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Dr Thomas Farmer is leader of the Clean Synthesis Technology Platform within the Green Chemistry Centre of Excellence at the University of York, UK. His research focuses on the development of cleaner manufacturing technologies and processes where efficiency is maximised and waste is minimised. This includes the application of microwave and ultrasound reactors, heterogeneous catalysis, enzymatic catalysis and the development of new sustainable solvents. Thomas is an expert in biomass building-block chemicals (platform molecules) for the production of higher value chemicals. He completed his PhD in at the University of York in 2008 on the synthesis of bio-based water-soluble polymers. He worked for Unilever PLC as a Polymer Scientist between 2008-2010 and then as post doc at the University of Leeds on the extraction of chemicals from seaweed. He returned to York in 2011 to take a position as a senior researcher for clean synthesis. His current research projects include the formation of various polymer classes using bio-derived platform molecules (Sustainable Polymers, EPSRC; EnzPoly, BBSRC) as well as new safer bio-based solvents (ReSolve, H2020/BBI).
2,2,5,5-tetramethyloxolane (TMO) has recently been identified and demonstrated as a safer solvent to replace toluene, THF, and hydrocarbons in a handful of applications. Herein, several bio-based routes to TMO are presented and assessed for greenness, assisted by the CHEM21 Metrics Toolkit and BioLogicTool plots. Using glucose as a common starting point, two chemocatalytic routes and two biochemical routes to TMO were identified and the pathways compared using the aforementioned tools. In addition, bio-based TMO was synthesised via one of these routes; from methyl levulinate supplied by Avantium, a by-product of the sugar dehydration step during the production of 2,5-furandicarboxylic acid. First, methyl levulinate underwent triple methylation using methyl magnesium chloride (MeMgCl) to yield 2,5-dimethylhexane-2,5-diol (DHL) in high yields of 89.7%. Then DHL was converted to high purity TMO (>98.5%) by cyclodehydration using H-BEA zeolites based on the previously reported approach. Bio-based content of this TMO was confirmed by ASTM D6866-20 Method B and found to have 64% bio-based carbon, well above the threshold of 25% set by CEN/TC 411 standards and matching the anticipated content. This study represents the first demonstration of a bio-based synthesis of TMO and confirmation of bio-content by accepted standards.
Fergal Byrne; James Clark; Carlo Angelici; Ed de Jong; Thomas Farmer. Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO). Sustainable Chemistry 2021, 2, 392 -406.
AMA StyleFergal Byrne, James Clark, Carlo Angelici, Ed de Jong, Thomas Farmer. Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO). Sustainable Chemistry. 2021; 2 (3):392-406.
Chicago/Turabian StyleFergal Byrne; James Clark; Carlo Angelici; Ed de Jong; Thomas Farmer. 2021. "Greenness Assessment and Synthesis for the Bio-Based Production of the Solvent 2,2,5,5-Tetramethyloxolane (TMO)." Sustainable Chemistry 2, no. 3: 392-406.
Following the environmental problems caused by non-degradable plastics there is a need to synthesise greener and more sustainable polymers. In this work we describe, for the first time, the facile enzyme-catalysed synthesis of linear polyesters using dimethyl malonate as the diester. These polymers, containing a different aliphatic diol component (C4, C6 or C8), were synthesised in solventless conditions using immobilized Candida antarctica lipase B as the biocatalyst. The potential of enzymes for catalysing this reaction is compared with the unsuccessful antimony- and titanium-catalysed synthesis (T > 150 °C). The application of the synthesized polymers as effective metal chelators in biphasic, green solvent systems was also described, together with the characterisation of the synthesised materials.
Fergal P. Byrne; Jamie M. Z. Assemat; Amy E. Stanford; Thomas James Farmer; James W. Comerford; Alessandro Pellis. Enzyme-catalyzed synthesis of malonate polyesters and their use as metal chelating materials. Green Chemistry 2021, 23, 5043 -5048.
AMA StyleFergal P. Byrne, Jamie M. Z. Assemat, Amy E. Stanford, Thomas James Farmer, James W. Comerford, Alessandro Pellis. Enzyme-catalyzed synthesis of malonate polyesters and their use as metal chelating materials. Green Chemistry. 2021; 23 (14):5043-5048.
Chicago/Turabian StyleFergal P. Byrne; Jamie M. Z. Assemat; Amy E. Stanford; Thomas James Farmer; James W. Comerford; Alessandro Pellis. 2021. "Enzyme-catalyzed synthesis of malonate polyesters and their use as metal chelating materials." Green Chemistry 23, no. 14: 5043-5048.
Hesperidin and rutin are two sought-after natural flavonoids, traditionally extracted from abundant natural citrus fruits and tea leaves using large amounts of ethanol or methanol solvents. Recent trends in extractions have focused on minimizing the use of solvents and creating simpler cost-effective processes. This study aims to apply the concept of chemical valorization in the context of a circular economy, by using agro-industrial waste and biobased alternatives to traditional solvents, which are of environmental concern. We use minimum amounts of solvent/sample (5 mL/0.25 or 0.5 g) to extract hesperidin and rutin in a single-stage solid–liquid extraction. Thirty individual solvents and HSPiP were applied to find the best solvents/blends for extraction. The type of solvent, sample preparation, maceration time, and extraction temperature were studied. Results showed that the biobased solvent Cyrene is very effective when mildly heated to 65 °C (up to 91%) or mixed with water. Adding water to Cyrene forms its geminal diol hydrate, this enhances the solubility and extraction of hesperidin and rutin up to ten times than those of the original pure ketone form. Quantitative sustainability metrics from the CHEM21 Toolkit demonstrated that our extraction methodology is environmentally friendly and offers future potential of isolation of other flavonoids.
