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RAFT polymerisation of renewable terpene (meth)acrylates and the convergent synthesis of methacrylate-acrylate-methacrylate triblock copolymers (2021)
Journal Article
Atkinson, R. L., Monaghan, O., Elsmore, M. T., Topham, P. D., Toolan, D. T. W., Derry, M. J., …Howdle, S. M. (2021). RAFT polymerisation of renewable terpene (meth)acrylates and the convergent synthesis of methacrylate-acrylate-methacrylate triblock copolymers. Polymer Chemistry, 12(21), 3177-3189. https://doi.org/10.1039/d1py00326g

Terpenes are ideal candidates for sustainable polymer feedstocks, due to their natural abundance and availability from existing waste streams. Previously, we have shown that a range of terpene(meth)acrylate monomers can be synthesised from the most c... Read More about RAFT polymerisation of renewable terpene (meth)acrylates and the convergent synthesis of methacrylate-acrylate-methacrylate triblock copolymers.

Synthesis of water-soluble surfactants using catalysed condensation polymerisation in green reaction media (2021)
Journal Article
Goddard, A. R., Apebende, E. A., Lentz, J. C., Carmichael, K., Taresco, V., Irvine, D. J., & Howdle, S. M. (2021). Synthesis of water-soluble surfactants using catalysed condensation polymerisation in green reaction media. Polymer Chemistry, 12(20), 2992-3003. https://doi.org/10.1039/d1py00415h

Sustainable and biobased surfactants are required for a wide range of everyday applications. Key drivers are cost, activity and efficiency of production. Polycondensation is an excellent route to build surfactant chains from bio-sourced monomers, but... Read More about Synthesis of water-soluble surfactants using catalysed condensation polymerisation in green reaction media.

Amylose/cellulose nanofiber composites for all-natural, fully biodegradable and flexible bioplastics (2020)
Journal Article
Xu, J., Sagnelli, D., Faisal, M., Perzon, A., Taresco, V., Mais, M., …Blennow, A. (2021). Amylose/cellulose nanofiber composites for all-natural, fully biodegradable and flexible bioplastics. Carbohydrate Polymers, 253, Article 117277. https://doi.org/10.1016/j.carbpol.2020.117277

Thermoplastic, polysaccharide-based plastics are environmentally friendly. However, typical shortcomings include lack of water resistance and poor mechanical properties. Nanocomposite manufacturing using pure, highly linear, polysaccharides can overc... Read More about Amylose/cellulose nanofiber composites for all-natural, fully biodegradable and flexible bioplastics.

On-line polymerisation monitoring in scCO2: a reliable and inexpensive sampling method in high pressure applications (2020)
Journal Article
Kortsen, K., Pacheco, A. A., Lentz, J. C., Taresco, V., & Howdle, S. M. (2021). On-line polymerisation monitoring in scCO2: a reliable and inexpensive sampling method in high pressure applications. Journal of Supercritical Fluids, 167, Article 105047. https://doi.org/10.1016/j.supflu.2020.105047

A versatile and reliable on-line sampling system for polymerisation reactions in supercritical fluids was developed. By withdrawing a small volume of a high-pressure reaction mixture and expanding it in a controlled volume, reliable kinetic data were... Read More about On-line polymerisation monitoring in scCO2: a reliable and inexpensive sampling method in high pressure applications.

Synthesis of Passerini-3CR Polymers and Assembly into Cytocompatible Polymersomes (2020)
Journal Article
Travanut, A., Monteiro, P. F., Oelmann, S., Howdle, S. M., Grabowska, A. M., Clarke, P. A., …Alexander, C. (2021). Synthesis of Passerini-3CR Polymers and Assembly into Cytocompatible Polymersomes. Macromolecular Rapid Communications, 42(6), Article 2000321. https://doi.org/10.1002/marc.202000321

© 2020 The Authors. Published by Wiley-VCH GmbH The versatility of the Passerini three component reaction (Passerini-3CR) is herein exploited for the synthesis of an amphiphilic diblock copolymer, which self-assembles into polymersomes. Carboxy-funct... Read More about Synthesis of Passerini-3CR Polymers and Assembly into Cytocompatible Polymersomes.

