bluuebunny/crossref_metadata_2025 huggingface dataset:
Ligand Assisted Co(II)‐Catalyzed Multicomponent Synthesis of Substituted Pyrroles and Pyridines
Authors: Chakraborty Subhajit , Singha Mohapatra Arijit , Saha Subhangi , Mandal Sutanuva , Paul Nanda D.
Published: December 2024

Herein, we describe a sustainable Co(II)‐catalyzed synthesis of pyrroles and pyridines. Using a Co(II)‐catalyst [CoII2(La)2Cl2] (1 a) bearing redox‐active 2‐(phenyldiazenyl)‐1,10‐phenanthroline) (La) scaffold, various substituted pyrroles and pyridines were synthesized in good yields, taking alcohol as one of the primary feedstock. Pyrroles were synthesized by the equimolar reaction of 2‐amino and secondary alcohols. A series of 2,4,6‐substituted symmetrical pyridines were prepared via a three‐component reaction of NH4OAc with 1 : 2.2 molar primary and secondary alcohols, respectively. Unsymmetrically substituted 2,4,6‐trisubstituted, 2,4,5,6‐tetrasubstituted, and 2,3,4,5,6‐pentasubstituted pyridines were achieved via a multi‐component coupling reaction of alcohols and NH4OAc. Catalyst 1 a showed encouraging results during the gram‐scale synthesis of these N‐heterocycles. Mechanistic investigation revealed synergistic involvement of cobalt metal and the ligand during the catalytic reactions.
Multifunctional Fluorescent Material Based Red‐emitting Carbon Dots for Cell Imaging and Photodynamic Sterilization
Authors: Xu Jiatong , Zhao Zhonghua , Cao Yasong , Huang Haowen , Shen Richao , Zeng Cheng , Lv Jiawei , Qi Chunxuan , Lei Ziqiang , Feng Hai‐Tao , Ma Hengchang
Published: December 2024

In this paper, a new carbon dot (R1‐CDs) was prepared by one‐pot hydrothermal method by using 1,8‐diaminonaphthalene and o‐phthalic acid (o‐PA) as precursors. Due to the high purity of R1‐CDs, NMR analysis was performed to identify the types of H and C atoms in their graphene sheets. From our research findings, three important information was disclosed such as (1) five types H atoms are presented in R1‐CDs; (2) 18 kinds of C atoms in the graphene sheets are observed, and 8 kinds of them are quaternary atoms, and 10 kinds of carbon atoms as tertiary one; (3) functional groups of ‐COOH and ‐NH2 from precursors cannot be inherited into the edges or defect sites of graphene sheet. Obviously, our research findings for the first time revealed the more details of chemical structures of CDs. We believe that our works can supply a general concept to fabricate CDs by selecting specific precursors, also can encourage CDs’ development in a more “chemistry” way by employing NMR as a powerful method.
Triazine‐Functionalized Nitrogen‐Rich Covalent Organic Framework as an Electrode Material for Aqueous Symmetric Supercapacitor
Authors: Ahmad Ikrar , Singh Omkar , Ahmed Jahangeer , Priyanka  , Alshehri Saad M. , Bharti Chitranjan , Vidivay
Published: December 2024

Covalent triazine frameworks, with their ordered pores and crystalline structure that exhibit heteroatom impacts, demonstrate outstanding chemical stability, making them designable for charge storage applications. In this study, the triazine‐based covalent organic frameworks (TPT@BDA‐COF) was synthesized using 4′,4′′′,4′′′′′‐(1,3,5‐Triazine‐2,4,6‐triyl) tris (([1,1′‐biphenyl]‐4‐amine)) (TPT) and 4,4′‐Oxydibenzaldehyde (BDA) following polycondensation process. Interestingly, these resulted in the fabrication of a well‐connected, orderly porous crystalline structure, redox‐active moiety, and significantly high doping atomic percentages of N (~13.6 %). The three‐electrode electrochemical study, showed a stable electrochemical potential window of 1.8 V (−0.45 to +1.35) in 1 M NaClO4 electrolyte, it exhibited a high specific capacitance of 92.6 mF/cm2 with a high energy density 41.7 Wh/kg respectively. The symmetric supercapacitor designed using TPT@BDA‐COF as both anode and cathode exhibited high specific capacitance (F/g) and gravimetric energy density (Wh/kg): 17.8, 36.9, 43.7, 47.7 and 3.5, 16.6, 13.7, 21.6 in 1 M CH3COONa, 1 M Na2SO4, 1 M NaNO3, 1 M NaClO4 electrolyte respectively. It showed excellent cyclic stability (105.2 %), and Coulombic efficiency (97.5 %) even after 10 k GCD cycles in 1 M NaClO4 at 2 A/g. Interestingly, ClO4− anions exhibited a better chaotropic nature (water structure breaker) as compared to CH3COO−, SO4−2, and NO3−. Their energy storage competence is supported by the illumination of 1 white and 1 red LED upon charging a single SSC for 50 sec each. A Quantum Mechanics (QM) calculation and Molecular Dynamics (MD) simulation are performed to investigate and validate the stability of Covalent Organic Frameworks (COFs). DFT calculations were carried out using the SCF approach B3LYP‐631G(d) basis set to compute the HOMO and LUMO energies and their respective location in COF.
Bimetallic Cooperativity of a Ferrocene‐Based Iridium NHC Complex in Water Oxidation Catalysis: A New Frontier for Efficient Oxygen Evolution
Authors: Bora Debashree , Pratim Bhattacharyya Himangshu , Rahaman Gayen Firdaus , Baguli Sudip , Patel Pitambar , Sarma Manabendra , Saha Biswajit
Published: December 2024

