TY - JOUR
T1 - Real-time 31P NMR reveals different gradient strengths in polyphosphoester copolymers as potential MRI-traceable nanomaterials
AU - Rheinberger, Timo
AU - Flögel, Ulrich
AU - Koshkina, Olga
AU - Wurm, Frederik R.
N1 - Funding Information:
The authors thank Dr. Jens C. Markwart, Dr. Ricardo E.P. Martinho (UT), Bianca Ruel (UT), Clemens Padberg (UT), and Ramon ten Elshof (UT) for discussions and support in the analyses of the copolymers. O.K. thanks to the Alexander-von-Humboldt Stiftung for support.
Publisher Copyright:
© 2023, Springer Nature Limited.
Financial transaction number:
2500090798
PY - 2023/9/1
Y1 - 2023/9/1
N2 - Polyphosphoesters (PPEs) are used in tissue engineering and drug delivery, as polyelectrolytes, and flame-retardants. Mostly polyphosphates have been investigated but copolymers involving different PPE subclasses have been rarely explored and the reactivity ratios of different cyclic phospholanes have not been reported. We synthesized binary and ternary PPE copolymers using cyclic comonomers, including side-chain phosphonates, phosphates, thiophosphate, and in-chain phosphonates, through organocatalyzed ring-opening copolymerization. Reactivity ratios were determined for all cases, including ternary PPE copolymers, using different nonterminal models. By combining different comonomers and organocatalysts, we created gradient copolymers with adjustable amphiphilicity and microstructure. Reactivity ratios ranging from 0.02 to 44 were observed for different comonomer sets. Statistical ring-opening copolymerization enabled the synthesis of amphiphilic gradient copolymers in a one-pot procedure, exhibiting tunable interfacial and magnetic resonance imaging (MRI) properties. These copolymers self-assembled in aqueous solutions, 31 P MRI imaging confirmed their potential as MRI-traceable nanostructures. This systematic study expands the possibilities of PPE-copolymers for drug delivery and theranostics.
AB - Polyphosphoesters (PPEs) are used in tissue engineering and drug delivery, as polyelectrolytes, and flame-retardants. Mostly polyphosphates have been investigated but copolymers involving different PPE subclasses have been rarely explored and the reactivity ratios of different cyclic phospholanes have not been reported. We synthesized binary and ternary PPE copolymers using cyclic comonomers, including side-chain phosphonates, phosphates, thiophosphate, and in-chain phosphonates, through organocatalyzed ring-opening copolymerization. Reactivity ratios were determined for all cases, including ternary PPE copolymers, using different nonterminal models. By combining different comonomers and organocatalysts, we created gradient copolymers with adjustable amphiphilicity and microstructure. Reactivity ratios ranging from 0.02 to 44 were observed for different comonomer sets. Statistical ring-opening copolymerization enabled the synthesis of amphiphilic gradient copolymers in a one-pot procedure, exhibiting tunable interfacial and magnetic resonance imaging (MRI) properties. These copolymers self-assembled in aqueous solutions, 31 P MRI imaging confirmed their potential as MRI-traceable nanostructures. This systematic study expands the possibilities of PPE-copolymers for drug delivery and theranostics.
UR - http://www.scopus.com/inward/record.url?scp=85169678443&partnerID=8YFLogxK
U2 - 10.1038/s42004-023-00954-x
DO - 10.1038/s42004-023-00954-x
M3 - Article
AN - SCOPUS:85169678443
SN - 2399-3669
VL - 6
JO - Communications Chemistry
JF - Communications Chemistry
IS - 1
M1 - 182
ER -