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International Journal of Bioprinting  Biocompatible BSA-GMA and TPP of 3D hydrogels with free radical type I photoinitiator






























            Figure 4. SEM images of arbitrary 3D structures of BSA-GMA hydrogels with different contents and degrees of methacrylation processed by TPP. (A) SEM
            images of four-pointed star structures of BSA-GMA hydrogels. Scale bar: 5 μm. (B) SEM images of woodpile structures of BSA-GMA hydrogels. Scale bar:
            5 μm. (C) SEM images of hollow cage construction of BSA-GMA hydrogels. Scale bar: 1 μm.

            Table 3. TPP parameters for 3D structures
             Sample      Four-pointed star            Woodpile structures         Hollow cage
             R D 52      P = 17.2 mW, V = 110 μm/s    P = 15.9 mW, V = 10 μm/s    P = 37.0 mW, V = 22 μm/s
              20
             R D         P = 14.2 mW, V = 110 μm/s    P = 17.7 mW, V = 10 μm/s    P = 11.0 mW, V = 22 μm/s
              30  52
             R D         P = 8.1 mW, V = 110 μm/s     P = 13.9 mW, V = 50 μm/s    P = 12.9 mW, V = 88 μm/s
              40  15
             R D         P = 6.1 mW, V = 110 μm/s     P = 13.9 mW, V = 50 μm/s    P = 12.8 mW, V = 22 μm/s
              40  35
             R D 52      P = 6.0 mW, V = 110 μm/s     P = 4.3 mW, V = 10 μm/s     P = 5 mW, V = 22 μm/s
              40
            to the BSA-GMA system. The minimum resolution of the   3D structure of each hydrogel system was obtained by
            line width decreases with decreasing concentration and   adjusting the processing parameters. We simulated the
            methacrylation degree, from 362 nm for R D  to 250 nm   printing of arbitrary shapes from 2D to complex 3D as
                                              40
                                                52
            for R D  and 199 nm for R D . Figure 3F shows the atomic   an example of a two-photon polymerized BSA-GMA
                                   15
                                 40
                20
                  52
            force microscopy (AFM) image of the R D  line structure,   hydrogel (Figure  4).  Table 3 shows the laser processing
                                              52
                                           40
            and the line height is 107 nm. The data of the BSA-GMA   parameters for the fabrication of 3D structures for each
            system are summarized in Figure 3G to thoroughly study   hydrogel system. As the concentration and the degree of
            the relationship between line width and polymerization   methacrylation increased, less laser power was required.
            power. The polymerization threshold power decreases with   Figure 4A shows the four-pointed star structures that
            increasing concentration and degree of methacrylation,   illustrate the ability of the BSA-GMA hydrogel to
            and the line width increases linearly with increasing power.   process sharp patterns with TPP. The BSA-GMA with
            The trend is similar for R D , R D , R D , and R D ,   concentrations of 20 wt% and 30 wt% used high laser
                                      40
                                   15
                                                      30
                                                         52
                                               52
                                         35
                                            20
                                40
            while R D  shows an abrupt change, and the line width   power, but only a shallow height of hydrogel structure was
                  40
                     52
            varies more with increasing power. BSA-GMA has better   obtained. In contrast, the polymerization power of the three
            TPP ability with free radical type I photoinitiator compared   samples with different degrees of methacrylation, R D ,
                                                                                                         40
            with pure BSA. The TPP characteristics of BSA-GMA can   R D , and R D , decreased with increasing degrees of
                                                                                                            15
                                                                40
                                                                             52
                                                                          40
                                                                   35
            be adjusted according to the degree of methacrylation   methacrylation, and the 3D structures were clear without
            and the concentration of BSA-GMA, where the degree of   significant differences. All five BSA-GMA woodpile
            methacrylation has a more obvious effect on the TPP.  structures shrunk at a small degree, among which R D ,
                                                                                                         20
                                                                                                            52
               To get the actual accuracy and 3D microstructure   R D , and R D  had low heights without obvious lays
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                                                                   15
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                                                                            35
            capability of this photoresist system in TPP, the optimal   (Figure 4B). The woodpile structures of R D  and R D
                                                                                                 30  52   40  52
            Volume 9 Issue 5 (2023)                         76                         https://doi.org/10.18063/ijb.752
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