Authors: Rivas David P. , Shah Zameer Hussain , Shum Henry , Das Sambeeta
Published: January 2025

Artificial active colloids are an active area of research in the field of active matter and microrobotic systems. In particular, light‐driven semiconductor particles are shown to display interesting behaviors ranging from phototaxis (movement toward or away from a light source), rising from the substrate, interparticle attraction, attraction to the substrate, or other phenomena. However, these observations involve using multiple different designs of particles in varying conditions, making it unclear how the experimental parameters, such as pH, peroxide concentration, and light intensity, affect the outcomes. In this work, a peanut‐shaped hematite semiconductor particle is shown to exhibit a rich range of behavior as a function of the experimental conditions. The particles show rising, sticking, phototaxis, and in‐plane alignment of their long axes perpendicular to a magnetic field. A theoretical model accounting for gravity, van der Waals forces, electric double layer interactions with the glass surface, and self‐diffusiophoresis is formulated to describe the system. Using experimental data on the dependence of particle behavior on pH and ionic concentrations, the model captures the interplay of competing effects and explains many of the observed behaviors, providing insight into the relevant physical phenomena and how different environmental conditions can lead to such a rich diversity of behavior.
A Portable High‐Efficiency Multi‐Material Electrospinning Device with Low Environmental Dependence
Authors: Zhang Yi , Liu Huazhen , Cai Weihuang , Dai Qiqi , Luo Kaidi , Lu Chunxiang , Jin Aoxiang , Liu Yuanyuan
Published: January 2025

The emergence of handheld in situ electrospinning systems provides an effective method to broaden the applications of electrospinning in areas such as emergency rescue, disaster relief, and pollution prevention. However, their further development is significantly hindered by low efficiency and the considerable impact of external environmental factors. Furthermore, their functionality is restricted due to the use of single‐material electrospinning. Here, a low environment‐dependent, portable, high‐speed multi‐material electrospinning device (LEPHE) is proposed based on a gas‐electric coupling field. With an internal electric field and airfield, LEPHE can decouple the electrospinning process into two stages: jet formation and delivery. This design eliminates the effects of environmental factors on film formation, which are common challenges in traditional electrospinning. By utilizing a multi‐needle gas‐electric coupling field head with alternating bifurcated channels inside, LEPHE significantly improves efficiency and allows for in situ composite film preparation. Experimental results demonstrate the system's excellent environment adaptability, high spinning efficiency, and good uniformity in film formation. Additionally, LEPHE is capable of achieving uniformly mixed deposition of multi‐material fibers. It allows for the on‐demand stacking of various material layers and the adjustment of material proportions in single layers to create composite films.
First Bromide‐Catalyzed Selenylation of 2‐Alkyn‐1‐One O‐Methyloximes Enabled the Synthesis of 4‐Selenylated Isoxazoles
Authors: Cai Jinhui , Zeng Zhouting
Published: January 2025

A series of 3,5‐diaryl‐4‐selanylisoxazoles were synthesized in 56–97% yields (most cases>80% yield), which was first accomplished via bromide‐catalyzed selenylation of 2‐alkyn‐1‐one O‐methyloximes using element Se and boronic acids as the selenyl source. Compared to traditional strategies, this method proceeded under simple catalytic system. Broad substrate scope, good functional group compatibility, metal‐free conditions, and easy operation was showed in this protocol. Additionally, this method was easily amendable to gram‐scale reaction and synthetic transformations. Furthermore, preliminary mechanistic experiments demonstrated that a radical pathway was possibly involved in this work.
Selective Synthesis of 2‐(Indol‐3‐Yl)Phenols via Iodine‐Catalyzed C3‐Arylation of Indoles with Cyclohexanones
Authors: Yin Qi , Zhou Xinlin , Zhang Chao , Chen Shanping , Li Yuxia , Deng Guo‐Jun
Published: January 2025

An iodine‐catalyzed C3‐arylation of indoles with cyclohexanones to selectively synthesize 2‐(indol‐3‐yl)phenols has been described. Mechanism studies indicate that the oxygen atom in 2‐(indol‐3‐yl)phenols is originally from DMSO. This cascade involving dehydration condensation, selective oxygenation, dehydrogenation, and aromatization was achieved in one pot under transition‐metal‐free conditions.
Regio‐ and Diastereoselective Cascade Synthesis of 5‐Alkylidene‐γ‐Lactams via Copper‐Catalyzed Hydro‐Oxycarbonylation
Authors: Llorente Galder , Teresa Herrero Maria , Urgoitia Garazi , SanMartin Raul
Published: January 2025

