Oxygen tolerant, photoinduced controlled radical polymerization approach for the synthesis of <i>giant amphiphiles</i>

Theodorou, Alexis; Mandriotis, Petros; Anastasaki, Athina; Velonia, Kelly

doi:10.1039/d0py01608j

Cited by 24 publications

(34 citation statements)

References 78 publications

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“…Anchoring polymers to proteins protects protein-polymer hybrids from denaturation, delays their clearance from the body, and reduces the immunological response toward them. 98 ATRP is very useful for the preparation of polymer-protein conjugates, 45,[99][100][101][102][103][104][105][106] but degassing prior to polymerization can trigger aggregation. 107 The dual EY/Cu system was applied in protein modications.…”

Section: Synthesis Of Biohybridsmentioning

confidence: 99%

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

et al. 2022

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Section: Synthesis Of Biohybridsmentioning

confidence: 99%

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

et al. 2022

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“…76,86,87 To this end, we recently reported an oxygen-tolerant, photoinduced CRP polymerization protocol, allowing the grafting of a wide range of monomers including styrenes, hydrophobic and hydrophilic acrylates, methacrylates, and acrylamides from different proteins. 88,89 By simply eliminating headspace in the reaction vessel, protein macroinitiators were quantitatively consumed within a few hours under UV light, blue light, or even sunlight in buffered aqueous media or nanopure water. 88,89 However, the use of light as an external stimulus can often be disadvantageous for the polymerization of light-sensitive monomers, 90,91 while prolonged irradiation times may also damage the secondary structure of certain proteins or peptides.…”

Section: Introductionmentioning

confidence: 99%

“…88,89 By simply eliminating headspace in the reaction vessel, protein macroinitiators were quantitatively consumed within a few hours under UV light, blue light, or even sunlight in buffered aqueous media or nanopure water. 88,89 However, the use of light as an external stimulus can often be disadvantageous for the polymerization of light-sensitive monomers, 90,91 while prolonged irradiation times may also damage the secondary structure of certain proteins or peptides. 92−94 To limit the exposure of proteins to light or any type of potentially harmful chemical environment, it is important to develop ultrafast innovative polymer−protein bioconjugate methodologies, ideally in the absence of any conventional stimulus.…”

Section: Introductionmentioning

confidence: 99%

Rapid Oxygen-Tolerant Synthesis of Protein-Polymer Bioconjugates via Aqueous Copper-Mediated Polymerization

et al. 2022

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The synthesis of protein−polymer conjugates usually requires extensive and costly deoxygenation procedures, thus limiting their availability and potential applications. In this work, we report the ultrafast synthesis of polymer−protein bioconjugates in the absence of any external deoxygenation via an aqueous copper-mediated methodology. Within 10 min and in the absence of any external stimulus such as light (which may limit the monomer scope and/or disrupt the secondary structure of the protein), a range of hydrophobic and hydrophilic monomers could be successfully grafted from a BSA macroinitiator, yielding well-defined polymer−protein bioconjugates at quantitative yields. Our approach is compatible with a wide range of monomer classes such as (meth) acrylates, styrene, and acrylamides as well as multiple macroinitiators including BSA, BSA nanoparticles, and betagalactosidase from Aspergillus oryzae. Notably, the synthesis of challenging protein−polymer−polymer triblock copolymers was also demonstrated, thus significantly expanding the scope of our strategy. Importantly, both lower and higher scale polymerizations (from 0.2 to 35 mL) were possible without compromising the overall efficiency and the final yields. This simple methodology paves the way for a plethora of applications in aqueous solutions without the need of external stimuli or tedious deoxygenation.

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“…Importantly, this process did not disrupt the secondary structure of the protein and required low amounts of catalyst. In a more recent report by the same group, the universal character of this aqueous ATRP-mediated photo-PISA procedure was further exploited for the synthesis of amphiphilic BSA-based spherical nano-objects utilizing a wide range of acrylic-, methacrylic-, and acrylamide-based core-forming monomers [ 56 ].…”

Section: Protein–polymer Hybrid Nanostructures Via Pisamentioning

confidence: 99%

Protein-, (Poly)peptide-, and Amino Acid-Based Nanostructures Prepared via Polymerization-Induced Self-Assembly

2021

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Proteins and peptides, built from precisely defined amino acid sequences, are an important class of biomolecules that play a vital role in most biological functions. Preparation of nanostructures through functionalization of natural, hydrophilic proteins/peptides with synthetic polymers or upon self-assembly of all-synthetic amphiphilic copolypept(o)ides and amino acid-containing polymers enables access to novel protein-mimicking biomaterials with superior physicochemical properties and immense biorelevant scope. In recent years, polymerization-induced self-assembly (PISA) has been established as an efficient and versatile alternative method to existing self-assembly procedures for the reproducible development of block copolymer nano-objects in situ at high concentrations and, thus, provides an ideal platform for engineering protein-inspired nanomaterials. In this review article, the different strategies employed for direct construction of protein-, (poly)peptide-, and amino acid-based nanostructures via PISA are described with particular focus on the characteristics of the developed block copolymer assemblies, as well as their utilization in various pharmaceutical and biomedical applications.

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Oxygen tolerant, photoinduced controlled radical polymerization approach for the synthesis of giant amphiphiles

Abstract: Amphiphilic protein-polymer conjugates form hybrid nanostructures with a broad range of potential applications. Herein, we expand the scope of amphiphilic protein-polymer bioconjugates via an oxygen tolerant, photoinduced RDRP method. A...

Cited by 24 publications

References 78 publications

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

Rapid Oxygen-Tolerant Synthesis of Protein-Polymer Bioconjugates via Aqueous Copper-Mediated Polymerization

Protein-, (Poly)peptide-, and Amino Acid-Based Nanostructures Prepared via Polymerization-Induced Self-Assembly

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