Olive Fruit Ripening Degree and Water Content Relationships with Phenolic Acids and Alcohols, Secoiridoids, Flavonoids and Pigments in Fruit and Oil.

Olive drupe traits (i.e., ripening index and pericarp water content) and minor components (i.e., phenols and pigments in both fruit and oil) are important for human health and are affected by agronomic background. The aim of this study was to investigate the relationship between fruit traits, phenols, and pigments in samples derived from different soil and water management practices. Chromatographic (UHPLC-MS/MS) and spectroscopic (1HNMR and near UV-Vis spectroscopy) techniques were employed for the characterization of olive fruits and oils. The use of various techniques allowed the identification of interesting trace compounds. We observed that most of the fruit phenols (a total of 29 compounds) were correlated with the degree of ripening: most of the phenolic acids (and their derivatives), phenolic alcohols, and secoiridoids were negatively correlated, whereas the majority of the studied flavonoids were positively correlated. The relationship between the ripening index and fruit phenolic compounds appears to be dependent on the metabolic pathway that controls the synthesis of each individual compound. Conversely, the secoiridoids and pigments in olive oil showed a negative correlation with pulp moisture, probably because of the influence of the water content on the extractability and transfer in the oil phase of these minor components.

Multi-Analytical Approach to Characterize the Degradation of Different Types of Microplastics: Identification and Quantification of Released Organic Compounds.

Microplastics and nanoplastics represent one of the major environmental issues nowadays due to their ubiquitous presence on Earth, and their high potential danger for living systems, ecosystems, and human life. The formation of both microplastics and nanoplastics strongly depends on both the type of pristine materials and the degradation processes related to biological and/or abiotic conditions. The aim of this study is to investigate the effect of two of the most relevant abiotic parameters, namely temperature and light, taken under direct control by using a Solar box, on five types of reference polymers: high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), and polyethylene terephthalate (PET). A multi-analytical approach was adopted to investigate in detail the first steps of plastics degradation. Samples of plastic materials at different degradation times were analyzed by means of 1H NMR spectroscopy and thermal desorption gas chromatography mass spectrometry (TD-GC-MS) technique. Several minor molecular species released during degradation were consistently identified by both techniques thus providing a comprehensive view of the various degradation products of these five types of microplastics.

Deuteron NMR investigation on orientational order parameter in polymer dispersed liquid crystal elastomers.

Polymer-dispersed liquid crystal elastomers have been recently introduced as a thermomechanically active composite material, consisting of magnetically oriented liquid crystal elastomer particles incorporated in a cured polymer matrix. Their thermomechanical properties are largely governed by the degree of imprinted particle alignment, which can be assessed by means of deuterium perturbed 2H-NMR. Spectra of samples with various degrees of imprinted particle alignment were recorded and the results simulated using the discrete reorientational exchange model developed for determining the dispersion of liquid crystal elastomer's domain orientational distribution. We show that the model can be applied to measure the orientational distribution of embedded liquid crystal microparticles and successfully determine the orientational order parameter in the composite system. Thermomechanical measurements correlate well with the obtained results, thus additionally confirming the validity of the applied method.

STEAM-MiTiS: An MR spectroscopy method for the detection of scalar-coupled metabolites and its application to glutamate at 7 T.

PURPOSE: We herein present a spectroscopic technique for the detection of scalar-coupled metabolites based on stimulated echo acquisition mode (STEAM). The method is based on the time evolution of scalar-coupled metabolites at different mixing times and a constant echo time. The technique is optimized for targeting the metabolite glutamate at 7T. METHODS: Numerical simulations were used to optimize the parameters to maximize the chosen metabolite signal. The maximum detection efficiency and metabolite signal as a function of echo time were used to identify the optimal parameters. In vitro and in vivo validations of the method were also performed. RESULTS: This method canceled all the strong singlet lines and signals from macromolecules and preserved signals originating from the scalar-coupled metabolites. The subtracted spectrum was strongly simplified, but the complete spectral information of the traditional STEAM acquisition was retained in the sum spectrum. CONCLUSIONS: The simulations performed in this study were in agreement with the experimental results, and a clear detection of the metabolite of interest was obtained. The applicability in vivo was also demonstrated, with the selective detection of glutamate in human brain. This technique is simple, suitable for standard MR systems without sequence programming and could be used to detect other metabolites.

