Frontiers in Chemistry最新文献

{"title":"Valorization of natural adsorbents for removing chromium (VI) from industrial wastewater: a review.","authors":"Hajira Haroon, Tayyab Ashfaq Butt, Jehanzeb Ali Shah, Alin Ciobica, Laura Ecaterina Romila, Vasile Burlui, Hamida Bibi, Muhammad Bilal","doi":"10.3389/fchem.2025.1608863","DOIUrl":"10.3389/fchem.2025.1608863","url":null,"abstract":"<p><p>Chromium (Cr(VI)) is often released from various industries in excess in developing countries, which constitutes non-compliance with environmental regulations. This metal is hazardous for the aquatic ecosystem and is responsible for toxicity, carcinogenicity, and mutagenicity in humans. Adsorption is an effective and relatively inexpensive approach for treating the excess Cr(VI) compared to conventional methods. Commercially available adsorbents cannot be considered economical yet for industrial applications, which has alternatively resulted in the use of natural adsorbents. The current study focuses on Cr(VI) removal using low-cost natural adsorbents and discusses the different conditions used for such treatments. Previous studies have shown the following order of average Cr(VI) removal using different adsorbents: leaves > bark > agriculture > dry shell > tea = fungi > yeast > algae > sawdust > bacteria. Moreover, acid modification has been reported to offer the best results. The adsorption data are best fitted to both the Langmuir and Freundlich isotherms. Hence, the abovementioned low-cost natural biomasses hold promising potential for Cr(VI) removal from wastewater, whose removal efficiency can be improved by adopting economical and effective pretreatment techniques. Literature also shows that leaves are more efficient and economical for Cr(VI) removal without pretreatment from among the various available bulk biomasses. The present review is expected to provide guidance for low-cost treatment of Cr(VI) at the industrial scale.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1608863"},"PeriodicalIF":3.8,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12198968/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144505343","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":"A systematic review of sensors to combat crime and routes to further sensor development.","authors":"Alice E Cozens, Shane D Johnson, Tung-Chun Lee","doi":"10.3389/fchem.2025.1568867","DOIUrl":"10.3389/fchem.2025.1568867","url":null,"abstract":"<p><p>Forensic science plays an important part in crime reduction but faces many challenges. These include the validity, cost and complexity of current sensors used, and a reliance on trained professionals to conduct analyses. Recent advances in sensor technologies present a promising opportunity for rapid, decentralized, and cost-effective analysis by untrained individuals in the field. To date, a comprehensive systematic review covering sensing technologies and use cases has been lacking. This paper addresses that gap. After the initial screening of papers, 1,482 publications were included in the review, from which data on target analytes and sensing technologies were extracted. Given that law enforcement have limited resources, a second screening examined papers that focused on low-cost sensing devices published from 2020 onwards (N = 791). Overall, our review identified eleven key analyte categories that had been researched: illicit drugs, fingerprints, explosives, body fluids, food safety, poisons and toxins, pollutants, counterfeits and documentation, fire, gunshot, and others. Low-cost sensing technologies identified were categorised into electrochemical, colourimetric, immunoassay, luminescence and SERS. We review trends in the research reported, barriers to commercialisation and adoption, and review the use of these types of sensors by law enforcement agencies. Current sensors used by authorities face challenges of high costs, specificity issues, limited detection capabilities and complex sample preparation. Emerging research focuses on cost-effective printed electrodes and dual detection techniques to enhance analyte sensitivity and detection accuracy. Notably, body fluid analysis plays a crucial role in criminal cases, but current sensors suffer issues like false positives, DNA degradation, and high costs. Studies investigating eco-friendly materials and dual-detection approaches show promise in addressing these issues. Illicit drug analysis constitutes over one-third (36%) of included publications. In the UK, police rely on NIK tests and DrugWipe sensors for on-site drug detection, but challenges related to sensitivity, specificity, and confirmatory testing persist. Ongoing research explores dual detection methods, lateral flow immunoassays, and electro-chemiluminescent screening to enhance specificity and matrix tolerance. Future efforts should prioritise refining dual detection methods, reducing matrix interference, low-cost/eco-friendly materials and fostering collaboration between academia and law enforcement for effective implementation in these areas.