Molecules最新文献

{"title":"Bio-Based Polyurethane Asphalt Binder with Continuous Polymer-Phase Structure: Critical Role of Isocyanate Index in Governing Thermomechanical Performance and Phase Morphology.","authors":"Haocheng Yang, Suzhou Cao, Chengwei Wu, Zhonghua Xi, Jun Cai, Zuanru Yuan, Junsheng Zhang, Hongfeng Xie","doi":"10.3390/molecules30112466","DOIUrl":"10.3390/molecules30112466","url":null,"abstract":"<p><p>Polyurethane asphalt (PUA) has attracted considerable attention in the field of pavement engineering. However, traditional PUA systems typically exhibit low concentrations of polyurethane (PU), leading to a continuous bitumen-dominated phase that adversely affects mechanical properties. Furthermore, the non-renewable nature of raw materials raises environmental concerns. To address these limitations, this study developed an eco-friendly and cost-efficient bio-based PUA binder (PUAB) featuring a continuous high-biomass PU matrix (over 70% biomass) and a high bitumen content (60 wt%). The effects of the isocyanate index (NCO/OH ratio) on the cure kinetics, rheological behavior (rotational viscosity over time), viscoelasticity, damping capacity, phase morphology, thermal stability, and mechanical performance were systematically investigated using Fourier-transform infrared spectroscopy, dynamic mechanical analysis, laser-scanning confocal microscopy, and tensile testing. Key findings revealed that while the rotational viscosity of PUABs increased with a higher isocyanate index, all formulations maintained a longer allowable construction time. Specifically, the time to reach 1 Pa·s for all PUABs at 120 °C exceeded 60 min. During curing, higher isocyanate indices reduced final conversions but enhanced the storage modulus and glass transition temperatures, indicating improved rigidity and thermal resistance. Phase structure analysis demonstrated that increasing NCO/OH ratios reduced bitumen domain size while improving dispersion uniformity. Notably, the PUAB with the NCO/OH ratio of 1.3 achieved a tensile strength of 1.27 MPa and an elongation at break of 238%, representing a 49% improvement in toughness compared to the counterpart with an NCO/OH ratio = 1.1. These results demonstrate the viability of bio-based PUAB as a sustainable pavement material, offering a promising solution for environmentally friendly infrastructure development.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12157612/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anticancer Effects of Withanolides: In Silico Prediction of Pharmacological Properties.","authors":"Gustavo Werneck de Souza E Silva, André Mesquita Marques, André Luiz Franco Sampaio","doi":"10.3390/molecules30112457","DOIUrl":"10.3390/molecules30112457","url":null,"abstract":"<p><p>Withanolides are a class of naturally occurring C-28 ergostane steroidal lactones with an abundance of biological activities, and their members are promising candidates for antineoplastic drug development. The ADMET properties of withanolides are still largely unknown, and in silico predictions can play a crucial role highlighting these characteristics for drug development, shortening time and resources spent on the development of a drug lead. In this work, ADMET properties of promising antitumoral withanolides were assessed. Each chemical structure was submitted to the prediction tools: SwissADME, pkCSM-pharmacokinetics, admetSAR v2.0, and Molinspiration Cheminformatics. The results indicate a good gastrointestinal absorption rate, inability to cross the blood-brain barrier, CYP3A4 metabolization, without inhibition of other P450 cytochromes, high interaction with nuclear receptors, and a low toxicity. It was also predicted for the inhibition of pharmacokinetics transporters and some ecotoxicity. This demonstrates a viability for oral drug development, with low probabilities of side effects.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156425/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285560","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modeling of the General Trends of Reactivity and Regioselectivity in Cyclopentadiene-Nitroalkene Diels-Alder Reactions.","authors":"Adrianna Fałowska, Stanisław Grzybowski, Daniel Kapuściński, Karol Sambora, Agnieszka Łapczuk","doi":"10.3390/molecules30112467","DOIUrl":"10.3390/molecules30112467","url":null,"abstract":"<p><p>This study presents a theoretical investigation of the electronic properties of mono- and pentasubstituted cyclopentadiene analogs and variously substituted conjugated nitroalkenes bearing electron-donating and electron-withdrawing groups. Conceptual Density Functional Theory (CDFT) and