Well-Defined Bifunctional Dendrimer Bearing 54 Nitric Oxide-Releasing Moieties and 54 Ursodeoxycholic Acid Groups Presenting High Anti-Inflammatory Activity.

Nitric oxide (NO) and ursodeoxycholic acid (UDCA) are endogenous molecules involved in physiological processes associated with inflammation. Since inflammatory processes are present in the mechanisms of many diseases, these molecules are important for the development of new drugs. Herein, we describe the synthesis of a well-defined bifunctional dendrimer with 108 termini bearing 54 NO-releasing groups and 54 UDCA units (Dendri-(NO/UDCA)54). For comparison, a lower-generation dendrimer bearing 18 NO-releasing groups and 18 UDCA units (Dendri-(NO/UDCA)18) was also synthesized. The anti-inflammatory activity of these dendrimers was evaluated, showing that the bifunctional dendrimers have an inverse correlation between concentration and anti-inflammatory activity, with an effect dramatically pronounced for Dendri-(NO/UDCA)54 20, which at just 0.25 nM inhibited 76.1% of IL-8 secretion. Data suggest that nanomolar concentrations of these dendrimers aid in releasing NO in a safe and controlled way. This bifunctional dendrimer has great potential as a drug against multifactorial diseases associated with inflammatory processes.

Synthesis of Carbon Nanodots from Sugarcane Syrup, and Their Incorporation into a Hydrogel-Based Composite to Fabricate Innovative Fluorescent Microstructured Polymer Optical Fibers.

Carbon nanodots (CNDs) are interesting materials due to their intrinsic fluorescence, electron-transfer properties, and low toxicity. Here, we report a sustainable, cheap, and scalable methodology to obtain CNDs from sugarcane syrup using a domestic microwave oven. The CNDs were characterized by infrared spectroscopy, dynamic light scattering, atomic force microscopy, absorption, and emission spectroscopies. The CNDs have 3 nm in diameter with low polydispersity and are fluorescent. A fluorescent hydrogel-CNDs composite was obtained using gelatin polypeptide as the polymeric matrix. The new hydrogel-CNDs composite was incorporated in the cavities of a double-clad optical fiber using an innovative approach that resulted in a microstructured polymer optical fiber with intrinsic fluorescence. This work shows a promising alternative for the fabrication of fluorescent materials since the CNDs synthesis is sustainable and environmentally friendly. These CNDs might substitute the rare-earth and other heavy metals of high cost and toxicity, which are usually incorporated in double-clad fibers for applications on lasers, amplifiers, and spectroscopy.

Synthesis and Characterization of Dendronized Gold Nanoparticles Bearing Charged Peripheral Groups with Antimicrobial Potential.

Dendronized gold nanoparticles (AuNPs) were synthesized bearing charged peripheral groups. Two novel AB3-type dendrons were synthesized with a thiol group at the focal point followed by their attachment to AuNPs. Dendrons were designed to have nine charged peripheral groups (carboxyl or amine), glycol solubilizing, units and one thiol moiety at the focal point. Both dendrons and all intermediates were synthesized in high yields and characterized by nuclear magnetic resonance spectroscopy (NMR) and mass spectrometry (MS). The amine- and carboxyl-terminated dendrons were used to functionalize gold nanoparticles (AuNPs) previously stabilized with citrate. The nanoparticles' diameters and their colloidal stability were investigated using dynamic light scattering (DLS). The size and morphology of the dendronized AuNPs were evaluated by scanning electron microscopy (SEM), which revealed individual particles with no aggregation after replacement of citrate by the dendrons, in agreement with the DLS data. The absorption spectroscopy reveals a prominent plasmonic band at 560 nm for all AuNPs. The zeta potential further confirmed the expected charged structures of the dendronized AuNPs. Considering all the physical-chemical properties of the charged dendronized AuNPs developed in this work, these AuNPs might be used as a weapon against multi-drug resistant bacterial infections.