Roxana Alina Milescu; Mateus Lodi Segatto; Aylon Stahl; Con Robert McElroy; Thomas James Farmer; James Hanley Clark; Vânia Gomes Zuin. Sustainable Single-Stage Solid–Liquid Extraction of Hesperidin and Rutin from Agro-Products Using Cyrene. ACS Sustainable Chemistry & Engineering 2020, 8, 18245 -18257.
AMA StyleRoxana Alina Milescu, Mateus Lodi Segatto, Aylon Stahl, Con Robert McElroy, Thomas James Farmer, James Hanley Clark, Vânia Gomes Zuin. Sustainable Single-Stage Solid–Liquid Extraction of Hesperidin and Rutin from Agro-Products Using Cyrene. ACS Sustainable Chemistry & Engineering. 2020; 8 (49):18245-18257.
Chicago/Turabian StyleRoxana Alina Milescu; Mateus Lodi Segatto; Aylon Stahl; Con Robert McElroy; Thomas James Farmer; James Hanley Clark; Vânia Gomes Zuin. 2020. "Sustainable Single-Stage Solid–Liquid Extraction of Hesperidin and Rutin from Agro-Products Using Cyrene." ACS Sustainable Chemistry & Engineering 8, no. 49: 18245-18257.
Furandioate-adipate copolyesters are an emerging class of biobased biodegradable polymers with great potential to replace fossil-derived terephthalic acid based copolyesters such as poly(butylene adipate-co-terephthalate) (PBAT). Furandioate-adipate polyesters have almost exclusively been prepared with conventional primary (1°) alcohol diols, while secondary (2°) alcohol diol monomers have up to now been largely overlooked, despite preliminary observations that using methyl branched diols increases the Tg of the resultant polyesters. Little is known of what impact the use of 2° alcohol diols has on other properties such as material strength, hydrophobicity, and rate of enzymatic hydrolysis; all key parameters for performance and end-of-life. To ascertain the effects of using 2° diols on the properties of furandioate-adipate copolyesters, a series of polymers from diethyl adipate (DEA) and 2,5-furandicarboxylic acid diethyl ester (FDEE) using different 1° and 2° alcohol diols was prepared. Longer transesterification times and greater excesses of diol (diol:diester molar ratio of 2:1) were found to be necessary to achieve Mws >20 kDa using 2° alcohol diols. All copolyesters from 2° diols were entirely amorphous and exhibited higher Tgs than their linear equivalents from 1° diols. Compared to linear poly(1,4-butyleneadipate-co-1,4-butylenefurandioate), methyl branched poly(2,5-hexamethyleneadipate-co-2,5-hexamethylenefurandioate) (0:7:0.3 furandioate:adipate ratio) displayed both a higher modulus (67.8 vs 19.1 MPa) and higher extension at break (89.7 vs 44.5 mm). All other methyl branched copolyesters displayed lower modulus but retained higher extension at break compared their linear analogues. Enzymatic hydrolysis studies using Humicola insolens cutinase revealed that copolyesters from 2° alcohol diols have significantly decreased rates of biodegradation than their linear equivalents synthesized using 1° alcohol diols, allowing for fine-tuning of polymer stability. Hydrophobicity, as revealed by water contact angle, was also found to generally increase through the introduction of methyl branching, demonstrating potential for these materials in coatings applications.
Alastair Little; Alessandro Pellis; James William Comerford; Edwin Naranjo-Valles; Nema Hafezi; Mark Mascal; Thomas J. Farmer. Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Biobased Secondary Diols. ACS Sustainable Chemistry & Engineering 2020, 8, 14471 -14483.
AMA StyleAlastair Little, Alessandro Pellis, James William Comerford, Edwin Naranjo-Valles, Nema Hafezi, Mark Mascal, Thomas J. Farmer. Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Biobased Secondary Diols. ACS Sustainable Chemistry & Engineering. 2020; 8 (38):14471-14483.
Chicago/Turabian StyleAlastair Little; Alessandro Pellis; James William Comerford; Edwin Naranjo-Valles; Nema Hafezi; Mark Mascal; Thomas J. Farmer. 2020. "Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Biobased Secondary Diols." ACS Sustainable Chemistry & Engineering 8, no. 38: 14471-14483.
Design of a photopolymer around a renewable furan‐derived chromophore is presented herein. An optimised semi‐continuous oxidation method using MnO 2 facilely afforded 2,5‐diformylfuran from 5‐(hydroxymethyl)furfural in gram quantities, allowing subsequent synthesis of 3,3’‐(2,5‐furandiyl)bisacrylic acid in good yield and excellent stereoselectivity. Photoactivity of the diester of this monomer was confirmed by reaction under UV irradiation, and the proposed [2+2] cycloaddition mechanism supported further by TD‐DFT calculations. Oligoesters of the photoreactive furan diacid with various aliphatic diols were prepared via chemo‐ and enzyme‐catalysed polycondensation. The latter enzyme‐catalysed ( Candida Antarctica lipase B) method resulted in the highest M n (3.6 kDa), suggesting milder conditions employed with this protocol minimised unwanted side reactions, including untimely [2+2] cycloadditions, whilst preserving the monomer’s photoactivity and stereoisomerism. The photoreactive polyester was solvent cast into a film where subsequent initiator‐free UV curing lead to an impressive increase in the material stiffness, with work‐hardening characteristics observed during tensile strength testing.