Electron Localization Function (ELF) analyses were employed to characterize the global and local reactivity indices of the reactants. The obtained data provided insights into the nucleophilic and electrophilic nature of the investigated systems, allowing for the prediction of their reactivity patterns in Diels-Alder reactions. A reactivity model for conjugated alkenes toward cyclopentadienes was developed based on correlation analysis using Hammett substituent constants. This approach enabled the prediction of reaction polarity in (4+2) cycloaddition processes, providing insight into how the electronic effects of substituents influence the reaction course. These findings contribute to a deeper understanding of structure-reactivity relationships in Diels-Alder processes.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156356/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285691","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Anti-Inflammatory Activity of Thymol and Thymol-Rich Essential Oils: Mechanisms, Applications, and Recent Findings.","authors":"Custódia Gago, Ana Serralheiro, Maria da Graça Miguel","doi":"10.3390/molecules30112450","DOIUrl":"10.3390/molecules30112450","url":null,"abstract":"<p><p>Thymol, a monoterpenoid phenol present in the essential oils of several aromatic plants, has attracted considerable attention for its anti-inflammatory effects, often in combination with other bioactive compounds. This work explores the mechanisms behind the anti-inflammatory activity of thymol and thymol-rich essential oils, summarizing recent experimental findings. Inflammation, a key factor in numerous chronic diseases, can be modulated by targeting essential molecular pathways, such as MAPK, NF-<i>κ</i>B, JAK/STAT, and arachidonic acid signaling. Thymol has been shown to influence these pathways, reducing the production of pro-inflammatory cytokines and mediators. Beyond its anti-inflammatory effects, thymol also exhibits a broad range of biological activities, including antimicrobial, antioxidant, and anticancer properties. The applications of thymol and thymol-containing essential oils in therapeutic formulations, food additives, and veterinary medicine are also reviewed. Despite promising preclinical results, challenges such as low bioavailability and toxicity at high doses limit their clinical use. Recent developments in drug delivery systems, such as encapsulation in micro- and nanoparticles, are suggested as strategies to enhance efficacy. Additionally, the synergistic effects of thymol with other natural products are examined, offering the potential for improved therapeutic outcomes.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12155930/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285562","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Finely Designing Dicarboxylic Acid-Based Protic Ionic Liquids System for Tailoring Lignin Structure via Demethylation Strategy.","authors":"Cheng Li, Xinyu Xiao, Qizhen Luo, Wanting Zhao, Wenzhe Xiao, Ling-Ping Xiao, Yao Tong, Shangru Zhai, Jian Sun","doi":"10.3390/molecules30112445","DOIUrl":"10.3390/molecules30112445","url":null,"abstract":"<p><p>As one kind of renewable aromatic polymer, lignin is severely underused due to its chemical recalcitrance. Lignin can endure demethylation modification to improve its activation by releasing more active functional groups. However, the process suffers from expensive, corrosive, and toxic issues by employing halogen-containing reagents, which has become an obstacle to industrial applications. Herein, a series of dicarboxylic acid-based protic ionic liquids (DAPILs) systems composed of ethanolamine and dibasic organic acids (e.g., aspartic acid (Asp), glutamic acid (Glu), succinic acid (SA), and glutaric acid (GA)) with 1~2:1 stoichiometric ratio, have been finely designed for the demethylation of industrial lignin. With [EOA][GA] treatment, the polyphenol content in lignin was favorably increased beyond 1.58 times. The structural tailoring and variation were fully characterized by 2D HSQC and ¹H NMR. The analysis results indicated that, with the increase of phenolic hydroxyl content in lignin, the β-<i>O</i>-4' bond was broken and the content of structural units (S, G) and the S/G ratio of lignin decreased accordingly. After the treatment, the used IL and tailored lignin can be recovered over 95%. This novel, halogen-free and environmentally friendly lignin-cutting strategy not only opens avenues for high-value utilization of lignin but also expands the field of application of dicarboxylic acid-based protic ionic liquids.