UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂
In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O₂ in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/F...
| Main Authors: | , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
Royal Society of Chemistry, The
2017
|
| Online Access: | http://hdl.handle.net/1721.1/109788 https://orcid.org/0000-0003-1720-0183 https://orcid.org/0000-0002-7096-138X |
| _version_ | 1826188450349449216 |
|---|---|
| author | Wang, Chen Bowman, Christopher N. Stansbury, Jeffrey W. Kaastrup, Kaja Aguirre Soto, Hector Alan Sikes Johnson, Hadley |
| author2 | Massachusetts Institute of Technology. Program in Polymers and Soft Matter |
| author_facet | Massachusetts Institute of Technology. Program in Polymers and Soft Matter Wang, Chen Bowman, Christopher N. Stansbury, Jeffrey W. Kaastrup, Kaja Aguirre Soto, Hector Alan Sikes Johnson, Hadley |
| author_sort | Wang, Chen |
| collection | MIT |
| description | In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O₂ in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/FT-NIR analytical tool for real-time, simultaneous monitoring of chromophore and monomer reactive group concentrations to investigate the eosin-activated photopolymerization of PEGDA-based hydrogels under ambient conditions. First, we address the challenges associated with spectroscopic monitoring of the polymerization of hydrogels using UV-Vis and FT-NIR, proposing metrics for quantifying the extent of signal loss from reflection and scattering, and showing their relation to microgelation and network formation. Second, having established a method for extracting kinetic information by eliminating the effects of changing refractive index and scattering, the coupled UV-Vis/FT-NIR system is applied to the study of eosin-activated photopolymerization of PEGDA in the presence of O₂. Analysis of the inhibition time, rate of polymerization, and rate of eosin consumption under ambient and purged conditions indicates that regeneration of eosin in the presence of oxygen and consumption of oxygen occur via a nonchain process. This suggests that the uniquely high O₂ resilience is due to alternative processes such as energy transfer from photo-activated eosin to oxygen. Uncovering the intricacies of the role of O₂ in eosin-mediated initiation aids the design of O₂ resistant free radical polymerization systems relevant to photonics, optoelectronics, biomaterials, and biosensing. |
| first_indexed | 2024-09-23T07:59:31Z |
| format | Article |
| id | mit-1721.1/109788 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T07:59:31Z |
| publishDate | 2017 |
| publisher | Royal Society of Chemistry, The |
| record_format | dspace |
| spelling | mit-1721.1/1097882022-09-23T10:09:09Z UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂ Wang, Chen Bowman, Christopher N. Stansbury, Jeffrey W. Kaastrup, Kaja Aguirre Soto, Hector Alan Sikes Johnson, Hadley Massachusetts Institute of Technology. Program in Polymers and Soft Matter Massachusetts Institute of Technology. Department of Chemical Engineering Kaastrup, Kaja Aguirre Soto, Hector Alan Sikes Johnson, Hadley In conjunction with a tertiary amine coinitiator, eosin, a photoreducible dye, has been shown to successfully circumvent oxygen inhibition in radical photopolymerization reactions. However, the role of O₂ in the initiation and polymerization processes remains inconclusive. Here, we employ a UV-Vis/FT-NIR analytical tool for real-time, simultaneous monitoring of chromophore and monomer reactive group concentrations to investigate the eosin-activated photopolymerization of PEGDA-based hydrogels under ambient conditions. First, we address the challenges associated with spectroscopic monitoring of the polymerization of hydrogels using UV-Vis and FT-NIR, proposing metrics for quantifying the extent of signal loss from reflection and scattering, and showing their relation to microgelation and network formation. Second, having established a method for extracting kinetic information by eliminating the effects of changing refractive index and scattering, the coupled UV-Vis/FT-NIR system is applied to the study of eosin-activated photopolymerization of PEGDA in the presence of O₂. Analysis of the inhibition time, rate of polymerization, and rate of eosin consumption under ambient and purged conditions indicates that regeneration of eosin in the presence of oxygen and consumption of oxygen occur via a nonchain process. This suggests that the uniquely high O₂ resilience is due to alternative processes such as energy transfer from photo-activated eosin to oxygen. Uncovering the intricacies of the role of O₂ in eosin-mediated initiation aids the design of O₂ resistant free radical polymerization systems relevant to photonics, optoelectronics, biomaterials, and biosensing. United States. Department of Defense (W81XWH-13-1-0272) 2017-06-12T14:47:17Z 2017-06-12T14:47:17Z 2015-11 2015-09 Article http://purl.org/eprint/type/JournalArticle 1759-9954 1759-9962 http://hdl.handle.net/1721.1/109788 Kaastrup, Kaja; Aguirre-Soto, Alan; Wang, Chen; Bowman, Christopher N.; Stansbury, Jeffrey W. and Sikes, Hadley D. “UV-Vis/FT-NIR in Situ Monitoring of Visible-Light Induced Polymerization of PEGDA Hydrogels Initiated by eosin/triethanolamine/O₂.” Polymer Chemistry 7, no. 3 (January 2016): 592–602 © 2016 The Royal Society of Chemistry https://orcid.org/0000-0003-1720-0183 https://orcid.org/0000-0002-7096-138X en_US http://dx.doi.org/10.1039/c5py01528f Polymer Chemistry Creative Commons Attribution-Noncommercial-Share Alike http://creativecommons.org/licenses/by-nc-sa/4.0/ application/pdf Royal Society of Chemistry, The PMC |
| spellingShingle | Wang, Chen Bowman, Christopher N. Stansbury, Jeffrey W. Kaastrup, Kaja Aguirre Soto, Hector Alan Sikes Johnson, Hadley UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂ |
| title | UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂ |
| title_full | UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂ |
| title_fullStr | UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂ |
| title_full_unstemmed | UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂ |
| title_short | UV-Vis/FT-NIR in situ monitoring of visible-light induced polymerization of PEGDA hydrogels initiated by eosin/triethanolamine/O₂ |
| title_sort | uv vis ft nir in situ monitoring of visible light induced polymerization of pegda hydrogels initiated by eosin triethanolamine o₂ |
| url | http://hdl.handle.net/1721.1/109788 https://orcid.org/0000-0003-1720-0183 https://orcid.org/0000-0002-7096-138X |
| work_keys_str_mv | AT wangchen uvvisftnirinsitumonitoringofvisiblelightinducedpolymerizationofpegdahydrogelsinitiatedbyeosintriethanolamineo2 AT bowmanchristophern uvvisftnirinsitumonitoringofvisiblelightinducedpolymerizationofpegdahydrogelsinitiatedbyeosintriethanolamineo2 AT stansburyjeffreyw uvvisftnirinsitumonitoringofvisiblelightinducedpolymerizationofpegdahydrogelsinitiatedbyeosintriethanolamineo2 AT kaastrupkaja uvvisftnirinsitumonitoringofvisiblelightinducedpolymerizationofpegdahydrogelsinitiatedbyeosintriethanolamineo2 AT aguirresotohectoralan uvvisftnirinsitumonitoringofvisiblelightinducedpolymerizationofpegdahydrogelsinitiatedbyeosintriethanolamineo2 AT sikesjohnsonhadley uvvisftnirinsitumonitoringofvisiblelightinducedpolymerizationofpegdahydrogelsinitiatedbyeosintriethanolamineo2 |