Abstract Polyacrylamide hydrogels are widely used in biomedical applications due to their tunable mechanical properties and charge neutrality. Our recent tribological investigations of polyacrylamide gels have revealed tunable and pH-dependent friction behavior. To determine the origins of this pH-responsiveness, we prepared polyacrylamide hydrogels with two different initiating chemistries: a reduction–oxidation (redox)-initiated system using ammonium persulfate (APS) andN,N,N′N′-tetramethylethylenediamine (TEMED) and a UV-initiated system with 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959). Hydrogel swelling, mechanical properties, and tribological behavior were investigated in response to solution pH (ranging from ≈ 0.34 to 13.5). For polyacrylamide hydrogels in sliding contact with glass hemispherical probes, friction coefficients decreased fromµ = 0.07 ± 0.02 toµ = 0.002 ± 0.002 (redox-initiated) and fromµ = 0.05 ± 0.03 toµ = 0.003 ± 0.003 (UV-initiated) with increasing solution pH. With hemispherical polytetrafluoroethylene (PTFE) probes, friction coefficients of redox-initiated hydrogels similarly decreased fromµ = 0.06 ± 0.01 toµ = 0.002 ± 0.001 with increasing pH. Raman spectroscopy measurements demonstrated hydrolysis and the conversion of amide groups to carboxylic acid in basic conditions. We therefore propose that the mechanism for pH-responsive friction in polyacrylamide hydrogels may be credited to hydrolysis-driven swelling through the conversion of side chain amide groups into carboxylic groups and/or crosslinker degradation. Our results could assist in the rational design of hydrogel-based tribological pairs for biomedical applications from acidic to alkaline conditions. Graphical abstract
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Biasing Buckling Direction in Shape‐Programmable Hydrogel Sheets with Through‐Thickness Gradients
Abstract A photocrosslinkable poly(N,N′‐diethylacrylamide) copolymer allows for the photolithographic fabrication of hydrogel sheets with nonuniform crosslinking density and swelling ratio. Using this material system, different 3D shapes with nonzero Gaussian curvatureKare successfully programmed by prescribing a “metric” defined by in‐plane variations in swelling. However, this methodology does not control the direction of buckling adopted by each positive K feature, and therefore cannot controllably select between different isometric shapes defined by a single metric. Here, by introducing gradients in swelling through the thickness of the gel sheet by tuning the absorption of the UV‐light used for crosslinking, a preferential buckling direction is locally specified for each feature by the direction of UV exposure. By also controlling the strength of coupling between neighboring features, this is shown to be an effective method to program buckling direction of each unit within a canonical corrugated surface shape.
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- Award ID(s):
- 1507377
- PAR ID:
- 10459375
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 29
- Issue:
- 48
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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