One-Pot Synthesis of Brush-Like Polymers via Integrated Ring-Opening Metathesis Polymerization and Polymerization of Amino Acid <i>N</i>-Carboxyanhydrides

Lu, Hua; Wang, Jing; Lin, Yao; Cheng, Jianjun

doi:10.1021/ja903425x

Cited by 103 publications

(95 citation statements)

References 23 publications

(20 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…To test this hypothesis, we prepared a 57mer of poly(γ-(3-aminopropyl)-l-glutamate) (PAPG 57 ), a 50mer of poly(γ-(5-aminopentanyl)-l-glutamate) (PAPTG 50 ) and a 57mer of poly(γ-(6-aminohexyl)-lglutamate) (PAHG 57 ) through the ROPs of γ-benzyl-l-glutamate N-carboxyanhydride (Glu-NCA) [25][26][27] followed by removing the benzyl ester PBLG side chains and grafting the corresponding amino alcohol to the pendant carboxylate groups of PLG by the formation of ester bonds (Fig. 2a, Supplemenary Figs S1-S3).…”

Section: Poly(l-glutamates) With Charged and Long Side Chainsmentioning

confidence: 99%

Ionic polypeptides with unusual helical stability

et al. 2011

Self Cite

View full text Add to dashboard Cite

Water-soluble peptides that adopt stable helical conformations are attractive motifs because of their importance in basic science and their broad utility in medicine and biotechnology. Incorporating charged amino-acid residues to improve peptide solubility, however, usually leads to reduced helical stability because of increased side-chain charge repulsion, reduced side-chain hydrophobicity and the disruption of intramolecular hydrogen bonding. Here, we show that water-soluble, ultra-stable α-helical polypeptides can be produced by elongating charge-containing amino-acid side chains to position the charges distally from the polypeptide backbone. The strategy has been successfully applied to the design and synthesis of watersoluble polypeptides bearing long, charged side chains and various functional moieties that possess unusual helical stability against changing environmental conditions, including changes in the pH and temperature and the presence of denaturing reagents.

show abstract

Section: Poly(l-glutamates) With Charged and Long Side Chainsmentioning

confidence: 99%

Ionic polypeptides with unusual helical stability

et al. 2011

Self Cite

View full text Add to dashboard Cite

show abstract

“…62 The polymer backbone is first prepared by ROMP of a norbornene having a trimethylsilyl-protected amino group, and then this polymer is used as a macromolecular initiator for subsequent NCA polymerization. The polymers form aggregates with sizes around 60-150 nm.…”

Section: Synthesis Of Amino Acid-and Peptide-based Polymers By Rompmentioning

confidence: 99%

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Sutthasupa

Shiotsuki

Sanda

2010

Polym J

328

273

View full text Add to dashboard Cite

This article reviews the development of catalysts for ring-opening metathesis polymerization (ROMP), synthesis of polymers bearing amino acids and peptides by ROMP of functionalized norbornenes, formation of aggregates and micelles, and applications of the polymers to medical materials. It also describes the control of monomer unit sequences, that is, living polymerization to synthesize block copolymers, and alternating copolymerization that is achieved on the basis of acid-base interactions. Polymer Journal (2010) 42, 905-915; doi:10.1038/pj.2010.94; published online 13 October 2010Keywords: alternating copolymerization; amino acid; block copolymerization; living polymerization; metathesis catalyst; peptide; ROMP INTRODUCTIONOlefin metathesis reactions are metal-mediated carbon-carbon (C-C) double bond exchange processes, 1,2 which were discovered in the mid 1950s. Chauvin proposed the commonly accepted mechanism for metathesis involving a metallacyclobutane, as illustrated in Scheme 1. 3 Initially, olefin metathesis was regarded as an odd reaction, but now it has undoubtedly established the position as one of the most important C-C bond formation reactions applicable to synthesis of a wide variety of useful products. In the early stages, transition metal chlorides were used as catalysts for the reaction, but the transition metal carbene complex catalysts designed by Schrock and Grubbs have remarkably advanced mechanistic analysis and control of catalytic activity by the choice of ligands. In 2005, Chauvin, Grubbs and Schrock were awarded the Nobel Prize in chemistry for development of the metathesis method in organic synthesis.Olefin metathesis polymerization is an application of metathesis reactions to polymer synthesis and includes ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polycondensation (Scheme 2). ADMET has been extensively developed by Wagener since 1987 4 for the synthesis of polyolefins having regularly spaced functional group branches and high thermal stability and crystallinity. 5,6 ADMET is also useful for synthesizing polymeric materials containing in-chain functionality. Although the general structures of the polymers obtained by ROMP and ADMET are illustratable in the same fashion as shown in Scheme 2, a completely different treatment is necessary from the viewpoint of polymerization kinetics. The former involves chain polymerization, whereas the latter is a step-growth polymerization process.

show abstract

“…The TMS-carbamate active chain-ends are highly moisture sensitive, yet this is not much of an issue since NCAs themselves are moisture senstitive and must be polymerized in an anhydrous environment. This methodology was used to prepare polypeptide-poly(norbornene diimide) brush copolymers via both "grafting from" and "grafting through" approaches [57]. In the grafting from approach, poly(norbornenes) bearing TMS amine functionalities were used as macroinitiators to grow polypeptide brush segments.…”

Section: Insert Equation 15mentioning

confidence: 99%

Synthesis and Self-Assembly of Well-Defined Block Copolypeptides via Controlled NCA Polymerization

Deming

2013

Hierarchical Macromolecular Structures: 60 Years After the Staudinger Nobel Prize II

View full text Add to dashboard Cite

One-Pot Synthesis of Brush-Like Polymers via Integrated Ring-Opening Metathesis Polymerization and Polymerization of Amino Acid N-Carboxyanhydrides

Cited by 103 publications

References 23 publications

Ionic polypeptides with unusual helical stability

Ionic polypeptides with unusual helical stability

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Synthesis and Self-Assembly of Well-Defined Block Copolypeptides via Controlled NCA Polymerization

Contact Info

Product

Resources

About