本實驗利用簡單化學合成之分子設計概念，由掌性分子組成之掌性鏈段之嵌段共聚物 (chiral block copolymer)為材料，探討掌性作用力與其自組裝建構之奈米結構之相依性。本實驗設計以聚苯乙烯-聚左旋乳酸(polystyrene-block-poly(L-lactide))，聚苯乙烯-聚右旋乳酸polystyrene-block-poly(D-lactide))為材料，探討掌性作用力對自組裝相行為之影響。首先，在較弱的相分離強度且在聚苯乙烯組成之體積分率高於聚左旋乳酸時，雙螺旋二十四面體(double gyroid)，以及奈米螺旋結構(helix)可以分別被形成。另外藉由混摻少量、小分子量之聚左旋乳酸均聚物於雙嵌段共聚物中，可使雙嵌段共聚物自組裝成雙鑽石結構 (double diamond)。此三種相分離結構之材料具有相似組成，並藉由圓二色光譜儀(electronic circular dichroism)之測定推論其具有相似分子掌性 (molecular chirality)。在相似分子掌性的條件下，利用紅外光圓偏振二色光譜儀(vibrational circular dichroism)進一步探討分子內與分子間掌性作用力對三種相分離結構之影響，發現其三種自組裝之結構具有相異之結構掌性，且結構掌性對光學訊號具有放大之效果。
由於聚左旋乳酸具有螺旋鏈構形，因此具有類棍狀特性，和相當柔軟之聚苯乙烯組成之雙嵌段共聚物具有構形之不對稱性，可視為半堅硬-柔曲(semiflexible rod-coil)之雙嵌段共聚物。在中等的相分離強度且材料組成之聚左旋乳酸體積分率高於聚苯乙烯時，棍狀構形所造成之類液晶排列行為(rod-rod interaction)，對於自組裝之影響遠大於組成不對稱性(compositional asymmetry)，唯一形成奈米層板結構。除此之外，在高的相分離強度下，聚苯乙烯-聚左旋乳酸在微觀相分離時，構形不對稱性(conformational asymmetry)形成傾向堅硬鏈段(聚左旋乳酸)之曲率，與分子間與分子內掌性作用力(chirality effect)的協調下，使奈米螺旋結構於相圖中的微觀相區間拓寬至跨越組成對稱點。另外，在高的相分離強度，高聚左旋乳酸體積分率之相區間，發現波動型層板結構之形成。此波動型層板結構同時具有兩種形式之波動。我們推論，其中較小週期之異相型波動，源自於組成之不對稱性，形成傾向堅硬鏈段(聚左旋乳酸)之曲率;而較大週期之同相型波動，則源自於分子間與分子內掌性作用力所誘發之扭轉和位移機制(twisting and shifting)，形成自組裝結構之曲率。此波動型層板結構之發現與自洽場理論的模擬結果相符。本實驗證實半堅硬-柔曲之雙嵌段共聚物其自組裝之結果為上作用力之協同效應，且確立掌性雙嵌段共聚物之不對稱相圖。
自組裝過程中之上述作用力之協同效應可以藉由動力學控制的方式進一步研討。聚左旋乳酸體積分率高於聚苯乙烯之材料，在快速的溶劑揮發條件下，具有類棍狀特性之聚左旋乳酸傾向形成類液晶排列之雙層層板結構，結合介面以及層板間堆疊之掌性立體障礙，導致雙層層板堆疊時產生扭轉和彎曲(twisting and bending) 之自發機制，自組裝形成扭曲之多層層板三級結構(multilayer lamellae)，且同時產生同心圓(concentric lamellar)或者是瑞士捲(roll-cake)般的型態。此結構之形態為動力學控制之暫穩態，而其中瑞士捲型態具有結構掌性，指出動力學控制之自組裝與各層級掌性作用力之傳遞之相依性。
除了聚苯乙烯-具左旋乳酸之外，藉由分子設計利用聚-N-取代甘氨酸(peptoid)為主體，系統性探討側鏈及主鏈掌性傳遞效應，控制其自組裝形成具備掌性之奈米結構。聚-N-取代甘氨酸高分子以N-C鍵為主鏈，相對於C-C鍵為主鏈之高分子有更旋轉能量障礙，因而使其具有較長之高分子鏈堅硬長度。藉由側鏈掌性官能基團的設計，本實驗進一步利用圓二色光譜儀，紅外光圓偏振二色光譜儀探討聚-N-取代甘氨酸高分子各層級掌性傳遞效應，並結合及中子散射(small angle neutron scattering)分析，探討其螺旋鏈段構形。研究發現，聚-N-取代甘氨酸高分子不符合單一掌性傳遞的機制，指出掌性傳遞機制值得更深入進行研討。
最後，本研究藉由合成設計，希望結合自組裝之研究和模板化無電電鍍的技術，製備奈米螺旋金陣列。本實驗設計以硫醇鍵作為以聚苯乙烯-聚左旋乳酸之兩鏈段連接點(PS-SS-PLLA)，藉由掌性傳遞的機制，誘導硫醇鍵在雙嵌段共聚物自組裝形成奈米螺旋結構的同時行成螺旋排列。進一步將聚左旋乳酸水解後，即可得到具螺旋排列之硫醇鍵之奈米螺旋高分子模板。利用硫醇鍵和奈米金相互吸引的特性將奈米金還原於硫醇鍵上，即可製備奈米螺旋金陣列，預期將會有特殊的光學應用價值。

Herein, we aim to examine the phase behaviors of self-assembled chiral block copolymers (BCPs*) for generalization of the chirality effects on self-assembly at various compositions under different segregation strengths. Enantiomeric polylactide-based BCPs*, polystyrene-b-poly(L-lactide) (PS-PLLA) and polystyrene-b- poly(D-lactide) (PS-PDLA), composed of achiral PS and chiral polylactide were designed and synthesized for examination of the chirality effects on self-assembly. As found before, for the PS-PLLA with volume fractions ranging from 0.30 to 0.40, self-assembled double gyroid phase (DG) and helical phase (H*) could be obtained in weak and intermediate segregation regions, respectively. The formation of the H* is attributed to the chirality effects on self-assembly, giving the twisting and bending of the microphase-separated domain with cylindrical curvature due to compositional asymmetry. Significant enhancement of vibrational circular dichroism (VCD) signals could be found in the H* from microphase separation due to the formation of mesoscale (hierarchical) chirality (H*). Interestingly, a recognizable enhancement on the VCD signal of the DG as compared to the disorder phase can also be identified, suggesting the formation of a chiral DG. By contrast, with slightly introducing low molecular weight chiral polylactide for blending, a double diamond phase (DD) with a pair of achiral networks was found to give the VCD signal approximately equal to the disorder one. Note that the ones with DG, DD and disorder phase at equivalent volume fraction and molecular weight possess nearly identical optical activity from constituted chiral entities, as evidenced by electronic circular dichroism (ECD). Those results implicitly reflect that the VCD amplification in the DG is intrinsically attributed to the bias on the twisting degree of helical polymer chains between constituted gyroid networks.
Owing to the conformational asymmetry between two constituted blocks in the PS-PLLA, giving the character of semiflexible rod-coil block copolymer, it is intuitive to expect the asymmetric phase diagram for the PS-PLLA. PLLA-rich PS-PLLAs were thus synthesized for examination of the phase behaviors through a low-conversion synthetic approach. Apparent asymmetry in the phase diagram of the PS-PLLA can be found but only lamellar phase (L) forms in the composition region of PLLA volume fraction up to 0.7. As a result, we speculate that the semiflexible rod PLLA in the PLLA-rich fraction gives rise to liquid crystalline-like character due to rod-rod interaction that overwhelms the effect of conformational asymmetry. With the increase of the segregation strength, the effects of conformational asymmetry and chirality can be enhanced, giving interfacial curvature toward the PLLA blocks with the twisting and shifting of PLLA cylindrical microdomain. Consequently, an enlargement of the H* forming window can be found in the composition window from 0.3 to 0.55 crossing over the composition symmetry. Moreover, in the strong segregation region, we found an interesting undulation mechanism for the forming L at which two undulation modes can be observed: out-phase undulation from the formation of interfacial curvature due to conformational asymmetry effect and in-phase undulation from the cholesteric twist ordering due to chirality effects. Obviously, there are synergetic effects of rod-rod interaction, conformational asymmetry and chirality under strong segregation strength for the self-assembly of chiral block copolymers.
To further examine the synergetic effects on self-assembly, we aim to kinetically control the self-assembly of PLLA-rich PS-PLLAs. Through controlled self-assembly by tuning the evaporation rate for self-assembly from solution, spiral hierarchical superstructures were found in the self-assembly of PLLA-rich PS-PLLA with PLLA volume fraction approximately nearby 0.7. Consequently, smectic liquid crystal-like bilayer sandwiched with PLLA and PS microdomains can be formed. Owing to twisting and bending due to chiral cholesteric liquid-crystal-like force field combined with steric hindrance at chiral interface, the forming bilayers (twisted ribbon) will develop into either concentric lamellar texture from scrolling or roll-cake textures from spiraling. Those results demonstrate that the rod-rod interaction and the chirality effect can be sufficiently coordinated through kinetically controlled self-assembly. Note that the forming spiral superstructures are attributed to the kinetically trapped metastable condition with local minimum of Gibbs free energy, indicating that the effects of chirality on BCP self-assembly should be strongly dependent upon the kinetic paths for morphological development through chirality transfer at different length scales.
