TY - JOUR

T1 - Amino Acid-Based Polyphosphorodiamidates with Hydrolytically Labile Bonds for Degradation-Tuned Photopolymers

AU - Haudum, Stephan

AU - Lenhart, Stefan

AU - Müller, Stefanie Monika

AU - Tupe, Disha

AU - Naderer, Christoph

AU - Dehne, Tilo

AU - Sittinger, Michael

AU - Major, Zoltan

AU - Grießer, Thomas

AU - Brüggemann, Oliver

AU - Jacak, Jaroslaw

AU - Teasdale, Ian

N1 - Publisher Copyright: © 2023 The Authors. Published by American Chemical Society

PY - 2023/5/9

Y1 - 2023/5/9

N2 - Photochemical additive manufacturing technologies can produce complex geometries in short production times and thus have considerable potential as a tool to fabricate medical devices such as individualized patient-specific implants, prosthetics and tissue engineering scaffolds. However, most photopolymer resins degrade only slowly under the mild conditions required for many biomedical applications. Herein we report a novel platform consisting of amino acid-based polyphosphorodiamidate (APdA) monomers with hydrolytically cleavable bonds. The substituent on the α-amino acid can be used as a handle for facile control of hydrolysis rates of the monomers into their endogenous components, namely phosphate and the corresponding amino acid. Furthermore, monomer hydrolysis is considerably accelerated at lower pH values. The monomers underwent thiol-yne photopolymerization and could be 3D structured via multiphoton lithography. Copolymerization with commonly used hydrophobic thiols demonstrates not only their ability to regulate the ambient degradation rate of thiol-yne polyester photopolymer resins, but also desirable surface erosion behavior. Such degradation profiles, in the appropriate time frames, in suitably mild conditions, combined with their low cytotoxicity and 3D printability, render these novel photomonomers of significant interest for a wide range of biomaterial applications.

AB - Photochemical additive manufacturing technologies can produce complex geometries in short production times and thus have considerable potential as a tool to fabricate medical devices such as individualized patient-specific implants, prosthetics and tissue engineering scaffolds. However, most photopolymer resins degrade only slowly under the mild conditions required for many biomedical applications. Herein we report a novel platform consisting of amino acid-based polyphosphorodiamidate (APdA) monomers with hydrolytically cleavable bonds. The substituent on the α-amino acid can be used as a handle for facile control of hydrolysis rates of the monomers into their endogenous components, namely phosphate and the corresponding amino acid. Furthermore, monomer hydrolysis is considerably accelerated at lower pH values. The monomers underwent thiol-yne photopolymerization and could be 3D structured via multiphoton lithography. Copolymerization with commonly used hydrophobic thiols demonstrates not only their ability to regulate the ambient degradation rate of thiol-yne polyester photopolymer resins, but also desirable surface erosion behavior. Such degradation profiles, in the appropriate time frames, in suitably mild conditions, combined with their low cytotoxicity and 3D printability, render these novel photomonomers of significant interest for a wide range of biomaterial applications.

UR - http://www.scopus.com/inward/record.url?scp=85159576935&partnerID=8YFLogxK

U2 - 10.1021/acsmacrolett.3c00173

DO - 10.1021/acsmacrolett.3c00173

M3 - Article

C2 - 37158040

AN - SCOPUS:85159576935

VL - 12.2023

SP - 673

EP - 678

JO - ACS Macro Letters

JF - ACS Macro Letters

SN - 2161-1653

IS - 6

ER -