Conformational properties and orientational order of a de Vries liquid crystal investigated through NMR spectroscopy.

Solid-state and liquid-state NMR spectroscopic techniques are used to describe at molecular level the behaviour of a de Vries liquid crystal (namely the mesogen 9HL) at the SmA-SmC* transition, which is characterized by the absence of the layer shrinkage, typical of non-de Vries smectogens. Previous (2)H NMR studies on the same smectogen, performed at a different magnetic field (from 4.70 to 18.80 T), provided evidence of the occurrence of a tilt of one of the three phenyl rings, constituting the aromatic core of 9HL, at the SmA-SmC* phase transition. In this work, the study is extended to the whole rigid aromatic core of the 9HL. In particular, the variable temperature behavior of the mesogen studied by 1D (13)C NMR cross-polarization (CP) and 2D (1)H-(13)C PDLF (proton-encoded (13)C-detected, local field) NMR experiments made possible the characterization of the conformational and orientational properties in the two smectic phases. These results are compared with various proposed models invoked to describe the SmA-SmC* transition in de Vries smectogens at a molecular level.

Brief overview on 2H NMR studies of polysiloxane-based side-chain nematic elastomers.

This is a brief overview on recent studies on liquid crystalline elastomers (LCEs) based on polysiloxane chain, in the form of monodomain films, selectively (2)H-labeled in different parts of the LCE samples, i.e. on the crosslinker or mesogenic units. (2)H NMR spectroscopic techniques were used to measure the temperature dependence of the quadrupolar splittings, line widths and relaxation times, T(1) and T(2). From these data, several information about the orientational order parameter, S, of various LCE fragments, thermodynamic features of the isotropic-nematic transition and main motional processes could be generalized for this type of elastomers.

Synthesis, chiroptical properties and density functional theory calculations of 3,3'-biphenyl-2,2'-bitropone.

The synthesis of new bitropone derivatives, namely, 3,3'-biphenyl-2,2'-bitropone and 7,7'-biphenyl-2,2'-bitropone, are reported. Isolation of enantiomers arising from restricted rotation around the C-C bond connecting the tropone moieties was attempted by means of chiral high performance liquid chromatography (HPLC). No separation was obtained for 7,7'-biphenyl-2,2'-bitropone. For 3,3'-biphenyl-2,2'-bitropone, difficulties were encountered because of the low separation factor of the peaks and the presence of a rapid racemization process. However, quantitative chiroptical data on the antipodes were obtained by linking a circular dichroism (CD) spectrometer and a UV-vis spectrophotometric detector in series to the HPLC instrument. The analysis of the CD and UV-vis spectra in terms of absolute conformations was done with the help of theoretical calculations performed at the Density Functional Theory (DFT) level. The most stable conformations of the 3,3'-biphenyl-2,2'-bitropone in its ground state were obtained. Starting from these minimum energy conformations, it was possible to compute theoretical CD and UV absorption spectra that fit well with the experimental ones. From this comparison the absolute configuration to the antipodes was assigned. Finally, the effect of the presence of the two lateral phenyl substituents on the structure of the bitropone and hence on the CD spectrum is discussed.

Polymer-dispersed liquid crystal elastomers as moldable shape-programmable material.