Bimetallic catalysts have gained attention as promising contenders, owing to the synergistic interaction between two distinct metal centers. In this study, we present two N‐heterocyclic carbene iridium(III) pentamethylcyclopentadienyl complexes [Cp*Ir(fcpyNHC)Cl]PF6 (1) and [Cp*Ir(pyNHC)Cl]PF6 (2) where 1 includes a ferrocene moiety making it a bimetallic complex. Using ceric ammonium nitrate as a sacrificial oxidant, both complexes were tested for water oxidation. Complex 2 achieved a maximum turnover number (TONmax) of 3240 and a turnover frequency (TOFmax) of 231 min−1. In comparison, complex 1 demonstrated nearly double the activity with a TONmax of 6047 and TOFmax of 431 min−1 compared to 2, which was attributed to the cooperative effect of the catalyst in water oxidation reaction. This bimetallic Fe Ir catalyst (1) exhibited outstanding catalytic efficiency for oxygen evolution from water at ambient conditions. We identified a proposed FeIII IrIV intermediate experimentally via UV‐Vis spectroscopy and XPS study. Theoretically, this intermediate was more stable by 7.84 kcal/mol than the traditional FeII IrV electromer intermediate. This delineates the pronounced bimetallic cooperative participation of both Fe and Ir metal centres for better activity.
Mesoporous NiFe2O4@g‐C3N4‐Based p–n Heterostructures for Boosting Solar‐Driven Photocatalytic Dye Degradation and Hydrogen Evolution
Authors: Das Suma , Pramanik Swapnamoy , Nair Ranjith G , Chowdhury Avijit
Published: December 2024

Mass‐fraction‐optimized heterojunction composites featuring precisely engineered interfaces and mesoporous structures are crucial for improving light absorption, minimizing electron‐hole recombination, and boosting overall catalytic efficiency. Herein, highly efficient mesoporous‐NiFe2O4@g‐C3N4 heterojunctions were developed by embedding p‐type NiFe2O4 nanoparticles (NPs) within n‐type porous ultrathin g‐C3N4 (p‐uCN) nanosheets. The optimized NiFe2O4@g‐C3N4, loaded with 20 wt % magnetic counterparts, exhibits exceptional photocatalytic methylene blue (MB) degradation, achieving the highest performance in both photocatalytic and photo‐Fenton processes with rate constants of 0.062 min−1 and 0.161 min−1, respectively. These performance metrics are 1.3 and 2.55 fold higher than p‐uCN (0.048 min−1 and 0.063 min−1) and 51.6 and 17.4 fold higher than NiFO (0.0012 min−1 and 0.009 min−1). Notably, mp‐NiF@uCN‐20 % with 1.0 wt % of Pt loading achieves the highest H2 evolution rate of 2294 μmolg−1h−1, which is 3.72, 1.52, and 13.49 times higher than that of pure CN, p‐uCN, and NiFO, respectively. The enhanced performance is corroborated by increased surface area, improved separation of charge carriers, and effective charge transfer, which enables simultaneous reduction and oxidation processes. Further, the magnetic nanocomposite exhibits remarkable stability even after multiple runs, indicating their reusability. The experimental findings emphasize the importance of p‐n heterojunctions, interfacial band alignment, and mesoporous architecture in enhancing the photocatalytic efficiency of NiFe2O4@g‐C3N4 nanocomposites.
Effect of Transition Metal Variability in NNN‐Pincer Complexes on Catalytic CO2 Reduction to Methanol
Authors: Vinod Parmar Saurabh , Avasare Vidya
Published: December 2024

The catalytic efficiency of M−H2tpda pincer complexes (M=Mn(I), Fe(II), Co(III)) in CO2 hydrogenation, emphasizing the role of transition metal variability have been discussed. The DFT analysis demonstrates that complexes with low αR values form weaker M−H bonds, enhancing catalyst reactivity with the elongation of M−H bond. The analysis further displays excellent catalytic performance for Mn−H2tpda (ΔE=20.3 kcal/mol), Fe−H2tpda (ΔE=21.0 kcal/mol) and Co−H2tpda (ΔE=23.6 kcal/mol) for CO2 to formic acid formation. The Co−H2tpda (ΔE=16.7 kcal/mol) is comparatively better than Mn−H2tpda (ΔE=20.7 kcal/mol) and Fe−H2tpda (ΔE=19.6 kcal/mol) in formaldehyde formation. All three catalysts exhibit excellent catalytic performance in the conversion of formaldehyde to methanol. The condensed Fukui function calculations of these catalyst complexes establish direct relationship between the ΔE for the rate limiting catalytic cycle and the electrophilicity of the metal centers. The TOF calculations further helped to understand the catalytic performance of the catalysts at various temperatures.
Minimal Mineral – Deckensysteme neu gedacht: Die Zukunft des Bauens nachhaltig gestalten
Authors: Aziz Saqib , Alexander Bradley , Gengnagel Christoph , Loutfi Jamila
Published: December 2024

