Objective Many in vivo procedures to repair chondral defects use ultraviolet (UV)-photoinitiated in situ polymerization within the cartilage matrix. Chemical species that absorb UV light might reduce the effectiveness of these procedures by acting as light absorption barriers. This study evaluated whether any of the individual native biochemical components in cartilage and synovial fluid interfered with the absorption of light by common scaffolding photosensitizers. Materials UV-visible spectroscopy was performed on each major component of cartilage in solution, on bovine synovial fluid, and on four photosensitizers, riboflavin, Irgacure 2959, quinine, and riboflavin-5'-phosphate. Molar extinction and absorption coefficients were calculated at wavelengths of maximum absorbance and 365 nm. Intact articular cartilage was also examined. Results The individual major biochemical components of cartilage, Irgacure 2959, and quinine did not exhibit a significant absorption at 365 nm. Riboflavin and riboflavin-5'-phosphate were more effectual light absorbers at 365 nm, compared with the individual native species. Intact cartilage absorbed a significantly greater amount of UV light in comparison with the native species. Conclusion Our results indicate that none of the individual native species in cartilage will interfere with the absorption of UV light at 365 nm by these commonly used photoinitiators. Intact cartilage slices exhibited significant light absorption at 365 nm, while also having distinct absorbance peaks at wavelengths less than 300 nm. Determining the UV absorptive properties of the biomolecules native to articular cartilage and synovial fluid will aid in optimizing scaffolding procedures to ensure sufficient scaffold polymerization at a minimum UV intensity.
There
remains no routine treatment for congenital tracheal abnormalities
affecting more than 1/3 of the length. Natural and artificial prostheses
are plagued by mechanical failure and inconsistent outcomes. Mimicking
native tissue mechanics in an engineered replacement may improve functional
and patient outcomes. We synthesized tubular constructs comprising
photo-cross-linked methyl acrylate-co-methyl methacrylate, p(MA-co-MMA), with patterned r- and z-axes in order to achieve mechanical properties similar
to lamb tracheae. Hard and soft alternating bands, and a soft vertical
section, mimic tracheal architecture. Patterned constructs were capable
of 46% elastic longitudinal extension. The construct longitudinal
composite modulus, 0.34 ± 0.09 MPa, was not significantly different
from ovine tracheae. The superior of two geometries evaluated supports
up to a 46% reduction of internal volume within the physiological
range of transmural pressures. Thus, these patterned hydrogels yielded
longitudinal elasticity and radial rigidity while allowing for radial
deformation required for effective coughing.
Crosslinked,
degradable, and cell-adhesive hydrogel microfibers
were synthesized via interfacial polymerization employing tetrazine
ligation, an exceptionally fast bioorthogonal reaction between strained trans-cyclooctene (TCO) and s-tetrazine
(Tz). A hydrophobic trisTCO crosslinker and homo-difunctional
poly(ethylene glycol) (PEG)-based macromers with the tetrazine group
conjugated to PEG via a stable carbamate (PEG-bisTz1) bond or a labile hydrazone (PEG-bisTz2) linkage
were synthesized. After laying an ethyl acetate solution of trisTCO over an aqueous solution of bisTz macromers, mechanically robust microfibers were continuously pulled
from the oil–water interface. The resultant microfibers exhibited
comparable mechanical and thermal properties but different aqueous
stability. Combining PEG-bisTz2 and PEG-bisTz3 with a dangling arginine–glycine–aspartic acid
(RGD) peptide in the aqueous phase yielded degradable fibers that
supported the attachment and growth of primary vocal fold fibroblasts.
The degradable and cell-adhesive hydrogel microfibers are expected
to find utility in a wide array of tissue engineering applications.
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