bluuebunny/crossref_metadata_2025 huggingface dataset:
METTL3 Potentiates M2 Macrophage‐Driven MMT to Aggravate Renal Allograft Fibrosis via the TGF‐β1/Smad3 Pathway
Authors: Yao Qinfan , Zheng Xiaoxiao , Zhang Xinyi , Wang Yucheng , Zhou Qin , Lv Junhao , Zheng Li , Lan Jiahua , Chen Wei , Chen Jianghua , Chen Dajin
Published: January 2025

METTL3, a key enzyme in N6‐methyladenosine (m6A) modification, plays a crucial role in the progression of renal fibrosis, particularly in chronic active renal allograft rejection (CAR). This study explored the mechanisms by which METTL3 promotes renal allograft fibrosis, focusing on its role in the macrophage‐to‐myofibroblast transition (MMT). Using a comprehensive experimental approach, including TGF‐β1‐induced MMT cell models, METTL3 conditional knockout (METTL3 KO) mice, and renal biopsy samples from patients with CAR, the study investigates the involvement of METTL3/Smad3 axis in driving MMT and renal fibrosis during the episodes of CAR. We found that elevated m6A modification and METTL3 levels strongly correlated with enhanced MMT and increased fibrotic severity. METTL3 knockout (METTL3 KO) significantly increased the m6A modification of Smad3, decreased Smad3 expression, and inhibited M2‐driven MMT. Smad3 knockdown with siRNA (siSmad3) further inhibited M2‐driven MMT, while Smad3 overexpression rescued the inhibitory effects of METTL3 silencing, restoring M2‐driven MMT and fibrotic tissue damage. Additionally, the METTL3 inhibitor STM2457 effectively reversed M2‐driven MMT and alleviated fibrotic tissue damage in CAR. These findings highlight that METTL3 enhances M2‐driven MMT in renal fibrosis during CAR by promoting the TGF‐β1/Smad3 axis, suggesting that METTL3 is a promising therapeutic target for mitigating renal fibrosis in CAR.
Orbital and Electrical Dual Function of Polymer Intercalant for Promoting NH4+ Storage in Vanadium Oxide Anode
Authors: Zhang Yue , Huang Zihang , Lei Lei , Fan Hua , Han Xu , Li Hui , Ma Tianyi
Published: January 2025

Polymer‐intercalated metal oxides have attracted considerable attention for ammonium ions (NH4+) storage due to their enhanced interlayer space, which, through the pillar effect, facilitates rapid and efficient transport of NH4+. However, the understanding remains limited regarding how polymer intercalants affect the intrinsic structure of host materials, especially the variations in atomic orbital and electronic structural induced by the intercalants. Herein, a polyaniline‐intercalated vanadium oxide (P‐VOx) is developed and, for the first time, its NH4+ storage behavior is validated as an anode material. Using various spectroscopy techniques combined with theoretical simulation, the changes are analyzed in atomic orbital and electronic structure induced by the intercalant. Spectroscopy studies reveal that the insertion of polyaniline optimizes the electronic structure of V2O5, promoting the transition of electrons to the V 3dxy state and increasing the occupation of the V t2g orbital, thereby enhancing electrical conductivity. Computational results confirm that P‐VOx lowers the NH4+ migration barrier, thereby enhancing electron/NH4+ transfer. As a result, the P‐VOx electrode demonstrates outstanding capacity and unprecedented long‐term cycling stability. This study provides new insights into the atomic and electronic structural changes induced by the polymer intercalant and underscores the advantages of polymer‐intercalated VOx as a high‐performance electrode for NH4+ storage.
Flexible Titanium Nitride‐Based Membrane Reactor for S8/Li2S and Dendrite Regulation in Lithium‐Sulfur Batteries
Authors: Ji Lei , Yang Daotong , Xue Jiayi , Jia Minxun , Wu Tong , Zhuang Quan , Zhang Yingying , Liu Jinghai , Zhang Yuegang
Published: January 2025

Simultaneous regulation of S8/Li2S solid‐liquid redox conversion at the cathode and lithium (Li) dendrite growth at the anode is essential for advancing lithium‐sulfur (Li─S) batteries. Herein, a flexible titanium nitride‐based membrane (TiNOCF) is developed as a membrane reactor (MR) to enhance sulfur redox kinetics, activates S8/Li2S solid and guide dendrite horizontal growth. The TiNOCF MR at the sulfur cathode side endows the Li─S cell with a remarkable high‐rate capacity of 851.4 mAh g−1 and a stable cycling retention of 94.8% after 200 cycles at 5 C. At the Li anode side, it maintains the Li/Li cell with stable cycling for 2000 h with an ultra‐low overpotential of 38.1 mV at a current density of 2 mA cm−2. For high sulfur‐loading, TiNOCF MR gives the full cells (10 mg sulfur cm−2) with an areal capacity of 10.2 mAh cm−2 at 0.1 C and the pouch cells (9.5 mg sulfur cm−2) with 10.9 mAh cm−2 at 36 mA. Mechanism analysis reveals the key roles of titanium (Ti3+) and nitrogen (N3−) sites in confinement catalysis and directional dendrite growth, enabling high‐areal capacity, fast‐charging and stable‐cycling features.
In Situ Copolymerizing ZrO2 with Hydrogel Electrolytes toward High‐Rate and Long‐Life Quasi‐Solid‐State Zn–Ion Batteries
Authors: Sun Yu , Song Li‐Na , Du Xing‐Yuan , Liang Shuang , Wang Yue , Wang Xiao‐Xue , Ji Gui‐Juan , Xu Ji‐Jing
Published: January 2025