Deckensysteme sind aufgrund ihres Volumens und ihrer Materialität – neben der Gründung – zentrale Schlüsselkomponenten für nachhaltiges Bauen. Innovationen in diesem Bereich können den Ressourcenverbrauch und die Treibhausgasemissionen erheblich reduzieren, während gleichzeitig die regionale Vielfalt im Bauwesen gestärkt wird. Der vorgestellte Forschungsansatz zielt nicht nur auf Materialeinsparungen ab, sondern strebt mithilfe digitaler Technologien eine umfassende Optimierung an. Dabei dienen historische Bausysteme mit bewährten zirkulären Eigenschaften als Grundlage für die Entwicklung. Im Rahmen des Projekts Minimal Mineral werden digitale Fertigungsmethoden erforscht, um einen Katalog innovativer, multimodaler Deckensysteme zu entwickeln. Die konsequente Anwendung computergestützter Entwurfs‐ und Analysewerkzeuge sowie digitaler Fertigungsverfahren wie 3D‐Druck und Robotik ermöglichen neue ressourcenschonende Bauweisen und den Einsatz nachhaltigerer Materialien. Der resultierende Bauteilkatalog basiert auf erprobten historischen Bauweisen und sichert so eine schnelle mögliche praktische Anwendung. Der Fokus des Berichts liegt auf Voruntersuchungen für eine prototypische Anwendung für ein aktuelles Bauvorhaben in Nordfrankreich, das sich derzeit in der Planungsphase befindet. Das geplante neuartige Deckensystem besteht aus vorgefertigten mineralischen Schalungskörpern mit integrierten Schallabsorptionsfunktionen.
Optical, Opto‐Mechanical, and Antimicrobial Characterization of TiO2 and ZnO‐Enhanced Polypropylene Fibers Using Interferometric Techniques and Fourier Transform Analysis
Authors: Aldosari F. M. , Sefrji Fatmah O. , Alsharari Abdulrhman M. , Al‐Ghamdi S. A. , Alqarni Sara A. , Hadi Muhammad , Alamoudi Wael M. , El‐Metwaly Nashwa M.
Published: December 2024

This study investigates the optical, mechanical, and antimicrobial properties of polypropylene (PP) fibers enhanced with titanium dioxide (TiO2) and zinc oxide (ZnO) nanoparticles. Using a Mach–Zehnder interferometric system, we examined the refractive indices, birefringence, and opto‐mechanical behavior of blank PP, PP/TiO2, and PP/ZnO nanocomposite fibers under various conditions, including different polarization orientations and during cold drawing processes. The 2D Fourier transform algorithm is employed to analyze interferometric data, enabling precise measurements of refractive index profiles and birefringence. Results show that both TiO2 and ZnO nanoparticles significantly enhance the optical and mechanical properties of PP fibers. PP/TiO2 fibers exhibited the highest refractive index (1.530) and birefringence (0.0459), followed by PP/ZnO (1.522 and 0.040) and blank PP (1.520 and 0.031). The maximum draw ratios achieved were 4.2, 3.9, and 3.5 for PP/TiO2, PP/ZnO, and blank PP fibers, respectively, indicating improved mechanical properties in the nanocomposites. Antimicrobial efficacy was evaluated using the shaking flask method and optical density measurements against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans. PP/ZnO fibers demonstrated the highest antimicrobial activity, with growth reductions ranging from 64.8% to 80.4%, followed by PP/TiO2 fibers (56.0% to 70.3%).
Impact of Hormone on Growth and GA3 Regulation of Anthocyanin Biosynthesis in Suspension‐Culture Cells of Cyclocarya paliurus
Authors: Pan Chuanqing , Liu Yuan , Tang Daobang , Chen Jiguang , Yin Zhongping
Published: December 2024

Hormones are effective in regulating plant metabolism and, therefore, are often used in plant cell culture to increase the yield of target products. This study investigated the effects of hormones on the growth and anthocyanin biosynthesis of suspension‐cultured red Cyclocarya paliurus cells. Additionally, the mechanism by which gibberellin induces anthocyanin biosynthesis was explored through multi‐omics integrated analysis and the assay of the dynamic changes in signaling molecule concentration. The results showed that the total anthocyanin content and yield of suspension‐cultured cells, when induced by 1.0 mg L⁻¹ Gibberellin A3 (GA3), experienced increases of 1.92‐ and 1.83‐fold, respectively. The application of exogenous GA3 activated the synthesis and transduction of four signaling molecules, that is, nitric oxide (NO), hydrogen peroxide (H2O2), salicylic acid (SA), and jasmonic acid (JA), in the cells and altered the expression patterns of transcription factors. The altered expression of transcription factors upregulated the expression of anthocyanin biosynthetic genes such as anthocyanin‐3‐O‐glucosyl transferase and leucoanthocyanidin dioxygenase, while downregulated the expression of anthocyanin reductase and flavonoid 3′,5′,‐hydroxylase, which activated the anthocyanin biosynthesis pathway, ultimately leading to a significant increase in anthocyanin biosynthesis. This research work establishes a foundation for further research on the role of hormones in regulating anthocyanin biosynthesis in suspension‐cultured plant cells.
Inhibitory Effect of PRMT5/MTA Inhibitor on MTAP‐Deficient Glioma May Be Influenced by Surrounding Normal Cells
Authors: Wang Yunjie , Sun Xiaohui , Ma Runchen , Zhang Xiaofan , Ji Shengmin , Liu Zhaofeng , Yang Gangqiang , Wang Hongbo , Zhang Peng , Zhang Jianzhao , Tian Jingwei
Published: December 2024

Background

Methylthioadenosine phosphorylase (MTAP) and protein arginine methyltransferase 5 (PRMT5) are considered to be a synthetic lethal pair of targets, due to the fact that deletion of MTAP leads to massive production of methylthioadenosine (MTA) decreasing the activity of PRMT5. In vitro and in vivo experiments have demonstrated that MRTX1719, a small molecule that selectively binds PRMT5/MTA complex, significantly inhibits the proliferation of MTAP‐deficient tumors and has a weak toxic effect on normal cells. However, it has been reported that MTAP‐deleted tumors did not significantly accumulate MTA in vivo due to metabolism of MTA by MTAP‐expressing stroma, which might lead to a diminished anti‐cancer effect of MRTX1719.

Methods

We first analyzed whether there were MTAP‐expressing normal intracerebral cells around MTAP‐deficient glioma tissues by paraffin‐embedded tissue microarray of human glioma specimens. Then, in vivo and in vitro models of MTAP‐deficient gliomas coexisting with neurons or glial cells were constructed for evaluating the effectiveness of the anti‐tumor effects of MRTX1719 in this setting.

