pH-triggered shape response of cubical ultrathin hydrogel capsules
Abstract
We report on two types of poly(methacrylic acid) (PMAA)-based hydrogel microcontainers (capsules) of cubical shape with distinctly different shape responses upon pH variations. The microcontainers were prepared as replicas of cubical inorganic templates through chemical cross-linking of hydrogen-bonded layer-by-layer (LbL) films. The two types of hollow hydrogels, a single-component (PMAA) and PMAA–poly(N-vinylpyrrolidone) (PMAA–PVPON), showed drastic differences in their shape response to pH variations. Cubical (PMAA)20 capsules turned into bulged sphere-like structures of the same size when transitioned from pH 3 to pH 8. In contrast, cubical (PMAA–PVPON)5 capsules retained their cubical shape at pH 3 while increasing in size at pH 8. The pH-triggered size change of cubical capsules was completely reversible. The difference in pH-triggered shape responses was rationalized through the difference in hydrogel rigidity expressed as the ratio of the polymer contour length between the neighboring cross-links to the persistence polymer length. The ratios of 22.7 and 2 for (PMAA) and (PMAA–PVPON) systems, respectively, suggested that the dual-component system is more rigid and therefore expands uniformly in all directions. We believe that the results provide new prospects for developing polymeric materials with predictable shape and size-changing properties for controlled drug delivery, cellular uptake, and pH-regulating transport behavior in microfluidic devices.
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Samples with higher carboxyl group density (1aNFC-2AP and 1aNFC-4AP) might have undergone incomplete protonation, leaving more unprotonated COO− groups and resulting in stronger antisymmetric stretching at 1600 cm−1.
“In contrast, samples with higher carboxyl groups density (e.g., 1aNFC-2AP and 1aNFC-4AP) might underwent incomplete protonation, leaving more unprotonated COO− groups and resulting in stronger antisymmetric stretching at 1600 cm−1 [39].”
From Amidated Pectin/Nanocellulose Hybrid Cryogel System with a pH-Responsive Release Profile for Small Intestinal Delivery (2025) · cites this paper as [39]
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Reversible shape-shifting in polymeric materials
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“In contrast, samples with higher carboxyl groups density (e.g., 1aNFC-2AP and 1aNFC-4AP) might underwent incomplete protonation, leaving more unprotonated COO − groups and resulting in stronger antisymmetric stretching at 1600 cm − 1 [39].”
- Authors
- Kozlovskaya, V., Wang, Y., Higgins, W., Chen, J., Chen, Y., & Kharlampieva, E.
- Affiliations
- University of Alabama at Birmingham (US)
- Corresponding author
- Kharlampieva, Eugenia
- Venue
- Soft Matter
- Publisher
- Royal Society of Chemistry (RSC)
- Published
- 2012
- Volume
- 8
- Issue
- 38
- Pages
- 9828
- ISSN
- 1744-683X (ISSN-L)
- 1744-6848
- OpenAlex
- W2018172263
- Cited by
- 53
- References
- 68
- Citations by year
- 2025: 1 · 2024: 3 · 2023: 2 · 2022: 2 · 2021: 5 · 2020: 2 · 2018: 7 · 2017: 1 · 2016: 6 · 2015: 8 · 2014: 8 · 2013: 7 · 2012: 1
- FWCI
- 3.52
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Soft Matter (publishedVersion)
- Funders
- National Institute of Biomedical Imaging and Bioengineering
- Topics
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Medicine › Hydrogels: synthesis, properties, applications
- Physical Sciences › Engineering › Mechanical Engineering › Advanced Materials and Mechanics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- pH-responsive hydrogels, poly(methacrylic acid), poly(N-vinylpyrrolidone), layer-by-layer films, persistence length, reversible swelling, drug delivery, microfluidics
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