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Spatial control over cross-linking dictates the pH-responsive behavior of poly(2-(tert-butylamino)ethyl methacrylate) brushes.

ABSTRACT: Surface-initiated atom transfer radical polymerization (ATRP) of 2-(tert-butylamino)ethyl methacrylate (TBAEMA) produced pH-responsive secondary amine-functionalized polymer brushes with dry thicknesses ranging from 4 to 28 nm, as determined by ellipsometry. At low pH, linear PTBAEMA brushes became protonated and highly swollen; brush collapse occurred when the solution pH was increased to ca. 7.7 due to deprotonation. PTBAEMA brushes were subsequently cross-linked using tolylene-2,4-diisocyanate-terminated poly(propylene glycol) (PPG-TGI) in either THF (a good solvent for PTBAEMA) or n-hexane (a poor solvent). The intensity of the C-C-O component (286.5 eV) in the C1s X-ray photoelectron spectrum increased after reaction with PPG-TDI, suggesting that cross-linking was successful in both solvents. Ellipsometry studies indicated that the pH-responsive behavior of these cross-linked brushes is dictated by the spatial location of the PPG-TDI cross-linker. Thus, uniformly cross-linked brushes prepared in THF became appreciably less swollen at a given (low) pH than surface-cross-linked brushes prepared in n-hexane. Micro- and nanopatterned PTBAEMA brushes were prepared via UV irradiation and interference lithography, respectively, and characterized by atomic force microscopy. The change in brush height was determined as a function of pH, and these AFM observations correlated closely with the ellipsometric studies.

SUBMITTER: Alswieleh AM

PROVIDER: S-EPMC4190050 | biostudies-literature | 2014 Feb

REPOSITORIES: biostudies-literature

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Spatial control over cross-linking dictates the pH-responsive behavior of poly(2-(tert-butylamino)ethyl methacrylate) brushes.

Alswieleh Abdullah M AM Cheng Nan N Leggett Graham J GJ Armes Steven P SP

Langmuir : the ACS journal of surfaces and colloids 20140128 5

Surface-initiated atom transfer radical polymerization (ATRP) of 2-(tert-butylamino)ethyl methacrylate (TBAEMA) produced pH-responsive secondary amine-functionalized polymer brushes with dry thicknesses ranging from 4 to 28 nm, as determined by ellipsometry. At low pH, linear PTBAEMA brushes became protonated and highly swollen; brush collapse occurred when the solution pH was increased to ca. 7.7 due to deprotonation. PTBAEMA brushes were subsequently cross-linked using tolylene-2,4-diisocyanat ...[more]

PMID: 24417283

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Project description:Conventional cryopreservation solutions rely on the addition of organic solvents such as DMSO or glycerol, but these do not give full recovery for all cell types, and innovative cryoprotectants may address damage pathways which these solvents do not protect against. Macromolecular cryoprotectants are emerging, but there is a need to understand their structure-property relationships and mechanisms of action. Here we synthesized and investigated the cryoprotective behavior of sulfoxide (i.e., "DMSO-like") side-chain polymers, which have been reported to be cryoprotective using poly(ethylene glycol)-based polymers. We also wanted to determine if the polarized sulfoxide bond (S+O- character) introduces cryoprotective effects, as this has been seen for mixed-charge cryoprotective polyampholytes, whose mechanism of action is not yet understood. Poly(2-(methylsulfinyl)ethyl methacrylate) was synthesized by RAFT polymerization of 2-(methylthio)ethyl methacrylate and subsequent oxidation to sulfoxide. A corresponding N-oxide polymer was also prepared and characterized: (poly(2-(dimethylamineoxide)ethyl methacrylate). Ice recrystallization inhibition assays and differential scanning calorimetry analysis show that the sulfoxide side chains do not modulate the frozen components during cryopreservation. In cytotoxicity assays, it was found that long-term (24 h) exposure of the polymers was not tolerated by cells, but shorter (30 min) incubation times, which are relevant for cryopreservation, were tolerated. It was also observed that overoxidation to the sulfone significantly increased the cytotoxicity, and hence, these materials require a precision oxidation step to be deployed. In suspension cell cryopreservation investigations, the polysulfoxides did not increase cell recovery 24 h post-thaw. These results show that unlike hydrophilic backboned polysulfides, which can aid cryopreservation, the installation of the sulfoxide group onto a polymer does not necessarily bring cryoprotective properties, highlighting the challenges of developing and discovering macromolecular cryoprotectants.

Dataset Information

Spatial control over cross-linking dictates the pH-responsive behavior of poly(2-(tert-butylamino)ethyl methacrylate) brushes.

Publications

Spatial control over cross-linking dictates the pH-responsive behavior of poly(2-(tert-butylamino)ethyl methacrylate) brushes.

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