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Qian, et al.
               Mesoporous silica (MS) particles have been widely   ethanol, and dried at 80°C for 12 h. Finally, the powders
           used in biomedicine, diagnostics, and tissue repair fields   were heated at 500°C for 2 h.
           due to their good biocompatibility, adjustable morphology,
           controllable particle size, and mesoporous structure [14-16] .   2.2 Physicochemical characterization of Zn-MS
           Particularly, MS is also a good vehicle for loading and   Zn-MS particles  were  observed  by  a  transmission
           sustained release of active constituents or functional drugs   electron  microscopy  (TEM,  JEOL,  2100F,  Japan).  The
           through mesopores . Meanwhile, MS possesses stable   microstructure of Zn-MS was analyzed using a scanning
                           [17]
           Si-O-Si  network  structure,  which  gives  the  flexibility   electron microscope (SEM, EVO18, ZEISS, Germany).
           for doping metal element into MS framework by partial   The phases of Zn-MS were determined using an X-ray
           substituting Si sites and forming Si-O-M bond (M=Ca,   diffractometry  (XRD,  DY2472, Malvern PANalytical,
           Mg, and Zn) . The Si-O-Zn bond is more stable than the   Netherlands).  The nitrogen adsorption desorption
                     [18]
           Zn-O-Zn bond of ZnO, thus guaranteeing the sustained   isotherm of Zn-MS was recording using a surface area
           release of Zn ion and its long-term stability.      and porosity analyzer (ASAP2460, Micromeritics, USA).
               Ideal  artificial  bones  not  only  require  excellent   The chemical  compositions of Zn-MS were measured
           osteogenic  activity  but  also  need  to  possess three-  using  an  X-ray  photoelectron  spectrometer  (XPS,
           dimensional  (3D) interconnected  pore  structures  for   Thermo, USA).
           ingrowth of new bone and blood vessel [19-21] . 3D printing
           technology  is  a  layer-by-layer  manufacturing  process   2.3 Preparation of Zn-MS/PLLA composite
           based on computer model, which can prepare scaffolds   scaffolds
           with sophisticated shape and internal structure . More
                                                   [22]
           encouragingly, bioprinting  is able  to print personalized   As for the preparation of mixed powders, Zn-MS powders
           live  tissues/organs and is expected  to achieve  the   were mixed with PLLA powders by manual grinding for
           substitute  of  patient-specific  tissues/organs.  Selective   1 h, and then the mixed powders were added in anhydrous
           laser sintering (SLS), as one of the 3D printing techniques,   ethanol  and  were  agitated  for 4  h  under  ultrasound
           involves powder bed laser fusion additive manufacturing   condition.  After  vacuum  filtration  and  dry,  the  mixed
           processes [23,24] . SLS exhibits  great  advantages  in the   powders were collected for laser forming. Zn-MS/PLLA
           preparation of artificial bones, because there is no need   composite scaffolds were prepared by self-developed SLS
           for support materials, binders, or organic solvents during   system. Specifically, the mixed powders were uniformly
           laser forming [25,26] . Meanwhile, it possesses high printing   spread  on the  platform,  and  the  laser  beam  selectively
           accuracy and material utilization rate.             melts powders according to the designed pattern. After
               In the  present  study, Zn-MS particles  were   finishing one layer, the platform moved down based on
           synthesized through one-pot hydrothermal method, and   the designed layer thickness, and then the powders were
           then incorporated into the PLLA scaffold fabricated by   spread on the platform again before melting  by laser
           SLS technology to improve  its osteogenic  activities.   beam; finally, the scaffolds were prepared after layer-by-
           The morphology, size, mesoporous  structure, and    layer melting. During the process of laser forming, the
           compositions  of  the  synthesized  Zn-MS particles  were   laser power, scanning speed, spot diameter, scanning
           analyzed.  Meanwhile, the effect of Zn-MS on the    line space, powder bed temperature, and powder layer
           hydrophilicity, mechanical  properties,  ionic  release,   thickness were set to 2.4 W, 200 mm/s, 580 μm, 0.8 mm,
           and  cellular  behaviors  of the  PLLA scaffold  was   20°C, and 0.2 mm, respectively. The composite scaffolds
           systematically evaluated.                           prepared with 2 wt.%, 4 wt.%, and 6 wt.% Zn-MS (with
                                                               respect to total weight of Zn-MS  and PLLA powders)
           2 Materials and methods                             were abbreviated as 2Zn-MS/PLLA, 4Zn-MS/PLLA, and
                                                               6Zn-MS/PLLA.
           2.1 Preparation of Zn-MS
                                                               2.4 Characterization of Zn-MS/PLLA composite
           In a typical method, 0.55 g of Zn(CH COO)  (Aladdin,   scaffolds
                                           3
                                                 2
           China) and 10 g of N,N-dimethylethanolamine (DMEA,
           Aladdin, China) were dissolved in 5 mL of ultrapure   The photos of Zn-MS/PLLA composite  scaffolds were
           water.  Then, 3.32 g of tetraethyl  orthosilicate  (TEOS,   took by a digital  camera.  The tensile  fracture  surfaces
           Aladdin,  China)  was added.  After  reacting  under  an   of the composite scaffolds were observed by SEM
           ultrasonic condition at 50°C for 10 min, the gels were then   equipped with an energy dispersive spectrometer (EDS).
           moved to Teflon vessels which were placed in stainless   The hydrophilic  property of the composite  scaffolds
           steel autoclaves, and then hydrothermally reacted in an   was measured  using  a  surface  contact  angle  analyzer
           oven at 160°C for 24 h. Afterward, the white precipitates   (DSA100, KRUSS, Germany).  The compressive
           were washed 3 times with ultrapure water and twice with   strengths and stress-strain curves of the composite

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