Hydrogel is adopted as a promising alternative electrolyte for the zinc–ion batteries (ZIBs) due to its water‐retaining capacity and high ionic conductivities. However, the high content of free water molecules will affect the operation of electrolytes in ZIBs, resulting in the uncontrolled growth of zinc dendrites and related side reactions. Herein, a functional hydrogel electrolyte is developed by in situ copolymerizing the ceramic ZrO2 with acrylamide and 2‐Acrylamido‐2‐methylpropane sulfonic acid to adjust the ion transport behavior, further improve zinc ions' depositional behavior. The interaction between ZrO2 and ─SO3H groups within the hydrogel is capable of inducing the free migration of zinc ions, resulting in a novel transport pathway, thereby enhancing the diffusion rate of zinc ions with an ionic conductivity of 38.3 mS cm−1. The hydrogen bonding between ceramic particles and free water molecules of the hydrogel electrolyte enables it to achieve stable operation under large current densities (8 mA cm−2, 4 mAh cm−2). Moreover, a full battery with polyaniline (PANI@ZrO2) displays excellent stability (1500 cycles) with a capacity retention rate of 79.2%. The proposed work provides an insightful design of high‐performance electrolyte materials for energy storage by manipulating the zinc behavior.
The combination of irrigation regime and water cutoff date increases the yield and water use efficiency of castor bean (Ricinus communis L.)
Authors: Avilez Alberto Mario Arroyo , Acevedo Andres Felipe Gaona , Giovanelli Luan Brioschi , Saad João Carlos Cury , Galvão Ícaro Monteiro , Zocoler João Luis , Zanotto Mauricio Dutra
Published: January 2025

Castor bean (Ricinus communis L.) is a fibrous and fast‐growing plant with increasing economic importance due to its ability to generate energy and in the pharmaceutical and chemical industries. This research aimed to determine the best combination of irrigation regime and irrigation cutoff date (ICD) that maximizes grain and oil yields and water use efficiency (WUE) in the castor bean hybrid AG IMA 110204. The experiments were conducted in greenhouses in randomized blocks using subdivided plots and four replicates. The plots were allocated to five irrigation regimes based on soil water tension: 20, 30, 40, 50, and 60 kPa, corresponding to I1, I2, I3, I4, and I5, respectively. The subplots show the four ICDs: 120, 130, 140, and 150 days after sowing (DAS). The I1, I2, and I3 treatments showed the highest values and did not differ in the two cycles for the following variables: weight of 100 grains, grain yield, oil yield, WUE of the grain (WUE‐grains), and WUE of the oil (WUE‐oil). When the irrigation cutoff was 120 DAS, in both cycles, the water regimes I1, I2, and I3 presented the highest values and did not differ in terms of grain or oil yields or WUE‐grains or WUE‐oil. Higher grain and oil yields with lower water demand for castor bean were obtained with the combination of 40 kPa soil water tension to define the time of irrigation and the irrigation cutoff at 120 DAS.
Assistance of Artificial Intelligence in Diagnosis of Vitreoretinal Lymphoma on Optical Coherence Tomography
Authors: Lin Aidi , Peng Yuanyuan , Lin Tian , Dai Jun , Li Jizhu , Shi Tingkun , Ke Xixuan , Liao Xulong , Fang Danqi , Chen Man , Liang Huiyu , Chen Shirong , Xia Honghe , Wang Jingtao , Jiang Zehua , Li Tao , Liang Dan , Yu Shanshan , Luo Jing , Gao Ling , Sun Dawei , Tham Yih Chung , Chen Xinjian , Chen Haoyu
Published: January 2025

Vitreoretinal lymphoma (VRL) remains a diagnostic challenge due to its scarce prevalence, and delayed diagnosis usually results in blindness and even fatal outcomes. Herein, an artificial intelligence (AI) system is developed to identify VRL among 16 retinal diseases and conditions on optical coherence tomography (OCT) images with the cross‐subject meta‐transfer learning (CS‐MTL) algorithm. Extensive experiments of few‐shot VRL recognition tasks prove the robustness of our model on 1‐, 3‐, and 5‐shot scenarios, achieving an F1 score of 0.8697 to 0.9367. The superiority of the model is shown with a higher F1 score (0.9310) compared with other state‐of‐the‐art algorithms (0.5487–0.9018) and three doctors whose clinical experiences range between 3 to 10 years without the help of the CS‐MTL (0.7773–0.8949). AI assistance significantly improves the F1 scores of doctors by 6.16–14.46% (p < 0.001). Moreover, the F1 scores of AI‐assisted senior doctor and retinal specialist (0.9414 and 0.9500), but not the junior doctor (0.8897), exceed that of the CS‐MTL (0.9310). This study presents a promising approach for aiding in the diagnosis of VRL on retinal OCT images and may provide a novel insight into the collaboration of doctors with AI techniques, resulting in reducing the risk of diagnostic delays of rare diseases.
Gear‐Switch‐Integrated Dual‐Mode Three‐Wheeled Exoskeleton that Empowers Cyborg Insects with Enhanced Open‐Loop Locomotion Control Precision and Load Capacity
Authors: Li Rui , Zhang Zezhong , Le Duc Long , Lv Chen , Lye Sun Woh , Sato Hirotaka
Published: January 2025

Cyborg insects are potential alternatives to small artificial robots, with promising applications in areas such as confined space exploration. However, its low open‐loop locomotion control precision makes it difficult to perform tasks requiring precise control, while the number of sensors that can be carried is limited due to their low load capacity, which significantly limits its application scenarios. To this end, an exoskeleton is proposed herein, which significantly improves the locomotion control accuracy and load capacity of cyborg insects. The exoskeleton, with a peripheral size of 7.2 cm × 14 cm, employs three wheels to carry the load and control the direction of motion of the cyborg insect. The exoskeleton‐integrated cyborg insect excels in locomotion control precision. Without feedback control, it completes continuous circular and linear motions with minor offset errors. Compared to other cyborg insects, its load capacity is increased from less than 20–400 g or more, allowing it to be equipped with large, energy‐intensive sensors. In addition, the exoskeleton supports switching between high‐precision controlled motion and insect‐driven active exploration modes. This design broadens the application scenarios of the cyborg insect and opens the possibility of performing more complex tasks.
Secular Trends in Birth Weight in Chile and Its Regions Between 1990 and 2021
Authors: Llorca‐Jaña Manuel , Morales‐Campos Daniel
Published: January 2025

Objective

The objective is to analyze secular trends in birth weight (BW) for Chile from 1990 to 2021, focusing on the mean BW and low birth weight (LBW) prevalence, and to assess differences across Chilean regions.

