Faraday Discussions最新文献

{"title":"Thermodynamics of Ring-Opening Polymerisation Informatics Collection (TROPIC): a database to enable polymer chemical recycling.","authors":"R M R Reese, A M Ganose, C Romain","doi":"10.1039/d5fd00098j","DOIUrl":"https://doi.org/10.1039/d5fd00098j","url":null,"abstract":"<p><p>The development of artificial intelligence and machine learning in chemistry is opening new avenues for data-driven discoveries. However, the application of such methodologies in polymer chemistry has been hampered due to the complex structure-properties relationship of polymers and the lack of (meta)data available. Recent efforts have been made to experimentally determine or computationally evaluate thermodynamic parameters associated with (de)polymerisation reactions, such as enthalpy and entropy of polymerisation, as well as ceiling temperature, to design polymers primed for chemical recycling. Here, we report TROPIC (Thermodynamics of Ring-Opening Polymerisation Informatics Collection), an open-source database harnessing experimental and computational thermodynamic parameters for ring-opening polymerisation (ROP) from the academic literature. TROPIC links thermodynamic parameters with the experimental conditions or the computation methodologies used to determine them, to allow further analysis. TROPIC can be accessed <i>via</i> an interactive website or application programming interface (API) and presents a first step towards facilitating the data-driven discovery of novel functional polymers.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145079255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Polyglycerol resin towards sustainable 3D-printing.","authors":"Katherine George, Eduards Krumins, Eileen Tan, Yinfeng He, Ricky Wildman, Robert Owen, Joel Segal, Valentina Cuzzucoli Crucitti, Vincenzo Taresco","doi":"10.1039/d5fd00043b","DOIUrl":"https://doi.org/10.1039/d5fd00043b","url":null,"abstract":"<p><p>Additive manufacturing (AM) techniques, also named three-dimensional (3D)-printing, have been widely recognised as promising technologies for rapid production of novel, personalised drug-delivery systems and scaffolds for biofabrication, and in food applications and many more fields. Although there has been promising progress in identifying new materials for 3D-printing, the range of resins/polymers available is still limited, with big reliance on petroleum-derived materials and the advancement is not up to date with the fast-developing hardware. Therefore, new building blocks that are renewably sourced and biodegradable are desirable for expanding applicability and recyclability. Specifically, glycerol, a readily available waste product from biodiesel processing, is highly functionalisable since it bears three hydroxyl groups. We previously reported that an acrylated glycerol-based oligomer, polyglycerol-6-acrylate, fulfils all the necessary criteria for volumetric printing (transparency, photo-reactivity and viscosity) and was successfully used to print a variety of models with intricate geometries and good resolution. In the present work, we want to expand the use of (meth)acrylated-polyglycerols (4 and 6 units of glycerol) to stereolithography (SLA), as this technique presents numerous advantages, being also more commercially available. Printability parameters, different geometries, and biocompatibility are explored to confirm the amenability of SLA to these \"greener\" resins. In addition, as initial proof of concept, the replacement of (meth)acrylate moieties is explored by ring opening of maleic and norbornene anhydrides in order to achieve acrylic-free resins and preliminary curability tests on these bioderived resins were performed. By developing and testing these new acrylic/acrylic-free resins based on glycerol, we aim to accelerate the adoption of greener alternatives in AM, contributing to a more sustainable future in the 3D-printing world.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145079243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Odor-free kraft lignin-based thermoset with remarkable mechanical properties.","authors":"Alexander Orebom, Aditya Babu, Zoya Zarafshani, Willem Böttger, Joseph S M Samec, Pierre Munier","doi":"10.1039/d5fd00053j","DOIUrl":"https://doi.org/10.1039/d5fd00053j","url":null,"abstract":"<p><p>Future materials should be made from renewable resources and be sustainable without compromising the mechanical properties compared to conventional products. Kraft lignin is an available renewable raw material, sourced globally as a by-product from paper pulp production, and currently burnt at a low