Temperature-Regulated Activity of Responsive Polymer−Protein Conjugates Prepared by Grafting-from via RAFT Polymerization

De, Priyadarsi; Li, Ming; Gondi, Sudershan; Sumerlin, Brent S.

doi:10.1021/ja804495v

Cited by 402 publications

(361 citation statements)

References 26 publications

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“…Thus, BSA was converted into a macro-RAFT agent through reaction of the BSA thiol group with a pyridyl disulfide functional RAFT agent 183 [366] or the maleimide functional RAFT agent 136. [329] These macro-RAFT agents were then used to synthesize conjugates through polymerization of NIPAM in aqueous media without denaturing the BSA.…”

Section: Block Copolymersmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process - A Second Update

Moad¹,

Rizzardo²,

Thang³

2009

Aust. J. Chem.

906

720

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This paper provides a second update to the review of reversible deactivation radical polymerization achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379-410). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669-692). This review cites over 500 papers that appeared during the period mid-2006 to mid-2009 covering various aspects of RAFT polymerization ranging from reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses and a diverse range of applications. Significant developments have occurred, particularly in the areas of novel RAFT agents, techniques for end-group removal and transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Section: Block Copolymersmentioning

confidence: 99%

Living Radical Polymerization by the RAFT Process - A Second Update

Moad¹,

Rizzardo²,

Thang³

2009

Aust. J. Chem.

906

720

View full text Add to dashboard Cite

show abstract

“…[36][37][38][39][40][41][42][43][44][45][46] As a consequence of the degenerative chain transfer mechanism, (co)polymers prepared by RAFT bear very specific end-groups, the chemical nature of which is dependent on the structure of the chain transfer agent (CTA) and, to a lesser extent, the CTA/initiator pair. Assuming no undesirable side reactions then the a terminus of a (co)polymer chain will be chemically identical to the R-group of the RAFT CTA while the x terminus bears a thiocarbonylthio functional group, the exact chemical structure of which will be dependent of the class of RAFT CTA used, that is, dithioester versus xanthate versus trithiocarbonate etc.…”

Section: Introductionmentioning

confidence: 99%

Sequential thiol‐ene/thiol‐ene and thiol‐ene/thiol‐yne reactions as a route to well‐defined mono and bis end‐functionalized poly(N‐isopropylacrylamide)

Chan

Hoyle

et al. 2009

J. Polym. Sci. A Polym. Chem.

211

191

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Sequential thiol-ene/thiol-ene and thiol-ene/thiol-yne reactions have been used as a facile and quantitative method for modifying end-groups on an N-isopropylacrylamide (NIPAm) homopolymer. A well-defined precursor of polyNIPAm (PNIPAm) was prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization in DMF at 70 C using the 1-cyano-1-methylethyl dithiobenzoate/2,2 0 -azobis(2-methylpropionitrile) chain transfer agent/initiator combination yielding a homopolymer with an absolute molecular weight of 5880 and polydispersity index of 1.18. The dithiobenzoate end-groups were modified in a one-pot process via primary amine cleavage followed by phosphine-mediated nucleophilic thiol-ene click reactions with either allyl methacrylate or propargyl acrylate yielding ene and yne terminal PNIPAm homopolymers quantitatively. The ene and yne groups were then modified, quantitatively as determined by 1 H NMR spectroscopy, via radical thiol-ene and radical thiol-yne reactions with three representative commercially available thiols yielding the mono and bis end functional NIPAm homopolymers. This is the first time such sequential thiol-ene/thiol-ene and thiol-ene/thiol-yne reactions have been used in polymer synthesis/end-group modification. The lower critical solution temperatures (LCST) were then determined for all PNIPAm homopolymers using a combination of optical measurements and dynamic light scattering. It is shown that the LCST varies depending on the chemical nature of the end-groups with measured values lying in the range 26-35 C.

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“…[18][19][20] When compared to the linear PEG with equivalent molecular weights, the comb-like PEG displays greater steric hindrance, thus potentially enhancing biostability and lowering clearance rates of the conjugated biotherapeutics. Moreover, comb-shaped PEG-(meth)acrylate polymers can be prepared by reversible addition fragmentation chain transfer (RAFT) polymerization [21][22][23][24][25] and atom transfer radical polymerization (ATRP) techniques, [26][27][28][29] which offer facile synthetic routes to the generation of polymers with controlled molecular weight, varying macromolecular architectures and defined endgroup functionalities. While control over the molecular weight and macromolecular structure of the conjugated polymer is crucial for improved pharmacokinetic properties of the bioconjugates, the defined end-group functionality enables varying synthetic strategies to be implemented for site-specific PEGylation.…”

Section: Introductionmentioning

confidence: 99%

Conjugation of siRNA with Comb‐Type PEG Enhances Serum Stability and Gene Silencing Efficiency

Gunasekaran

Nguyen

Maynard

et al. 2011

Macromol. Rapid Commun.

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A thiol‐modified siRNA targeting the enhanced green fluorescence protein (eGFP) gene was conjugated with RAFT‐synthesized, pyridyl disulfide‐functional poly(PEG methyl ether acrylate)s (p(PEGA)s). siRNA‐p(PEGA) conjugates demonstrated significantly enhanced in vitro serum stability and nuclease resistance compared to the unmodified and thiol‐modified siRNA. The complexes of siRNA‐p(PEGA) conjugates with a fusogenic peptide, KALA ((+)/(–) = 2) inhibited the protein expression approximately 28‐fold more than the KALA complex of the unmodified siRNA. The protein inhibition caused by siRNA‐p(PEGA)‐KALA complexes (56 ± 5%–58 ± 3% of the fluorescence expressed in non‐treated cells) was comparable to the effect of the unmodified siRNA‐lipofectamine complex (77 ± 7%). magnified image

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Temperature-Regulated Activity of Responsive Polymer−Protein Conjugates Prepared by Grafting-from via RAFT Polymerization

Cited by 402 publications

References 26 publications

Living Radical Polymerization by the RAFT Process - A Second Update

Living Radical Polymerization by the RAFT Process - A Second Update

Sequential thiol‐ene/thiol‐ene and thiol‐ene/thiol‐yne reactions as a route to well‐defined mono and bis end‐functionalized poly(N‐isopropylacrylamide)

Conjugation of siRNA with Comb‐Type PEG Enhances Serum Stability and Gene Silencing Efficiency

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