DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Radical free crosslinking of direct-write 3D printed hydrogels through a base catalyzed thiol-Michael reaction


3D printed micelle-based hydrogels were mechanically stabilized and crosslinked through the base catalyzed thiol-Michael addition in PBS buffer, without the use of potentially cytotoxic radical chemistry.

ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, The University of Texas at Dallas, Richardson, USA
Publication Date:
Sponsoring Org.:
OSTI Identifier:
Grant/Contract Number:  
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Polymer Chemistry
Additional Journal Information:
Journal Name: Polymer Chemistry Journal Volume: 10 Journal Issue: 44; Journal ID: ISSN 1759-9954
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom

Citation Formats

Berry, Danielle R., Díaz, Brisa K., Durand-Silva, Alejandra, and Smaldone, Ronald A. Radical free crosslinking of direct-write 3D printed hydrogels through a base catalyzed thiol-Michael reaction. United Kingdom: N. p., 2019. Web. doi:10.1039/C9PY00953A.
Berry, Danielle R., Díaz, Brisa K., Durand-Silva, Alejandra, & Smaldone, Ronald A. Radical free crosslinking of direct-write 3D printed hydrogels through a base catalyzed thiol-Michael reaction. United Kingdom.
Berry, Danielle R., Díaz, Brisa K., Durand-Silva, Alejandra, and Smaldone, Ronald A. Tue . "Radical free crosslinking of direct-write 3D printed hydrogels through a base catalyzed thiol-Michael reaction". United Kingdom.
title = {Radical free crosslinking of direct-write 3D printed hydrogels through a base catalyzed thiol-Michael reaction},
author = {Berry, Danielle R. and Díaz, Brisa K. and Durand-Silva, Alejandra and Smaldone, Ronald A.},
abstractNote = {3D printed micelle-based hydrogels were mechanically stabilized and crosslinked through the base catalyzed thiol-Michael addition in PBS buffer, without the use of potentially cytotoxic radical chemistry.},
doi = {10.1039/C9PY00953A},
journal = {Polymer Chemistry},
number = 44,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {11}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

A tough double network hydrogel for cartilage tissue engineering
journal, January 2013

  • Fan, Changjiang; Liao, Liqiong; Zhang, Chao
  • Journal of Materials Chemistry B, Vol. 1, Issue 34
  • DOI: 10.1039/c3tb20600a

Ultrastiff, Thermoresponsive Nanocomposite Hydrogels Composed of Ternary Polymer–Clay–Silica Networks
journal, January 2018

Hydrogels as controlled release devices in agriculture
journal, January 2002

From topological gels to slide-ring materials: Review
journal, February 2014

  • Noda, Yumiki; Hayashi, Yuki; Ito, Kohzo
  • Journal of Applied Polymer Science, Vol. 131, Issue 15
  • DOI: 10.1002/app.40509

3D Printing of Living Responsive Materials and Devices
journal, December 2017

High-Strength, Tough, Fatigue Resistant, and Self-Healing Hydrogel Based on Dual Physically Cross-Linked Network
journal, August 2016

  • Gong, Zhengyu; Zhang, Guoping; Zeng, Xiaoliang
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 36
  • DOI: 10.1021/acsami.6b05627

Hydrogels for tissue engineering: scaffold design variables and applications
journal, November 2003

Shape Memory Hydrogels via Micellar Copolymerization of Acrylic Acid and n -Octadecyl Acrylate in Aqueous Media
journal, April 2013

Study of Salt Effects on the Micellization of PEO−PPO−PEO Block Copolymer in Aqueous Solution by FTIR Spectroscopy
journal, February 2002

  • Su, Yan-lei; Liu, Hui-zhou; Wang, Jing
  • Langmuir, Vol. 18, Issue 3
  • DOI: 10.1021/la0106687

Photopolymerizable Resins for 3D-Printing Solid-Cured Tissue Engineered Implants
journal, May 2019

Reactive macromolecular micelle crosslinked highly elastic hydrogel with water-triggered shape-memory behaviour
journal, January 2014

  • Zhao, Tingting; Tan, Mei; Cui, Yulin
  • Polymer Chemistry, Vol. 5, Issue 17
  • DOI: 10.1039/C4PY00554F

Double-Network Hydrogels with Extremely High Mechanical Strength
journal, July 2003