Yann Lie; Alessandro Pellis; Ignacio Funes‐Ardoiz; Diego Sampedro; Duncan J. MacQuarrie; Thomas James Farmer. Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid. ChemSusChem 2020, 13, 4140 -4150.
AMA StyleYann Lie, Alessandro Pellis, Ignacio Funes‐Ardoiz, Diego Sampedro, Duncan J. MacQuarrie, Thomas James Farmer. Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid. ChemSusChem. 2020; 13 (16):4140-4150.
Chicago/Turabian StyleYann Lie; Alessandro Pellis; Ignacio Funes‐Ardoiz; Diego Sampedro; Duncan J. MacQuarrie; Thomas James Farmer. 2020. "Work‐hardening Photopolymer from Renewable Photoactive 3,3’‐(2,5‐Furandiyl)bisacrylic Acid." ChemSusChem 13, no. 16: 4140-4150.
In the present work, the biocatalyzed synthesis of a series of aromatic-aliphatic polyesters based on the aliphatic diesters dimethyl succinate, dimethyl adipate and dimethyl sebacate and the aromatic diols 2,5-bis(hydroxymethyl)furan, 3,4-bis(hydroxymethyl)furan and 2,6-pyridinedimethanol were investigated. A similar series of polyesters based on the petroleum-based 1,3-benzenedimethanol, 1,4-benzenedimethanol and 1,4-benzenediethanol were also synthesized for comparison. Data show that the enzymatic syntheses were successful starting from all diols, with the obtained polymers having isolated yields between 67 and over 90%, number average molecular weights between 3000 Da and 5000 Da and degree of polymerization (DP) of 6–18 (based on the used aliphatic diesters and aromatic diols) when polymerized in diphenyl ether as solvent. Only using 3,4-bis(hydroxymethyl)furan as the diol led to shorter oligomers with isolated yields around 50% and DPs of 3–5. DSC and TGA thermal analyses show clear correlation between polymer crystallinity and aliphatic carbon chain length of the diester.
Alessandro Pellis; Simone Weinberger; Matteo Gigli; Georg M. Guebitz; Thomas J. Farmer. Enzymatic synthesis of biobased polyesters utilizing aromatic diols as the rigid component. European Polymer Journal 2020, 130, 109680 .
AMA StyleAlessandro Pellis, Simone Weinberger, Matteo Gigli, Georg M. Guebitz, Thomas J. Farmer. Enzymatic synthesis of biobased polyesters utilizing aromatic diols as the rigid component. European Polymer Journal. 2020; 130 ():109680.
Chicago/Turabian StyleAlessandro Pellis; Simone Weinberger; Matteo Gigli; Georg M. Guebitz; Thomas J. Farmer. 2020. "Enzymatic synthesis of biobased polyesters utilizing aromatic diols as the rigid component." European Polymer Journal 130, no. : 109680.
Three dipolar aprotic solvents were designed to possess high dipolarity and low toxicity: N , N , N ’, N ’‐tetrabutylsuccindiamide (TBSA), N , N ’‐diethyl‐ N , N ’‐dibutylsuccindiamide (EBSA), N , N ’‐dimethyl‐ N , N ’‐dibutylsuccindiamide (MBSA). They were synthesized catalytically using a K60 silica catalyst in a solventless system. Their water‐immiscibility stands out as an unusual and useful property for dipolar aprotic solvents. They were tested in a model Heck reaction, metal‐organic framework syntheses, and a selection of polymer solubility experiments where their performances were found to be comparable to traditional solvents. Furthermore, MBSA was found to be suitable for the production of an industrially‐relevant membrane from polyethersulphone. An integrated approach involving in silico analysis based on available experimental information, prediction model outcomes and read across data, as well as a panel of in vitro reporter gene assays covering a broad range of toxicological endpoints was used to assess toxicity. These in silico and in vitro tests suggested no alarming indications of toxicity in the new solvents.
Fergal Patrick Byrne; Clara Nussbaumer; Elise J. Savin; Roxana A. Milescu; Con R. McElroy; James H. Clark; Barbara M. A. Van Vugt‐Lussenburg; Bart Van Der Burg; Marie Y. Meima; Harrie E. Buist; E. Dinant Kroese; Andrew J. Hunt; Thomas J. Farmer. A Family of Water‐Immiscible, Dipolar Aprotic, Diamide Solvents from Succinic Acid. ChemSusChem 2020, 13, 3212 -3221.
AMA StyleFergal Patrick Byrne, Clara Nussbaumer, Elise J. Savin, Roxana A. Milescu, Con R. McElroy, James H. Clark, Barbara M. A. Van Vugt‐Lussenburg, Bart Van Der Burg, Marie Y. Meima, Harrie E. Buist, E. Dinant Kroese, Andrew J. Hunt, Thomas J. Farmer. A Family of Water‐Immiscible, Dipolar Aprotic, Diamide Solvents from Succinic Acid. ChemSusChem. 2020; 13 (12):3212-3221.