In contrast to the PS-PLLA, we are expecting that chiral segment with higher persistence length might give larger conformational asymmetry effect on self-assembly. Polypeptoid with chiral centers in the main chain are expected to have higher persistence length, arising from higher rotational barrier of amide group, as compared to ester group in polylactide-containing system. Notably, polypepotoid can be synthesized to give side-chain and main-chain chirality; herein, we aim to carry out systematic comparison between main-chain and side-chain chirality effects on BCP self-assembly. As found, the backbone helical conformation of polypeptoids appears as the same handedness regardless of the helical sense of the chiral center, different to the homochiral evolution from molecular to conformational chirality in the polylactide-based BCPs*. Moreover, the degree of helicity for the polypeptoids examined can be varied by surrounding environment. Those results indicate that the homochiral evolution in the self-assembly of BCPs* remains as an open question.
Recently, the chiroptics of helix-arranged Au nanoparticles has attracted much attention due to its novel optical activities such as enhancing surface plasmonic resonance (SPR). Herein, to exploit the applications of using the self-assembled polylactide-containing BCPs* with controlled helicity, BCPs* with thiol junction (PS-ss-PLLA) was synthesized. By taking advantage of induced chirality for those thiol junctions, it is expected to give the thiol junction preferentially arranged in a one-handed helical array at the microphase-separated interface. After degeneration of polylactide, nanoporous polymer materials with thiol-decorated nanochannels can be prepared on the vitrified PS surface, giving a chiral template for association of reduced gold from electroless plating. Consequently, gold nanoparticles arranged in a helical contour with specific handedness can be fabricated as a monolith for chiroptical applications.

Contents

Abstract………………………………………………………………………………………………………………………………………………………I
Acknowledgements………………………………………………………………………………………………………………………………IX
Contents……………………………………………………………………………………………………………………………………………………XI
List of Figures…………………………………………………………………………………………………………………………………XV
List of Schemes…………………………………………………………………………………………………………………………XXXII
List of Tables…………………………………………………………………………………………………………………………XXXIII
List of Abbreviations…………………………………………………………………………………………………………XXXIV
Chapter 1 Introduction
1.1 Supramolecular Self-assembly………………………………………………………………………………………1
1.2 Block Copolymers (BCPs) Self-assembly………………………………………………………………5
1.3 Chain Conformational Effect on Block Copolymer Self-assembly…8
1.3.1 Conformational asymmetry effect on BCP Self-assembly…………………8
1.3.2 Rod-coil Block Copolymer Self-assembly………………………………………………………9
1.3.3 Persistence Length Effect on BCP Self-assembly………………………………12
1.4 Chirality Effects on Self-assembly……………………………………………………………14
1.4.1 Self-assembly of Chiral Superstructures…………………………………………………14
1.4.2 Chiral Block Copolymers (BCPs*) Self-assembly…………………………………16
1.4.2.1 Homochiral Evolution from Chiral Molecular to Chiral Chain Conformation…………………………………………………………………………………………………………………………………………18
1.4.2.2 Homochiral Evolution from Chiral Chain Conformation to Helical Phase………………………………………………………………………………………………………………………………………21
1.4.2.3 Universal Behaviors of BCPs* Self-assembly……………………………………22
1.5 Mechanism for the formation of Chiral Phase……………………………………………27
1.5.1 Experimental Study on the Origin of Twisting and Shifting…27
1.5.2 Theories of Tilt Chiral Lipid Bilayers……………………………………………………31
1.5.3 Orientational Self Consistent Field Theory…………………………………………32
1.6. Controlled BCPs* self-assembly……………………………………………………………………………36
1.6.1 BCPs* Phase Transition Kinetics………………………………………………………………………36
1.6.2 BCP* Phase Transition by Blending of Homopolymer…………………………38
1.7. Application of Block Copolymer (BCP) Chiral Phase on Chiroptical Applications…………………………………………………………………………………………………………41
1.7.1 Luminescence Enhancement by Morphological Evolution…………………41
1.7.2 Surface Plasmonic with Chiral Geometry……………………………………………………43
1.7.3 Optical Chiral Metamaterials………………………………………………………………………………47
Chapter 2 Objectives……………………………………………………………………………………………………………………51
Chapter 3 Experimental Section…………………………………………………………………………………………57
3.1 Materials………………………………………………………………………………………………………………………………………57
3.1.1 Synthesis and Characterization of PS-PLLA BCPs* with High
Volume Fraction of PLLA……………………………………………………………………………………………………………57
3.1.2 Synthesis of Low Molecular Weight Polylactide Homopolymer
…………………………………………………………………………………………………………………………………………………………………………62
3.1.3 Synthesis of PS-PLLA BCP* with Thiol Junction…………………………………63
3.1.4 Synthesis of Polypeptoid…………………………………………………………………………………………65
3.2 Preparation of Bulk Sample…………………………………………………………………………………………68
3.3 Characterization and Instrumentation………………………………………………………………69
3.3.1 Differential Scanning Calorimetry (DSC)…………………………………………………69
3.3.2 Wide-angle X-ray Diffraction (WXRD)……………………………………………………………69
3.3.3 Small-angle X-ray Scattering (SAXS)……………………………………………………………69
3.3.4 Field-Emission Scanning Electron Microscopy (FESEM)…………………70
3.3.5 Transmission Electron Microscopy (TEM)……………………………………………………70
3.3.6 Electron Tomography (3D-TEM)………………………………………………………………………………71
3.3.7 Electronic Circular Dichroism Spectroscopy (ECD)…………………………71
3.3.8 Vibrational Circular Dichroism (VCD)…………………………………………………………72
3.3.9 Polarizing Light Microscopic (PLM)………………………………………………………………72
Chapter 4 Results and Discussion
4.1 Amplification of Vibrational Circular Dichroism for Chiral Block Copolymers Driven by Self-Assembly………………………………………………………………73
4.1.1 Controlled Self-assembly of PS-PLLA and PS-PLLA/PLLA Blends…………………………………………………………………………………………………………………………………………………………75
4.1.2 Molecular Chirality and Conformational Chirality in Synthe-
sized PS-PLLA and PS-PLLA/PLLA Blends………………………………………………………………………79
4.1.3 Vibrational Circular Dichroism in Self-Assembled BCP* Phase……………………………………………………………………………………………………………………………………………………………84
4.1.4 Self-Assembled Phase with Inter-chain Chiral Interactions…………………………………………………………………………………………………………………………………………88
4.2 Phase Behaviors of Chiral Block Copolymers………………………………………93
4.2.1 Phase Behaviors of PS-rich PS-PLLA…………………………………………………………….97
4.2.2 Phase Behaviors of PLLA-rich PS-PLLA………………………………………………………100
4.2.3 Enlargement of H* Forming Window…………………………………………………………………107
4.2.4 Lamellar Undulation……………………………………………………………………………………………………116
4.2.5 Comprehensive Phase Behaviors for Chiral Block Copolymer
Self-assembly……………………………………………………………………………………………………………………………………122
4.3 Spiral Hierarchical Superstructures from Twisted Ribbons of Self-Assembled Chiral Block Copolymers………………………………………………………………128
4.3.1 Phase Behaviors of PLLA-rich PS-PLLA with Control Self-assembly…………………………………………………………………………………………………………………………………………………130
4.3.2 Hypothetical Mechanism for Formation of Multilayer lamellae……………………………………………………………………………………………………………………………………………….145
4.2.3 Homochiral Evolution on Chiral Segment-Rich Self-assemble Superstructures………………………………………………………………………………………………………………………………150
4.4 Helical Conformation of High Persistence Length Polymer…160
4.4.1 Molecular and Conformational Chirality of Side-Chain Chiral
Peptoid……………………………………………………………………………………………………………………………………………………163
4.4.2 Effects on Peptoid Helical Conformation………………………………………………171
4.5 Helix-arranged Au nanoparticles…………………………………………………………………………175
Chapter 5 Conclusion…………………………………………………………………………………………………………………179
Chapter 6 References…………………………………………………………………………………………………………………183
Publications………………………………………………………………………………………………………………………………………197

List of Figures

Figure 1.1. (A) Aggregation occurs when there is a net attraction and an equilibrium separation between the components. The equilibrium separation normally represents a balance between attraction and repulsion. These two interactions are fixed in molecular self-assembly but can be engineered independently in macroscopic self-assembly. (B) and (C) Schematic illustration of the essential differences between irreversible aggregation and ordered self-assembly. (B) Components (shown in blue) that interact with one another irreversibly form disordered glasses (shown in green). (C) Components that can equilibrate, or adjust their positions once in contact, can form ordered crystals if the ordered form is the lowest-energy form (shown in red). (D) Biology provides many examples of self-assembly (here, the formation of a protein, an asymmetric, catalytically active nanostructure); these examples will stimulate the design of biomimetic processes………………………………………………………………………………………………………………………………………………………………2
Figure 1.2. Examples of static self-assembly. (A) Crystal structure of a ribosome. (B) Self-assembled peptideamphiphile nanofibers. (C) An array of millimeter sized polymeric plates. (D) Thin film of a nematic liquid crystal. (E) Micrometersized metallic polyhedra folded. (F) A three-dimensional aggregate of micrometer plates………………………………………………………3