Variable cytocompatibility of six cell lines with photoinitiators used for polymerizing hydrogels and cell encapsulation
journal, April 2005

Synthesis, properties, and biomedical applications of gelatin methacryloyl (GelMA) hydrogels
journal, December 2015

Hydrogels for Engineering of Perfusable Vascular Networks
journal, July 2015

  • Liu, Juan; Zheng, Huaiyuan; Poh, Patrina
  • International Journal of Molecular Sciences, Vol. 16, Issue 7
  • DOI: 10.3390/ijms160715997

Omnidirectional Printing of 3D Microvascular Networks
journal, March 2011

  • Wu, Willie; DeConinck, Adam; Lewis, Jennifer A.
  • Advanced Materials, Vol. 23, Issue 24
  • DOI: 10.1002/adma.201004625

Semicrystalline physical hydrogels with shape-memory and self-healing properties
journal, January 2019

Chemical modification and printability of shear-thinning hydrogel inks for direct-write 3D printing
journal, September 2018

Chemical and pH sensors based on the swelling behavior of hydrogels
journal, November 2005

  • Gerlach, Gerald; Guenther, Margarita; Sorber, Joerg
  • Sensors and Actuators B: Chemical, Vol. 111-112
  • DOI: 10.1016/j.snb.2005.03.040

One-Pot “Click” Fabrication of Slide-Ring Gels
journal, October 2015

Novel entropic elasticity of polymeric materials: why is slide-ring gel so soft?
journal, September 2011

A review on the construction of hydrogel scaffolds by various chemically techniques for tissue engineering
journal, August 2019

Salt effects on the diffusion and release rate of propranolol from poloxamer 407 gels
journal, June 1998

Ring Shuttling Controls Macroscopic Motion in a Three-Dimensional Printed Polyrotaxane Monolith
journal, March 2017

  • Lin, Qianming; Hou, Xisen; Ke, Chenfeng
  • Angewandte Chemie International Edition, Vol. 56, Issue 16
  • DOI: 10.1002/anie.201612440

All-in-One Cellulose Nanocrystals for 3D Printing of Nanocomposite Hydrogels
journal, January 2018

  • Wang, Jieping; Chiappone, Annalisa; Roppolo, Ignazio
  • Angewandte Chemie International Edition, Vol. 57, Issue 9
  • DOI: 10.1002/anie.201710951

Photopolymerization of cell-encapsulating hydrogels: Crosslinking efficiency versus cytotoxicity
journal, May 2012

Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics
journal, August 2015

  • Grindy, Scott C.; Learsch, Robert; Mozhdehi, Davoud
  • Nature Materials, Vol. 14, Issue 12
  • DOI: 10.1038/nmat4401

Extremely Stretchable Strain Sensors Based on Conductive Self-Healing Dynamic Cross-Links Hydrogels for Human-Motion Detection
journal, September 2016

Direct ink writing with high-strength and swelling-resistant biocompatible physically crosslinked hydrogels
journal, January 2019

  • Jiang, Pan; Yan, Changyou; Guo, Yuxiong
  • Biomaterials Science, Vol. 7, Issue 5
  • DOI: 10.1039/C9BM00081J

Hydrogels for tissue engineering and regenerative medicine
journal, January 2014

  • Hunt, John A.; Chen, Rui; van Veen, Theun
  • J. Mater. Chem. B, Vol. 2, Issue 33
  • DOI: 10.1039/C4TB00775A

Enzyme-mediated cross-linking of Pluronic copolymer micelles for injectable and in situ forming hydrogels
journal, April 2011

Artificial skin I. Preparation and properties of pluronic F-127 gels for treatment of burns
journal, November 1972

  • Schmolka, Irving R.
  • Journal of Biomedical Materials Research, Vol. 6, Issue 6
  • DOI: 10.1002/jbm.820060609

Modern Strategies To Achieve Tissue-Mimetic, Mechanically Robust Hydrogels
journal, May 2019

Direct 3D Printing of Shear-Thinning Hydrogels into Self-Healing Hydrogels
journal, July 2015

  • Highley, Christopher B.; Rodell, Christopher B.; Burdick, Jason A.
  • Advanced Materials, Vol. 27, Issue 34
  • DOI: 10.1002/adma.201501234