Chicago/Turabian StyleFergal Patrick Byrne; Clara Nussbaumer; Elise J. Savin; Roxana A. Milescu; Con R. McElroy; James H. Clark; Barbara M. A. Van Vugt‐Lussenburg; Bart Van Der Burg; Marie Y. Meima; Harrie E. Buist; E. Dinant Kroese; Andrew J. Hunt; Thomas J. Farmer. 2020. "A Family of Water‐Immiscible, Dipolar Aprotic, Diamide Solvents from Succinic Acid." ChemSusChem 13, no. 12: 3212-3221.
Editorial: From Biomass to Advanced Bio-Based Chemicals & Materials: A Multidisciplinary Perspective
Florent Allais; Xavier Coqueret; Thomas Farmer; Warwick Raverty; Caroline Rémond; Gabriel Paës. Editorial: From Biomass to Advanced Bio-Based Chemicals & Materials: A Multidisciplinary Perspective. Frontiers in Chemistry 2020, 8, 1 .
AMA StyleFlorent Allais, Xavier Coqueret, Thomas Farmer, Warwick Raverty, Caroline Rémond, Gabriel Paës. Editorial: From Biomass to Advanced Bio-Based Chemicals & Materials: A Multidisciplinary Perspective. Frontiers in Chemistry. 2020; 8 ():1.
Chicago/Turabian StyleFlorent Allais; Xavier Coqueret; Thomas Farmer; Warwick Raverty; Caroline Rémond; Gabriel Paës. 2020. "Editorial: From Biomass to Advanced Bio-Based Chemicals & Materials: A Multidisciplinary Perspective." Frontiers in Chemistry 8, no. : 1.
The enzymatic synthesis of polyesters in solventless systems is an environmentally friendly and sustainable method for synthetizing bio-derived materials. Despite the greenness of the technique, in most cases only short oligoesters are obtained, with limited practical applications or requiring further chemical processing for their elongation. In this work, we present a catalyst-free thermal upgrade of enzymatically synthesized oligoesters. Different aliphatic and aromatic oligoesters were synthesized using immobilized Candida antarctica lipase B (iCaLB) as the catalyst (70 °C, 24 h) yielding poly(1,4-butylene adipate) (PBA, Mw = 2200), poly(1,4-butylene isophthalate) (PBI, Mw = 1000), poly(1,4-butylene 2,5-furandicarboxylate) (PBF, Mw = 600), and poly(1,4-butylene 2,4-pyridinedicarboxylate) (PBP, Mw = 1000). These polyesters were successfully thermally treated to obtain an increase in Mw of 8.5, 2.6, 3.3, and 2.7 folds, respectively. This investigation focused on the most successful upgrade, poly(1,4-butylene adipate), then discussed the possible effect of di-ester monomers as compared to di-acids in the thermally driven polycondensation. The herein-described two-step synthesis method represents a practical and cost-effective way to synthesize higher-molecular-weight polymers without the use of toxic metal catalysts such as titanium(IV) tert-butoxide, tin(II) 2-ethylhexanoate, and in particular, antimony(IV) oxide. At the same time, the method allows for the extension of the number of reuses of the biocatalyst by preventing its exposure to extreme denaturating conditions.
James W. Comerford; Fergal P. Byrne; Simone Weinberger; Thomas J. Farmer; Georg M. Guebitz; Lucia Gardossi; Alessandro Pellis. Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters. Materials 2020, 13, 368 .
AMA StyleJames W. Comerford, Fergal P. Byrne, Simone Weinberger, Thomas J. Farmer, Georg M. Guebitz, Lucia Gardossi, Alessandro Pellis. Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters. Materials. 2020; 13 (2):368.
Chicago/Turabian StyleJames W. Comerford; Fergal P. Byrne; Simone Weinberger; Thomas J. Farmer; Georg M. Guebitz; Lucia Gardossi; Alessandro Pellis. 2020. "Thermal Upgrade of Enzymatically Synthesized Aliphatic and Aromatic Oligoesters." Materials 13, no. 2: 368.
Large amounts of agricultural wastes are rich in pectins that, in many cases, disrupt the processing of food residues due to gelation. Despite pectins being a promising sustainable feedstock for bio‐based chemical production, the current pathways to produce platform molecules from this polysaccharide are hazardous and entail the use of strong acids. The present work describes a sequence of biocatalyzed reactions that involves 1) the extraction of pectin from sugar beet pulp and enzymatic recovery of galacturonic acid (GalA), followed by 2) the enzymatic oxidation of the GalA aldehyde and the recovery of galactaric acid (GA), and 3) the biocatalyzed polycondensation of GA to obtain fully bio‐based polyesters carrying lateral hydroxy functionalities. The acid‐free pectin extraction is optimized using enzymes and microwave technology. The conditions for enzymatic oxidation of GalA allow the separation of the GA produced by a simple centrifugation step that leads to the enzyme‐catalyzed polycondensation reactions.
Marco Vastano; Alessandro Pellis; Carla Botelho Machado; Rachael Simister; Simon J. McQueen‐Mason; Thomas Farmer; Leonardo D. Gomez. Sustainable Galactarate‐Based Polymers: Multi‐Enzymatic Production of Pectin‐Derived Polyesters. Macromolecular Rapid Communications 2019, 40, e1900361 .
AMA StyleMarco Vastano, Alessandro Pellis, Carla Botelho Machado, Rachael Simister, Simon J. McQueen‐Mason, Thomas Farmer, Leonardo D. Gomez. Sustainable Galactarate‐Based Polymers: Multi‐Enzymatic Production of Pectin‐Derived Polyesters. Macromolecular Rapid Communications. 2019; 40 (22):e1900361.
