Photoinduced Thiol‐ene Chemistry Applied to the Synthesis of Self‐Assembling Elastin‐Inspired Glycopeptides

Abstract

Synthetic (glyco)peptides inspired by proteins able to self-assemble are appealing biomaterials in the field of tissue engineering and regenerative medicine. Herein, for the first time, taking advantage of thiol-ene chemistry coupled to solid-phase peptide synthesis, a self-assembling peptide inspired by elastin protein was bioconjugated to three carbohydrates in order to obtain the corresponding glycopeptides. They were studied at the molecular and supramolecular level. The results show that the carbohydrate influences the molecular conformation of the glycopeptide and its self-aggregation properties as well. As future perspective, the results could enable us to tune the final self-aggregation properties of the glycopeptide by changing the sugar moiety.

Elastin‐Hyaluronan Bioconjugate as Bioactive Component in Electrospun Scaffolds

“…[20] Concerning carboxyl group, the transformation into active ester by reaction with carbodiimide/HOBT was a successful strategy for coupling different amine groups to HA which could be useful for carrying out coupling or crosslinking reactions under mild physiological conditions. [21] Taking advantage of previous experience in conjugating peptides to carbohydrates, [22] in this work we have synthesised an elastin-hyaluronan bioconjugate (ELHA). The methacrylated hyaluronic acid has been covalently conjugated using thiol-Michael coupling reaction [23] to a 21-residues conjugated elastin-derived peptide containing a N-terminal cysteine.…”

“…Taking advantage of previous experience in conjugating peptides to carbohydrates, [22] in this work we have synthesised an elastin‐hyaluronan bioconjugate (ELHA). The methacrylated hyaluronic acid has been covalently conjugated using thiol‐Michael coupling reaction [23] to a 21‐residues conjugated elastin‐derived peptide containing a N‐terminal cysteine.…”

Thiol−Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti‐Markovnikov‐Selective Hydrothiolation of Olefins

“…Bochicchio et al . described a photo‐induced thiol‐ene reaction for synthesis of glycopeptides 150 by using 148 and 149 (Scheme ) . In this paper, the author synthesized a self‐assembling peptide inspired by elastin protein bioconjugated to different carbohydrates to obtain the corresponding glycopeptides.…”

Synthesis of glycopeptides and glycopeptide conjugates

“…Another class of thiol selective chemistry that can be applied to cysteine is the photoinduced thiole-ene reaction, 127 which has been used to produce glycoconjugate 76 using allyl glycoside 75. 128,129 Alternatively, the reactivity of thiols can also be used in the opposite direction. The thiol-ene reaction can also be performed by reacting a thiol glycoside (78) to an alkene containing peptide (76), producing neoglycopeptide 79.…”