Tailoring the swelling and glass‐transition temperature of acrylonitrile/hydroxyethyl acrylate copolymers

Aran, Bengi; Sankır, Mehmet; Vargün, Elif; Sankır, Nurdan Demirci; Usanmaz, Ali

doi:10.1002/app.30854

Cited by 12 publications

(5 citation statements)

References 26 publications

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“…The phase separation within the shell was confirmed by differential scanning calorimetry (DSC) of the APCN microcapsules, which revealed two glass transition temperatures, at -123 °C, corresponding to PDMS, 86 and 4 °C, corresponding to PHEA 87,88 (Figure S1a). Thermogravimetric analysis under a nitrogen atmosphere indicated a mass loss with an onset at 150 °C and mass loss of 7% until 265 °C, after which the main mass loss proceeded over a relatively large temperature range up to 470 °C (Figure S1b).…”

Section: Resultsmentioning

confidence: 92%

Microfluidically produced microcapsules with amphiphilic polymer conetwork shells

Velasquez,

Belluati,

Tervoort

et al. 2023

Preprint

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Microcapsules with aqueous core can be conveniently prepared by water-in-oil-in-water double emulsion microfluidics. However, conventional shell materials are either based on polymers or monomers that are soluble in the oil phase, or based on hydrophobic colloidal particles. As a result, microcapsules derived from double emulsions usually feature a hydrophobic shell that is not semipermeable for water-soluble compounds. While capsules with semipermeable hydrogel shells have been demonstrated, these may exhibit poor mechanical properties and lack the robustness required in many applications. In this study, amphiphilic polymer conetworks (APCNs) based on poly(2-hydroxyethyl acrylate)-linked by-polydimethylsiloxane (PHEA-l-PDMS) are introduced as a new class of wall materials in double emulsion microcapsules. These APCNs are mechanically robust silicone hydrogels that are swellable and permeable to water, and are soft and elastic in the dry and swollen states. Thus, the microcapsules can be dried and rehydrated multiple times or shrunken in sodium chloride salt solutions without getting damaged. Moreover, the APCNs are semipermeable for hydrophilic organic compounds, while being impermeable for macromolecules and colloids. Thus, they can be loaded with macromolecules or nanoparticles during microfluidic formation, and with organic molecules after capsule synthesis. Uptake into and release from the capsules were studied with the model compounds fluorescein and fluorescently labelled dextran. Moreover, the microcapsules served as microreactors for catalytically active platinum nanoparticles that decomposed hydrogen peroxide. Finally, the surface of APCN microcapsules can be selectively functionalized with a cholesterol-based linker that non-covalently binds to the hydrophobic domains of the APCN. Thus, APCN microcapsules represent versatile and broadly applicable capsules that could find application for the controlled delivery of drugs, as microreactors for synthesis, or even as scaffolds for synthetic cells.

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Section: Resultsmentioning

confidence: 92%

Microfluidically produced microcapsules with amphiphilic polymer conetwork shells

Velasquez,

Belluati,

Tervoort

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…[26] The morphology of the APCN microcapsules did not change significantly upon repeated rehydration and drying in water (Figure 2; Figure S1, Supporting Information). DSC of the APCN microcapsules revealed two glass transition temperatures at −123 °C, corresponding to PDMS, [96] and 4 °C, corresponding to PHEA [97,98] (Figure S2a, Supporting Information), which indicate polymer phase separation.…”

Section: Resultsmentioning

confidence: 99%

Microfluidically Produced Microcapsules with Amphiphilic Polymer Conetwork Shells

Velasquez,

Belluati,

Tervoort

et al. 2024

Adv Materials Technologies

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Microcapsules with an aqueous core can be conveniently prepared by water‐in‐oil‐in‐water double emulsion microfluidics. However, conventional shell materials are based on hydrophobic polymers or colloidal particles. Thus, these microcapsules feature a hydrophobic shell impermeable to water‐soluble compounds. Capsules with semipermeable hydrogel shells have been demonstrated but may exhibit poor mechanical properties. Here, amphiphilic polymer conetworks (APCNs) based on poly(2‐hydroxyethyl acrylate)‐linked by‐polydimethylsiloxane (PHEA‐l‐PDMS) are introduced as a new class of wall materials in double emulsion microcapsules. These APCNs are mechanically robust silicone hydrogels that are swellable and permeable to water and are soft and elastic when dry or swollen. Therefore, the microcapsules can be dried and rehydrated multiple times or shrunken in sodium chloride salt solutions without getting damaged. Moreover, the APCNs are permeable for hydrophilic organic compounds and impermeable for macromolecules. Thus, they can be loaded with macromolecules or nanoparticles during microfluidic formation and with organic molecules after capsule synthesis. The microcapsules serve as microreactors for catalytically active platinum nanoparticles that decompose hydrogen peroxide. Finally, the surface of the APCN microcapsules can be selectively functionalized with a cholesterol‐based linker. Concluding, APCN microcapsules could find applications for the controlled delivery of drugs, as microreactors for synthesis, or as scaffolds for synthetic cells.

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“…A random copolymer network system consisting of hydrophobic n -butyl acrylate (B) and hydrophilic 2-hydroxyethyl acrylate (H) repeat units was selected to demonstrate the screening approach. The glass transition temperatures of the component homopolymers, poly( n -butyl acrylate) ( T g ≈ −52 °C) and poly(2-hydroxyethyl acrylate) ( T g ≈ 3.5 °C), are low enough to yield rubbery copolymers at room temperature. Both acrylate monomers are readily polymerized in bulk or in solution by simple free-radical techniques, and they are miscible across their entire composition range.…”

Section: Resultsmentioning

confidence: 99%

Combinatorial Methodology for Screening Selectivity in Polymeric Pervaporation Membranes

Godbole

Doerfert

et al. 2015

ACS Comb. Sci.

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Combinatorial methodology is described for rapid screening of selectivity in polymeric pervaporation membrane materials for alcohol-water separations. The screening technique is demonstrated for ethanol-water separation using a model polyacrylate system. The materials studied are cross-linked random copolymers of a hydrophobic comonomer (n-butyl acrylate, B) and a hydrophilic comonomer (2-hydroxyethyl acrylate, H). A matrix of materials is prepared that has orthogonal variations in two key variables, H:B ratio and cross-linker concentration. For mixtures of ethanol and water, equilibrium selectivities and distribution coefficients are obtained by combining swelling measurements with high-throughput HPLC analysis. Based on the screening results, two copolymers are selected for further study as pervaporation membranes to quantify permeability selectivity and the flux of ethanol. The screening methodology described has good potential to accelerate the search for new membrane materials, as it is adaptable to a broad range of polymer chemistries.

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Tailoring the swelling and glass‐transition temperature of acrylonitrile/hydroxyethyl acrylate copolymers

Cited by 12 publications

References 26 publications

Microfluidically produced microcapsules with amphiphilic polymer conetwork shells

Microfluidically produced microcapsules with amphiphilic polymer conetwork shells

Microfluidically Produced Microcapsules with Amphiphilic Polymer Conetwork Shells

Combinatorial Methodology for Screening Selectivity in Polymeric Pervaporation Membranes

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