Chicago/Turabian StyleMarco Vastano; Alessandro Pellis; Carla Botelho Machado; Rachael Simister; Simon J. McQueen‐Mason; Thomas Farmer; Leonardo D. Gomez. 2019. "Sustainable Galactarate‐Based Polymers: Multi‐Enzymatic Production of Pectin‐Derived Polyesters." Macromolecular Rapid Communications 40, no. 22: e1900361.
Short chain alkenyl succinimides (ASIs) were synthesised and used as high purity chemical models to investigate the autoxidative degradation at 170 oC of polyisobutenyl succinimide dispersants (PIBSIs), a significant additive in automotive engine lubricants. Degradation products were characterised by GC-EI-MS and quantified by GC-FID. The rate of autoxidation of ASIs in a model lubricant, squalane, was also investigated. Although this is a complex molecule containing many possible sites of radical attack, all of the autoxidation products identified result from attack at the double bond or the adjacent allylic hydrogen atoms, which indicates the controlling influence of the double bond in the degradation of alkenyl succinimides, and therefore of commercial polyisobutenyl succinimide dispersants. The observed site-selective cleavage of the ASI structure, and by analogy PIBSI dispersants, would yield products that both reduce dispersancy and promote the formation of insoluble products that could have a detrimental effect on lubricant performance.
Jonathan E. Ruffell; Thomas J. Farmer; Duncan J. MacQuarrie; Moray S. Stark. The Autoxidation of Alkenyl Succinimides—Mimics for Polyisobutenyl Succinimide Dispersants. Industrial & Engineering Chemistry Research 2019, 58, 19649 -19660.
AMA StyleJonathan E. Ruffell, Thomas J. Farmer, Duncan J. MacQuarrie, Moray S. Stark. The Autoxidation of Alkenyl Succinimides—Mimics for Polyisobutenyl Succinimide Dispersants. Industrial & Engineering Chemistry Research. 2019; 58 (42):19649-19660.
Chicago/Turabian StyleJonathan E. Ruffell; Thomas J. Farmer; Duncan J. MacQuarrie; Moray S. Stark. 2019. "The Autoxidation of Alkenyl Succinimides—Mimics for Polyisobutenyl Succinimide Dispersants." Industrial & Engineering Chemistry Research 58, no. 42: 19649-19660.
2,2,5,5-tetramethyloxolane [previously published as 2,2,5,5-tetramethyltetrahydrofuran (TMTHF)] has recently been demonstrated as a greener and cleaner alternative to toluene in several applications. Assessing similarities in properties of toluene and 2,2,5,5-tetramethyloxolane is crucial for establishing this molecules potential to replace traditional non-polar organic solvents in the cleaner production of chemicals and materials. However, the Hansen solubility parameters (HSP) and Kamlet-Taft parameters (KT) give conflicting views on their similarities and differences, which necessitates a full comparative characterisation of the solvation environment of these two solvents. Such comparisons have been achieved through a direct and extensive determination of partition coefficients between each of the two solvents and water. The partition coefficients and Abraham's solvation parameter model have quantitatively clarified the similarities and differences in properties of 2,2,5,5-tetramethyloxolane and toluene. Solutes of high dipolarity and hydrogen-bond accepting ability tended to favour the aqueous phase in both systems, while large molar volume and high refractive indices favoured the organic phase. A significant difference between 2,2,5,5-tetramethyloxolane and toluene was observed for hydrogen-bond donating solutes. In general, such solutes strongly preferred the aqueous phase in the toluene/water system but preferred the organic phase in the 2,2,5,5-tetramethyloxolane/water system. This was due to the interaction of the protic solutes with the lone pairs of electrons on the ethereal oxygen of 2,2,5,5-tetramethyloxolane, a feature that is not present on toluene, and opens up new possibilities for applications of this sustainable solvent in liquid-liquid extraction, particularly in the isolation of natural products. As toluene is such an important solvent in the chemical industry, its replacement with a greener alternative such as 2,2,5,5-tetramethyloxolane would be hugely significant for cleaner synthesis, extractions and separations.
Fergal P. Byrne; William M. Hodds; Seishi Shimizu; Thomas J. Farmer; Andrew J. Hunt. A comparison of the solvation power of the green solvent 2,2,5,5-tetramethyloxolane versus toluene via partition coefficients. Journal of Cleaner Production 2019, 240, 118175 .
AMA StyleFergal P. Byrne, William M. Hodds, Seishi Shimizu, Thomas J. Farmer, Andrew J. Hunt. A comparison of the solvation power of the green solvent 2,2,5,5-tetramethyloxolane versus toluene via partition coefficients. Journal of Cleaner Production. 2019; 240 ():118175.
Chicago/Turabian StyleFergal P. Byrne; William M. Hodds; Seishi Shimizu; Thomas J. Farmer; Andrew J. Hunt. 2019. "A comparison of the solvation power of the green solvent 2,2,5,5-tetramethyloxolane versus toluene via partition coefficients." Journal of Cleaner Production 240, no. : 118175.