Methods

Our sample, obtained from the Chilean National Statistics Office, contains information on 7 822 975 births, including the total births that took place in Chile from 1990 to 2021. We calculated mean BW and LBW prevalence at a national and a regional level. We also gathered national aggregates from 1974 to 1989 from secondary sources.

Results

At a national level, mean BW increased sharply in Chile from 1983 to 1994 (6%), remained stagnant thereafter, and fell slightly during the last decade and a half. LBW prevalence declined substantially from the mid‐1970s to the mid‐1990s, from 12% to 5%. It stagnated during the early 1990s, after which there was a small but continuous increase to over 6.5%. Antofagasta is the only outlier: its mean BW and the percentage of LBW are permanently lower and higher, respectively.

Conclusions

A sharp increase in mean BW from the mid‐1980s to the mid‐1990s, together with the declining percentage of LBW from the mid‐1970s to the mid‐1990s, should be due to the better nutritional status of mothers. The decline in mean BW from the early 2000s (as well as the increasing percentage of LBW) may be due to an increasing proportion of preterm births and the increase in the age of women giving birth. The relatively poor performance of Antofagasta is explained by the region's high altitude, which affected large numbers of the population.
A neuropathology case report of a woman with Down syndrome who remained cognitively stable: Implications for resilience to neuropathology
Authors: Liou Jr‐Jiun , Lou Jerry , Flores‐Aguilar Lisi , Nakagiri Jamie , Yong William , Hom Christy L. , Doran Eric W. , Totoiu Minodora O. , Lott Ira , Mapstone Mark , Keator David B. , Brickman Adam M. , Wright Sierra T. , Nelson Brittany , Lai Florence , Xicota Laura , Dang Lam‐Ha T. , Li Jinghang , Santini Tales , Mettenburg Joseph M. , Ikonomovic Milos D. , Kofler Julia , Ibrahim Tamer , Head Elizabeth ,   for the Alzheimer Biomarker Consortium ‐ Down Syndrome
Published: January 2025

INTRODUCTION

Aging adults with Down syndrome (DS) accumulate Alzheimer's disease (AD) neuropathology, including amyloid beta plaques and neurofibrillary tangles, by age 40.

METHODS

We present findings from an individual with DS who remained cognitively stable despite AD neuropathology. Clinical assessments, fluid biomarkers, neuroimaging, and neuropathological examinations were conducted to characterize her condition.

RESULTS

Her apolipoprotein E was ε2/ε3 and genome‐wide association study data indicated mosaicism. Neuroimaging revealed stable yet elevated amyloid and moderately elevated tau levels, while neuropathology indicated intermediate AD neuropathologic change with Lewy body and cerebrovascular pathologies. The participant demonstrated stable cognitive functioning in her 60s, potentially attributed to genetic variations, cognitive resilience, and environmental enrichment.

DISCUSSION

These findings emphasize the complexity of AD progression in DS. Further investigation into factors influencing cognitive resilience in individuals with DS is warranted. Understanding the mechanisms underlying cognitive stability in DS could offer insights into resilience to AD neuropathology in people with DS and inform future interventions.

Highlights

Findings from clinical assessments, fluid biomarkers, genotyping, neuroimaging, and neuropathological examinations of an individual with Down syndrome (DS) who remained cognitively stable despite Alzheimer's disease (AD) neuropathology are presented.

Neuroimaging revealed stable yet elevated amyloid profiles and moderately elevated tau levels, while neuropathology indicated intermediate AD neuropathologic change with Lewy body and cerebrovascular pathologies.

Despite the presence of AD pathology, the participant demonstrated intact cognitive functioning, potentially attributed to genetic variations, cognitive resilience, and environmental enrichment, emphasizing the complexity of AD progression in DS.
Heparin‐Binding Protein in Cerebrospinal Fluid as a Biomarker for Bacterial Meningitis: A Study of Diagnostic Accuracy
Authors: Olie Sabine E. , Staal Steven L. , da Cruz Campos Ana C. , Bodilsen Jacob , Nielsen Henrik , van de Beek Diederik , Brouwer Matthijs C.
Published: January 2025

Objective

We aimed to evaluate the diagnostic accuracy of heparin‐binding protein (HBP) in cerebrospinal fluid for the diagnosis of bacterial meningitis in patients with a suspected central nervous system infection.

Methods

This prospective multicenter cohort study determined the diagnostic accuracy of HBP in cerebrospinal fluid (CSF) for bacterial meningitis among a cohort of consecutive patients with a suspected central nervous infection. The final clinical diagnosis was considered the reference standard. The results were validated in a separate cohort.

