Faraday Discussions最新文献

{"title":"Determining the biodegradation of functionalised cellulose esters.","authors":"Katrina Entwistle, Sandhya Moise, Fatma Guler, Katherine A Smart, Matthew Crow, Christopher J Chuck","doi":"10.1039/d5fd00040h","DOIUrl":"https://doi.org/10.1039/d5fd00040h","url":null,"abstract":"<p><p>Recently, there has been an increased interest in developing functionalised carbohydrates, such as cellulose palmitate, as novel replacements for petroplastics. The functionalisation gives the materials excellent water barrier properties, as well as processability and mechanical properties akin to PET, while potentially having superior biodegradability to conventional first-generation biopolymers. However, the true biodegradability of these novel polymers is still unknown with some recent reports suggesting that it is limited. In this study, we investigated the potential of cellulose palmitate to biodegrade under controlled laboratory conditions, comparing the polymer to cellulose acetate. To this end, studies using specific enzymes, targeted whole cell fungal degradation and model edibility experiments were devised to study the biodegradability at end-of-life. On an enzymatic level, a combination of cellulase and lipase enzymes were found to hydrolyse the fatty acid linkages, allowing the cellulases to access the carbohydrate chain and release glucose. Under optimal conditions the biopolymer was completely hydrolysed within 6 hours. A soil fungi was then isolated from a compost heap that had been loaded with the functional material, to establish the most suitable species for whole cell degradation. This common soil fungi, <i>Mucor</i> sp., was then grown successfully under lab conditions on the functional material as a 95% carbon source. Finally, an edibility experiment was designed, using pepsin and pancreatic enzymes at precise pH concentrations found in the gastrointestinal tract to mimic real life conditions of ingestion by birds. While cellulose acetate broke down under just the acidic conditions, with no enzymes, the cellulose palmitate was found to be stable at the acidic conditions, but hydrolyse over 7 days when the enzymes were present. To the best of our knowledge this is the first study to confirm the biodegradability of functionalised cellulose highlighting the large promise of functionalised carbohydrates as a sustainable alternative to petrochemical plastics within the packaging industry.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135950","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":"An empirical assessment of the physicochemical properties of lignin solutions in aqueous sodium hydroxide - corroboration and demystification of some widely accepted statements.","authors":"Antonio L Alves, Veronica Calado","doi":"10.1039/d5fd00071h","DOIUrl":"https://doi.org/10.1039/d5fd00071h","url":null,"abstract":"<p><p>Lignin is one of the main byproducts of the pulp, paper, and cellulosic ethanol industries. For the past 35 years, it has received increased interest in applications other than its use as an energy source. Although much of this research requires the use of lignin solubilized in solvents such as alkalis, little is known about the impact of the main process conditions - initial lignin mass, alkali concentration, and temperature and time of dissolution - on key solution properties - density, mass fraction of lignin, and pH. A central composite design, with these process conditions as input variables and these key solution properties as output variables, was made by varying the temperature from 30 to 80 °C, the time from 1 to 3 h, the concentration from 0.1 to 0.5 M, and, instead of directly working with lignin mass, a ratio of added lignin to alkali concentration of 30 to 60 g L mol^-1. The hypothesis made by Sarkanen <i>et al.</i> (<i>Macromolecules</i>, 1984, <b>17</b>(12), 2588-2597) that lignin may aggregate under strong alkaline media and Lindströmn's (<i>Colloid Polym. Sci.</i>, 1979, <b>257</b>, 277-285) hypothesis that there are thermally induced processes that also cause aggregation - and further agglomeration - were attested and updated to indicate a joint action of both factors. Surprisingly, mass fraction displayed a maximum value using fixed ratio conditions instead of a saturation point. That shows lignin solubilization depends on more factors than simply the ratio of hydroxide anions <i>vs.</i> phenolic-OH groups and the pH. pH evolution was governed by slow aggregation and agglomeration reactions and conformational changes sensitive to time and temperature. The resulting polynomial models achieved adjusted <i>R</i>² > 0.996 for all responses, and ten validation experiments exhibited maximum relative errors ≤1.6%. These results furnish quantitative guidelines for tailoring lignin solution properties and suggest further studies into rheology, extended factor ranges, alternative lignin sources, and developing theoretical - and possibly more universal - models to predict lignin solution properties.