Synthesis of two-phase polymer particles in supercritical carbon dioxide (2020)
Journal Article
Haddleton, A., Bennett, T. M., Chen, X., Atkinson, R. L., Taresco, V., & Howdle, S. M. (2020). Synthesis of two-phase polymer particles in supercritical carbon dioxide. Polymer Chemistry, 11(31), 5029-5039. https://doi.org/10.1039/d0py00729c

The synthesis of particles with discrete phases using traditional emulsion polymerisation is a well-established process. Phase-separated particles have a wide range of applications, such as in coatings, drug delivery, impact modification and as suppo... Read More about Synthesis of two-phase polymer particles in supercritical carbon dioxide.

Clean synthesis of linear and star amphiphilic poly(ε-caprolactone)-block-poly(ethyl ethylene phosphonate) block copolymers: assessing self-assembly and surface activity (2020)
Journal Article
Baheti, P., Rheinberger, T., Gimello, O., Bouilhac, C., Wurm, F. R., Lacroix-Desmazes, P., & Howdle, S. M. (2020). Clean synthesis of linear and star amphiphilic poly(ε-caprolactone)-block-poly(ethyl ethylene phosphonate) block copolymers: assessing self-assembly and surface activity. Green Chemistry, 22(10), 3248-3261. https://doi.org/10.1039/d0gc00819b

2‐Methyltetrahydrofuran (2‐MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP, FRP, and RAFT tandem polymerizations (2020)
Journal Article
Englezou, G., Kortsen, K., Pacheco, A. A. C., Cavanagh, R., Lentz, J. C., Krumins, E., …Taresco, V. (2020). 2‐Methyltetrahydrofuran (2‐MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP, FRP, and RAFT tandem polymerizations. Journal of Polymer Science, 58(11), 1571-1581. https://doi.org/10.1002/pol.20200183

2‐methyltetrahydrofuran (2‐MeTHF) is a readily available, inexpensive, neoteric, bio‐based solvent. It has been adopted across a wide range of chemical processes including the batch manufacture of fine chemicals, enzymatic polycondensations and ring... Read More about 2‐Methyltetrahydrofuran (2‐MeTHF) as a versatile green solvent for the synthesis of amphiphilic copolymers via ROP, FRP, and RAFT tandem polymerizations.

Starch/Poly(glycerol-adipate) Nanocomposites: A Novel Oral Drug Delivery Device (2020)
Journal Article
Vestri, A., Pearce, A. K., Cavanagh, R., Styliari, I. D., Sanders, C., Couturaud, B., …Sagnelli, D. (2020). Starch/Poly(glycerol-adipate) Nanocomposites: A Novel Oral Drug Delivery Device. Coatings, 10(2), Article 125. https://doi.org/10.3390/coatings10020125

Biocompatible and bio-based materials are an appealing resource for the pharmaceutical industry. Poly(glycerol-adipate) (PGA) is a biocompatible and biodegradable polymer that can be used to produce self-assembled nanoparticles (NPs) able to encapsul... Read More about Starch/Poly(glycerol-adipate) Nanocomposites: A Novel Oral Drug Delivery Device.

Enzymatic One-Pot Synthesis of Renewable and Biodegradable Surfactants in Supercritical Carbon Dioxide (scCO2) (2020)
Journal Article
d’Almeida Gamiero, M., Goddard, A. . R., Taresco, V., & Howdle, S. M. (2020). Enzymatic One-Pot Synthesis of Renewable and Biodegradable Surfactants in Supercritical Carbon Dioxide (scCO2). Green Chemistry, 22(4), 1308-1318. https://doi.org/10.1039/c9gc04011k

We seek to expand the opportunities to exploit glycerol, a largely untapped renewable feedstock, by exploiting enzymatic catalysis in supercritical carbon dioxide (scCO2). This work highlights a promising and clean approach to bio-renewable amphiphil... Read More about Enzymatic One-Pot Synthesis of Renewable and Biodegradable Surfactants in Supercritical Carbon Dioxide (scCO2).