value. Kraft lignin has been converted into thermoplastics, however the mechanical properties worsen by degree of blending. Thermosets containing kraft lignin give materials with high strength, where the lignin matrix contributes to the mechanical properties. However, pre-fractionation or multistep chemistries have been applied to give high performance materials. Herein, we have combined kraft lignin with bio-based glycerol 1,3-diglycidyl ether to give a resin with enhanced mechanical properties. This resin - LigniSet® - is odorless, which is a unique property for kraft lignin-based products. The resin is, due to its hydrophilicity, compatible with natural fibers to give strong composite materials. The material can be recycled to give new materials without reduction in performance. Life cycle assessment shows that transformation of lignin to materials instead of burning shows significant benefits with respect to environmental sustainability.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145079179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Post-polymerisation oxyfunctionalisation of styrene and butadiene-based (co-)polymers using a homogeneous manganese catalyst.","authors":"Maartje Otten, Jeroen Hendriks, Nino Kalános, Arnaud Thevenon, Pieter C A Bruijnincx","doi":"10.1039/d5fd00093a","DOIUrl":"10.1039/d5fd00093a","url":null,"abstract":"<p><p>Post-polymerisation modification of commodity hydrocarbon-based polymers provides access to functional polymers not readily available through bottom-up synthesis methods. Here, we demonstrate the oxyfunctionalisation of different styrenic and rubbery (co-)polymers using a well-established and robust manganese-based homogeneous catalyst, MnTACN, a 1,4,7-trimethyl-1,4,7-triazacyclononane ligand-bearing di-nuclear tri-μ-oxo bridged Mn(IV) compound, and hydrogen peroxide as a green oxidant. Using various grades of polystyrene (PS) and polybutadiene (PBD), we successfully oxyfunctionalised the polymer backbones with alcohol (PS and PBD), ketone (PS) and epoxide (PBD) functional groups. Under optimised conditions, total functionalisation degrees up to 5% for PS and 18% for PBD can be achieved. Next to the homopolymers, we also show oxyfunctionalisation degrees as high as 11%, of the butadiene-derived part of a styrene-butadiene-styrene block-co-polymer (SBS). These results underscore the versatility of a single catalytic system for the oxyfunctionalisation of various C-H bonds as well as the CC bonds found in these commodity hydrocarbon polymers. Detailed analysis of the oxidised polymers before and after subsequent oxidative cleavage of the installed diol moieties on the PBD backbone suggest that the functional groups are randomly spaced along the polymer backbone. Moreover, this second oxidative cleavage also offers the possibility to selectively break down the polymer backbone after oxyfunctionalisation into a mixture of dialdehyde oligomers consisting of 4 up to 32 monomeric units. For PBD and low/mid <i>M</i>_w PS, oxyfunctionalisation coincided with minimal backbone cleavage or crosslinking, as evidenced by gel permeation chromatography (GPC). For the high molecular weight PS samples and SBS, GPC analysis suggests that backbone cleavage is in contrast more pronounced upon oxyfunctionalisation. The thermal properties of the oxyfunctionalised materials are largely unchanged, with decomposition temperatures decreasing with increasing functionalisation degrees, but overall remaining in the high thermal stability regime.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12442954/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145074313","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":"More than ring-strain: revisiting the definition of enthalpy in ring-opening polymerization.","authors":"Vincent Nieboer, Jakob Wohlert, Peter Olsén, Karin Odelius","doi":"10.1039/d5fd00060b","DOIUrl":"https://doi.org/10.1039/d5fd00060b","url":null,"abstract":"<p><p>The thermodynamics of ring-opening polymerization (ROP) are central when predicting the chemical recyclability of aliphatic polyesters and polycarbonates. Conceptually, the enthalpy of polymerization, , is widely understood as a measure of ring-strain for a given monomer. However, the ring-strain is commonly larger than , generating the question of how the release of ring-strain energy during ring-opening transforms. In this work, we propose that is the sum of the energy released by the ring-strain and the energy absorbed by the polymer conformations . Owing to the similar ring-strain, but vastly different values, δ-valerolactone, δ-caprolactone, δ-octalactone, and δ-decalactone were used as model compounds to evaluate the energy cost of polymer conformational freedom. Polymer conformation, measured by ¹³C NMR, DSC, and molecular dynamics, results are in good agreement with the hypothesis and can explain previous literature observations <i>i.e.