Surface-initiated controlled radical polymerizations from silica nanoparticles, gold nanocrystals, and bionanoparticles

Abstract

In recent years, core/shell nanohybrids containing a nanoparticle core and a distinct surrounding shell of polymer brushes have received extensive attention in nanoelectronics, nanophotonics, catalysis, nanopatterning, drug delivery, biosensing, and many others. From the large variety of existing polymerization methods on the one hand and strategies for grafting onto nanoparticle surfaces on the other hand, the combination of grafting-from with controlled radical polymerization (CRP) techniques has turned out to be the best suited for synthesizing these well-defined core/shell nanohybrids and is known as surface-initiated CRP. Most common among these are surface-initiated atom transfer radical polymerization (ATRP), surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, and surface-initiated nitroxide-mediated polymerization (NMP). This review highlights the state of the art of growing polymers from nanoparticles using surface-initiated CRP techniques. We focus on mechanistic aspects, synthetic procedures, and the formation of complex architectures as well as novel properties. From the vast number of examples of nanoparticle/polymer hybrids formed by surface-initiated CRP techniques, we present nanohybrid formation from the particularly important and most studied silica nanoparticles, gold nanocrystals, and proteins which can be regarded as bionanoparticles

Synthesis of Polystyrene and Poly(4‐vinylpyridine) Mixed Grafted Silica Nanoparticles via a Combination of ATRP and CuI‐Catalyzed Azide‐Alkyne Click Chemistry

“…The grafting‐to method is the easiest and most convenient among the three approaches . In the method, functional polymers are usually synthesized via ATRP, RAFT polymerization, or NMP prior to their attachment . SNPs are surface modified according to the designed polymers' linking moieties .…”

“…In combination with the CRP techniques, there are usually three different approaches to synthesize such silica polymer core/shell nanohybrids: grafting-to, graftingfrom, and grafting-through methods. [24] The graftingto method is the easiest and most convenient among the three approaches. [15,25,26] In the method, functional polymers are usually synthesized via ATRP, RAFT polymerization, or NMP prior to their attachment.…”

“…[15,25,26] In the method, functional polymers are usually synthesized via ATRP, RAFT polymerization, or NMP prior to their attachment. [24] SNPs are surface modified according to the designed polymers' linking moieties. [24] Afterward, silica polymer hybrids are synthesized by attaching the two components together.…”

Recent Advances in the Fabrication of Superhydrophobic Surfaces

“…13,19,29,74,8992 Among those, surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the prominent grafting methods to prepare superhydrophobic coatings. 93 It is particularly attractive for its mild reaction conditions, tolerance of impurities, and compatibility of wide monomers. 91 SI-ATRP is generally used to immobilize initiators on the substrate after creating suitable roughness, and then graft the low-surface-energy polymer on the as-prepared surface.…”

Facile synthesis of thermo-responsive episulfide group-containing diblock copolymers as robust protecting ligands of gold nanoparticles for catalytic applications

“…RAFT polymerization was selected due to the fact that this controlled living radical polymerization technique can be performed under mild reaction conditions, and has a high tolerance towards functional groups. 47 We synthesized three block copolymers of P(NIPAM-co-ETMA)-b-P(PEGMA) with different contents of PETMA segments, P(NIPAM 53 -co-ETMA 10 ) 63 -b-P(PEGMA) 111 (P1), P(NIPAM 48 -co-ETMA 27 ) 75 -b-P(PEGMA) 113 (P2) and P(NIPAM 42 -co-ETMA 35 ) 77 -b-P(PEGMA) 114 (P3), respectively. The resulting block copolymers can be dispersed in water and self-assembled to form polymer micelles because the block polymer contains hydrophobic PETMA segments, and a stable micelle system is formed because the hydrophilic block is larger than the hydrophobic block.…”