Synthesis and self-assembly of macromolecules containing light-responsive groups = 광감응성기를 포함하는 거대분자의 합성과 자기조립에 관한 연구

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Self-assembly is considered as strong methods of synthetic chemistry to mimic biomacromolecules in living organisms and to construct complex structures which are complicated to prepare by traditional synthetic methodologies. In addition, numerous biomacromolecules change their properties in response to external stimuli. Consequently, development of stimuli-responsive materials has received significant interests. Light is one of the external stimuli and available to control remotely and accurately. Moreover, irradiation of light can be achieved into specific areas to exhibit light-responsive behavior only at desired area. In this dissertation, various kinds of researches about synthesis and self-assembly of macromolecules containing light-responsive groups were demonstrated. Self-assembled structures are designed to reveal intriguing properties such as dual stimuli-responsive behaviors or chirality by irradiation of light. In chapter 2 of the dissertation, external stimuli-responsive behavior of self-assembled structures consist of rod-coil block copolymers containing light-responsive azobenzene and temperature-responsive ethylene glycol derivatives. Rod block polymerized from azobenezene derivatives exhibit hydrophobic property and coil block polymerized from ethylene glycol derivatives exhibit hydrophilic property. Therefore, rod-coil block copolymers showed amphiphilic property and self-assembled structures with micellar aggregates were constructed in aqueous solution. The micellar aggregates revealed light- and temperature-responsive behaviors. Moreover, dual stimuli-responsive system was demonstrated since light-responsive behavior affects temperature-responsive behavior. In chapter 3,4 and 5 of the dissertation, supramolecular structures composed of triarylamine derivatives were described. First, we investigated the dependence between wavelength of light for irradiation and absorbance wavelength of triarylamine derivatives during self-assembly process in chlorinated solvents. As a result, we demonstrated that self-assembly of triarylamine derivatives through irradiation of light requires not only radical generation of chlorinated solvents but also excitation of supramolecular synthons to form triarylammonium radical cation through transfer of radical to nitrogen center atom of triarylamine moieties. In chapter 4 and 5 of the dissertation, solid thin film and organogel was formed to induce stability to self-assembled structures. Furthermore, irradiation of circularly polarized light during self-assembly process induced chirality with desired handedness by changing the rotational direction of circularly polarized light. In particular, homochiral supramolecular thin film was obtained in chapter 4 of the dissertation. In chapter 5 of the dissertation, induced chirality was maintained at room temperature through physical crosslinks although photopolymerization of supramolecular assemblies was not achieved.
Advisors
Kim, Sang Youlresearcher김상율researcher
Description
한국과학기술원 :화학과,
Publisher
한국과학기술원
Issue Date
2020
Identifier
325007
Language
eng
Description

학위논문(박사) - 한국과학기술원 : 화학과, 2020.2,[vii, 79 p. :]

Keywords

Light-responsive materials▼aSelf-assembly▼aAzobenzene▼aRod-coil block copolymer▼aTemperature-responsive behavior▼aTriarylamine▼aCircularly polarized light▼aChirality; 광감응성 물질▼a자기조립▼a아조벤젠▼a로드-코일 블록 공중합체▼a온도감응성▼a트리아릴아민▼a원편광▼a키랄성

URI
http://hdl.handle.net/10203/283532
Link
http://library.kaist.ac.kr/search/detail/view.do?bibCtrlNo=907043&flag=dissertation
Appears in Collection
CH-Theses_Ph.D.(박사논문)
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