Transition metal‐catalyzed hydrofunctionalization of alkynes and, more precisely, the intramolecular hydro‐oxycarbonylation (cycloisomerization) of acetylenic acids, has been widely employed as a key step in cascade processes for the construction of valuable and complex molecules. However, in contrast with other aminonucleophiles, no method has been reported for the reaction between primary monoamines and non‐activated alkynoic acids. Hence, a procedure has been devised for the regio‐ and diastereoselective preparation of 5‐alkylidene‐γ‐lactams via a copper‐catalyzed cascade reaction between alkynoic acids and amines. The developed protocol proves to be scalable and demonstrates significant tolerance to a wide range of structurally diverse alkynoic acids and amines bearing various functional groups, as evidenced by 60 high‐yielding examples. An exhaustive experimental and computational analysis of the reaction is also provided to unravel the nature and role of the copper catalyst, the observed regioselectivity and the mechanism of the reaction.
Detrimental Effect of T261I and R287W SMAD3 Variants on Early Osteoarthritis: A Potential Anti‐Inflammatory Molecule for Personalized Treatment
Authors: V Janakiraman , M Sudhan , Ahmad Sheikh F. , Al‐Mazroua Haneen A. , Ahmed Shiek S. S. J.
Published: January 2025

Osteoarthritis (OA) is an inflammatory disease that primarily impacts the elder population worldwide. Mothers against decapentaplegic homolog 3 (SMAD3), a member of the SMAD family, activates multiple cytokines and suggested as a therapeutic target for OA. SMAD3 variations may affect its protein structure and drug response. This study aimed to screen 195 SMAD3 variants to determine their structural consequences affecting the binding site and affinity of its known inhibitor (SIS‐3). Of these, T261I and R287W are associated with the early onset of OA causing deleterious effects. Molecular docking with SIS‐3 against native (−4.57 kcal mol−1) and variants shows a change in binding affinities (T261I, −5.02 kcal mol−1, and R287W, −4.20 kcal mol−1). Consequently screening 3363 anti‐inflammatory compounds,N‐[[2‐(3,5‐dimethoxyphenyl)‐6‐(trifluoromethyl)pyridin‐3‐yl]methyl]‐2‐[3‐fluoro‐4‐(methanesulfonamido)phenyl]propanamide (N2P) exhibits increased affinity with native (−6.81 kcal mol−1), T261I (−6.91 kcal mol−1), and R287W (−6.90 kcal mol−1) along with MM/GBSA binding energy of −49.20, −50.49, and −50.46 kcal mol−1 than SIS‐3. Further, dynamics simulations reveal conformational stability of N2P with SMAD3 native and variants. The density functional theory confirms the electron transfer capability of N2P in binding with SMAD3 variants. These findings provide insights into structural consequences of SMAD3 variants, improving the understanding of its role in OA and treatment strategies.
Accelerated Discovery of Gas Response in CuO via First‐Principles Calculations and Machine Learning
Authors: Chen Yu , Sun Yujiao , Yang Zijiang , Huang Sheng , Gu Xiuquan
Published: January 2025

Recent advancements in gas‐sensitive materials based on metal oxides have mainly relied on experimental trial and error, which is time‐consuming and costly. To address this, a novel approach combining first‐principles calculations and machine learning is proposed to predict the gas response properties of materials. Copper oxide (CuO) is used as a representative material for validation. Six characteristic parameters are selected at the electron and atomic structure level, including adsorption energy (Eads), bandgap (Eg), distortion degree, conduction band minimum (CBM), valence band maximum (VBM), and bond length (d), to build an accelerated gas response discovery model. The results indicate that gas response is determined by changes in these parameters upon gas adsorption, though no direct correlation is found. Machine learning algorithms are applied to establish correlation models, achieving an accuracy of 83.75%. Analysis reveals that the distortion degree has the most significant impact on a gas response (28.57%), while the VBM contributes the least (4.76%). CuO exhibits a strong response to gases like C3H8O, C4H10O, CO, H2, and NO2, but minimal response to C6H15N and C8H10, consistent with literature findings. This work offers new insights for sensor development and could enhance the efficiency of material discovery in gas sensing applications.
Controlled Inflammation Drives Neutrophil‐Mediated Precision Drug Delivery in Heterogeneous Tumors
Authors: Guo Yunfei , Li Yiming , Li Jianmin , Cai Haoran , Liu Kangkang , Duan Dengyi , Zhang Wenyi , Han Gang , Zhao Yang
Published: January 2025

