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Free, publicly-accessible full text available June 3, 2026
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pH-responsive polymeric nanoparticles are an exciting class of stimuli-responsive materials that can respond to changes in pH and, as a result, have been developed for numerous applications in biomedicine, such as the loading and delivery of various cargoes. One common transformation is nanoparticle swelling due to the protonation or deprotonation of specific side chain moieties in the polymer structure. When the pH trigger is removed, the swelling can be reversed, and this process can be continually cycled by adjusting the pH. In this work, we are leveraging this swelling–deswelling–reswelling mechanism to develop a simple, fast, and easy loading strategy for a class of cross-linked polymeric nanoparticles, poly-2-(diethylamino) ethyl methacrylate (pDEAEMA), that can reversibly swell below pH 7.3, and a dye, rhodamine B isothiocyanate (RITC), as a proof-of-concept cargo molecule while comparing to poly(methyl methacrylate) (pMMA) nanoparticles as a nonswelling control. A free radical polymerization was used to generate pDEAEMA nanoparticles at three different sizes by varying the synthesis temperature. Their pH-dependent swelling and deswelling were extensively characterized using dynamic light scattering and transmission electron microscopy, which revealed a reversible increase in size for pDEAEMA nanoparticles in acidic media, whereas pMMA nanoparticles remain constant. Following dye loading, pDEAEMA nanoparticles show significant fluorescence intensity when compared to pMMA nanoparticles, suggesting that the reversible swelling is key for successful loading. Upon acidic treatment, there is a significant decrease in the fluorescence intensity when compared to the dye-loaded nanoparticles in basic media, which could be due to dilution of the dye when released in the acidic medium solution. Interestingly, nanoparticle size had no impact on dye loading properties, suggesting that the dye molecules only go so far into the polymer nanoparticle. Additionally, confocal microscopy images reveal pDEAEMA nanoparticles with higher RITC fluorescence intensity in acidic media but a lower RITC fluorescence intensity in basic media, while pMMA nanoparticles show no differences. Together, these results showcase a size reversibility-driven cargo loading mechanism that has the potential to be applied to other beneficial cargoes and for various applications.more » « less
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There is a need to develop new and sustainable agricultural technologies to help provide global food security, and nanoscale materials show promising results in this area. In this study, mesoporous silica nanoparticles (MSNs) and chitosan-coated mesoporous silica nanoparticles (CTS-MSNs) were synthesized and applied to soybeans (Glycine max) by two different strategies in greenhouse and field studies to study the role of dissolved silicic acid and chitosan in enhancing plant growth and suppressing disease damage caused by Fusarium virguliforme. Plant growth and health were assessed by measuring the soybean biomass and chlorophyll content in both healthy and Fusarium-infected plants at harvest. In the greenhouse study, foliar and seed applications with 250 mg/L nanoparticle treatments were compared. A single seed treatment of MSNs reduced disease severity by 30% and increased chlorophyll content in both healthy and infected plants by 12%. Based on greenhouse results, seed application was used in the follow-up field study and MSNs and CTS-MSNs reduced disease progression by 12 and 15%, respectively. A significant 32% increase was observed for chlorophyll content for plants treated with CTS-MSNs. Perhaps most importantly, nanoscale silica seed treatment significantly increased (23–68%) the micronutrient (Zn, Mn, Mg, K, B) content of soybean pods, suggesting a potential sustainable strategy for nano-enabled biofortification to address nutrition insecurity. Overall, these findings indicate that MSN and CTS-MSN seed treatments in soybeans enable disease suppression and increase plant health as part of a nano-enabled strategy for sustainable agriculture.more » « less
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Silica nanomaterials have been studied based on their potential applications in a variety of fields, including biomedicine and agriculture. A number of different molecules have been condensed onto silica nanoparticles’ surfaces to present the surface chemistry needed for a given application. Among those molecules, (3-aminopropyl)triethoxysilane (APS) is one of the most commonly applied silanes used for nanoparticle surface functionalization to achieve charge reversal as well as to enable cargo loading. However, the colloidal stability of APS-functionalized silica nanoparticles has not been thoroughly studied, which can be problematic when the high reactivity of amine groups is considered. In this study, four different types of silica nanoparticles with varied location of added APS have been prepared via a reverse micro emulsion process, and their colloidal stability and dissolution behavior have been investigated. Systematic characterization has been accomplished using transmission electron microscopy (TEM), silicomolybdic acid (SMA) spectrophotometric assay, nitrogen adsorption–desorption surface area measurement, and aerosol ion mobility-mass spectrometry to track the nanoparticles’ physical and chemical changes during dissolution. We find that when APS is on the interior of the silica nanoparticle, it facilitates dissolution, but when APS is condensed both on the interior and exterior, only the exterior siloxane bonds experience catalytic hydrolysis, and the interior dissolution is dramatically suppressed. The observation and analyses that silica nanoparticles show different hydrolysis behaviors dependent on the location of the functional group will be important in future design of silica nanoparticles for specific biomedical and agricultural applications.more » « less
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null (Ed.)An emerging interest regarding nanoparticles (NPs) concerns their potential immunomodulatory and pro-inflammatory activities, as well as their impact in the circulatory system. These biological activities of NPs can be related to the intensity and type of the responses, which can raise concerns about adverse side effects and limit the biomedical applicability of these nanomaterials. Therefore, the purpose of this study was to investigate the impact of a library of cationic cellulose nanocrystals (CNCs) in the human blood and endothelial cells using cell-based assays. First, we evaluated whether the cationic CNCs would cause hemolysis and aggregation or alteration on the morphology of red blood cells (RBC). We observed that although these nanomaterials did not alter RBC morphology or cause aggregation, at 24 h exposure, a mild hemolysis was detected mainly with unmodified CNCs. Then, we analyzed the effect of various concentrations of CNCs on the cell viability of human umbilical vein endothelial cells (HUVECs) in a time-dependent manner. None of the cationic CNCs caused a dose-response decrease in the cell viability of HUVEC at 24 h or 48 h of exposure. The findings of this study, together with the immunomodulatory properties of these cationic CNCs previously published, support the development of engineered cationic CNCs for biomedical applications, in particular as vaccine nanoadjuvants.more » « less
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null (Ed.)Polysaccharides have been shown to have immunomodulatory properties. Modulation of the immune system plays a crucial role in physiological processes as well as in the treatment and/or prevention of autoimmune and infectious diseases. Cellulose nanocrystals (CNCs) are derived from cellulose, the most abundant polysaccharide on the earth. CNCs are an emerging class of crystalline nanomaterials with exceptional physico-chemical properties for high-end applications and commercialization prospects. The aim of this study was to design, synthesize, and evaluate the cytotoxicity of a series of biocompatible, wood-based, cationic CNCs as potential immunomodulators. The anionic CNCs were rendered cationic by grafting with cationic polymers having pendant +NMe3 and +NH3 moieties. The success of the synthesis of the cationic CNCs was evidenced by Fourier transform infrared spectroscopy, dynamic light scattering, zeta potential, and elemental analysis. No modification in the nanocrystals rod-like shape was observed in transmission electron microscopy and atomic force microscopy analyses. Cytotoxicity studies using three different cell-based assays (MTT, Neutral Red, and LIVE/DEAD®) and three relevant mouse and human immune cells indicated very low cytotoxicity of the cationic CNCs in all tested experimental conditions. Overall, our results showed that cationic CNCs are suitable to be further investigated as immunomodulators and potential vaccine nanoadjuvants.more » « less