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. 2021 Mar 17;10(9):2002026. doi: 10.1002/adhm.202002026

Table 2.

Overview of PGS used in 3D printing approaches. Printing techniques are separated into extrusion‐based and laser‐based methods

Printing technique Material combination Mechanical properties Cell response Special features Proposed application Ref.
Extrusion‐based commercially available 3D filament printer (Revolution XL, Quintessential Universal Building Devices) modified for syringe extrusion Photocurable PGSA combining a ratio of 10:90 of
  • Low molecular weight PGS, M n = 5.78 kDa

  • High molecular weight PGS, M n = 6.32 kDa

Depending on printing density a) :
  • Low density

E‐modulus: 310 kPa

Tensile strength: 120 kPa

Failure strain: 40%

  • Medium density

E‐modulus: 350 kPa

Tensile strength: 210 kPa

Failure strain: 67%

  • High density

E‐modulus: 480 kPa

Tensile strength: 330 kPa

Failure strain: 70%

No cytotoxic response in contact with NIH 3T3 fibroblasts, increased cell proliferation within 4 d of culture
  • Rapid fabrication of spatially complex, elastomeric scaffolds

  • Multiscale structures, supporting cell cultures, replicating native tissue shapes

Complex biocompatible, elastomeric tissue replacements

(Soft TE)

[ 231 ]
Specific functionalized photocurable Nor‐PGS with thiol–ene click chemistry Depending on thiol/norbornene ratios (N):
  • N = 0.5

E‐modulus: 110 kPa

Tensile strength: 260 kPa

Failure strain: 240%

  • N = 0.75

E‐modulus: 340 kPa

Tensile strength: 690 kPa

Failure strain: 200%

  • N = 1

E‐modulus: 400 kPa

Tensile strength: 790 kPa

Failure strain: 170%

No cytotoxic response in contact with NIH 3T3 fibroblasts, increased cell proliferation within 8 d of culture
  • Tunable mechanical properties and degradation rates

  • Fast cross‐linking (< 1 min) under UV‐light

Elastomeric, biodegradable and cytocompatible scaffolds for soft tissue applications [ 58 ]
Commercially available fused depositioning system (HTS‐400; Fochif Mechatronics Technology) Neat PGS with NaCl (NaCl‐PGS) at a ratio of PGS:NaCl = 1:2 Depending on used needle gauge (G):
  • G = 21 (Ø = 500 µm)

E‐modulus: 150.7 kPa

Tensile strength: ≈80 kPa

Failure strain: ≈40%

  • G = 23 (Ø = 300 µm)

E‐modulus: 239.4 kPa

Tensile strength: ≈90 kPa

Failure strain: ≈30%

Cytocompatible, biocompatible and biodegradable in vivo after subcutaneous and epicardial implantation in male Sprague Dawley rats

Thickening of the LV wall and attenuated LV dilatation after 28 d postimplantation of 3D‐printed PGS patches

  • Similar mechanical properties to those of native myocardium

  • Carrier material (salt) can be easily replaced by or combined with other additive materials (nanoclays, graphene, carbon nanotubes) to fabricate thermosetting composites

Used in a vapo‐mechanical sensor and soft actuator or as a myocardial patch [ 31 ]
PGS:PCL combination in a ratio of 9:1 mixed with NaCl (NaCl‐PGS/PCL) at a 1:2 weight ratio (PGS/PCL : NaCl)
  • Neat PGS

E‐modulus: 190.1 kPa

Tensile strength: 62.2 MPa

Failure strain: 28.9%

  • Neat PCL

E‐modulus: 31.5 MPa

Tensile strength: 3.3 MPa

Failure strain: 475.0%

  • PGS/PCL

E‐modulus: 748.5 kPa

Tensile strength: 302.7 kPa

Failure strain: 57.3%

Epicardial implantation in male Sprague Dawley rats showed preserved heart function, increased LV wall thickness, reduced infarct size, promoted vascularization, induced tissue repair by recruiting M2 macrophages, and inhibited myocardial apoptosis
  • 3D‐printed PGS–PCL scaffold is responsive to rolling, folding, and compression, making it suitable for minimally invasive delivery via a catheter or mini‐thoracotomy

Potential for treating multiple cardiovascular diseases (CTE) [ 37 ]
Combination of a DIW‐3D printer (HTS‐400; Fochif Mechatronics Technology) and a rotary receiver Neat PGS with NaCl (NaCl–PGS) at a ratio of PGS:NaCl = 1:2 combined with an electrospun gelatin fiber mesh post‐printing Mechanical properties after 12 weeks in vivo implantation with and without cells:
  • Without cells

