Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect
ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Probing the Internal Morphology of Injectable Poly(oligoethylene glycol methacrylate) Hydrogels by Light and Small-Angle Neutron Scattering

View Author Information
Department of Chemical Engineering and Department of Physics and Astronomy, McMaster University, 1280 Main Street West, Hamilton, Ontario, Canada L8S 4L8
*E-mail [email protected] (T.H.).
Cite this: Macromolecules 2014, 47, 17, 6017–6027
Publication Date (Web):August 20, 2014
https://doi.org/10.1021/ma5011827
Copyright © 2014 American Chemical Society

    Article Views

    1034

    Altmetric

    -

    Citations

    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    While injectable, in situ gelling hydrogels have attracted increasing attention in the biomedical literature due to their minimally invasive administration potential, little is known about the internal morphology of these hydrogels and thus how to engineer precursor polymer compositions to achieve desired hydrogel properties. In this paper, the internal morphology of injectable in situ gelling hydrogels based on hydrazide and aldehyde-functionalized poly(oligoethylene glycol methacrylate) precursors with varying lower critical solution temperatures (LCSTs) is investigated using a combination of spectrophotometry, small-angle neutron scattering, and light scattering. If two precursor polymers with similar LCSTs are used to prepare the hydrogel, relatively homogeneous hydrogels are produced (analogous to conventional step-growth polymerized hydrogels); this result is observed provided that gelation is sufficiently slow for diffusional mixing to compensate for any incomplete mechanical mixing in the double-barrel syringe and the volume phase transition temperature (VPTT) of the hydrogel is sufficiently high that phase separation does not occur on the time scale of gelation. Hydrogels prepared from precursor polymers with different LCSTs (1 polymer/barrel) also retain transparency, although their internal morphology is significantly less homogeneous. However, if functionalized polymers with different LCSTs are mixed in each barrel (i.e., 2 polymers/barrel, such that a gelling pair of precursors with both low and high LCSTs is present), opaque hydrogels are produced that contain significant inhomogeneities that are enhanced as the temperature is increased; this suggests phase separation of the hydrogel into lower and higher LCST domains. Based on this work, the internal morphology of injectable hydrogels can be tuned by engineering the gelation time and the physical properties (i.e., miscibility) of the precursor polymers, insight that can be applied to improve the design of such hydrogels for biomedical applications.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    UV–vis gelation experiments and curve-fitted data for all measured SANS profiles. This material is available free of charge via the Internet at http://pubs.acs.org.

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article is cited by 16 publications.