Figure 1.3. Levels of a protein structure. (A) The amino-acid sequence of a protein (primary structure) contains all the information needed to specify (B) the regular repeating patterns of hydrogen-bonded backbone conformations (secondary structure) such as alpha helices (red) and beta sheets (blue). As well as the (C) the way these elements pack together to form the overall fold of the protein (tertiary structure). (D) The relative arrangement of two or more individual polypeptide chains is called quaternary structure.……………………………………………………………………………………………………………………………………………………………4
Figure 1.4. Four ordered morphologies for diblock copolymer melts, spheres (S), cylinders (C), gyroid (G), and lamellae (L), are controlled by the composition fA and the product of the segment–segment interaction parameter and degree of polymerization χN……………………6
Figure 1.5. Phase diagram of PS310-PAA52 in dioxane plus water; the full ternary phase diagram with separate water, dioxane, and copolymer axes looks similar. The colored regions between sphere and rod phases and between rod and vesicle phases correspond to coexistence regions…7
Figure 1.6. Influence of compositional and conformational asymmetry on the spontaneous interfacial curvature for a diblock copolymer during microphase separation. The effects are illustrated by using BCP with (a) symmetric conformation with asymmetric composition, (b) asymmetric conformation with symmetric composition, and (c) asymmetric conformation with asymmetric composition…………………………………………………………………………10
Figure 1.7. Mean-field phase diagrams for diblock copolymer melts for a series of conformational asymmetries. The ordered phases are labeled as lamellar (L), gyroid (G), cylinder (C), sphere (S) and close-packed sphere (Scp). The dots denote mean-field critical points, and the dashed curves are extrapolated phase boundaries………………………………………………………11
Figure 1.8. Phase diagram for rod-coil block copolymers in (a) the weak segregation limit and (b) the moderately segregated region……………12
Figure 1.9. (a) Unstructured chain composed of a racemic mix of side group. (b) Incorporating bulky side groups with identical R-chiralities into the polypeptoid induces a helix. (c) Schematic depicting packing of PnBA-b-polypeptoid into hexagonally packed cylinders with varying helical versus unstructured polypeptoid components………………………………………………………………………………………………………………………………………………………13
Figure 1.10. (a) Chemical structures of 2Cn-Glu-CmN+ amphiphiles and (b) self-assembled chiral superstructures micrographs. (c) Chemical structure of the sugar-appended Schiff base chiral rodcoil amphiphiles and (d) self-assembled chiral superstructures examined by FESEM (left) and TEM (right) micrographs of compounds LC11……………………………………………………………15
Figure 1.11. (a) TEM micrographs of self-assembled H*L (b) 1D SAXS profiles of self-assembled H*L (c) Schematic of PS-PLLA self-assembled H*L in which the helical microdomains are packed in a hexagonal lattice with an interdigitated character (d) Phase diagram of the PS−PLLA BCPs* with respect to χN and composition………………………………………………….17
Figure 1.12. ECD and corresponding UV-Vis absorption spectra of (a) L- and D- lactide acid monomer and (c) P(L-/D-)LA homopolymer in dilute ACN solution (0.05 wt%). (b) VCD and corresponding FTIR absorption spectra of L- and D- lactide acid monomer and (d) P(L-/D-)LA homopolymer in dilute DCM solution (2 wt%)……………………………………………………………………19
Figure 1.13. Schematic illustration handedness determination of H* phase by TEM tomography. Left-handed and right-handed helices in (a) 3D space and (b) 2D projection. (c) Left-handed (left side) and right-handed (right side) helical nanostructures reconstructed from PS/SiO2 helical nanohybrids fabricated using templates from PS−PLLA and PS−PDLA, respectively, for templated sol−gel reaction………………………………………22
Figure 1.14. Schematic illustration of the chirality transfer from molecular chirality to conformation chirality and finally hierarchical chirality BCPs* whereas the molecular chirality as examined by electronic circular dichroism (ECD); the conformation chirality is examined by vibrational circular dichroism (VCD); the self-assembled helical phase from BCPs* can be directly visualized by reconstruction image from three-dimensional TEM tomography (3D TEM)………………………………………23
Figure 1.15. Chemical structures of BCPs*: (a) PBnMA-PDCG; (b) PS-PDLA BCPs*. VCD and corresponding FTIR absorption of (c) C=O and (d) C–O–C vibration in chiral PCGs in the solid state after solution casting. (e) Illustration of inter-chain chiral interactions…………………………………………24
Figure 1.16. Schematic illustration of the chirality transfer from molecular chirality to conformation chirality and finally hierarchical chirality BCPs*. The bulkier aromatic rings side group increase intra twisting power and thus gives obvious inter chain chiral interaction during self-assembly.…………………………………………………………………………………………………………………………26
Figure 1.17. TEM microscopy for (a) PS0.63−PLLA0.18−PLA0.19 and (b) PS0.63−PLA0.17−PLLA0.20 with similar composition but difference sequence; (c) PS0.66−PLLA0.11−PLA0.23 and (d) PS0.66−PLLA0.06−PLA0.28 with both chiral chain as the middle block but different chiral chain length; (e) PS0.63−PLA0.14−PLLA0.23 and (f) PS0.63−PLA0.08−PLLA0.29 with achiral chain as the middle block but different chiral chain length. (g) Schematic illustration of the origins of twisting in self-assembled PS−PLLA−PLA and PS−PLA−PLLA BCPs*………………………………………………………………29
Figure 1.18. Schematic illustrations of the (a) wound-ribbon helix and (b) two types of twisted strip helix (c) transition sequence from the vesicle to helical structure. The arrows represent the local tilt direction…………………………………………………………………………………………………………………………………………………………33
Figure 1.19. oSCF solution of equilibrium H* phase morphology of BCP* melts. The AB interface (ϕA = ϕB =0.5 contour) is shown as transparent purple surface, and blue and green surfaces show high-density contours of (chiral) A-block ends and A-B conjugation points. In horizontal sections, profiles of mean chiral segment orientation, t(x), are indicated by red arrows. A unit cell of H* is shown in (a), while (b) highlights the rotation of the domain and cholesteric twist of segments along the backbone of the helical domain…………………………………………………33
Figure 1.20. Minority chiral component and weak segregation oSCF phase diagrams: (a) fixed segregation (χN = 14); (b) fixed chiral strength = 3.6). Along with standard achiral morphologies (L, lamella; C, cylinder; S, sphere; DG, double-gyroid), chirality stabilizes two new morphopogies: H*, helical cylinder, and UL*, undulated lamella (whose chiral block composition profiles are shown in c and d, respectively)…………………………………………………………………………………………………………………………………………………35
Figure 1.21. Illustration of suggested Gibbs free energy versus transition path from H* and HC to DG……………………………………………………………………………………38
Figure 1.22. Illustration of self-assembly mode for (a) pseudo-H aggregates and (b) pseudo-J aggregates and corresponding illumination from the gels…………………………………………………………………………………………………………………………………………………42
Figure 1.23. Schematic illustration of molecular dispositions for the spin-coated PY/CM thin film before solvent annealing and templated PY/CM nanoarrays. Fluorescence spectra of spin-coated PY/CM thin films on glass substrates (b) with; (c) without the deposition of nanoporous PS template before (solid line) and after (dotted line) solvent annealing………………………………………………………………………………………………………………………………………………………….44
Figure 1.24 (a) Scheme for gold nanoparticle double helices. TEM and reconstruction image for (b) left- and (c) right-handed chiral gold nanoparticle double helices. (d) Experimental CD data for left- and right-handed gold nanoparticle double helices. (e) Illustration for Helical ribbon assembly. (f) TEM images point out the effect of the increase of aliphatic tail length on helical pitch and nanoparticle size and shape in a family of single-helical superstructures. (g) CD signal of gold nanoparticle single helices self-assembly from various aliphatic tail length indicating the decrease of chiroptical properties with increase of aliphatic tail length………………………………………………45
Figure 1.25. (a) Model two-turn gold nanohelix showing critical dimensions. (b) Normalized circular dichroism (CD) spectra of left-handed and right-handed helices. Inset: TEM images of grown structures with left (top) and right (bottom) chirality. (c) Oblique-view and (d) top-view of a left-handed helix structure. (e) Transmittance spectra of helical gold at which RCP and LCP refer to right and left-handed circular polarization of the incident light………………………………………………………………47
Figure 1.26. (a) The resonant transverse bands of chiral materials results in a foreseen negative refraction range of frequencies below . (b) Suggested chiral structure for giving negative refractive index. Each cylinder is a Swiss roll structure wound in a helical fashion. Each layer of foil is separated from the next by a distance d, and the total thickness of foil is N layers……………………………………………………………………………………49
Figure 1.27. Structure of the geomatically chiral metamaterials. (a) Schematics of the 4-layered metamaterial’s unit cell and a photograph of part of a bilayered metamaterial sheet. The gammadions in neighboring layers have a relative twist of 15◦. The RCP excites an anti-symmetric current mode at 4.7 GHz (b), while LCP excites a symmetric current mode at 6.2 GHz (c) (blue and red correspond to currents in opposite directions). (d) Schematics of bilayer cross-wire design. The simulated current density distribution for (e) the right circularly polarized EM wave at 6.5 GHz and (f) the left circularly polarized EM wave at 7.5 GHz (red and blue corresponding to largest and smallest values of current density)…………………………………………………………………………50