E‐modulus: ≈2.40 MPa

  • With cells

E‐modulus: ≈8.00 MPa

  • Native trachea cartilage

E‐modulus: ≈11.5 MPa

Chondrocytes from auricular cartilage of New Zealand white rabbits showed excellent cell proliferation without noticeable apoptosis within 4 d of culture;

In vivo results in nude mice showed an increased DNA, GAG as well as collagen content after 12 weeks of implantation

  • Four‐axis printing system for hierarchical tubular structures

  • Controllable mesh structure, radial elasticity, good flexibility, as well as luminal patency

Potential for tracheal cartilage reconstruction [ 138 ]
Commercially available 3D‐Bioplotter Developer Series (EnvisionTec) PGS/PCL combination in a ratio of PGS:PCL = 1:1 combined with BG particles and an electrospun PGS/PCL fiber mat postprinting Depending on the amount of incorporated BG particles:
  • PGS/PCL + fiber mat

E‐modulus: 250 MPa

Maximum load: 6 N

Failure length: 1.5 mm

  • PGS/PCL/5wt%BG + fiber mat

E‐modulus: 241 MPa

Maximum load: ≈4 N

Failure length: ≈1.4 mm

  • PGS/PCL/10wt%BG + fiber mat

E‐modulus: 311 MPa

Maximum load: ≈3.5 N

Failure length: ≈0.6 mm

NIH 3T3 fibroblasts showed no cytotoxic response with an improved cell proliferation within 7 d of culture
  • Combination of 3D printing and electrospinning

  • Multiscale 3D porosity

  • Control over degradation and mechanical properties via BG incorporation

Potential for tendon and ligament TE applications [ 46 ]
Commercially available 3D‐Bioplotter Allevi 2 Photocurable PGSA with chemically sintered Zn powder in various ratios

Depending on the amount of incorporated Zn powder:

Conductivity: up to 11.8 mS m‐1

Compression modulus: up to 1179.5 kPa

E‐modulus: up to 1099.9 kPa

No cytotoxic response in contact with C2C12 myoblasts as well as in in vivo studies using Wistar rat models
  • Highly elastic as well as bendable and electrically conductive

  • Biocompatible

Bio‐integrated electronics in wearable electronics, electronic skin, robotics, implantable electronics and human–machine interfacing [ 161 ]
Laser‐based DLP‐AM system developed by the Cheng lab at the National Taiwan University of Science and Technology Photocurable PGSA with an altered degree of acrylation (30, 15, and 7%) combined with PCLDA (PGSA: PCLDA = 2:1) or PEGDA (PGSA: PEGDA = 1:1) Depending on the degree of acrylation and mixing ratio:
  • PGSA7

E‐modulus: 0.12 MPa

Tensile strength: 0.10 MPa

Failure strain: 121.23%

  • PGSA15

E‐modulus: 1.55 MPa

Tensile strength: 0.63 MPa

Failure strain: 46.95%

  • PGSA30

E‐modulus: 5.10 MPa

Tensile strength: 1.36 MPa

Failure strain: 28.43%

  • PEDGA

E‐modulus: 18.98 MPa

Tensile strength: 3.19 MPa

Failure strain: 21.50%

  • PGSA7‐PEGDA

E‐modulus: 4.25 MPa

Tensile strength: 0.80 MPa

Failure strain: 21.29%

  • PGSA15‐PEGDA

E‐modulus: 7.58 MPa

Tensile strength: 0.91 MPa

Failure strain: 13.63%

  • PGSA30–PEGDA

E‐modulus: 10.54 MPa

Tensile strength: 1.10 MPa

Failure strain: 12.96%

Not conducted in this study
  • Printing of polymers with similar composition, but quite different mechanical and degradation properties, in a continuous motion via the instantaneous blending of the polymers at various ratios

Potential for multiple TE applications [ 62 ]
  • PCLDA

E‐modulus: 4.35 MPa

Tensile strength: 0.58 MPa

Failure strain: 15.34%

  • PGSA7‐PCLDA

E‐modulus: 1.42 MPa

Tensile strength: 0.19 MPa

Failure strain: 22.39%

  • PGSA15‐PCLDA

E‐modulus: 2.85 MPa

Tensile strength: 0.20 MPa

Failure strain: 11.28%

  • PGSA30‐PCLDA

E‐modulus: 7.00 MPa

Tensile strength: 0.69 MPa

Failure strain: 14.08%

Femtosecond DLW using 2PP with a PHAROS femtosecond Yb:KGW laser (Light Conversion Ltd) Photocurable mAcr‐PGS of
  • Low molecular weight PGS, M w = 5,420 g mol‐1