Tumor heterogeneity remains a formidable obstacle in targeted cancer therapy, often leading to suboptimal treatment outcomes. This study presents an innovative approach that harnesses controlled inflammation to guide neutrophil‐mediated drug delivery, effectively overcoming the limitations imposed by tumor heterogeneity. By inducing localized inflammation within tumors using lipopolysaccharide, it significantly amplify the recruitment of drug‐laden neutrophils to tumor sites, irrespective of specific tumor markers. This strategy not only enhances targeted drug delivery but also triggers the release of neutrophil extracellular traps, further potentiating the anti‐tumor effect. Crucially, this study demonstrates that potential systemic inflammatory responses can be effectively mitigated through neutrophil transfusion, ensuring the safety and clinical viability of this approach. In a murine breast cancer model, the method significantly impedes tumor growth compared to conventional treatments. This work offers a versatile strategy for precise drug delivery across diverse tumor types. The findings pave the way for more effective and broadly applicable cancer treatments, potentially addressing the long‐standing challenge of tumor heterogeneity.
Endothelial Cpt1a Inhibits Neonatal Hyperoxia‐Induced Pulmonary Vascular Remodeling by Repressing Endothelial‐Mesenchymal Transition
Authors: Li Xiaoyun , Hegarty Katy , Lin Fanjie , Chang Jason L. , Abdalla Amro , Dhanabalan Karthik , Solomevich Sergey O. , Song Wenliang , Roder Karim , Yao Chenrui , Lu Wenju , Carmeliet Peter , Choudhary Gaurav , Dennery Phyllis A. , Yao Hongwei
Published: January 2025

Pulmonary hypertension (PH) increases the mortality of preterm infants with bronchopulmonary dysplasia (BPD). There are no curative therapies for this disease. Lung endothelial carnitine palmitoyltransferase 1a (Cpt1a), the rate‐limiting enzyme of the carnitine shuttle system, is reduced in a rodent model of BPD. It is unknown whether endothelial Cpt1a reduction causes pulmonary vascular (PV) remodeling. The latter can be the result of endothelial‐mesenchymal transition (EndoMT). Here, endothelial cell (EC)‐specific Cpt1a KO and WT mice (<12 h old) are exposed to hyperoxia (70% O2) for 14 days and allow them to recover in normoxia until postnatal day 28. Hyperoxia causes PH, which is aggravated in EC‐specific Cpt1a KO mice. Upregulating endothelial Cpt1a expression inhibits hyperoxia‐induced PV remodeling. Hyperoxia causes lung EndoMT, detected by immunofluorescence, scRNA‐sequencing, and EC lineage tracing, which is further increased in EC‐specific Cpt1a KO mice. Blocking EndoMT inhibits hyperoxia‐induced PV remodeling. Male mice under the same high oxygen conditions develop a higher degree of PH than females, which is associated with reduced endothelial Cpt1a expression. Conclusively, neonatal hyperoxia causes PH by decreasing endothelial Cpt1a expression and upregulating EndoMT. This provides a valuable strategy for developing targeted therapies by upregulating endothelial Cpt1a levels or inhibiting EndoMT to treat BPD‐associated PH.
Incorporating Interstitial Carbon Atoms and Graphene Quantum Dots in Crystalline Ni(OH)Cl for Ultrastable and Superior Rate Supercapacitors
Authors: Wang Guanwen , Zhou Wenbo , Chi Chunlei , Zhou Yufei , Liu Zheng , Qiu Zhipeng , Yan Yingchun , Huangfu Chao , Qi Bin , Li Zhiyuan , Gao Pengfei , Wang Chuanqing , Gao Wenpei , Wei Tong , Fan Zhuangjun
Published: January 2025

Despite their high theoretical capacity, Ni‐based materials are hindered by significant issues such as structural degradation, low intrinsic conductivity, and sluggish kinetics, resulting in poor stability and rate performance. Herein, the Ni(OH)Cl‐ICA‐GQDs incorporated with interstitial carbon atoms (ICAs) and graphene quantum dots (GQDs) are proposed to radically reverse its structural stability and electronic transport capability. ICAs can induce lattice micro‐strain that adjusts bond lengths and angles, leading to intrinsically ameliorated structural stability under alkaline and even acidic conditions. GQDs promote the formation of micro‐conductive circuits, optimizing the electronic configuration and redox kinetics. As a result, the Ni(OH)Cl‐ICA‐GQDs electrode achieves exceptional cyclic stability (91.5% retention after 20 000 cycles versus 70.3% retention after 2000 cycles for Ni(OH)Cl) and remarkable rate capability (312C g−1 at 100 A g−1 vs 109C g−1 at 50 A g−1 for Ni(OH)Cl). Furthermore, the Ni(OH)Cl‐ICA‐GQDs//AC hybrid supercapacitor achieves an ultrahigh power density of 41.5 kW kg−1 with an energy density of 28.8 Wh kg−1, surpassing most Ni‐based supercapacitors. This approach offers a promising strategy for the precise modification of high‐performance electrodes for energy storage applications.
Catalytic Asymmetric 1,4‐Hydrocarbonation of 1,3‐Enynes via Photoredox/Cobalt/Chromium Triple Catalysis
Authors: Yang Ju‐Song , Wang Xing‐Yu , Li Yong‐Yao , Zhang Fu‐Min , Zhang Xiao‐Ming , Tu Yong‐Qiang
Published: January 2025