Starch/Poly (Glycerol-Adipate) Nanocomposite Film as Novel Biocompatible Materials (2019)
Journal Article
Sagnelli, Cavanagh, Xu, Swainson, Blennow, Duncan, …Howdle. (2019). Starch/Poly (Glycerol-Adipate) Nanocomposite Film as Novel Biocompatible Materials. Coatings, 9(8), Article 482. https://doi.org/10.3390/coatings9080482

Starch is one of the most abundant polysaccharides on the earth and it is the most important source of energy intake for humans. Thermoplastic starch (TPS) is also widely used for new bio-based materials. The blending of starch with other molecules m... Read More about Starch/Poly (Glycerol-Adipate) Nanocomposite Film as Novel Biocompatible Materials.

Polyacrylates Derived from Biobased Ethyl Lactate Solvent via SET-LRP (2019)
Journal Article
Bensabeh, N., Moreno, A., Roig, A., Monaghan, O. R., Ronda, J. C., Cádiz, V., …Percec, V. (2019). Polyacrylates Derived from Biobased Ethyl Lactate Solvent via SET-LRP. Biomacromolecules, 20(5), 2135-2147. https://doi.org/10.1021/acs.biomac.9b00435

The precise synthesis of polymers derived from alkyl lactate ester acrylates is reported for the first time. Kinetic experiments were conducted to demonstrate that Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP)... Read More about Polyacrylates Derived from Biobased Ethyl Lactate Solvent via SET-LRP.

New renewably-sourced polyesters from limonene-derived monomers (2018)
Journal Article
Thomsett, M. R., Moore, J. C., Buchard, A., Stockman, R. A., & Howdle, S. M. (2019). New renewably-sourced polyesters from limonene-derived monomers. Green Chemistry, 21(1), 149-156. https://doi.org/10.1039/c8gc02957a

The functionalisation of limonene has enabled the synthesis of two renewably-sourced monomers for the formation of terpene-derived polyesters. Three methods for the synthesis of the novel hydroxy-acid 6 are reported and their green-credentials scruti... Read More about New renewably-sourced polyesters from limonene-derived monomers.

Sustainable synthesis and precise characterisation of bio-based star polycaprolactone synthesised with a metal catalyst and with lipase (2018)
Journal Article
Baheti, P., Gimello, O., Bouilhac, C., Lacroix-Desmazes, P., & Howdle, S. M. (2018). Sustainable synthesis and precise characterisation of bio-based star polycaprolactone synthesised with a metal catalyst and with lipase. Polymer Chemistry, 9(47), 5594-5607. https://doi.org/10.1039/c8py01266k

Bio-based building blocks and sustainable synthesis pathways were used to synthesise star-shaped polymers composed of a D-sorbitol core and polycaprolactone arms by ring opening polymerisation (ROP). The use of volatile organic solvents was avoided a... Read More about Sustainable synthesis and precise characterisation of bio-based star polycaprolactone synthesised with a metal catalyst and with lipase.

Antimicrobial peptide encapsulation and sustained release from polymer network particles prepared in supercritical carbon dioxide (2018)
Journal Article
Parilti, R., Caprasse, J., Riva, R., Alexandre, M., Vandegaart, H., Bebrone, C., …Jérôme, C. (2018). Antimicrobial peptide encapsulation and sustained release from polymer network particles prepared in supercritical carbon dioxide. Journal of Colloid and Interface Science, 532, 112-117. https://doi.org/10.1016/j.jcis.2018.07.125

© 2018 Antimicrobial peptide loaded poly(2-hydroxyethyl methacrylate) particles were synthesized in supercritical carbon dioxide via one-pot free-radical dispersion polymerisation of 2-hydroxyethyl methacrylate and a cross-linker. Discrete particles... Read More about Antimicrobial peptide encapsulation and sustained release from polymer network particles prepared in supercritical carbon dioxide.