  • High molecular weight PGS, M w = 17,340 g mol‐1

Depending on the degree of methacrylation (N) and molecular weight:
  • N = 30%

Low M w

E‐modulus: ≈0.50 MPa

Tensile strength: ≈0.80 MPa

High M w

E‐modulus: ≈0.90 MPa

Tensile strength: ≈0.60 MPa

  • N = 50%

Low M w

E‐modulus: ≈1.50 MPa

Tensile strength: ≈0.90 MPa

High M w

E‐modulus: ≈1.50 MPa

Tensile strength: ≈0.90 MPa

  • N = 80%

Low M w

E‐modulus: ≈6.80 MPa

Tensile strength: ≈3.80 MPa

Cytocompatible with human dermal fibroblasts, human adipose‐derived stem cells (ADSCs) and human coronary artery SMCs, enhanced cell proliferation during the 7 and 14 d of culture, respectively
  • Minimum feature sizes of ≈10 µm

  • Tunable physical properties and compatible with diverse cell types

Potential for multiple TE applications both in vitro and in vivo [ 165 ]
In house designed micro SLA set‐up

Photocurable mAcr‐PGS with altered degree of methacrylation

(N = 0.22–1.00)

Mechanical compression testing of a produced NGC (N = 0.75b):

Max compression: 0.57 mm

Compression at break: 11.4%

Stiffness: 3.2 MPa

Suture retention strength: 12.3 MPa

Neuronal NG108‐15 cells as well as primary SCs from male Wistar rats showed improved neuronal and glial cell growth in vitro

  • High conduit flexibility, resistance to kinking and ability to withstand suturing

  • Intricate micro‐and macroscopic structure

Potential for nerve conduit guidance (nerve TE) [ 162 ]

In vivo: an increased regeneration of axons, oriented axonal growth without an increase of neuropathic pain in comparison to native nerve grafts

DLP‐based 3D printing using a DMD chip (Texas Instruments) Photocurable PGSA combined with altered amounts of PEDGA (1%, 5% and 10%) Depending on light exposure time (in s) and printed structure (single or double network):
  • Single network 30s

E‐modulus: 11.91 kPa

Tensile strength: 5.92 kPa

Tensile strain: 62.58%

  • Single network 60s

E‐modulus: 47.66 kPa

Tensile strength: 14.11 kPa

Tensile strain: 43.31%

  • Double network

E‐modulus: 32.09 kPa

Tensile strength: 15.08 kPa

Tensile strain: 64.18%

HUVECs showed excellent viability (>90%) within 7 d of culture
  • Enhanced toughness by introducing soft sacrificial beams to absorb the energy during tensile testing while the hard segments maintained the overall shape of the structure

Specifically optimizable for different biomedical applications (soft TE) [ 166 ]
DLP‐based 3D printing using an Ember desktop 3D printer (Autodesk) with a built‐in light‐emitting diode projector Photocurable PGSA with different degrees of acrylation mixed with 1wt% dipehyl (2,4,6‐trimethylbenzoyl) phosphine oxide photoinitiator Mechanical tensile testing on films:
  • Degree of acrylation 16.7%

E‐modulus: 192.3 kPa

Tensile strength: 460.2 kPa

Tensile strain: 239%

  • Degree of acrylation 35.2%

E‐modulus: 859.0 kPa

Tensile strength: 326.8 kPa

Tensile strain: 39%

  • Degree of acrylation 35.2%

E‐modulus: 3668.7 kPa

Tensile strength: 919.1 kPa

Tensile strain: 26%

  • After 4 min UV cross‐linking

E‐modulus: 226.8 kPa

Tensile strength: 556.9 kPa

Tensile strain: 244%

  • After 24 h thermal cross‐linking

E‐modulus: 3097.6 kPa

Tensile strength: 1273.3 kPa

Tensile Strain: 42%

Not conducted in this study
  • Elastomeric properties and limited swelling

  • Thermal postprocessing provided predictable control of mechanical properties and degradation behavior

Potential for multiple TE applications [ 167 ]
a)

Printing density referred to as the amount of interior volume designated to be occupied by material (fill density setting, in Slic3r), including 30% for low density, 45% for medium density, and 60% for high density; b)NGC = nerve guidance conduit, Hounslow mechanical analysis was conducted along the axial direction of the NGC.