Figure 3.1. Comparison of GPC curves (for sample of Table 4.3.1) between (a) PS24-PLLA67 and (b) PS-OH. The PS-PLLA is synthesized through ROP using (b) as a macroinitiator……………………………………………………………………61
Figure 3.2. 1H NMR spectrum (500 MHz) of PS24-PLLA67.The measurement was carried out using deuterated chloroform as a solvent at 25 oC……………………………………………………………………………………………………………………………………………………………………………61
Figure 4.1. TEM image for (a) H*L; (b) DG; (c) DD; (d) corresponding 1D SAXS profiles………………………………………………………………………………………………………………………………………76
Figure 4.2. (a) Visualization of DD phase from solution casting of sample C. Reconstructed images of tetrapod building unit for DD phase (b) and tripod building unit for DG phase (c)…………………………………………………………77
Figure 4.3. (a) TEM image for H*R and (b) corresponding 1D SAXS profiles……………………………………………………………………………………………………………………………………………………………78
Figure 4.4. ECD and corresponding UV-vis absorption spectra of (a) PS-PLLA (samples A, B and C) and PS-PDLA sample (sample D) in dilute AcCN solution……………………………………………………………………………………………………………………………………………………………80
Figure 4.5. ECD and corresponding UV-vis absorption spectra of (a) PS-PLLA (samples A, B and C) and PS-PDLA sample (sample D) in the disordered PS-PLLA thin film state, and (b) H*L-, DG-, DD-forming PS-PLLA and H*R-forming PS-PDLA…………………………………………………………………………………………………………81
Figure 4.6. VCD and corresponding FT-IR absorption spectra of PS-PLLA (samples A, B and C) and PS-PDLA sample (sample D) in dilute CH2Cl2 solution………………………………………………………………………………………………………………………………………………………………83
Figure 4.7. VCD and corresponding FT-IR absorption spectra of disordered PS-PLLA thin films samples…………………………………………………………………………………85
Figure 4.8. (a) VCD and corresponding FT-IR absorption spectra of H*L-, DG-, DD-forming PS-PLLA, H*R-forming PS-PDLA and disordered PS-PLLA. (b) The enlarged VCD spectra of (a) for the comparison between DG-, DD-forming and disordered PS-PLLA………………………………………………………………………………85
Figure 4.9. VLD and corresponding FT-IR absorption spectra of ordered PS-PLLA thin films samples…………………………………………………………………………………………………………….87
Figure 4.10. PLM observations of ordered PS-PLLA thin film at the 0o (left) and 90o (right) position for (a) DD; (b) DG; (c) H*…………………………87
Figure 4.11. Illustration of the formation of a variety of phases including H*, DG and DD from the self-assembly of chiral block copolymers with equivalent volume fraction of chiral segment through chirality transfer from conformational to hierarchical chirality………89
Figure 4.12. DG phase constructed by a pair of single chiral gyroid networks with opposite handedness at which the degrees of chirality are different in these two networks, giving the gyroid networks in the DG phase with different degree of chiral sense. The scale bar in the right shows the degree of chirality in color……………………………………………………………90
Figure 4.13. Volume difference between the two interpenetrating networks of DG, and mean segment twist given from DG plotted as a function of chiral strength ………………………………………………………………………………………………………91
Figure 4.14. (a) and (c) show chiral block domains predicted for H* and DG, respectively, from oSCF theory of chiral diblocks. (b) and (d) show maps of the inter-segment twist in the chiral domains, with color bars indicating positive/right-handed (red) and negative/left-handed (blue)…………………………………………………………………………………………………………………………………………………………………92
Figure 4.15. Phase behaviors of the PS-rich PS−PLLA in the weak and intermediate segregation strength regions; described by composition (fPLLAv) as the abscissa and segregation strength (χN) as the ordinate. The data points were reproduced from J. Am. Chem. Soc. 2009, 51, 18533. The temperature of the phase behaviors is at 140 oC……………………………………………………………………………………………………………………………………………………………………………99
Figure 4.16. Synthetic routes of PLLA-rich PS-PLLA using two-step polymerization starting with ATRP of PS-OH followed by ROP of PLLA……………………………………………………………………………………………………………………………………………………………………101
Figure 4.17. Phase behaviors of the PS−PLLA in the intermediate segregation strength region described by composition (fPLLAv) as the abscissa and segregation strength (χN) as the ordinate. The data points for PS-rich PS-PLLA were reproduced from J. Am. Chem. Soc. 2009, 51, 18533. The temperature of the phase behaviors is at 140 oC…………………………………………………………………………………………………………………………………………………………………………103
Figure 4.18. TEM micrographs of PLLA-rich PS-PLLA samples in the intermediate segregation region. All the samples examined were prepared from solution casting with slow evaporation rate followed by thermal treatment as mentioned. The PS microdomains appear dark and PLLA microdomains appear bright due to RuO4 staining……………………………………104
Figure 4.19. SAXS profiles of PLLA-rich PS-PLLA samples in the intermediate segregation region; all the samples examined were prepared from solution casting with slow evaporation rate, followed by thermal treatment as mentioned………………………………………………………………………………………………105
Figure 4.20. Phase behaviors of the PS-rich PS−PLLA in the strong segregation strength region; the phase diagram was described by composition (fPLLAv) as the abscissa and segregation strength (χN) as the ordinate. The temperature of the phase behaviors is at 140 oC…………………………………………………………………………………………………………………………………………………………………………109
Figure 4.21. TEM micrographs for strong-segregated PS-PLLA samples with PLLA volume fraction ranging from 0.3 to 0.53; all the samples examined were prepared from solution casting with slow evaporation rate, followed by thermal treatment as mentioned. The PS microdomains appear dark and PLLA microdomains appear bright due to RuO4 staining…………………………………………………………………………………………………………………………………………………………110
Figure 4.22. SAXS profiles of strong-segregated PS-PLLA samples with PLLA volume fraction ranging from 0.3 to 0.53; all the samples examined were prepared from solution casting with slow evaporation rate, followed by thermal treatment as mentioned. The results reveal the hexagonal packing for self-assembled PS-PLLA in wide range of volume fraction…………………………………………………………………………………………………………………………………………………………112
Figure 4.23. DSC thermograms of strong-segregated PS-PLLA samples. The heating rate is 10 oC/min……………………………………………………………………………………………………………113
Figure 4.24. Illustration for the formation of helical phase with compositional symmetry, at which (a) the conformational asymmetry effect and (b) chirality effects stabilized the formation of H*…………115
Figure 4.25. One-dimensional WAXD profiles of PS-PLLA after (a) solution casting, followed with thermally annealed at (b)140 ℃ for 2hr or (c) 95 ℃ for 2hr…………………………………………………………………………………………………………………118
Figure 4.26. Phase behaviors of the PS-rich PS−PLLA in the strong segregation strength region; the phase diagram is described by composition (fPLLAv) as the abscissa and segregation strength (χN) as the ordinate. The temperature of the phase behaviors is examined at 140 oC…………………………………………………………………………………………………………………………………………………………………119
Figure 4.27. SAXS profiles of strong-segregated PS-PLLA samples with PLLA volume fraction ranging from 0.55 to 0.70 self-assembled from solution casting at slow evaporation rate, revealing the lamellar packing………………………………………………………………...120
Figure 4.28. TEM micrographs for lamellae-forming PLLA-rich PS-PLLA in the strong segregation region with (a) out-phase undulation and (b) in-phase undulation attributed to the effects of (c) conformational asymmetry and (d) chirality on self-assembly…………………………………………………………121
Figure 4.29. Comprehensive phase behaviors of PS−PLLA; the phase diagram is described by composition (fPLLAv) as the abscissa and segregation strength (χN) as the ordinate. The temperature of the phase behaviors is at 140 oC……………………………………………………………………………………………………124
Figure 4.30. 1D WAXD profiles of solution-cast (a) PS10-PLLA24, (b) PS17-PLLA42 and (c) PS24-PLLA67 after thermal annealing at 180 oC followed by rapid cooling at 150 oC min-1 to 0 oC. The WAXD results appear typical amorphous scattering profile, suggesting that there is no PLLA crystallization effect on microphase-separated morphology……………………………………………………………………………………………………………………………………………………133
Figure 4.31. 1D SAXS profiles of self-assembled PS24-PLLA67 from solution casting with solvent evaporation rate of (a) 0.4 ml hr-1; (d) 0.04 ml hr-1; (e) 0.027 ml hr-1. (b) Corresponding TEM micrograph of (a). (c) Enlarged micrograph of tortuous lamellae in (b)…………………………134
Figure 4.32. TEM micrographs of self-assembled PS24-PLLA67 from solution casting with solvent evaporation rate of 0.04 ml hr-1: (a) concentric lamellar and (b) roll-cake textures from curved multilayered lamellae………………………………………………………………………………………………………………………134
Figure 4.33. 1D WAXD profiles of solution-cast PS24-PLLA67 (fPLLAv = 0.70) after thermal annealing at 180 oC followed by rapid cooling at 150 oC min-1 to 0 oC. The solution-cast samples were prepared by solution casting with solvent evaporation rate of (a) 0.4 ml hr-1; (b) 0.04 ml hr-1; (c) 0.027 ml hr-1……………………………………………………………………………………………136