Results

MTAP‐deficient gliomas were surrounded by a large number of MTAP‐expressing normal cells, and the presence of these cells significantly reduced the inhibitory effect of MRTX1719 on MTAP‐deficient glioma cells in vitro and in vivo.

Conclusions

Due to the complexity of the tumor environment in vivo, the anti‐tumor effects of PRMT5/MTA‐specific inhibitors may be somewhat attenuated, and their ability to achieve suitable therapeutic effects in the clinic might require more in‐depth studies.
Beyond BRAFV600E: Investigating the Clinical and Genetic Spectrum of Langerhans Cell Histiocytosis in Children
Authors: Tang Xue , Gao Ju , Guo Xia , Wan Zhi , Sun Jing‐jing
Published: December 2024

Background

Langerhans cell histiocytosis (LCH) is the most prevalent histiocytic disorder in pediatric populations, with a highly heterogeneous clinical presentation. Currently, the correlation between clinical phenotypes and molecular alterations in childhood LCH, besides the BRAFV600E mutation, has not been sufficiently studied.

Methods

This study presented data on 33 pediatric LCH patients treated at our center who exhibited various molecular alterations other than the BRAFV600E mutation. Additionally, we comprehensively reviewed pediatric LCH cases with non‐BRAFV600E molecular alterations reported from January 2010 to August 2024.

Results

A total of 309 pediatric LCH patients with molecular alterations beyond BRAFV600E were enrolled in the study, among whom 33 were from our center. In these LCH cases, 49 kinds of MAP2K1 mutations, 31 kinds of BRAF mutations, and 4 kinds of ARAF mutations were found. At our center, two patients with multisystem LCH with risk organ involvement, both with BRAFN486_P490del mutation, showed poor response to induction chemotherapy for 6 weeks. Among the 303 LCH patients with MAP2K1 or other BRAF alterations, patients with the MAP2K1 mutation had a higher prevalence of single‐system bone involvement (SS‐bone) than patients carrying the BRAF mutation (p = 0.0072). Within the MAP2K1 group, exon 3 mutations exhibited a stronger association with SS‐bone than exon 2 mutations (p = 0.042). Additionally, patients with the BRAF exon 15 mutation and MAP2K1 exon 2 mutation had higher rates of LCH onset before age 3 compared with patients carrying the BRAF exon 12 mutation and MAP2K1 exon 3 mutation (p = 0.037; p = 0.0015). Patients carrying the BRAF mutation in exon 15 had higher rates of liver involvement compared with patients carrying the exon 12 (p = 0.042).

Conclusions

Pediatric LCH patients often carry recurrent somatic MAP2K1 and BRAF mutations, which are associated with clinical manifestations.
Peer Victimization Among a Clinical Sample of Turkish Youth With Autism Spectrum Disorder
Authors: Gündüz Yagmur , Alnak Alper , Coskun Murat
Published: December 2024

Young subjects with developmental disabilities are vulnerable and may experience frequent peer victimization. Quantifying the risk and associated factors and consequences of peer victimization among this vulnerable population would have clinical and public health implications. In this descriptive cross‐sectional study, we aimed to investigate peer victimization and relationships with psychiatric comorbidity and sociodemographic/socioeconomic variables in a clinical sample of young subjects with ASD without ID in a nonwestern country. The Revised Olweus Bully/Victim Questionnaire and a semistructured diagnostic instrument were used to investigate victimization experiences and psychiatric disorders, respectively. The majority of the subjects (68.8%) experienced victimization (verbal, relational or physical) by their peers. Only 45% (18/40) of the victims' parents were aware of their child's victimization status. Frequency of generalized anxiety disorder and self‐reported anxiety scores were higher in those with more severe victimization. A binary logistic regression analysis for victimization yielded significant associations for having a single parent, a higher maternal educational level, a lower paternal educational level and higher depression scores. Psychiatric evaluation of young subjects with ASD should include questioning about bullying experiences. Because parents may not be aware of bullying experience, disclosing bullying experience only depending on the parental report may cause an underreport of bullying among young subjects with ASD.
Indole Derivatives as Promising Anti‐Dengue Agents: A Review of Recent Advances
Authors: Januário Marcelo Augusto Pereira , Junior Celso de Oliveira Rezende , Castro‐Gamboa Ian
Published: December 2024

Dengue, a mosquito‐borne disease transmitted by Aedes mosquitoes, is a significant global health concern. Despite extensive research, effective treatments remain limited. The indole nucleus, known for its diverse pharmacological properties, has emerged as a promising scaffold for anti‐dengue drug discovery. This review comprehensively examines recent advancements in the fields of natural products, medicinal chemistry, and computer‐aided drug design focused on discovering indole‐based anti‐dengue agents. We discuss the rationale for targeting indole frameworks, highlight key structural features associated with anti‐dengue activity, and summarize recent research findings. The review aims to provide valuable insights for researchers working on developing novel anti‐dengue therapeutics.
Entrapment of Lipase from Candida antarctica in a Xerogel for the Production of Biodiesel from Waste Cooking Oil
Authors: Decarpigny Cédric , Bigan Muriel , Froidevaux Rénato
Published: December 2024

The process to synthesize biodiesel is well‐developed and optimized to overcome the disadvantages like the competition with agriculture using feedstock, and the problematics in the process. Oils from waste and enzymatic catalysis have proven to be good solutions to these problems. Lipases are currently the most commonly used enzymes in the transesterification of oils; nevertheless, enzymes have a high cost and must be immobilized to offer repetitive reuse. This work focuses on the synthesis and the optimization of the conditions of a xerogel where the lipase from Candida antarctica is immobilized by entrapment. The xerogel synthesized here, a glass‐like material, proved to be very effective in maintaining the enzyme on its structure, with an immobilization yield of 96 % and an activity of 5.3 U/mg (free lipase=12.1 U/mg). By grinding this xerogel, the immobilization yield remained constant (94 %). Nevertheless, grinding the xerogel allowed better diffusion of reagents, and the activity reached 9.7 U/mg. Using this xerogel in biodiesel production had a positive effect on CALB efficiency by increasing the biodiesel yield, 46.1 % against 15.1 % with free CALB. Finally, the catalyst could be reused for five runs without loss of activity.
Recent Advance in Sensitive Detection of Demethylase FTO
Authors: Shang Min , Qin Jingying , Zhao Bingyue , Luo Qian , Wang Huimin , Yang Changying , Liu Hanghang , Ran Jiabing , Yang Wei
Published: December 2024