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1568867"},"PeriodicalIF":3.8,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12198248/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144505342","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>In silico</i> molecular studies of Phosphinogold(I) thiocarbohydrate complexes: insights into multi-target anticancer mechanisms.","authors":"Alkhair Adam Khalil Mohamed, Isaac Asiamah, Ghazi Elamin, James Darkwa, Christian K Adokoh","doi":"10.3389/fchem.2025.1533026","DOIUrl":"10.3389/fchem.2025.1533026","url":null,"abstract":"<p><strong>Introduction: </strong>This study employed in silico methods to investigate the anticancer potential and mechanisms of twenty novel phosphinogold(I) thiocarbohydrate complexes.</p><p><strong>Methods: </strong>Molecular docking and Prime MM-GBSA screening of seventeen cancer-related protein targets, including Human Double Minute 2 protein (HDM2), DNA methyltransferase-1 (DNMT1), Protein Kinase B (AKT2), and Poly (ADP-ribose) polymerase 1 (PARP-1), were conducted. Molecular dynamics simulations were performed for complex <b>9</b>.</p><p><strong>Results: </strong>Virtual screening revealed strong binding affinities for several complexes, often surpassing native ligands. All the complexes except <b>16</b>, <b>18</b>, and <b>19</b> exhibited strong binding affinity with one or two cancer protein targets compared to native ligands. Complex <b>9</b> emerged as the best candidate, demonstrating promising binding affinity particularly against AKT2 (-82.40 kcal/mol) and PARP-1 (-75.7 kcal/mol). Molecular dynamics simulations of complex <b>9</b> with PARP-1 and AKT2 revealed distinct binding profiles, with a more stable interaction with PARP-1, suggesting its potential for disrupting DNA repair mechanisms. Binuclear complexes generally exhibited higher affinities than mononuclear counterparts, particularly for DNMT1 and HDM2. Complex <b>13</b> demonstrated high <i>in vitro</i> activity against prostate, colon, and breast cancer cell lines (IC50 = 0.03, 0.25, and 0.07 μM respectively), collaborating with a significant interaction with Human Epidermal Growth Factor Receptor 2 (HER2) (-71.15 kcal/mol binding affinity) <i>in silico</i>. While acetylation decreased binding affinity; it enhanced cellular activity as reported in <i>in vitro</i> studies indicative of the need to balance lipophilicity and binding strength in future ligand design.</p><p><strong>Discussion: </strong>These findings provide valuable insights into multi-target anticancer mechanisms, with a particular emphasis on complex <b>9</b> as a potential PARP-1 inhibitor, and guide future optimization and experimental validation of these novel gold-based complexes. The stable interaction of complex <b>9</b> with PARP-1 highlights PARP-1 as a particularly promising therapeutic target. Binuclear complexes' superior affinities for DNMT1 and HDM2 suggest structural advantages for multi-target inhibition.</p><p><strong>Conclusion: </strong>The paradoxical effect of acetylation underscores the importance of balancing lipophilicity and binding strength in ligand design.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1533026"},"PeriodicalIF":3.8,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12198200/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144505341","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":"Effect of acid washing and torrefaction combined pretreatment on the properties of waste tobacco stem biomass and the quality of pyrolysis bio-oil.","authors":"Anni Wang, Jianhang Hu, Long Zhang, Hua Wang","doi":"10.3389/fchem.2025.1603584","DOIUrl":"10.3389/fchem.2025.1603584","url":null,"abstract":"<p><p>Aiming at the issues of low yield and poor quality of bio-oil obtained from direct pyrolysis of biomass, in this study, waste tobacco stems (TS) were used as raw materials, and the pretreatment methods of torrefaction and acid washing were adopted to study the effects of different torrefaction temperatures and pretreatment sequences on the quality of TS biomass and bio-oil. Results showed that combined pretreatment synergistically integrated deoxygenation from torrefaction and deashing from acid washing. High-temperature