Sulindac encapsulation and release from functional poly(HEMA) microparticles prepared in supercritical carbon dioxide (2018)
Journal Article
Parilti, R., Riva, R., Howdle, S. M., Dupont-Gillain, C., & Jerome, C. (2018). Sulindac encapsulation and release from functional poly(HEMA) microparticles prepared in supercritical carbon dioxide. International Journal of Pharmaceutics, 549(1-2), 161-168. https://doi.org/10.1016/j.ijpharm.2018.07.060

Sulindac loaded poly(HEMA) cross-linked microparticles were synthesized via one-pot free radical dispersion polymerisation in supercritical carbon dioxide (scCO2) in presence of photocleavable diblock stabilisers based on polyethylene oxide (PEO) and... Read More about Sulindac encapsulation and release from functional poly(HEMA) microparticles prepared in supercritical carbon dioxide.

Synthesis and control of crosslinked poly(acrylic acid) based viscosity modifiers using dense phase carbon dioxide as a solvent (2018)
Journal Article
Alexander, W., Wickson, J., Duncan, J., Carmichael, K., Irvine, D., & Howdle, S. (2018). Synthesis and control of crosslinked poly(acrylic acid) based viscosity modifiers using dense phase carbon dioxide as a solvent. Journal of Supercritical Fluids, 139, 38-44. https://doi.org/10.1016/j.supflu.2018.05.003

We investigate the clean synthesis of a cross-linked poly(acrylic acid) viscosity modifier using supercritical CO2 to replace more hazardous volatile organic solvents that are typically used for this process. The polymers were analysed by aqueous swe... Read More about Synthesis and control of crosslinked poly(acrylic acid) based viscosity modifiers using dense phase carbon dioxide as a solvent.

Can a combination of poly(ethylene glycol) and dense phase carbon dioxide improve processing of polylactide? A high pressure rheology investigation (2017)
Journal Article
Pepper, K., Masson, T., De Focatiis, D. S., & Howdle, S. M. (in press). Can a combination of poly(ethylene glycol) and dense phase carbon dioxide improve processing of polylactide? A high pressure rheology investigation. Journal of Supercritical Fluids, 133(1), https://doi.org/10.1016/j.supflu.2017.10.014

High temperature melts or use of organic solvents are not practicable approaches for encapsulating protein based or thermally labile drugs into degradable polymers. Here, we demonstrate that poly(ethylene glycol) (PEG) in combination with supercritic... Read More about Can a combination of poly(ethylene glycol) and dense phase carbon dioxide improve processing of polylactide? A high pressure rheology investigation.

One-pot synthesis of micron-sized polybetaine particles: innovative use of supercritical carbon dioxide (2017)
Journal Article
Bassett, S. P., Birkin, N. A., Jennings, J., Champman, E., O'Reilly, R. K., Howdle, S. M., & Willcock, H. (in press). One-pot synthesis of micron-sized polybetaine particles: innovative use of supercritical carbon dioxide. Polymer Chemistry, 8, https://doi.org/10.1039/C7PY00455A

Polybetaines exhibit unique properties combining anti-polyelectrolyte and low protein fouling behaviour, as well as biocompatibility. To date, the synthesis of polybetaine particles >50 nm has proved to be extremely challenging with standard emulsion... Read More about One-pot synthesis of micron-sized polybetaine particles: innovative use of supercritical carbon dioxide.

Mild synthesis of poly(HEMA)-networks as well-defined nanoparticles in supercritical carbon dioxide (2017)
Journal Article
Parilti, R., Alaimo, D., Grignard, B., Boury, F., Howdle, S., & Jerome, C. (2017). Mild synthesis of poly(HEMA)-networks as well-defined nanoparticles in supercritical carbon dioxide. Journal of Materials Chemistry B, 5, https://doi.org/10.1039/C7TB00740J

Free-radical dispersion polymerisation of 2-hydroxyethyl methacrylate was carried out in supercritical carbon dioxide (scCO2) in the presence of stabilisers based on polyethylene oxide (PEO) and poly(heptadecafluorodecyl acrylate) (PFDA). Different a... Read More about Mild synthesis of poly(HEMA)-networks as well-defined nanoparticles in supercritical carbon dioxide.