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156136/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Chemical Markers for Differentiating Yellow Prickly Pear (<i>Opuntia ficus-indica</i>) from Southern Greece: Insights from Physicochemical Parameters, Elemental Composition, Antioxidants, and Vitamins.","authors":"Artemis P Louppis, Michael G Kontominas, Michalis S Constantinou, Ioanna S Kosma, Anastasia V Badeka, Georgios Stamatakos","doi":"10.3390/molecules30112448","DOIUrl":"10.3390/molecules30112448","url":null,"abstract":"<p><p>This study presents an innovative approach to differentiate Southern Greek yellow prickly pear samples according to geographical origin based on physicochemical parameters, mineral composition, and bioactive compounds using advanced chemometrics. A total of 56 yellow prickly pear samples were collected from four distinct Greek regions (Crete, Paros, Symi, Peloponnese) during the 2019 and 2020 harvest seasons. A multi-platform analytical strategy was employed, combining classical physicochemical analyses and UV spectrophotometry for total antioxidant activity with cutting-edge techniques such as UPLC-MS/MS for precise quantification of vitamins and antioxidants, and ICP-MS for mineral profiling. In total, thirteen physicochemical parameters, nineteen macro-, micro-, and trace elements, nine vitamins, and seven antioxidants were identified and quantified. Application of MANOVA and Linear discriminant analysis (LDA) revealed that eight physicochemical parameters, ten mineral elements, and sixteen bioactive compounds played a crucial role in sample geographical differentiation. The classification success rates using the cross-validation method were 82.1% for physicochemical parameters, 75.0% for minerals, and an impressive 96.4% for vitamins and antioxidants highlighting the robust tool for the geographical differentiation of Southern Greek yellow prickly pears.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156975/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of a Multigram Synthetic Route to RM-581, an Orally Active Aminosteroid Derivative Against Several Types of Cancers.","authors":"René Maltais, Doriane de Sainte Maresville, Vincent Desrosiers, Donald Poirier","doi":"10.3390/molecules30112441","DOIUrl":"10.3390/molecules30112441","url":null,"abstract":"<p><p>Aminosteroid derivative RM-581 stands out as an anticancer agent, supported by positive in vitro and in vivo studies on resistant cancers of the breast, prostate, and pancreas. A synthetic route has already been developed to obtain aminosteroid RM-581 in small quantities (scale of milligrams to a few grams). However, this route has significant limitations in view of its transposition to scaling up to larger quantities to support late preclinical and clinical trials. Among the problems are the use of toxic reagents, the moderate overall yield, and the need for multiple purifications through chromatographic columns. The development of a new synthetic route has therefore been explored. Starting from commercially available estrone, 2,4-dibromo-estrone was rapidly formed, followed by the regioselective introduction of a nitro group at the C2 position and by the methylation of phenol at the C3 position. The 4-bromo-2-nitro-3-<i>O</i>-methylestrone was then reduced to 2-amino-3-<i>O</i>-methylestrone and the primary amine was used to form the piperazine ring. Once the cyclization step was carried out, the last two steps were identical to the first synthetic route previously reported, i.e., introducing an ethynyl group at the C-17α position and then adding the quinoline-proline side chain with an <i>N</i>-acylation, assisted by a peptide coupling reagent. Importantly, no purification by chromatography was necessary during the whole sequence of reactions and only a final silica gel filtration, followed by recrystallization, led to RM-581 at a very high level of purity. The structure was also fully characterized by 2D NMR analysis.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156004/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285624","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modern Analytical Chemistry Meets Heritage Books: Analysis of Volatile Organic Compounds (VOCs) from Two Books Preserved at the Biblioteca Capitolare of Busto Arsizio.","authors":"Chiara Chiodini, Pierangela Rovellini, Matteo Chiodini, Luca Giacomelli, Daniela Baglio, The B Iiss Torno Working Group","doi":"10.3390/molecules30112447","DOIUrl":"10.3390/molecules30112447","url":null,"abstract":"<p><p>The development of sensitive, non-invasive methods is essential for the preservation and study of heritage books, allowing insights into their historical