ACS Omega最新文献

{"title":"Light-Mediated Antibacterial Activity of Composites of Polypyrrole and Green Zinc Oxide Nanoparticles Synthesized using Sarcomphalus joazeiro Extract","authors":"Milena L. Guimarães,&nbsp;, ,&nbsp;Ricardo F. Ferraz,&nbsp;, ,&nbsp;Raquel A. P. Oliveira,&nbsp;, ,&nbsp;José Galberto M. da Costa,&nbsp;, ,&nbsp;Débora Odília D. Leite,&nbsp;, ,&nbsp;Mateus M. da Costa,&nbsp;, and ,&nbsp;Helinando P. de Oliveira*,&nbsp;","doi":"10.1021/acsomega.5c03456","DOIUrl":"https://doi.org/10.1021/acsomega.5c03456","url":null,"abstract":"<p >The preparation of zinc oxide nanoparticles and zinc oxide-polypyrrole (ZnONPs@PPy) composites can be considered a critical step for enhancement in the antibacterial activity of the synthesized material, established by its electrostatic interactions with the bacterial cell wall. Herein, the reported novelty is based on the biosynthesis of ZnONPs by <i>Sarcomphalus joazeiro</i> and their subsequent incorporation into a composite with polypyrrole for impregnation into cotton fibers, enabling their use in wound dressing applications. The samples were characterized using HPLC, FTIR, SEM, TEM, XRD, and UV–visible spectroscopy, with the band gap determined by the Tauc method. HPLC analysis confirmed the presence of phenolic compounds in the extract applied to reduce ZnONPs. At the same time, FTIR indicated the presence of specific bonds of Zn–O in the synthesized ZnONPs. XRD assays indicated a hexagonal structure of ZnO, with crystallites of 46.69 nm, and TEM showed a distribution of particles with diameters ranging from 12 to 38 nm. By comparison, the UV–vis spectrum confirmed a plasmon band at 368 nm and a reduction in the band gap from 2.97 to 2.88 eV in the composite (ZnONPs@PPy). Antibacterial tests against <i>Escherichia coli</i> and <i>Staphylococcus aureus</i> demonstrated good efficacy of compounds under sunlight exposure, indicating that the smaller band gap width favored the interaction of ZnONPs and PPy with bacterial membranes, with the release of reactive oxygen species enhancing the antimicrobial action, resulting in significant bacterial cell damage and killing.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"43591–43606"},"PeriodicalIF":4.3,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c03456","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195701","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":"Electrocatalytic CO2 Reduction Mechanisms on Two-Dimensional TM2B3 (TM = V, Cr, Fe, Co) Catalysts: A Density Functional Theory Investigation","authors":"Qiyuan Peng,&nbsp;, ,&nbsp;Anjie Chen,&nbsp;, ,&nbsp;Peng Zhou,&nbsp;, ,&nbsp;Yi Sun*,&nbsp;, ,&nbsp;Lijuan Meng,&nbsp;, ,&nbsp;Li Fan*,&nbsp;, and ,&nbsp;Xiuyun Zhang*,&nbsp;","doi":"10.1021/acsomega.5c05206","DOIUrl":"https://doi.org/10.1021/acsomega.5c05206","url":null,"abstract":"<p >The electrocatalytic CO₂ reduction reaction (CO₂RR) can create value-added chemicals and offer a dual solution for addressing climate change and energy crises. MBenes, a class of two-dimensional transition metal borides, exhibit promising potential in catalysis due to their unique electronic properties and uniformly exposed metal sites. Here, we theoretically evaluated the CO₂RR performance of a class of MBene, TM₂B₃ (TM = V, Cr, Fe, Co), monolayers. These materials effectively activated CO₂ due to the significant charge transfer from TM₂B₃ to *CO₂. Among them, Cr₂B₃ exhibits superior catalytic selectivity due to its ability to suppress the competing hydrogen evolution reaction (HER) and its low limiting potential (<i>U</i>_L = −0.31 V) in the process of the conversion of CO₂ to CH₄. Furthermore, the Gibbs free energies of various CO₂RR intermediates show a strong correlation with the *CO adsorption energy, highlighting its pivotal role as a descriptor for predicting the CO₂RR activity in these catalysts.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"44048–44055"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c05206","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195691","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":"Itauba Wood Fiber (Mezilaurus lindaviana) and Itauba Wooden Board: A Survey on the Physical, Chemical, Thermal, and Mechanical Properties","authors":"Heitor Luiz Ornaghi Júnior,&nbsp;, ,&nbsp;Matheus Poletto,&nbsp;, ,&nbsp;Matheus de Prá Andrade*,&nbsp;, ,&nbsp;Francisco Maciel Monticeli,&nbsp;, ,&nbsp;Everton Hillig,&nbsp;, ,&nbsp;Pierre Blanchet,&nbsp;, ,&nbsp;Amirouche Sadaoui,&nbsp;, and ,&nbsp;Ademir José