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International Journal of Bioprinting                 Zn-doped coatings with osteogenic and antibacterial properties



            A                                B                              C














            D                                E                              F
















            Figure 4. (A) The survey XPS spectra of CHA-0 and CHA-H. (B) O 1s spectra, A – D: CHA-0, CHA-L, CHA-M, and CHA-H, respectively. (C) C 1s and
            (D) N 1s spectra of CHA-0 and CHA-H, respectively. (E) Ca 2p spectra and (F) Zn 2p spectra of CHA-H.

            were also detected from CHA-0, except Zn. N was only   1s spectra. In Figure 4E and 4F, the binding energies of
            ascribed to chitosan in the coating, so the content was low   351.4 and 347.8 eV were classified to the Ca 2p1/2 and Ca
            and the spectral peak was not obvious. Furthermore, CaCl    2p3/2 orbitals of the Ca  in CHA-0 group, while 1045.1
                                                                                   2+
                                                          2
            and ZnCl  were employed as crosslinking agent, in which   and 1022 eV were classified to the Zn 2p1/2 and Zn 2p3/2
                    2
            divalent metal ions interact strongly with carboxyl groups   orbitals of the Zn  in CHA-H group . The relative atomic
                                                                            2+
                                                                                            [38]
            of sodium alginate. However, there were no groups in the   ratios of Zn and Ca elements on the coating surface are
            coating that could interact with Cl ions, so its content   given in Table 1. There were some acceptable differences
                                         - 
            was almost negligible. Similarly, the Na  ions in sodium   between experimental and theoretical values caused by
                                            +
            alginate were replaced by Ca  and Zn  ions, resulting in   experimental errors. Therefore, the concentration of Zn
                                           2+
                                   2+
            an insignificant spectral peak.                    ions in the coating could be adjusted by changing the
              The O 1s XPS spectra (Figure 4B) were deconvoluted   proportion of Ca/Zn ions in the solution without changing
            into 4 peaks near 533.5, 532.7, 531.5, and 531 eV,   the concentration of the crosslinking agent solution.
            corresponding to C=O, C-OH, C-O-C, and O…Zn/Ca .   3.2. Mechanical properties of samples
                                                        [34]
            The peak of O…Zn/Ca shifted rightward with the increase
            of  Zn concentration  in  coatings  caused by  the  different   To evaluate the effect of coating on mechanical properties
            interaction forces of Zn  and Ca  on carboxyl groups,   of scaffolds, the compressive strength and compressive
                                2+
                                        2+
            and the detailed values for CHA-0, CHA-L, CHA-M, and   modulus values of the bare scaffold and coated scaffold are
            CHA-H groups were 531.1, 530.95, 530.85, and 531.7 eV,   compared. As shown in Figure 5, compressive strength of
            respectively. The C 1s spectra are shown in  Figure  4C.   bare scaffold was 10.42 ± 0.56 MPa, while that of the coated
            They  were  deconvoluted  into  three  principal  peaks  near   scaffold was 11.52 ± 0.3 MPa. These results suggested that
            288.2, 286.6 and 284.8 eV, which were assigned O-C=O,   the  coating  could  improve  the  mechanical  properties  of
            C-O/C-N, and C-C bonds, respectively [35,36] .  Figure  4D   scaffolds, although the improvement was not significant.
            showed that the N 1s spectra and the peaks near 399.8 eV   The reasons could be attributed to two components. On
            were attributed to amidogen groups (-NH ) . CHA-0   the one hand, although the mechanical strength of the
                                               3+ [37]
            and CHA-H were selected because they were most likely   polymer coating material was extremely poor, it could
            to differ, and in fact all samples had similar C 1s and N   still play a certain supporting role under pressure . On
                                                                                                        [39]

            Volume 9 Issue 2 (2023)                        297                      https://doi.org/10.18063/ijb.v9i2.668
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