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International Journal of Bioprinting                                  3D printed hydrogels for tumor therapy




            formation.  The EDS mapping images shown in Figure 6D    GelMA, and MgHAp/GelMA-PDA hydrogels in the wet
                    56
            indicate the  element  distribution  in the  cross-sectional   state were 0.114 ± 0.005, 0.195 ± 0.033, 0.211 ± 0.019, and
            area of the printed MgHAp/GelMA hydrogel. It clearly   0.111 ± 0.059 MPa, respectively. While in the dry state,
            showed the distribution of MgHAp nanocomposites in   the Young’s modulus of GelMA, HAp/GelMA, MgHAp/
            MgHAp/GelMA hydrogel. Also, EDS pattern in Figure S3,   GelMA, and MgHAp/GelMA-PDA hydrogels were 10.020
            Supporting Information reveals the presence of Mg in the   ±  3.343,  28.750  ±  9.248,  36.190  ±  11.186,  and  31.913  ±
            printed MgHAp/GelMA-PDA hydrogel. Furthermore, the   10.770 MPa, respectively. Notably, the mechanical strength
            thermogravimetric analysis (TGA) results in  Figure S4,   of 3D-printed MgHAp/GelMA-PDA hydrogels was still far
            Supporting Information shows the thermal degradation   behind that of the native bone. Hydrogel scaffolds usually
            behavior  of  3D-printed  GelMA,  HAp/GelMA,  MgHAp/  possess insufficient mechanical strength for bone tissue
            GelMA, and MgHAp/GelMA-PDA hydrogels. This         regeneration. To reinforce the mechanical properties of
            indicates that due to the addition of HAp and MgHAp   hydrogels, ceramic particles have been widely used. In the
            nanocomposites, the remained weight percentages of   current study, the addition of 10% of MgHAp significantly
            HAp/GelMA, MgHAp/GelMA, and MgHAp/GelMA-PDA        increased the modulus of hydrogels in both dry and wet
            scaffolds increased after sintering at 800°C in comparison   state. To further improve the mechanical properties,
            to that of GelMA hydrogel. However, the fastest thermal   more MgHAp nanocomposites could be incorporated
            degradation temperature stayed nearly the same for   into hydrogels. However, a higher percentage of MgHAp
            GelMA (333.6°C), HAp/GelMA (324.1°C), MgHAp/       can lead to the formation of a compact network within
            GelMA (333.5°C), and MgHAp/GelMA-PDA (337.8°C)     hydrogels, thereby impacting the swelling and degradation
            hydrogels. Overall, HAp and MgHAp nanocomposites   behavior of MgHAp/GelMA-PDA hydrogels as well as
            were well-dispersed in the printed hydrogels.      influencing DOX release and cellular metabolism. Hence,
                                                               striking  a  balance  among  the  mechanical  properties  of
               Generally, GelMA hydrogels have poor mechanical
            properties. For example, Rizwan et al. found that the   hydrogels is critical.
            compression modulus of 15% GelMA hydrogels was below   The swelling behavior of hydrogels is related to their
            50 kPa.  O’connell et al. showed that the peak storage   structural  and dimensional stability  as  hydrogels  tend
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            modulus of 10% GelMA hydrogels could not exceed 10   to swell upon interaction with biological fluids, leading
            kPa, even with a high photoinitiator concentration and   to changes in weight and size. Therefore, the swelling
            light intensity and a long exposure time of UV light.    behavior of hydrogels is essential for diffusion/migration
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            Consequently, ceramic particles were encapsulated   of encapsulated small biomolecules, drugs, and cells.
            in GelMA hydrogels to reinforce their mechanical   As shown in Figure 8A, printed hydrogels reached their
            strength.  In the current study, the mechanical properties   swelling equilibrium after being immersed in PBS for 12
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            of 3D-printed GelMA, HAp/GelMA, MgHAp/GelMA,       h. The swelling ratios of GelMA, HAp/GelMA, MgHAp/
            and MgHAp/GelMA-PDA hydrogels were investigated    GelMA, and MgHAp/GelMA-PDA hydrogels were 328.05
            through compression tests. As shown in  Figures 7 and   ± 9.01%, 326.64 ± 3.97%, 322.01 ± 3.77%, and 307.59 ±
            S5, Supporting Information the compression strength of   7.41%, respectively. The degradation of a hydrogel could
            3D-printed GelMA hydrogels in the wet and dry states   facilitate the formation of extracellular matrix (ECM),
            was 0.124 ± 0.014 and 2.590 ± 0.475 MPa, respectively.   thereby  creating  an  optimal  microenvironment  for cell
            The combination of GelMAH and GelMAL significantly   growth.  Moreover, the biodegradation rate of hydrogels
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            increased the mechanical strength because GelMAH   should be compatible with the rate at which new tissue
            could be efficiently crosslinked by UV light and GelMAL   is formed.  Figure 8B displays the  in vitro degradation
            had a high sol–gel transition temperature and thus   behavior of the printed hydrogels. Printed GelMA, HAp/
            could be efficiently thermally crosslinked. On the other   GelMA, and MgHAp/GelMA hydrogels manifested
            hand, the addition of 10% HAp or MgHAp in GelMA    similar degradation behavior. Following an immersion in
            hydrogels significantly  increased  mechanical  strength.   PBS for 4 weeks, the degradation rates of GelMA, HAp/
            The compression strength of 3D-printed HAp/GelMA and   GelMA, and MgHAp/GelMA hydrogels were 50.41 ±
            MgHAp/GelMA hydrogels in the wet state was 0.171 ±   1.27%, 54.40 ± 0.85%, and 60.87 ± 0.99%, respectively.
            0.011 and 0.182 ± 0.023 MPa, respectively. However, the   However, MgHAp/GelMA-PDA hydrogels exhibited a
            compression strength of MgHAp/GelMA-PDA hydrogels   higher degradation rate. After 4 weeks of degradation, the
            in the wet state decreased to 0.099 ± 0.012 MPa, which   degradation rate of MgHAp/GelMA-PDA hydrogels was
            could be attributed to the addition of PDA particles   84.32 ± 0.79%. The relatively high degradation rate was
            decreasing the UV crosslinking efficiency. As a result,   attributed to the addition of PDA particles, which reduced
            the Young’s modulus of GelMA, HAp/GelMA, MgHAp/    the UV crosslinking efficiency.


            Volume 10 Issue 5 (2024)                       244                                doi: 10.36922/ijb.3526
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