Abstract

Clean use of photons from light to activate chemical reactions offers many possibilities in different fields, from chemistry and biology to materials science and medicine. This review article describes the advances carried out in last decades toward the phototriggered synthesis of single-chain polymer nanoparticles (SCNPs) as soft nanomaterials with promising applications in enzyme-mimicking catalysis and nanomedicine, among other different uses. First, we summarize some different strategies developed to synthesize SCNPs based on photoactivated intrachain homocoupling, phototriggered intrachain heterocoupling and photogenerated collapse induced by an external cross-linker. Next, we comprehensively review the emergent topic of photoactivated multifolding applied to SCNP construction. Finally, we conclude by summarizing recent strategies towards phototriggered disassembly of SCNPs.

Highlights

  • Light from the sun is one of the cheapest and most available energy sources in the Earth

  • We describe the different strategies developed to synthesize single-chain polymer nanoparticles (SCNPs) based on photochemical reactions, including methods such as (i) photoactivated intrachain homocoupling, (ii) phototriggered intrachain heterocoupling and (iii) photogenerated collapse induced by external cross-linkers

  • Barner-Kowollik and coworkers [33] have shown in an elegant work, the significant advances offered by performing the photodimerization of styrylpyrene units (Figure 2d) in a confined macromolecular environment, such as that offered by a SCNP precursor, when compared to a control styrylpyrene [2 + 2] photocycloaddition carried out in free solution with a low-molecular-weight photoreactive compound at exactly the same absolute concentration

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Summary

Introduction

Single chain technology allows constructing bioinspired, ultra-small (3–30 nm) SCNPs via intra-chain cross-linking at high dilution conditions. Both covalent and non-covalent bonds have been employed to produce SCNPs. On one hand, the use of non-covalent interactions leads to adaptive nano-objects, which can respond to different stimuli. We describe the different strategies developed to synthesize SCNPs based on photochemical reactions (see Scheme 1), including methods such as (i) photoactivated intrachain homocoupling, (ii) phototriggered intrachain heterocoupling and (iii) photogenerated collapse induced by external cross-linkers. In a broad sense, photoactivated intrachain homocoupling refers to the folding/collapse process induced by photons to an isolated polymer chain through the involvement of a single type of photoresponsive functional group (see Scheme 1A). (ii) photocyclization, (iii) photoisomerization, (iv) photogeneration of reactive species and (iv) self-assembly induced by photodeprotection

Photodimerization
Cinnamoyl Functional Groups
Coumarin Functional Groups
Anthracene Functional Groups
Styrylpyrene Functional Groups
Stilbene Functional Groups
Ketyl Radical Functional Groups
Carboxyl Radical Functional Groups
Nitrile Imine Functional Groups
Photocyclization
Photoisomerization
Nitrenes
Carbenes
Hydrogen-Bonded Dimers
Hydrogen-Bonded Helical Stacks
Simultaneous Photoactivated Multifolding
Without External Cross-Linkers
With External Cross-Linkers
Main-Chain Disassembly
External Cross-Linker Disassembly
Applications of SCNPs Prepared from Photocross-linking
Conclusions
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