Azacrown Ethers with Naphthyl Branches. Fluorescence Properties,Protonation and Metal Coordination

Starting from 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, we have prepared two compounds by replacing the amine hydrogens with naphthyl or 3,5-bis(2′-oxymethylnaphthyl)benzyl units. The absorption and emission spectra of compounds 2 (N,N′-bis(2-naphthylmethyl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane) and 3 (N,N′-bis[3,5-bis(2′-oxymethylnaphthyl)benzyl]-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane) have been studied in CH₃CN:CH₂Cl₂ 1:1 (v/v) solution. For comparison purposes, the spectroscopic properties of N-methyl(2-methylnaphthalene)ethylamine (1) have also been investigated. For each compound, the absorption spectra are qualitatively very similar to that of naphthalene, with molar absorption coefficients as expected for the presence of one (1), two (2), and four (3) naphthyl chromophoric groups. The fluorescence spectra, however, are quite different from that of naphthalene. The naphthalene-type fluorescence (λ_max = 337 nm) is strongly quenched, particularly for compounds 1 and 2 which also exhibit a broad emission band in the visible region (λ_max ≈ 480 nm) assigned to a low lying charge-transfer excited state. In the case of compound 3, a quenched naphthalene-type band is accompanied by weak exciplex and excimer emissions. Upon titration with CF₃SO₃H, the charge transfer bands of 1 and 2 and the exciplex emission of 3 disappear and the naphthalene-type bands regain intensity. Titration plots show that in compounds 2 and 3 the protonation of the two nitrogens occurs stoichiometrically in two distinct steps. Titration with Zn²⁺ gives rise to 2.Zn²⁺ and 3.Zn²⁺ complexes. This article is dedicated to Professor Dedier Astruc.     

Use of ionic liquids based on phosphonium salts for preparing biocomposites by in situ polymerization

A sodium montmorillonite, Dellite HPS, was modified with ionic liquids based on phosphonium salts, such as octadecyltriphenylphosphonium tetrafluoroborate and octadecyltriphenylphosphonium bromide. Thanks to their high thermal stability, these salts can be used during in situ polymerization, a method that favors the achievement of a good dispersion of the clay. Poly(1,4‐dimethylcyclohexane adipate) (PCHA), was chosen as an example of aliphatic polyester which can be a suitable matrix for new biocomposites with organo‐clays. The organo modified clays prepared were characterized by X‐ray diffraction (XRD), ATR‐FTIR spectroscopy, and thermal gravimetric analysis (TGA) while biocomposites were analyzed in terms of molecular structure, thermal and thermomechanical properties. The degree of dispersion of the clays in the polymer matrix was studied by XRD. The results show that the clays are well dispersed in the biocomposites, despite an intercalated structure highlighted by XRD analysis. Moreover, the clays confer a certain improvement in mechanical properties to the final materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42467.     

Cold groundwater temperatures and conductive heat flow in the Mt. Amiata geothermal area, Tuscany, Italy

The hydrogeochemical study of the cold springs present in the Mt. Amiata geothermal area, where the Bagnore and Piancastagnaio geothermal fields are situated, has defined the different shallow groundwater systems.The cold groundwater temperature of the volcanic phreatic aquifer is largely correlated with the geothermal heat flow. Through the analysis of the temperature of cold groundwaters, a possible method for geothermal prospection has been developed, supported by the results obtained in the studied area. Through the enthalpic balance of the aquifer and in agreement with available data, a geothermal flow of about 200 mW m^-2 has been calculated.     

Pulsed laser deposition of organic and biological materials

We report on the deposition of soft matter thin films by Matrix Assisted Pulsed Laser Evaporation (MAPLE). In particular, thin layers of biological material (Bovine Serum Albumin) and polymers (polyfluorene) for medical and optoelectronic applications, were realized by laser irradiating a frozen solution containing a low amount of material diluted in a laser absorbing volatile solvent. The depositions were carried out varying different parameters as solvent–solute concentration, solvent nature, laser fluencies, etc. The optical, morphological, structural and spectroscopical properties were detected by means of different analyses as FTIR, photoluminescence, AFM and SDS.     

