Polymerized High Internal Phase Emulsions

An SEM image of a porous PDMS polyHIPE

An SEM image of a PDMS polyHIPE prepared in our Lab

We are preparing soft porous materials using emulsion templating. Materials prepared using this technique are often referred to as polymerized high internal phase emulsions. We have initially focused on preparing polydimethylsiloxane polyHIPEs and demonstrated how we can use thiol-ene chemistry to polymerize PDMS macromolecules into porous materials. Our initial materials have been tested as acoustic materials by Prof. Thomas Brunet and Prof. Olivier Mondain-Monval at the University of Bordeaux, and the polyHIPEs have been seen to reduce the sound of sound waves to very low values.

OUR RECENT PUBLICATIONS IN THIS AREA

  • Tucker J. McKenzie, Kathryn Rost, Soren Smail, Olivier Mondain-Monval, Thomas Brunet, and Neil Ayres (2022) Mechanically tunable PDMS-based polyHIPE acoustic materials Journal of Materials Chemistry C 10, 6222-6226

  • Tucker J. McKenzie, Soren Smail, Kathryn Rost, Kabir Rishi, Gregory Beaucage, and Neil Ayres (2021) Multi-layered polymerized high internal phase emulsions with controllable porosity and strong interfaces Polymer 231, 124116

  • Tucker J. McKenzie, Paul S. Heaton, Kabir Rishi, Raj Kumar, Thomas Brunet, Gregory Beaucage, Olivier Mondain-Monval, and Neil Ayres (2020) Storage moduli and porosity of soft PDMS PolyMIPEs can be controlled independently using thiol−ene click chemistry Macromolecules 53, 3719-3727


Three supramolecular polymer organogels prepared in our lab

 POLYMER GELS AND NETWORKS

We have a growing interest in stimuli-responsive polymer networks, including hydrogels, organogels, those made by permanent covalent crosslinks, and those made using supramolecular crosslinks. In newer work we have been investigating how the physical properties of hydrogels and polymer networks can be changed based on the chemistry of the polymers.

OUR RECENT PUBLICATIONS IN THIS AREA

  • Prathyusha Chimala, M. Mario Perera, Aissatou Wade, Tucker McKenzie, Joshua Allor and Neil Ayres (2021) Hyperbranched polymer hydrogels with large stimuli-responsive changes in storage moduli and peroxide-induced healing Polymer Chemistry 12, 4384-4393

  • M. Mario Perera, Prathyusha Chimala, Abdul Elhusain-Elnegres, Paul Heaton, and Neil Ayres (2020) Reversibly Softening and Stiffening Organogels Using a Wavelength-Controlled Disulfide-Diselenide Exchange ACS Macro Letters 9, 1552-1557

  • M. Mario Perera and Neil Ayres (2020) Dynamic covalent bonds in self-healing, shape memory, and controllable stiffness hydrogels Polymer Chemistry 11, 1410-1423

  • M. Mario Perera, Demetria M. Fischesser, Jeffery D. Molkentin, and Neil Ayres Stiffness of thermoresponsive gelatin-based dynamic hydrogels affects fibroblast activation Polymer Chemistry (2019) 10, 6360-6367

  • M. Mario Perera and Neil Ayres (2017) Gelatin based dynamic hydrogels via thiol-norbornene reactions Polymer Chemistry 8 6741-6749

  • Yongshun Huang, Qinyuan Chai, Mary R. Warmin, and Neil Ayres (2016) Lactose-containing hydrogels for enzyme stabilization Journal of Polymer Science, Part A: Polymer Chemistry 2507-2514

  • Xinjun Yu, Xiaoping Chen, Qinyuan Chai and Neil Ayres (2016) Synthesis of polymer organogelators using hydrogen bonding as physical cross-links Colloid and Polymer Science 294 (1) 59-68

  • Xiaoping Chen, Pengzhan Fei, Kevin A Cavicchi, WenwenYang, and Neil Ayres (2014) The poor solubility of ureidopyrimidone can be used to form gels of low molecular weight N-alkyl urea oligomers in organic solvents Colloid and Polymer Science 292 (2) 477-484

  • Chen X., Ding K., Ayres N. (2011) Investigation into fiber formation in N-alkyl urea peptoid oligomers and the synthesis of a water-soluble PEG/N-alkyl urea peptoid oligomer conjugate Polymer Chemistry 2 2635-2642


Sugar-Containing Biomaterials and Shape Memory Materials

Platelets adhering to a polyurethane surface

One focus of our research has been investigating blood compatible polymers that are inspired by the naturally occurring anticoagulant molecule, heparin.  Our polymers are based on polyureas and polyurethanes with N-alkyl pendent sugar groups including mannose, glucose, lactose, and glucosamine. We have found that the blood compatibility of the polymers is dependent upon factors including the nature of the sugar, the flexibility of the polymer backbone, and the degree of sulfation of the sugar ring. We recently presented a route to lactose-functionalized polyurethanes materials and hydrogels that have showed shape memory properties. We redesigned our monomer synthesis to yield 100g scales of monomers.

A shape memory polymer foam made in our lab.

OUR RECENT PUBLICATIONS IN THIS AREA

  • Emily Dalton, Zachary Morris, and Neil Ayres (2022) Synthesis and characterization of sulfated-lactose polyurethane hydrogels Polymer Chemistry, 2022, 13, 2933-2940

  • Emily Dalton, Qinyuan Chai, Molly W. Shaw, Tucker J. McKenzie, Eric S. Mullins, and Neil Ayres (2019) Hydrogel-coated polyurethane/urea shape memory polymer foams Journal of Polymer Science, Part A: Polymer Chemistry, 57 1389-1395

  • Qinyuan Chai, Yongshun Huang, Terrence Kirley, and Neil Ayres (2017) Shape memory polymer foams prepared from a heparin-inspired polyurethane/urea 8, 5039-5048

  • Yongshun Huang, Maureen A. Shaw, Mary R. Warmin, Eric S. Mullins and Neil Ayres (2016) Blood compatibility of heparin inspired, lactose containing, polyureas depends on the chemistry of the polymer backbone Polymer Chemistry 7 3897-3905

  • Qinyuan Chai, Yongshun Huang and Neil Ayres (2015) Shape memory biomaterials prepared from polyurethane/ureas containing sulfated glucose Journal of Polymer Science, Part A: Polymer Chemistry 53(19) 2252-2257 (Spotlight Article)

  • Yongshun Huang, Maureen A. Shaw, Eric S. Mullins, Terence L. Kirley, and Neil Ayres (2014) Synthesis and Anticoagulant Activity of Polyureas Containing Sulfated Carbohydrates Biomacromolecules 15(12) 4455-4466

  • Yongshun Huang, Leeanne Taylor, Xiaoping Chen, and Neil Ayres (2013) Synthesis of a polyurea from a glucose or mannose containing N-alkyl urea peptoid oligomer Journal of Polymer Science, Part A: Polymer Chemistry 51(24) 5230-5238

  • Taylor L., Chen X., Ayres N. (2014) Synthesis of a glycosaminoglycan polymer mimetic using an N-alkyl-N,N-linked urea oligomer containing glucose pendant groups Polymer International 63 127-135