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Deng Y, et al.

            4.3  The Effect of β-TCP on Degradation             of ZK60/8β-TCP was believed to be closely related to
            Behavior                                            the enhanced corrosion resistance. As shown in Figure
                                                                6A, the pH value significantly increased during the
            It was well known that Mg had a lively chemical     immersion due to the rapid degradation of Mg-based
            property. As Mg based alloys were exposed to aqueous   composites. In general, a weak alkaline environment
            solution, Mg would degrade according to the following   with pH value ranging from 7.4 to 7.8 was more suitable
                            [26]
            chemical reactions :                                for cell survival. An increased pH would significantly
                                2+
                Anodic: Mg → Mg  + 2e −                 (4.1)   impair the enzyme activity, thus affecting the transport
                                                                of substance for cell membrane. Meanwhile, a high pH
                                                                                         −
                                                                                 2+
                Cathodic: 2H 2 O + 2e  → H 2 ↑ + 2OH    (4.2)   value with high Mg  and OH  concentration led to a too
                                 −
                                              −
                                                                high osmotic pressure in culture medium [29] . Thus, the
                                          −
                                   2+
                Product formation: Mg  + 2OH → Mg(OH) 2 ↓   (4.3)  significantly increased pH had obvious inhibitory effects
                                                                on cell proliferation. For ZK60/8β-TCP, the pH value
            Hence a heavy layer of Mg(OH) , which exhibited a                           2+    −
                                          2

            porous structure, was observed on the surface of ZK60   and ion concentration (Mg , OH ) in culture medium
                                        −
            (Figure 7A). Meanwhile, the Cl  ions contained in SBF   were considerably reduced compared with ZK60,
            could transformed Mg(OH)  into resoluble MgCl  as   resulting in more appropriate pH value and osmolality
                                     2
                                                                                                        2+
                                                         2
            follows :                                           for cell proliferation. Besides, the released Ca  caused
                   [16]
                                                                by the degradation of β-TCP should also be responsible
                                            −
                             −
                Mg(OH) 2  + 2Cl  → MgCl 2  + 2OH        (4.4)   for the improvement of cytocompatibility for ZK60/8β-
            Thus, the coated Mg(OH)  layer could not provide an   TCP. Ca, as a nutrient element for the human body, is
                                   2
                                                                                                   [30]
            effective protection for the inner fresh Mg matrix from   essential in chemical signaling with cells . Li et al. also
                                                                               2+
            further degradation. Compared with ZK60, ZK60/8β-   reported that Ca  enhanced the proliferation of bone-
                                                                                                 2+
                                                                          [31]
            TCP had an enhanced corrosion resistance. This could   derived cell . Thus, the release of Ca  from ZK60/8β-
            be confirmed by the reduced pH value of SBF after   TCP might exert a positive effect on the cell growth and
            immersion of ZK60/8β-TCP composite. The enhanced    proliferation.
            corrosion resistance of ZK60/8β-TCP was due to a more   5. Conclusions
            protective film formed on the corrosion surface. The
            β-TCP distributed in Mg matrix would dissolve in the   In this study, β-TCP was composited with ZK60 via
                                    [27]
            aqueous solution as follows :                       laser rapid solidification with an aim to improve the
                                           −
                                     2-
                                                2+
                                                       3−
                3Ca 3 (PO 4 ) 2  + H 2 O→HPO 4   + OH +9Ca + 5PO 4         degradation behavior. It was revealed that laser rapid
                                                                solidification restrained the segregation of β-TCP
                                                        (4.5)   particles in Mg matrix. In addition, β-TCP particles
            The released calcium ion and phosphate ion favored   uniformly distributed along grains boundaries in
            for the formation of apatite layer on surface. On the   ZK60/8β-TCP. The results showed that the laser rapidly
            other hand, the β-TCP usually acted as the apatite nuclei   solidified ZK60/8β-TCP had an enhanced corrosion
            leading to the deposition of apatite spontaneously [28] .   resistance and mechanical properties as compared
            Therefore, a large amount of apatite deposited on   with ZK60. Besides, the results of in vitro cell culture
            the surface and filled the pores of Mg(OH)  layer.   assays also revealed that ZK60/8β-TCP composite
                                                      2
            As a result, a more compact surface film formed and   had an improved cytocompatibility to MG-63 cells.
            effectively retarded the further degradation.       It was suggested that ZK60/8β-TCP was a potential
              It should be noted that the corrosion rate accelerated   biodegradable implant.
            as the β-TCP content increased up to 12 wt. %. This
            was because too much β-TCP aggregated at the grain   Conflict of Interest and Funding
            boundaries and reduced the relative density of the   No conflict of interest was reported by the authors. The
            matrix. As a consequence, the strongly corrosive Cl  ion   authors gratefully acknowledge the following projects
                                                        −
            easily invaded into the matrix, which accelerated the   and funds for the financial support: (1) The Natural
            degradation.                                        Science Foundation of China (51575537, 81572577,
            4.4  In Vitro Cell Response of ZK60/xβ-TCP          51705540, 81472058); (2) Hunan Provincial Natural
                                                                Science Foundation of China (2016JJ1027); (3) The
            In the presented study, the extracts of ZK60/xβ-TCP were   Project of Innovation-driven Plan of Central South
            utilized to mimic the environment during implantation.   University (2016CX023); (4) The Open-End Fund for
            In vitro cell culture experiments indicated that MG-63   the Valuable and Precision Instruments of Central South
            cells exhibited better growth in extracts of ZK60/8β-TCP   University; (5) The fund of the State Key Laboratory of
            than in that of ZK60. The improved cytocompatibility   Solidification Processing at NWPU (SKLSP201605);
                                         International Journal of Bioprinting (2018)–Volume 4, Issue 1         9
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