</i> positive for systems with ring-strain, substituent effects, and solvent effects, that are difficult to understand when only using the analogy of ring-strain and . We believe that our results provide a deeper understanding of the underlying thermodynamics and their interpretation in ROP.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145074347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermally and base-triggered 'debond-on-demand' crosslinked polyurethane adhesives.","authors":"Alarqam Zyaad Tareq, Matthew Hyder, Josephine L Harries, Wayne Hayes","doi":"10.1039/d5fd00051c","DOIUrl":"https://doi.org/10.1039/d5fd00051c","url":null,"abstract":"<p><p>To address current industrial needs and modern legislation, a series of rapidly degradable and strongly adhering crosslinked polyurethanes featuring the commercially available and degradable chain-extender 2,2'-sulfonyldiethanol have been made for use as depolymerisable coatings and 'debond-on-demand' hot-melt adhesives. Variation of the chain-extended polyurethane (CEPU) composition, through increased hard segment content, provided a route to tailor the mechanical, adhesive, and degradable characteristics, whereby CEPUs with ultimate tensile strengths and elongation at break of up to 42.68 MPa and 17.59 ε, respectively, could be achieved. The adhesive shear strength of the CEPUs was investigated on a selection of substrates with the highest shear strength observed of 7.80 MPa on aluminium. Depolymerization was triggered <i>via</i> exposure of the CEPUs to tetrabutylammonium fluoride (TBAF), causing the solubilisation of the CEPUs and the generation of low molecular weight species. Rapid 'debond-on-demand' adhesion was also achieved upon exposure to 1 M TBAF_(aq), with losses in shear strength of up to 34% on aluminium when exposed for 30 minutes.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145074296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ocean biomass-derived feedstocks for non-isocyanate polyurethane synthesis.","authors":"Jane E Peddle, Courtney M Laprise, Mikhailey D Wheeler, Megan M Fitzgerald, Francesca M Kerton, Christopher M Kozak","doi":"10.1039/d5fd00059a","DOIUrl":"https://doi.org/10.1039/d5fd00059a","url":null,"abstract":"<p><p>Non-isocyanate polyurethanes (NIPUs) can be prepared from the highly unsaturated oils or fatty acid methyl esters obtained from waste fish and algae oil. The abundant carbon-carbon double bonds can be epoxidized and reacted with CO₂ to produce cyclic carbonates. Upon reaction with a bioderived amine from waste cashew nutshells, a NIPU is obtained. Fish-oil derived NIPUs were studied for biodegradation and were found to be susceptible to degradation by bacteria and fungi. Algae oil tri- and diacylglycerides were converted to their fatty acid methyl esters (FAMEs) and used for the preparation of NIPUs in a similar fashion to fish oil. NIPUs could be obtained as thermoset films, which were characterized <i>via</i> infrared spectroscopy to verify urethane linkage formation and dynamic mechanical analysis for their physical properties. These processes can lead to new opportunities in waste valorization of the aquaculture industry and demonstrate the promise of algae as an abundant source of biomass.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145074307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-selective polymerization: achieving chemoselectivity and stereoselectivity in a single catalytic system.","authors":"Hengxu Liu, Jiayun Jiang, Xue Liang, Wenli Wang, Hongru Qiang, Yuanzu Zhang, Yunqing Zhu","doi":"10.1039/d5fd00039d","DOIUrl":"https://doi.org/10.1039/d5fd00039d","url":null,"abstract":"<p><p>The precise synthesis of multifunctional block copolymers with tailored architectures remains a pivotal challenge in polymer chemistry, particularly when balancing chemoselectivity and stereoselectivity within a single catalytic system. To address this challenge, we report the dual chemoselective and stereoselective capabilities of a commercially available chiral thiourea catalyst, (<i>S</i>,<i>S</i>)-TUC, for the synthesis of well-defined block copolymers. By leveraging its dual selectivity, (<i>S</i>,<i>S</i>)-TUC enables distinct polymerization pathways dictated by monomer composition. In the TMC/<i>rac</i>-LA system, stereoselective ring-opening polymerization (ROP) of <i>rac</i>-LA preferentially consumes D-LA to form PDLA blocks, followed by simultaneous ROP of TMC and L-LA, yielding pentablock copolymers. Conversely, in the PA/PO/<i>rac</i>-LA system, alternating copolymerization of PA and PO precedes stereoselective ROP of <i>rac</i>-LA, generating pentablock architectures. Comprehensive characterization (NMR, SEC, <i>in situ</i> IR, CD spectroscopy) confirms the catalyst's dual selectivity and adaptability. Notably, (<i>S</i>,<i>S</i>)-TUC operates under mild conditions, eliminates the need for multiple catalysts, and offers cost-effectiveness and low environmental toxicity. This work establishes a unified platform for synthesizing structurally complex copolymers, bridging the gap between precision polymerization and sustainable manufacturing. The methodology holds promise for applications in biodegradable materials, high-performance composites, and biomedical devices, where tailored polymer properties are critical.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068644","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"On-demand manufacture of circular 3D-printable resins.","authors":"Nailah N Moghal, Daniele Giannantonio, Megan R Elliott, Neha Mehta, Andrew P Dove, Arianna Brandolese","doi":"10.1039/d5fd00073d","DOIUrl":"https://doi.org/10.1039/d5fd00073d","url":null,"abstract":"<p><p>Recent progress in circular 3D-printable photocurable resins that enable closed-loop recycling marks a significant step forward in reducing wasteful manufacturing methods and non-recyclable printed plastics. However, with 3D printing technologies shifting from prototyping to full-scale production, the demand for high-scale processes and easily tuneable resin compositions can benefit from the design of automated systems. Herein, we report on the on-demand preparation of a circular 3D-printable resin, achieved through a continuous flow approach. A supported enzyme (Lipase B from <i>Candida antarctica</i>) was used to promote a green esterification of the lipoic acid with biobased alcohols to prepare circular biobased photocurable resins. The supported enzyme was employed for the preparation of a packed bed reactor and was easily recycled and reused to achieve the continuous production of lipoate-based photocurable resins with tuneable composition. Lastly, the environmental impact of the developed on-demand manufacturing process was compared to the previously reported esterification protocols through life cycle assessment, showing the effectiveness of continuous enzymatic flow synthesis in enhancing environmental performance across multiple areas, from human health to ecosystem impact and resources.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068656","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Borane-catalysed cyclodepolymerization of CO₂-derived polycarbonates.","authors":"Mikhailey D Wheeler, Francesca M Kerton","doi":"10.1039/d5fd00050e","DOIUrl":"https://doi.org/10.1039/d5fd00050e","url":null,"abstract":"<p><p>The Lewis acidic borane tris(pentafluorophenyl)borane, B(C₆F₅)₃ or BCF, has been found to selectively depolymerize polycarbonates to their corresponding cyclic carbonates without the need of a co-catalyst. Depolymerizations of poly(propylene carbonate) (PPC) and poly(cyclohexene carbonate) (PCHC) in toluene were studied with varying catalyst loadings and temperatures. Good conversions to the respective cyclic carbonates were observed down to 2.5 mol% BCF and at temperatures down to 75 °C. No conversion was observed under solvent-free or liquid-assisted grinding conditions in a mixer mill. Kinetic studies <i>via in situ</i> infrared spectroscopy of the system showed an activation energy of 50.2 ± 6.7 kJ mol^-1 for PPC and 83.5 ± 1.7 kJ mol^-1 for PCHC. Entropy of activation values were found to be -190.6 ± 18.4 J K^-1 mol^-1 for PPC and -114.7 ± 3.8 J K^-1 mol^-1 for PCHC. Initial rates of conversion were significantly faster for PPC than PCHC. Aliquots were taken from reaction mixtures and analyzed <i>via</i>¹H NMR spectroscopy and gel permeation chromatography to understand the reaction mechanism, which was found to occur <i>via</i> chain-end backbiting rather than random chain scission. Depolymerization attempts were performed on systems containing various additives/impurities including poly(bisphenol A carbonate), H₂O and CO₂. H₂O was seen to inhibit the reaction. Therefore, it was not surprising that a commercial polycarbonate-diol did not depolymerize under the reaction conditions explored.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145068627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}