A dynamic covalent polymer driven by disulfidemetathesis under photoirradiation

Otsuka, Hideyuki; Nagano, Shinsuke; Kobashi, Yasuharu; Maeda, Takeshi; Takahara, Atsushi

doi:10.1039/b916128g

Cited by 284 publications

(224 citation statements)

References 36 publications

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“…The reason a dialkyl disulfide was chosen for the cross-over experiment was that the exchange between two aromatic disulfides can occur via a concerted mechanism without light. [29][30][31] The photo-addition of disulfide to terminal alkyne under UV was first observed for dialkyl disulfide by Heiba and Dessau in 1960s. [32] A recent example was reported by Ogawa, [14] in which diphenyl disulfide could be trapped by 1-octyne with light from a medium-pressure Hg lamp.…”

Section: Scheme 1 Summary Of Previous Oco Methodsmentioning

confidence: 99%

Disulfide‐Catalyzed Visible‐Light‐Mediated Oxidative Cleavage of C=C Bonds and Evidence of an Olefin–Disulfide Charge‐Transfer Complex

et al. 2016

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Section: Scheme 1 Summary Of Previous Oco Methodsmentioning

confidence: 99%

Disulfide‐Catalyzed Visible‐Light‐Mediated Oxidative Cleavage of C=C Bonds and Evidence of an Olefin–Disulfide Charge‐Transfer Complex

et al. 2016

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“…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 are performed on the same substrate.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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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“…The incorporation of thermoplastic additives into the epoxy matrix can achieve a degree of reversible reaction; however, this will come with some modification of properties, including optimum properties [31,45]. Some examples with reversible covalent bonds include disulphide bonds, reverse Diels-Alder reaction, ring-chain reactions, trithiocarbonate reactions, reversible hydrozone linkages, and alkoxyamine linakages [90][91][92][93][94][95][96][97][98][99][100].…”

Section: Reversible Chemical Bondsmentioning

confidence: 99%

Self-healing coatings

Hughés¹

2015

Recent Advances in Smart Self-Healing Polymers and Composites

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A dynamic covalent polymer driven by disulfidemetathesis under photoirradiation

Abstract: A disulfide-containing polyester indicates a dynamic nature in a bulk state based on a disulfide metathesis reaction driven by photoirradiation.

Cited by 284 publications

References 36 publications

Disulfide‐Catalyzed Visible‐Light‐Mediated Oxidative Cleavage of C=C Bonds and Evidence of an Olefin–Disulfide Charge‐Transfer Complex

Disulfide‐Catalyzed Visible‐Light‐Mediated Oxidative Cleavage of C=C Bonds and Evidence of an Olefin–Disulfide Charge‐Transfer Complex

Reversible and Rewritable Surface Functionalization and Patterning via Photodynamic Disulfide Exchange

Self-healing coatings

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