Controlled Handedness of Twisted Lamellae in Banded Spherulites of Isotactic Poly(2‐vinylpyridine) as Induced by Chiral Dopants

Wen, Tao; Shên, Hui; Wang, Hsiao Fang; Mao, Yung Cheng; Chuang, Wei Tsung; Tsai, Jing Cherng; Ho, Rong Ming

doi:10.1002/anie.201506186

Cited by 37 publications

(36 citation statements)

References 25 publications

(24 reference statements)

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“…For example, when (R)-or (S)hexahydromandelic acid (HMA), which can associate with isotactic poly(2-vinylpyridine) (iP2VP), was introduced as a chiral dopant, mirror-image CD spectra in the complex systems were observed. [34] Moreover, a preferential sense of the twisted crystalline lamellae was also obtained in the iP2VP/HMA complex, thus suggesting the homochirality evolution from conformational to hierarchical chirality. The handedness of twisted lamellae in banded spherulites could be controlled by the chiral dopants.…”

Section: Crystallization With the Participation Of Chiralitymentioning

confidence: 89%

Supramolecular Chirality Transfer toward Chiral Aggregation: Asymmetric Hierarchical Self‐Assembly

2021

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Self-assembly, as a typical bottom-up strategy for the fabrication of functional materials, has been applied to fabricate chiral materials with subtle chiral nanostructures. The chiral nanostructures exhibit great potential in asymmetric catalysis, chiral sensing, chiral electronics, photonics, and even the realization of several biological functions. According to existing studies, the supramolecular chirality transfer process combined with hierarchical self-assembly plays a vital role in the fabrication of multiscale chiral structures. This progress report focuses on the hierarchical self-assembly of chiral or achiral molecules that aggregate with asymmetric spatial structures such as twisted bands, helices, and superhelices in different environments. Herein, recent studies on the chirality transfer induced self-assembly based on a variety of supramolecular interactions are summarized. In addition, the influence of different environments and the states of systems including solutions, condensed states, gel systems, interfaces on the asymmetric hierarchical self-assembly, and the expression of chirality are explored. Moreover, both the driving forces that facilitate chiral bias and the supramolecular interactions that play an important role in the expression, transfer, and amplification of the chiral sense are correspondingly discussed.

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Section: Crystallization With the Participation Of Chiralitymentioning

confidence: 89%

Supramolecular Chirality Transfer toward Chiral Aggregation: Asymmetric Hierarchical Self‐Assembly

2021

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“…This also stands for PCL [75][76][77][78]. Recently, Ho et al [79] reported that chiral dopants can tune the twisting chirality of lamellar crystals of nonchiral isotactic poly(2-vinylpyridine), where (R)-and (S)-hexahydromandelic acid dopant induced right-handed and left-handed lamellar twisting, respectively.…”

Section: Factors Affecting Band Spacingmentioning

confidence: 99%

Organization of Twisting Lamellar Crystals in Birefringent Banded Polymer Spherulites: A Mini-Review

Zhang

et al. 2017

Crystals

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Abstract:In this mini-review, we summarize the evidences of lamellar twisting in the birefringent banded polymer spherulites demonstrated by various characterization techniques, such as polarized optical microscopy, real-time atomic force microscopy, micro-focus wide angle X-ray diffraction, etc. The real-time observation of lamellar growth under atomic force microscopy unveiled the fine details of lamellar twisting and branching in the banded spherulites of poly(R-3-hydroxybutyrate-co-17 mol % R-3-hydroxyhexanoate). Organization of the twisting lamellar crystals in the banded spherulites was revealed as well. The lamellar crystals change the orientation via twisting rather than the macro screw dislocations. In fact, macro screw dislocation provides the mechanism of synchronous twisting of neighboring lamellar crystals. The driving force of lamellar twisting is attributed to the anisotropic and unbalanced surface stresses. Besides molecular chirality, variation of the growth axis and the chemical groups on lamellar surface can change the distribution of the surface stresses, and thus may invert the handedness of lamellar twisting. Thus, based on both experimental results and physical reasoning, the relation between crystal chirality and chemical molecular structures has been suggested, via the bridge of the distribution of surface stresses. The factors affecting band spacing are briefly discussed. Some remaining questions and the perspective of the topic are highlighted.Keywords: banded polymer spherulite; ringed spherulite; lamellar twisting; organization of lamellar crystals; surface stresses; chirality When crystallized from quiescent melt or concentrated solution, polymer chains usually form spherulites consisted of multiple lamellar crystals radiating from the spherulite center. Observed under polarized optical microscope (POM), a spherulite shows the characteristic Maltese-cross extinction. Besides the Maltese cross, some spherulites demonstrate alternative bright and dark bands under POM. These spherulites are termed as banded spherulites or ringed spherulites. The band structure with different light intensities may result from different thicknesses or different birefringences but similar thickness. In the former case, the bands are due to the periodical modulation of sample thickness and there is no variation of refractive index in the spherulite. These nonbirefringent banded spherulites have been observed in some polymer single crystals formed from thin melt films [1] or solutions [2] and are reviewed by Li et al. [3] in this special issue. In the latter case, the birefringent bands can result from the wavy bending growth or twisting growth of crystals. The wavy bands have been reported in sheared liquid crystals [4,5], which do not form spherulites under the condition. In this mini-review, we focus on the birefringent banded spherulites, which consist of synchronously twisted lamellar crystals. The organization of the twisted lamellar crystals in the banded spherulites and the driving force for lamell...

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“…The mirror imaging of the CD spectra suggests the formation of right-and left-handed helical chains of the achiral polymer through complexation with the chiral guest [43]. Poly(phenylacetylene)s (PPAs) have also shown to present distinct chiroptical responses associated with their helicity.…”

Section: Induced Chiralitymentioning

confidence: 99%

“…The helical sense depends exclusively on the chiral monomer/donor cosolvent ratio, and this allows a flexible and controlled on/off tuning of the helicity of the copolymer. The mirror imaging of the CD spectra suggests the formation of right-and left-handed helical chains of the achiral polymer through complexation with the chiral guest [43]. Poly(phenylacetylene)s (PPAs) have also shown to present distinct chiroptical responses associated with their helicity.…”

Section: Induced Chiralitymentioning

confidence: 99%

Chiroptical Sensing: A Conceptual Introduction

Ozcelik

Ulrih

Petrovic

et al. 2020

Sensors

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Chiroptical responses have been an essential tool over the last decades for chemical structural elucidation due to their exceptional sensitivity to geometry and intermolecular interactions. In recent times, there has been an increasing interest in the search for more efficient sensing by the rational design of tailored chiroptical systems. In this review article, advances made in chiroptical systems towards their implementation in sensing applications are summarized. Strategies to generate chiroptical responses are illustrated. Theoretical approaches to assist in the design of these systems are discussed. The development of efficient chiroptical reporters in different states of matter, essential for the implementation in sensing devises, is reviewed. In the last part, remarkable examples of chiroptical sensing applications are highlighted.

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Controlled Handedness of Twisted Lamellae in Banded Spherulites of Isotactic Poly(2‐vinylpyridine) as Induced by Chiral Dopants

Cited by 37 publications

References 25 publications

Supramolecular Chirality Transfer toward Chiral Aggregation: Asymmetric Hierarchical Self‐Assembly

Supramolecular Chirality Transfer toward Chiral Aggregation: Asymmetric Hierarchical Self‐Assembly

Organization of Twisting Lamellar Crystals in Birefringent Banded Polymer Spherulites: A Mini-Review

Chiroptical Sensing: A Conceptual Introduction

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