torrefaction-based combined pretreatment reduced TS oxygen content from 54.83% to 20.14%. Acid washing pretreatment achieved more than 90% removal of inorganic elements (K, Cl and Mg). The order of combined pretreatment also had an important influence on biomass pyrolysis. Torrefaction-acid washing pretreatment decreased ash content of TS, increased the relative content of sugars and aromatic compounds in bio-oil, reduced alcohols and ketones relative contents, and improved bio-oil higher heating value (HHV) and pH. Acid washing-torrefaction pretreatment enhanced bio-oil productivity, increased nitrogen-containing compounds and phenols relative content, reduced acids and aldehydes contents, and lowered bio-oil water and ash contents. Additionally, with the increase in torrefaction temperature, the O/C molar ratio of TS decreased, the HHV of TS increased, and the thermal cracking of nicotine in bio-oil to generate pyridine compounds was promoted. This study demonstrates a viable pathway to convert TS into high-quality fuels and bio-oil via combined pretreatment, offering new insights for optimizing biomass pyrolysis technology and enhancing resource utilization efficiency.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1603584"},"PeriodicalIF":3.8,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12187669/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144495605","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":"Two-dimensional QSAR-driven virtual screening for potential therapeutics against <i>Trypanosoma cruzi</i>.","authors":"Naseer Maliyakkal, Sunil Kumar, Ratul Bhowmik, Harish Chandra Vishwakarma, Prabha Yadav, Bijo Mathew","doi":"10.3389/fchem.2025.1600945","DOIUrl":"10.3389/fchem.2025.1600945","url":null,"abstract":"<p><p><i>Trypanosoma cruzi</i> is the cause of Chagas disease (CD), a major health issue that affects 6-7 million individuals globally. Once considered a local problem, migration and non-vector transmission have caused it to spread. Efforts to eliminate CD remain challenging due to insufficient awareness, inadequate diagnostic tools, and limited access to healthcare, despite its classification as a neglected tropical disease (NTD) by the WHO. One of the foremost concerns remains the development of safer and more effective anti-Chagas therapies. In our study, we developed a standardized and robust machine learning-driven QSAR (ML-QSAR) model using a dataset of 1,183 <i>Trypanosoma cruzi</i> inhibitors curated from the ChEMBL database to speed up the drug discovery process. Following the calculation of molecular descriptors and feature selection approaches, Support Vector Machine (SVM), Artificial Neural Network (ANN), and Random Forest (RF) models were developed and optimized to elucidate and predict the inhibition mechanism of novel inhibitors. The ANN-driven QSAR model utilizing CDK fingerprints exhibited the highest performance, proven by a Pearson correlation coefficient of 0.9874 for the training set and 0.6872 for the test set, demonstrating exceptional prediction accuracy. Twelve possible inhibitors with pIC₅₀ ≥ 5 were further identified through screening of large chemical libraries using the ANN-QSAR model and ADMET-based filtering approaches. Molecular docking studies revealed that F6609-0134 was the best hit molecule. Finally, the stability and high binding affinity of F6609-0134 were further validated by molecular dynamics simulations and free energy analysis, bolstering its continued assessment as a possible treatment option for Chagas disease.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1600945"},"PeriodicalIF":3.8,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12188446/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144495609","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":"The role of intrinsically disordered regions of SARS-CoV-2 nucleocapsid and non-structural protein 1 proteins.","authors":"Getasew Shitaye, Nataliia Ventserova, Gianluca D'Abrosca, Martina Dragone, Eunice Wairimu Maina, Roberto Fattorusso, Rosa Iacovino, Luigi Russo, Carla Isernia, Gaetano Malgieri","doi":"10.3389/fchem.2025.1597656","DOIUrl":"10.3389/fchem.2025.1597656","url":null,"abstract":"<p><p>Virus survival inside the host cell depends on the intricate mechanisms that recruit proteins involved in the arms race. Severe Acute Respiratory Syndrome Coronavirus-2 (SARS-CoV-2) proteome exhibits important levels of structural order. However, some of the SARS-CoV-2 proteins, such as the Nucleocapsid (N) and Non-structural protein 1 (Nsp1), contain a considerably significant amount of intrinsically disordered regions (IDRs) that play indispensable roles in the intra-viral and virus-host interaction. Here, focusing on proteins that contain a relevant percentage of IDRs, we discuss experimental and computational studies sought to support IDRs as a key player in the interplay with ordered domains, the biological role as potential origin for variants of SARS-CoV-2, and their association with virus transmissibility. Furthermore, we also highlight the potential involvement of IDRs in the viral-host protein interaction and host cellular machinery. Thus, shading lights on the dark proteome of the virus and looking for therapeutic approaches beyond the classic structure-function paradigm may contribute to the efforts sparking the quest for therapeutics.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1597656"},"PeriodicalIF":3.8,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12187666/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144495608","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":"Computational methodology and molecular dynamics analysis of andrographolide bioactivity against <i>Cutibacterium acnes</i>.","authors":"Min Lin, Lihui He, Guodong Ye, Xiaotian Zhao","doi":"10.3389/fchem.2025.1627758","DOIUrl":"10.3389/fchem.2025.1627758","url":null,"abstract":"<p><p><i>Cutibacterium acnes</i> (formerly known as <i>Propionibacterium acnes</i>) is a Gram-positive anaerobic bacterium that is frequently found in sebaceous glands and human skin hair follicles. Although it is a normal component of the skin microbiota, acne may result from its overgrowth in specific situations. Andrographis paniculate, a traditional Chinese herb, contains a diterpenoid compound called andrographolide (AGP), which has anti-inflammatory, antibacterial and antioxidant. AGP can strengthen the skin barrier functions by preventing the release of inflammatory factors like TNF-α and IL-6. It has also shown that its antibacterial qualities can inhibit pathogens such as <i>Cutibacterium acnes.</i> In this study, through the use of the quantum chemistry approach, we investigated AGP in DMSO and gas phase, in connection to the geometric foundations and energy dynamics by Density Functional Theory (DFT). Furthermore, this work has been carried out on the structural analysis by orbital examination and electrostatic potential (ESP) assessment. Subsequently, we derived the molecular interactions utilizing the independent gradient model within Hirshfeld molecular density partitioning (IGMH). Additionally, the stability and interaction of AGP and fusidic acid with the protein _CAlipase of <i>Cutibacterium acnes</i> have been investigated by molecular docking and molecular dynamics simulations. This study might provide a fresh perspective for investigating an effective extraction process via methodological analytical discussions.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1627758"},"PeriodicalIF":3.8,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12187781/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144495604","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":"Molecular functional mechanisms of two alcohol acetyltransferases in <i>Lavandula x intermedia</i> (lavandin).","authors":"Dafeng Liu, Yanyan Du, Ablikim Abdiriyim, Lvxia Zhang, Daoqi Song, Huashui Deng, Xiongying Wen, Yanyan Zhang, Bingwang Sun","doi":"10.3389/fchem.2025.1627286","DOIUrl":"10.3389/fchem.2025.1627286","url":null,"abstract":"<p><p>Volatile esters are key flavor components in most plants, including <i>Lavandula x intermedia</i> (lavandin). The final step in ester biosynthesis is catalyzed by <i>Lavandula x intermedia</i> alcohol acyltransferases (LiAATases), which attach alcohols to acyl groups. However, the functional role and mechanism of LiAATases remain poorly understood. Here, we predicted their structural models using AlphaFold2 and identified potential active site residues through the GalaxyWEB program. Catalytic assays were optimized at pH 7.5 and 30 °C. Substrate specificity for alcohols was assessed for both enzymes. Gene expression analysis revealed that <i>LiAATase1</i> and <i>LiAATase2</i> were most highly expressed in the petals and pistils, respectively, with peak expression occurring at stage 4 for <i>LiAATase1</i> and stage 1 for <i>LiAATase2</i>. Our study aims to elucidate the functional properties of alcohol acyltransferases in <i>Lavandula x intermedia</i>, contributing to an understanding of ester biosynthesis and specificity in this species.