Results

A total of 631 Dutch patients were evaluated for the current study, of which 73 (12%) had a final diagnosis of bacterial meningitis. For the differentiation of bacterial meningitis from all other disorders, diagnostic accuracy was high with an area under the curve (AUC) of 0.98 (95% confidence interval [CI] 0.96–1.00). With the proposed cutoff of 5.2 ng/ml, sensitivity was 97% with a specificity of 96%. In the population of patients with a CSF leukocyte count of 5‐1,000/mm3, the AUC was 0.96 (95% CI 0.87–1.00), outperforming CSF leukocytes (AUC 0.88 [95% CI 0.79–0.97]). Combining HBP with CSF C‐reactive protein (CRP) significantly increased accuracy in this population and reached a 100% sensitivity (AUC 1.00 [95% CI 0.99–1.00], cutoff 0.07, sensitivity 100%, specificity 96%). These results remained robust in an external validation cohort of 120 Danish patients (AUC 0.97 [95% CI 0.93–1.00]).

Interpretation

HBP can correctly distinguish bacterial meningitis from other disorders. It can be of additional value to current diagnostics in cases where CSF leukocyte count is relatively low, particularly when combined with CSF CRP. ANN NEUROL 2025
Sulfur Conversion to Donor‐Acceptor Ladder Polymer Networks through Mechanochemical Nucleophilic Aromatic Substitution for Efficient CO2 Photoreduction
Authors: Yang Na , Zhou Zi‐Jian , Zhu Xiang , Wu Jiwei , Zhang Yifan , Wang Tao , Wu Xin‐Ping , Tian Chengcheng , Jiang Xia , Dai Sheng
Published: January 2025

The development of synthetic methods capable of converting elemental sulfur into conjugated porous sulfur‐rich polymers remains a great challenge, although direct utilization of this readily available feedstock can significantly enrich its uses and circumvent environmental problems during sulfur storage. We report herein mechanochemical (MC) nucleophilic aromatic substitution (SNAr) that enables sulfur conversion into thianthrene‐bridged porous ladder polymer networks with dense donor‐acceptor (D−A) molecular junctions. We demonstrate that the key lies in the generation of bent thianthrene units through a solid‐state ball‐milling condensation reaction between 1,2‐dihaloarenes and elemental sulfur. We also show that the assembling of D−A structural motifs into porous networks affords efficient visible‐light‐driven photocatalytic reduction of carbon dioxide (CO2) with water (H2O) vapor, in the absence of any additional photosensitizer, sacrificial agents or cocatalysts. Exceptional photoinduced charge separation along with boosted exciton dissociation results in a high‐performance of carbon monoxide (CO) production rate of 306.1 μmol g−1 h−1 with near 100 % CO selectivity, which is accompanied by H2O oxidation to O2, as confirmed by both experimental and theoretical results. We anticipate this novel MC SNAr approach will advance processing techniques for direct sulfur utilization and facilitate new possibilities for the synthesis of D−A ladder polymer networks with promising potential in photocatalysis.
Wohin geht das Proton? Struktur und Dynamik der Wasserstoffbrückenbindungsschaltung in Aminophosphinchalkogeniden
Authors: Huber Tanja , Mayer Gabriel , Kümper Manuel , Silva Wagner , Fontana Nicolò , Falk Alexander , Schreiner Simon H. F. , Gramüller Johannes , Scrimgeour Alexander , Groß Emily , Gschwind Ruth M. , Horinek Dominik , Nuernberger Patrick , Bauer Jonathan O.
Published: January 2025

Aminophosphate stehen im Mittelpunkt der Forschung zur präbiotischen Phosphorylierungschemie. Ihre bifunktionelle Beschaffenheit macht sie auch zu einer leistungsstarken Klasse von Organokatalysatoren. Allerdings sind die Strukturchemie und Dynamik der Protonenbindung in Phosphorylierungs‐ und organokatalytischen Mechanismen noch immer nicht vollständig verstanden. Aminophosphinchalkogenide, die das zentrale H2N−P+−Ch−‐Strukturmotiv bewahren, stellen geeignete molekulare Modelle dar, welche die Protonenbindung, das Schalten von Wasserstoffbrückenbindungen und das supramolekulare Selbstorganisationsverhalten katalytisch und präbiotisch relevanter Moleküle nachahmen. Durch spektroskopische (IR, 1H‐DOSY, 15N‐NMR), moleküldynamische und computergestützte Untersuchungen wurde die dynamische Protonenschaltfähigkeit von aminophosphatanalogen Verbindungen nachgewiesen. Es wurde gezeigt, unter welchen Bedingungen die Amino‐ (NH2) oder Chalkogen‐ (Ch) Funktionen in H2N−P+−Ch−‐Struktureinheiten protoniert werden. In der Tat wurden alle denkbaren Arten der Wasserstoffbrückenbindung identifiziert, was erhebliche Unterschiede zwischen dem Sauerstoffderivat und den schwereren Congeneren offenbarte. Bei Verwendung koordinierender Anionen wurden supramolekulare Zickzack‐ und würfelförmige Anordnungen im Festkörper und in Lösung gefunden. Nach dem Aufbrechen der Würfelstruktur gehen die Sulfide und Selenide keine stabilen Wechselwirkungen mehr mit HCl‐Molekülen ein. In Abwesenheit koordinierender Anionen findet hingegen bevorzugt die Protonierung der Chalkogenfunktion statt. Im Gegensatz zum Sauerstoffderivat zeigen die schwereren protonierten Congenere ein dynamisches intramolekulares Protonenhüpfen zwischen der Chalkogen‐ und der Aminofunktion.
Machine Learning‐Guided Modulation of Li+ Solvation Structures towards Optimal Electrolyte Systems for High‐Performance Li−O2 Battery
Authors: Liu Dapeng , Fu Zerui , Wang Shu , Gong Xiangrui , You Tingting , Yu Haohan , Jiang Ying , Zhang Yu
Published: January 2025