Bio-based platform molecules such as itaconic, fumaric, and muconic acid offer much promise in the formation of sustainable unsaturated polyester resins upon reaction with suitable diols and polyols. The C=C bonds present in these polyester chains allows for post-polymerization modification and such moieties are conventionally utilized in curing processes during the manufacture of coatings. The C=C modification sites can also act as points to add useful pendants which can alter the polymers final properties such as glass transition temperature, biodegradability, hardness, polarity, and strength. A commonly observed modification is the addition of secondary amines via an aza-Michael addition. Conventional procedures for the addition of amines onto itaconate polyesters require reaction times of several days as a result of undesired side reactions, in particular, the formation of the less reactive mesaconate regioisomer. The slow reversion of the mesaconate back to itaconate, followed by subsequent amine addition, is the primary reason for such extended reaction times. Herein we report our efforts toward finding a suitable catalyst for the aza-Michael addition of diethylamine onto a model substrate, dimethyl itaconate, with the aim of being able to add amine onto the itaconate units without excessive regioisomerization to the inactive mesaconate. A catalyst screen showed that iodine on acidic alumina results in an effective, heterogeneous, reusable catalyst for the investigated aza-Michael addition. Extending the study further, itaconate polyester was prepared by Candida Antartica Lipase B (CaL-B) via enzymatic polytranesterification and subsequently modified with diethylamine using the iodine on acidic alumina catalyst, dramatically reducing the required length of reaction (>70% addition after 4 h). The approach represents a multidisciplinary example whereby biocatalytic polymerization is combined with chemocatalytic modification of the resultant polyester for the formation of useful bio-based polyesters.
Oliver B. Moore; Polly-Ann Hanson; James W. Comerford; Alessandro Pellis; Thomas J. Farmer. Improving the Post-polymerization Modification of Bio-Based Itaconate Unsaturated Polyesters: Catalyzing Aza-Michael Additions With Reusable Iodine on Acidic Alumina. Frontiers in Chemistry 2019, 7, 501 .
AMA StyleOliver B. Moore, Polly-Ann Hanson, James W. Comerford, Alessandro Pellis, Thomas J. Farmer. Improving the Post-polymerization Modification of Bio-Based Itaconate Unsaturated Polyesters: Catalyzing Aza-Michael Additions With Reusable Iodine on Acidic Alumina. Frontiers in Chemistry. 2019; 7 ():501.
Chicago/Turabian StyleOliver B. Moore; Polly-Ann Hanson; James W. Comerford; Alessandro Pellis; Thomas J. Farmer. 2019. "Improving the Post-polymerization Modification of Bio-Based Itaconate Unsaturated Polyesters: Catalyzing Aza-Michael Additions With Reusable Iodine on Acidic Alumina." Frontiers in Chemistry 7, no. : 501.
A more sustainable dialysis and water filtration membrane has been developed, by using the new, safer, bio-based solvent Cyrene® in place of N-methyl pyrrolidinone (NMP). The effects of solvent choice, solvent evaporation time, the temperature of casting gel, and coagulation bath together with the additive concentration on porosity and pore size distribution were studied. The results, combined with infrared spectra, SEM images, porosity results, water contact angle (WCA), and water permeation, confirm that Cyrene® is better media to produce polyethersulfone (PES) membranes. New methods, Mercury Intrusion Porosimetry (MIP) and NMR-based pore structure model, were applied to estimate the porosity and pore size distribution of the new membranes produced for the first time with Cyrene® and PVP as additive. Hansen Solubility Parameters in Practice (HSPiP) was used to predict polymer-solvent interactions. The use of Cyrene® resulted in reduced polyvinylpyrrolidone (PVP) loading than required when using NMP and gave materials with larger pores and overall porosity. Two different conditions of casting gel were applied in this study: a hot (70°C) and cold gel (17°C) were cast to obtain membranes with different morphologies and water filtration behaviours.
Roxana A. Milescu; C. Robert McElroy; Thomas J. Farmer; Paul M. Williams; Matthew J. Walters; James H. Clark. Fabrication of PES/PVP Water Filtration Membranes Using Cyrene®, a Safer Bio-Based Polar Aprotic Solvent. Advances in Polymer Technology 2019, 2019, 1 -15.
AMA StyleRoxana A. Milescu, C. Robert McElroy, Thomas J. Farmer, Paul M. Williams, Matthew J. Walters, James H. Clark. Fabrication of PES/PVP Water Filtration Membranes Using Cyrene®, a Safer Bio-Based Polar Aprotic Solvent. Advances in Polymer Technology. 2019; 2019 ():1-15.
Chicago/Turabian StyleRoxana A. Milescu; C. Robert McElroy; Thomas J. Farmer; Paul M. Williams; Matthew J. Walters; James H. Clark. 2019. "Fabrication of PES/PVP Water Filtration Membranes Using Cyrene®, a Safer Bio-Based Polar Aprotic Solvent." Advances in Polymer Technology 2019, no. : 1-15.
The biocatalyzed synthesis of polyesters is a field exploited since the 1980s when the potential of enzymes for catalyzing selective and stereospecific reactions was reported in several breakthrough studies. This chapter focuses on the most recent developments of enzymatic catalysis when applied in the field of bio-based polyester synthesis. A brief introduction summarizes the history and refreshes the memory of the reader on the most relevant reaction mechanisms. Subsequent sections discuss first the possibility of using novel biocatalysts for the synthesis of aliphatic polyesters, moving to polymers where the selectivity of enzymes and their mild reaction conditions are the key of success for producing functional products and ending with aliphatic-aromatic polyesters, highlighting issues and challenges that arose for the polycondensation of these important monomers. Finally, an outlook on the future perspectives and industrialization potential of this technology is given, supporting the ambitions of moving toward a greener polymer chemistry therefore fitting the current needs of moving away from the traditionally used petrochemical monomers.