The current development of soft shape-memory materials often results in materials that are typically limited to the synthesis of thin-walled specimens and usually rely on complex, low-yield manufacturing techniques to fabricate macro-sized, solid three-dimensional objects. However, such geometrical limitations and slow production rates can significantly hinder their practical implementation. In this work, we demonstrate a shape-memory composite material that can be effortlessly molded into arbitrary shapes or sizes. The composite material is made from main-chain liquid crystal elastomer (MC-LCE) microparticles dispersed in a silicone polymer matrix. Shape-programmability is achieved via low-temperature induced glassiness and hardening of MC-LCE inclusions, which effectively freezes-in any mechanically instilled deformations. Once thermally reset, the composite returns to its initial shape and can be shape-programmed again. Magnetically aligning MC-LCE microparticles prior to curing allows the shape-programmed artefacts to be additionally thermomechanically functionalized. Therefore, our material enables efficient morphing among the virgin, thermally-programmed, and thermomechanically-controlled shapes.

A photosensitive liquid crystal studied by 14N NMR, 2H NMR, and DFT calculations.

An azobenzene derivative, namely diheptylazobenzene, showing the nematic and smectic A liquid crystalline phases, was investigated by means of a combined approach based on NMR and DFT calculations. (14)N NMR quadrupole- and chemical-shift-perturbed spectra were acquired in the whole mesophasic range, providing both experimental quadrupolar splittings and chemical shift anisotropy values. On the same mesogen, deuterium labelled at the α-position of the hydrocarbon chain, (2)H NMR quadrupole-perturbed spectra were recorded. The analysis of these NMR data was performed with the help of ab initio calculations, in vacuo and by taking into account the effect of the anisotropic environment typical of liquid crystals, by using the IEF-PCM model. The geometry optimizations of the azomesogen in the trans and cis configurations were performed by DFT calculations employing the combination of B3LYP functional with the 6-311G(d) basis set. The analysis of experimental NMR data was performed by considering the trans configuration as the most populated one and the corresponding quadrupolar tensors and chemical shielding tensors were determined at the DFT level of theory. The main result of this work is the determination of a relatively high and temperature-dependent molecular biaxiality of the trans state of this azomesogen.

Study of the Evolution of Pigments from Freshly Pressed to 'On-the-Shelf' Extra-Virgin Olive Oils by Means of Near-UV Visible Spectroscopy.

Spectroscopic non-destructive methods have high potentialities as fast, cheap and easy-to-be-used approaches to address olive oil quality and authenticity. Based on previous research where near-UV Visible spectroscopy was used to investigate extra-virgin olive oils (EVOOs) and their main pigments' content (i.e., ß-carotene, lutein, pheophytin a and pheophytin b), we have implemented the spectral deconvolution method in order to follow the EVOO's life, from 'freshly pressed' to 'on-the-shelf' EVOO samples at different storage time. In the first part of the manuscript, the new implemented deconvolution spectroscopic method aimed to quantify two additional pigments, namely chlorophyll a and chlorophyll b, is described and tested on 'ad hoc' samples with known concentrations of chlorophylls. The effect of light exposure and acidification was investigated to test the reliability and robustness of the spectral deconvolution. In the second part of the work, this approach was used to study the kinetic of pigments' degradation in several monocultivar fresh EVOO samples under optimal storage's conditions. The results here reported show that this spectroscopic deconvolution approach is a good method to study fresh EVOOs too; moreover, the proposed method revealed to be sensitive to detect eventual stresses of olive oil samples stored in not-good conditions.

Analysis of Extra Virgin Olive Oils from Two Italian Regions by Means of Proton Nuclear Magnetic Resonance Relaxation and Relaxometry Measurements.

The interest in development of new non-destructive methods for characterization of extra virgin olive oils (EVOOs) has been increasing in the recent years. Among different experimental techniques, nuclear magnetic resonance (NMR) relaxation measurements are very promising in the field of food characterization and authentication. In this study, we focused on relaxation times T1 and T2 measured at different magnetic field strengths (namely, 2, 100, and 400 MHz) and 1H NMR T1 relaxometry dispersions directly on olive oil samples without any chemical/physical treatments. A large set of EVOO samples produced in two regions of Italy, Tuscany and Apulia, were investigated by means of 1H NMR relaxation techniques. The relaxation studies reported here show several common features between the two sets of EVOO samples, thus indicating that relaxation properties, namely, the ranges of values of T1 and T2 at 2 and 100 MHz, are characteristic of EVOOs, independently from the cultivars, climate, and geographic origin. This is a promising result in view of quality control and monitoring.