Methylation modification is a critical regulatory mechanism in epigenetics and plays a significant role in various biological processes. N6‐methyladenosine (m6A) is the most common modification found in RNA. The fat mass and obesity‐associated protein (FTO) facilitate the demethylation of m6A in RNA, and its abnormal expression is closely linked to the development of several diseases. As a result, FTO has the potential to serve as an important biomarker for clinical disease diagnosis. Despite its significance, there has been a lack of comprehensive reviews addressing advancements in detection methods for the demethylase FTO. This review provides an overview of the progress in FTO detection methods, ranging from traditional approaches to innovative techniques, with a particular emphasis on recently reported advancements. These novel detection methods can be categorized into strategies based on enzymes, functional nucleic acids (FNA), and conformational changes. We summarize the principles and applications of these detection methods and discuss the current challenges and prospects in this field.
Mechanochemical Ball Milling Approach to C(sp3)‐H Functionalization of 8‐Methylquinolines
Authors: Narayanan Nanditha Kattukudiyil , Schnürch Michael
Published: December 2024

A mechanochemical, highly regioselective rhodium(III)‐catalyzed C─H methylation of 8‐methylquinolines is reported. The methylation method reported in this study, is often solvent‐free or uses minimal solvent (liquid assisted grinding), operates without external heating under mild reaction conditions, demonstrating tolerance for various functional groups. Moreover, the reaction time is significantly reduced compared to the solvent‐based variant. Notably, the reaction can be carried out using a pestle and mortar instead of ball milling as well, highlighting the operational simplicity of this approach for achieving challenging C(sp3)‐H activation under more sustainable conditions.
Recent Advances in Electrochemical CO2 Reduction Catalyzed by Single‐Atom Alloys
Authors: Wu Wenjie , Long Jun , Xiao Jianping
Published: December 2024

With the extensive use of fossil fuels and CO2 emission, the development of effective electrocatalysts to convert CO2 into high‐value‐added chemical products has become an important issue in academia community. Single‐atom alloys (SAA) integrate the advantages of single‐atoms catalysts and alloys, which can improve the activity and selectivity of CO2 electroreduction (CO2RR) by adjusting the electronic and geometric structure of the host and guest metals simultaneously. This article provides a comprehensive review on the research advances of SAA catalysts used for CO2RR, including the synthesis and characterizations, computational design, experimental performances, and electronic structure effects of different SAA. Specifically, the correlations between experimental results and theoretical studies have been highlighted and discussed clearly in this review, which provide unique fundamental insights on the CO2RR performances of SAA catalysts. Based on these understanding, we finally propose a workflow combining both computational and experimental methods to rationally design the SAA, which can help the further development of CO2RR catalysts in the future.
A Dual‐Functional Sulfur‐Rich Copolymers for Stable Anchoring and Enhanced Conversion of Polysulfide in Lithium‐Sulfur Batteries
Authors: Fu Yao , Jin Yang , Guo Fang‐Fei , Cao Fei , He Bin
Published: December 2024

Sulfur‐rich copolymers have gained a great deal of attention as promising cathode materials in Li−S batteries due to their low cost and naturally uniform sulfur dispersion. However, the poor electrical conductivity and shuttle effect cause rapid capacity decay and low sulfur utilization especially under high sulfur loading and low electrolyte/sulfur ratio. Herein, the Fe1‐xS/C dispersed and Se‐containing sulfur‐rich copolymer (FSP) was synthesized by one‐pot reaction of ferrocene, trithiocyanuric acid with SexSy. In such process, the trithiocyanuric acid reacts with SexSy to form Se‐containing sulfur‐rich copolymers. Simultaneously, ferrocene reacts with sulfur to form highly dispersed Fe1‐xS/C within sulfur‐rich copolymers. The covalent chemical binding of sulfur in the FSP effectively suppress the shuttle effect of polysulfides by chemical binding. Meanwhile, the Se improves the conductivity of FSP, which enhances the reaction kinetics. Moreover, the highly dispersed Fe1‐xS/C in the FSP is able to effectively catalyze polysulfide conversion and inhibit the shuttle effect. As a result, the optimized FSP electrode exhibits a high capacity of 1330 mAh g−1 at 0.2 C. Even under high sulfur loading (4.08 mg cm−2) and low E/S ratio (6 μL mg−1), the FSP cathode demonstrates a remarkable capacity of 734.7 mAh g−1 at 0.2 C.
Reversible Metal‐Mediated Molecular Switching of a Phosphaethene Polyaromatic Hydrocarbon
Authors: Bhowmick Toma , Wells Jordann A. L. , Asif Ansari Mohd , Steen Jorn D. , Crespi Stefano , Orthaber Andreas
Published: December 2024

This experimental and theoretical study illustrates how phosphaalkenes, which are isolobal to alkenes, can utilize a variety of external triggers for molecular switching. The E/Z isomerization of a truxene‐based phosphaalkene, i. e. TruxC=P‐Mes* (Mes*=2,4,6‐tris‐t‐butyl‐benzene), is accomplished by irradiation, metal coordination, or deprotonation of the truxene core. The reversible and quantitative Z/E double bond isomerization by gold(I) coordination/decoordination of the phosphorous lone pair represents a novel fuelling strategy for molecular switches.
Exploring the Catalytic Potential of Bioinspired Taurine‐Functionalized Carbon Quantum Dots as Bifunctional Catalysts for Diverse Sustainable Organic Transformations in Water
Authors: Jyoti Nirmal , Raigar Ashok K. , Saini Kamlesh , Manju  , Guleria Anjali
Published: December 2024

