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Design of Synthetic Macromolecules: Leveraging Nonequilibrium Behavior and Computational Insights
Design of Synthetic Macromolecules: Leveraging Nonequilibrium Behavior and Computational Insights
상세정보
- 자료유형
- 학위논문 서양
- 최종처리일시
- 20260202104649
- ISBN
- 9798291554333
- DDC
- 547
- 서명/저자
- Design of Synthetic Macromolecules: Leveraging Nonequilibrium Behavior and Computational Insights
- 발행사항
- [Sl] : The University of North Carolina at Chapel Hill, 2025
- 발행사항
- Ann Arbor : ProQuest Dissertations & Theses, 2025
- 형태사항
- 304 p
- 주기사항
- Source: Dissertations Abstracts International, Volume: 87-02, Section: B.
- 주기사항
- Advisor: Knight, Abigail S.;Lu, Zhiyue.
- 학위논문주기
- Thesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2025.
- 초록/해제
- 요약Biomacromolecules are unrivaled as molecular machines, exhibiting well-defined hierarchical structures that result in precisely tuned functionality. Spanning single conformations to self-assemblies, the necessity for specific structures to result in emergent properties has been explored in biochemistry for decades. However, biomacromolecules can be challenging to adapt beyond their native contexts, due to limited stability in ambient conditions and narrow design scope (i.e., 20 amino acids for proteins). This need has led to the search for synthetic macromolecules to mimic and potentially even surpass their biological counterparts. A larger chemical design scope promises greater modularity within these materials, but this high-dimensional landscape is difficult to effectively navigate, with complex feature-feature dependence between different chemistries, architectures, and chemical patterning. Further, nonequilibrium effects (e.g., stimulus history dependence) add complexity and remain poorly understood in synthetic scaffolds. We herein address these challenges through an integrated experimental-computational strategy, where thorough characterization of model systems has yielded chemical principles towards effective macromolecule design. First, we describe thermal hysteresis within thermoresponsive synthetic copolymers as a model system to understand nonequilibrium effects in self-assembly. We further extend these experimental insights by developing a geometric framework to help design nonequilibrium control protocols to steer self-assemblies. We also derive and validate a kinetic Monte Carlo strategy specific for time-dependent processes such as feedback and open-loop control protocols, and we validate this algorithm on minimal models. We then leverage stimulus-responsive self-assembly towards rational design of lanthanide precipitants and describe effects of thermal incubation, chemical composition and chemical patterning on ion extraction efficiency and metal-mediated structural changes. Finally, drawing inspiration from numerical simulation, we develop an empirical formalism to estimate relevant kinetic rates from experimental data to reconstruct sequence ensembles of synthetic copolymers, and by using an information-theoretic approach, we demonstrate strategies to visualize and quantitate differences between distributions. Taken together, these interdisciplinary studies help bridge the gap between fundamental and functional insights, shedding light onto how previously confounding factors such as nonequilibrium properties can be better leveraged and developing workflows at the interface of experimental and computational chemistry.
- 일반주제명
- Polymer chemistry
- 일반주제명
- Chemistry
- 일반주제명
- Bioinformatics
- 일반주제명
- Computational chemistry
- 기타저자
- The University of North Carolina at Chapel Hill Chemistry
- 기본자료저록
- Dissertations Abstracts International. 87-02B.
- 전자적 위치 및 접속
- 로그인 후 원문을 볼 수 있습니다.
MARC
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■006m o d
■007cr#unu||||||||
■020 ▼a9798291554333
■035 ▼a(MiAaPQ)AAI32115106
■040 ▼aMiAaPQ▼cMiAaPQ
■0820 ▼a547
■1001 ▼aChittari, Supraja S.
■24510▼aDesign of Synthetic Macromolecules: Leveraging Nonequilibrium Behavior and Computational Insights
■260 ▼a[Sl]▼bThe University of North Carolina at Chapel Hill▼c2025
■260 1▼aAnn Arbor▼bProQuest Dissertations & Theses▼c2025
■300 ▼a304 p
■500 ▼aSource: Dissertations Abstracts International, Volume: 87-02, Section: B.
■500 ▼aAdvisor: Knight, Abigail S.;Lu, Zhiyue.
■5021 ▼aThesis (Ph.D.)--The University of North Carolina at Chapel Hill, 2025.
■520 ▼aBiomacromolecules are unrivaled as molecular machines, exhibiting well-defined hierarchical structures that result in precisely tuned functionality. Spanning single conformations to self-assemblies, the necessity for specific structures to result in emergent properties has been explored in biochemistry for decades. However, biomacromolecules can be challenging to adapt beyond their native contexts, due to limited stability in ambient conditions and narrow design scope (i.e., 20 amino acids for proteins). This need has led to the search for synthetic macromolecules to mimic and potentially even surpass their biological counterparts. A larger chemical design scope promises greater modularity within these materials, but this high-dimensional landscape is difficult to effectively navigate, with complex feature-feature dependence between different chemistries, architectures, and chemical patterning. Further, nonequilibrium effects (e.g., stimulus history dependence) add complexity and remain poorly understood in synthetic scaffolds. We herein address these challenges through an integrated experimental-computational strategy, where thorough characterization of model systems has yielded chemical principles towards effective macromolecule design. First, we describe thermal hysteresis within thermoresponsive synthetic copolymers as a model system to understand nonequilibrium effects in self-assembly. We further extend these experimental insights by developing a geometric framework to help design nonequilibrium control protocols to steer self-assemblies. We also derive and validate a kinetic Monte Carlo strategy specific for time-dependent processes such as feedback and open-loop control protocols, and we validate this algorithm on minimal models. We then leverage stimulus-responsive self-assembly towards rational design of lanthanide precipitants and describe effects of thermal incubation, chemical composition and chemical patterning on ion extraction efficiency and metal-mediated structural changes. Finally, drawing inspiration from numerical simulation, we develop an empirical formalism to estimate relevant kinetic rates from experimental data to reconstruct sequence ensembles of synthetic copolymers, and by using an information-theoretic approach, we demonstrate strategies to visualize and quantitate differences between distributions. Taken together, these interdisciplinary studies help bridge the gap between fundamental and functional insights, shedding light onto how previously confounding factors such as nonequilibrium properties can be better leveraged and developing workflows at the interface of experimental and computational chemistry.
■590 ▼aSchool code: 0153.
■650 4▼aPolymer chemistry
■650 4▼aChemistry
■650 4▼aBioinformatics
■650 4▼aComputational chemistry
■653 ▼aBiomacromolecules
■653 ▼aSynthetic scaffolds
■653 ▼aNumerical simulation
■653 ▼aNonequilibrium properties
■653 ▼aOpen-loop control
■690 ▼a0495
■690 ▼a0219
■690 ▼a0715
■690 ▼a0485
■71020▼aThe University of North Carolina at Chapel Hill▼bChemistry.
■7730 ▼tDissertations Abstracts International▼g87-02B.
■790 ▼a0153
■791 ▼aPh.D.
■792 ▼a2025
■793 ▼aEnglish
■85640▼uhttp://www.riss.kr/pdu/ddodLink.do?id=T17358359▼nKERIS▼z이 자료의 원문은 한국교육학술정보원에서 제공합니다.
