Frontiers in Chemistry最新文献

{"title":"Emerging NO₂ gas sensing on substitutionally doped Fe on NiWO₄ SCES insulators.","authors":"Jong Hyun Lee, Se Hwang Kang, Gi Hyun Park, Min Young Kim, Sanghyun Ji, Ha Eun Choa, Gi Hyeon Han, Jeong Yun Hwang, Seung Yong Lee, Kyu Hyoung Lee","doi":"10.3389/fchem.2024.1480356","DOIUrl":"https://doi.org/10.3389/fchem.2024.1480356","url":null,"abstract":"<p><p>In this study, we demonstrate the emergence of NO₂ gas sensing capabilities in the typically non-active NiWO₄, a strongly correlated electron system (SCES), by introducing substitutional Fe at the Ni site. NiWO₄ typically exhibits strong Coulombic repulsion between Ni atoms, resulting in a large band gap of over 3.0 eV and insulating behavior. This correlated behavior is clearly reflected in the significant increase of band gap when considering the Hubbard <i>U</i> correction for the cations, bringing the theoretical value closer to the observed value. The single-phase Fe_0.5Ni_0.5WO₄ displays a notable shift in the [NiO₆] symmetric vibration mode and an increase in magnetization. Additionally, theoretical calculations confirm the preservation of the wide band gap, with the Fe and O levels generated within the band gap. These findings indicate that Fe located in the Ni sites modulate Coulombic repulsion in NiWO₄ SCES insulators. Unlike the poor gas-sensing performance of intrinsic NiWO₄, Fe_0.5Ni_0.5WO₄ exhibits a significant NO₂ response (R_g/R_a) of 11 at 200°C than other gases and a limit of detection (LOD) of 46.4 ppb. This study provides a pathway for realizing gas-sensing performance in strongly correlated electron insulators with large band gaps through the introduction of dopant levels at the cation sites.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1480356"},"PeriodicalIF":3.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11574712/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142675023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Carborane-based BODIPY dyes: synthesis, structural analysis, photophysics and applications.","authors":"Javier Ordóñez-Hernández, José Giner Planas, Rosario Núñez","doi":"10.3389/fchem.2024.1485301","DOIUrl":"https://doi.org/10.3389/fchem.2024.1485301","url":null,"abstract":"<p><p>Icosahedral boron clusters-based BODIPY dyes represent a cutting-edge class of compounds that merge the unique properties of boron clusters with the exceptional fluorescence characteristics of BODIPY dyes. These kinds of molecules have garnered substantial interest due to their potential applications across various fields, mainly including optoelectronics, bioimaging, and potential use as boron carriers for Boron Neutron Capture Therapy (BNCT). Carborane clusters are known for their exceptional stability, rigid geometry, and 3D-aromaticity, while BODIPY dyes are renowned for their strong absorption, high fluorescence quantum yields, and photostability. The integration of carborane into BODIPY structures leverages the stability and versatility of carboranes while enhancing the photophysical properties of BODIPY-based fluorophores. This review explores the synthesis and structural diversity of boron clusters-based BODIPY dyes, highlighting how carborane incorporation can lead to significant changes in the electronic and optical properties of the dyes. We discuss the enhanced photophysical characteristics, such as red-shifted absorption and emission poperties, charge and electronic transfer effects, and improved cellular uptake, resulting from carborane substitution. The review also delves into the diverse applications of these compounds. In bioimaging, carborane-BODIPY dyes offer superior fluorescence properties and cellular internalization, making them ideal for cell tracking. In photodynamic therapy, (PDT) these dyes can act as potent photosensitizers capable of generating reactive oxygen species (ROS) for targeted cancer treatment making them excellent candidates for PDT. Additionally, their unique electronic properties make them suitable candidates for optoelectronic applications, including organic light-emitting diodes (OLEDs) and sensors. Overall, carborane-BODIPY dyes represent a versatile and promising class of materials with significant potential for innovation in scientific and technological applications. This review aims to provide a comprehensive overview of the current state of research on carborane-BODIPY dyes, highlighting their synthesis, properties, and broad application spectrum.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1485301"},"PeriodicalIF":3.