“On Water” Surface‐initiated Polymerization of Hydrophobic Monomers

Abstract

We present the "on water" surface-initiated Cumediated controlled radical polymerization ("on water" SI-CuCRP) that converts hydrophobic monomers in aqueous reaction medium to polymer brushes at unparalleled speed and efficiency.The method allows the facile conversion of avariety of common monomers under most simple reaction conditions and with minimal monomer amounts to thicka nd homogeneous polymer brushes.The highly living character of the "on water" SI-CuCRP allowed the preparation of decablock (homo)polymer brushes and opens the pathway to sequentially controlled polymer brushes on solids.

Oxygen Tolerant and Cytocompatible Iron(0)-Mediated ATRP Enables the Controlled Growth of Polymer Brushes from Mammalian Cell Cultures

“…1 The most prominent examples of such processes have involved the application of oxygen scavengers, in the form of photosensitizers, 2,3 reducing agents, 4 enzymes, 5 or zerovalent metal surfaces. [6][7][8][9][10][11][12][13] While the evolution of oxygen-tolerant, surface-initiated RDRP (SI-RDRP) is paving the way for the translation of "grafted-from" polymers from fundamental studies into technology, the development of controlled polymerizations that are additionally compatible with physiological environments would substantially broaden the applicability of SI-RDRP in materials design. In particular, an RDRP process capable of modifying the physicochemical properties of cellular microenvironments through polymer grafting, without altering cell viability, would allow one to adjust the biological affinity of scaffolds towards a particular cell type during culturing, or alternatively to tune the presentation of biochemical cues triggering a defined cell behavior.…”

Facile Fabrication of Bio‐ and Dual‐Functional Poly(2‐oxazoline) Bottle‐Brush Brush Surfaces

“…The swollen thickness ( h swollen =155±6 nm) of the BBBs in water was determined by liquid AFM. As such, the BBB grafting density, as estimated through the swelling ratio ( S r (%)=100 ( h swollen − h dry )/ h dry ), is calculated to 0.42 chains nm −2 (Figure b and Table S1) . In comparison, only 15±1 nm PIPOx layer was obtained in 24 h SIPGP.…”

“…The recently emerged SI‐Cu 0 CRP is a very effective and versatile technique to fabricate polymer brushes on planar substrates . The brush growth rate was found among the highest for surface‐initiated controlled radical polymerization reported to date . More importantly, the SI‐Cu 0 CRP is oxygen tolerant and requires very limited amount of monomers (μL), and therefore can be used to prepare polymer brushes with low cost .…”

Fully oxygen-tolerant atom transfer radical polymerization triggered by sodium pyruvate

“…In 1998, we demonstrated that a well-controlled ATRP could occur in the presence of a limited amount of oxygen using a zero-valent copper powder as a reducing agent. 18 This concept was later extended to ATRP with copper wire [19][20][21] or copper plate [22][23][24][25] and other reducing agents, such as ascorbic acid, [26][27][28][29] tin(II) 2-ethylhexanoate, 30 tertiary amine, 31 nitrogen-based ligands, 32 phenols, 33 alcohols, 34 sodium dithionite, 35 and zerovalent iron. 36 Another area where signicant progress has been made towards oxygen-tolerant ATRP is photoinduced polymerization.…”