Super tough bilayer actuators based on multi-responsive hydrogels crosslinked by functional triblock copolymer micelle macro-crosslinkers
journal, January 2019

  • Sun, Peng; Zhang, Hua; Xu, Dan
  • Journal of Materials Chemistry B, Vol. 7, Issue 16
  • DOI: 10.1039/C9TB00249A

Mussel-Inspired Histidine-Based Transient Network Metal Coordination Hydrogels
journal, January 2013

  • Fullenkamp, Dominic E.; He, Lihong; Barrett, Devin G.
  • Macromolecules, Vol. 46, Issue 3
  • DOI: 10.1021/ma301791n

Effects of neighboring sulfides and pH on ester hydrolysis in thiol–acrylate photopolymers
journal, July 2007

25th Anniversary Article: Rational Design and Applications of Hydrogels in Regenerative Medicine
journal, November 2013

  • Annabi, Nasim; Tamayol, Ali; Uquillas, Jorge Alfredo
  • Advanced Materials, Vol. 26, Issue 1
  • DOI: 10.1002/adma.201303233

Cytocompatibility studies of an in situ photopolymerized thermoresponsive hydrogel nanoparticle system using human aortic smooth muscle cells
journal, October 2009

  • Sabnis, Abhimanyu; Rahimi, Maham; Chapman, Christopher
  • Journal of Biomedical Materials Research Part A, Vol. 91A, Issue 1
  • DOI: 10.1002/jbm.a.32194

Stimuli-Responsive Supramolecular Hydrogels and Their Applications in Regenerative Medicine
journal, October 2018

  • Hoque, Jiaul; Sangaj, Nivedita; Varghese, Shyni
  • Macromolecular Bioscience, Vol. 19, Issue 1
  • DOI: 10.1002/mabi.201800259

A biopolymer‐based 3D printable hydrogel for toxic metal adsorption from water
journal, March 2019

  • Appuhamillage, Gayan A.; Berry, Danielle R.; Benjamin, Candace E.
  • Polymer International, Vol. 68, Issue 5
  • DOI: 10.1002/pi.5787

Stimuli-Responsive Conductive Nanocomposite Hydrogels with High Stretchability, Self-Healing, Adhesiveness, and 3D Printability for Human Motion Sensing
journal, January 2019

  • Deng, Zexing; Hu, Tianli; Lei, Qi
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 7
  • DOI: 10.1021/acsami.8b20178

Skin‐Inspired Antibacterial Conductive Hydrogels for Epidermal Sensors and Diabetic Foot Wound Dressings
journal, April 2019

  • Zhao, Yue; Li, Zuhao; Song, Shanliang
  • Advanced Functional Materials, Vol. 29, Issue 31
  • DOI: 10.1002/adfm.201901474

The Thiol-Michael Addition Click Reaction: A Powerful and Widely Used Tool in Materials Chemistry
journal, September 2013

  • Nair, Devatha P.; Podgórski, Maciej; Chatani, Shunsuke
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm402180t

Hierarchical Co-Assembly Enhanced Direct Ink Writing
journal, March 2018

  • Li, Longyu; Zhang, Pengfei; Zhang, Zhiyun
  • Angewandte Chemie International Edition, Vol. 57, Issue 18
  • DOI: 10.1002/anie.201800593

Biofunctional rapid prototyping for tissue-engineering applications: 3D bioplotting versus 3D printing: Biofunctional Rapid Prototyping
journal, December 2003

  • Pfister, Andreas; Landers, Rüdiger; Laib, Andres
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 42, Issue 3
  • DOI: 10.1002/pola.10807

Hydrogel: Preparation, characterization, and applications: A review
journal, March 2015

Additive Manufacturing of Catalytically Active Living Materials
journal, April 2018

  • Saha, Abhijit; Johnston, Trevor G.; Shafranek, Ryan T.
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 16
  • DOI: 10.1021/acsami.8b02719

3D Printing of Shear-Thinning Hyaluronic Acid Hydrogels with Secondary Cross-Linking
journal, May 2016

  • Ouyang, Liliang; Highley, Christopher B.; Rodell, Christopher B.
  • ACS Biomaterials Science & Engineering, Vol. 2, Issue 10
  • DOI: 10.1021/acsbiomaterials.6b00158