Dendrimers as Color-Stabilizers of Pyranoanthocyanins: The Dye Concentration Governs the Host-Guest Interaction Mechanisms.

Anionic dendrimers have recently emerged as hosts (H) for the color stabilization of the flavylium cation of anthocyanin guests (G). The interaction with a promising, more hydrophobic pyranoanthocyanin illustrates how the structure and concentration of the dye modulate the host-guest interaction mechanisms. NMR and UV-vis titrations (host over guest, from G/H ratio 2089 to 45) showed that at relatively low dendrimer-to-dye concentrations, ion pairs at the dendrimer periphery prevail over dye encapsulation. This promotes the deaggregation of the dye, not previously observed with anthocyanins, and related to the more hydrophobic nature of this dye (deshielding of the dye 1H signals, higher T 2 relaxation times, constant diffusion coefficient). As the dendrimer concentration increases, the dye encapsulation, earlier unseen with structurally simpler flavylium dyes, becomes dominant (shielding and broadening of the dye 1H signals and lower T 2 and diffusion coefficient). The interaction parameters of the encapsulation process (K ∼ 4.51 × 104 M-1, n ∼ 150) indicate the binding of ca. one pyranoanthocyanin molecule by each sulfate terminal group. Our results provide insights into the ability of dendrimers to host structurally diverse pyranoflavylium-based dyes and how the structure of the latter modulates the range of interactions involved. The encapsulation ability of this dendrimer to such pH-sensitive dyes is envisioned for the host-guest sensing applications such as pH-responsive systems used for example in food smart packaging.

Impact of a Water-Soluble Gallic Acid-Based Dendrimer on the Color-Stabilizing Mechanisms of Anthocyanins.

The interaction of two anthocyanins with a water-soluble polyanionic dendrimer was studied through UV/Vis, stopped-flow, and NMR spectroscopy. Cyanidin-3-glucoside (cy3glc) revealed a stronger interaction than malvidin-3-glucoside (mv3glc) at pH 1 according to their apparent association constants. A higher color increased was also obtained for cy3glc at pH 3.5 as a result of this stronger interaction. A high-frequency chemical shift of the cy3glc aromatic protons suggest the formation of ionic pairs. The interaction parameters (K≈700 m-1 , n≈295) indicated the binding of approximately two anthocyanin molecules by each sulfate group. The equilibrium and rate constants of cy3glc in the presence of dendrimer showed an increased stability of the flavylium cation and a higher protection of this species from hydration (pK'a and pKh increased almost one pH unit). The tuning and color stabilization of anthocyanins by using this dendrimer allow novel applications as colorimetric sensors for food packaging.

Multivalent Affidendrons with High Affinity and Specificity toward Staphylococcus aureus as Versatile Tools for Modulating Multicellular Behaviors.

Multivalency is a widely occurring natural phenomenon often exploited in nanotechnology to enhance biorecognition. We report the preparation and characterization of versatile, multivalent Affitin-dendrimer conjugates (Affidendrons) showcased by a set targeting Staphylococcus aureus ( S. aureus), an opportunistic pathogen causing numerous hospital- and community-acquired infections. Affitins are small affinity proteins characterized by higher stability and lower cost-effective production than antibodies. The strategy presented provides a platform for the rational design of multivalent nanodevices that, retaining the ability of Affitins to recognize their target with high specificity, achieve a largely enhanced affinity. Affidendrons with precisely designed size and valency have been exploited to modulate complex multicellular behaviors of S. aureus, such as agglutination and biofilm formation. Agglutination assays showed that Affidendrons rapidly cross-link S. aureus strains with high bacterial cell selectivity. Moreover, remarkably low concentrations of Affidendrons were able to effectively prevent biofilm formation. Overall, Affidendrons represent a promising platform for the rapid and selective pathogen identification, infection imaging, and theranostic applications.

Tuning the Size of Nanoassembles: A Hierarchical Transfer of Information from Dendrimers to Polyion Complexes.

The generation of dendrimers is a powerful tool in the control of the size and biodistribution of polyion complexes (PIC). Using a combinatorial screening of six dendrimers (18-243 terminal groups) and five oppositely charged PEGylated copolymers, a dendrimer-to-PIC hierarchical transfer of structural information was revealed with PIC diameters that increased from 80 to 500 nm on decreasing the dendrimer generation. This rise in size, which was also accompanied by a micelle-to-vesicle transition, is interpreted according to a cone- to rod-shaped progression in the architecture of the unit PIC (uPIC). This precise size tuning enabled dendritic PICs to act as nanorulers for controlled biodistribution. Overall, a domino-like control of the size and biological properties of PIC that is not attainable with linear polymers is feasible through dendrimer generation.