Organic-Inorganic Hybrid Pigments Based on Bentonite: Strategies to Stabilize the Quinoidal Base Form of Anthocyanin.

Anthocyanins are one of the natural pigments that humanity has employed the most and can substitute synthetic food dyes, which are considered toxic. They are responsible for most purple, blue, and red pigment nuances in tubers, fruits, and flowers. However, they have some limitations in light, pH, oxygen, and temperature conditions. Combining biomolecules and inorganic materials such as clay minerals can help to reverse these limitations. The present work aims to produce materials obtained using cetyltrimethylammonium bromide in bentonite clay for incorporation and photostabilization of anthocyanin dye. Characterizations showed that the organic molecules were intercalated between the clay mineral layers, and the dye was successfully incorporated at a different pH. Visible light-driven photostability tests were performed with 200 h of irradiation, confirming that the organic-inorganic matrices were efficient enough to stabilize the quinoidal base form of anthocyanin. The pigment prepared at pH 10 was three-fold more stable than pH 4, showing that the increase in the synthesis pH promotes more stable colors, probably due to the stronger intermolecular interaction obtained under these conditions. Therefore, organobentonite hybrids allow to stabilize the fragile color coming from the quinoidal base form of anthocyanin dyes.

Organo magadiites for diclofenac adsorption: influence of the surfactant chain.

The presence of drugs in aquatic environments has been considered a global challenge and several remediation technologies have been proposed, including adsorption. In this study, new diclofenac adsorbents were obtained from the reaction of sodium magadiite (Na-Mag) with surfactants dodecylpyridinium chloride hydrate (C12pyCl) and hexadecylpyridinium chloride monohydrate (C16pyCl)), 1-hexadecyltrimethylammonium bromide (C16Br), and dodecyltrimethylammonium bromide (C12Br). The synthesis was carried out in the microwave at 50 °C for 5 min using surfactant amounts of 100% and 200% in relation to the cation exchange capacity of Na-Mag. The elemental analysis indicated that surfactants with a longer organic chain were more incorporated into Na-Mag, whose values were 1.42 and 1.32 mmol g-1 for C16pyMag200% and C16Mag200%, respectively. X-ray diffraction results suggested formation of intercalated products with basal space in the range of 2.81-4.00 nm. Diclofenac was quickly adsorbed on all organophilic magadiites, at an equilibrium time of 1 min. Drug capacity adsorption was influenced by the arrangement and packing density of organic cations, the basal distance, and the organic contents of the samples at high drug concentrations. Alkylpyridinium magadiites exhibited maximum adsorption capacities higher than alkylammonium magadiites, of 96.4, 100.7, 131.7, and 166.1 mg g-1 for C12pyMag100%, C12pyMag200%, C16pyMag100%, and C16pyMag200%, respectively, at pH 6.0 and 30 °C. Diclofenac removal by samples was not affected by the presence of ibuprofen, which was also removed from binary system by organophilic magadiites reaching removal of 76.5% and 86.9% by C16pyMag100% and C16pyMag200%, respectively. Regeneration studies demonstrated a drug removal percentage of 83-92% for C16pyMag and C16Mag after three cycles of adsorption.

Enhancing the mechanical properties and providing bioactive potential for graphene oxide/montmorillonite hybrid dental resin composites.

This in vitro study synthetized hybrid composite nanoparticles of graphene oxide (GO) and montmorillonite MMt (GO-MMt) by ultrasound treatments. Samples were characterized by X-ray diffraction, FT-Raman, FTIR, TEM and SEM. The effect of their incorporation (0.3% and 0.5%) on the mechanical properties in a resin-based composite (RBC) and their bioactivity potential were evaluated. The specimens were characterized by evaluating their 3-point flexural strength (n = 6), modulus of elasticity (n = 6), degree of conversion (n = 6), microhardness (n = 6), contact angle (n = 3) and SEM analysis (n = 3). In vitro test in SBF were conducted in the RBCs modified by the hybrid. Overall, the synthetized hybrid composite demonstrated that GO was intercalated with MMt, showing a more stable compound. ANOVA and Tukey test showed that RBC + 0.3% GO-MMt demonstrated superior values of flexural strength, followed by RBC + 0.5% GO-MMt (p < 0.05) and both materials showed higher values of microhardness. All groups presented a contact angle below 90°, characterizing hydrophilic materials. RBCs modified by the hybrid showed Ca and P deposition after 14 days in SBF. In conclusion, RBCs composed by the hybrid showed promising results in terms of mechanical properties and bioactive potential, extending the application of GO in dental materials.

In Vitro Evaluation of Desensitizing Agents Containing Bioactive Scaffolds of Nanofibers on Dentin Remineralization.

This study evaluated the effect of the incorporation of bioactive nanofibers in desensitizing agents on dentin permeability. Sixty disks of dentin were randomly distributed in four groups (n = 15). Distribution was based on the desensitizing agents, fluoride varnish and self-etching adhesive, and the presence of nanofibers: C (self-etching adhesive Clearfil SE Bond), CN (Clearfil SE Bond with 1% nanofiber), D (Duraphat varnish), and DN (Duraphat varnish with 1% nanofiber). Dentin permeability was determined using hydraulic conductivity. For a qualitative analysis, confocal laser microscopy and scanning electron microscopy were performed. The C group showed the lowest hydraulic conductance (Lp%) (89.33), while the DN group showed the highest Lp% (116.06). No statistical significance was observed in the Lp% values in all groups after the treatment and 6% citric acid challenge (p > 0.239). In the images, the CN group presented a higher superficial and intratubular deposition. In addition, this group presented a more homogeneous dentin surface and wide occlusion of dentinal tubules than the other treatments. Despite there being no statistical differences among the treatments employed, the images showed that the CN group presented a higher surface and intratubular deposition compared to the other treatments, even after the acid challenge.