A synergistic photoredox/cobalt/chromium triple catalysis system for regioselective, enantioselective, and diastereoselective 1,4‐hydrocarbonation of readily available 1,3‐enyne precursors was explored, providing a modular synthetic platform for various trisubstituted axially chiral allenes bearing an extra central chirality. The protocol features a broad substrate scope, good functional group tolerance, excellent selectivity, and mild reaction conditions. Furthermore, a possible reaction mechanism is proposed based on numerous control experiments and density functional theory calculations.
Establishing the Link Between Oxygen Vacancy and Activity Enhancement in Acidic Water Oxidation of Trigonal Iridium Oxide
Authors: Zhu Wenxiang , Ma Mengjie , Gao Dongdong , Chen Jinxin , Huang Hui , Feng Kun , Wang Qun , Wu Jie , Li Penghao , Guo Jinzeng , Fan Zhenglong , Zhong Jun , Shao Qi , Liao Fan , Liu Yang , Shao Mingwang , Kang Zhenhui
Published: January 2025

Developing durable IrO2‐based electrocatalysts with high oxygen evolution reaction (OER) activity under acidic condition is crucial for proton exchange membrane electrolyzers. While oxygen defects are considered potentially important in OER, their direct relationship with catalytic activity has yet to be established. In this study, we introduced abundant oxygen vacancies through Re doping in 2D IrO2 (Re0.03Ir0.97O2), demonstrating their decisive role in enhancing OER performance. The Re0.03Ir0.97O2 catalyst exhibited excellent OER performance with an overpotential of 193 mV at 10 mA cm−2 and sustained activity for over 650 hours, significantly surpassing the undoped catalyst. Moreover, it maintained operation at a cell voltage of 1.70 V (~1200 mA cm−2) for over 140 hours without significant performance degradation. Theoretical calculations coupled with cyclic voltammetry, transient potential scanning and in situ characterizations confirmed the adsorbate evolving mechanism on Re0.03Ir0.97O2, as well as the critical role of Re‐induced oxygen vacancies in enhancing OER performance. These findings highlight that oxygen defects directly influence OER activity, providing guidance for the application of oxygen vacancy engineering in electrocatalyst design.
Synergistic Effect Promotes Visible‐Light–Driven CO2‐To‐CO Conversion by Macrocyclic Dinuclear Mixed‐Valence Co (II)/Co (III) Complexes
Authors: Huang Chunzhao , Chen Zilu , Hao Hongmei , Huang Zubing , Liao Caizhen , Su Donghui , Mo Anna , Hu Huancheng , Hou Cheng , Liang Fupei , Liu Dongcheng
Published: January 2025

The catalytic conversion of carbon dioxide (CO2) into valuable energy under light sources is one of the effective ways to achieve carbon cycle. The reported nonprecious metal complex catalysts still show the shortcomings of low catalytic activity and low selectivity in visible‐light–driven CO2 reduction, especially in aqueous systems. Herein, we report three dinuclear mixed‐valence Co (II)/Co (III) complexes 1–3 bearing macrocyclic ligands that exhibit high activity and selectivity for visible‐light–driven photocatalytic CO2 reduction in an aqueous system. Moreover, the TONCO and CO selectivity for macrocyclic dinuclear mixed‐valence complex 3 reach as high as 4100 and 96%, respectively, which is about 4.9 times higher than that of mononuclear Co (II) complex 4. Through electrochemical and DFT calculations, we found that the increase in photocatalytic activity of 3 is due to the synergistic effect between the two metal centers, in which one Co site stabilizes the *COOH intermediate and reduces the energy barrier of the rate‐determining step, thereby increasing the catalytic activity.
Efficient Capture of Pb (II) Ions From Aqueous Solutions Using Metal Organic Frameworks@Covalent Organic Framework Composites With Abundant Carboxyl Groups
Authors: Zhang Shaopeng , Ding Jie , Tian Dayong , Kang Ruiqin , Wang Xiaolong , He Haoyang , Lu Minghua
Published: January 2025

