A Highly Stable Nonbiofouling Surface with Well-Packed Grafted Zwitterionic Polysulfobetaine for Plasma Protein Repulsion

Abstract

An ideal nonbiofouling surface for biomedical applications requires both high-efficient antifouling characteristics in relation to biological components and long-term material stability from biological systems. In this study we demonstrate the performance and stability of an antifouling surface with grafted zwitterionic sulfobetaine methacrylate (SBMA). The SBMA was grafted from a bromide-covered gold surface via surface-initiated atom transfer radical polymerization to form well-packed polymer brushes. Plasma protein adsorption on poly(sulfobetaine methacrylate) (polySBMA) grafted surfaces was measured with a surface plasmon resonance sensor. It is revealed that an excellent stable nonbiofouling surface with grafted polySBMA can be performed with a cycling test of the adsorption of three model proteins in a wide range of various salt types, buffer compositions, solution pH levels, and temperatures. This work also demonstrates the adsorption of plasma proteins and the adhesion of platelets from human blood plasma on the polySBMA grafted surface. It was found that the polySBMA grafted surface effectively reduces the plasma protein adsorption from platelet-poor plasma solution to a level superior to that of adsorption on a surface terminated with tetra(ethylene glycol). The adhesion and activation of platelets from platelet-rich plasma solution were not observed on the polySBMA grafted surface. This work further concludes that a surface with good hemocompatibility can be achieved by the well-packed surface-grafted polySBMA brushes.

Improving the Stability in Aqueous Media of Polymer Brushes Grafted from Silicon Oxide Substrates by Surface‐Initiated Atom Transfer Radical Polymerization

“…Materials Copper(I)bromide (99.995 þ %), copper(II)bromide (99.999%), 2,2 0 -bipyridyl (!99%), ethyl a-bromoisobutyrate (EBiB, 97%), 1,4,8,4,8, Cyclam, 98%), 4,4 0 -dinonyl-2,2 0 -bipyridyl (dnbpy, 97%), 1,1,4,7,10,10-hexamethyltriethylene tetramine (HMTETA, 97%), sodium methacrylate (NaMA, 99%), 2-hydroxyethyl methacrylate (HEMA, 99%), poly-(ethylene glycol) methacrylate (PEGMA, M n ¼ 360), poly(ethylene glycol) methyl ether methacrylate (PEGMEMA, M n ¼ 300), tertbutyl methacrylate (tBMA, 98%), methyl methacrylate (MMA, 99%), 2-ethylhexyl methacrylate (EHMA, 98%), allylamine (98%), triethylamine, chlorodimethylsilane (98%), and Pt/C (10% Pt) were purchased from Sigma-Aldrich and used as received unless specified otherwise. Trifluoroacetic acid (TFA, HPLC grade) and triisopropylsilane (TIS) were used as received from Fluka Chemie GmbH (Buchs, Switzerland).…”

“…[1][2][3][4] Hydrophilic polymer brushes grafted using surface-initiated controlled radical polymerization have attracted interest for a variety of applications including stimuli-responsive [3,4] and low friction surfaces, [5] antibacterial coatings, [6] chromatography supports, [7] as well as non-biofouling coatings, i.e., surface coatings that prevent non-specific protein adsorption and cell adhesion. [8,9] Typically, these hydrophilic polymer brushes are based on polymers such as poly(2-hydroxyethyl methacrylate) (PHEMA), [10] poly[poly(ethylene glycol) methacrylate] (PPEGMA), [6] poly(methacrylic acid) (PMAA), [11] or poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC). [12] Often they are prepared via surface-initiated atom transfer radical polymerization (SI-ATRP) and grown from glass, quartz or silicon oxide substrates that are modified with an appropriate chloro-or alkoxysilane-functionalized polymerization initiator.…”

Surface Modification to Control Protein/Surface Interactions

“…[20] Several typical hydrophilic polymer brushes [21][22][23][24][25] have been prepared by SI-ATRP and these surfaces have exhibited excellent antifouling properties. Very recently, we prepared wellcontrolled poly(N-vinylpyrrolidone) (PVP)-grafted silicon surfaces for the first time using SI-ATRP.…”

“…In addition to the neutral polymers discussed above, another major class of hydrophilic polymers are the zwitterionic polymers including poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), [22] poly(sulfobetaine methacrylate) (PSBMA), [24] and poly(carboxybetaine methacrylate) (PCBMA). [25] As the neutral polymers form hydration layers via hydrogen bonding, the zwitterionic polymers can bind water molecules even more strongly via electrostatically induced hydration.…”

On the friction and adhesion hysteresis between polymer brushes attached to curved surfaces: Rate and solvation effects

“…Over the last decades, many applications have been devised using such polymer brushes [2]. They are employed, for example to stabilize colloidal suspensions [3], in oil recovery [4], for protein analysis [5], as anti-fouling coatings [6,7] and as "smart" responsive systems [8], such as drug-delivery systems [9], nano sensors [10,11] and "pick-up and place" systems [12]. Especially promising is the utilisation of polymer brushes in a biomimetic approach as low-friction surface coatings [13][14][15][16][17][18][19][20], e.g., in artificial joints [21] or industrial applications [22].…”