Photoreactive Polymer Brushes for High-Density Patterned Surface Derivatization Using a Diels–Alder Photoclick Reaction

Arumugam, Selvanathan; Orski, Sara V.; Locklin, Jason; Popik, Vladimir V.

doi:10.1021/ja210350d

Cited by 98 publications

(90 citation statements)

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“…Proteins, DNA fragments, peptides and antibodies, [1][2][3][4][5][6] as well as hydrogels, [7] have been immobilized and patterned using a number of photochemical methods, such as thiol-yne, [8] thiol-ene, [9] azide-yne (by photoreduction of copper II), [10] terazole-ene, [11] photo-triggered Diels-Alder reaction, [12] Paterno-Buchi reaction, [13] and some other chemistries capable of photo-triggered formation of reactive functional groups. [14][15][16][17] However, most of the existing photochemical methods lead to irreversible permanent surface functionalization, limiting possible applications in the formation of materials and surfaces with dynamic and responsive properties or reusable 2 functionalities. Reversible surface functionalization methods can be applied to introduce, exchange, or remove a functionality and, thus, generate "smart" surfaces and patterns.…”

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confidence: 99%

“…[14][15][16][17] However, most of the existing photochemical methods lead to irreversible permanent surface functionalization, limiting possible applications in the formation of materials and surfaces with dynamic and responsive properties or reusable functionalities. Reversible surface functionalization methods can be applied to introduce, exchange, or remove a functionality and, thus, generate "smart" surfaces and patterns.…”

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confidence: 99%

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Reversible and Rewritable Surface Functionalization and Patterning via Photodynamic Disulfide Exchange

Welle

et al. 2015

Advanced Materials

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Light-promoted precise spatial control of target molecules on surfaces is crucial in the development of novel bioanalytical, diagnostic, or sensor tools. Proteins, DNA fragments, peptides and antibodies, [1][2][3][4][5][6] as well as hydrogels, [7] have been immobilized and patterned using a number of photochemical methods, such as thiol-yne, [8] thiol-ene, [9] azide-yne (by photoreduction of copper II), [10] terazole-ene, [11] photo-triggered Diels-Alder reaction, [12] Paterno-Buchi reaction, [13] and some other chemistries capable of photo-triggered formation of reactive functional groups. [14][15][16][17] However, most of the existing photochemical methods lead to irreversible permanent surface functionalization, limiting possible applications in the formation of materials and surfaces with dynamic and responsive properties or reusable 2 functionalities. Reversible surface functionalization methods can be applied to introduce, exchange, or remove a functionality and, thus, generate "smart" surfaces and patterns.Examples of possible applications of such dynamic surfaces are reusability of substrates, possibility to perform "write and erase" procedures (i.e., rewritable surfaces), formation of complex, multi-component and gradient patterns, capture-and-release properties, and the possibility of in-situ manipulation of local environments.To the best of our knowledge, only two photo-induced reversible patterning strategies have been reported so far. Popik et al. [18] showed that reactive o-naphthoquinone methides (oNQMs) produced under UV light from 3-(hydroxymethyl)-2-naphtholcould react with surface thiol groups to yield thioether conjugates, which could be subsequently cleaved by a secondary UV irradiation to regenerate surface thiol groups. [18] In a recent publication, Anseth et al. described the use of allyl sulfides incorporated into a hydrogel to achieve reversible modification with thiol-containing biomolecules.[19]Here, we present a new reversible photo-patterning strategy based on a photo-induced disulfide exchange reaction that allows for reversible photo-functionalization, patterning, as well as exchange or removal of surface functional groups (Figure 1).Disulfide bonds are known to undergo reversible cleavage under basic conditions via thiol-disulfide exchange reactions through intermediate thiolate anions. [20][21][22] However, disulfides can also undergo dynamic exchange reactions by homolytic photo-cleavage to become sulfanyl radicals (Figure1a). This reaction was recently adopted for the synthesis of self-healing polymers. [23,24] We hypothesized that the dynamic nature of disulfide homolysis and recombination under UV irradiation could be utilized to achieve reversible dynamic .In order to demonstrate the reversibility of the photo-induced disulfide exchange, the reaction was repeated 20 times (10 cycles). The results shown in Figure 2b confirm perfect 4 reversibility of the surface modification without significant change of wettability even after 20 consecutive UV-induced functionalizations ar...

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Reversible and Rewritable Surface Functionalization and Patterning via Photodynamic Disulfide Exchange

Welle

et al. 2015

Advanced Materials

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“…In 2011, Popik and co-workers reported photochemical dehydration of 3-hydroxy-2-naphthalenemethanol ( o -naphthoquinone precursor, NQMP, 79 ) derivatives to o -naphthoquinone methides ( o NQMs, 80 ) [78, 79]. The in situ generated reactive intermediate o NQM underwent facile cycloaddition with vinyl ethers ( 81 ) to form photostable benzochromans ( 82 ) (Scheme 12).…”

Section: Photoinduced Hetero Diels–alder Reactionsmentioning

confidence: 99%

Photo-Triggered Click Chemistry for Biological Applications

2015

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In the last decade and a half, numerous bioorthogonal reactions have been developed with a goal to study biological processes in their native environment, i.e., in living cells and animals. Among them, the photo-triggered reactions offer several unique advantages including operational simplicity with the use of light rather than toxic metal catalysts and ligands, and exceptional spatiotemporal control through the application of an appropriate light source with pre-selected wavelength, light intensity and exposure time. While the photoinduced reactions have been studied extensively in materials research, e.g., on macromolecular surface, the adaptation of these reactions for chemical biology applications is still in its infancy. In this chapter, we review the recent efforts in the discovery and optimization the photo-triggered bioorthogonal reactions, with a focus on those that have shown broad utility in biological systems. We discuss in each cases the chemical and mechanistic background, the kinetics of the reactions and the biological applicability together with the limiting factors.

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“…In 2011, Popik and co-workers reported photochemical dehydration of 3-hydroxy-2-naphthalenemethanol (o-naphthoquinone precursor, NQMP, 79) derivatives to onaphthoquinone methides (oNQMs, 80) [78,79]. The in situ generated reactive intermediate oNQM underwent facile cycloaddition with vinyl ethers (81) to form photostable benzochromans (82) (Scheme 12).…”

Section: Naphthoquinone Methidementioning

confidence: 99%