As the “blood” of Li−O2 batteries (LOBs), electrolytes with various solvation structures of Li+ can greatly influence the composition of solid electrolyte interphase (SEI) on anode and the growth kinetics of Li2O2 on cathode, and further the battery performance. However, achieving delicate modulation of the multi‐composition electrolytes remains significantly challenging to simultaneously give consideration to both the anode and cathode reactions. In this work, we employed Bayesian optimization to develop advanced electrolytes for LOBs, enabling the formation of a stable inorganic‐rich SEI, and modulation of Li2O2 morphologies. Thus obtained LOBs using the optimized dual‐solvent electrolyte could deliver a discharge capacity of 14,063 mAh g−1 at a current density of 500 mA g−1, which is far higher than those using the single‐solvent electrolytes. This study not only highlights the critical role of the solvation structure for improving the battery performance, but also provides new insights and important theoretical guidance for delicate modulation of electrolyte compositions.
Molecular Engineering of Amino Acid Crystals with Enhanced Piezoelectric Performance for Biodegradable Sensors
Authors: Cheng Yuanqi , Wang Tianjian , Zhu Haoqi , Hu Xueli , Mi Jing , Li Lan , Zhang Yu , Yang Jiapeng , Dong Liang , Li Ying , Sun Wenxu , Lu Xiaomei , Wang Wei , Cao Yi , Xue Bin
Published: January 2025

Amino acid crystals have emerged as promising piezoelectric materials for biodegradable and biocompatible sensors; however, their relatively low piezoelectric coefficients constrain practical applications. Here, we introduce a fluoro‐substitution strategy to overcome this limitation and enhance the piezoelectric performance of amino acid crystals. Specifically, we substituted hydrogen atoms on the aromatic rings of L‐tryptophan, L‐phenylalanine, and N‐Cbz‐L‐phenylalanine with fluorine, resulting in significantly elevated piezoelectric coefficients. Density functional theory calculations further indicate that fluorination strengthens polarization by modifying molecular dipole moments. Consequently, these fluoro‐substituted crystals achieve piezoelectric coefficients of up to 50.36 pm/V, surpassing those of other organic piezoelectric materials such as polyvinylidene fluoride (PVDF), poly(L‐lactic acid) (PLLA), and gelatin. When integrated into flexible, biodegradable force sensors, the fluoro‐substituted crystals exhibit a broad sensing range, high sensitivity, and stable in vivo operation over extended periods. This work establishes a versatile route for boosting piezoelectricity in biomaterials, thereby broadening their scope in biomedical applications.
Tailoring molecular diffusion in core‐shell zeolite imidazolate framework composites realizes efficient kinetic separation of xylene isomers
Authors: Yang Linghe , Hai Guangtong , Liu Ying , Zheng Fang , Shen Fuxing , Chen Lihang , Liu Baojian , Zhang Zhiguo , Yang Qiwei , Ren Qilong , Luo Yong , Bao Zongbi
Published: January 2025

The separation of xylene isomers is a critical and energy‐intensive process in the petrochemical industry, primarily due to their closely similar molecular structures and boiling points. In this work, we report the synthesis and application of a novel core‐shell zeolitic imidazolate framework (ZIF) composite, ZIF‐65@ZIF‐67, designed to significantly enhance the kinetic separation of xylene isomers through a synergistic "shell‐gated diffusion and core‐facilitated transport" strategy. The external ZIF‐67 shell selectively restricts the diffusion of larger isomers (MX and OX), while the internal ZIF‐65 core accelerates the diffusion of PX, thereby amplifying the diffusion differences among the isomers. This architecture yields remarkable improvements in both selectivity and diffusion rates, as demonstrated by vapor‐phase adsorption studies and molecular dynamics simulations. The ZIF‐65@ZIF‐67 composite exhibits up to 12.5 times higher PX/OX selectivity in liquid‐phase adsorption and 3.4 times higher dynamic selectivity in fixed‐column breakthrough experiments compared to the individual ZIF components. Theoretical simulations further corroborate the heterogeneous diffusion control mechanism, revealing the time‐dependent diffusion regulation within the core‐shell architecture. This work underscores the great potential of core‐shell MOF composites in optimizing molecular sieving processes for industrially significant separations and highlights a new route for enhancing kinetic separation efficiency in complex multicomponent systems.
Photochromic Color Tuning of Copper‐Doped Zinc Sulfide Nanocrystals by Control of Local Dopant Environments
Authors: Kimura Mayu , Yoshioka Daisuke , Chang I‐Ya , Irizawa Akinori , Shibata Daisuke , Imada Shin , Kobayashi Yoichi
Published: January 2025

Inorganic photochromic materials offer several advantages over organic compounds, including relatively inexpensive and higher thermal stability. However, tuning their color with the same component has remained a significant challenge. In this study, we demonstrate that the photochromic color of Cu‐doped ZnS nanocrystals (NCs), which is initially pale yellow before light irradiation, can be tuned from gray to brown by adjusting the surface stoichiometry of Zn and S, which is controlled through the use of thiol and non‐thiol ligands. Several experiments and quantum chemical calculations using model clusters revealed that the color change is determined by the distribution of Cu, which significantly contributes to the coloration, specifically whether it resides on the Zn‐rich or S‐rich surface. In contrast, particle size and Cu concentration were found to have little effect on the photochromic color. This study expands the diversity of photochromic responses in inorganic NCs and marks an important step toward the development of further advanced photochromic nanomaterials.
The Proximal Protonation Source in Cu−NHx−C Single Atom Catalysts Selectively Boosts CO2 to Methane Electroreduction
Authors: Cai Rongming , Zhu Hong , Yang Fei , Ju Min , Huang Xianzhen , Wang Jian , Gu M. Danny , Gao Jiali , Yang Shihe
Published: January 2025