Zattera,&nbsp;","doi":"10.1021/acsomega.5c05179","DOIUrl":"https://doi.org/10.1021/acsomega.5c05179","url":null,"abstract":"<p >The aim of this research is to evaluate the physical, chemical, thermal, and mechanical properties of Itauba (<i>Mezilaurus itauba</i>) wood fiber and Itauba wooden board. The chemical composition presented 33, 29, and 10% lignin, cellulose, and hemicellulose, respectively. The thermal stability was found to be 250 °C for both atmospheres (air and nitrogen), and the simulated TG curve was similar to the one performed on a nitrogen atmosphere. Cone calorimetric results showed a higher steady state when compared to other wood fibers found in the literature with peak heat release rates of 281.762, 424.029, and 482.335 kW/m² when exposed to constant levels of radiant heat flux of 25, 50, and 75 kW/m² at similar weights and densities. Furthermore, X-ray diffraction (13.5% crystallinity) and mechanical tests (flexural and tensile Young’s modulus of 12010 and 969.9 MPa, respectively) were performed on the Itauba wooden board. The tensile results showed to be higher than propylene composites reinforced with 40% wood fiber found in the literature while the storage modulus obtained in the dynamic mechanical thermal analysis found to be higher (11.5 GPa at −130 °C) than most of the commercial thermoplastics used in the industry (polypropylene (9 × 10² MPa), high-density polyethylene (2 × 10³ MPa), and polyvinyl chloride (3000 MPa)). This study showed the potential in using Itauba wooden boards in replacing many commercial products, mainly when an adequate mechanical performance is required.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"44038–44047"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c05179","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195717","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 Reduced Graphene Oxide Film Thickness on a Chemiresistor’s Response to Volatile Organic Compounds and Warfare Agents","authors":"Ilhem Bargaoui,&nbsp;, ,&nbsp;Nabila Bitri,&nbsp;, and ,&nbsp;Jean-Michel Ménard*,&nbsp;","doi":"10.1021/acsomega.5c07277","DOIUrl":"https://doi.org/10.1021/acsomega.5c07277","url":null,"abstract":"<p >We explore the performance of a chemiresistor sensor array based on thin layers of reduced graphene oxide (rGO). The rGO is deposited with a spray coating technique to fabricate three samples of different layer thicknesses, which are characterized by atomic force microscopy (AFM) and Raman spectroscopy. We expose the chemiresistors to water vapor, three volatile organic compounds (VOC), ethanol, acetone, and formaldehyde, and two simulants of chemical warfare agents (CWA), dimethyl–methyl phosphonate (DMMP) and dipropylene glycol monomethyl ether (DPGME). The rGO-based sensors show noticeable changes in resistance upon parts per million variations of the analyte concentrations. The largest detection sensitivity 0.02%/ppm is observed with DPGME. Furthermore, we investigate a thickness-dependent signal that depends on the nature of the analyte. We show that comparing the signal measured with only a few rGO layers of different thicknesses can be used to distinguish formaldehyde from other VOC and DMMP from DPGME. Our findings represent a step toward the development of practical sensor arrays based on low cost, scalable graphene-based materials, enabling both sensitive and selective detection of analytes.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"44642–44650"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c07277","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195741","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":"Multicomposition 3D Printing Using Tunable Ecoflex/Nanosilica Inks for Stretchable Electronics","authors":"Jie Zhang,&nbsp;, ,&nbsp;Qingzhen Zhao,&nbsp;, ,&nbsp;Jianke Du*,&nbsp;, ,&nbsp;Minghua Zhang,&nbsp;, ,&nbsp;Aibing Zhang,&nbsp;, ,&nbsp;Yuan Jin,&nbsp;, ,&nbsp;Licheng Hua,&nbsp;, ,&nbsp;Changshun Huang*,&nbsp;, and ,&nbsp;Guangyong Li*,&nbsp;","doi":"10.1021/acsomega.5c02840","DOIUrl":"https://doi.org/10.1021/acsomega.5c02840","url":null,"abstract":"<p >Additive manufacturing enables the 3D printing of various soft matter structures. Achieving the integrated printing of multicomposition 3D structures, such as ear-like structures containing both hard and soft tissue, has become a research hotspot. However, current multicomposition 3D printing technology still faces numerous challenges, including limited material selection, difficulties in achieving precise transitions between multimodulus regions, and issues with printing