Surface properties of phenolic compounds and their influence on the dispersion degree and oxidative stability of olive oil O/W emulsions

The surface and interfacial properties of gallic acid, catechin and quercetin, and their effect on the dispersion degree and the oxidative stability of olive oil oil-in-water (O/W) emulsions prepared using β-lactoglobulin and Tween 20 were studied.Gallic acid showed no effect on the surface properties while catechin was proven to be able to accumulate at the air/water interface, decreasing the surface tension values with increasing its concentration. All the phenolic antioxidants caused a decrease in the interfacial tension at the oil/water interface, even though only catechin and quercetin showed a concentration dependent behaviour.In emulsions, gallic acid did not affect the droplet size of the systems, catechin caused the formation of oil droplets bigger than those of the control, whilst quercetin improved the dispersion state of the emulsions with the increasing of its concentration. Gallic acid, despite its partitioning in the water phase due to its polarity, delayed the formation of both the hydroperoxides and TBARs and limited their accumulation. Catechin did not affect the formation of oxidation products whilst quercetin, among the tested antioxidants, caused the lowest formation of both hydroperoxides and TBARs through 33 days of storage.     

Integrated mass spectrometry approach to profile proanthocyanidins occurring in food supplements: Analysis of Potentilla erecta L. rhizomes

Potentilla erecta (L.) is known for the high concentration of proanthocyanidin oligomers (PAs) in its underground parts. The use of its preparations as food supplements and the lack of chemical–analytical studies concerning with an efficient chromatographic separation procedure for these compounds led us to develop a strategy to profile PAs occurring in this species.     

Synthesis, Molecular Characterization and Preliminary Antioxidant Activity Evaluation of Quercetin Fatty Esters

Quercetin shows interesting pharmacological effects, but its use in topical applications is limited by its low skin permeability and solubility. In this work, the synthesis of highly lipophilic quercetin esters with oleic, linoleic and linolenic acid useful as topical quercetin prodrugs is reported. Partial OH esterification is advisable to maintain the antioxidant activity of these compounds; tetraesters and triesters can be achieved by modulating the reaction conditions utilized for the total esterification of quercetin. The chemical structures of the esters were proven by spectroscopic techniques; quantum chemical NMR calculation were mandatory to unequivocally assign the free position in triesters. Finally, the antioxidant activity of all the synthesized compounds was determined by the 2,2-diphenyl-1-picryl-hydrazyl method and by 2,2-azinobis(3-ethyl-benzothiazoline-6-sulfonic acid) assay.     

Soil Moisture Measurements: Comparison of Instrumentation Performances

It has long been recognized that reliable, robust, and automated instrumentation for the measurement of soil moisture content can be extremely useful, if not essential, in hydrological, environmental, and agricultural applications. A number of automated techniques for point measurement of soil water content have been developed to operational level over the past few decades. While each of those techniques has been individually calibrated by the gravimetric method, typically under laboratory conditions, there have been few studies that made a direct comparison between the various techniques, particularly under field conditions. This paper compares ECH2O probes, EC-5 (both sensors based on capacitance measurements, developed by Decagon Devices) and time domain reflectometer sensors (CS616 Campbell Scientific Water Content Reflectometer), with gravimetric data and with each other, under field conditions. Data were collected during two field experiments characterized by different soils and a wide range of soil moistures, resulting from irrigation/drying cycle. Results show that all the tested probes give acceptable results after being calibrated in the field. The capacitive sensors can be used in each type of soil with the same calibration equation, independently from depth, with root mean square error (RMSE) ranging between 2.5 and 3.6%. Time Domain Reflectometry probes showed a dependence on depth but a lower RMSE (1.6%).