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11574714/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142675576","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Supramolecular systems and their connection with metal-organic structures.","authors":"Rodrigo Cué-Sampedro, José Antonio Sánchez-Fernández","doi":"10.3389/fchem.2024.1468916","DOIUrl":"https://doi.org/10.3389/fchem.2024.1468916","url":null,"abstract":"<p><p>Supramolecular structures with specific applications are a pillar in several areas of science. Thus, from a contemporary point of view, there are several reasons to embrace a systematic order of the supramolecular concept itself. First, the structuring of a supramolecular material seems safer now than it did decades ago. Second, the interactions of metal-organic frameworks (MOFs) and supramolecular chemistry and, conversely, supramolecularity to assemble MOFs and create efficient complex systems in multiple cutting-edge applications are an image to be safeguarded. Third, perhaps we should simply limit ourselves to considering how researchers in these fields have attempted to correlate the notion of supramolecular systems by linking self-assembly considerations. In any case, these topics present advantages to optimize innovative geometries that are useful to highlight significant practical applications. This review covers a general introduction to MOFs and supramolecularity, the key unit of the study presented here, followed by a survey of recent advances in confined space chemistry, the relationships of MOFs with supramolecular structures, and the synthesis electrochemistry of MOFs and switchable MOFs to obtain a greater understanding of structure-property relationships. To conclude, some future perspectives on this promising and plausible field of science will be mentioned.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1468916"},"PeriodicalIF":3.8,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11573591/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142675024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Flame retardants of the future: biobased, organophosphorus, reactive or oligomeric.","authors":"Bob A Howell","doi":"10.3389/fchem.2024.1500782","DOIUrl":"10.3389/fchem.2024.1500782","url":null,"abstract":"<p><p>Polymeric materials have been a great boon to the development and wellbeing of mankind. However, in the main, these materials are flammable and must be flame retarded for most applications. Many substances have been utilized to impart a measure of flame retardancy. The most widely used and most effective have been organic: organohalogen and organophosphorus compounds. Organohalogen compounds have been popular, low-cost, very effective flame retardants for polymeric materials. However, with the recognition that these compounds readily migrate from a polymer matrix into which they have been incorporated, persist in the environment and pose serious risks to human health, the use of organophosphorus compounds has become prominent. In particular, organophosphorus compounds of appropriate structure derived from readily-available, renewable, low-cost, non-toxic biobased precursors are attractive. Avoidance of the issues of environmental persistence and toxicity associated with organohalogen compounds is possible with these materials. Migration from a polymer matrix may be removed as a deficiency through the use of reactive compounds, i.e., compounds that may be incorporated directly into the polymer structure either by copolymerization or grafting, or oligomeric compounds. Oligomeric materials of branched structure display characteristics of broad compatibility, high effectiveness and lack of migration.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1500782"},"PeriodicalIF":3.8,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11564728/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142647419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Magnetocaloric effect in a high-spin ferromagnetic molecular cluster.","authors":"Eleftheria Agapaki, Emmanouil K Charkiolakis, Gary S Nichol, David Gracia, Marco Evangelisti, Euan K Brechin","doi":"10.3389/fchem.2024.1494609","DOIUrl":"10.3389/fchem.2024.1494609","url":null,"abstract":"<p><p>The reaction of MnCl₂·4H₂O with HL ((1-methyl-1H-imidazol-2-yl)methanol) and pdH₂ (1, 3 propanediol) in a basic MeCN solution results in the formation of a mixed-valence [Mn₂₀] cationic cluster and two [Mn^IICl₄] counter anions. The metallic skeleton of the cluster describes two geometrically equivalent mixed-valent, linked [Mn^III ₆Mn^II ₄] supertetrahedra in which nearest-neighbor metal ions have a different oxidation state. Magnetic susceptibility, magnetization data and heat capacity measurements support evidence of predominant ferromagnetic correlations, leading to a <i>s</i> = 22 spin ground state for the [Mn^III ₆Mn^II ₄] supertetrahedra, which are pair-linked by a weak antiferromagnetic coupling. The properties are discussed in the context of the magnetocaloric effect and the potential application of this compound in cryogenic refrigeration.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1494609"},"PeriodicalIF":3.