TU Darmstadt / ULB / TUbiblio

Influence of Nanoconfinement on the pKa of Polyelectrolyte Functionalized Silica Mesopores

Brilmayer, Robert ; Kübelbeck, Sonja ; Khalil, Adnan ; Brodrecht, Martin ; Kunz, Ulrike ; Kleebe, Hans-Joachim ; Buntkowsky, Gerd ; Baier, Grit ; Andrieu‐Brunsen, Annette (2021)
Influence of Nanoconfinement on the pKa of Polyelectrolyte Functionalized Silica Mesopores.
In: Advanced Materials Interfaces, 2020, 7 (7)
doi: 10.26083/tuprints-00019915
Article, Secondary publication, Publisher's Version

WarningThere is a more recent version of this item available.

Abstract

Functionalized ordered mesoporous materials are relevant in technologies, such as drug release, sensing, and separation. To design functionality, the silica framework can be functionalized with responsive molecules or polymers. Often, the pH value in those hybrid materials determines performance. Even though pH/pKa differences between polymers in bulk solutions and nanoscale confinement have been observed, the influence of confinement on pH- and pore filling dependent polyelectrolyte oligomer chain charge has yet not been investigated systematically. Here, mesoporous silica films are functionalized with (2-dimethylamino)ethyl methacrylate) (DMAEMA) and 2-(methacryloyloxy)ethyl phosphate (MEP) oligomers using photoiniferter initiated polymerization. This approach allows a controlled and environmentally friendly mesopore functionalization in water. The obtained oligomer functionalized pores are tunable with respect to pore filling. For both, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2-(methacryloxy)ethyl phosphate) (PMEP), the charge generation inside mesopore confinement is significantly delayed toward harsher pH conditions resulting in pKa shifts of 1–2 pH units. Polymer amount and ionic strength show to further influence the pKa of PDMAEMA in mesopores. The technological importance of the pH value in confinement and its effect on enzyme stabilization is demonstrated. Lipase from Aspergillus oryzae loses its activity upon encapsulation in silica nanoparticles at pH values where the enzyme is stable in bulk solution.

Item Type: Article
Erschienen: 2021
Creators: Brilmayer, Robert ; Kübelbeck, Sonja ; Khalil, Adnan ; Brodrecht, Martin ; Kunz, Ulrike ; Kleebe, Hans-Joachim ; Buntkowsky, Gerd ; Baier, Grit ; Andrieu‐Brunsen, Annette
Type of entry: Secondary publication
Title: Influence of Nanoconfinement on the pKa of Polyelectrolyte Functionalized Silica Mesopores
Language: English
Date: 2021
Year of primary publication: 2020
Publisher: Wiley
Journal or Publication Title: Advanced Materials Interfaces
Volume of the journal: 7
Issue Number: 7
Collation: 10 Seiten
DOI: 10.26083/tuprints-00019915
URL / URN: https://tuprints.ulb.tu-darmstadt.de/19915
Corresponding Links:
Origin: Secondary publication service
Abstract:

Functionalized ordered mesoporous materials are relevant in technologies, such as drug release, sensing, and separation. To design functionality, the silica framework can be functionalized with responsive molecules or polymers. Often, the pH value in those hybrid materials determines performance. Even though pH/pKa differences between polymers in bulk solutions and nanoscale confinement have been observed, the influence of confinement on pH- and pore filling dependent polyelectrolyte oligomer chain charge has yet not been investigated systematically. Here, mesoporous silica films are functionalized with (2-dimethylamino)ethyl methacrylate) (DMAEMA) and 2-(methacryloyloxy)ethyl phosphate (MEP) oligomers using photoiniferter initiated polymerization. This approach allows a controlled and environmentally friendly mesopore functionalization in water. The obtained oligomer functionalized pores are tunable with respect to pore filling. For both, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2-(methacryloxy)ethyl phosphate) (PMEP), the charge generation inside mesopore confinement is significantly delayed toward harsher pH conditions resulting in pKa shifts of 1–2 pH units. Polymer amount and ionic strength show to further influence the pKa of PDMAEMA in mesopores. The technological importance of the pH value in confinement and its effect on enzyme stabilization is demonstrated. Lipase from Aspergillus oryzae loses its activity upon encapsulation in silica nanoparticles at pH values where the enzyme is stable in bulk solution.

Status: Publisher's Version
URN: urn:nbn:de:tuda-tuprints-199152
Classification DDC: 500 Science and mathematics > 540 Chemistry
Divisions: DFG-Collaborative Research Centres (incl. Transregio)
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 1194: Interaction between Transport and Wetting Processes
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 1194: Interaction between Transport and Wetting Processes > Research Area C: New and Improved Applications
DFG-Collaborative Research Centres (incl. Transregio) > Collaborative Research Centres > CRC 1194: Interaction between Transport and Wetting Processes > Research Area C: New and Improved Applications > C04: Controlled Dynamic Wetting and the Influence of Ionic Mass Transport in Mesoporous Film
Date Deposited: 19 Nov 2021 13:14
Last Modified: 01 Dec 2021 12:46
PPN:
Export:
Suche nach Titel in: TUfind oder in Google

Available Versions of this Item

Send an inquiry Send an inquiry

Options (only for editors)
Show editorial Details Show editorial Details