Effects of crystallinity and dispersity on the self-assembly behavior of block co-oligomers in water

Vleugels, Marle E. J.; Zwart, Marnie E. de; Magana, José Rodrigo; Lamers, Brigitte A. G.; Voets, Ilja K.; Meijer, E. W.; Petkau-Milroy, K Katja; Palmans, Anja R. A.

doi:10.1039/d0py01161d

Cited by 16 publications

(24 citation statements)

References 54 publications

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“…There could be many reasons for the mixed morphology of the structures, which differ in the interfacial curvature that appeared, but most likely is the OCL polydispersity index [ 99 , 100 ].…”

Section: Resultsmentioning

confidence: 99%

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2021

Polymers

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End-group functionalization of homopolymers is a valuable way to produce high-fidelity nanostructured and functional soft materials when the structures obtained have the capacity for self-assembly (SA) encoded in their structural details. Herein, an end-functionalized PCL with a π-conjugated EDOT moiety, (EDOT-PCL), designed exclusively from hydrophobic domains, as a functional “hydrophobic amphiphile”, was synthesized in the bulk ROP of ε-caprolactone. The experimental results obtained by spectroscopic methods, including NMR, UV-vis, and fluorescence, using DLS and by AFM, confirm that in solvents with extremely different polarities (chloroform and acetonitrile), EDOT-PCL presents an interaction- and structure-based bias, which is strong and selective enough to exert control over supramolecular packing, both in dispersions and in the film state. This leads to the diversity of SA structures, including spheroidal, straight, and helical rods, as well as orthorhombic single crystals, with solvent-dependent shapes and sizes, confirming that EDOT-PCL behaves as a “block-molecule”. According to the results from AFM imaging, an unexpected transformation of micelle-type nanostructures into single 2D lamellar crystals, through breakout crystallization, took place by simple acetonitrile evaporation during the formation of the film on the mica support at room temperature. Moreover, EDOT-PCL’s propensity for spontaneous oxidant-free oligomerization in acidic media was proposed as a presumptive answer for the unexpected appearance of blue color during its dissolution in CDCl3 at a high concentration. FT-IR, UV-vis, and fluorescence techniques were used to support this claim. Besides being intriguing and unforeseen, the experimental findings concerning EDOT-PCL have raised new and interesting questions that deserve to be addressed in future research.

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Section: Resultsmentioning

confidence: 99%

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Bendrea¹,

Cianga²,

Ailiesei³

et al. 2021

Polymers

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“…Significantly, the formed structures could be tailored via the individual block length and were predictable via self‐consistent field computations. Furthermore, the effect of LA block crystallinity on solution self‐assembly of amphiphilic oEG‐ b ‐oLA was investigated 166 …”

Section: Properties Of Oligomer‐based Materialsmentioning

confidence: 99%

“…Furthermore, the effect of LA block crystallinity on solution self-assembly of amphiphilic oEG-b-oLA was investigated. 166 F I G U R E 1 9 Self-assembly of amphiphilic BCOs: (a) SANS scattering intensity, normalized by the polymer volume fraction and analysis of the micellar solutions of sequence-defined peptoid block copolymers bearing a single ionic monomer (b) the data vertically scaled, (c) chemical structures of representative sequences of ionic peptoid block copolymers, (d) a cartoon representation of the micellar structure with respect to the ionic monomer position along the peptoid polymer chain. Reprinted with permission.…”

Section: Self-assembly and Molecular Recognitionmentioning

confidence: 99%

Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Genabeek

Lamers

Hawker

et al. 2021

Journal of Polymer Science

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Precise oligomeric materials constitute a growing area of research with implications for various applications as well as fundamental studies. Notably, this field of science which can be termed macro‐organic chemistry, draws inspiration from both traditional polymer chemistry and organic synthesis, combining the molecular precision of organic chemistry with the materials properties of macromolecules. Discrete oligomers enable access to unprecedented materials properties, for example, in self‐assembled structures, crystallization, or optical properties. The degree of control over oligomer structures resembles many biological systems and enables the design of materials with tailored properties and the development of fundamental structure–property relationships. This Review highlights recent developments in macro‐organic chemistry from synthetic concepts to materials properties, with a focus on self‐assembly and molecular recognition. Finally, an outlook for future research directions is provided.

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“…Only recently, the use of isotactic hydrophobic blocks has attracted increasing interest. [6][7][8][9][10][11][12] In particular, isotactic poly(lactic acid) (PLA) has been used to elucidate the effect of stereoregularity in the main chain of BCPs on the formation and morphology of aqueous self-assemblies. For example, poly(L-lactic acid)-blockpoly(acrylic acid) (PLLA-b-PAA) BCPs formed cylindrical micelles, whereas spherical micelles were obtained when atactic PLA was employed.…”

Section: Introductionmentioning

confidence: 99%

“…7,8 Differences between atactic and isotactic PLA-b-PEG self-assemblies were not observed regarding the morphology of spherical micelles, cylindrical micelles and vesicles; only the packing of chains within the vesicle membrane was affected, as isotactic BCPs showed a denser and more elongated conformation within the membrane. 12 In general, all of the aforementioned studies were based on crystallisation-driven self-assembly (CDSA). Thus, the isotacticity of the PLLA block served solely as means to introduce crystallinity within the membrane.…”

Section: Introductionmentioning

confidence: 99%

Fully amorphous atactic and isotactic block copolymers and their self-assembly into nano- and microscopic vesicles

et al. 2021

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Effects of crystallinity and dispersity on the self-assembly behavior of block co-oligomers in water

Abstract: Self-assembly of block copolymers in solution is a topic of great interest in polymer science due to the potential for applications as a drug carrier system. In bulk, fully discrete...

Cited by 16 publications

References 54 publications

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

3,4-Ethylenedioxythiophene (EDOT) End-Group Functionalized Poly-ε-caprolactone (PCL): Self-Assembly in Organic Solvents and Its Coincidentally Observed Peculiar Behavior in Thin Film and Protonated Media

Properties and applications of precision oligomer materials; where organic and polymer chemistry join forces

Fully amorphous atactic and isotactic block copolymers and their self-assembly into nano- and microscopic vesicles

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