accuracy and stability for low-viscosity and fast-curing materials. This study modified Ecoflex by incorporating nanosilica particles and developed a series of Ecoflex/nanosilica composite (ESC) ink formulations suitable for multicomposition 3D printing. The rheological and mechanical properties of ESC inks were thoroughly evaluated, and the weight percentage of nanosilica particles in different Ecoflex types was optimized to identify the most effective formulation. Additionally, 3D printing process parameters were refined to enhance printing accuracy, facilitating the multicomposition printing of complex 3D structures such as hollow columns, nose-like structures, and ear-like structures. These inks were further utilized to print stretchable electronic substrates with strain-isolating properties, and their performance was validated through experimental studies and simulations. The results confirm that the developed ink provides robust technical support for multicomposition 3D integrated printing of stretchable electronics.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"43550–43560"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c02840","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195705","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":"New Machine Learning Models for Predicting the Organic Cation Transporters OCT1, OCT2, and OCT3 Uptake","authors":"Giovanni Bocci*,&nbsp;, ,&nbsp;Neann Mathai,&nbsp;, ,&nbsp;Benjamin Suutari,&nbsp;, ,&nbsp;Jonathan Harrison,&nbsp;, ,&nbsp;Stefanie Speichert,&nbsp;, ,&nbsp;Major Gooyit,&nbsp;, ,&nbsp;Douglas E. V. Pires,&nbsp;, and ,&nbsp;John P. Overington,&nbsp;","doi":"10.1021/acsomega.5c05605","DOIUrl":"https://doi.org/10.1021/acsomega.5c05605","url":null,"abstract":"<p >Organic cation transporters (OCTs) are a small family of transmembrane proteins that regulate the pharmacokinetics (PK) of natural metabolites and xenobiotics by facilitating drug uptake and elimination. Measuring the modulation (either inhibition or substrate) of OCTs by small molecules requires expensive experiments. More cost-effective <i>in silico</i> models that accurately predict OCT-mediated uptake would enable the forecasting of potential PK liabilities of new drug candidates at an early stage. In this paper, we present new machine learning (ML) models to predict the uptake of OCT1, OCT2, and OCT3. Built using advanced decision tree ensemble algorithms and VolSurf molecular features, these models are based on the largest and most well-curated data sets available in the current literature. Several rounds of validation with different external test sets have confirmed the predictive power of these models, with Matthews correlation coefficient (MCC) values above 0.45. We believe that these models will shed new light on the impact of OCTs on drug discovery and development.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"44190–44200"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c05605","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195733","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":"Understanding the Phase Transition of FAPbI3 Films through In Situ Raman Studies for Enhanced Solar Cell Performance","authors":"Sanjeev Sajan,&nbsp;, ,&nbsp;Shana Sudhakaran,&nbsp;, and ,&nbsp;Vinod E. Madhavan*,&nbsp;","doi":"10.1021/acsomega.5c02596","DOIUrl":"https://doi.org/10.1021/acsomega.5c02596","url":null,"abstract":"<p >Perovskite solar cells have attracted considerable attention because of their potential to achieve high efficiency at low costs. In this study, the temperature-dependent phase transitions and decomposition pathways of formamidinium lead iodide (FAPbI₃) thin films were studied using in situ Raman spectroscopy. FAPbI₃ is a promising material for perovskite solar cells due to its narrow bandgap and high thermal stability. This study explores the evolution of the photoactive α-phase and metastable intermediate phases during thermal annealing over a temperature range of −150 to 250 °C by in situ Raman spectroscopy at ambient conditions. Also, annealing at 125, 150, and 175 °C under an inert atmosphere resulted in systematic tuning of the optical bandgap, as confirmed by photoluminescence measurements and Tauc plot analysis. XRD and Raman spectroscopy revealed the presence of mixed phases at lower temperatures and stabilization of the cubic α-phase at higher temperatures. SEM imaging correlated the annealing temperature to morphological changes, showing improved crystallinity and film quality at higher temperatures. These findings provide valuable insights into the phase formation behavior and thermal evolution of FAPbI₃ films, contributing to the development of more stable and efficient perovskite solar cells with improved performance. The comprehensive exploration of crystallization mechanisms through Raman studies and phase transition dynamics helps to address one of the most pressing challenges: structural stability in the FAPbI₃ perovskite.