The development of efficient adsorbents with high selectivity is essential for mitigating environmental pollution. This study introduces a novel adsorbent comprising a metal–organic framework (i.e., MIL‐101(Fe)‐NH2) and a covalent organic framework (COF) enriched with carboxyl groups, which is designated MIL‐101(Fe)‐NH2/COF‐COOH. The adsorbent is synthesized through a Schiff base reaction followed by carboxymethylation and is subsequently employed for Pb (II) adsorption. The structure of MIL‐101(Fe)‐NH2/COF‐COOH is confirmed using various characterization techniques, including Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, thermogravimetric analysis, and Brunauer, Emmett, and Teller surface area analysis. The adsorption capacity (qe) value of MIL‐101(Fe)‐NH2/COF‐COOH is estimated through batch adsorption experiments. The effects of several factors, including pH, adsorbent dosage, contact time, Pb (II) concentration, solution ionic strength, and temperature, on the adsorption process are systematically assessed. MIL‐101(Fe)‐NH2/COF‐COOH achieves the highest adsorption of 184 mg/g at pH 6. The adsorption kinetics, isotherms, and thermodynamics indicate that the adsorption process occur through a spontaneous monolayer chemical process. Moreover, MIL‐101(Fe)‐NH2/COF‐COOH displays remarkable anti‐interference capability, and its qe decreases by only 10% after 10 cycles. Based on the characterization results, the Pb (II) adsorption mechanism is determined to be primarily electrostatic and chelation interactions between Pb (II) and O‐ and N‐containing functional groups. Thus, this highly efficient and recyclable adsorbent exhibits considerable potential for removing Pb (II) from aquatic ecosystems.
Curing Mechanism and Properties Epoxy Resins With Main‐Chain Polyimidazolium Ionic Liquids
Authors: Liang Jingshi , Liu Bo , Wang Ye , Jiao Delai , Shi Xiaolin , Pan Zhiming , Zhang Chunling
Published: January 2025

Ionic liquids have aroused considerable attention in the fields of polymer and materials science due to their designability and distinctive qualities. Epoxy resin (EP) with antimicrobial and stain‐resistant properties is important for the service life of the material and for eliminating potential health hazards. In this study, a series of main‐chain polyimidazolium ionic liquids (PIMILs) differing in the alkyl chain length of cation sizes (propyl, butyl, hexyl, octyl, decyl, dodecyl, 3,6‐dioxaoctyl, and 4,7,10‐trioxatridecyl) were synthesized by the Debus–Radziszewski reaction, and used as curing agents for EPs. The results of the curing conditions of their corresponding EPs revealed the regularity in the curing conditions dependent mainly on alkyl chain length. Meanwhile, the influence of the chloride anion and cation size on thermal stability, the glass transition temperature (T
g), and thermomechanical properties of the epoxy composites were discussed, Finally, the water contact angles of thermosets ranged from 78.1° to 104.5°, and the thermosets could effectively kill multiple strains of bacteria and remove the biofilm.
Effect of Modified Carbon Black on the Performance of Semiconductive Composites for High‐Voltage Direct‐Current Cable Applications
Authors: Kang Yuanyi , Wang Qingyu , Han Weihua , Xing Zhaoliang , Xu Hongwei , Zhang Tao , Xin Meng , Hao Chuncheng
Published: January 2025

The semiconductive shielding layer is located between the conductive core and the insulation layer of high‐voltage direct current cables, which plays a role in homogenizing the electric field and suppressing the effect of space charge injection into the insulation layer. However, the positive temperature coefficient (PTC) effect is still the main cause of thermal breakdown and interface failure of the insulation layer. In this paper, carbon black was etched and modified, and then blended with low density polyethylene (LDPE) and Ethylene‐vinyl acetate (EVA) to prepare composites. The modification of carbon black enhanced suppression of space charge injection. Moreover, the PTC effect decreased by 15.4%.
High‐Efficient Photochromic P123/WOx Films via Semi‐Annealing for Enhanced Optical Data Storage
Authors: Dou Xuanyu , Li Xin , Zhang Zhihao , Jiang Xinxin , Miao Jingying , Qi Xiuping , Fu Shencheng , Zhang Xintong
Published: January 2025