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129609","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":"In-depth analysis of kraft lignin epoxy thermosets.","authors":"Saeid Nikafshar, Kevin Dunne, Sajad Nikafshar, Mojgan Nejad","doi":"10.1039/d5fd00047e","DOIUrl":"https://doi.org/10.1039/d5fd00047e","url":null,"abstract":"<p><p>In this study, epoxidized lignins were prepared by reacting softwood (SW) and hardwood (HW) technical (kraft) lignins with a biobased epichlorohydrin. The chemical structures, rheological behaviors, and thermomechanical properties of the epoxidized lignins were measured and compared with those of petroleum-based (DGEBA) epoxy resin. First, the chemical and physical properties of the lignin samples were assessed using Fourier-transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), quantitative phosphorus nuclear magnetic resonance spectroscopy (³¹P NMR), and 2D-heteronuclear single quantum coherence (HSQC) NMR analyses. Subsequently, the unmodified lignins were epoxidized over a short period (3 hours), using ethyl lactate as a biobased co-solvent. The ³¹P NMR and HSQC analysis of the epoxidized lignins confirmed that phenolic hydroxyl and carboxylic acid groups in lignin were selectively epoxidized without any other significant changes to the chemical structure of lignin. Rheological multi-wave curing studies of both lignin-based and bisphenol A-based (DGEBA) resins cured with a biobased curing agent revealed that the lignin-based systems exhibited significantly shorter gelation times and lower activation energies. Further analyses, including gel fraction, swelling ratio, thermal gravimetric analysis (TGA), and dynamic mechanical analysis (DMA) results, demonstrated that lignin-based thermosets had comparable properties to the petroleum-based epoxy system when both were prepared with solvent (40 wt%) inclusion. Notably, the thermoset resin made with kraft hardwood lignin exhibited superior thermomechanical properties compared to the softwood system.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129567","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":"Structural purification of technical lignins <i>via</i> fractional dissolution using non-azeotropic solvent mixtures.","authors":"Reza Ebrahimi Majdar, Federica Ferruti, Marco Orlandi, Claudia Crestini, Heiko Lange","doi":"10.1039/d5fd00075k","DOIUrl":"https://doi.org/10.1039/d5fd00075k","url":null,"abstract":"<p><p>Two technical lignins, a softwood kraft lignin (SKL) and a wheat straw organosolv lignin (WSOSL) were fractionated using a Soxhlet extractor that was connected to a piston pump for solvent movement such that Soxhlet extraction using non-azeotropic solvent mixtures was feasible. Fractionation of the lignins using such solvent mixtures that could be tuned in terms of hydrogen-bond acceptor and donor characteristics and polarities yielded novel fractions not accessible in standard Soxhlet-based fractionations. Two SKL fractions could be obtained applying aqueous acetone that displayed homogeneous structural characteristics while differing significantly in molecular weights. WSOSL could be gradually purified, allowing for the generation of a rather pure lignin carbohydrate complex (LCC) fraction and a purified high molecular weight lignin fraction.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129604","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":"Efficient hydrogenolysis of lignocellulose into phenolic monomers over a CuO/m-ZrO₂ catalyst.","authors":"Peng Qi, Qiang Wang, Zi-Mu Liu, Peng Zhu, Jing-Shu Dong, Jun-Li Ren, Yu-Meng Wang, Ling-Ping Xiao, Run-Cang Sun","doi":"10.1039/d5fd00058k","DOIUrl":"https://doi.org/10.1039/d5fd00058k","url":null,"abstract":"<p><p>The catalytic reduction of lignin into bio-chemicals is desirable yet remains a challenge due to its heterogeneity and complexes. Herein, a copper oxide supported monoclinic ZrO₂ (CuO/m-ZrO₂) catalyst is fabricated for efficient reductive catalytic fractionation (RCF) of softwood lignin, affording a yield of monophenols up to 18.7 wt% with a high selectivity (82.3%) for 4-<i>n</i>-propanol guaiacol. Some key parameters, such as β-O-4' models, solvent, mass ratio, reaction temperature and time, are systematically investigated to reveal their effects on the yields of monomers. Notably, mechanistic studies indicate the interactions between metal and acid sites enhance catalytic activity toward the effective scission of C-O bonds. Furthermore, a successful isolation of 68.3% monophenols is achieved in the gram scale amplification reaction. The monophenol formation pathway is deduced by the expansion of β-O-4' model compounds and other substrates. The insights from this work pave a new way for the rational design of non-precious catalysts for the transformation of lignin into fine chemicals.