Surface-active and stimuli-responsive polymer--Si(100) hybrids from surface-initiated atom transfer radical polymerization for control of cell adhesion.
ABSTRACT A simple two-step method was developed for the covalent immobilization of atom-transfer radical polymerization (ATRP) initiators on the hydrogen-terminated Si(100) (Si-H) surface. Well-defined functional polymer-Si hybrids, consisting of covalently tethered brushes of poly(ethylene glycol) monomethacrylate (PEGMA) polymer, N-isopropylacrylamide (NIPAAm) polymer, and NIPAAm-PEGMA copolymers and block copolymers on Si-H surfaces, were prepared via surface-initiated ATRP. Kinetics study revealed that the chain growth from the silicon surface was consistent with a "controlled" process. Surface cultures of the cell line 3T3-Swiss albino on the hybrids were evaluated. The PEGMA graft-polymerized silicon [Si-g-P(PEGMA)] surface is very effective in preventing cell attachment and growth. At 37 degrees C [above the lower critical solution temperature (LCST, approximately 32 degrees C) of NIPAAm], the seeded cells adhered, spread, and proliferated on the NIPAAm graft polymerized silicon [Si-g-P(NIPAAm)] surface. Below the LCST, the cells detached from the Si-g-P(NIPAAm) surface spontaneously. Incorporation of PEGMA units into the NIPAAm chains of the Si-g-P(NIPAAm) surface via copolymerization resulted in more rapid cell detachment during the temperature transition. The "active" chain ends on the Si-g-P(PEGMA) and Si-g-P(NIPAAm) hybrids were also used as the macroinitiators for the synthesis of diblock copolymer brushes. Thus, not only are the hybrids potentially useful as stimuli-responsive adhesion modifiers for cells in silicon-based biomedical microdevices but also the active chain ends on the hybrid surfaces offer opportunities for further surface functionalization and molecular design.
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ABSTRACT: Materials offering the ability to change their characteristics in response to presented stimuli have demonstrated application in the biomedical arena, allowing control over drug delivery, protein adsorption and cell attachment to materials. Many of these smart systems are reversible, giving rise to finer control over material properties and biological interaction, useful for various therapeutic treatment strategies. Many smart materials intended for biological interaction are based around pH or thermo-responsive materials, although the use of magnetic materials, particularly in neural regeneration, has increased over the past decade. This review draws together a background of literature describing the design principles and mechanisms of smart materials. Discussion centres on recent literature regarding pH-, thermo-, magnetic and dual responsive materials, and their current applications for the treatment of neural tissue.Advanced drug delivery reviews 07/2012; · 11.96 Impact Factor
Article: Theoretical considerations on mechanisms of harvesting cells cultured on thermoresponsive polymer brushes.[show abstract] [hide abstract]
ABSTRACT: Poly (N-isopropylacrylamide) (PNIPAM) brushes and hydrogels serve as temperature-responsive cell culture substrates. The cells adhere at 37 °C and are detached by cooling to below the lower critical solution temperature T(LCST) ≈ 32 °C, an effect hitherto attributed to change in PNIPAM hydration. The article proposes a mechanism coupling the change of hydration to integrin mediated environmental sensing for cell culture on brushes and hydrogels in serum containing medium. Hydration is associated with swelling and higher osmotic pressure leading to two effects: (i) The lower osmotic pressure in the collapsed brush/hydrogel favors the adsorption of serum borne extracellular matrix (ECM) proteins enabling cell adhesion; (ii) Brush/hydrogel swelling at T < T(LCST) gives rise to a disjoining force f(cell) due to confinement by the ventral membrane of a cell adhering via integrin-ECM bonds. f(cell) places the integrin-ECM bonds under tension thus accelerating their dissociation and promoting desorption of ECM proteins. Self consistent field theory of PNIPAM brushes quantifies the effect of the polymerization degree N, the area per chain Σ, and the temperature, T on ECM adsorption, f(cell) and the dissociation rate of integrin-ECM bonds. It suggests guidelines for tuning Σ and N to optimize adhesion at 37 °C and detachment at T < T(LCST). The mechanism rationalizes existing experimental results on the influence of the dry thickness and the RGD fraction on adhesion and detachment.Biomaterials 04/2012; 33(20):4975-87. · 7.40 Impact Factor