Carbene-Based Bioadhesive Blended with Amine, Thiol, and Acrylate Liquid Additives

Abstract

Light-activated carbenes provide a unique method of non-specific covalent bond formation needed in bioadhesives and rapid gelation. The highly reactive carbenes formed upon UV irradiation allow for binding to a wide range of natural and synthetic substrates in addition to cohesive bonds. However, little is known about how these crosslinkers would behave in the presence of additives, which are important for tuning material properties. This work investigates carbene-based bioadhesives in the presence of various liquid additives containing reactive functional groups of hydroxyl, thiol, amine, or acrylate. Steady shear viscosity, dynamic mechanical properties, microstructure, and reactive functional groups are evaluated by photorheometry, scanning electron microscopy, and FTIR spectroscopy. The triol hydroxy additive maintains the storage modulus despite dilution of the diazirine crosslinker. The thiol additive reduces apparent viscosity while maintaining material properties. Polyamine accelerates ester hydrolysis and increases hydrophilicity. For the first time, diacrylate polymerization is demonstrated by photoactivated diazirine, the carbene precursor. The diacrylate additive displays synergistic enhancement of the dynamic modulus within the binary composite, reaching 977 kPa compared to 82 kPa of neat carbene-based bioadhesive. The polymerization of acrylates initiated by diazirine photolysis opens possibilities for acrylate initiation and hybrid composite biomaterials.

Color changing bioadhesive barrier for peripherally inserted central catheters

“…3A and B), in line with previously reported work. 27 Hydrophobic organic additives are known to decrease the shear modulus and shear strength. 27 Molar mass analysis of irradiated CG − and CG + dissolved in THF found a 7× difference in weight-averaged molar mass with 960 kDa vs. 140 kDa, respectively (see ESI †).…”

“…27 Hydrophobic organic additives are known to decrease the shear modulus and shear strength. 27 Molar mass analysis of irradiated CG − and CG + dissolved in THF found a 7× difference in weight-averaged molar mass with 960 kDa vs. 140 kDa, respectively (see ESI †). Both formulations exceed 20 kPa shear strength and relatively flexible strain at break of 56% (Fig.…”

“…24 One advantage of the hydrophobic liquid formulation is its ability to dissolve organic additives. [25][26][27] Herein, this is exploited for incorporation of organic pH indicator for colorimetric detection of bacterial infection (Fig. 1).…”

Thermal/Blue Light Induced Cross‐Linking of Acrylic Coatings with Diazo Compounds

“…Despite the large body of work on visible-light-curing of acrylates, research toward other visible-light-induced paint curing strategies is still in its infancy, with only a few reported examples thus far. [4][5][6] Carbene-based cross-linkers have seen a large commercial impact in materials chemistry, finding applications as fabric strengtheners, [7] adhesives [8] and in mixed plastics recycling. [9] In particular, diazirine compounds have shown high efficiency in cross-linking polymers bereft of specific functionality (e.g., polypropylene [10] and polydimethylsiloxane [11] ) through C─H insertion, and functional polymers (e.g., containing hydroxyl and thiol functionalities [8,12] ) through X─H insertion.…”

“…[4][5][6] Carbene-based cross-linkers have seen a large commercial impact in materials chemistry, finding applications as fabric strengtheners, [7] adhesives [8] and in mixed plastics recycling. [9] In particular, diazirine compounds have shown high efficiency in cross-linking polymers bereft of specific functionality (e.g., polypropylene [10] and polydimethylsiloxane [11] ) through C─H insertion, and functional polymers (e.g., containing hydroxyl and thiol functionalities [8,12] ) through X─H insertion. These diazirines generally require UV-light to activate the diazirine carbene precursor, which next to introducing again a high energyconsumption can cause several selectivity problems.…”