Fabrication of Unique Chemical Patterns and Concentration Gradients with Visible Light

Fors, Brett P.; Poelma, Justin E.; Menyo, Matthew S.; Robb, Maxwell J.; Spokoyny, Daniel M.; Kramer, John W.; Waite, J. Herbert; Hawker, Craig J.

doi:10.1021/ja408467b

Cited by 107 publications

(109 citation statements)

References 34 publications

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“…We then performed light‐mediated atom transfer radical addition (ATRA) of ethyl vinyl ether (EVE) under a 2.5 × 25 μm 2 photomask. Light‐mediated ATRA has recently been presented as a powerful technique to add alkenes onto surface‐bound ATRP initiators . The addition of EVE to the living chain end results in the permanent termination of irradiated brush areas through the formation of ├p(PEGMA)‐EVE.…”

Section: Methodsmentioning

confidence: 99%

Ambiguous anti‐fouling surfaces: Facile synthesis by light‐mediated radical polymerization

Pester

Poelma

Narupai

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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ABSTRACT:In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/ hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional coppercatalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. V C 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253-262

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Section: Methodsmentioning

confidence: 99%

Ambiguous anti‐fouling surfaces: Facile synthesis by light‐mediated radical polymerization

Pester

Poelma

Narupai

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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“…Moreover, a first metal‐free system (based on the use of 10‐phenylphenothiazine in the photomediated process) has been successfully developed for photo‐ATRP . This will likely push the field to new horizons as photo‐CRP processes have already demonstrated incredible advantages for the precise design and fabrication of various polymeric materials …”

Section: Introductionmentioning

confidence: 99%

Copper and iron complexes as visible‐light‐sensitive photoinitiators of polymerization

Xiao

Zhang

Campolo

et al. 2015

J. Polym. Sci., Part A: Polym. Chem.

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International audienceThe utilization of visible lights for the fabrication of polymeric materials is recognized as a promising and environmentally friendly approach. This process relies on the photochemical generation of reactive species (e.g., radicals, radical cations, or cations) from well-designed photoinitiators (PIs) or photoinitiating systems (PISs) to initiate the polymerization reactions of different monomers (acrylates, methacrylates, epoxides, and vinyl ethers). In spite of the fact that metal complexes such as ruthenium- or iridium-based complexes have found applications in organic and polymer synthesis, the search of other low-cost metal-based complexes as PISs is emerging and attracting increasing attentions. Particularly, the concept of the photoredox catalysis has appeared recently as a unique tool for polymer synthesis upon soft conditions (use of light emitting diodes and household lamp). This highlight focuses on recently designed copper and iron complexes as PI catalysts in the application of photoinduced polymerizations (radical, cationic, interpenetrated polymer networks, and thiol-ene) or controlled radical polymerization under visible light irradiatio

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“…The general mechanisms involving all modes of photoinitiated ATRP are presented in Scheme . Following these developments, many other studies on photochemically mediated controlled/living radical polymerization including those utilizing Ir‐ or Mn‐based photoredox catalyst have been reported …”

Section: Introductionmentioning

confidence: 99%

Simultaneous Photoinduced ATRP and CuAAC Reactions for the Synthesis of Block Copolymers

Murtezi

Yaǧcı

2014

Macromol. Rapid Commun.

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Atom transfer radical polymerization (ATRP) and copper-catalyzed azide-alkyne cycloaddition (CuAAC) reactions, both utilizing copper(I) (Cu(I)) complexes, make a tremendous progress in synthetic polymer chemistry. Independently or in combination with other polymerization processes, they give access to the synthesis of polymers with well-defined structures, desired molecular architectures, and a wide variety of functionalities. Here, a novel in situ photoinduced formation of block copolymers is described by simultaneous ATRP and CuAAC processes. This approach relies on the direct reduction of initially charged copper(II) complexes to Cu(I) complexes to trigger both ATRP and CuAAC reactions coinciding under UV light at ambient temperature in one pot. Its synthetic utility is demonstrated on a model block copolymerization process by photoinduced ATRP of methyl methacrylate (MMA) using an initiator possessing acetylene functionality and concomitant click reaction between thus formed α-acetylene-poly(methyl methacrylate) (Ac-PMMA) and independently prepared azide functional polystyrene (PS-N ). Successful formation of PS-b-PMMA block copolymer is confirmed by FT-IR and H NMR spectral analysis and gel permeation chromatography (GPC) measurements.

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Fabrication of Unique Chemical Patterns and Concentration Gradients with Visible Light

Cited by 107 publications

References 34 publications

Ambiguous anti‐fouling surfaces: Facile synthesis by light‐mediated radical polymerization

Ambiguous anti‐fouling surfaces: Facile synthesis by light‐mediated radical polymerization

Copper and iron complexes as visible‐light‐sensitive photoinitiators of polymerization

Simultaneous Photoinduced ATRP and CuAAC Reactions for the Synthesis of Block Copolymers

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