Alessandro Pellis; Gibson S. Nyanhongo; Thomas J. Farmer. Recent Advances on Enzymatic Catalysis as a Powerful Tool for the Sustainable Synthesis of Bio-Based Polyesters. Biorefinery 2019, 555 -570.
AMA StyleAlessandro Pellis, Gibson S. Nyanhongo, Thomas J. Farmer. Recent Advances on Enzymatic Catalysis as a Powerful Tool for the Sustainable Synthesis of Bio-Based Polyesters. Biorefinery. 2019; ():555-570.
Chicago/Turabian StyleAlessandro Pellis; Gibson S. Nyanhongo; Thomas J. Farmer. 2019. "Recent Advances on Enzymatic Catalysis as a Powerful Tool for the Sustainable Synthesis of Bio-Based Polyesters." Biorefinery , no. : 555-570.
Following concerns over increasing global plastic pollution, interest in the production and characterization of bio-based and biodegradable alternatives is rising. In the present work, the synthesis of a series of fully bio-based alternatives based on 2,4-, 2,5-, and 2,6-pyridinedicarboxylic acid-derived polymers produced via enzymatic catalysis are reported. A similar series of aromatic-aliphatic polyesters based on diethyl-2,5-furandicarboxylate and of the petroleum-based diethyl terephthalate and diethyl isophthalate were also synthesized. Here we show that the enzymatic synthesis starting from 2,4-diethyl pyridinedicarboxylate leads to the best polymers in terms of molecular weights (Mn = 14.3 and Mw of 32.1 kDa when combined with 1,8-octanediol) when polymerized in diphenyl ether. Polymerization in solventless conditions were also successful leading to the synthesis of bio-based oligoesters that can be further functionalized. DSC analysis show a clear similarity in the thermal behavior between 2,4-diethyl pyridinedicarboxylate and diethyl isophthalate (amorphous polymers) and between 2,5-diethyl pyridinedicarboxylate and diethyl terephthalate (crystalline polymers). The increasing concern of global plastic pollution has led to an increase in the production and characterization of bio-based and biodegradable alternatives. Here the authors show the synthesis of a series of fully bio-based alternatives based on 2,4-, 2,5-, and 2,6- pyridinedicarboxylic acids, via enzymatic catalysis.
Alessandro Pellis; James W. Comerford; Simone Weinberger; Georg M. Guebitz; James H. Clark; Thomas J. Farmer. Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics. Nature Communications 2019, 10, 1 -9.
AMA StyleAlessandro Pellis, James W. Comerford, Simone Weinberger, Georg M. Guebitz, James H. Clark, Thomas J. Farmer. Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics. Nature Communications. 2019; 10 (1):1-9.
Chicago/Turabian StyleAlessandro Pellis; James W. Comerford; Simone Weinberger; Georg M. Guebitz; James H. Clark; Thomas J. Farmer. 2019. "Enzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics." Nature Communications 10, no. 1: 1-9.
Poly(ethylene terephthalate) (PET) is a ubiquitous thermoplastic currently produced from non-renewable fossil resources; as such, sustainable bio-based routes to the key terephthalate monomer are being widely pursued. Herein is demonstrated a greener solventless route to bio-based diethyl tereph-thalate via a one-pot heterogeneous Lewis acid catalysed Diels-Alder addition and dehydration of 2,5-furandicarboxylic acid diethyl ester with ethylene, giving yields of terephthalate up to 59% for the key Diels-Alder addition step. A metrics-based comparison against alternative published bio-based routes (available from sugars, cellulose and hemicellulose) shows that the clean synthetic pathway developed herein gives a practical atom economy, overall yield and selectivity, making it a viable alternative to routes currently under development.
Joseph Kolawole Ogunjobi; Thomas J. Farmer; Con Robert McElroy; Simon W. Breeden; Duncan J. Macquarrie; David Thornthwaite; James Hanley Clark. Synthesis of Biobased Diethyl Terephthalate via Diels–Alder Addition of Ethylene to 2,5-Furandicarboxylic Acid Diethyl Ester: An Alternative Route to 100% Biobased Poly(ethylene terephthalate). ACS Sustainable Chemistry & Engineering 2019, 7, 8183 -8194.
AMA StyleJoseph Kolawole Ogunjobi, Thomas J. Farmer, Con Robert McElroy, Simon W. Breeden, Duncan J. Macquarrie, David Thornthwaite, James Hanley Clark. Synthesis of Biobased Diethyl Terephthalate via Diels–Alder Addition of Ethylene to 2,5-Furandicarboxylic Acid Diethyl Ester: An Alternative Route to 100% Biobased Poly(ethylene terephthalate). ACS Sustainable Chemistry & Engineering. 2019; 7 (9):8183-8194.
Chicago/Turabian StyleJoseph Kolawole Ogunjobi; Thomas J. Farmer; Con Robert McElroy; Simon W. Breeden; Duncan J. Macquarrie; David Thornthwaite; James Hanley Clark. 2019. "Synthesis of Biobased Diethyl Terephthalate via Diels–Alder Addition of Ethylene to 2,5-Furandicarboxylic Acid Diethyl Ester: An Alternative Route to 100% Biobased Poly(ethylene terephthalate)." ACS Sustainable Chemistry & Engineering 7, no. 9: 8183-8194.
