Architecture-dependent interplay between self-assembly and crystallization in discrete block co-oligomers

Katja Petkau-Milroy (Corresponding author), Alessandro Ianiro, Melanie M.L. Ahn, Jose Rodrigo Magana, Marle E.J. Vleugels, Brigitte A.G. Lamers, Remco Tuinier, Ilja K. Voets, Anja R.A. Palmans (Corresponding author), E.W. Meijer (Corresponding author)

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Access to versatile and stable nanostructures formed by the self-assembly of block copolymers in water is essential for biomedical applications. These applications require control over the stability, morphology, and size of the formed nanostructures. Here, we study the self-assembly in water of a library of fully discrete and sequence-controlled AB-type block co-oligomers (BCOs) of oligo(l-lactic acid)-b-oligo(ethylene glycol). In this series, we eliminate all the inherent uncertainty associated with molar mass, ratio, and compositional dispersity, but vary the ratio between the water-soluble and water-insoluble parts. The BCO library is designed in such a way that vesicles, spherical micelles, and cylindrical micelles are generated in solution, hereby covering a variety of common morphologies. With the help of self-consistent field (SCF) computations, the thermodynamic structures in water are predicted for all structures. The morphologies formed were experimentally analyzed using a combination of calorimetry and scattering techniques. When comparing the experimentally found structures with those predicted, we find an excellent agreement. Intriguingly, calorimetry showed the presence of crystallized l-lactic acid (LLA) units in the bilayer of the lamellar forming BCO. Despite this crystallinity, there is no mismatch between the predicted and observed bilayer thicknesses upon self-assembly in water. In this case, phase separation driven by the hydrophobic LLA block coincides with crystallization, resulting in stable morphologies. Thus, SCF guided library design and sample preparation can lead toward robust formulations of nanoparticles.

Originele taal-2Engels
Pagina's (van-tot)38-42
Aantal pagina's5
TijdschriftACS Macro Letters
Volume9
Nummer van het tijdschrift1
DOI's
StatusGepubliceerd - 21 jan 2020

Vingerafdruk

Crystallization
Oligomers
Self assembly
Water
Lactic acid
Lactic Acid
Micelles
Calorimetry
Nanostructures
Ethylene Glycol
Molar mass
Ethylene glycol
Phase separation
Block copolymers
Thermodynamics
Scattering
Nanoparticles

Citeer dit

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abstract = "Access to versatile and stable nanostructures formed by the self-assembly of block copolymers in water is essential for biomedical applications. These applications require control over the stability, morphology, and size of the formed nanostructures. Here, we study the self-assembly in water of a library of fully discrete and sequence-controlled AB-type block co-oligomers (BCOs) of oligo(l-lactic acid)-b-oligo(ethylene glycol). In this series, we eliminate all the inherent uncertainty associated with molar mass, ratio, and compositional dispersity, but vary the ratio between the water-soluble and water-insoluble parts. The BCO library is designed in such a way that vesicles, spherical micelles, and cylindrical micelles are generated in solution, hereby covering a variety of common morphologies. With the help of self-consistent field (SCF) computations, the thermodynamic structures in water are predicted for all structures. The morphologies formed were experimentally analyzed using a combination of calorimetry and scattering techniques. When comparing the experimentally found structures with those predicted, we find an excellent agreement. Intriguingly, calorimetry showed the presence of crystallized l-lactic acid (LLA) units in the bilayer of the lamellar forming BCO. Despite this crystallinity, there is no mismatch between the predicted and observed bilayer thicknesses upon self-assembly in water. In this case, phase separation driven by the hydrophobic LLA block coincides with crystallization, resulting in stable morphologies. Thus, SCF guided library design and sample preparation can lead toward robust formulations of nanoparticles.",
author = "Katja Petkau-Milroy and Alessandro Ianiro and Ahn, {Melanie M.L.} and Magana, {Jose Rodrigo} and Vleugels, {Marle E.J.} and Lamers, {Brigitte A.G.} and Remco Tuinier and Voets, {Ilja K.} and Palmans, {Anja R.A.} and E.W. Meijer",
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AU - Petkau-Milroy, Katja

AU - Ianiro, Alessandro

AU - Ahn, Melanie M.L.

AU - Magana, Jose Rodrigo

AU - Vleugels, Marle E.J.

AU - Lamers, Brigitte A.G.

AU - Tuinier, Remco

AU - Voets, Ilja K.

AU - Palmans, Anja R.A.

AU - Meijer, E.W.

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AB - Access to versatile and stable nanostructures formed by the self-assembly of block copolymers in water is essential for biomedical applications. These applications require control over the stability, morphology, and size of the formed nanostructures. Here, we study the self-assembly in water of a library of fully discrete and sequence-controlled AB-type block co-oligomers (BCOs) of oligo(l-lactic acid)-b-oligo(ethylene glycol). In this series, we eliminate all the inherent uncertainty associated with molar mass, ratio, and compositional dispersity, but vary the ratio between the water-soluble and water-insoluble parts. The BCO library is designed in such a way that vesicles, spherical micelles, and cylindrical micelles are generated in solution, hereby covering a variety of common morphologies. With the help of self-consistent field (SCF) computations, the thermodynamic structures in water are predicted for all structures. The morphologies formed were experimentally analyzed using a combination of calorimetry and scattering techniques. When comparing the experimentally found structures with those predicted, we find an excellent agreement. Intriguingly, calorimetry showed the presence of crystallized l-lactic acid (LLA) units in the bilayer of the lamellar forming BCO. Despite this crystallinity, there is no mismatch between the predicted and observed bilayer thicknesses upon self-assembly in water. In this case, phase separation driven by the hydrophobic LLA block coincides with crystallization, resulting in stable morphologies. Thus, SCF guided library design and sample preparation can lead toward robust formulations of nanoparticles.

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