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11560423/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142617415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"<i>Aspidosperma nitidum</i> reduces parasite load and modulates cytokines in BALB/c mice infected with <i>Leishmania</i> (Leishmania) <i>amazonensis</i>.","authors":"Heliton Patrick Cordovil Brígido, Everton Luiz Pompeu Varela, Antônio Rafael Quadros Gomes, Jorddy Neves Cruz, Juliana Correa-Barbosa, José Edson de Sousa Siqueira, Cristian Kallahan Silva Chagas, Andrey Moacir do Rosário Marinho, Liliane Almeida Carneiro, Márlia Regina Coelho-Ferreira, Sandro Percário, Maria Fâni Dolabela","doi":"10.3389/fchem.2024.1492770","DOIUrl":"10.3389/fchem.2024.1492770","url":null,"abstract":"<p><p>The lack of vaccines shows the need for alternative leishmaniasis treatments. <i>In vitro</i> study previously demonstrated the leishmanicidal activity of <i>A. nitidum</i> extracts. This study describes for the first time, the antileishmanial activity of <i>A. nitidum</i> extracts in infected Balb/c mice and its immunomodulatory effect. The extract (EE) was obtained by maceration of the peel powder with ethanol, which was fractionated by acid-base partition, originating the alkaloid (FA) and neutral (FN) fractions. EE and FA were analyzed using mass spectroscopy. Daily intragastric treatment was performed with EE and FA, at doses of 200 mg/kg and 400 mg/kg, in Balb/c mice with 28 days of infection by <i>Leishmania amazonensis</i>. A thickness gauge was used to assess the progression of the lesion and the MTT method to determine the parasite load in the spleen. The quantification of IL-10 and IFN-γ was performed by ELISA. Analysis of the mass spectrum of EE indicated the presence of the alkaloids corynantheol and yohimbine, while in FA the alkaloid dihydrocorynantheol was identified. To elucidate the mode of interaction of these alkaloids with the TR protein, molecular target of antileishmanial drugs, we used molecular modeling approaches such as docking, molecular dynamics simulations and free energy affinity. Treatment with EE for 28 days at the highest dose tested, significantly reduced the size of the lesion. EE and FA after 28 days of treatment showed dose-dependent antileishmanial activity, which reduced the parasite load in the spleen of infected mice by 42.5% and 22.1%, respectively. Both EE and FA presented immunomodulatory effect, as they decreased IL-10 expression and increased IFN-y levels. The effectiveness of <i>A. nitidum</i> in the treatment of cutaneous leishmaniasis was proven in this study. The results obtained <i>in silico</i> demonstrated that the compounds are capable of interacting with the catalytic residues of the TR. The affinity energy results demonstrated that the complexes formed are favorable for enzymatic inhibition. The alkaloids present in the plant have demonstrated not only antileishmanial activity, but also the ability to modulate the host's immune response. These promising results open perspectives for developing more effective and comprehensive treatments against cutaneous leishmaniasis.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1492770"},"PeriodicalIF":3.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11565433/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142647415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Laser-induced graphene gas sensors for environmental monitoring.","authors":"Cadré Francis, Attila Rektor, Tony Valayil-Varghese, Nicholas McKibben, Isaac Estrada, Jennifer Forbey, David Estrada","doi":"10.3389/fchem.2024.1448205","DOIUrl":"10.3389/fchem.2024.1448205","url":null,"abstract":"<p><p><i>Artemesia tridentata</i> is a foundational plant taxon in western North America and an important medicinal plant threatened by climate change. Low-cost fabrication of sensors is critical for developing large-area sensor networks for understanding and monitoring a range of environmental conditions. However, the availability of materials and manufacturing processes is still in the early stages, limiting the capacity to develop cost-effective sensors at a large scale. In this study, we demonstrate the fabrication of low-cost flexible sensors using laser-induced graphene (LIG); a graphitic material synthesized using a 450-nm wavelength bench top laser patterned onto polyimide substrates. We demonstrate the effect of the intensity and focus of the incident beam on the morphology and electrical properties of the synthesized material. Raman analyses of the synthesized LIG show a defect-rich graphene with a crystallite size in the tens of nanometers. This shows that the high level of disorder within the LIG structure, along with the porous nature of the material provide a good surface for gas adsorption. The initial characterization of the material has shown an analyte response represented by a change in resistance of up to 5% in the presence of volatile organic compounds (VOCs) that are emitted and detected by <i>Artemisia</i> species. Bend testing up to 100 cycles provides evidence that these sensors will remain resilient when deployed across the landscapes to assess VOC signaling in plant communities. The versatile low-cost laser writing technique highlights the promise of low-cost and scalable fabrication of LIG sensors for gas sensor monitoring.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1448205"},"PeriodicalIF":3.