Regulating the coordination environment of active sites has proved powerful for tapping into their catalytic activity and selectivity in homogeneous catalysis, yet the heterogeneous nature of copper single‐atom catalysts (SACs) makes it challenging. This work reports a bottom‐up approach to construct a SAC (rGO@Cu−N(Hx)−C) by inlaying preformed amine coordinated Cu2+ units into reduced graphene oxide (rGO), permitting molecular level revelation on how the proximal N‐site functional groups (N−H or N−CH3) impact on the carbon dioxide reduction reaction (CO2RR). It is demonstrated that the N−H moiety of rGO@Cu−NHx−C can serve as an in situ protonation agent to accelerate the CO2‐to‐methane reduction kinetics, delivering a methane current density (163 mA/cm2) 2.42‐times that with the ‐CH3 substituted counterpart rGO@Cu−N−C. Operando spectroscopic studies and theoretical calculations elucidate that the high methane faradaic efficiency (77.1 %) achieved here is enabled by opening up the energetically favorable formyl pathway (*OCHO pathway) against the traditional *CO pathway that normally leads to various CO2RR products other than methane. Our strategy sets the stage to precisely modulate single‐atom catalysts for efficient and selective electrochemical CO2 reduction.
Accelerated Destruction of Passive Film and Microbial Corrosion of 316 L Stainless Steel via Extracellular Electron Transfer
Authors: Li Zhong , Wang Jie , Li Feng , Li Zhengtao , Zhou Enze , Fan Yongqiang , Song Hao , Xu Zhaodong , Gu Tingyue , Wang Fuhui , Xu Dake
Published: January 2025

The dense passive film on 316 L stainless steel is the key in its corrosion resistance. Its interactions with an electroactive biofilm are critical in deciphering microbial corrosion. Herein, an in‐depth investigation using genetic manipulations and addition of an exogenous electron mediator found that extracellular electron transfer (EET) mediated by the electroactive S. oneidensis biofilm grown aerobically accelerated the destruction of the microstructure and weakened the passive film. The changes in surface properties accelerated the electrochemical reactions and increased pitting corrosion. The redox state on the surface also changed due to the activity of the electroactive biofilm. A synergistic EET corrosion mechanism, including both direct and mediated electron transfer with passive film destruction was proposed to illustrate the corrosion caused by electroactive S. oneidensis. The techniques used in this work provide a systematic approach to probe EET impact on microbial corrosion by electroactive biofilms with electron transfer across the biotic‐abiotic interfaces.
Rhodamine‐Gold Hybrid Nanosensor for Rapid and Selective Detection of Hg2+ Ions in Environmental Samples
Authors: Kaewtong Chatthai , Norrasarn Jukkraphop , Wanno Banchob , Hayami Shinya , Tuntulani Thawatchai , Pulpoka Buncha
Published: January 2025

This research focuses on the selective detection of Hg2+ ions using hybrid nanosensors composed of rhodamine building blocks linked to polyamine units of varying chain lengths to produce Rho1–Rho4, which were subsequently conjugated with thioctic acid (RT1–RT4) and attached to the surface of gold nanoparticles to create hybrid nanosensors (GRT1–GRT4) designed for detecting heavy metals. The chemical structures, purity, morphology, and chemical composition were characterized through XRD, NMR, TEM, ATR‐FTIR, and mass spectrometry. These hybrid nanosensors demonstrated excellent selectivity and sensitivity in colorimetric and fluorescence responses towards Hg2+, outperforming other metal ions. In their spirolactam form, the sensors were non‐fluorescent but transformed into a fluorescent form upon interaction with Hg2+, resulting in enhanced fluorescence and colorimetric changes. Theoretical calculations indicated that Hg2+ could form stable complexes with the RT1 sensor by binding to the oxygen and nitrogen atoms in the spirolactam structure, as well as coordinating with the oxygen atom of the amide bond. The detection limit (LOD) was 1.68×10−7 M with a response time of less than 40 seconds. This method offers a simple and highly sensitive approach for detecting Hg2+ ions in both environmental and biological applications, as confirmed by the characterization and experimental data.
Synthesis of SnO₂/COF Green Nanomaterials for Effective Pesticide Decomposition and Promoting Tomato Plants Growth
Authors: Khan Shoaib , Wang Aoxue , Liu Jiayin , Khan Iltaf , Mujahid Laiba , Ruijin Meng , Sadiq Samreen , Zaman Saeed , Khan Aftab , Khan Sohail , Khan Mansoor , Miao Yuanyang
Published: January 2025

In last few decades, the agriculture sector is facing various type of crops diseases originated by crop pests. Among various crops the tomato plant is greatly affected by many pests such as aphids and whiteflies, which are badly decreasing tomato plant yield and effecting its growth. In last few years, various type of pesticides such as Neonicotinoids and Pyrethroids are employed which are badly effecting eco‐system and water bodies. In this research work, we prepared SnO2 nanosheets (SONS) by in‐situ and green synthesis approach. Remarkably, SONS exhibit a larger surface area, tailored pore size, and higher catalytic performance than SnO2 nanoparticles (SONP). To further improve the efficiency of SONS, we coupled it with covalent organic farmwork nanosheets (COFNS) via the hydrothermal approach. The SONS@COFNS hybrid nanocatalysts exhibit improved carrier migration, enhanced porosity, multiple active sites, and exceptional light absorption capabilities. The as prepared green nanomaterials delivered improved activities for Neonicotinoids and Pyrethroids degradation. Remarkably, the most active sample 6COFNS/SONS showed the highest degradation efficiency (94 %), which is approximately 1.92 times higher than the degradation efficiency of pristine SONS (49 %). This work will ultimately contribute to developing green, ecofriendly nanomaterials for pesticides degradation and promoting tomato plants growth.
Progress and Challenges of Water‐in‐Salt Electrolytes: Exploring Physical Chemistry Properties and Solid Electrolyte Interphase Formation Mechanisms
Authors: Wang Xuanze , Jommongkol Rossukon , Deng Jie , Liu Kexin , Qian Jiangfeng , Zhu Yachao , Fontaine Olivier
Published: January 2025

