An official website of the United States government
A novel composite hydrogel bead composed of sodium alginate (SA) and aldehyde cellulose nanocrystal (DCNC) was developed for antibiotic remediation through a one-step cross-linking process in a calcium chloride bath. Structural and physical properties of the hydrogel bead, with varying composition ratios, were analyzed using techniques such as BET analysis, SEM imaging, tensile testing, and rheology measurement. The optimal composition ratio was found to be 40% (SA) and 60% (DCNC) by weight. The performance of the SA–DCNC hydrogel bead for antibiotic remediation was evaluated using doxycycline (DOXY) and three other tetracyclines in both single- and multidrug systems, yielding a maximum adsorption capacity of 421.5 mg g−1 at pH 7 and 649.9 mg g−1 at pH 11 for DOXY. The adsorption mechanisms were investigated through adsorption studies focusing on the effects of contact time, pH, concentration, and competitive contaminants, along with X-ray photoelectron spectroscopy analysis of samples. The adsorption of DOXY was confirmed to be the synergetic effects of chemical reaction, electrostatic interaction, hydrogen bonding, and pore diffusion/surface deposition. The SA–DCNC composite hydrogel demonstrated high reusability, with more than 80% of its adsorption efficiency remaining after five cycles of the adsorption–desorption test. The SA–DCNC composite hydrogel bead could be a promising biomaterial for future antibiotic remediation applications in both pilot and industrial scales because of its high adsorption efficiency and ease of recycling.
more »
« less
Tailoring polyvinyl alcohol-sodium alginate (PVA-SA) hydrogel beads by controlling crosslinking pH and time
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.
more »
« less
- Award ID(s):
- 1937290
- PAR ID:
- 10383390
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Scientific Reports
- Volume:
- 12
- Issue:
- 1
- ISSN:
- 2045-2322
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
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.more » « less
-
Despite national and international regulations, plastic microbeads are still widely used in personal care and consumer products (PCCPs) as exfoliants and rheological modifiers, causing significant microplastic pollution following use. As a sustainable alternative, microbeads were produced by extrusion of biomass solutions and precipitation into anti-solvent. Despite using novel blends of biodegradable, non-derivatized biomass including cellulose and Kraft lignin, resulting microbeads are within the shape, size, and stiffness range of commercial plastic microbeads, even without crosslinking. Solution processability and resulting bead shape and Young’s modulus can be tuned via biomass source, concentration, and degree of polymerization; biomass concentration, extrusion geometry, and precipitation and extraction conditions control the bead size. Lignin incorporation reduces the solution viscosity, which improves processability but also produces flatter beads with higher moduli than cellulose-only microbeads. While some lignin leaches from the beads when stored in water, adding surfactants like sodium dodecyl sulfate suppresses this effect, resulting in good mechanical stability over 2 months with no noticeable structural degradation. The stability of these mixed-source biomass microbeads—despite the absence of chemical crosslinking or derivatization—makes this route a promising, robust approach for obtaining environmentally-benign microbeads of tunable size and stiffness for use in PCCPs.more » « less
-
Abstract Managing water resources has become one of the most pressing concerns of scientists in both academia and industry. Broadening access to nontraditional water feedstocks, such as brackish water, seawater and wastewater, requires a robust pretreatment process to prolong the lifetime and improve the efficiency of reverse osmosis treatment processes. Herein, pretreatment membranes with tunable hydrophilic characteristics and mechanical properties were developed through a facile and scalable technique. Specifically, poly(vinyl alcohol) (PVA) and poly(vinyl chloride) (PVC) were electrospun at various PVA‐to‐PVC mass ratios and then crosslinked with a poly(ethylene glycol) diacid. Fiber diameters and morphologies were characterized using scanning electron microscopy (SEM); Fourier transform infrared spectroscopy and confocal fluorescence microscopy further confirmed the presence of both polymers. Moreover, a rigorous analysis to map the PVA/PVC concentration was established to accurately determine the relative concentrations of the two polymers on the co‐spun mat. The crosslinking reaction noted above tuned the membrane porosity from 500 to 80 nm, as seen using SEM, and the mechanical properties were probed using tensile testing. The data revealed that the PVC content controlled the mechanical strength; moreover, higher PVA contents were expected to increase water permeation by enhancing the hydrophilicity, but the higher degree of crosslinking in these materials actually reduced water permeation. This work introduces a facile, scalable route for the manufacture of pretreatment membranes with tunable porosity, mechanical properties and water permeation behavior. © 2021 Society of Industrial Chemistry.more » « less
-
AbstractPolyvinyl alcohol (PVA) is a water-soluble synthetic polymer that can be used to make hydrogels for biomedical applications as well as biodegradable bags and films; however, compared to other plastics currently used for containers, it lacks mechanical strength, thermal stability, and can easily absorb water from humid environments. Although mechanical improvement has been observed by blending PVA with collagen in a hybrid hydrogel, there is a lack of fundamental understanding of the molecular mechanism, and it is not clear whether the improvement is limited to a hydrated state. Here, using classical molecular dynamics simulations based on fully atomistic models, we develop the equilibrated molecular structure of PVA with collagen and characterize its mechanics. We show that by interacting with a collagen molecule, PVA is equilibrated to a more ordered structure with each residue interacting with the near neighbors by forming more hydrogen bonds locally, making the structure stiffer than pure PVA. The structure shows higher thermal stability before melting, as well as higher rigidity in water. Our results provide the mechanism of the mechanical advantages of hybrid PVA-collagen polymer. The study demonstrates that the structure and mechanics of a synthetic polymer can be tuned by a tiny amount of a natural polymer at the molecular interface. Moreover, it may shed light on identifying a way to improve the mechanics of biodegradable polymer materials without adding much cost, which is crucial for environmental safety. Impact statementBlending natural and synthetic polymers (e.g., polyvinyl alcohol [PVA] and collagen in a hybrid hydrogel) has shown advantages in polymer mechanics, but there is a lack of fundamental understanding. Using molecular dynamics (MD) simulations based on fully atomistic models, we develop the equilibrated structure of the PVA with collagen and characterize its mechanics. We show that by interacting with a collagen molecule, PVA is equilibrated to a more ordered structure with each residue interacting with the near neighbors by forming more H-bonds locally and the structure is stiffer than pure PVA. Moreover, the structure shows a higher thermal stability before the melting point of PVA, as well as higher rigidity in water. Our results demonstrate that the structure and mechanics of a synthetic polymer can be tuned by a tiny amount of a natural polymer at the molecular interface. It provides the mechanism of the mechanical advantages as experimentally observed. This study paves the way for the multiscale modeling and mechanical design of the hybrid polymer material. It sheds light on identifying a way to improve the mechanics of biodegradable materials without adding much cost for both material functionality and environmental safety. Graphical abstractmore » « less