Figure 4.34. FESEM micrographs of hydrolyzed PS24-PLLA67 from solution casting with solution evaporation rate of 0.04 ml hr-1: (a) concentric columnar-like texture and (b) rolling lamellar texture in a spiral fashion of the PS microdomains after removal of the PLLA…………………………137
Figure 4.35. SEM micrographs of nanostructured SiO2 fabricated by templated sol-gel reaction using nanoporous PS as a template prepared by hydrolysis of self-assembled PS24-PLLA67 with concentric lamellar texture (a) and roll-cake texture (b), followed by removal of PS through UV exposure. The insets show the corresponding illustrations of the forming textures…………………………………………………………………………………………………………………138
Figure 4.36. 3D visualization of self-assembled multilayered lamellae of PLLA microdomain with concentric lamellar texture (a) and roll-cake texture (b)…………………………………………………………………………………………………………………………………………………139
Figure 4.37. Low magnification TEM micrograph of self-assembled PS24-PLLA67 from solution casting with solvent evaporation rate of 0.04 ml hr-1 giving curved multilayered lamellae wiht both concentric and roll-cake texture.………………………………………………………………………………………………………………………………140
Figure 4.38. TEM micrographs of self-assembled PS24-PLLA67 from solution casting with solvent evaporation rate of 0.027 ml hr-1: (a) concentric lamellar and (b) roll-cake textures from curved multilayered lamellae………………………………………………………………………………………………………………………141
Figure 4.39. (a)TEM micrograph and (b) SAXS result of self-assembled PS24-PLLA67 from solution casting with extremely slow solvent evaporation rate at 0.0008 ml hr-1. Undulated lamellae with long-range order can be observed by TEM along with the appearance of reflections at high q region at which the d-spacing was approximately 54 nm determined by the primary reflection in the SAXS profile. The inset shows the corresponding illustration of the forming texture…………………142
Figure 4.40. TEM micrographs of self-assembled (a) PS10-PLLA24 and (b) PS17-PLLA42 from solution casting after thermal annealing at 180 oC followed by thermal treatment as mentioned. The PS microdomains appear dark and PLLA microdomains appear bright due to RuO4 staining……………143
Figure 4.41. (a) SAXS profiles of PLLA-rich PS-PLLA with various molecular weights. (b) The plot of calculated interdomain spacing versus molecular weight on the basis of the primary reflection in SAXS………………………………………………………………………………………………………………………………………………………………….143
Figure 4.42. Schematic illustration for semi-flexible rod-coil block copolymer with helical chain as major block (a), resulting in smectic liquid crystal-like bilayer (b), followed by twisting and bending due to chiral cholesteric liquid-crystal-like force field (c) combined with steric hindrance at chiral interface (d) to scroll the twisted ribbon into concentric texture or develop in a spiral fashion to form roll-cake texture (e) through nucleation and growth mechanism for microphase separation………………………………………………………………………………………………………………………146
Figure 4.43. VCD and corresponding FTIR absorption spectra of C-O-C vibrational mode of PLLA-rich PS24-PLLA67 in the (a) DCM solution and (b) solid states. The concentration of solution is 2 wt%………………………………………………………………………………………………………………………………………………………………………148
Figure 4.44. VLD and corresponding FTIR absorption spectra of C-O-C vibrational mode of PLLA-rich PS24-PLLA67 in the (a) DCM solution and (b) solid states. The concentration of solution is 2 wt%………………………………………………………………………………………………………………………………………………………………………149
Figure 4.45. (a) ECD and corresponding UV-vis absorption spectra and (b) VCD and corresponding FT-IR absorption spectra of the solution state PLLA-rich PS-PLLA (black) and PDLA-rich PS-PDLA (red)…………………152
Figure 4.46. (a) ECD and corresponding UV-vis absorption spectra; VCD and corresponding FT-IR absorption spectra of (b) C=O and (c) C–O–C of PLLA-rich PS-PLLA (black) and PDLA-rich PS-PDLA (red) in the solid state…………………………………………………………………………………………………………………………………………………………………154
Figure 4.47. TEM micrographs of (a) concentric lamellar and (b) roll-cake textures from curved multilayered lamellae, and (c) 1D SAXS profiles of of self-assembled PS24-PDLA67 from solution casting with solvent evaporation rate of 0.04 ml hr-1……………………………………………………………………156
Figure 4.48. Illustration the difficulty for handedness determination for curved multilayered lamellae by TEM 2D projection and 3D tomography. The superstructure become superimposable after flattening by microtomy………………………………………………………………………………………………………………………………………………157
Figure 4.49. TEM micrographs of self-assembled (a) PS24-PLLA67 and (b) PS24-PDLA67 at which PS appear dark and PLLA appear bright due to RuO4 staining; FESEM micrographs of hydrolyzed (c) PS24-PLLA67 and (d) PS24-PDLA67 from solution casting with roll-cake texture in a spiral fashion of the PS microdomains after removal of the PLLA…...158
Figure 4.50. Scheme illustration for the prepared sequence-defined peptoid including homochiral ChirRX and ChiraSX, racemic peptoid RacX, and achiral peptoid AchirX, while X is the total number of monomers…………………………………………………………………………………………………………………………………………………………164
Figure 4.51. ECD and corresponding UV−vis absorption spectra of (a) monomeric ChirR1 and ChirS1 (b) ChirR36, ChirS36, Achir36 and Rac36 (c) overlay of chiral polypeptoid in various chin length including R- and S-form Chir1, Chir6 and Chir36 in dilute AcCN solution. The concentration of solution is 0.1wt%…………………………………………………………………………………165
Figure 4.52. ELD and corresponding UV−vis absorption spectra of monomeric ChirR1 and ChirS1, and polypeptoids ChirR36, ChirS36, Achir36 and Rac36. The concentration of solution is 0.1wt%………………………………………………………………………………………………………………………………………………………………167
Figure 4.53. VCD and corresponding FT-IR absorption spectra of (a) ChirR36, ChirS36, Achir36 and Rac36 peptoid polymers and (b) monomeric ChirR1 and ChirS1 in dilute CDCl3 solution. The concentration of solution is 0.2M……………………………………………………………………………………………………………………………………168
Figure 4.54. VLD and corresponding FT-IR absorption spectra of ChirR36, ChirS36, Achir36 and Rac36 peptoid polymers in dilute CDCl3 solution. The concentration of solution is 0.2M…………………………………………………169
Figure 4.55. Illustration for polypeptoids constituting opposite handedness of chiral aromatic side group give identical right-handed chain conformation………………………………………………………………………………………………………………………………170
Figure 4.56. (a) VCD and corresponding FT-IR absorption spectra and (b) SANS profile for ChirR36 in various solvent (the result is provided by Prof. Segalman from UCSB)……………………………………………………………………………172
Figure 4.57. VCD and corresponding FT-IR absorption spectra for ChirR36 at which measurement at 10 oC, 30 oC and 50 oC was processed………………………………………………………………………………………………………………………………………………………173
Figure 4.58. (a) TEM micrographs of self-assembled PS-ss-PLLA and (b) corresponding 1D SAXS profile…………………………………………………………………………………………………176
Figure 4.59. FESEM micrograph of nanoporous PS template from H*-forming PS-PLLA after hydrolysis of the PLLA.…………………………………………………….177
Figure 4.60. TEM images of Au nanoparticles within the BCP* template via templated electroless plating approach with (a) and (b) in different projection angles; (c) is an enlarge image for the Au nanoparticles……………………………………………………………………………………………………………………………………………178

List of Schemes

Scheme 1. Synthetic routes of PS-PLLA. Similar synthetic routes are executed with D-lactide and D,L-lactide as monomers for PS-PDLA and PS-PLA, respectively…………………………………………………………………………………………………………………………58
Scheme 2. Synthetic route of polylactide homopolymer……………………………………62
Scheme 3. Synthetic routes of PS-ss-PLLA. Similar synthetic routes are executed with D-lactide and D,L-lactide as monomers for PS-ss-PDLA and PS-ss-PLA, respectively……………………………………………………………………………………………………………………64
Scheme 4. Synthetic routes of side chain chiral peptoid with sequence control by two-step cycle on a solid support……………………………………………………………66
Scheme 5. Repeat units incorporated in polypeptoid sequences including homochiral NRpe or NSpe used to form helical blocks…………………………………………67
Scheme 6. Designed sequence of polypeptoid with chiral, racemic and achiral chain conformations (provided by Prof. Segalman from UCSB)…67

List of Tables

Table 4.2.1 Characterization of synthesized PLLA-rich PS-PLLA with PLLA volume fraction ranging from 0.5 to 0.75………………………………………………………102
Table 4.2.2 Characterization of synthesized strong-segregated PLLA-rich PS-PLLA with various volume fraction…………………………………………………………………109
Table 4.3.1. Characterization of synthesized PLLA-rich PS-PLLA samples with various molecular weights…………………………………………………………………………………………….131
Table 4.3.2. Characterization of synthesized PS-PLLA and PS-PDLA BCPs*……………………………………………………………………………………………………………………………………………………………….151

1. Lehn, J.-M., Supramolecular Chemistry: Receptors, Catalysts, and Carriers. Science 1985, 227 (4689), 849.
2. Whitesides, G. M.; Grzybowski, B., Self-Assembly at All Scales. Science 2002, 295 (5564), 2418.
3. Whitesides, G. M.; Boncheva, M., Beyond molecules: Self-assembly of mesoscopic and macroscopic components. Proceedings of the National Academy of Sciences 2002, 99 (8), 4769.