Taurine‐functionalized Carbon Quantum Dots (Tau‐CQDs) were synthesized and evaluated for their catalytic potential under metal‐, acid‐, and base‐free sustainable conditions, using water as a solvent for various organic transformations, including Knoevenagel condensation, the Biginelli reaction, and the Knoevenagel–Michael cascade. These bioinspired N, S‐doped CQDs exhibit bifunctionality, acting as hydrogen bond donors and acceptors for C−C, C−N, and C−O bond formation. Comprehensive characterization of the catalyst was performed using HRTEM, PXRD, XPS, FTIR, AFM, Zeta potential, UV–Vis, and photoluminescence spectrometry. The Tau‐CQDs demonstrated excellent reusability, maintaining catalytic performance over 10 cycles. Green chemistry metrics, including a low E‐factor, high atom economy, and favorable PMI, CE, and RME values, highlight this approach's environmental and economic advantages. Key properties, such as high reaction yields, short reaction times, water solubility, enhanced surface functionality, non‐toxicity, and mild operating conditions, underscore the broader significance of Tau‐CQDs as an efficient, sustainable catalytic platform. Additionally, the simple recovery of the catalyst via filtration, without the need for further purification, enhances its practical applicability.
Unusual Reaction of Isocyanides with Aromatic Aldehydes Catalyzed by a Supramolecular Capsule
Authors: Fiorini Luca , Köster Jesper , Piccini GiovanniMaria , Goldfuss Bernd , Prescimone Alessandro , Fabris Fabrizio , Tiefenbacher Konrad , Scarso Alessandro
Published: December 2024

The supramolecular resorcinarene hexameric capsule efficiently promotes the unprecedented reaction between isocyanides and electron‐deficient aromatic aldehydes leading to the formation of imines and carbon monoxide. The mechanism of the reaction was investigated via isotope labelling, kinetic analysis of the reaction, computational studies and the independent synthesis of a proposed intermediate. Control experiments indicate that the formation of the key aziridinone intermediate is limited to the cavity of the capsule.
Photoinduced Deprotection of 2‐Nitrophenylneopentyl Glycol Boronates Enables Light‐Triggered Polycondensation of Siloxanes
Authors: Boyet Marion , Colin Boris , Michaud Guillaume , Genin Emilie , Pinet Sandra , Chabaud Laurent , Pucheault Mathieu
Published: December 2024

Various protecting groups have been developed for boronic acids, mostly based on diols. Alternatives include trifluoroborates and amine complexes, which offer easier synthesis and release under milder conditions. We present here a new strategy involving photocleavable protecting groups for boronic and borinic acids, based on the 2‐nitrobenzyl motif. A screening of several 1,2‐ and 1,3‐diols bearing a 2‐nitrobenzyl group led us to identify 1‐(2‐nitrophenyl)neopentyl glycol (npnp) for the protection of boronic acid derivatives. This diol is easily prepared in a single step on gram scale, and the corresponding npnp boronates are stable in wet acetonitrile at 90 °C for several days, and under under acidic conditions. Irradiation at 365 nm in acetonitrile allows for the controlled liberation of boronic acids in good to excellent yields, a method also applied to a dimesitylborinic ester bearing a 2‐nitrobenzylalcohol moiety. 1‐(2‐Nitrophenyl)neopentyl glycol boronates ArB(npnp) demonstrated their utility in light‐triggered siloxane crosslinking. We showed that catalysts incorporated into a polymer matrix, irradiated, and then incubated at 50 °C for 7 days resulted in efficient polymerization, forming solid materials in some cases.
Design, Synthesis, and Biological Assessment of Novel Aminobenzidazole Agonists Targeting the Stimulator of Interferon Genes (STING) Receptor Signaling Pathway for Oncology Immunotherapy
Authors: Fan Yiqing , Zeng Zeqi , Mo Jiaxian , Wang Zike , Jiang Hongyu , Liu Juanjuan , Qian Hai , Shi Wei
Published: December 2024

The activation of the STING‐mediated signaling pathway leads to the secretion of type I interferon (IFN) and the activation of tumor‐specific T cells. STING, a pattern recognition receptor located on the endoplasmic reticulum membrane of immune cells, binds with endogenous cyclic dinucleotides. STING undergoes phosphorylation, triggering the STING‐TBK1‐IRF3 pathway and NF‐κB pathway, resulting in the release of IFN‐β and other pro‐inflammatory cytokines, ultimately enhancing the activation of tumor‐specific T cells. This mechanism serves to complement the limitations of immune checkpoint inhibitors and enhances the efficiency of the immune response. This study selected benzimidazole compounds GSK and SR‐717, which exhibit promising potential as patented medicines, as our lead compounds. Aiming to address the challenges associated with the short half‐life of benzimidazole compounds and the limited molecular activity of SR‐717, we designed and synthesized a series of STING agonists (compounds 6~29). The compound 17 showed excellent agonistic activity on hSTING protein in vitro. The cytotoxicity tests of all the synthesized compounds were performed in vitro. Performed in vivo pharmacokinetic studies on the most promising compounds and conducted molecular docking analyses.
Fluorescence Detection of DNA/RNA G‐Quadruplexes (G4s) by Twice‐as‐Smart Ligands
Authors: Ledvinka Jiri , Rota Sperti Francesco , Paragi Gabor , Pirrotta Marc , Chéron Nicolas , Valverde Ibai E. , Menova Petra , Monchaud David
Published: December 2024

