Cross-linkable gelatin methacryloyl (GM) is widely used for the generation of artificial extracellular matrix (ECM) in tissue engineering. However, the quantification of modified groups in GM is still an unsolved issue, although this is the key factor for tailoring the physicochemical material properties. In this contribution, H-C-HSQC NMR spectra are used to gain detailed structural information on GMs and of 2-fold modified gelatin containing methacryloyl and acetyl groups (GMAs). Distinctive identification of methacrylate, methacrylamide, and acetyl groups present in GMs and GMAs revealed an overlap of methacrylamide and modified hydroxyproline signals in the H NMR spectrum. Considering this, we suggest a method to quantify methacrylate and methacrylamide groups in GMs precisely based on simpleH NMR spectroscopy with an internal standard. Quantification of acetylation in GMAs is also possible, yet, 2D NMR spectra are necessary. The described methods allow direct quantification of modified groups in gelatin derivatives, making them superior to other, indirect methods known so far.
Gelatin methacryloyl (acetyl) (GM(A)) is increasingly investigated for various applications in life sciences and medicine, for example, drug release or tissue engineering. Gelatin type A and type B are utilized for GAM(A) and GBM(A) preparation, but the impact of gelatin raw material on modification reaction and resulting polymer properties is rather unknown so far. Therefore, the degrees of modification (DMA) and physicochemical properties of five GAM(A) and GBM(A) derivatives are compared: The degrees of methacryloylation (0.32–0.98 mmol g−1) are indistinguishable for GAM(A) and GBM(A) as are the sol‐gel temperatures. Isoelectric points, solution viscosities, and hydrodynamic radii which are distinct for GA and GB, converge with increasing DMA. Interestingly, differences are measured for the storage moduli and equilibrium degrees of swelling of respective GA and GB derivative‐based hydrogels, in spite of their comparable DMA. This underlines the importance of GM(A) characterization beyond the modification degree.
Bio-based release systems for pro-angiogenic growth factors are of interest, to overcome insufficient vascularization and bio-integration of implants. In this study, we investigated heparin-functionalized hydrogels based on gelatin type A or albumin as storage and release systems for vascular endothelial growth factor (VEGF). The hydrogels were crosslinked using carbodiimide chemistry in presence of heparin. Heparin-functionalization of the hydrogels was monitored by critical electrolyte concentration (CEC) staining. The hydrogels were characterized in terms of swelling in buffer solution and VEGF-containing solutions, and their loading with and release of VEGF was monitored. The equilibrium degree of swelling (EDS) was lower for albumin-based gels compared to gelatin-based gels. EDS was adjustable with the used carbodiimide concentration for both biopolymers. Furthermore, VEGF-loading and release were dependent on the carbodiimide concentration and loading conditions for both biopolymers. Loading of albumin-based gels was higher compared to gelatin-based gels, and its burst release was lower. Finally, elevated cumulative VEGF release after 21 days was determined for albumin-based hydrogels compared to gelatin A-based hydrogels. We consider the characteristic net charges of the proteins and degradation of albumin during release time as reasons for the observed effects. Both heparin-functionalized biomaterial systems, chemically crosslinked gelatin type A or albumin, had tunable physicochemical properties, and can be considered for controlled delivery of the pro-angiogenic growth factor VEGF.
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