4. Petsko, G. A.; Ringe, D., Protein structure and function. New Science Press: 2004.
5. Mai, Y.; Eisenberg, A., Self-assembly of block copolymers. Chemical Society Reviews 2012, 41 (18), 5969-5985.
6. Thomas, E. L.; Anderson, D. M.; Henkee, C. S.; Hoffman, D., Periodic area-minimizing surfaces in block copolymers. Nature 1988, 334 (6183), 598-601.
7. Matsen, M. W.; Bates, F. S., Origins of Complex Self-Assembly in Block Copolymers. Macromolecules 1996, 29 (23), 7641-7644.
8. Bates, F. S.; Fredrickson, G., Block copolymers-designer soft materials. Physics today 1999, 52, 32.
9. Bates, F. S.; Fredrickson, G. H., Block Copolymer Thermodynamics: Theory and Experiment. Annual Review of Physical Chemistry 1990, 41 (1), 525-557.
10. Shen, H.; Eisenberg, A., Morphological Phase Diagram for a Ternary System of Block Copolymer PS310-b-PAA52/Dioxane/H2O. The Journal of Physical Chemistry B 1999, 103 (44), 9473-9487.
11. Discher, D. E.; Eisenberg, A., Polymer Vesicles. Science 2002, 297 (5583), 967.
12. Li, L.; Raghupathi, K.; Song, C.; Prasad, P.; Thayumanavan, S., Self-assembly of random copolymers. Chemical Communications 2014, 50 (88), 13417-13432.
13. Chen, J. T.; Thomas, E. L.; Ober, C. K.; Hwang, S. S., Zigzag Morphology of a Poly(styrene-b-hexyl isocyanate) Rod-Coil Block Copolymer. Macromolecules 1995, 28 (5), 1688-1697.
14. Müller, M.; Schick, M., Ordered Phases in Rod−Coil Diblock Copolymers. Macromolecules 1996, 29 (27), 8900-8903.
15. Jenekhe, S. A.; Chen, X. L., Self-Assembled Aggregates of Rod-Coil Block Copolymers and Their Solubilization and Encapsulation of Fullerenes. Science 1998, 279 (5358), 1903-1907.
16. Jenekhe, S. A.; Chen, X. L., Self-Assembly of Ordered Microporous Materials from Rod-Coil Block Copolymers. Science 1999, 283 (5400), 372-375.
17. Sary, N.; Rubatat, L.; Brochon, C.; Hadziioannou, G.; Ruokolainen, J.; Mezzenga, R., Self-Assembly of Poly(diethylhexyloxy-p-phenylenevinylene)-b-poly(4-vinylpyridine) Rod−Coil Block Copolymer Systems. Macromolecules 2007, 40 (19), 6990-6997.
18. Olsen, B. D.; Segalman, R. A., Self-assembly of rod–coil block copolymers. Materials Science and Engineering: R: Reports 2008, 62 (2), 37-66.
19. Wang, Q., Theory and simulation of the self-assembly of rod–coil block copolymer melts: recent progress. Soft Matter 2011, 7 (8), 3711-3716.
20. Song, W.; Tang, P.; Zhang, H.; Yang, Y.; Shi, A.-C., New Numerical Implementation of Self-Consistent Field Theory for Semiflexible Polymers. Macromolecules 2009, 42 (16), 6300-6309.
21. Kumar, N. A.; Ganesan, V., Communication: Self-assembly of semiflexible-flexible block copolymers. The Journal of Chemical Physics 2012, 136 (10), 101101.
22. Gao, J.; Tang, P.; Yang, Y., Non-lamellae structures of coil–semiflexible diblock copolymers. Soft Matter 2013, 9 (1), 69-81.
23. Bates, F. S.; Fredrickson, G. H., Conformational asymmetry and polymer-polymer thermodynamics. Macromolecules 1994, 27 (4), 1065-1067.
24. Bates, F. S.; Schulz, M. F.; Khandpur, A. K.; Förster, S.; Rosedale, J. H.; Almdal, K.; Mortensen, K., Fluctuations, conformational asymmetry and block copolymer phase behaviour. Faraday Discussions 1994, 98, 7-18.
25. Matsen, M.; Bates, F. S., Conformationally asymmetric block copolymers. Journal of Polymer Science Part B: Polymer Physics 1997, 35 (6), 945-952.
26. Chen, J. T.; Thomas, E. L.; Ober, C. K.; Mao, G.-P., Self-Assembled Smectic Phases in Rod-Coil Block Copolymers. Science 1996, 273 (5273), 343-346.
27. Structure and Thermodynamics of Weakly Segregated Rod−Coil Block Copolymers. Macromolecules 2005, 38 (24), 10127-10137.
28. Olsen, B. D.; Segalman, R. A., Nonlamellar phases in asymmetric rod− coil block copolymers at increased segregation strengths. Macromolecules 2007, 40 (19), 6922-6929.
29. Kirshenbaum, K.; Barron, A. E.; Goldsmith, R. A.; Armand, P.; Bradley, E. K.; Truong, K. T. V.; Dill, K. A.; Cohen, F. E.; Zuckermann, R. N., Sequence-specific polypeptoids: A diverse family of heteropolymers with stable secondary structure. Proceedings of the National Academy of Sciences 1998, 95 (8), 4303-4308.
30. Murnen, H. K.; Rosales, A. M.; Jaworski, J. N.; Segalman, R. A.; Zuckermann, R. N., Hierarchical Self-Assembly of a Biomimetic Diblock Copolypeptoid into Homochiral Superhelices. Journal of the American Chemical Society 2010, 132 (45), 16112-16119.
31. Rosales, A. M.; Murnen, H. K.; Kline, S. R.; Zuckermann, R. N.; Segalman, R. A., Determination of the persistence length of helical and non-helical polypeptoids in solution. Soft Matter 2012, 8 (13), 3673-3680.
32. Davidson, E. C.; Rosales, A. M.; Patterson, A. L.; Russ, B.; Yu, B.; Zuckermann, R. N.; Segalman, R. A., Impact of Helical Chain Shape in Sequence-Defined Polymers on Polypeptoid Block Copolymer Self-Assembly. Macromolecules 2018, 51 (5), 2089-2098.
33. Yu, B.; Danielsen, S. P. O.; Patterson, A. L.; Davidson, E. C.; Segalman, R. A., Effects of Helical Chain Shape on Lamellae-Forming Block Copolymer Self-Assembly. Macromolecules 2019, 52 (6), 2560-2568.
34. Hanan, G. S.; Lehn, J.-M.; Kyritsakas, N.; Fischer, J., Molecular helicity: a general approach for helicity induction in a polyheterocyclic molecular strand. Journal of the Chemical Society, Chemical Communications 1995, (7), 765-766.
35. Krappe, U.; Stadler, R.; Voigt-Martin, I., Chiral Assembly in Amorphous ABC Triblock Copolymers. Formation of a Helical Morphology in Polystyrene-block-polybutadiene-block-poly(methyl methacrylate) Block Copolymers. Macromolecules 1995, 28 (13), 4558-4561.
36. Nelson, J. C.; Saven, J. G.; Moore, J. S.; Wolynes, P. G., Solvophobically Driven Folding of Nonbiological Oligomers. Science 1997, 277 (5333), 1793-1796.
37. Cornelissen, J. J. L. M.; Fischer, M.; Sommerdijk, N. A. J. M.; Nolte, R. J. M., Helical Superstructures from Charged Poly(styrene)-Poly(isocyanodipeptide) Block Copolymers. Science 1998, 280 (5368), 1427-1430.
38. Yashima, E.; Ousaka, N.; Taura, D.; Shimomura, K.; Ikai, T.; Maeda, K., Supramolecular Helical Systems: Helical Assemblies of Small Molecules, Foldamers, and Polymers with Chiral Amplification and Their Functions. Chemical Reviews 2016, 116 (22), 13752-13990.
39. Nakashima, N.; Asakuma, S.; Kunitake, T., Optical microscopic study of helical superstructures of chiral bilayer membranes. Journal of the American Chemical Society 1985, 107 (2), 509-510.
40. Lin, T.-F.; Ho, R.-M.; Sung, C.-H.; Hsu, C.-S., Helical Morphologies of Thermotropic Liquid-Crystalline Chiral Schiff-Based Rod−Coil Amphiphiles. Chemistry of Materials 2006, 18 (23), 5510-5519.
