Synthesis of Submicrometric Chitosan Particles Loaded with Calcium Phosphate for Biomedical Applications.

Chitosan particles loaded with dibasic calcium phosphate anhydrous (DCPA) is a promising strategy for combining antimicrobial and osteoconduction properties in regenerative medicine. However, mostly micrometer-sized particles have been reported in the literature, limiting their use and reducing their effect in the biomedical field. We have recently overcome this limitation by developing submicrometer-sized particles with electrospray technique. The objective of this study was to understand how the process parameters control the size and properties of submicrometer chitosan particles loaded with DCPA. Solutions of 10 mg/mL chitosan and 2.5 mg/mL DCPA in a 90% acetic acid were electrosprayed under three distinct flow rate conditions: 0.2, 0.5, and 1.0 mL/h. The particles were crosslinked in a glutaraldehyde atmosphere and characterized in terms of their morphology, inorganic content, zeta potential, and minimum inhibitory concentration (MIC) against S. mutans. All conditions showed particles with two similar morphologies: one small-sized with a spherical shape and another larger-sized with a bi-concave shape. All generated a broad particle size distribution, with a similar mean size of ~ 235 nm. The addition of DCPA decreased the zeta potential for all the samples, but it was above 30 mV, indicating a low aggregation potential. The lower flow rate showed the worst efficacy for DCPA incorporation. Antimicrobial activity was greater in chitosan/DCPA particles with flow rate of 0.5 mL/h. It can be concluded that the flow rate of 0.5 mL/h presents the best compromise solution in terms of morphology, zeta potential, MIC, and inorganic content.

Effects of the crosslinking of chitosan/DCPA particles in the antimicrobial and mechanical properties of dental restorative composites.

The development of restorative materials containing antibacterial agents is an alternative to reduce the progression of caries lesions. OBJECTIVE: to compare the influence of the degree of crosslinking of chitosan particles loaded with dibasic calcium phosphate (DCPA) on the mechanical properties, degree of conversion (DC), and antimicrobial properties of experimental composites. METHODS: Chitosan/DCPA particles were synthesized by the electrospraying, crosslinked by 0, 8, or 16 h in glutaraldehyde, and characterized by zeta potential and minimum inhibitory concentration (MIC) against S. mutans. Experimental resin composites of Bis-GMA and TEGDMA and 59.5% of barium glass were synthesized, chitosan/DCPA particles were added at 0 or 0.5 wt% with the different crosslinking time. The materials were subject to DC analysis, three-point bending test at 24 h and 7 days, and antimicrobial assays. Data were submitted to one-way ANOVA and Tukey test (α = 0.05). RESULTS: The particles with longer crosslinking time presented higher zeta potential and MIC, and the composite containing these particles showed significantly higher biofilm inhibition than the control group. The other two groups were similar to each other and the control. The composite containing particles with 88 h crosslinking time showed the lowest flexural strength at 7 days in water, and materials with non-crosslinked particles and longer crosslinking time presented flexural strength similar to control. The flexural modulus and DC showed no statistical difference among groups. SIGNIFICANCE: composite resin containing 0.5% chitosan/DCPA particles crosslinked by 16 h showed a reduction of biofilm formation without affecting the mechanical properties in relation to the control.

Modular Design of Programmable Mechanofluorescent DNA Hydrogels.

Mechanosensing systems are ubiquitous in nature and control many functions from cell spreading to wound healing. Biologic systems typically rely on supramolecular transformations and secondary reporter systems to sense weak forces. By contrast, synthetic mechanosensitive materials often use covalent transformations of chromophores, serving both as force sensor and reporter, which hinders orthogonal engineering of their sensitivity, response and modularity. Here, we introduce FRET-based, rationally tunable DNA tension probes into macroscopic 3D all-DNA hydrogels to prepare mechanofluorescent materials with programmable sacrificial bonds and stress relaxation. This design addresses current limitations of mechanochromic system by offering spatiotemporal resolution, as well as quantitative and modular force sensing in soft hydrogels. The programmable force probe design further grants temporal control over the recovery of the mechanofluorescence during stress relaxation, enabling reversible and irreversible strain sensing. We show proof-of-concept applications to study strain fields in composites and to visualize freezing-induced strain patterns in homogeneous hydrogels.