Interfacial Ring-Opening Polymerization of Amino-Acid-Derived <i>N</i>-Thiocarboxyanhydrides Toward Well-Defined Polypeptides

Cao, Jinbao; Siefker, David; Chan, Brandon A.; Yu, Tianyi; Lu, Lu; Saputra, Mirza A.; Fronczek, Frank R.; Xie, Weiwei; Zhang, Donghui

doi:10.1021/acsmacrolett.7b00411

Cited by 46 publications

(53 citation statements)

References 36 publications

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“…However, there are two limitations in the use of NTAs for the polypeptide synthesis in terms of upscaling. First, dithiocarbonate used for the conversion of amino acids to the An attractive alternative method for the ROP of NCAs is the use of the sulfur-containing analogs of NCAs (Scheme 3) [9][10][11]. Amino acid N-thiocarboxyanhydrides (NTAs), which are synthesized using α-amino acids, undergo ROP in a manner similar to that of NCAs.…”

Section: Scheme 1 Ring-opening Polymerization (Rop) Of N-carboxyanhymentioning

confidence: 99%

“…An alternative synthesis route to O-4-(nitrophenyl)urethane derivatives 1 is the reaction of amino acid tert-butyl ester with bis(4-nitrophenyl)carbonate (Scheme 6) [10]. The tert-butyl group of the resulting urethane is removed using trifluoroacetic acid to produce 1.…”

Section: Scheme 5 Synthesis Of the O-4-(nitrophenyl)urethane Derivatmentioning

confidence: 99%

“…The first step is the treatment of amino acids with tetrabutylammonium hydroxide (commercially available as a methanolic solution) in aqueous media. The resulting salts are soluble in a wide range of organic solvents: the nucleophilicity of the amino group and the solubility of the salts allowed the highly An alternative synthesis route to O-4-(nitrophenyl)urethane derivatives 1 is the reaction of amino acid tert-butyl ester with bis(4-nitrophenyl)carbonate (Scheme 6) [10]. The tert-butyl group of the resulting urethane is removed using trifluoroacetic acid to produce 1.…”

Section: Scheme 5 Synthesis Of the O-4-(nitrophenyl)urethane Derivatmentioning

confidence: 99%

“…An attractive alternative method for the ROP of NCAs is the use of the sulfur-containing analogs of NCAs ( Scheme 3 ) [ 9 , 10 , 11 ]. Amino acid N -thiocarboxyanhydrides (NTAs), which are synthesized using α-amino acids, undergo ROP in a manner similar to that of NCAs.…”

Section: Introductionmentioning

confidence: 99%

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Well-Defined Construction of Functional Macromolecular Architectures Based on Polymerization of Amino Acid Urethanes

Endō

Sudo

2020

Biomedicines

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Polypeptide synthesis was accomplished using the urethane derivatives of amino acids as monomers, which can be easily prepared, purified, and stored at ambient temperature without the requirement for special precautions. The urethanes of amino acids are readily synthesized by the N-carbamoylation of onium salts of amino acids using diphenyl carbonate (DPC). The prepared urethanes are then efficiently cyclized to produce amino acid N-carboxyanhydrides (NCAs). Thereafter, in the presence of primary amines, the ring-opening polymerization (ROP) of NCAs is initiated using the amines, to yield polypeptides with controlled molecular weights. The polypeptides have propagating chains bearing reactive amino groups and initiating chain ends endowed with functional moieties that originate from the amines. Aiming to benefit from these interesting characteristics of the polypeptide synthesis using the urethanes of amino acids, various macromolecular architectures containing polypeptide components have been constructed and applied as biofunctional materials in highly efficient antifouling coatings against proteins and cells, as biosensors for specific molecules, and in targeted drug delivery.

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Section: Scheme 1 Ring-opening Polymerization (Rop) Of N-carboxyanhymentioning

confidence: 99%

Section: Scheme 5 Synthesis Of the O-4-(nitrophenyl)urethane Derivatmentioning

confidence: 99%

Section: Scheme 5 Synthesis Of the O-4-(nitrophenyl)urethane Derivatmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Well-Defined Construction of Functional Macromolecular Architectures Based on Polymerization of Amino Acid Urethanes

Endō

Sudo

2020

Biomedicines

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“…α-Amino acids N-thiocarboxyanhydrides (NTAs) are more stable monomers than NCAs [43][44][45][46] . Our group has reported that NTAs and their polymerizations tolerate mercaptans 47 , alcohols 48 , phenols 49 and water 50,51 .…”

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confidence: 99%

Direct N-substituted N-thiocarboxyanhydride polymerization towards polypeptoids bearing unprotected carboxyl groups

et al. 2020

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Synthesis of poly(α-amino acid)s bearing carboxyl groups is a critical pathway to prepare biomaterials to simulate functional proteins. The traditional approaches call for carboxyl-protected monomers to prevent degradation of monomers or wrong linkage. In this contribution, we synthesize N-carboxypentyl glycine N-thiocarboxyanhydride (CPG-NTA) and iminodiacetic acid N-thiocarboxyanhydride (IDA-NTA) without protection. Initiated by amines, CPG-NTA directly polymerizes into polyCPG bearing unprotected carboxyl groups with controlled molecular weight (2.8–9.3 kg mol−1) and low dispersities (1.08–1.12). Block and random copolymerizations of CPG-NTA with N-ethyl glycine N-thiocarboxyanhydride (NEG-NTA) demonstrate its versatile construction of complicated polypeptoids. On the contrary, IDA-NTA transforms amines into cyclic IDA dimer-capped species with carboxyl end group in decent yields (>89%) regio-selectively. Density functional theory calculation elucidates that IDA repeating unit is prone to cyclize to be the six-membered ring product with low ΔG. The polymer is a good adhesive reagent to various materials with adhesive strength of 33–229 kPa.

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Ring‐Opening Polymerization of α‐Amino Acid N ‐Carboxyanhydrides and Side‐Chain Functionalized Polypeptides

Sun

2019

Encyclopedia of Polymer Science and Technology

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Synthetic polypeptides from ring‐opening polymerization of α‐amino acid N ‐carboxyanhydrides (NCA) are versatile materials for various biomedical applications due to their biocompatibility, biodegradability, and bioactivity. This article overviews recent progress in NCA polymerizations and side‐chain functionalization of polypeptides. Initiating systems, mechanism studies, and optimized polymerization conditions for the NCA polymerization are comprehensively reviewed and evaluated here. The substituents of NCA monomers are also described. Finally, the design and synthesis of functional polypeptides is summarized and discussed.

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Interfacial Ring-Opening Polymerization of Amino-Acid-Derived N-Thiocarboxyanhydrides Toward Well-Defined Polypeptides

Cited by 46 publications

References 36 publications

Well-Defined Construction of Functional Macromolecular Architectures Based on Polymerization of Amino Acid Urethanes

Well-Defined Construction of Functional Macromolecular Architectures Based on Polymerization of Amino Acid Urethanes

Direct N-substituted N-thiocarboxyanhydride polymerization towards polypeptoids bearing unprotected carboxyl groups

Ring‐Opening Polymerization of α‐Amino Acid N ‐Carboxyanhydrides and Side‐Chain Functionalized Polypeptides

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