Solid State NMR Study of the Mixing Degree Between Ginkgo Biloba Extract and a Soy-Lecithin-Phosphatidylserine in a Composite Prepared by the Phytosome® Method

Leaves extract of Ginkgo biloba, known in China since the most ancient times, has been widely used in the area of senile dementia thanks to its improving effects on cognitive function. A promising formulation of this botanical ingredient consists in a Ginkgo biloba-soy-lecithin-phosphatidylserine association obtained by the Phytosome® process. The precise assess- ment of the mixing degree between Ginkgo biloba and soy-lecithin-phosphatidylserine in this formulation is an important piece of information for understanding the reasons of its final performances. To this aim in the present study we carried out for the first time a Solid State Nuclear Magnetic Resonance investigation on Ginkgo biloba-soy-lecithin-phosphatidylserine association, on its constituents and on a mechanical mixture. The analysis of different observables highlighted a very intimate mixing (domains of single components not larger than 60 nm) of Ginkgo biloba and soy-lecithin-phosphatidylserine in their association obtained by Phytosome® process, together with a slight modification of their molecular dynamics, not observed in the case of the mechanical mixture

Thermochromic polyethylene films doped with perylene chromophores: experimental evidence and methods for characterization of their phase behaviour

We report on a thermochromic system suitable for sensing temperature changes in the 30-70 degrees C regime based on linear low density polyethylene (LLDPE) films doped with N,N'-bis-(1'-phenylethyl)-perylene-3,4,9,10-tetracarboxydiimide (PE-Pery), a fluorescent aggregachromic dye. At low PE-Pery concentration (0.01-0.02 wt%), the dye monomers were well dispersed in the polymer matrix showing their maximum fluorescence intensity at 525 nm. As the dye content was increased, monomers emission quenched whereas dye aggregates prevailed above 0.05 wt% as well as their red fluorescence band at 620-680 nm. Upon heating from 30 to 70 degrees C, all films displayed a thermochromic response, more evident for the less concentrated samples (<0.05 wt%) in which the emission of the dye as a monomer continuously increased with increasing temperature. This phenomenon promoted effective color changes from a dull red-violet at 30 degrees C to a bright yellow-green at 70 degrees C. Combined DSC and variable-temperature Solid State NMR (SSNMR) measurements addressed the thermochromic behavior to the increased amount of the available amorphous phase and to the increased mobility of both the interphase and amorphous components with temperature, which favored PE-Pery dispersion and diffusion, thus recovering their fluorescence. Overall, the present results support the use of PE-Pery-enriched LLDPE films as a chromogenic material suitable for the detection of temperature changes close to the physiological regime

Anisotropy and NMR spectroscopy

Abstract In this paper, different aspects concerning anisotropy in Nuclear Magnetic Resonance (NMR) spectroscopy have been reviewed. In particular, the relevant theory has been presented, showing how anisotropy stems from the dependence of internal nuclear spin interactions on the molecular orientation with respect to the external magnetic field direction. The consequences of anisotropy in the use of NMR spectroscopy have been critically discussed: on one side, the availability of very detailed structural and dynamic information, and on the other side, the loss of spectral resolution. The experiments used to measure the anisotropic properties in solid and soft materials, where, in contrast to liquids, such properties are not averaged out by the molecular tumbling, have been described. Such experiments can be based either on static low-resolution techniques or on one- and two-dimensional pulse sequences exploiting Magic Angle Spinning (MAS). Examples of applications of NMR spectroscopy have been shown, which exploit anisotropy to obtain important physico-chemical information on several categories of systems, including pharmaceuticals, inorganic materials, polymers, liquid crystals, and self-assembling amphiphiles in water. Solid-state NMR spectroscopy can be considered, nowadays, one of the most powerful characterization techniques for all kinds of solid, either amorphous or crystalline, and semi-solid systems for the obtainment of both structural and dynamic properties on a molecular and supra-molecular scale. Graphic abstrac

Epoxy resin doped with Coumarin 6: Example of accessible luminescent collectors

We report on the preparation of luminescent collectors based on epoxy resins containing Coumarin 6 as fluorescent dye. Fluorescent epoxy slabs were obtained by carefully mixing from 60 to 150 ppm of the fluorophore with bisphenol A diglycidyl ether and 4,4′-methylenebis(2-methylcyclohexylamine) as curing agent. Spectroscopic (FT-IR, solid-state NMR, Raman) investigations and calorimetric analysis evidence the success of the preparation procedure in terms of slab homogeneity, fluorophore dispersibility and its role in promoting the crosslinking extent. The concentrating ability and the derived optical efficiencies of the epoxy-based collectors are determined with a properly designed set-up and result greater (∼10%) than that of poly(methyl methacrylate) concentrators with the same fluorophore and geometry. Optical efficiencies as high as 7.4% are obtained and enable the potential use of epoxy resins as bulk thermosetting materials for solar collectors

Phase transitions in hydrophobe/phospholipid mixtures: hints at connections between pheromones and anaesthetic activity