The current chemical industry has been heavily optimised for the use of petroleum-derived base chemicals as its primary source of building-blocks. However, incorporation of heteroatoms, absent in the base chemicals, is necessary to meet the different property requirements in the plethora of products the industry makes such as plastics, cosmetics and pharmaceuticals. As global oil reserves deplete, a shift towards renewable bio-derived building-blocks, so called platform molecules, will become a necessity. Bio-derived platform molecules are typically rich in heteroatoms as a result of their biomass feedstock also being heteroatom rich, and it would therefore seem logical to carry these heteroatoms through to the aforementioned products. A tool was herein developed to assess the rationality of a synthetic route from feedstock to product, designed specifically to give a visual representation of the pathways and options available. BioLogicTool plots (%heteroatom by mass vs M) are an alternative to the conventional van Krevelen diagram, and are designed to better consider the diversity in heteroatom content encountered in bio-based chemicals. The tool can rapidly help its user to design more logical multi-step synthetic routes and enhance the mass efficiency of pathways. Several examples were selected to demonstrate the power and limitations of the BioLogicTool, but it was clear from these examples that removing heteroatoms from platform molecules to reincorporate them later in the final product is, in most cases, not logical in mass efficiency sense.
Yann Lie; Pablo Ortiz; Richard Vendamme; Karolien Vanbroekhoven; Thomas J. Farmer. BioLogicTool: A Simple Visual Tool for Assisting in the Logical Selection of Pathways from Biomass to Products. Industrial & Engineering Chemistry Research 2019, 58, 15945 -15957.
AMA StyleYann Lie, Pablo Ortiz, Richard Vendamme, Karolien Vanbroekhoven, Thomas J. Farmer. BioLogicTool: A Simple Visual Tool for Assisting in the Logical Selection of Pathways from Biomass to Products. Industrial & Engineering Chemistry Research. 2019; 58 (35):15945-15957.
Chicago/Turabian StyleYann Lie; Pablo Ortiz; Richard Vendamme; Karolien Vanbroekhoven; Thomas J. Farmer. 2019. "BioLogicTool: A Simple Visual Tool for Assisting in the Logical Selection of Pathways from Biomass to Products." Industrial & Engineering Chemistry Research 58, no. 35: 15945-15957.
Well‐controlled and extremely rapid ring‐opening metathesis polymerization of unusual oxa‐norbornene lactam esters by Grubbs 3rd generation catalyst is used to prepare a range of bio‐based homo‐ and co‐polymers. Bio‐derived oxa‐norbornene lactam monomers were prepared at room‐temperature from maleic anhydride and secondary furfuryl amines using a 100% atom economical, tandem Diels‐Alder‐lactamization reaction, followed by esterification. Several of the resulting homo‐ and co‐polymers show good control over polymer molecular weight and have narrow molecular weight distributions.
Anna Blanpain; James H. Clark; Thomas J. Farmer; Yuanlong Guo; Ian D. V. Ingram; John E. Kendrick; Stefan B. Lawrenson; Michael North; George Rodgers; Adrian C. Whitwood. Rapid Ring‐Opening Metathesis Polymerization of Monomers Obtained from Biomass‐Derived Furfuryl Amines and Maleic Anhydride. ChemSusChem 2019, 12, 2393 -2401.
AMA StyleAnna Blanpain, James H. Clark, Thomas J. Farmer, Yuanlong Guo, Ian D. V. Ingram, John E. Kendrick, Stefan B. Lawrenson, Michael North, George Rodgers, Adrian C. Whitwood. Rapid Ring‐Opening Metathesis Polymerization of Monomers Obtained from Biomass‐Derived Furfuryl Amines and Maleic Anhydride. ChemSusChem. 2019; 12 (11):2393-2401.
Chicago/Turabian StyleAnna Blanpain; James H. Clark; Thomas J. Farmer; Yuanlong Guo; Ian D. V. Ingram; John E. Kendrick; Stefan B. Lawrenson; Michael North; George Rodgers; Adrian C. Whitwood. 2019. "Rapid Ring‐Opening Metathesis Polymerization of Monomers Obtained from Biomass‐Derived Furfuryl Amines and Maleic Anhydride." ChemSusChem 12, no. 11: 2393-2401.
Biocatalyzed synthesis of aliphatic and furan-based polyesters in safer, bio-derived solvents for the substitution of toluene and tetrahydrofuran.
Alessandro Pellis; Fergal P. Byrne; James Sherwood; Marco Vastano; James W. Comerford; Thomas J. Farmer. Safer bio-based solvents to replace toluene and tetrahydrofuran for the biocatalyzed synthesis of polyesters. Green Chemistry 2019, 21, 1686 -1694.
AMA StyleAlessandro Pellis, Fergal P. Byrne, James Sherwood, Marco Vastano, James W. Comerford, Thomas J. Farmer. Safer bio-based solvents to replace toluene and tetrahydrofuran for the biocatalyzed synthesis of polyesters. Green Chemistry. 2019; 21 (7):1686-1694.
Chicago/Turabian StyleAlessandro Pellis; Fergal P. Byrne; James Sherwood; Marco Vastano; James W. Comerford; Thomas J. Farmer. 2019. "Safer bio-based solvents to replace toluene and tetrahydrofuran for the biocatalyzed synthesis of polyesters." Green Chemistry 21, no. 7: 1686-1694.