Hemoglobin and Red Blood Cells Catalyze Atom Transfer Radical Polymerization

Silva, Tilana B.; Spulber, Mariana; Kocik, Marzena K.; Seidi, Farzad; Charan, Himanshu; Rother, Martin; Sigg, Severin J.; Renggli, Kasper; Kali, Gergely; Bruns, Nico

doi:10.1021/bm400556x

Cited by 90 publications

(88 citation statements)

References 65 publications

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“…Therefore, blood offers an extremely important supply of iron that can potentially be employed for catalysis in a biological environment. Hb has been used in iron‐mediated controlled polymerizations via atom transfer radical polymerization (ATRP), however, pretreatment of the Hb was typically required for the iron to become an effective activator of the reaction. We therefore aimed to employ native Hb contained within red blood cells to drive a controlled polymerization, with the view of eventually conducting synthetic polymerization reactions in biological environments in situ, where no modification of the biological components is required.…”

Section: Methodsmentioning

confidence: 99%

Blood‐Catalyzed RAFT Polymerization

et al. 2018

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The use of hemoglobin (Hb) contained within red blood cells to drive a controlled radical polymerization via a reversible addition‐fragmentation chain transfer (RAFT) process is reported for the first time. No pre‐treatment of the Hb or cells was required prior to their use as polymerization catalysts, indicating the potential for synthetic engineering in complex biological microenvironments without the need for ex vivo techniques. Owing to the naturally occurring prevalence of the reagents employed in the catalytic system (Hb and hydrogen peroxide), this approach may facilitate the development of new strategies for in vivo cell engineering with synthetic macromolecules.

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Section: Methodsmentioning

confidence: 99%

Blood‐Catalyzed RAFT Polymerization

et al. 2018

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“…With the emergence of RDRP methods such as atom transfer radical polymerization (ATRP), nitroxide‐mediated polymerization (NMP), and reversible addition–fragmentation transfer (RAFT) there has been significant effort to control these techniques via different physical and chemical stimuli . Of these, RAFT holds particular promise due to its compatibility with a diverse range of solvents, monomers, and operating conditions .…”

Section: Redox Reaction In Initiating Polymerizationsmentioning

confidence: 99%

Fenton‐Chemistry‐Mediated Radical Polymerization

Reyhani

McKenzie

et al. 2019

Macromol. Rapid Commun.

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have been developed for the synthesis of polymers with diverse structures (linear, star, cyclic, etc.), compositions ( • mopolymer, gradient, alternating, block, etc.), and functionalities (thiol, amine, etc.). [11] The main mechanism of RDRP which results in controllable polymerization is the establishment of a dynamic equilibrium between the propagating radicals (active polymers) and the dormant species via a reversible activation-deactivation process with rate constants k act. and k deact. , respectively. [7,12] With the emergence of RDRP methods such as atom transfer radical polymerization (ATRP), [13][14][15] nitroxide-mediated polymerization (NMP), [16] and reversible addition-fragmentation transfer (RAFT) [11,17,18] there has been significant effort to control these techniques via different physical and chemical stimuli. [19][20][21][22][23][24][25][26][27] Of these, RAFT holds particular promise due to its compatibility with a diverse range of solvents, monomers, and operating conditions. [11,24,[28][29][30][31][32][33][34][35] Among RDRP methods, one might argue that RAFT is the most similar to traditional FRP, with the simple addition of a thiocarbonylthio-containing compound chain transfer agent (CTA, termed as RAFT agent) [36] that can mediate the polymerization, allowing the synthesis of well-defined polymers (Scheme 1). In fact, RAFT CTAs aid in achieving control of the radical polymerization via reversible addition of the thiocarbonylthio group and rapid fragmentation reactions. [37,38] Therefore, relatively analogous activation/initiation systems such as thermal, [4,11,[28][29][30][31][39][40][41] photo, [2,24,[32][33][34][42][43][44][45][46][47][48][49] enzyme, [5,23,[50][51][52][53][54] and redox [3,[55][56][57][58][59] based radical formation can be employed to initiate both FRP and RAFT processes. Despite the huge advances made in this field, new techniques that can overcome some of the drawbacks of these systems are continuously sought. For example, using a thermal initiator requires a high operating temperature, limiting the possibility for in situ FRP/RAFT methods in biological systems, where temperature control is limited. The rate of visible light-activated RAFT polymerization without using photocatalysts is relatively slow, [34,60] while photocatalysts, e.g. iridium and rutheniumbased ones, [24,61] employed in photo-activated processes are expensive. Moreover, photo-mediated polymerization faces difficulties in terms of the equipment requisite to perform photoinitiation at scale. [29] Redox-responsive polymerization systems have many advantages, including a low activation energy (40-85 kJ mol −1 ), easy and facile control over the polymerization at ambient temperatures, very short induction periods, etc. [56,62] Polymerizations initiated by a redox reaction between an oxidizing and a reducing agent are referred to as "redox polymerizations." [63] Use of Radical PolymerizationIn this review, the power of a classical chemical reaction, the Fenton reaction for initiating radical polymeriza...

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“…Polymerization from the Hb macroinitiator (≈12 initiating sites) was less controlled upon analysis of the cleaved polymers ( Đ = 1.68, NIPAM; Đ = 1.62, OEGA). This was attributed to the presence of the heme groups, which themselves have been shown to mediate AGET‐ATRP, and can interact with the Cu II present in the aqueous SET‐LRP system, sequestering it from solution leading to poorer control and broader dispersities.…”

Section: Synthetic Approaches To Covalently‐linked Protein/peptide‐pomentioning

confidence: 99%

Synthesis and Applications of Protein/Peptide-Polymer Conjugates

Wilson

2017

Macromol. Chem. Phys.

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Recent advances in synthetic methodologies have brought us closer than ever to the precision conferred by nature. For example, the control possible in reversible deactivation radical polymerization enables us to design and synthesize macromolecules with unprecedented control over not only the polymer chain ends, but also the side chain functionality. Furthermore, this functionality can be exploited to afford chemical modification of peptides and proteins, with ever‐improving site‐specificity, yielding a range of well‐defined protein/peptide‐hybrid materials. Such materials benefit from the amalgamation of the properties of proteins/peptides with those of the synthetic (macro)molecules in question. Here, the latest developments in the synthesis of functional polymers and their use for preparation of well‐defined protein/peptide‐polymer conjugates will be discussed, with particular attention focused on modulating the stability, efficacy and/or administration of therapeutic peptides.

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Hemoglobin and Red Blood Cells Catalyze Atom Transfer Radical Polymerization

Cited by 90 publications

References 65 publications

Blood‐Catalyzed RAFT Polymerization

Blood‐Catalyzed RAFT Polymerization

Fenton‐Chemistry‐Mediated Radical Polymerization

Synthesis and Applications of Protein/Peptide-Polymer Conjugates

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