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International Journal of Bioprinting                              3D-printed hydrogel with antioxidant activity




            Table 1. Rheological modeling of the inks
             Model         Parameter     CMF           w/1% gg      w/3% gg       w/5% gg       w/7% gg
             τ = τ  + kγ˙ n  τ  (Pa)      4.74 ± 0.13 e  75.60 ± 2.28 d  194.59 ± 9.07 c  958.37 ± 22.49 b  1249.00 ± 8.49 a
                0           o
                           k (Pa·s)       0.78 ± 0.04 e  110.18 ± 5.40 d  211.00 ± 9.90 c  186.27 ± 1.80 b  469.66 ± 3.31 a
                           N              0.11 ± 0.01 c  0.19 ± 0.03 b  0.19 ± 0.01 b  0.27 ± 0.01 a  0.14 ± 0.04b c
                           R  (%)        81.09          86.61         95.54         97.13        88.04
                            2
             G¢ = K¢(ω) ¢ n  K¢          44.49 ± 0.72 e  173.59 ± 4.82 d  272.59 ± 4.82 c  1062.42± 14.96 b  2529.05 ± 8.83 a
                           n¢            0.024 ± 0.010 d  0.066 ± 0.002 b  0.069 ± 0.007 b  0.056 ± 0.003 c  0.085 ± 0.001 a
                           R  (%)        92.29          94.05         95.89         94.09        93.53
                            2
             G² = K²(ω) ²  K²            11.40 ± 0.10 e  35.47 ± 1.44 d  251.59 ± 1.73 c  860.14 ± 4.40 b  1687.66 ± 9.29 a
                    n
                           n²            0.028 ± 0.014 b  0.042 ± 0.017 a  0.019 ± 0.006 c  0.003 ± 0.000 e  0.013 ± 0.001 d
                           R  (%)        97.23          88.65         83.38         84.67        84.98
                            2
             G* = A  (w) 1/z  A (Pa.s)   45.90 ± 0.20 e  176.85 ± 0.21 d  345.81 ± 6.43 c  1274.87 ± 3.68 b  2886.21 ± 7.11 a
                            F
                 F
                           z             41.32 ± 1.20 a  15.29 ± 0.62 d  16.42 ± 0.08 d  20.33 ± 1.88 c  25.19 ± 0.51 b
                           R  (%)        93.60          94.05         96.44         95.12        94.49
                            2
            Data are expressed as the mean ± standard deviation (n = 3).
            The means indicated with different letters within the same row are significantly different at p < 0.05.
            Abbreviations: gg, guar gum ; w/,100 mL of 1% CMFs
            by the Herschel–Bulkley model (R  = 81.09%–97.13%),   higher storage energy as a result of increased exposure
                                         2
            varied  significantly  depending  on  the  level  of guar  gum   of hydrophobic groups to hydrogel matrix.  Among the
                                                                                                  35
            in the matrix (Table 1). The τ  of the hydrogel increased,   hybrid  hydrogels, the  5% guar  gum  had the  lowest n’,
                                    o
            by 15.95–263.50 folds, with an increasing guar gum level,   indicating that its elasticity had the least dependence on
            indicating a variation in the stability of inks in the nozzle   frequency, and implying its higher post-printing stability.
                                                                                                             5
            of the 3D printer before the application of force.  Yield   Besides, this ink has the least n’’ compared to CMFs and
                                                    34
            stress is positively correlated with the potential energy   other hybrid hydrogels, validating its good extrudability.
            required to be overcome before flow can begin under   The 7% guar gum had the highest n’ while the 1% guar gum
            given shear stress;  therefore, the moderately high yield   had the highest n², suggesting poor printability and post-
                           5
            stress of inks containing 3%–5% guar gum would ensure   printing stability of the inks. These could be due to the
            good extrudability owing to optimum shear-thinning   volume exclusion effect of CMFs following its exfoliation
            viscosity.  The k increased, by 270.51 folds, following the   because of the high guar gum level in the matrix, resulting
                   34
            addition of 3% guar gum. A lower k was obtained using 5%   in ink with poor ductility. 35
            guar gum compared to 3% and 7% guar gum, likely due   The weak gel model,  R  = 93.60%–96.44%, shows
                                                                                      2
            to the variation in apparent viscosity of the inks. The n of   that A  of CMFs increased, by 3.85–62.88 folds, with
            all the inks was < 1, which validated their shear-thinning   increasing guar gum level, due to hydrophobic interactions
                                                                    F
            property.  The n increased with increasing guar gum level   of molecules and fibrillar crowding, resulting in high
                   24
            in the matrix (up to 5%) probably because of increasing   storage energy.  CMFs had the highest z value, numbers of
                                                                           35
            inter-molecular networks, leading to improved self-  interacting rheological units, likely due to the homogeneity
            assembly of polymer chains with water molecules.  The   of its fiber.  Lower z values of the hybrid hydrogels gave
                                                      7
                                                                        36
            high k and low n obtained for 7% guar gum were likely due   a significantly higher A , due to increased interaction and
            to the volume exclusion effect of CMFs  that would make   crosslinking of macromolecules, which suggests increasing
                                           35
                                                                                  F
            extrudability difficult, consistent with the poor injectability   mechanical or gel strength as guar gum increased in the
            of a high-concentration tragacanth acid hydrogel. 24
                                                               matrix. 13
               The  storage  and  loss  moduli  of  the  inks  at  different
            angular frequencies varied (Figure 1A and B). K¢ and K²   3.3. Morphological and structural properties of
            increased with an increasing level of guar gum, indicating   CMFs/guar gum-based ink
            increasing elasticity and viscosity of the inks, respectively.    The morphological and structural properties of CMFs
                                                         35
            A K¢ higher than the corresponding K² and a low loss   incorporated with guar gums (1%–7%) were investigated
            factor < 1 (Figure 1C), which are suggestive of viscoelastic   (Figure 2), as good miscibility of polymers in the hydrogel
            behavior, were obtained for all the inks, likely due to   can  help  confer  favorable  post-printing  stability  on  the

            Volume 10 Issue 1 (2024)                       247                          https://doi.org/10.36922/ijb.0164
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