41. Palmans, A. R. A.; Meijer, E. W., Amplification of Chirality in Dynamic Supramolecular Aggregates. Angewandte Chemie International Edition 2007, 46 (47), 8948-8968.
42. Aida, T.; Meijer, E. W.; Stupp, S. I., Functional Supramolecular Polymers. Science 2012, 335 (6070), 813-817.
43. Chiang, Y.-W.; Ho, R.-M.; Ko, B.-T.; Lin, C.-C., Springlike Nanohelical Structures in Chiral Block Copolymers. Angewandte Chemie International Edition 2005, 44 (48), 7969-7972.
44. Ho, R.-M.; Chen, C.-K.; Chiang, Y.-W.; Ko, B.-T.; Lin, C.-C., Tubular Nanostructures from Degradable Core–Shell Cylinder Microstructures in Chiral Diblock Copolymers. Advanced Materials 2006, 18 (18), 2355-2358.
45. Ho, R.-M.; Chen, C.-K.; Chiang, Y.-W., Novel Nanostructures from Self-Assembly of Chiral Block Copolymers. Macromolecular Rapid Communications 2009, 30 (17), 1439-1456.
46. Ho, R.-M.; Chiang, Y.-W.; Chen, C.-K.; Wang, H.-W.; Hasegawa, H.; Akasaka, S.; Thomas, E. L.; Burger, C.; Hsiao, B. S., Block Copolymers with a Twist. Journal of the American Chemical Society 2009, 131 (51), 18533-18542.
47. Fujiki, M., Optically Active Polysilylenes: State-of-the-Art Chiroptical Polymers. Macromolecular Rapid Communications 2001, 22 (8), 539-563.
48. Ho, R.-M.; Li, M.-C.; Lin, S.-C.; Wang, H.-F.; Lee, Y.-D.; Hasegawa, H.; Thomas, E. L., Transfer of Chirality from Molecule to Phase in Self-Assembled Chiral Block Copolymers. Journal of the American Chemical Society 2012, 134 (26), 10974-10986.
49. Wen, T.; Wang, H.-F.; Li, M.-C.; Ho, R.-M., Homochiral Evolution in Self-Assembled Chiral Polymers and Block Copolymers. Accounts of Chemical Research 2017, 50 (4), 1011-1021.
50. Hsueh, H.-Y.; Ho, R.-M., Bicontinuous Ceramics with High Surface Area from Block Copolymer Templates. Langmuir 2012, 28 (22), 8518-8529.
51. Hsueh, H.-Y.; Yao, C.-T.; Ho, R.-M., Well-ordered nanohybrids and nanoporous materials from gyroid block copolymer templates. Chemical Society Reviews 2015, 44 (7), 1974-2018.
52. Chung, T.-M.; Wang, H.-F.; Lin, T.; Chiang, Y.-W.; Chen, Y.-C.; Ko, B.-T.; Ho, R.-M., Helical Phase Driven by Solvent Evaporation in Self-Assembly of Poly(4-vinylpyridine)-block-poly(l-lactide) Chiral Block Copolymers. Macromolecules 2012, 45 (24), 9727-9733.
53. Wang, H. F.; Yang, K. C.; Hsu, W. C.; Lee, J. Y.; Hsu, J. T.; Grason, G. M.; Thomas, E. L.; Tsai, J. C.; Ho, R. M., Generalizing the effects of chirality on block copolymer assembly. Proceedings of the National Academy of Sciences of the United States of America 2019, 116 (10), 4080-9.
54. Wen, T.; Ho, R.-M., Effects of the Chiral Interface and Orientation-Dependent Segmental Interactions on Twisting of Self-Assembled Block Copolymers. ACS Macro Letters 2017, 6 (4), 370-374.
55. Helfrich, W., Elastic properties of lipid bilayers: theory and possible experiments. Zeitschrift für Naturforschung C 1973, 28 (11-12), 693-703.
56. Deuling, H.; Helfrich, W., The curvature elasticity of fluid membranes: a catalogue of vesicle shapes. Journal de Physique 1976, 37 (11), 1335-1345.
57. Zhong-can, Ou-Yang, Ji-xing, L., Helical structures of tilted chiral lipid bilayers viewed as cholesteric liquid crystals. Physical Review Letters 1990, 65 (13), 1679-1682.
58. Ou-Yang, Z.-c.; Liu, J., Theory of helical structures of tilted chiral lipid bilayers. Physical Review A 1991, 43 (12), 6826-6836.
59. Grason, G. M., Chirality Transfer in Block Copolymer Melts: Emerging Concepts. ACS Macro Letters 2015, 4 (5), 526-532.
60. Zhao, W.; Russell, T. P.; Grason, G. M., Chirality in Block Copolymer Melts: Mesoscopic Helicity from Intersegment Twist. Physical Review Letters 2013, 110 (5), 058301.
61. Foerster, S.; Khandpur, A. K.; Zhao, J.; Bates, F. S.; Hamley, I. W.; Ryan, A. J.; Bras, W., Complex Phase Behavior of Polyisoprene-Polystyrene Diblock Copolymers Near the Order-Disorder Transition. Macromolecules 1994, 27 (23), 6922-6935.
62. Schulz, M. F.; Bates, F. S.; Almdal, K.; Mortensen, K., Epitaxial Relationship for Hexagonal-to-Cubic Phase Transition in a Book Copolymer Mixture. Physical Review Letters 1994, 73 (1), 86-89.
63. Hajduk, D. A.; Takenouchi, H.; Hillmyer, M. A.; Bates, F. S.; Vigild, M. E.; Almdal, K., Stability of the Perforated Layer (PL) Phase in Diblock Copolymer Melts. Macromolecules 1997, 30 (13), 3788-3795.
64. Chastek, T. Q.; Lodge, T. P., Measurement of Gyroid Single Grain Growth Rates in Block Copolymer Solutions. Macromolecules 2003, 36 (20), 7672-7680.
65. Chen, C.-K.; Hsueh, H.-Y.; Chiang, Y.-W.; Ho, R.-M.; Akasaka, S.; Hasegawa, H., Single Helix to Double Gyroid in Chiral Block Copolymers. Macromolecules 2010, 43 (20), 8637-8644.
66. Wang, H.-F.; Yu, L.-H.; Wang, X.-B.; Ho, R.-M., A Facile Method To Fabricate Double Gyroid as a Polymer Template for Nanohybrids. Macromolecules 2014, 47 (22), 7993-8001.
67. Hashimoto, T.; Tanaka, H.; Hasegawa, H., Ordered structure in mixtures of a block copolymer and homopolymers. 2. Effects of molecular weights of homopolymers. Macromolecules 1990, 23 (20), 4378-4386.
68. Tanaka, H.; Hasegawa, H.; Hashimoto, T., Ordered structure in mixtures of a block copolymer and homopolymers. 1. Solubilization of low molecular weight homopolymers. Macromolecules 1991, 24 (1), 240-251.
69. Koizumi, S.; Hasegawa, H.; Hashimoto, T., Ordered Structures of Block Copolymer/Homopolymer Mixtures. 5. Interplay of Macro- and Microphase Transitions. Macromolecules 1994, 27 (22), 6532-6540.
70. Wang, H.-F.; Wang, H.-W.; Ho, R.-M., Helical phase from blending of chiral block copolymer and homopolymer. Chemical Communications 2012, 48 (30), 3665-3667.
71. Schenning, A. P. H. J.; Jonkheijm, P.; Peeters, E.; Meijer, E. W., Hierarchical Order in Supramolecular Assemblies of Hydrogen-Bonded Oligo(p-phenylene vinylene)s. Journal of the American Chemical Society 2001, 123 (3), 409-416.
72. Lee, C. C.; Grenier, C.; Meijer, E. W.; Schenning, A. P. H. J., Preparation and characterization of helical self-assembled nanofibers. Chemical Society Reviews 2009, 38 (3), 671-683.
73. Lewis, F. D.; Zhang, L.; Zuo, X., Orientation Control of Fluorescence Resonance Energy Transfer Using DNA as a Helical Scaffold. Journal of the American Chemical Society 2005, 127 (28), 10002-10003.
74. Ajayaghosh, A.; Praveen, V. K., π-Organogels of Self-Assembled p-Phenylenevinylenes: Soft Materials with Distinct Size, Shape, and Functions. Accounts of Chemical Research 2007, 40 (8), 644-656.
75. Figueira-Duarte, T. M.; Müllen, K., Pyrene-Based Materials for Organic Electronics. Chemical Reviews 2011, 111 (11), 7260-7314.
76. Niko, Y.; Kawauchi, S.; Otsu, S.; Tokumaru, K.; Konishi, G.-i., Fluorescence Enhancement of Pyrene Chromophores Induced by Alkyl Groups through σ–π Conjugation: Systematic Synthesis of Primary, Secondary, and Tertiary Alkylated Pyrenes at the 1, 3, 6, and 8 Positions and Their Photophysical Properties. The Journal of Organic Chemistry 2013, 78 (7), 3196-3207.
