skip to main content

This content will become publicly available on September 2, 2023

Title: Investigation of Hydronium Diffusion in Poly(vinyl alcohol) Hydrogels: A Critical First Step to Describe Acid Transport for Encapsulated Bioremediation
Bioremediation of chlorinated aliphatic hydrocarbon-contaminated aquifers can be hindered by high contaminant concentrations and acids generated during remediation. Encapsulating microbes in hydrogels may provide a protective, tunable environment from inhibiting compounds; however, current approaches to formulate successful encapsulated systems rely on trial and error rather than engineering approaches because fundamental information on mass-transfer coefficients is lacking. To address this knowledge gap, hydronium ion mass-transfer rates through two commonly used hydrogel materials, poly(vinyl alcohol) and alginic acid, under two solidification methods (chemical and cryogenic) were measured. Variations in hydrogel crosslinking conditions, polymer composition, and solvent ionic strength were investigated to understand how each influenced hydronium ion diffusivity. A three-way ANOVA indicated that the ionic strength, membrane type, and crosslinking method significantly (p < 0.001) contributed to changes in hydronium ion mass transfer. Hydronium ion diffusion increased with ionic strength, counter to what is observed in aqueous-only (no polymer) solutions. Co-occurring mechanisms correlated to increased hydronium ion diffusion with ionic strength included an increased water fraction within hydrogel matrices and hydrogel contraction. Measured diffusion rates determined in this study provide first principal design information to further optimize encapsulating hydrogels for bioremediation.
; ; ; ; ;
Award ID(s):
Publication Date:
Journal Name:
ACS ES&T Engineering
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Hydrogel-encapsulated catalysts are an attractive tool for low-cost intensification of (bio)-processes. Polyvinyl alcohol-sodium alginate hydrogels crosslinked with boric acid and post-cured with sulfate (PVA-SA-BS) have been applied in bioproduction and water treatment processes, but the low pH required for crosslinking may negatively affect biocatalyst functionality. Here, we investigate how crosslinking pH (3, 4, and 5) and time (1, 2, and 8 h) affect the physicochemical, elastic, and process properties of PVA-SA-BS beads. Overall, bead properties were most affected by crosslinking pH. Beads produced at pH 3 and 4 were smaller and contained larger internal cavities, while optical coherence tomography suggested polymer cross-linking density was higher. Optical coherence elastography revealed PVA-SA-BS beads produced at pH 3 and 4 were stiffer than pH 5 beads. Dextran Blue release showed that pH 3-produced beads enabled higher diffusion rates and were more porous. Last, over a 28-day incubation, pH 3 and 4 beads lost more microspheres (as cell proxies) than beads produced at pH 5, while the latter released more polymer material. Overall, this study provides a path forward to tailor PVA-SA-BS hydrogel bead properties towards a broad range of applications, such as chemical, enzymatic, and microbially catalyzed (bio)-processes.

