Nanocomposite Films of Laponite/PEG-Grafted Polymers and Polymer Brushes with Nonfouling Properties.

We explore the suitability of nanocomposite thin films based on laponite nanomaterial and grafted antiadhesive polymers as transparent nonfouling surfaces. For this purpose, two polymers were chosen: a linear poly(ethylene glycol) (PEG) silane, 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane), and thermoresponsive poly(oligo ethylene glycol)-methyl ether-methacrylate (POEGMA) brushes. PEG silane was grafted on the laponite nanoparticles in solution yielding homogeneous and transparent thin films via a dip coating procedure on glass and silicon substrates. POEGMA was grafted on laponite-(3-Aminopropyl)trimethoxysilane (APTMS) nanocomposite films that were processed similarly to PEG-silane using atom transfer radical polymerization (ATRP). Film characterization with, among others, Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM) attests to successful grafting of the polymers to the laponite nanoparticles. In particular, evidence of basal plane expansion of laponite with increasing silane concentration are obtained using XRD, while patent morphological changes are revealed with AFM. The results are discussed in terms of the different grafting sites on laponite and compared with literature. While LP-PEG-silane is easily applied to a surface from a precursor solution via a dip coating procedure LP-APTMS-OEGMA requires lots more chemicals, a thorough control of reaction parameters, and longer reaction time in order to generate films with the desirable properties. We therefore also addressed the antifouling properties of the films. These were tested together with control samples of bare glass and laponite thin films for 30 days in an algae container. More tests were conducted with fibroblast cell cultures. Our preliminary results show that grafting of PEG containing polymers and polymer brushes alters the properties of the laponite films from fouling to nonfouling surfaces. As a first estimate, the adhesion of particles (diatoms, algae, etc.) to surfaces is reduced by approximately 85% in the case of LP-PEG-silane and up to 92% in the case of LP-APTMS-POEGMA, in comparison to the control surfaces. Furthermore, practically no cell adhesion on such surfaces could be observed.

Thickness Dependence of Bovine Serum Albumin Adsorption on Thin Thermoresponsive Poly(diethylene glycol) Methyl Ether Methacrylate Brushes by Surface Plasmon Resonance Measurements.

This study reports on the dependence of the temperature-induced changes in the properties of thin thermoresponsive poly(diethylene glycol) methyl ether methacrylate (PDEGMA) layers of end-tethered chains on polymer thickness and grafting density. PDEGMA layers with a dry ellipsometric thickness of 5-40 nm were synthesized by surface-initiated atom transfer radical polymerization on gold. To assess the temperature-induced changes, the adsorption of bovine serum albumin (BSA) was investigated systematically as a function of film thickness, temperature, and grafting density by surface plasmon resonance (SPR), complemented by wettability and quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. BSA adsorption on PDEGMA brushes is shown to differ significantly above and below an apparent transition temperature. This surface transition temperature was found to depend linearly on the PDEGMA thickness and changed from 35 °C at 5 nm thickness to 48 °C at 23 nm. Similarly, a change of the grafting density enables the adjustment of this transition temperature presumably via a transition from the mushroom to the brush regime. Finally, BSA that adsorbed irreversibly on polymer brushes at temperatures above the transition temperature can be desorbed by reducing the temperature to 25 °C, underlining the reversibly switchable properties of PDEGMA brushes in response to temperature changes.

Data supporting polymerization of anti-fouling polymer brushes polymerized on the pore walls of porous aluminium and titanium oxides.

The data presented in this article affords insight into the fabrication and ensuing microstructure of the supported porous anodic aluminum oxide (AAO) and TiO2-nanotubes (NT) films that are used for the subsequent grafting of antifouling poly(oligo ethyleneglycol) methylether methacrylate (POEGMA) and poly acrylamide (PAAm) brushes. The experimental procedure for the grafting of POEGMA and PAAm via atom transfer radical polymerization (ATRP) is described in Wassel et al. (2019) https://doi.org/10.1016/j.matdes.2018.107542 [1]. The FTIR spectra of the porous oxides before and after attachment of (3-Aminopropyl)trimethoxysilane (APTMS) are presented. Microscopic images of thick POEGMA films and PAAm on AAO are displayed, and an FTIR spectrum of AAO/PAAm is shown. An EDX mapping of carbon is shown on an AAO/POEGMA sample. The adsorption behavior of Fluorescein isothiocyanate (FITC) marked bovine serum albumin (BSA) on patterned porous TiO2-NT films is documented. Finally microscopic images are presented to compare the scratch resistance behavior of pristine porous films with those functionalized with POEGMA.

Thin Poly(Di(Ethylene Glycol)Methyl Ether Methacrylate) Homopolymer Brushes Allow Controlled Adsorption and Desorption of PaTu 8988t Cells.

Poly(di(ethylene glycol)methyl ether methacrylate) (PDEGMA) brushes, which are known to suppress protein adsorption and prevent cell attachment, are reported here to possess interesting and tunable thermoresponsive behavior, if the brush thickness is reduced or the grafting density is altered. PDEGMA brushes with a dry ellipsometric thickness of 5 ± 1 nm can be switched from cell adherent behavior at 37 °C to cell nonadherent at 25 °C. This behavior coincides with the temperature-dependent irreversible adsorption of fibronectin from phosphate saline buffer and proteins present in the cell culture medium, as unveiled by surface plasmon resonance measurements. Unlike for tissue culture polystyrene reference surfaces, swelling of the PDEGMA chains below the lower critical solution temperature results in the absence of paxillin and actin containing cellular filaments responsible for cell attachment. These tunable properties of very thin homopolymer PDEGMA brushes render this system interesting as an alternative thermoresponsive layer for continuous cell culture or enzyme-free cell culture systems.