Sensitivity of Proton NMR Relaxation and Proton NMR Diffusion Measurements to Olive Oil Adulterations with Vegetable Oils.

Olive oils and, in particular, extra-virgin olive oils (EVOOs) are one of the most frauded food. Among the different adulterations of EVOOs, the mixture of high-quality olive oils with vegetable oils is one of the most common in the market. The need for fast and cheap techniques able to detect extra-virgin olive oil adulterations was the main motivation for the present research work based on 1H NMR relaxation and diffusion measurements. In particular, the 1H NMR relaxation times, T1 and T2, measured at 2 and 100 MHz on about 60 EVOO samples produced in Italy are compared with those measured on four different vegetable oils, produced from macadamia nuts, linseeds, sunflower seeds, and soybeans. Self-diffusion coefficients on this set of olive oils and vegetable oil samples were measured by means of the 1H NMR diffusion ordered spectroscopy (DOSY) technique, showing that, except for the macadamia oil, other vegetable oils are characterized by an average diffusion coefficient sensibly different from extra-virgin olive oils. Preliminary tests based on both NMR relaxation and diffusometry methods indicate that eventual adulterations of EVOO with linseed oil and macadamia oil are the easiest and the most difficult frauds to be detected, respectively.

Near UV-Vis and NMR Spectroscopic Methods for Rapid Screening of Antioxidant Molecules in Extra-Virgin Olive Oil.

Several spectroscopic techniques have been optimized to check extra-virgin olive oil quality and authenticity, as well as to detect eventual adulterations. These methods are usually complementary and can give information about different olive oil chemical components with bioactive and antioxidant properties. In the present work, a well-characterized set of extra-virgin olive oil (cultivar Frantoio) samples from a specific area of Tuscany (Italy) were investigated by combining near UV-Vis absorption spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) to identify and quantify different chemical components, such as pigments, secoiridoids and squalene, related to the nutritional and quality properties of olive oils. Moreover, the pigmentation index of olives, organoleptic and sensory properties, total phenolic compound contents and the lipidic fractions of olive oils were investigated. The results obtained are, finally, compared and discussed in order to correlate several properties of both olives and olive oils with specific features of the cultivation area.

Antioxidant, Nutraceutical Properties, and Fluorescence Spectral Profiles of Bee Pollen Samples from Different Botanical Origins.

Bee pollen is made by honey bees (Apis Mellifera) from the pollen of plants and flowers and represents an apiary product enriched in essential amino acids, polyphenols, omega-3, and omega-6 fatty acids. This study investigated the botanical origin, micronutrient profile, and antioxidant activity of bee pollen samples (n = 10) harvested in Lucca and Massa Carrara (Tuscany, Italy) between 2016 and 2017. The palynological analysis showed that bee pollen samples were composed of nine botanical families. Front-face fluorescence spectroscopy was performed on bee pollen samples in bulk, without any treatment, and in ethanol extracts to determine the characteristic fluorescent profile and, to identify the main chemical compounds with biological activity. The main chemical compounds detected were polyphenols (mainly flavonoids and phenolic acids), hydro-soluble vitamins (B2, B3, B6, and B9), amino acids, and pigments. Furthermore, the antioxidant activity was investigated, and one of the two Viburnum pollens resulted in the highest polyphenols and flavonoids content (20.15 ± 0.15 mg GAE/g fw and 23.46 ± 0.08 mg CE/g fw, respectively). However, Prunus and Eucalyptus families showed the highest in vitro (190.27 ± 8.30 µmol Fe2+/g) and ex vivo (54.61 ± 8.51 CAA unit) antioxidant capacity, respectively. These results suggested that Tuscan bee pollen, depending on the botanical family, is rich in essential nutrients and potential nutraceutical product.