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"43540–43549"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c02596","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195710","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":"Graphene Oxide–Chitosan Composite for Efficient Adsorptive Removal of Cu(II), Co(II), and Ni(II) from Simulated E-Waste Effluents","authors":"Malinee Promkatkaew,&nbsp;, ,&nbsp;Pailin Srisuratsiri,&nbsp;, ,&nbsp;Umarin Sangpanich,&nbsp;, ,&nbsp;Kullawadee Somboonviwat,&nbsp;, and ,&nbsp;Sunan Kitjaruwankul*,&nbsp;","doi":"10.1021/acsomega.5c05350","DOIUrl":"https://doi.org/10.1021/acsomega.5c05350","url":null,"abstract":"<p >Electronic waste (E-waste) is a major source of copper, cobalt, and nickel, metals commonly present in batteries, displays, and computer components. Their uncontrolled release into water systems contributes to metal accumulation and environmental contamination. In this study, a graphene oxide–chitosan (GOCS) composite was synthesized as an eco-friendly biosorbent and applied for the removal of Cu(II), Co(II), and Ni(II) ions from simulated E-waste effluents. The composite was prepared using a modified Hummers’ method and characterized by Fourier-transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller surface area analysis. Structural characterization revealed an amorphous, nonporous composite in which CS reduced the surface area of graphene oxide but introduced abundant functional groups. Despite its low surface area, the composite exhibited high adsorption efficiencies, recording 99.98% for Cu(II) at pH 7 in 30 min, 92.55% for Co(II) at pH 9 in 120 min, and 72.36% for Ni(II) at pH 5 in 180 min. Complementary molecular dynamics simulations confirmed the stability of the graphene oxide–chitosan–metal systems and identified nitrogen atoms of chitosan as primary coordination sites, consistent with experimental findings. Binding free energy analysis further supported the stronger affinity toward Cu(II). Collectively, these results demonstrate that the adsorption efficiency of GOCS composites arises from the combined effects of pH-dependent functional group speciation, hard–soft acid–base binding preferences, and chitosan-induced pore blocking. These synergistic mechanisms underscore their potential as sustainable adsorbents for wastewater derived from electronic waste.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"44111–44124"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c05350","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195716","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":"Design, Synthesis, Antidiabetic Activity and In Silico Studies of New Hydrazone Derivatives Derived from Acetohexamide","authors":"Bedriye Seda Kurşun Aktar*,&nbsp;, ,&nbsp;Yusuf Sıcak,&nbsp;, ,&nbsp;Emine Elçin Oruç-Emre,&nbsp;, ,&nbsp;Rabia Kılıç,&nbsp;, ,&nbsp;Ebru Sağlam,&nbsp;, ,&nbsp;Demet Taşdemir,&nbsp;, ,&nbsp;Süleyman Kaya,&nbsp;, ,&nbsp;Gizem Tatar Yılmaz,&nbsp;, and ,&nbsp;Ayse Sahin Yaglioglu,&nbsp;","doi":"10.1021/acsomega.5c04642","DOIUrl":"https://doi.org/10.1021/acsomega.5c04642","url":null,"abstract":"<p ><i>Diabetes mellitus</i> affects over 500 million people globally and is expected to rise significantly in the coming decades. Existing antidiabetic drugs, including α-glucosidase and α-amylase inhibitors, often exhibit side effects and limited efficacy, prompting the search for safer alternatives. Hydrazone derivatives have shown promising antidiabetic activity due to their structural diversity and enzyme-targeting potential. In this study, 10 novel hydrazone compounds were synthesized and evaluated for their inhibitory effects against α-amylase and α-glucosidase. Compounds <b>8</b> and <b>10</b> showed the highest dual inhibition: compound <b>8</b> with IC₅₀ = 30.21 ± 0.16 μM (α-amylase) and 38.06 ± 0.80 μM (α-glucosidase); compound <b>10</b> with IC₅₀ = 34.49 ± 0.37 and 40.44 ± 0.23 μM, respectively. Cytotoxicity on HEK293 cells via MTT assay revealed IC₅₀ values of 61.04 μM (compound <b>7</b>) and 69.25 μM (compound <b>9</b>), while other compounds and acarbose were nontoxic up to 100 μM. In silico drug-likeness analysis showed that 80% of the compounds complied with Lipinski’s rules, with topological polar surface area (TPSA) values ranging between 63 and 112 Ų. Gastrointestinal absorption was high for 7 out of 10 compounds; none showed blood–brain barrier permeability. Molecular docking confirmed strong binding interactions of compounds <b>8</b> and <b>10</b> with both enzymes’ active sites. These findings highlight hydrazone scaffolds as potent and safe candidates for further antidiabetic drug development.