77. Lo, K.-H.; Li, M.-C.; Ho, R.-M.; Zhao, Y.-C.; Massuyeau, F.; Chuang, W.-T.; Duvail, J.-L.; Lefrant, S.; Hsu, C.-S., Luminescence Enhancement of Pyrene/Dispersant Nanoarrays Driven by the Nanoscale Spatial Effect on Mixing. Langmuir 2013, 29 (5), 1627-1633.
78. Homola, J.; Yee, S. S.; Gauglitz, G., Surface plasmon resonance sensors: review. Sensors and Actuators B: Chemical 1999, 54 (1), 3-15.
79. Mayer, K. M.; Hafner, J. H., Localized Surface Plasmon Resonance Sensors. Chemical Reviews 2011, 111 (6), 3828-3857.
80. Kuzyk, A.; Schreiber, R.; Fan, Z.; Pardatscher, G.; Roller, E.-M.; Högele, A.; Simmel, F. C.; Govorov, A. O.; Liedl, T., DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 2012, 483 (7389), 311-314.
81. Schreiber, R.; Luong, N.; Fan, Z.; Kuzyk, A.; Nickels, P. C.; Zhang, T.; Smith, D. M.; Yurke, B.; Kuang, W.; Govorov, A. O.; Liedl, T., Chiral plasmonic DNA nanostructures with switchable circular dichroism. Nature Communications 2013, 4 (1), 2948.
82. Song, C.; Blaber, M. G.; Zhao, G.; Zhang, P.; Fry, H. C.; Schatz, G. C.; Rosi, N. L., Tailorable Plasmonic Circular Dichroism Properties of Helical Nanoparticle Superstructures. Nano Letters 2013, 13 (7), 3256-3261.
83. Merg, A. D.; Boatz, J. C.; Mandal, A.; Zhao, G.; Mokashi-Punekar, S.; Liu, C.; Wang, X.; Zhang, P.; van der Wel, P. C. A.; Rosi, N. L., Peptide-Directed Assembly of Single-Helical Gold Nanoparticle Superstructures Exhibiting Intense Chiroptical Activity. Journal of the American Chemical Society 2016, 138 (41), 13655-13663.
84. Mokashi-Punekar, S.; Merg, A. D.; Rosi, N. L., Systematic Adjustment of Pitch and Particle Dimensions within a Family of Chiral Plasmonic Gold Nanoparticle Single Helices. Journal of the American Chemical Society 2017, 139 (42), 15043-15048.
85. Hentschel, M.; Schäferling, M.; Duan, X.; Giessen, H.; Liu, N., Chiral plasmonics. Science Advances 2017, 3 (5), e1602735.
86. Querejeta-Fernández, A.; Chauve, G.; Methot, M.; Bouchard, J.; Kumacheva, E., Chiral Plasmonic Films Formed by Gold Nanorods and Cellulose Nanocrystals. Journal of the American Chemical Society 2014, 136 (12), 4788-4793.
87. Gansel, J. K.; Thiel, M.; Rill, M. S.; Decker, M.; Bade, K.; Saile, V.; von Freymann, G.; Linden, S.; Wegener, M., Gold Helix Photonic Metamaterial as Broadband Circular Polarizer. Science 2009, 325 (5947), 1513-1515.
88. Gibbs, J. G.; Mark, A. G.; Eslami, S.; Fischer, P., Plasmonic nanohelix metamaterials with tailorable giant circular dichroism. Applied Physics Letters 2013, 103 (21), 213101.
89. Mark, A. G.; Gibbs, J. G.; Lee, T.-C.; Fischer, P., Hybrid nanocolloids with programmed three-dimensional shape and material composition. Nature Materials 2013, 12, 802.
90. Esposito, M.; Tasco, V.; Cuscunà, M.; Todisco, F.; Benedetti, A.; Tarantini, I.; Giorgi, M. D.; Sanvitto, D.; Passaseo, A., Nanoscale 3D Chiral Plasmonic Helices with Circular Dichroism at Visible Frequencies. ACS Photonics 2015, 2 (1), 105-114.
91. Barranco, A.; Borras, A.; Gonzalez-Elipe, A. R.; Palmero, A., Perspectives on oblique angle deposition of thin films: From fundamentals to devices. Progress in Materials Science 2016, 76, 59-153.
92. Wang, Z.; Cheng, F.; Winsor, T.; Liu, Y., Optical chiral metamaterials: A review of the fundamentals, fabrication methods and applications. Nanotechnology 2016, 27, 412001.
93. Pendry, J. B., Negative Refraction Makes a Perfect Lens. Physical Review Letters 2000, 85 (18), 3966-3969.
94. Smith, D. R.; Kroll, N., Negative Refractive Index in Left-Handed Materials. Physical Review Letters 2000, 85 (14), 2933-2936.
95. Smith, D. R.; Pendry, J. B.; Wiltshire, M. C. K., Metamaterials and Negative Refractive Index. Science 2004, 305 (5685), 788-792.
96. Pendry, J. B., A Chiral Route to Negative Refraction. Science 2004, 306 (5700), 1353-1355.
97. Soukoulis, C. M.; Linden, S.; Wegener, M., Negative Refractive Index at Optical Wavelengths. Science 2007, 315 (5808), 47-49.
98. Zhang, S.; Park, Y.-S.; Li, J.; Lu, X.; Zhang, W.; Zhang, X., Negative Refractive Index in Chiral Metamaterials. Physical Review Letters 2009, 102 (2), 023901.
99. Plum, E.; Zhou, J.; Dong, J.; Fedotov, V. A.; Koschny, T.; Soukoulis, C. M.; Zheludev, N. I., Metamaterial with negative index due to chirality. Physical Review B 2009, 79 (3), 035407.
100. Zhou, J.; Dong, J.; Wang, B.; Koschny, T.; Kafesaki, M.; Soukoulis, C. M., Negative refractive index due to chirality. Physical Review B 2009, 79 (12), 121104.
101. Sharma, V.; Crne, M.; Park, J. O.; Srinivasarao, M., Structural Origin of Circularly Polarized Iridescence in Jeweled Beetles. Science 2009, 325 (5939), 449-451.
102. Nelson, J. C.; Saven, J. G.; Moore, J. S.; Wolynes, P. G., Solvophobically Driven Folding of Nonbiological Oligomers. Science 1997, 277 (5333), 1793-1796.
103. Li, M.-C.; Ousaka, N.; Wang, H.-F.; Yashima, E.; Ho, R.-M., Chirality Control and Its Memory at Microphase-Separated Interface of Self-Assembled Chiral Block Copolymers for Nanostructured Chiral Materials. ACS Macro Letters 2017, 6 (9), 980-986.
104. Matsen, M. W.; Bates, F. S., Block copolymer microstructures in the intermediate-segregation regime. The Journal of Chemical Physics 1997, 106 (6), 2436-2448.
105. Ho, R.-M.; Lin, F.-H.; Tsai, C.-C.; Lin, C.-C.; Ko, B.-T.; Hsiao, B. S.; Sics, I., Crystallization-Induced Undulated Morphology in Polystyrene-b-Poly(l-lactide) Block Copolymer. Macromolecules 2004, 37 (16), 5985-5994.
106. Yashima, E.; Maeda, K.; Nishimura, T., Detection and Amplification of Chirality by Helical Polymers. Chemistry – A European Journal 2004, 10 (1), 42-51.
107. Wu, C. W.; Sanborn, T. J.; Huang, K.; Zuckermann, R. N.; Barron, A. E., Peptoid Oligomers with α-Chiral, Aromatic Side Chains:  Sequence Requirements for the Formation of Stable Peptoid Helices. Journal of the American Chemical Society 2001, 123 (28), 6778-6784.
108. Amendola, V.; Pilot, R.; Frasconi, M.; Maragò, O. M.; Iatì, M. A., Surface plasmon resonance in gold nanoparticles: a review. Journal of Physics: Condensed Matter 2017, 29 (20), 203002.
109. Hentschel, MSchäferling, M.; Duan, X.; Giessen, H.; Liu, N., Chiral plasmonics. Science Advances 2017, 3 (5), e1602735.
110. Kuzyk, A.; Schreiber, R.; Fan, Z.; Pardatscher, G.; Roller, E.-M.; Högele, A.; Simmel, F. C.; Govorov, A. O.; Liedl, T., DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 2012, 483 (7389), 311-314.
111. Cheng, J.; Le Saux, G.; Gao, J.; Buffeteau, T.; Battie, Y.; Barois, P.; Ponsinet, V.; Delville, M.-H.; Ersen, O.; Pouget, E.; Oda, R., GoldHelix: Gold Nanoparticles Forming 3D Helical Superstructures with Controlled Morphology and Strong Chiroptical Property. ACS Nano 2017, 11 (4), 3806-3818.
112. Mokashi-Punekar, S.; Merg, A. D.; Rosi, N. L., Systematic Adjustment of Pitch and Particle Dimensions within a Family of Chiral Plasmonic Gold Nanoparticle Single Helices. Journal of the American Chemical Society 2017, 139 (42), 15043-15048.
113. Le Droumaguet, B.; Poupart, R.; Grande, D., “Clickable” thiol-functionalized nanoporous polymers: from their synthesis to further adsorption of gold nanoparticles and subsequent use as efficient catalytic supports. Polymer Chemistry 2015, 6 (47), 8105-8111.