    1. Trevor Gilbert, Matthew A. Campea, Nahieli Preciado Rivera, Michael Majcher, Richard Alsop, Mouhanad Babi, Thomas Kalab, Jose Moran-Mirabal, Maikel Rheinstadter, Todd Hoare. Injectable Poly(N-isopropylacrylamide)/Poly(vinylpyrrolidone) Interpenetrating Network Hydrogels Formed via Hydrazone/Disulfide Cross-Linking. Macromolecules 2023, 56 (17) , 6679-6691. https://doi.org/10.1021/acs.macromol.3c00045
    2. Michael J. Majcher, Sebastian Himbert, Francesco Vito, Matthew A. Campea, Ridhdhi Dave, Grethe Vetergaard Jensen, Maikel C. Rheinstadter, Niels M. B. Smeets, Todd Hoare. Investigating the Kinetics and Structure of Network Formation in Ultraviolet-Photopolymerizable Starch Nanogel Network Hydrogels via Very Small-Angle Neutron Scattering and Small-Amplitude Oscillatory Shear Rheology. Macromolecules 2022, 55 (16) , 7303-7317. https://doi.org/10.1021/acs.macromol.2c00874
    3. Fei Xu, Angus Lam, Zhicheng Pan, Gurpreet Randhawa, Makenzie Lamb, Heather Sheardown, Todd Hoare. Fast Thermoresponsive Poly(oligoethylene glycol methacrylate) (POEGMA)-Based Nanostructured Hydrogels for Reversible Tuning of Cell Interactions. ACS Biomaterials Science & Engineering 2021, 7 (9) , 4258-4268. https://doi.org/10.1021/acsbiomaterials.0c01552
    4. Milana Pikula, M. Monsur Ali, Carlos Filipe, Todd Hoare. Single-Step Printable Hydrogel Microarray Integrating Long-Chain DNA for the Discriminative and Size-Specific Sensing of Nucleic Acids. ACS Applied Materials & Interfaces 2021, 13 (2) , 2360-2370. https://doi.org/10.1021/acsami.0c21061
    5. Kevin J. De France, Maryam Badv, Jonathan Dorogin, Emily Siebers, Vishrut Panchal, Mouhanad Babi, Jose Moran-Mirabal, Michael Lawlor, Emily D. Cranston, Todd Hoare. Tissue Response and Biodistribution of Injectable Cellulose Nanocrystal Composite Hydrogels. ACS Biomaterials Science & Engineering 2019, 5 (5) , 2235-2246. https://doi.org/10.1021/acsbiomaterials.9b00522
    6. Eva Mueller, Richard J. Alsop, Andrea Scotti, Markus Bleuel, Maikel C. Rheinstädter, Walter Richtering, and Todd Hoare . Dynamically Cross-Linked Self-Assembled Thermoresponsive Microgels with Homogeneous Internal Structures. Langmuir 2018, 34 (4) , 1601-1612. https://doi.org/10.1021/acs.langmuir.7b03664
    7. Kevin J. De France, Kevin G. Yager, Katelyn J. W. Chan, Brandon Corbett, Emily D. Cranston, and Todd Hoare . Injectable Anisotropic Nanocomposite Hydrogels Direct in Situ Growth and Alignment of Myotubes. Nano Letters 2017, 17 (10) , 6487-6495. https://doi.org/10.1021/acs.nanolett.7b03600
    8. Emilia Bakaic, Niels M. B. Smeets, Owen Barrigar, Richard Alsop, Maikel C. Rheinstädter, and Todd Hoare . pH-Ionizable in Situ Gelling Poly(oligo ethylene glycol methacrylate)-Based Hydrogels: The Role of Internal Network Structures in Controlling Macroscopic Properties. Macromolecules 2017, 50 (19) , 7687-7698. https://doi.org/10.1021/acs.macromol.7b01505
    9. Kevin J. De France, Katelyn J. W. Chan, Emily D. Cranston, and Todd Hoare . Enhanced Mechanical Properties in Cellulose Nanocrystal–Poly(oligoethylene glycol methacrylate) Injectable Nanocomposite Hydrogels through Control of Physical and Chemical Cross-Linking. Biomacromolecules 2016, 17 (2) , 649-660. https://doi.org/10.1021/acs.biomac.5b01598
    10. Yosuke Hisamatsu, Go Toriyama, Katsuhiro Yamamoto, Hiroshi Takase, Tsunehiko Higuchi, Naoki Umezawa. Temperature Control of the Self‐Assembly Process of 4‐Aminoquinoline Amphiphile: Selective Construction of Perforated Vesicles and Nanofibers, and Structural Restoration Capability. Chemistry – A European Journal 2024, 5 https://doi.org/10.1002/chem.202400134
    11. Hui Yang, Charles‐André Fustin. Design and Applications of Dynamic Hydrogels Based on Reversible C═N Bonds. Macromolecular Chemistry and Physics 2023, 224 (20) https://doi.org/10.1002/macp.202300211
    12. Fei Xu, Chloe Dawson, Makenzie Lamb, Eva Mueller, Evan Stefanek, Mohsen Akbari, Todd Hoare. Hydrogels for Tissue Engineering: Addressing Key Design Needs Toward Clinical Translation. Frontiers in Bioengineering and Biotechnology 2022, 10 https://doi.org/10.3389/fbioe.2022.849831
    13. Rabia Mateen, M. Monsur Ali, Todd Hoare. A printable hydrogel microarray for drug screening avoids false positives associated with promiscuous aggregating inhibitors. Nature Communications 2018, 9 (1) https://doi.org/10.1038/s41467-018-02956-z
    14. Emilia Bakaic, Niels M. B. Smeets, Todd Hoare. Injectable hydrogels based on poly(ethylene glycol) and derivatives as functional biomaterials. RSC Advances 2015, 5 (45) , 35469-35486. https://doi.org/10.1039/C4RA13581D
    15. Wenbo Sheng, Shuanhong Ma, Wei Li, Zhiqing Liu, Xuhong Guo, Xin Jia. A facile route to fabricate a biodegradable hydrogel for controlled pesticide release. RSC Advances 2015, 5 (18) , 13867-13870. https://doi.org/10.1039/C4RA15139A
    16. Emilia Bakaic, Niels M. B. Smeets, Helen Dorrington, Todd Hoare. “Off-the-shelf” thermoresponsive hydrogel design: tuning hydrogel properties by mixing precursor polymers with different lower-critical solution temperatures. RSC Advances 2015, 5 (42) , 33364-33376. https://doi.org/10.1039/C5RA00920K