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Lu, et al.
           total scalp irradiation . In addition, Munoz et al. used   results in a slow printing speed, which will greatly limit
                             [9]
           SLA method to create a customized nose bolus composed   the  manufacturing  efficiency  of  personalized  bolus.  In
           of elastomeric materials, which showed compliant, elastic,   contrast, photocuring printing can selectively  solidify
           and water equivalent  properties .  Compared  to  the   the polymers from a liquid tank, which can perform the
                                       [84]
           rigid bolus, the soft bolus created by these two methods   patterning process and curing process at the same time.
           greatly reduces the patient discomfort and unwanted air   Especially for the DLP- and CLIP-based layer-by-layer
           gaps. It suggests that the customization of bolus is not   printing  mode, these photocuring  printing  methods
           only related with the selection of 3D printing methods,   enable  the  direct  and  rapid  construction  of  bolus.  As
           but also dependent on the properties of printed materials.  an emerging photocuring printing technology, the CAL
               Direct printing is a promising approach to rapidly   shows  a faster patterning  speed in comparison to the
           achieve the customization of bolus, but 3D printing of   DLP  method.  However,  this  technology  is  premature,
           bolus using soft polymers is still in the early stage of   costly, and the printing precision is still relatively low.
           development.  An  ideal  bolus  should  not  only  provide   Therefore, among different 3D printing techniques, the
           a close contact with the patients’ irregular  surface, but   DLP and CLIP methods based on layer photocuring are
           also  possess  excellent  properties,  such  as  flexibility,   probably the most ideal technology to print personalized
           biocompatibility, and adhesion. The 3D printing methods   bolus at present.
           determine  the  printing  speed  and  printing  accuracy  of   Up to now, the printable materials  suitable
           bolus, while the printed materials mainly influence the   for DLP-based photocuring printing  are  mainly
           performance  of  bolus.  With  the  current  3D  printing   photosensitive resins, which have the basic characteristic
           technology, the bottleneck restricting the application of   of photocurability .  Photosensitive  resins  are  a  class
                                                                              [86]
           3D  printed  bolus  is  mainly  the  deficient  development   of relatively  mature  photocurable  prepolymers  with
           of printable  polymer  materials.  The  advances  in   low molecular weights, which mainly include esterified
           materials science and 3D printing technology lead to the   acrylate  epoxy  resin,  unsaturated  polyester,  PU, and
           development of more printable polymers, which will be   polymercaptan/polyene  photocurable  resin  systems .
                                                                                                            [87]
           used for 3D printing of bolus.                      Although the photo-resins (Young modulus, ~GPa) have
                                                               been widely used in the manufacturing industry, they are
           5. Summary and outlook                              not suitable for constructing bolus by DLP-based printing

           Various materials that are able to be processed into bolus   due to their higher hardness compared to patients’ skin
           have been used in radiation therapy, but the development   tissues  (~KPa).  The  mismatching  in  hardness  between
           of customized bolus prepared by 3D printing of polymers   bolus and skin tissues will inevitably lead to the failure of
           is  still  in  its  infancy.  To  achieve  the  personalized   radiotherapy. Besides, the potential toxicity of photo-resin
           customization  of  bolus,  this  review  aims  at  providing   makes it even less likely to be used in clinic. Therefore,
           comprehensive insights into the 3D printing bolus. How   it is urgent to develop a kind of material that can not only
           to choose an appropriate  3D printing  technique  and to   be used for DLP printing, but also has an elastic modulus
           design a suitable printable polymer is an urgent issue to   equivalent to skin tissues.
           be solved in customizing bolus. We focus on three points:   Hydrogels and silicon gels have an elastic modulus
           (i)  polymer  materials  used  for  fabricating  bolus,  (ii)   close to that of human skin tissue, while most of these
           3D printing techniques suitable for processing polymer   materials cannot be directly used for photocuring printing
           materials, and (iii) personalized customization of bolus   due to a lack of photosensitive properties. To endow the
           through 3D printing technology.                     gels with photocurable ability, some photopolymerizable
               Various  3D  printing  techniques  utilizing  different   functional groups have been grafted onto the molecular
           principle  to pattern  are suitable  for  different  materials.   chain  of  the  gels.  The  modified  gels  with  both
           The choice of 3D printing methods is mainly determined   photocurable ability and bionic hardness will be a kind of
           by the  actual  requirements  of application .  A  3D   ideal materials for constructing bolus. In addition, it has
                                                 [85]
           printing technique suitable for processing bolus should   been recognized that the bolus-assisted radiotherapy can
           have the following three characteristics:  rapid printing   efficiently control the recurrence of subcutaneous tumor,
           speed (<1 h), medium printing scale (X-Y-Z three axis   but it also causes some side effects. For example, it is likely
           ≤30  cm),  and  general  printing  accuracy  (≤200  µm).   to damage the normal tissues around tumors and cause
           The  extrusion  printing  and  the  inkjet  printing  utilize  a   dermatitis in the exposed areas. More severely, inflamed
           nozzle to deliver the polymers to the designed position   areas are susceptible  to bacterial infection,  which may
           and  solidify  the  polymers  by  a  curing  process. As  for   prevent irradiated skin from healing and even aggravate
           the  nozzle-based  printing  techniques,  most  polymers   skin necrosis. Therefore, to improve the curative effect of
           can be printed as long as they have suitable rheological   radiotherapy, it is urgent and necessary to design a new-
           properties.  However,  the  point-to-point  printing  mode   type bolus with combined features, including printability,

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