The phase behavior of a mixture of a typical insect pheromone (olean) and a phospholipid (DOPC)/water dispersion is extensively explored through SAXS, NMR and DSC experiments. The results mimic those obtained with anaesthetics in phospholipid/water systems. They also mimic the behavior and microstructure of ternary mixtures of a membrane mimetic, bilayer-forming double chained surfactants, oils and water. Taken together with recent models for conduction of the nervous impulse, all hint at lipid involvement and the underlying unity in mechanisms of pheromone, anaesthetic and hydrophobic drugs, where a local phase change in the lipid membrane architecture may be at least partly involved in the transmission of the signal

Solid-State Nuclear Magnetic Resonance of Triple-Cation Mixed-Halide Perovskites

Mixed-cation lead mixed-halide perovskites are the best candidates for perovskite-based photovoltaics, thanks to their higher efficiency and stability compared to the single-cation single-halide parent compounds. TripleMix (Cs0.05MA0.14FA0.81PbI2.55Br0.45 with FA = formamidinium and MA = methylammonium) is one of the most efficient and stable mixed perovskites for single-junction solar cells. The microscopic reasons why triplecation perovskites perform so well are still under debate. In this work, we investigated the structure and dynamics of TripleMix by exploiting multinuclear solid-state nuclear magnetic resonance (SSNMR), which can provide this information at a level of detail not accessible by other techniques. 133Cs, 13C, 1 H, and 207Pb SSNMR spectra confirmed the inclusion of all ions in the perovskite, without phase segregation. Complementary measurements showed a peculiar longitudinal relaxation behavior for the 1 H and 207Pb nuclei in TripleMix with respect to single-cation single-halide perovskites, suggesting slower dynamics of both organic cations and halide anions, possibly related to the high photovoltaic performances

Polymer-based black phosphorus (bP) hybrid materials by in situ radical polymerization: an effective tool to exfoliate bP and stabilize bP nanoflakes

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) towards both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: i) the mixing of conventionally liquid-phase exfoliated bP (in DMSO) with PMMA solution; ii) the direct exfoliation of bP in a polymeric solution; iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn-MMA by sonication-assisted liquid phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of bPn results particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-Solid State NMR studies) and are particularly stable to air and UV light exposure

Measuring 19F shift anisotropies and 1H–19F dipolar interactions with ultrafast MAS NMR

A new 19F anisotropic–isotropic shift correlation experiment is described that operates with ultrafast MAS, resulting in good resolution of isotropic 19F shifts in the detection dimension. The new experiment makes use of a recoupling sequence designed using symmetry principles that reintroduces the 19F chemical shift anisotropy in the indirect dimension. The situations in which the new experiment is appropriate are discussed, and the 19F shift anisotropy parameters in poly(difluoroethylene) (PVDF) are measured. In addition, similar recoupling sequences are shown to be effective for measuring 1H–19F distances via the heteronuclear dipolar interaction. This is demonstrated by application to a recently synthesized zirconium phosphonate material that contains one-dimensional chains linked by H–F hydrogen bonds

Comparison of the dielectric and NMR results for liquid crystals : dynamic aspects

Critical analysis of the results of studies of molecular rotational dynamics in liquid crystalline substances with the aid of the dielectric spectroscopy (DS) and nuclear magnetic resonance (NMR) is given. Both methods are known to be sensitive to different aspects of molecular rotations: the polarization vector and the relaxation time (DS) in the case of DS, a tensor describing a nuclear interaction and the correlation time (NMR) for NMR method. Furthermore, both methods provide correlation functions with different rank values. A common basis for the comparison between (DS) and (NMR) is postulated. Several examples of the temperature dependence of the correlation times coming from the two spectroscopic methods are presented. Qualitative agreements of the correlation times were achieved in most cases

Organic protic ionics based on Nitrilo(trimethylenephosphonic acid) as water-free, proton-conducting materials

We produced two solid protic ionics by stoichiometric acid-base reaction between Nonafluorobutanesulfonic or p-Toluenesulfonic acid with Nitrilotri(methylenephosphonic acid). The latter behaves as a Bronsted base by means of the nucleophilic nitrogen atom which captures the proton from the Nonafluorobutanesulfonic or p-Toluenesulfonic acid. Moreover, the Nitrilotri(methylenephosphonic acid) moiety possesses six POH terminating units. 1H MAS NMR evidenced hydrogen-bonding activity of these units, which enables proton transport through the lattice by a hopping-site mechanism. Homogeneous, transparent and mechanically and thermally robust disks from these materials were obtained by sintering the powders under mild pressure and temperature. We showed, using electrochemical impedance spectroscopy, that these protic ionics possess good proton conductivity, in excess of 10–2 –1 cm–1, under fully anhydrous conditions at 190 °C. As such, these materials appear potentially attractive for application in high-temperature electrochemical devices, such as polymer electrolyte fuel cells and water electrolyzers operating at elevated temperature, typically above 130 °C and up to 200 °C for fuel cells. The proton-transport mechanism is also discussed in the light of the NMR- and impedance-spectroscopy results