Tungsten oxide has attracted much attention as a fascinating medium for optical energy transformation due to the significant color‐changing under light irradiation. By now, most of the photochromism enhancement strategies focus on the interaction between the tungsten oxide and its surrounding medium, such as semiconductors or polymers, to promote the spatial separation between electrons and holes in tungsten oxide. However, modulating the intrinsic photochromism of tungsten oxide is rather difficult. Herein, we construct a humidity‐dependent P123/WOx composite film via a semi‐annealing method. The transparency of the film is significantly improved with the decrease of environmental humidity. By setting different annealing temperatures, the photochromic performance can be adjusted from two aspects: the population of oxygen vacancies in WOx and the hydrogen bond ratio in P123/WOx, respectively. Compared to commercial WO3 films, the P123/WOx film shows an obvious increase in photochromic amplitude, photo‐response speed, and holographic storage efficiency. The hybrid film is also used as a sandwiched layer to construct a polarization multiplexed optical storage, exhibiting the promising advantages in high‐density information storage and photochromism‐adjustable devices.
Plasmon‐Enhanced Luminescence of Gold Nanoclusters by Using Silver and Gold Metal Nanostructures
Authors: Jofré Javiera , Douglas‐Gallardo Oscar A. , Bachmann Cristian , Danna Caroline S. , Troncoso Loreto , Peña‐Bermudes María , Iberlucea‐Salinas Isadora , Mendizábal Fernando , Osorio‐Román Igor O. , Segura Camilo
Published: January 2025

Plasmonic materials can be utilized as effective platforms to enhance luminescent signals of luminescent metal nanoclusters (LMNCs). Both surface enhanced fluorescence (SEF) and shell‐isolated nanoparticle‐enhanced fluorescence (SHINEF) strategies take advantage of the localized and increased external electric field created around the plasmonic metal surface when excited at or near their characteristic plasmonic resonance. In this context, we present an experimental and computational study of different plasmonic composites, (Ag) Ag@SiO2 and (Au) Au@SiO2 nanoparticles, which were used to enhance the luminescent signal of Au nanoclusters coated with glutathione (GSH) molecule (Au25GSH NCs). This specific LMNC has recently attracted particular interest due to its luminescent response and characteristic photostability. Our study presents a wide characterization of the optical and morphologic features of the synthetized particles: plasmonic metal nanostructures and Au25GSH NCs through different experimental techniques including UV‐Visible, IR, luminescent spectroscopies, along with TEM and AFM microscopies. Additionally, we have carried out computational simulations based on time‐dependent density functional theory (TD‐DFT) and classical electrodynamics simulation based on Mie Theory to support our experimental findings. In this study, we report up to 3‐fold luminescence enhancement of Au25GSH NCs which is mainly attributed to slow dynamic SEF.
Direct Knitting of Pincer Palladium Complexes into Hyper‐Crosslinked Polymers for Superior Catalytic Performance in Suzuki‐Miyaura Reactions
Authors: Peng Mengjie , Zhang Yaqing , Wang Xiaoyan , Gao Hui , Tan Bien
Published: January 2025

Using a direct knitting strategy, we successfully prepared a novel heterogeneous catalyst consisting of pyridine‐bridged bis(imidazolium‐2‐ylidene) palladium complexes (CNC−Pd) embedded in a knitted network polymer. The resulting catalysts (HCP‐CNC−Pd‐d) exhibited high specific surface areas of 982 m2 g−1 with microporous and mesoporous structures. The large surface area enhances contact between the substrate and the catalytic center, while the strong chelation between CNC and the metal ion ensures the catalyst's durability. The HCP‐CNC−Pd‐d catalysts exhibited superior performance, achieving an impressive 99 % yield in the Suzuki coupling reaction between bromobenzene and phenylboronic acid. The catalyst also demonstrated good performance across a range of substrates in the Suzuki‐Miyaura coupling reactions. Furthermore, the catalyst could be recycled for over 10 cycles without any significant loss in activity and selectivity. This highly cost‐effective and convenient approach provides valuable insights into the design and application of heterogeneous catalysts in various fields.
Consistent Crust‐Core Interpolation and Its Effect on Non‐radial Neutron Star Oscillations
Authors: Canullán‐Pascual Martín O. , Mariani Mauro , Ranea‐Sandoval Ignacio F. , Orsaria Milva G. , Weber Fridolin
Published: January 2025

To model the structure of neutron stars (NSs) theoretically, it is common to consider layers with different density regimes. Matching the equation of state (EoS) for the crust and core and obtaining a suitable description of these extreme conditions are crucial for understanding the properties of these compact objects. In this work, we construct 10 different NS EoSs incorporating three distinct crust models, which are connected to the core using a thermodynamically and causally consistent formalism. For cold NSs, we propose a linear relationship between pressure and energy density in a narrow region between the crust and core, effectively establishing an interpolation function in the pressure‐baryonic chemical potential plane. We then compare this EoS matching method with the classical approach, which neglects causal and thermodynamic consistency. We solve the Tolman–Oppenheimer–Volkoff equation to obtain the mass‐radius relationship and compare our results with observational constraints on NSs. Furthermore, we investigate the influence of the new matching formalism on non‐radial oscillation frequencies and damping times. Our findings suggest that the method used to glue the crust and core EoS impacts NS observables, such as the radius, oscillation frequencies, and damping times of non‐radial modes, which may be crucial for interpreting future gravitational wave observations from neutron star mergers or isolated pulsars. The effects are particularly noticeable for low‐mass NSs, regardless of the specific EoS model chosen. In particular, we find that the oscillation mode exhibits significant differences in frequencies among alternative matching methods, whereas the fundamental ‐mode remains unaffected by changes in crust models or interpolation schemes.
Heterologous Expression and Optimization of Fermentation Conditions for Recombinant Ikarugamycin Production
Authors: Evers Julia K. , Glöckle Anna , Wiegand Monique , Schuler Sebastian , Einsiedler Manuel , Gulder Tobias A. M.
Published: January 2025