Robust Mn(III) N-pyridylporphyrin-based biomimetic catalysts for hydrocarbon oxidations: heterogenization on non-functionalized silica gel versus chloropropyl-functionalized silica gel.

Two classes of heterogenized biomimetic catalysts were prepared and characterized for hydrocarbon oxidations: (1) by covalent anchorage of the three Mn(iii) meso-tetrakis(2-, 3-, or 4-pyridyl)porphyrin isomers by in situ alkylation with chloropropyl-functionalized silica gel (Sil-Cl) to yield Sil-Cl/MnPY (Y = 1, 2, 3) materials, and (2) by electrostatic immobilization of the three Mn(iii) meso-tetrakis(N-methylpyridinium-2, 3, or 4-yl)porphyrin isomers (MnPY, Y = 4, 5, 6) on non-modified silica gel (SiO2) to yield SiO2/MnPY (Y = 4, 5, 6) materials. Silica gel used was of column chromatography grade and Mn porphyrin loadings were deliberately kept at a low level (0.3% w/w). These resulting materials were explored as catalysts for iodosylbenzene (PhIO) oxidation of cyclohexane, n-heptane, and adamantane to yield the corresponding alcohols and ketones; the oxidation of cyclohexanol to cyclohexanone was also investigated. The heterogenized catalysts exhibited higher efficiency and selectivity than the corresponding Mn porphyrins under homogeneous conditions. Recycling studies were consistent with low leaching/destruction of the supported Mn porphyrins. The Sil-Cl/MnPY catalysts were more efficient and more selective than SiO2/MnPY ones; alcohol selectivity may be associated with hydrophobic silica surface modification reminiscent of biological cytochrome P450 oxidations. The use of widespread, column chromatography, amorphous silica yielded Sil-Cl/MnPY or SiO2/MnPY catalysts considerably more efficient than the corresponding, previously reported materials with mesoporous Santa Barbara Amorphous No 15 (SBA-15) silica. Among the materials studied, in situ derivatization of Mn(iii) 2-N-pyridylporphyrin by covalent immobilization on Sil-Cl to yield Sil-Cl/MnP1 showed the best catalytic performance with high stability against oxidative destruction and reusability/recyclability.

Mesoporous calcium phosphate using casein as a template: Application to bovine serum albumin sorption.

Mesoporous hydroxyapatites were synthesized at room temperature using casein as a template, and key experimental factors, such as casein concentration, pH and extraction of casein in the final solids by washing and thermal treatment, were systematically investigated. The X-Ray Diffraction (XRD) patterns confirmed the synthesis of well-crystallized hydroxyapatite. The N2 adsorption/desorption isotherms were in agreement with the formation of mesoporous hydroxyapatite with a maximum surface area of 106m2g-1. Infrared spectroscopy and thermogravimetry analysis were performed to investigate the extraction of casein in water in the post-synthesis stage. Pure mesoporous hydroxyapatite exhibited good BSA adsorption capacity higher than the one obtained for conventional hydroxyapatite.

Thermal stability of the prototypical Mn porphyrin-based superoxide dismutase mimic and potent oxidative-stress redox modulator Mn(III) meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin chloride, MnTE-2-PyP(5+).

Cationic Mn porphyrins are among the most potent catalytic antioxidants and/or cellular redox modulators. Mn(III) meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin chloride (MnTE-2-PyPCl(5)) is the Mn porphyrin most studied in vivo and has successfully rescued animal models of a variety of oxidative stress-related diseases. The stability of an authentic MnTE-2-PyPCl(5) sample was investigated hereon by thermogravimetric, derivative thermogravimetric, and differential thermal analyses (TG/DTG/DTA), under dynamic air, followed by studies at selected temperatures to evaluate the decomposition path and appropriate conditions for storage and handling of these materials. All residues were analyzed by thin-layer chromatography (TLC) and UV-vis spectroscopy. Three thermal processes were observed by TG/DTG. The first event (endothermic) corresponded to dehydration, and did not alter the MnTE-2-PyPCl(5) moiety. The second event (endothermic) corresponded to the loss of EtCl (dealkylation), which was characterized by gas chromatography-mass spectrometry. The residue at 279°C had UV-vis and TLC data consistent with those of the authentic, completely dealkylated analog, MnT-2-PyPCl. The final, multi-step event corresponded to the loss of the remaining organic matter to yield Mn(3)O(4) which was characterized by IR spectroscopy. Isothermal treatment at 188°C under static air for 3h yielded a mixture of partially dealkylated MnPs and traces of the free-base, dealkylated ligand, H(2)T-2-PyP, which reveals that dealkylation is accompanied by thermal demetallation under static air conditions. Dealkylation was not observed if the sample was heated as a solid or in aqueous solution up to ∼100°C. Whereas moderate heating changes sample composition by loss of H(2)O, the dehydrated sample is indistinguishable from the original sample upon dissolution in water, which indicates that catalytic activity (on Mn basis) remains unaltered. Evidently, dealkylation at high temperature compromises sample activity.