The effect of sourdough fermentation on Triticum dicoccum from Garfagnana: 1H NMR characterization and analysis of the antioxidant activity.

The fermentation of Triticum dicoccum with sourdough enhances the nutritional aspects of the final product by the enrichment of several compounds with potential medical and biological activity, hence, could improve the health of consumers. This study analyzed the chemical composition of fermented spelt flour from Garfagnana (Province of Lucca, Tuscany) by 1H Nuclear Magnetic Resonance (1H NMR) spectroscopy and its in vitro antioxidant properties by FRAP and DPPH tests. Beyond this, the ex vivo CAA-RBC assay determined the cellular antioxidant activity on human erythrocytes under oxidative condition. Carbohydrate reduction was observed, while amino acids, organic acids and aromatic compounds with potential antioxidant activity increased during the fermentation time. Moreover, both in vitro and ex vivo outcomes showed an improved antioxidant profile. As a possible industrial application, the fermentation process adopted in this research could be reproduced on a large scale for the commercialization of the products by the food industry.

From the SmA to the hexatic, including the SmC*, SmC*(A) and SmC*(re) phases: a 2H NMR relaxation study.

The molecular dynamics of a ferroelectric liquid crystal, denoted ZLL 7/*, is investigated by means of (2)H NMR relaxation. The spin-lattice (T(1Q) and T(1Z)) and spin-spin (T(2)) relaxation times of two isotopomers of ZLL 7/*, labeled on the phenyl and biphenyl fragments, are measured and their behavior upon passing from the SmA to the hexatic phase, through the ferroelectric SmC*, antiferroelectric SmC*(A), and re-entrant ferroelectric SmC*(re) phases, is discussed. A comparison between the measured T(2) and T(2)*, directly related to the experimental linewidth, provides information on the heterogeneity of the system, thus allowing confirmation of previous hypotheses concerning the structural and ordering properties of the SmC*(A) and SmC*(re) phases. The possibility to look at different sites of the core of the ZLL 7/* smectogen reveals a peculiar sensitivity of the phenyl moiety with respect to the biphenyl fragment, which may be justified by its vicinity to the chiral centers. Interestingly, the trend of the longitudinal relaxation times is characterized by a minimum that corresponds to the SmC*(A) and SmC*(re) phases, which is reproducible for the two isotopomers and at several Larmor frequencies. A quantitative analysis of T(1Q) and T(1Z) is performed in the SmA and SmC* phases, for which the narrowing regime approximation is valid. A multifrequency approach is applied to self-consistently determine the diffusion coefficients for the overall molecular motions, namely spinning and tumbling, and the internal rotations around the para axes of the phenyl and biphenyl fragments. The effect of the magnetic field in unwinding the helical structure of the SmC* phase (for H>9 T) allows observation of a sensitive change in the rotational diffusion coefficients in the frustrated unwound SmC* phase with respect to the SmC* phase.

Dynamics of partially oriented L-phenylalanine-d(8) in the CsPFO/H(2)O lyotropic system via (2)H NMR relaxation studies.

Dynamics of the l-phenylalanine-d(8) has been here investigated by analyzing the (2)H NMR spin-lattice relaxation times of this selectively deuterium enriched amino acid diluted in the cesium pentadecafluorooctanoate/water (CsPFO/H(2)O) lyotropic system both in the nematic (N(+)(D)) and in the lamellar (L(D)) phases. Information on the internal and overall molecular motions as well as on collective motions has been achieved by a global fitting procedure. The dynamic processes affecting this probe molecule reflect its particular conformational and interaction properties with respect to the lyotropic environment. The best reproduction of the experimental data is obtained by assuming free internal reorientations of the benzylic moiety, which results in diffusion constants of the same order of magnitude of the overall molecular spinning motion. Moreover, the contribution of collective motions (order director fluctuations and layer undulations) is estimated to be greater than that commonly observed by other techniques in lyotropic systems.