Self-Assembly of a Triazolylferrocenyl Dendrimer in Water Yields Nontraditional Intrinsic Green Fluorescent Vesosomes for Nanotheranostic Applications.

The promising field of nanomedicine stimulates a continuous search for multifunctional nanotheranostic systems for imaging and drug delivery. Herein, we demonstrate that application of supramolecular chemistry's concepts in dendritic assemblies can enable the formation of advanced dendrimer-based nanotheranostic devices. A dendrimer bearing 81 triazolylferrocenyl terminal groups adopts a more compact shell-like structure in polar solvents with the ferrocenyl peripheral groups backfolding toward the hydrophobic dendrimer interior, while exposing the more polar triazole moieties as the dendritic shell. Akin to lipids, the compact dendritic structure self-assembles into uniform nanovesicles that in turn self-assemble into larger vesosomes in water. The vesosomes emit green nontraditional intrinsic fluorescence (NTIL), which is an emerging property as there are no classical fluorophores in the dendritic macromolecular structure. This work confirms the hypothesis that the NTIL emission is greatly enhanced by rigidification of the supramolecular assemblies containing heteroatomic subluminophores (HASLs) and by the presence of electron rich functional groups on the periphery of dendrimers. This work is the first one detecting NTIL in ferrocenyl-terminated dendrimers. Moreover, the vesosomes are stable in biological medium, are uptaken by cells, and show cytotoxic activity against cancer cells. Accordingly, the self-organization of these dendrimers into tertiary structures promotes the emergence of new properties enabling the same component, in this case, ferrocenyl group, to function as both antitumoral drug and fluorophore.

The structure-property relationship in LAPONITE® materials: from Wigner glasses to strong self-healing hydrogels formed by non-covalent interactions.

Rheology, small-angle X-ray scattering (SAXS), and dynamic light scattering (DLS) analysis, zeta potential measurement, scanning electron microscopy (SEM), and micro-FTIR and absorbance spectroscopy were used to enlighten the controversial literature about LAPONITE® materials. Our data suggest that pristine LAPONITE® in water does not form hydrogels induced by the so-called "house of cards" assembly, but rather forms Wigner glasses governed by repulsive forces. Ionic interactions between anisotropic LAPONITE® nanodiscs, sodium polyacrylate and inorganic salts afforded hydrogels that were transparent, self-standing, moldable, strong, and biocompatible with shear-thinning and self-healing behavior. An extensive study on the role of salts in the gelification process dictates a trend that relates the valence of cations with the viscoelastic properties of the bulk material (G' values follow the trend, monovalent < divalent < trivalent). These hydrogels present G' values up to 5.1 × 104 Pa, which are considered high values for non-covalent hydrogels. Hydrogels crosslinked with sodium phosphate salts are biocompatible, and might be valid candidates for injectable drug delivery systems due to their shear-thinning behavior with rapid self-healing after injection.

General Protocol to Obtain D-Glucosamine from Biomass Residues: Shrimp Shells, Cicada Sloughs and Cockroaches.

A general protocol is developed to obtain D-glucosamine from three widely available biomass residues: shrimp shells, cicada sloughs, and cockroaches. The protocol includes three steps: (1) demineralization, (2) deproteinization, and (3) chitin hydrolysis. This simple, general protocol opens the door to obtain an invaluable nitrogen-containing compound from three biomass residues, and it can potentially be applied to other chitin sources. White needle-like crystals of pure D-glucosamine are obtained in all cases upon purification by crystallization. Characterization data (NMR, IR, and mass spectrometry) of D-glucosamine obtained from the three chitin sources are similar and confirm its high purity. NMR investigation demonstrates that D-glucosamine is obtained mainly as the α-anomer, which undergoes mutarotation in aqueous solution achieving equilibrium after 440 min, in which the anomeric glucosamine distribution is 60% α-anomer and 40% ß-anomer.