production processes and conservation needs. Volatile organic compound (VOC) analysis provides a valuable, non-destructive approach to assess paper composition and degradation in historical volumes. In this study, we analyzed VOC emissions from two books preserved at the Biblioteca Capitolare of Busto Arsizio, Italy: a 16th-century Latin grammar book and a 19th-century mathematics handbook for measurement conversions. Using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS), VOCs were sampled after 24 h of storage at room temperature. The results revealed distinct degradation markers: Straight-chain aldehydes, indicative of lipid oxidation, were more prevalent in the 16th-century book, reflecting the higher quality and durability of its rag-based paper. In contrast, elevated furfural levels in the 19th-century book suggest accelerated cellulose hydrolysis typical of wood pulp paper. Additionally, the presence of menthol and anethole in both volumes points to the use of bacteriostatic agents for preservation. These findings not only highlight differences in material composition but also underscore the importance of tailored conservation approaches for historical documents from different eras.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156301/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Quantum Data-Driven Modeling of Interactions and Vibrational Spectral Bands in Cationic Light Noble-Gas Hydrides: [He₂H]⁺ and [Ne₂H]<sup />.","authors":"María Judit Montes de Oca-Estévez, Álvaro Valdés, Rita Prosmiti","doi":"10.3390/molecules30112440","DOIUrl":"10.3390/molecules30112440","url":null,"abstract":"<p><p>Motivated by two of the most unexpected discoveries in recent years-the detection of ArH⁺ and HeH+ noble gas molecules in the cold, low-pressure regions of the Universe-we investigate [He₂H]⁺ and [Ne₂H]⁺ as potentially detectable species in the interstellar medium, providing new insights into their energetic and spectral properties. These findings are crucial for advancing our understanding of noble gas chemistry in astrophysical environments. To achieve this, we employed a data-driven approach to construct a high-accuracy machine-learning potential energy surface using the reproducing kernel Hilbert space method. Training and testing datasets are generated via high-level CCSD(T)/CBS[56] quantum chemistry computations, followed by a rigorous validation protocol to ensure the reliability of the potential. The ML-PES is then used to compute vibrational states within the MCTDH framework, and assign spectral transitions for the most common isotopologues of these species in the interstellar medium. Our results are compared with previously recorded values, revealing that both cations exhibit a prominent proton-shuttle motion within the infrared spectral range, making them strong candidates for telescopic observation. This study provides a solid computational foundation, based on rigorous, fully quantum treatments, aiming to assist in the identification of these yet unobserved He/Ne hydride cations in astrophysical environments.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156169/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Isomeric 3-Pyridinylmethylcoumarins Differ in Erk1/2-Inhibition and Modulation of BV2 Microglia-Mediated Neuroinflammation.","authors":"Rami Schulzki, Matthias Apweiler, Caroline Röttger, Christoph W Grathwol, Nora Struchtrup, Sophia Abou El Mirate, Claus Normann, Stefan Bräse, Bernd L Fiebich","doi":"10.3390/molecules30112452","DOIUrl":"10.3390/molecules30112452","url":null,"abstract":"<p><p>Coumarins are known for their multiple biological effects and have been established as anti-coagulative drugs for years. Furthermore, some coumarins can promote anti-inflammatory effects via the GPR55 receptor, and dual target coumarins have been synthesized. Anti-inflammatory drugs might be beneficial in the treatment of neuropsychiatric disorders, as the inflammatory hypothesis suggests. For the current study, we compared isomeric 3-pyridinylmethylcoumarins with altered N-atom position regarding their effects on cytokine and chemokine synthesis and expression in LPS-stimulated BV2 microglial cells. The 3-pyridin-4-yl-methylcoumarin showed the most potent anti-inflammatory effects, followed by the 3-pyridin-2-ylmethylcoumarin analog. The observed effects might be mediated by an inhibition of ERK phosphorylation.</p>","PeriodicalId":19041,"journal":{"name":"Molecules","volume":"30 11","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12156390/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144285685","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}