Fluorescence detection of DNA and RNA G‐quadruplexes (G4s) is a very efficient strategy to assess not only the existence and prevalence of cellular G4s but also their relevance as targets for therapeutic interventions. Among the fluorophores used to this end, turn‐on probes are the most interesting since their fluorescence is triggered only upon interaction with their G4 targets, which ensures a high sensitivity and selectivity of detection. We reported on a series of twice‐as‐smart G4 probes, which are both smart G4 ligands (whose structure is reorganized upon interaction with G4s) and smart fluorescent probes (whose fluorescence is turned on upon interaction with G4s). The fine mechanistic details behind the excellent properties of the best prototype N‐TASQ remain to be deciphered: to investigate this, we report here on the synthesis and studies of two analogues, TzN‐TASQ and AlkN‐TASQ, and on a careful analysis of their G4‐interacting properties, investigated both in vitro and in silico. Our results show that fine‐tuning their constitutive structural elements allows for increasing the efficiency of both their ‘off’ (i. e., a conformation with a low fluorescence) and ‘on’ states (i. e., a conformation with a high fluorescence), which opens interesting ways for the design of more efficient fluorogenic G4 probes.
Glucagon‐Like Peptide‐1 Links Ingestion, Homeostasis, and the Heart
Authors: Krieger Jean‐Philippe , Daniels Derek , Lee Shin , Mastitskaya Svetlana , Langhans Wolfgang
Published: December 2024

Glucagon‐like peptide‐1 (GLP‐1), a hormone released from enteroendocrine cells in the distal small and large intestines in response to nutrients and other stimuli, not only controls eating and insulin release, but is also involved in drinking control as well as renal and cardiovascular functions. Moreover, GLP‐1 functions as a central nervous system peptide transmitter, produced by preproglucagon (PPG) neurons in the hindbrain. Intestinal GLP‐1 inhibits eating by activating vagal sensory neurons directly, via GLP‐1 receptors (GLP‐1Rs), but presumably also indirectly, by triggering the release of serotonin from enterochromaffin cells. GLP‐1 enhances glucose‐dependent insulin release via a vago‐vagal reflex and by direct action on beta cells. Finally, intestinal GLP‐1 acts on the kidneys to modulate electrolyte and water movements, and on the heart, where it provides numerous benefits, including anti‐inflammatory, antiatherogenic, and vasodilatory effects, as well as protection against ischemia/reperfusion injury and arrhythmias. Hindbrain PPG neurons receive multiple inputs and project to many GLP‐1R‐expressing brain areas involved in reward, autonomic functions, and stress. PPG neuron‐derived GLP‐1 is involved in the termination of large meals and is implicated in the inhibition of water intake. This review details GLP‐1's roles in these interconnected systems, highlighting recent findings and unresolved issues, and integrating them to discuss the physiological and pathological relevance of endogenous GLP‐1 in coordinating these functions. As eating poses significant threats to metabolic, fluid, and immune homeostasis, the body needs mechanisms to mitigate these challenges while sustaining essential nutrient intake. Endogenous GLP‐1 plays a crucial role in this “ingestive homeostasis.”
Robust genomic prediction and heritability estimation using density power divergence
Authors: Chowdhury Upama Paul , Bhattacharjee Ronit , Das Susmita , Ghosh Abhik
Published: December 2024

This manuscript delves into the intersection of genomics and phenotypic prediction, focusing on the statistical innovation required to navigate the complexities introduced by noisy covariates and confounders. The primary emphasis is on the development of advanced robust statistical models tailored for genomic prediction from single nucleotide polymorphism data in plant and animal breeding and multi‐field trials. The manuscript highlights the significance of incorporating all estimated effects of marker loci into the statistical framework and aiming to reduce the high dimensionality of data while preserving critical information. This paper introduces a new robust statistical framework for genomic prediction, employing one‐stage and two‐stage linear mixed model analyses along with utilizing the popular robust minimum density power divergence estimator (MDPDE) to estimate genetic effects on phenotypic traits. The study illustrates the superior performance of the proposed MDPDE‐based genomic prediction and associated heritability estimation procedures over existing competitors through extensive empirical experiments on artificial datasets and application to a real‐life maize breeding dataset. The results showcase the robustness and accuracy of the proposed MDPDE‐based approaches, especially in the presence of data contamination, emphasizing their potential applications in improving breeding programs and advancing genomic prediction of phenotyping traits.
Developing a Fluorinated Benzothiadiazole‐Based Polymer Donor as Guest to Construct High‐Performance Ternary Solar Cells
Authors: Shao Jianfeng , Li Min , Chen Guo , Fang Yu , Young Jeong Sang , Ke Yuqiu , Yi Xiaoqing , Young Woo Han , Huang Bin
Published: December 2024

Benzothiadiazole (BT) has shown promising applications in fullerene solar cells. However, few BT‐based polymer donors exhibited a noticeable power conversion efficiency (PCE) for the fused‐ring small molecular acceptor‐based polymer solar cells (PSCs). Herein, we developed a D‐A (D: donor, A: acceptor) polymer donor F‐1 based on fluorinated BT (ffBT) as A unit and chlorinated benzo [1,2‐b : 4,5‐b′] dithiophene (BDT‐2Cl) as D unit. Thanks to the strong electron‐withdrawing of ffBT unit, F‐1 not only exhibited low‐lying energy levels to increase open circuit voltage, but also existence noncovalent S ⋅ ⋅ ⋅ F to enhance molecular planarity and crystallinity. After incorporated F‐1 as guest materials on PM6 : L8‐BO‐based system to construct ternary device, the addition of F‐1 can efficient promote the blend films exhibit excellent morphological compatibility, favorable phase separation, and molecular arrangement. As a result, the F‐1 (5 %) : PM6 : L8‐BO‐based device obtained an impressive PCE up to 19.47 %, which is much higher than the counterparts as PCE is 18.35 % for PM6 : L8‐BO‐based binary device. This study not only provided a practical and promising strategy to develop high‐performance polymer donors by utilizing the advantages of noncovalent conformational locks, but also suggested an efficient strategy to further improve device performance by constructing ternary solar cells for BT unit‐based PSCs.
One‐Pot Depolymerization of Mixed Plastics Using a Dual Enzyme System
Authors: Branson Yannick , Liu Jiawei , Schmidt Louis , Griebel Jan , Prager Andrea , Stieler Lena , Breite Daniel , Bayer Thomas , Besenmatter Werner , Dong Weiliang , Garscha Ulrike , Bornscheuer Uwe T. , Wei Ren
Published: December 2024

