Developing protein confinement platforms is an attractive research area that not only promotes protein delivery but also can result in artificial environment mimicking of the cellular one, impacting both the controlled release of proteins and the fundamental protein biophysics. Polymeric nanoparticles (PNPs) are attractive platforms to confine proteins due to their superior biocompatibility, low cytotoxicity, and controllable release under external stimuli. However, loading proteins into PNPs can be challenging due to the potential protein structural perturbation upon contacting the interior of PNPs. In this work, we developed a novel approach to encapsulate proteins in PNPs with the assistance of the zeolitic imidazolate framework (ZIF). Here, ZIF offers an additional protection layer to the target protein by forming the protein@ZIF composite via aqueous-phase cocrystallization. We demonstrated our platform using a model protein, lysozyme, and a widely studied PNP composed of poly(ethylene glycol)-poly(lactic-co-glycolic acid) (PEG–PLGA). A comprehensive study via standard loading and release tests as well as various spectroscopic techniques was carried out on lysozyme loaded onto PEG–PLGA with and without ZIF protection. As compared with the direct protein encapsulation, an additional layer with ZIF prior to loading offered enhanced loading capacity, reduced leaching, especially in the initial stage, led to slower release kinetics, and reduced secondary structural perturbation. Meanwhile, the function, cytotoxicity, and cellular uptake of proteins encapsulated within the ZIF-bound systems are decent. Our results demonstrated the use of ZIF in assisting in protein encapsulation in PNPs and established the basis for developing more sophisticated protein encapsulation platforms using a combination of materials of diverse molecular architectures and disciplines. As such, we anticipate that the protein-encapsulated ZIF systems will serve as future polymer protein confinement and delivery platforms for both fundamental biophysics and biochemistry research and biomedical applications where protein delivery is needed to support therapeutics and/or nutrients.
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Modifying soluble NPK release with hydrophobized nanocellulose-based hydrogels for sustainable enhanced efficiency fertilizers
Enhancing the delivery efficiency of NPK fertilizers benefits both crops and the environment through moderating the supplied dosage of nutrients in the soil, avoiding side reactions, maximizing absorption by the plant, and minimizing leaching and runoff. Bio-based materials such as cellulose are ideal scaffolds for nutrient delivery due to their inherent biocompatibility, biodegradability, and significant water uptake. In this work, nanocellulose-based hydrogels were regenerated from mixed softwood in acidic media and loaded with NPK by immersion in varied concentrations of an NPK-rich fertilizer solution. High loading of NPK was achieved within the hydrogel, but immersion in the matrix provided only slight slowing of nutrient release compared to rapid solubility of conventional formulations. Densification, crosslinking, and coating of the hydrogels with beeswax were ineffective strategies to further slow NPK release. Following these results, both gas and solution-phase esterification reactions of the cellulosic matrix with hexanoyl chloride were performed after NPK loading to introduce a hydrophobic surface layer. While solution-phase modification led to phosphorus leaching and was overall ineffective in altering nutrient release, the gas-phase modification slowed the release of P and K by more than an order of magnitude. Moreover, it was found that varying both the properties of the hydrophobic surface layer and the nutrient loading provide a means to tune release rates. Overall, this work demonstrates the potential of nanocellulose-based hydrogels to be used as an environmentally safe and sustainable vehicle for the controlled release of nutrients in agricultural applications.
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- PAR ID:
- 10464931
- Date Published:
- Journal Name:
- Environmental Science: Nano
- ISSN:
- 2051-8153
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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