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129625","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":"Predictive modelling and optimization of lignin extraction efficiency and quality in birch-wood mild ethanosolv fractionation in a semi-continuous flow-through reactor.","authors":"Amponsah Preko Appiah, Bertran-Llorens Salvador, Pelle van Aefst, Peter J Deuss","doi":"10.1039/d5fd00104h","DOIUrl":"https://doi.org/10.1039/d5fd00104h","url":null,"abstract":"<p><p>Lignin, a complex and abundant biopolymer found in plants, holds immense potential for sustainable materials and chemicals. However, conventional extraction methods often lead to structural deterioration of the native-like aryl ether structure <i>via</i> condensation and other chemical alterations, limiting lignin utility. High delignification in conjunction with preservation of the versatility and functionality of lignin structure for high-value applications can be achieved using advanced mild extraction techniques. In this study, an integrated modeling-experimental approach is used to attain a scalable framework for lignin-first biorefining. Temperature and flow rate were optimized in a flow-through mild ethanosolv system utilizing crude birch-wood chips (without extractive-removal) to balance solvent use, delignification, and structure preservation. Delignification and lignin yield were monitored separately as was its quality in terms of preservation of its native aryl-ether structure, as determined <i>via</i> 2D HSQC NMR and GPC. Extraction kinetics were monitored using UV-Vis spectroscopy to allow for maximizing efficient solvent utilization. Response surface methodology identified optimal conditions (145-151 °C, 8 g_solvent min^-1 flow rate), revealing temperature as the primary driver for extraction, exhibiting synergistic effects with the flow rate. Notably, higher flow rates at elevated temperatures (≥140 °C) mitigated β-O-4 linkage degradation without compromising delignification efficiency. Experimental validation of the optimized model at 150 °C and 8 g_solvent min^-1 achieved 82 wt% delignification and yielded lignin with high β-O-4 linkage content (59.4 per 100 aromatic units (ArU)), aligning closely with model predictions (81-87 wt%, ≥52 β-O-4 per 100 ArU). Solvent consumption was optimized from the model (13.1 mL g^-1, solvent : biomass) and realized a reduction of over 40% of solvent consumption when compared with solvent consumption from typical batch organosolv systems (22.9 mL g^-1, solvent : biomass). Finally, the optimization reduced the extraction time significantly from typically 2 hours to 30 min when compared with previous standard extraction conditions (120 °C, 2 g_solvent min^-1 flow rate), without compromising on extraction efficiency and lignin quality. This study shows the potential of mild organosolv extraction with alcohol with optimized conditions.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129599","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":"The use of kraft lignin to enhance nanocellulose film properties.","authors":"Raquel Martín-Sampedro, Antonio Ovejero-Pérez, Mercedes Oliet, Virginia Alonso, Francisco Rodríguez, David Ibarra, María E Eugenio","doi":"10.1039/d5fd00063g","DOIUrl":"https://doi.org/10.1039/d5fd00063g","url":null,"abstract":"<p><p>The pressing need to replace petroleum-based plastics with renewable and biodegradable alternatives has sparked growing interest in biopolymers derived from lignocellulosic biomass as sustainable solutions. Among these, nanocellulose stands out as a versatile product capable of forming strong, transparent, and flexible films. However, these films lack active properties like antioxidant, antibacterial and UV-shielding capacity, essential for applications such as food packaging. To address this, incorporating lignin, a byproduct of lignocellulosic biorefineries, offers a promising route to enhance the functionality of nanocellulose films. In line with this idea, this work studies the incorporation of kraft lignin into nanocellulose films by two different protocols: the first protocol involves directly mixing a cellulose nanofiber (CNF) suspension with an aqueous lignin suspension; the second protocol uses lignin dissolved in acetone : water (9 : 1) which is transformed into lignin nanoparticles (LNPs) <i>via</i> solvent shifting when mixed with the aqueous CNF suspension. The resulting suspensions of CNFs and lignin were subsequently used to produce casting films. It was found that incorporating lignin into the CNF film not only conferred UV-shielding capacity, but also enhanced barrier properties without compromising the mechanical properties, particularly when lignin was introduced as LNPs (even at 10-20% LNP content). However, adding bulk lignin at a high concentration (20%) negatively affected water vapor permeability and mechanical properties. Antioxidant and antibacterial capacities correlated with lignin content, showing greater enhancement when lignin was present as nanoparticles compared to bulk lignin. These results indicate that forming LNPs <i>in situ</i> within the CNF suspension is a more effective approach to optimize the properties of nanocellulose films. Thus, the obtained films presented good active properties with mechanical properties comparable to those of traditional plastics, but significantly lower barrier properties.