“Water‐in‐salt” (WIS) electrolytes endow the possibility of commercial aqueous devices due to the extending electrochemical stability window (ESW). However, there is still a long way to address current issues until future practical applications, such as the high cost of salts, the cathodic limit, and the controversial mechanism of solid‐electrolyte interphase (SEI). In this review, we first introduce cutting‐edge WIS electrolytes and display their current issues. After, the reported tactics of solving issues and achievements in our group are listed, including four sections: 1) physical structure; 2) SEI formation analysis; 3) additives contributions; and 4) devices. In the end, we focus on the current challenges and perspectives of WIS electrolytes for aiming at the practical applications of aqueous energy storage devices.
Exploring Biophysical and Chemoinformatics Approaches for Interactions of Ionic Liquids With Hemoglobin, DNA, BSA, and HSA
Authors: Sangeeta  , Mehra Komal , Sarkar Anjana , Tomar Ravi
Published: January 2025

This review article provides an inclusive overview of the intricate interactions amid ionic liquids (ILs) and essential biomacromolecules, mainly hemoglobin (Hb), bovine serum albumin (BSA), human serum albumin (HSA), and calf thymus‐DNA (CT‐DNA). ILs have recently become a topic of great attention because of their inimitable physicochemical properties and potential uses in different fields. The review systematically explores the binding mechanisms, thermodynamics, and structural changes induced by ILs on Hb, BSA, HSA, and CT‐DNA using spectroscopic, thermodynamic, and computational techniques. The article highlighted various experimental and computational methodologies to explore the interactions between ILs and biomacromolecules. It offers an in‐depth analysis of the techniques employed to decode the intricate nature of these molecular associations and the influence of ILs along with their structural characteristics on the conformational stability, activity, and functionality of biomacromolecules. This foundational understanding is essential for advancing research and developing strategies that exploit the distinctive properties of ILs to foster innovative and sustainable applications within the biomedical field.
New α‐Glucosidase Inhibitors from Vietnamese Garcinia schomburgkiana Fruits
Authors: Tran Quyen H. N. , Nguyen Huong T. M. , Nguyen Thuy L. T. , Sichaem Jirapast , Do Lien T. M.
Published: January 2025

The chemical investigation of the fruits of Garcinia schomburgkiana growing in Vietnam led to the isolation of a new anofinic acid derivative, 5‐hydroxy‐8‐methoxyanofinic acid (1), a new xanthone, xanthoschome C (2), and a known synthetic phenolic analog, 4‐(2‐hydroxybenzyl)‐2‐(4‐hydroxybenzyl) phenol (3), along with seven known xanthones (4–10). The structures of all isolated compounds were determined using spectroscopic techniques (nuclear magnetic resonance and mass spectrometry), in conjunction with a comparison to existing literature data. All isolated compounds were assessed for their α‐glucosidase inhibitory activity and showed significant inhibition, with half‐maximal inhibitory concentration (IC50) values ranging from 12.1 to 65.7 µM, surpassing the potency of the positive control, acarbose (IC50 179 ± 6.02 µM). Among them, compound 8 exhibited the strongest inhibitory activity, with an IC50 value of 12.1 ± 0.44 µM.
Laccase Functional Analysis: Substrates, Activity Assays, Challenges, and Prospects
Authors: Babinskas Justinas , Matijošytė Inga
Published: January 2025

Enzyme functional analysis is a multifaceted process that can be used for various purposes, such as screening for specific activities, as well as developing, optimising, and validating processes or final products. Functional analysis methods are crucial for assessing enzyme performance and catalytic properties. Laccase, a well‐known blue multi‐copper oxidase, holds immense potential in diverse industries such as pharmaceuticals, paper and pulp, food and beverages, textiles, and biorefineries due to its clean oxidation process and versatility in handling a wide range of substrates. Despite its prominence, the use of laccase encounters challenges in selecting appropriate functional analysis substrates and methods. This review delves into the substrates utilised in qualitative and quantitative techniques for laccase activity analysis. Although laccase catalyses mono‐electron oxidation of aromatic hydroxyl, amine, and thiol compounds efficiently, using molecular oxygen as an electron acceptor, the review identifies limitations in the specificity of the commonly employed substrates, concerns regarding the stability of certain compounds and highlights potential strategies.
Influence of Sample Preparation Method on Total Dietary Fiber Content Measurement of Low Carbohydrate Bread Containing High Levels of Cross‐Linked Phosphorylated RS4 Wheat Starch
Authors: Shi Jialiang , Jeradechachai Tanya , Maningat Clodualdo C. , Jo Myeongsu , Chen Zhongwei , Shi Yong‐Cheng
Published: January 2025

Background and Objectives

Cross‐linked phosphorylated (CLP) RS4 wheat starch has been approved as a dietary fiber source by FDA because it can reduce insulin levels following a meal containing a carbohydrate that raises blood glucose levels. It has been successfully formulated in many high‐fiber and low‐carbohydrate bread products. This study aimed to determine the influence of sample preparation methods on the total dietary fiber content of these fiber‐fortified bread products during the assay with AOAC Method 991.43. In addition, the effects of CLP RS4 wheat starch on the morphology, crystallinity, and thermal properties of the bread were investigated.

Findings

The total dietary fiber content of breads formulated with unmodified wheat starch or CLP RS4 wheat starch was influenced by the sample preparation methods (drying, grinding, and sieving). Preferred methods are forced air oven over freeze‐drier and vacuum oven; coffee grinder over mortar and pestle; and 35‐mesh over 70‐mesh sieve. The proposed method excludes influence of operator and shows more repeatable results. CLP RS4 wheat starch in the bread was gelatinized and had restricted swelling, reduced enthalpy, and reduced crystallinity.