  2. Injectable hydrogels are attractive for therapeutic delivery because they can be locally administered through minimally-invasive routes. Charge-complementary peptide nanofibers provide hydrogels that are suitable for encapsulation of biotherapeutics, such as cells and proteins, because they assemble under physiological temperature, pH, and ionic strength. However, relationships between the sequences of charge-complementary peptides and the physical properties of the hydrogels that they form are not well understood. Here we show that hydrogel viscoelasticity, pore size, and pore structure depend on the pairing of charge-complementary “CATCH(+/−)” peptides. Oscillatory rheology demonstrated that co-assemblies of CATCH(4+/4−), CATCH(4+/6−), CATCH(6+/4−), and CATCH(6+/6−) formed viscoelastic gels that can recover after high-shear and high-strain disruption, although the extent of recovery depends on the peptide pairing. Cryogenic scanning electron microscopy demonstrated that hydrogel pore size and pore wall also depend on peptide pairing, and that these properties change to different extents after injection. In contrast, no obvious correlation was observed between nanofiber charge state, measured with ζ-potential, and hydrogel physical properties. CATCH(4+/6−) hydrogels injected into the subcutaneous space elicited weak, transient inflammation whereas CATCH(6+/4−) hydrogels induced stronger inflammation. No antibodies were raised against the CATCH(4+) or CATCH(6−) peptides following multiple challenges in vehicle or when co-administered with an adjuvant. Thesemore »results demonstrate that CATCH(+/−) peptides form biocompatible injectable hydrogels with viscoelastic properties that can be tuned by varying peptide sequence, establishing their potential as carriers for localized delivery of therapeutic cargoes.« less
  3. When a hydrogel simply won’t cut it – either because it dries out too quickly, or it does not tolerate more than roughly one volt when applied in an electrochemical device – where is the savvy materials researcher to turn? This is where two important classes of nonaqueous gel counterparts, known as ionogels and eutectogels, can truly shine. Replacing the aqueous liquid phase of a hydrogel with either an ionic liquid (IL) or a deep eutectic solvent (DES) allows one to realize an array of versatile gel electrolyte materials that offer outstanding nonvolatility, wider windows of electrochemical stability, reasonably high ionic conductivity, and nearly unlimited chemical design possibilities. In addition to choosing a specific IL or DES, there are a myriad of options when it comes to constructing a solid, three-dimensional, volume-spanning network (or scaffold) that will support the nonaqueous liquid phase of an ionogel or eutectogel. In this focused review, several recent approaches to forming these gels using noncovalent scaffold assembly and cross-linking are examined, and the primary noncovalent interactions responsible ( e.g. hydrogen bonding, solvophobicity, coulombic interactions) are identified. Noncovalent scaffold assembly in nonaqueous, ion-dense electrolytes often leads to supramolecular gel materials that can exhibit extreme stretchability, goodmore »toughness, and an ability to self-heal in many cases. After reviewing several strategies that have been recently employed for creating ionogels and eutectogels, a brief inspection of some motivating noncovalently cross-linked scaffolds reported for hydrogels is presented with the hopes that these may provide inspiration for the future design of novel ionogels and eutectogels by the materials research community.« less
  4. Development of highly stretchable and sensitive soft strain sensors is of great importance for broad applications in artificial intelligence, wearable devices, and soft robotics, but it proved to be a profound challenge to integrate the two seemingly opposite properties of high stretchability and sensitivity into a single material. Herein, we designed and synthesized a new fully polymeric conductive hydrogel with an interpenetrating polymer network (IPN) structure made of conductive PEDOT:PSS polymers and zwitterionic poly(HEAA- co -SBAA) polymers to achieve a combination of high mechanical, biocompatible, and sensing properties. The presence of hydrogen bonding, electrostatic interactions, and IPN structures enabled poly(HEAA- co -SBAA)/PEDOT:PSS hydrogels to achieve an ultra-high stretchability of 4000–5000%, a tensile strength of ∼0.5 MPa, a rapid mechanical recovery of 70–80% within 5 min, fast self-healing in 3 min, and a strong surface adhesion of ∼1700 J m −2 on different hard and soft substrates. Moreover, the integration of zwitterionic polySBAA and conductive PEDOT:PSS facilitated charge transfer via optimal conductive pathways. Due to the unique combination of superior stretchable, self-adhesive, and conductive properties, the hydrogels were further designed into strain sensors with high sensing stability and robustness for rapidly and accurately detecting subtle strain- and pressure-induced deformation and humanmore »motions. Moreover, an in-house mechanosensing platform provides a new tool to real-time explore the changes and relationship between network structures, tensile stress, and electronic resistance. This new fully polymeric hydrogel strain sensor, without any conductive fillers, holds great promise for broad human-machine interface applications.« less
  5. Abstract Teaching experiments involving edible, biodegradable calcium alginate beads serve as an attractive model system to introduce upper secondary age students to core chemistry topics through innovations in sustainable consumer products. A teaching experiment is described that engages students with the synthesis of calcium alginate hydrogel beads from sodium alginate and calcium lactate, two food-safe and renewable materials. The beads’ outer membranes are a result of ionic interactions between carboxylate groups from alginate strands and the divalent calcium cations between them, thus forming cross-linked polymers. Protonation of the carboxylate groups on the alginate strands decreases crosslinking density affecting bead formation. First, various concentrations of citric acid are used to lower the pH of the sodium alginate solution and the effect on the calcium alginate bead formation is observed. A correlation between pH and bead shape and firmness is derived. This information is then used to explore juices with varying natural acidities. The experiment is amenable to implementation in the classroom or as an at-home activity. Learning outcomes include acid-base reactions, chemical bonding, polymer structures, and green chemistry concepts. Students consider the environmental challenges of traditional plastics used in packaging and how innovative new commercial products are attempting to provide solutions.