Versatile synthesis and micropatterning of nonfouling polymer brushes on the wafer scale

Hucknall, Angus; Simnick, Andrew J.; Hill, Ryan T.; Chilkoti, Ashutosh; García, Alberto Luis García; Johannes, Matthew S.; Clark, Robert; Zauscher, Stefan; Ratner, Buddy D.

doi:10.1116/1.3151968

Cited by 64 publications

(63 citation statements)

References 38 publications

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“…27 Further wetlab work with this system by Chilkoti and Zauscher in collaboration with Ratner has shown that SI-ATRP can be used to pattern non-fouling regions on surfaces that are resistant to protein and cellular adherence and absorption. 28 …”

Section: 0 Non-fouling Surface Coatingsmentioning

confidence: 99%

Biocompatible and Bioactive Surface Modifications for Prolonged In Vivo Efficacy

2011

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Section: 0 Non-fouling Surface Coatingsmentioning

confidence: 99%

Biocompatible and Bioactive Surface Modifications for Prolonged In Vivo Efficacy

2011

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“…Polymer brushes can be described as an assembly of flexible linear macromolecules which are tethered by one end to a surface, forming a compact layer of polymer chains which are stretched perpendicularly to the surface. 43 Polymer brushes have recently attracted considerable attention, due to numerous applications in a broad range of fields, 44 such as enhancement of lubrication properties of surfaces, 45,46 tailoring of adhesion and wetting properties, 47 improvement of drugs biocompatibility, 48 creation of protective coatings to prevent protein adsorption in biological environments, 49 biomolecules analysis in microfluidic devices, 50 and design of thermosensitive surfaces or interfaces. 51 Polymer brushes have been used in combination with soft-lithography techniques to create complex three-dimensional pattern to allow the capture and release of medicine and nanoparticles.…”

Section: Introductionmentioning

confidence: 99%

Red blood cell dynamics in polymer brush-coated microcapillaries: A model of endothelial glycocalyx in vitro

et al. 2014

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The confined flow of red blood cells (RBCs) in microvasculature is essential for oxygen delivery to body tissues and has been extensively investigated in the literature, both in vivo and in vitro. One of the main problems still open in microcirculation is that flow resistance in microcapillaries in vivo is higher than that in vitro. This discrepancy has been attributed to the glycocalyx, a macromolecular layer lining the inner walls of vessels in vivo, but no direct experimental evidence of this hypothesis has been provided so far. Here, we investigate the flow behavior of RBCs in glass microcapillaries coated with a polymer brush (referred to as "hairy" microcapillaries as opposed to "bare" ones with no coating), an experimental model system of the glycocalyx. By high-speed microscopy imaging and image analysis, a velocity reduction of RBCs flowing in hairy microcapillaries as compared to bare ones is indeed found at the same pressure drop. Interestingly, such slowing down is larger than expected from lumen reduction due to the polymer brush and displays an on-off trend with a threshold around 70 nm of polymer brush dry thickness. Above this threshold, the presence of the polymer brush is associated with an increased RBC deformation, and RBC velocity is independent on polymer brush thickness (at the same pressure drop). In conclusion, this work provides direct support to the hypothesis that the glycocalyx is the main factor responsible of the higher flow resistance found in microcapillaries in vivo.

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“…The compromise between both is offered by surface-initiated controlled radical polymerizations (SI-CRP) and especially surface-initiated atom transfer radical polymerization (SI-ATRP). 12,13 Lately, several strategies have been developed to minimize the metal (i.e. 10,11 Hence, only few reports on the large-scale synthesis of polymer brushes by SI-ATRP can be found.…”

Section: Introductionmentioning

confidence: 99%

Wafer-scale synthesis of defined polymer brushes under ambient conditions

et al. 2015

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A method is presented that allows for the first time the preparation of highly defined polymer brush coatings on the wafer-scale under ambient conditions (room temperature, exposure to air) from a broad variety of monomers. The discovered high oxygen-tolerance of the surface-initiated Cu(0)-mediated controlled radical polymerization (SI-CuCRP) yields entire wafers homogeneously covered by a polymer brush of linear, high molar mass polymers with narrow dispersities (Đ = 1.1) at extremely high grafting densities (≈1 chain per nm 2 ). The low-tech and air tolerant method requires only ≲4 mL reaction solution containing a monomer and a ligand between two facing substrates. Thus, the SI-CuCRP is scalable to any surface area with minimal costs and minimal equipment. Despite the simplicity of the method, the high endgroup fidelity of SI-CuCRP is demonstrated by the preparation of a tetrablock copolymer brush which is the first example of a higher order block copolymer brush prepared by any surface-initiated polymerization. Finally, we present a new facile lithographic technique, the copper plate proximity printing (CP 3 ), which relies on the proximity of the bulk copper surface to the initiator-bearing substrate. The CP 3 is resist-and development-free and transfers the copper plate profile (of a copper coin) directly into an image composed of a 3D polymer brush. † Electronic supplementary information (ESI) available. See

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Versatile synthesis and micropatterning of nonfouling polymer brushes on the wafer scale

Cited by 64 publications

References 38 publications

Biocompatible and Bioactive Surface Modifications for Prolonged In Vivo Efficacy

Biocompatible and Bioactive Surface Modifications for Prolonged In Vivo Efficacy

Red blood cell dynamics in polymer brush-coated microcapillaries: A model of endothelial glycocalyx in vitro

Wafer-scale synthesis of defined polymer brushes under ambient conditions

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