Conclusions

The proposed sample preparation method generated from this study involves drying the bread in a forced air oven at 40°C, particle size reduction using a coffee grinder, and screening the ground samples in a 35‐mesh sieve before total dietary fiber assay using AOAC Method 991.43.

Significance and Novelty

Our study provided new and useful information on sample preparation methodology for total dietary fiber measurement of high‐fiber or low‐carbohydrate bread products containing CLP RS4 wheat starch. This methodology has potential applications in many high‐fiber flour‐based products other than bread.
Applicability of Semiconductor Photocatalysts in Photoredox Reactions: Highlighting the Performance of Polymeric Carbon Nitrides in Radical Three‐Component Couplings
Authors: Lorenz Felix , Peppel Tim , Brasholz Malte , Strunk Jennifer
Published: January 2025

A set of five polymeric carbon nitrides (pCNs) made from diverse low‐molecular precursors was compared with metal chalcogenide and pnictogenide semiconductors for their effectiveness in visible light‐induced organic radical reactions. The productivity of the heterogenous photocatalysts in the decarboxylative Giese addition of N‐phenylglycine with cyclopentenone was studied at different irradiation wavelengths ranging from 380 to 450 nm, as well as in the deaminative radical donor–acceptor–donor (DAD) three‐component coupling of N‐benzyl pyridinium salts with N‐methylmaleimide and 1,1‐diarylethylenes. The heterogenous photocatalytic radical three‐component reactions were achieved in high diastereoselectivities and with high yields if the electronic and steric properties of the reactants were matched with the appropriate heterogeneous photocatalyst.
Organocatalytic Asymmetric (3+3) Cycloaddition of 4‐Hydroxycoumarins with α,β‐Unsaturated Aryl Esters
Authors: Chen Hao , Yang Shuang , Wang Ning-Yi , Tian Ya-Ping , Zhang Yu-Chen , Shi Feng
Published: January 2025

A chiral isothiourea‐catalyzed asymmetric (3+3) cycloaddition of 4‐hydroxycoumarins with β‐fluoroalkyl‐substituted α,β‐unsaturated aryl esters was established, which afforded chiral fluoroalkyl‐substituted caprolactone‐fused coumarins in moderate to good yields (up to 88%) and overall excellent enantioselectivities (up to 98% ee). This reaction not only enriches the chemistry of catalytic asymmetric (3+3) cycloadditions involving 4‐hydroxycoumarins, but also provides a new strategy for the synthesis of chiral six‐membered O‐heterocycle‐fused coumarins.
Mechanically Adaptive Materials Based on Dynamic Chemical Bonds
Authors: Dong Jiamei , Zhao Zi‐Han , Li Cheng‐Hui
Published: January 2025

Adaptiveness is an important feature for biological creatures to survive and interact with variable environments. Mechanically adaptive polymers (MAPs), which have been developed recently inspired by this adaptive nature, can regulate their mechanical properties in response to external stimuli or environmental changes. Specifically, MAPs based on dynamic chemical bonds have been synthesized and reported as an emerging material because of the intrinsic self‐adaptability, outstanding mechanical properties and durable applications. This review primarily focuses on the recent advancements in the fabrication of MAPs through the utilization of dynamic covalent bonds and non‐covalent bonds. A comprehensive summary of the methodologies and mechanisms employed to attain high energy dissipation in MAPs is provided. Subsequently, the review offers incisive analyses of the intrinsic functionalities of MAPs, such as high impact‐stiffening, damping, and buffering capabilities. Finally, the developmental achievements within this domain are recapitulated, the potential challenges, and future research perspectives in MAPs are deliberated.
150 Years of the Tetrahedral Carbon: A Toast to Chirality
Authors: Cintas Pedro
Published: January 2025

We have recently celebrated the 150th anniversary of the tetrahedral carbon (1874–2024), as postulated by van't Hoff and Le Bel, who published their seminal breakthrough only 2‐months apart, on September 5 and November 5, 1874, respectively. The concept is a fundamental pillar of structural chemistry and, if we may say so, of molecular sciences. How two young men in their early careers dared to disturb the established way of thinking constitutes the jumping‐off of scientific theories as constructive elements, rather than arguments derived from experiments. Chirality makes no sense without geometry. Nor can we interpret a molecular scenario devoid of spatial considerations. All in all, a felicitous celebration to be highlighted.
Iron‐histidine Coordination in Cytochrome b5: A Local Vibrational Mode Study
Authors: Freindorf Marek , Fleming Kevin , Kraka Elfi
Published: January 2025

We analyzed the intrinsic strength of distal and proximal FeN bonds and the stiffness of the axial NFeN bond angle in a series of cytochrome b5 proteins isolated from various species, including bacteria, animals, and humans. Ferric and ferrous oxidation states were considered. As assess‐ ment tool, we employed local vibrational stretching force constants ka(FeN) and bending force constants ka(NFeN) derived from our local mode theory. All calculations were conducted with the QM/MM method‐ ology. We found that  transition from ferric to ferrous state makes the FeN axial bonds weaker, longer, less covalent, and less polar. Additionally, the axial NFeN bond angle becomes stiffer and less flexible. Local mode force constants turned out as far more sensitive to the protein environment than geometries; unraveling trends across di‐ verse protein groups and monitoring changes in the axial heme‐framework caused a change between ferric and fer‐ rous oxidation states. These characteristics qualify them as perfect features for machine learning models predicting cytochrome b5 redox potentials, which currently rely more on geometric data and qualitative descriptors of the protein environment. The insights gained through our investigation also offer valuable guidance for strategically fine‐tuning ar‐ tificial cytochrome b5 proteins and designing new, versatile variants.