Ikarugamycin is a member of the natural product family of the polycyclic tetramate macrolactams (PoTeMs). The compound exhibits a diverse range of biological activities, including antimicrobial, antiprotozoal, anti‐leukemic, and anti‐inflammatory properties. In addition, it interferes with several crucial cellular functions, such as oxidized low‐density lipoprotein uptake in macrophages, Nef‐induced CD4 cell surface downregulation, and mechanisms of endocytosis. It is, therefore, used as a tool compound to study diverse biological processes. However, ikarugamycin commercial prices are very high, with up to 1300 € per 1 mg, thus limiting its application. We, therefore, set out to develop a high‐yielding recombinant production platform of ikarugamycin by screening different expression vectors, recombinant host strains, and cultivation conditions. Overall, this has led to overproduction levels of more than 100 mg/L, which, together with a straightforward purification protocol, establishes biotechnological access to affordable ikarugamycin enabling its increased use in biomedical research in the future.
In Vitro Biological Evaluation and In Silico Studies of a New Anthraquinone From Zingiber Cassumunar Roxb. in Type 2 Diabetes Management
Authors: Le Tho Huu , Nguyen Minh Hien , Le Anh Lan Tran , Nguyen Mai Thanh Thi , Nguyen Hai Xuan , Do Truong Nhat Van , Nguyen Nhan Trung
Published: January 2025

A novel diphenyl‐anthraquinone compound, cassuquinone A (CA), was isolated from the rhizomes of Zingiber cassumunar. Structural elucidation was accomplished using detailed nuclear magnetic resonance and high‐resolution mass spectroscopy‐electrospray ionization techniques, revealing a symmetrical anthraquinone core with methoxylated aromatic rings. CA exhibited potent α‐glucosidase (AR) inhibitory activity with an IC₅₀ of 11.72 µM, significantly more potent than the positive control, acarbose (IC₅₀ = 190.60 µM), highlighting its potential as an antidiabetic agent. Molecular docking studies indicated stable binding of CA to AR, with key interactions involving Arg315, Phe314, Glu411, Val232, and Ser240, contributing to its high docking score. Additionally, molecular dynamics simulations demonstrated that CA stabilizes the AR structure by reducing the enzyme's flexibility, especially within the active site, which may hinder substrate access and product release.
Proteomic Profiling of Potential E6AP Substrates via Ubiquitin‐based Photo‐Crosslinking Assisted Affinity Enrichment
Authors: Schuck Julian , Bernecker Christine , Scheffner Martin , Marx Andreas
Published: January 2025

The ubiquitin (Ub) ligase E6AP, encoded by the UBE3A gene, has been causally associated with human diseases including cervical cancer and Angelman syndrome, a neurodevelopmental disorder. Yet, our knowledge about disease‐relevant substrates of E6AP is still limited, presumably because at least some of these interactions are rather transient, a phenomenon observed for many enzyme‐substrate interactions. Here, we introduce a novel approach to trap such potential transient interactions by combining a stable E6AP‐Ub conjugate mimicking the active state of this enzyme with photo‐crosslinking (PCL) followed by affinity enrichment coupled to mass spectrometry (AE‐MS). To enable PCL, we equipped Ub with diazirine moieties at distinct positions. We validated our PCL assisted AE‐MS approach by identification of known (e. g. PSMD4, UCHL5) and potential new (e. g. MSH2) substrates of E6AP. Our findings suggest that PCL assisted AE‐MS is indeed suited to identify substrates of E6AP, thereby providing insights into E6AP‐associated pathologies, and, potentially, of other enzymes of the Ub‐conjugating system.
Methionine‐Derived Fluorescent Probes Targeting Mitochondria: A Tool for Real‐Time Oxidative Stress Monitoring in Live Cells
Authors: Pareek Niharika , Kalita Nripankar , Pandey Roopam , Samanta Animesh
Published: January 2025