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"43916–43931"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c04642","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195718","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":"AI-Optimized Quantitative RINEPT (AIOQ-RINEPT) 1D 13C NMR for Rapid Polyolefin Microstructure Analysis","authors":"Shan Ye*,&nbsp;, ,&nbsp;Xuelei Duan*,&nbsp;, ,&nbsp;Youlin Xia*,&nbsp;, ,&nbsp;Aitor Moreno,&nbsp;, ,&nbsp;Rongjuan Cong*,&nbsp;, ,&nbsp;Fuyue Tian,&nbsp;, ,&nbsp;Yu Zhou,&nbsp;, ,&nbsp;Lin Liu,&nbsp;, ,&nbsp;Yue Yu,&nbsp;, ,&nbsp;Peiqian Yu,&nbsp;, ,&nbsp;Linfeng Chen,&nbsp;, ,&nbsp;Shuai Shao,&nbsp;, ,&nbsp;Congyun Liu,&nbsp;, ,&nbsp;Linge Ma,&nbsp;, and ,&nbsp;Zhe Zhou*,&nbsp;","doi":"10.1021/acsomega.5c07128","DOIUrl":"https://doi.org/10.1021/acsomega.5c07128","url":null,"abstract":"<p >Polyolefins, which are vital materials in a wide range of industries, demand accurate and rapid microstructural analysis to enhance and optimize their performance characteristics. Triad sequence distributions are widely used to evaluate critical parameters, including comonomer content, monomer number-average sequence length, and the blockiness Koenig B value. While conventional algebraic methods for determining these values often lack accuracy, this study presents a more precise approach based on matrix operations. Traditional quantitative ¹³C NMR has long served as the primary technique for analyzing polyolefin microstructures. However, its low sensitivity and lengthy acquisition time limit high-throughput analysis and hinder the practical determination of certain microstructural details. To overcome these limitations, we propose a synergistic approach that combines chromium(III) acetylacetonate (Cr(acac)₃), a relaxation agent, with an artificial intelligence (AI)-optimized quantitative RINEPT (AIOQ-RINEPT) pulse sequence. Using a customized simulated annealing algorithm, a machine learning technique commonly used in AI model training, we optimized the variable delays τ₂ in the RINEPT sequence while keeping the delay τ₁ fixed. This optimization leads to uniform sensitivity enhancement across CH, CH₂, and CH₃ signals. The AIOQ-RINEPT technique, incorporating triply compensated 180° pulses (G5), ensures a broad excitation bandwidth. This method achieved a 7.5-fold increase in sensitivity, equivalent to a 56.3-fold reduction in acquisition time compared to conventional inverse-gated ¹³C NMR. When combined with cryoprobe technology, a 41.3-fold improvement in sensitivity could be realized, resulting in a 1,706-fold decrease in acquisition time, making high-throughput analysis feasible. Experimental validation using a poly(ethylene-<i>co</i>-1-butene) (EB) copolymer with a sufficiently high weight-average molecular weight (<i>M</i>_w = 120,700 kg/mol) demonstrated accurate quantification of triad sequence distributions, comonomer content, and blockiness parameters. Two additional EB samples with lower weight-average molecular weights (<i>M</i>_w = 86,000 and 58,000 kg/mol) were also employed to further validate the method. The method also effectively resolved signal overlap issues commonly encountered in samples with a high comonomer content. Moreover, the approach is broadly applicable to a wide range of polyolefins. This advancement enables rapid, automated ¹³C NMR analysis of virgin and recycled polyolefins, allowing high-throughput characterization and sensitive detection of low-abundance features like long-chain branching (LCB). Additionally, the technique is suitable for analyzing low molecular weight saturated hydrocarbons, including Fischer–Tropsch products, such as waxes, lubricating oils, and jet fuel.</p>","PeriodicalId":22,"journal":{"name":"ACS Omega","volume":"10 38","pages":"44633–44641"},"PeriodicalIF":4.3,"publicationDate":"2025-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsomega.5c07128","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195671","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}