Quantitative analysis of 2H NMR T1Q, T1Z and T2 relaxation times in the SmA phase of a liquid crystal dendrimer.

In this work the 2H NMR spin-lattice relaxation times, T1Z and T1Q, and the spin-spin relaxation times measured by means of the quadrupolar echo sequence, T2, have been analyzed in order to study the dynamic processes of a liquid crystalline dendrimer labelled on the aromatic core of the lateral mesogenic units in the SmA phase. Several theoretical models describing both internal and overall molecular diffusion motions have been used to reproduce the temperature dependence of the spectral densities J(0)(0), J1(omega0) and J2(2omega0) experimentally determined at the Larmor frequency omega0 of 61.3 MHz. This analysis identifies in the internal rotation of the deuterated phenyl ring around its para axis the main contribution to the longitudinal relaxation. Moreover, the best fitting of the minimum in the trend of both T1Z and T1Q was obtained by introducing a distribution of activation energies for such internal motion, thus confirming previous hypothesis of dynamic heterogeneity. A much slower motion, affecting the sole transverse relaxation and ascribable to the reorientation of the whole macromolecular dendrimers, was modelled through the so called "slowly relaxing local structure" approach.

Orientational and structural properties of ferroelectric liquid crystal with a broad temperature range in the SmC(*) phase by (13)C NMR, x-ray scattering and dielectric spectroscopy.

Thermotropic liquid crystalline materials laterally substituted by a methyl group on the aromatic ring of the alkoxybenzoate unit far from the chiral centre exhibit a very broad temperature range in the ferroelectric smectic C* (SmC(*)) phase on cooling (including supercooling) with a very high spontaneous polarization (∼210 nC cm(-2)) and tilt angle (∼43°) at saturation. We are presenting a detailed study of the physical properties of a ferroelectric compound, representative of this category of liquid crystals, by means of solid state (13)C-NMR, small angle x-ray scattering, dielectric spectroscopy and optical methods of the tilted SmC(*). Values of the spontaneous tilt angle measured optically are compared to those determined from the x-ray data and discussed. In addition, the viscosity has been determined in the SmC(*) phase by different experimental methods. (13)C NMR data allowed us to get information about the degree of orientational order of the SmC(*) phase and revealed the complete unwinding of the helical axis at the magnetic field of 9.4 T. This result is discussed in the framework of recent publications on the effect of the magnetic field on the supra-molecular structure of the SmC(*) phase.

Determination of Pigments in Virgin and Extra-Virgin Olive Oils: A Comparison between Two Near UV-Vis Spectroscopic Techniques.

The colour of olive oil is due to the presence of natural pigments belonging to the class of carotenoids, chlorophylls, and their derivatives. These substances, other than being responsible for the colour, an important qualitative feature of the oil, have antioxidant and, more generally, nutraceutical properties and their quantification can be related to the product's quality and authenticity. In this work, we have quantified the total amount of carotenoids and chlorophylls' derivatives in several virgin and extra-virgin olive oils produced in Italy, by using two different methods that are based on near-ultraviolet-visible absorption spectroscopy. The first method defines two indexes, K670 and K470, related to absorbance values of oil at wavelengths of 670 and 470 nm, respectively. The second method is based on the mathematical deconvolution of the whole absorption spectrum of the oil to obtain the concentrations of four main pigments present in olive oils: ß-carotene, lutein, pheophytin A, and pheophytin B. The concentrations of the total carotenoids and total chlorophylls' derivatives, as obtained by the two spectroscopic methods, are compared and the results are discussed in view of the practical usefulness of spectroscopic techniques for a fast determination of pigments in olive oil.