Reactive oxygen species (ROS) play crucial roles in both cell signaling and defense mechanisms. Hypochlorous acid (HOCl), a strong oxidant, aids the immune response by damaging pathogens. In this study, we developed two pyridinium‐based fluorophores PSSM and PSSE for selective hypochlorite detection. Out of these two fluorescent probes, PSSM shows a strong turn‐on emission via a photoinduced electron transfer (PeT) mechanism, excellent mitochondrial localization, and rapid response to HOCl with high selectivity among reactive oxygen species by achieving a detection limit of 2.41 μM. It successfully detects both exogenous and endogenous HOCl in live cells, enabling the study of HOCl's role at the organelle level. Structural analysis of PSSM via thioether oxidation confirmed by HPLC, NMR and HRMS further supports its specificity. Confocal imaging and flow cytometry studies further highlights its utility in investigating oxidative stress, positioning this fluorophore as a valuable tool for monitoring HOCl imbalances in biological systems.
Alkaline Earth Metal Enhancement of Cerium‐Manganese‐Based Three‐Dimensional Ordered Macroporous Catalysts for NO Oxidation
Authors: Xue Yingshan , Wang Ping , Yang Cheng , Zhang Tianbao , Zhang Xin , Xiong Jing , Sun Xiaohua , Wei Yuechang , Li Zhenxing
Published: January 2025

Nitrogen oxides are an industrial and domestic waste gas, which pollutes the air and affects health. In this paper, we use the template method to achieve the doping of alkaline earth metals, and the alkaline earth metals are doped into cerium‐manganese‐based 3D ordered macroporous (3DOM) catalysts to detect NO oxidation. The introduction of alkaline earth metals can improve the stability and thickness of macroporous results, which increases the contact area between the catalyst and reactant gases. At the same time, alkaline earth metal doping can promote the formation of more oxygen vacancies and unsaturated structures and improve the catalytic activity of NO oxidation. The NO conversion rate of CM‐3Mg doped with 3% Mg was 61.25% at 250 °C, and the NO conversion rate was the highest at 303 °C, which was 79.2%. This study provides a promising catalyst candidate for NO oxidation in practical applications.
Exploring the Metal‐Centered Reactivity of Isomeric, N‐Bridged Biscyclometalated Platinum(II) Complexes
Authors: Matharu Gunwant K. , Soto Miguel A. , Huang Ben Zhen , Lelj Francesco , MacLachlan Mark J.
Published: January 2025

The field of platinum chemistry is ubiquitous in the research of anticancer drugs and new OLED materials. Within the vast library of existing compounds, the majority of work focuses on complexes in the +2 and +4 oxidation states, with comparatively few examples of PtIII complexes reported without bridging ligands. PtIII complexes with metal‐metal bonding can be made by mild oxidation of PtII complexes having bis(phenylpyridine) ligands. Here, we report the synthesis and characterization of two new PtII complexes bearing tetradentate N‐bridged bis(phenylpyridine) ligands with N^C*C^N and C^N*N^C coordinating atoms. Through chemical oxidation with PhICl2 and N‐chlorosuccinimide, we obtained four new complexes containing PtIV and PtIII centres. The dynamics of the PtIII complexes were explored by variable‐temperature NMR studies and showed surprisingly free rotation of the appended N‐aryl group. This work uncovers the importance of the destabilizing nature of the bulky N‐aryl group on intermetallic bonds, and sheds light on how the molecular rotation observed in the PtIII compounds could inspire new molecular rotors driven by intermetallic bonds.
All‐Optical Spatial Self‐Phase and Cross Phase Modulation Using an NLO Active Pyrylium Dye towards an Optical OR Gate
Authors: Saif Safna , Lekshmanan Lekshmi , Sankar Karthika , Thomas Titu , Pillai Saju , Ajayaghosh Ayyappanpillai , Rose Thankamani Priya
Published: January 2025

All‐optical modulation and optical switching with nonlinear materials are integral parts of the advancing all‐optical communication network. This report discusses the synthesis of a promising pyrylium dye, pyrylium‐NH2 for NLO based applications and probes its spatial self‐phase and cross phase modulation (XPM) properties. This dye can be effectively used for all‐optical modulation and OR logic gate operation. A 532 nm DPSS laser of tunable power is used to study the intensity dependent nonlinear refractive indices (n2) of the dye in ethanol, methanol and acetone. The dye has shown significant n2 compared to the existing literature. Concentration dependence, incident intensity dependence and temporal evolution of the far field diffraction annuli rings in these three solvents were studied. The all‐optical modulation of a weak signal beam is demonstrated using a high intensity pump beam via cross phase modulation, paving the way to optical switching applications.