As global plastic consumption and littering escalate, innovative approaches to sustainable waste management are crucial. Enzymatic depolymerization has emerged as a promising recycling method for polyesters via monomer recovery under mild conditions. However, current research mainly focuses on using a single plastic feedstock, which can only be derived from complex and costly plastic waste sorting. This study investigated the enzymatic depolymerization of mixed plastics using a dual‐enzyme system in a one‐pot approach. Employing the polyester hydrolase PES‐H1 FY and the (poly)urethanase UMG‐SP‐2, mixed or blended polymers consisting of polyethylene terephthalate (PET), polybutylene adipate‐co‐terephthalate (PBAT), and thermoplastic polyester‐polyurethane (TPU) were depolymerized into their monomers. Chromatographic quantification revealed a total yield of monomeric products of up to 39.8±4.4 % after 96 h reactions, which was consistent with the weight loss measurements of 40.9±2.5 %. In addition, a modified dissolution‐precipitation method was shown to easily blend the three different polymers while improving their degradability. Our findings suggest that using mixed enzymes is a viable method for recycling mixed or blended waste plastics without polymer sorting. Individual monomers can be separated and purified to produce virgin polymers, while their mixture in the hydrolysate can easily serve as feedstock for microbial upcycling into value‐added products.
Nickel‐Based Cocatalysts on Titanium‐Doped Hematite Empower Direct Photoelectrochemical Valorisation of 5‐Hydroxymethylfurfural
Authors: Carrai Irene , Mazzaro Raffaello , Bellatreccia Caterina , Piccioni Alberto , Salvi Marco , Grandi Silvia , Caramori Stefano , Ceroni Paola , Pasquini Luca
Published: December 2024

The photoelectrochemical oxidation of 5‐hydroxymethylfurfural (HMF), a biomass‐derived intermediate, to 2,5‐furandicarboxylic acid (FDCA), a key building block for industrial applications, is a well‐studied anodic reaction. This photoelectrochemical (PEC) conversion typically requires an electron mediator, such as TEMPO, regardless of the semiconductor used. Various electrocatalysts can also perform this reaction electrochemically, without additional organic species in the electrolyte. In this study, Ti‐doped hematite (Ti:Fe2O3) photoanodes were employed for the HMF photoelectrochemical conversion at the anodic side of a two‐compartments PEC cell. To avoid the need of an electron mediator, nickel‐based electrocatalysts were deposited on the electrode′s surface. The Ni(OH)2‐electrodeposited (Ti:Fe2O3−Ni) and the NiMo‐sputtered Ti:Fe2O3 photoanodes (Ti:Fe2O3−NiMo) were characterised and tested for the HMF oxidation in 0.1 M NaOH (pH 13) electrolyte. Partial HMF photoelectrochemical conversion to FDCA was achieved, pointing out the beneficial effect of Ni‐based cocatalyst in shifting the selectivity towards the di‐carboxylic acid. Fixed Energy X‐ray Absorption Voltammetry (FEXRAV) and X‐ray Absorption Near‐Edge Structure (XANES) measurements were conducted to investigate the interaction between HMF and the two deposited electrocatalysts. These techniques offered valuable insights into the oxidation mechanism, which were further validated using a rate deconvolution procedure.
Latitudinal Clines in an Ectothermic Vertebrate: Patterns in Body Size, Growth Rate, and Reproductive Effort Suggest Countergradient Responses in the Prairie Lizard
Authors: Robbins Travis R. , Hegdahl Tiffany R.
Published: December 2024

Although we have evidence that many organisms are exhibiting declines in body size in response to climate warming, we have little knowledge of underlying mechanisms or how associated phenotypic suites may coevolve. The better we understand coadaptations among physiology, morphology, and life history, the more accurate our predictions will be of organismal response to changing thermal environments. This is especially salient for ectotherms because they comprise 99% of species worldwide and are key to functioning ecosystems. Here, we assess body size, growth rates, and reproductive traits of a vertebrate ectotherm, the prairie lizard, Sceloporus consobrinus, for multiple populations along a latitudinal thermal gradient and compare body size clines between S. consobrinus and eastern fence lizard (S. undulatus) populations. We found that phenotypic values increased as environmental temperatures decreased for all traits examined, resulting in a pattern representative of countergradient variation. The positive covariation of phenotypes across the thermal gradient exemplifies the enigma of “master of all traits.” This enigma was further illustrated by the energy expenditure toward growth and reproduction increasing as phenotypic values increased. The evolutionary responses appear to reveal overcompensation because annual energy expenditure toward growth and reproduction increased even as activity periods decreased. Overall, compensatory responses to cooler thermal environments were exhibited by prairie lizards in body size, growth rate, egg size, and clutch size, resulting in cold‐adapted populations allocating more energy toward maintenance, growth, and reproduction than lower latitude, warm‐adapted populations. If larger body size in ectotherms is a result of intrinsically faster physiological rates compensating for cooler temperatures and shorter activity periods, then smaller body sizes in warmer environments may be a result of greater reliance on available environmental temperatures for physiological rates and time for assimilating resources.