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1627286"},"PeriodicalIF":3.8,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12187743/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144495607","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":"Effective removal of naphthalene from water using bacteria and bacteria-load carrier materials.","authors":"Kui Liu, Wen-Chieh Cheng, Yi-Xin Xie, Lin Wang, Zhong-Fei Xue, Bowen Yang, Hao Zhang, Jia Min, Miao Yao","doi":"10.3389/fchem.2025.1597470","DOIUrl":"10.3389/fchem.2025.1597470","url":null,"abstract":"<p><p>The volatilization of naphthalene unavoidably poses significant risks to health, the environment, and safety. Traditional remediation approaches have been criticized for their inefficiency in removing naphthalene and transforming its toxicity. This study proposed a bacteria-loaded carrier material and evaluated its degradation efficiency compared to that of free bacteria. High concentrations made it more challenging for <i>Microbacterium paraoxydans</i> (ms) to achieve effective degradation of naphthalene. Additionally, the degradation process was not timely, thereby exacerbating the risks associated with the volatilization of naphthalene. Three carrier materials-activated carbon (AC), calcium alginate (CA), and composite gel beads (CO)-were evaluated for their adsorption, biocompatibility, and thermal stability. CO's adsorption of naphthalene occurred mainly through chemisorption, with π-π conjugation and Ca-π interaction enhancing the adsorption process. The adsorption peaks did not exhibit any shifts after the involvement of bacteria, indicating the best biocompatibility among the carrier materials, despite having the second lowest total weight loss (CA > CO > AC) during the heating process. The salicylic acid pathway and the phthalic acid pathway were involved in the degradation of naphthalene. No signs of naphthalene were seen in the samples from confocal laser scanning microscope (CLSM) tests, indicating that ms fully degraded naphthalene after its adsorption. While ms degraded naphthalene on day 4 for 50 mg/L and 100 mg/L concentrations, 31.2 mg/L remained for the 200 mg/L concentration. In contrast, ms-loaded CO degraded most of the naphthalene on day 1, with only 2.8 mg/L remaining from the initial 200 mg/L concentration. This study underscored the relative merits of applying ms-loaded CO to the degradation of naphthalene.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1597470"},"PeriodicalIF":3.8,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12187639/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144495606","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":"Atomistic simulation of olefin polymerization reaction by organometallic catalyst: significant role of microscopic structural dynamics of (pyridylamido) Hf(IV) complex in catalytic reactivity.","authors":"Kentaro Matsumoto, Nana Misawa, Shuhei Kanesato, Masataka Nagaoka","doi":"10.3389/fchem.2025.1618025","DOIUrl":"10.3389/fchem.2025.1618025","url":null,"abstract":"<p><p>Understanding the microscopic catalytic mechanism of the olefin polymerization reaction is crucial for the rational design of next-generation catalysts. However, the dynamic nature of the active species, including the fluctuations of the ion pair structure and the orientation of substituents, presents significant challenges for theoretical approaches. In this paper, we present an overview of our recent computational studies on the role of the structural dynamics of the active species of olefin polymerization catalyst in determining reactivity, especially focusing on a novel olefin polymerization catalyst (pyridylamido) Hf(IV) complex. Utilizing the molecular dynamics method and our Red Moon method, a novel methodology we have developed for atomistic simulation of complex chemical reaction systems, we elucidate how the dynamic features, including anion coordination and steric interaction, govern the reactivity in key steps such as ligand modification and propagation reactions. In addition, we demonstrate how machine learning techniques can be applied to extract chemically meaningful descriptors from the structural ensemble obtained from atomistic simulation data of complex chemical reaction systems, thereby identifying the substituents that play an important role in propagation reactions. Our studies highlight the importance of incorporating molecular-level dynamic features of catalysts into mechanistic models.</p>","PeriodicalId":12421,"journal":{"name":"Frontiers in Chemistry","volume":"13 ","pages":"1618025"},"PeriodicalIF":3.8,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12185512/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144483764","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}