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11560773/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142617246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Predicting the solubility of CO₂ and N₂ in ionic liquids based on COSMO-RS and machine learning.","authors":"Hongling Qin, Ke Wang, Xifei Ma, Fangfang Li, Yanrong Liu, Xiaoyan Ji","doi":"10.3389/fchem.2024.1480468","DOIUrl":"10.3389/fchem.2024.1480468","url":null,"abstract":"<p><p>As ionic liquids (ILs) continue to be prepared, there is a growing need to develop theoretical methods for predicting the properties of ILs, such as gas solubility. In this work, different strategies were employed to obtain the solubility of CO₂ and N₂, where a conductor-like screening model for real solvents (COSMO-RS) was used as the basis. First, experimental data on the solubility of CO₂ and N₂ in ILs were collected. Then, the solubility of CO₂ and N₂ in ILs was predicted using COSMO-RS based on the structures of cations, anions, and gases. To further improve the performance of COSMO-RS, two options were used, i.e., the polynomial expression to correct the COSMO-RS results and the combination of COSMO-RS and machine learning algorithms (eXtreme Gradient Boosting, XGBoost) to develop a hybrid model. The results show that the COSMO-RS with correction can significantly improve the prediction of CO₂ solubility, and the corresponding average absolute relative deviation (AARD) is decreased from 43.4% to 11.9%. In contrast, such an option cannot improve that of the N₂ dataset. Instead, the results obtained from coupling machine learning algorithms with the COSMO-RS model agree well with the experimental results, with an AARD of 0.94% for the solubility of CO₂ and an average absolute deviation (AAD) of 0.15% for the solubility of N₂.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1480468"},"PeriodicalIF":3.8,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11560425/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142617433","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Flexible highly-sensitive pressure sensor based on rGO/Fe nanowires composites for wearable human health detection.","authors":"Liang Cao, Rui Wu, Hong Xiang, Xiaodong Wu, Xiaoyan Hu, Gaohui He, Yingang Gui","doi":"10.3389/fchem.2024.1477651","DOIUrl":"10.3389/fchem.2024.1477651","url":null,"abstract":"<p><p>Flexible pressure sensors applied in wearable detection often face challenges, such as low sensitivity, large device size, poor flexibility, and long response time. This study aims to design and develop high-performance pressure-sensitive materials for wearable human detection applications. Using a sensitive layer composite and microstructural design, rGO/Fe nanowires (NWs) composites were proposed as the pressure-sensitive material. This approach yields a compact sensor with high flexibility, good mechanical properties, and excellent sensing performance. Firstly, rGO/Fe NWs composites were prepared by the Hummers method and an <i>in situ</i> reduction technique under a magnetic field. Secondly, the structural design, component construction, and sensing mechanism of the sensors were thoroughly investigated. Finally, the performance of the flexible pressure sensor was tested, and its application in the wearable field was explored. The results demonstrate that the sensor exhibits excellent performance with a good response to both large and small pressures within the range of 0-30 kPa, providing an effective method for wearable human health detection.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1477651"},"PeriodicalIF":3.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11557412/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142617309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hybrid Pd_0.1Cu_0.9Co₂O₄ nano-flakes: a novel, efficient and reusable catalyst for the one-pot heck and Suzuki couplings with simultaneous transesterification reactions under microwave irradiation.","authors":"Ashok Raj Patel, Gurupada Maity, Tanmay K Pati, Laksmikanta Adak, Christopher L Cioffi, Subhash Banerjee","doi":"10.3389/fchem.2024.1496234","DOIUrl":"10.3389/fchem.2024.1496234","url":null,"abstract":"<p><p>We report the fabrication of a novel spinel-type Pd₀.₁Cu₀.₉Co₂O₄ nano-flake material designed for Mizoroki-Heck and Suzuki coupling-cum-transesterification reactions. The Pd₀.₁Cu₀.₉Co₂O₄ material was synthesized using a simple co-precipitation method, and its crystalline phase and morphology were characterized through powder XRD, UV-Vis, FESEM, and EDX studies. This material demonstrated excellent catalytic activity in Mizoroki-Heck and Suzuki cross-coupling reactions, performed in the presence of a mild base (K₂CO₃), ethanol as the solvent, and microwave irradiation under ligand-free conditions. Notably, the Heck coupling of acrylic esters proceeded concurrently with transesterification using various alcohols as solvents. The catalyst exhibited remarkable stability under reaction conditions and could be recycled and reused up to ten times while maintaining its catalytic integrity.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"12 ","pages":"1496234"},"PeriodicalIF":3.8,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11557397/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142617334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}