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129582","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":"Unleashing the power of non-toxic Zn-guanidine catalysts for sustainable lactide polymerization through smart modeling.","authors":"Jinbo Ke, Niclas Conen, Filip Latz, Jan Niclas Neumann, Martin Fuchs, Alexander Hoffmann, Andreas Jupke, Sonja Herres-Pawlis","doi":"10.1039/d5fd00062a","DOIUrl":"https://doi.org/10.1039/d5fd00062a","url":null,"abstract":"<p><p>Polylactide (PLA) is one of the most promising bioplastics and is therefore often quoted as a solution to fight today's global plastics crisis. However, current PLA production <i>via</i> the ring-opening polymerization (ROP) of lactide is not yet sustainable since it heavily relies on the toxic catalyst tin octoate. To overcome the hurdles in scale-up and to accelerate the transition of promising new non-toxic alternative ROP catalysts from laboratory to industry, model-based analysis is a highly effective tool. Herein, our previously introduced kinetic model for the ROP of L-lactide using a non-toxic and robust Zn guanidine \"asme\"-type catalyst under industrially relevant melt conditions is expanded upon using two new co-initiators. The experimental data is evaluated using \"traditional\" kinetic analysis following pseudo-first-order kinetics to approximate a relationship between co-initiator concentration and the rate of polymerization. The range of validity of these findings is considerably expanded by taking model data into account to compare the performance of the different co-initiators in lactide ROP.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123828","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":"Synthesis and characterization of stable nickel(II) complexes bearing long alkyl chains.","authors":"Yuya Miyake, Koichiro Masada, Kyoko Nozaki","doi":"10.1039/d5fd00083a","DOIUrl":"https://doi.org/10.1039/d5fd00083a","url":null,"abstract":"<p><p>Nickel(II) complexes bearing long alkyl chains are successfully obtained as stable solids by ethylene oligomerization using a Shell Higher Olefin Process (SHOP)-type anionic bidentate (P-O) ligand. In contrast to the salient stability of the alkyl-Ni(II) complexes in the solid state, their chemical derivatization implied the occurrence of non-negligible chain-transfer during the ethylene oligomerization process.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123764","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":"Spiers Memorial Lecture: organic, physical & polymer aspects pivotal in lignin valorization.","authors":"Nicolò Pajer, Claudia Crestini, Dimitris S Argyropoulos","doi":"10.1039/d5fd00108k","DOIUrl":"https://doi.org/10.1039/d5fd00108k","url":null,"abstract":"<p><p>This article addresses current challenges in lignin chemistry by exploring four thematic areas. We begin by examining the major chemical transformations that occur in lignin and discuss the emerging structural understanding of technical lignins. The discussion then shifts to lignin fractionation strategies, which are essential for reducing its inherent heterogeneity and complexity, thereby enabling its use in practical applications. Next, we delve into the chemical and physical behavior of lignin in solution, with particular emphasis on its self-assembly processes relevant to nanoparticle formation. The supramolecular interactions driving these assemblies - such as π-π stacking, hydrogen bonding, and solvent polarity - are analyzed to identify key parameters for designing lignin-based nanomaterials. These materials show promising applications across sectors including agriculture, packaging, cosmetics, and pharmaceuticals. We then consider the broader valorization of lignin, focusing on the rheological and antioxidant properties of lignin fractions. Particular attention is given to their role in forming polymer blends with polyethylene, highlighting their influence on thermal stability and mechanical performance. Finally, we explore lignin's potential as a non-petroleum precursor for carbon fiber production. We critically assess the main barriers in this field, such as lignin's relatively low molecular weight and thermal behavior, which hinder effective fiber formation and graphitization. Strategies to address these challenges, including the integration of fractionation techniques with chemical modifications, are discussed. The article concludes with a review of recent efforts to overcome the limitations of lignin graphitization and enhance its viability as a sustainable carbon fiber source.</p>","PeriodicalId":76,"journal":{"name":"Faraday Discussions","volume":" ","pages":""},"PeriodicalIF":3.1,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145111569","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}