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Dynamic Viologen Materials : = Working Toward Fully Integrated Photoresponsive Hydrogels.

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	Dynamic Viologen Materials :/
Reminder of title:	Working Toward Fully Integrated Photoresponsive Hydrogels.
Author:	Danielson, Mary.
Description:	1 online resource (212 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 85-02, Section: B.
Contained By:	Dissertations Abstracts International85-02B.
Subject:	Polymer chemistry. -
Online resource:	click for full text (PQDT)
ISBN:	9798380151917

Dynamic Viologen Materials : = Working Toward Fully Integrated Photoresponsive Hydrogels.
Danielson, Mary.

Dynamic Viologen Materials :Working Toward Fully Integrated Photoresponsive Hydrogels. - 1 online resource (212 pages)

Source: Dissertations Abstracts International, Volume: 85-02, Section: B.

Thesis (Ph.D.)--Washington University in St. Louis, 2023.

Includes bibliographical references

Every day technology is advancing exponentially. In order to keep pace with the speed of discovery, both new materials, new devices, and new methods of thinking are needed. Materials that change shape, as well as charge, provide possibilities for new types of cell growth matrices, robotic soft muscles, as well as water harvesting. To this end, we posit that the use of novel photoredox mechanisms could be used to develop another dimension of material properties. In this work I will describe the immense utility of both hydrogels as a model material and viologens as an effective method of understanding the material potential of radical stacking. Because of their wide applicability, both hydrogels and viologens have been thoroughly investigated. However, we describe a new type of viologen polymer: a unimolecular crosslinker capable of encouraging viologen-based radical molecular recognition at very low total concentration. This type of material is capable of stimuli-responsive changes. Here, I describe three types of stimuli-responsiveness that our viologen hydrogels have been shown to respond to: chemical reductants, heat, and light. However, given its wide applicability, our most current and advanced responsive hydrogels are based on photoelectron transfer initiated by irradiation with visible light. While much work has already been done by the previous scientists from our lab, there was a fundamental gap in understanding how the photoelectron transfer (PET) changes between small molecule viologen and our polymeric viscoelastic materials. In Chapter 2, I describe a study done in the solid phase to understand how the PET mechanism works between a water-soluble polythiophene and a highly charged, and highly crosslinked viologen thin film. A wide variety of tests were conducted, including transient absorption spectroscopy to understand the time scale of the PET. Water droplet contract angle analysis was completed as well to describe any changes in the surface energy of the viologen film as it drops from a net +2 charge per unit to a net +1 charge per viologen unit. In Chapter 3, I use the information gleaned from the bilayered film study to design a fully integrated viologen hydrogel. This gel required no replenishment of any gel component except water due to the electrostatic incorporation of the photocatalyst and the covalent binding of a new sacrificial reductant monomer. I then show how this new system could be used to desalinate existing saltwater, Chapter 4, and propose further experiments on how to incorporate a desiccant system for atmospheric water harvesting, Chapter 5.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2024

Mode of access: World Wide Web

ISBN: 9798380151917Subjects--Topical Terms:

1182163
Polymer chemistry.
Subjects--Index Terms:

Unimolecular crosslinkerIndex Terms--Genre/Form:

554714
Electronic books.

Dynamic Viologen Materials : = Working Toward Fully Integrated Photoresponsive Hydrogels.
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504 $a Includes bibliographical references
520 $a Every day technology is advancing exponentially. In order to keep pace with the speed of discovery, both new materials, new devices, and new methods of thinking are needed. Materials that change shape, as well as charge, provide possibilities for new types of cell growth matrices, robotic soft muscles, as well as water harvesting. To this end, we posit that the use of novel photoredox mechanisms could be used to develop another dimension of material properties. In this work I will describe the immense utility of both hydrogels as a model material and viologens as an effective method of understanding the material potential of radical stacking. Because of their wide applicability, both hydrogels and viologens have been thoroughly investigated. However, we describe a new type of viologen polymer: a unimolecular crosslinker capable of encouraging viologen-based radical molecular recognition at very low total concentration. This type of material is capable of stimuli-responsive changes. Here, I describe three types of stimuli-responsiveness that our viologen hydrogels have been shown to respond to: chemical reductants, heat, and light. However, given its wide applicability, our most current and advanced responsive hydrogels are based on photoelectron transfer initiated by irradiation with visible light. While much work has already been done by the previous scientists from our lab, there was a fundamental gap in understanding how the photoelectron transfer (PET) changes between small molecule viologen and our polymeric viscoelastic materials. In Chapter 2, I describe a study done in the solid phase to understand how the PET mechanism works between a water-soluble polythiophene and a highly charged, and highly crosslinked viologen thin film. A wide variety of tests were conducted, including transient absorption spectroscopy to understand the time scale of the PET. Water droplet contract angle analysis was completed as well to describe any changes in the surface energy of the viologen film as it drops from a net +2 charge per unit to a net +1 charge per viologen unit. In Chapter 3, I use the information gleaned from the bilayered film study to design a fully integrated viologen hydrogel. This gel required no replenishment of any gel component except water due to the electrostatic incorporation of the photocatalyst and the covalent binding of a new sacrificial reductant monomer. I then show how this new system could be used to desalinate existing saltwater, Chapter 4, and propose further experiments on how to incorporate a desiccant system for atmospheric water harvesting, Chapter 5.
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650 4 $a Organic chemistry. $3 1148722
650 4 $a Materials science. $3 557839
653 $a Unimolecular crosslinker
653 $a Hydrogel
653 $a Polythiophene
653 $a Styrene
653 $a Triethanolamine acrylate
653 $a Viologen
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