Fabrication of Complex Three‐Dimensional Polymer Brush Nanostructures through Light‐Mediated Living Radical Polymerization

Poelma, Justin E.; Fors, Brett P.; Meyers, Gregory F.; Kramer, John W.; Hawker, Craig J.

doi:10.1002/anie.201301845

Cited by 221 publications

(216 citation statements)

References 39 publications

Supporting

Mentioning

213

Contrasting

Unclassified

Order By: Relevance

“…The synthesis, processing and characterization of such complex brush structures, for example, mixed brushes [193][194][195][196][197], multiblock copolymer brushes [114,115,198], gradient polymer brushes [199,200], nanopatterned polymer brushes [107,116], polymer carpet/Janus membrane [8,[201][202][203] and polymer nanochannels [114,117] are of great interest from a fundamental as well as technological perspective. Comprehensive understanding of structure-property relationships in well-defined and fully characterized polymer brushes aided by new synthesis as well as predictive modeling can open up newer applications for polymer brushes.…”

Section: Discussionmentioning

confidence: 99%

From Self-Assembled Monolayers to Coatings: Advances in the Synthesis and Nanobio Applications of Polymer Brushes

et al. 2015

View full text Add to dashboard Cite

Abstract:In this review, we describe the latest advances in synthesis, characterization, and applications of polymer brushes. Synthetic advances towards well-defined polymer brushes, which meet criteria such as: (i) Efficient and fast grafting, (ii) Applicability on a wide range of substrates; and (iii) Precise control of surface initiator concentration and hence, chain density are discussed. On the characterization end advances in methods for the determination of relevant physical parameters such as surface initiator concentration and grafting density are discussed. The impact of these advances specifically in emerging fields of nano-and bio-technology where interfacial properties such as surface energies are controlled to create nanopatterned polymer brushes and their implications in mediating with biological systems is discussed.

show abstract

Section: Discussionmentioning

confidence: 99%

From Self-Assembled Monolayers to Coatings: Advances in the Synthesis and Nanobio Applications of Polymer Brushes

et al. 2015

View full text Add to dashboard Cite

show abstract

“…25 The key to the success of this method is the use of light as a mild, noninvasive stimulus for selective polymer growth, allowing access to three-dimensional nanostructures in a single step. While this process provides a significant advancement in patterned polymer brush fabrication, the need for a metal catalyst remains problematic for a number of applications in areas such as microelectronics and bioinspired materials.…”

mentioning

confidence: 99%

Simple Benchtop Approach to Polymer Brush Nanostructures Using Visible-Light-Mediated Metal-Free Atom Transfer Radical Polymerization

et al. 2016

Self Cite

View full text Add to dashboard Cite

ABSTRACT:The development of an operationally simple, metal-free surface-initiated atom transfer radical polymerization (SI-ATRP) based on visible-light mediation is reported. The facile nature of this process enables the fabrication of well-defined polymer brushes from flat and curved surfaces using a "benchtop" setup that can be easily scaled to four-inch wafers. This circumvents the requirement of stringent air-free environments (i.e., glovebox), and mediation by visible light allows for spatial control on the micron scale, with complex three-dimensional patterns achieved in a single step. This robust approach leads to unprecedented access to brush architectures for nonexperts.

show abstract

“…Moreover, the spatial and temporal control of Ir-catalyzed photomediated processes has been exploited for patterning polymer brushes on surfaces to give novel, 3-D nanostructures. 30 Our previous reports on photomediated radical polymerizations focused exclusively on methacrylates. In order to increase the scope and applicability of this strategy, extension to other monomer families is required.…”

mentioning

confidence: 99%

Controlled Radical Polymerization of Acrylates Regulated by Visible Light

Treat¹,

Fors²,

et al. 2014

Self Cite

View full text Add to dashboard Cite

ABSTRACT:The controlled radical polymerization of a variety of acrylate monomers is reported using an Ir-catalyzed visible light mediated process leading to well-defined homo-, random, and block copolymers. The polymerizations could be efficiently activated and deactivated using light while maintaining a linear increase in molecular weight with conversion and first order kinetics. The robust nature of the fac-[Ir(ppy) 3 ] catalyst allows carboxylic acids to be directly introduced at the chain ends through functional initiators or along the backbone of random copolymers (controlled process up to 50 mol % acrylic acid incorporation). In contrast to traditional ATRP procedures, low polydispersity block copolymers, poly(acrylate)-b-(acrylate), poly(methacrylate)-b-(acrylate), and poly(acrylate)-b-(methacrylate), could be prepared with no monomer sequence requirements. These results illustrate the increasing generality and utility of light mediated Ircatalyzed polymerization as a platform for polymer synthesis. have revolutionized the field of polymer chemistry, allowing for the synthesis of well-defined macromolecular structures with excellent functional group tolerance. Perhaps of greater importance is the facile reaction conditions that allow nonexperts access to these materials, enabling significant advances across a number of fields. More recently, additional control over living radical polymerizations has been achieved through regulation of the chain growth process by an external stimulus. 5 For example, electrochemical ATRP has been used to pattern polymer brushes on surfaces, 6− 8 as well as gain control over aqueous polymerizations.9 While the employment of externally regulated polymerizations is in its infancy, the potential for further innovation is significant.In considering the wide range of possible external stimuli, light offers many attractive features such as readily available light sources, tunability, and both spatial and temporal control. On this basis, significant work has been dedicated to the development of photoinitiated 10− 17 and photoregulated radical polymerizations (i.e., photocontrolled RAFT, 29 This approach uses a simple reaction setup with only ppm levels of Ir(ppy) 3 and enables efficient activation and deactivation of polymerization leading to control over molecular weight and molecular weight distributions. A fundamental element of this process is that in the absence of irradiation, the chain end rests as the dormant alkyl bromide, protected from deleterious radical reactions but available for reactivation upon re-exposure to light. Moreover, the spatial and temporal control of Ir-catalyzed photomediated processes has been exploited for patterning polymer brushes on surfaces to give novel, 3-D nanostructures. 30Our previous reports on photomediated radical polymerizations focused exclusively on methacrylates. In order to increase the scope and applicability of this strategy, extension to other monomer families is required. Our attention was therefore drawn to acrylate-based polymer...

show abstract

Fabrication of Complex Three‐Dimensional Polymer Brush Nanostructures through Light‐Mediated Living Radical Polymerization

Cited by 221 publications

References 39 publications

From Self-Assembled Monolayers to Coatings: Advances in the Synthesis and Nanobio Applications of Polymer Brushes

From Self-Assembled Monolayers to Coatings: Advances in the Synthesis and Nanobio Applications of Polymer Brushes

Simple Benchtop Approach to Polymer Brush Nanostructures Using Visible-Light-Mediated Metal-Free Atom Transfer Radical Polymerization

Controlled Radical Polymerization of Acrylates Regulated by Visible Light

Contact Info

Product

Resources

About