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Light-Responsive Materials via the S...

Feeney, Matthew J.

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Light-Responsive Materials via the Self-Assembly of Synthetic Polymers.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Light-Responsive Materials via the Self-Assembly of Synthetic Polymers./
Author:	Feeney, Matthew J.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2020,
Description:	236 p.
Notes:	Source: Dissertations Abstracts International, Volume: 81-10, Section: B.
Contained By:	Dissertations Abstracts International81-10B.
Subject:	Organic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=27735729
ISBN:	9781658416504

Light-Responsive Materials via the Self-Assembly of Synthetic Polymers.
Feeney, Matthew J.

Light-Responsive Materials via the Self-Assembly of Synthetic Polymers. - Ann Arbor : ProQuest Dissertations & Theses, 2020 - 236 p.

Source: Dissertations Abstracts International, Volume: 81-10, Section: B.

Thesis (Ph.D.)--Tufts University, 2020.

This item must not be sold to any third party vendors.

The ability to exert precise structural and chemical control over material interfaces is a powerful tool that is not readily available for many material fabrication techniques. Layer-by-layer self-assembly (LbL) utilizes the association of polymer components to build films from the bottom-up, affording nanometer-scale structural resolution in the thickness of the films. By further imbuing LbL materials with light responsivity, a great deal of material precision is possible in three dimensions. By utilizing three specific photochemical reactions - photolysis, photocycloaddition, and photochromism - precision over LbL is exerted in distinct ways that highlight the versatility of the films towards numerous functions.Chapter 2 discusses the development of a PEM film that undergoes triggered dissolution upon NIR-induced photolysis. This is an important undertaking from an applied perspective, as light-responsive materials designed for use as potential therapeutic platforms should be sensitive to colors of light that are biologically transparent. Additionally, the demonstration of pH-gated photolytic dissolution provides fundamental insight into the role of polyelectrolyte hydrophobicity in stabilizing PEMs. Specifically, these experiments provide an elegant example of the plurality of interactive forces working in unison to stabilize PEM films. Chapter 3 introduces the second photo response, photocycloaddition, to reversibly crosslink free-standing LbL materials. A major challenge for free-standing LbL materials is their difficult handling and relative ease of degradation, due in large part to their minute (often submicron) thicknesses. Contrary to Chapter 2, photocrosslinking of LbL films enhances their material properties, protecting them from dissolution and degradation. By utilizing this chemistry, the material properties of submicron-thick free-standing membranes can be improved. Additionally, film properties can be precisely tuned by designing the crosslinking chemistry to be reversible.Chapter 4 describes the incorporation of spiropyran into water soluble polymers in order to study its behavior in aqueous systems. Both the charge of inert comonomers and the substituents on spiropyran were found to have profound effects on photochromic behavior. Upon exploring the structure-property space, the application of the various spiropyran polymers as photoacids and charge shifting materials is discussed.

ISBN: 9781658416504Subjects--Topical Terms:

523952
Organic chemistry.
Subjects--Index Terms:

Layer-by-layer

Light-Responsive Materials via the Self-Assembly of Synthetic Polymers.
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245 1 0 $a Light-Responsive Materials via the Self-Assembly of Synthetic Polymers.
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300 $a 236 p.
500 $a Source: Dissertations Abstracts International, Volume: 81-10, Section: B.
500 $a Advisor: Thomas, Samuel W.
502 $a Thesis (Ph.D.)--Tufts University, 2020.
506 $a This item must not be sold to any third party vendors.
506 $a This item must not be added to any third party search indexes.
520 $a The ability to exert precise structural and chemical control over material interfaces is a powerful tool that is not readily available for many material fabrication techniques. Layer-by-layer self-assembly (LbL) utilizes the association of polymer components to build films from the bottom-up, affording nanometer-scale structural resolution in the thickness of the films. By further imbuing LbL materials with light responsivity, a great deal of material precision is possible in three dimensions. By utilizing three specific photochemical reactions - photolysis, photocycloaddition, and photochromism - precision over LbL is exerted in distinct ways that highlight the versatility of the films towards numerous functions.Chapter 2 discusses the development of a PEM film that undergoes triggered dissolution upon NIR-induced photolysis. This is an important undertaking from an applied perspective, as light-responsive materials designed for use as potential therapeutic platforms should be sensitive to colors of light that are biologically transparent. Additionally, the demonstration of pH-gated photolytic dissolution provides fundamental insight into the role of polyelectrolyte hydrophobicity in stabilizing PEMs. Specifically, these experiments provide an elegant example of the plurality of interactive forces working in unison to stabilize PEM films. Chapter 3 introduces the second photo response, photocycloaddition, to reversibly crosslink free-standing LbL materials. A major challenge for free-standing LbL materials is their difficult handling and relative ease of degradation, due in large part to their minute (often submicron) thicknesses. Contrary to Chapter 2, photocrosslinking of LbL films enhances their material properties, protecting them from dissolution and degradation. By utilizing this chemistry, the material properties of submicron-thick free-standing membranes can be improved. Additionally, film properties can be precisely tuned by designing the crosslinking chemistry to be reversible.Chapter 4 describes the incorporation of spiropyran into water soluble polymers in order to study its behavior in aqueous systems. Both the charge of inert comonomers and the substituents on spiropyran were found to have profound effects on photochromic behavior. Upon exploring the structure-property space, the application of the various spiropyran polymers as photoacids and charge shifting materials is discussed.
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650 4 $a Materials science. $3 543314
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653 $a Photochemistry
653 $a Photochromism
653 $a Photodimerization
653 $a Photolysis
653 $a Polymers
690 $a 0490
690 $a 0794
710 2 $a Tufts University. $b Chemistry. $3 1058685
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791 $a Ph.D.
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793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=27735729