Kabuli and Apulian black Chickpea Milling By-Products as Innovative Ingredients to Provide High Levels of Dietary Fibre and Bioactive Compounds in Gluten-Free Fresh Pasta

Gluten-free (GF) products, including pasta, are often characterised by nutritional deficiencies, such as scarce dietary fibre and excess of calories. Chickpea flour is increasingly being used by the food industries. Hulls, rich in dietary fibre and bioactive compounds, are discarded after milling. The aim of this work was to evaluate the quality features of short-cut GF fresh pasta added of hull (8% w/w) derived from kabuli (KH) or Apulian black (ABH) chickpeas, in comparison with control GF pasta prepared without hull. The enriched pasta, which could be labelled as “high fibre”, was characterised by a higher level of bioactive compounds and antioxidant activity than the control. ABH-enriched pasta showed the highest anthocyanins (33.37 ± 1.20 and 20.59 ± 0.11 mg/kg of cyanidin-3-O-glucoside on dry matter in raw and cooked pasta, respectively). Hull addition increased colour intensity and structural quality of GF pasta: ABH-enriched pasta had the lowest cooking loss and the highest water absorption capacity; KH-enriched pasta showed the highest firmness. No significant differences in sensory liking were found among the samples, except for “aftertaste”. Chickpea hull can be used as an innovative ingredient to produce potentially functional GF pasta, meeting the dietary needs of consumers without affecting quality.     

Calorimetric evaluation of the interaction and absorption of eicosapentaenoic acid by biomembrane models

The interaction of eicosapentaenoic acid, a polyunsaturated fatty acid belonging to the omega-3 class, with biomembrane models represented by multilamellar or unilamellar vesicles made of dimyristoylphosphatidylcholine was monitored by means of differential scanning calorimetry technique. The calorimetric analysis of vesicle prepared in the presence of increasing molar fraction of eicosapentaenoic acid was carried out to show its maximum interaction with biomembrane models evaluating the effects of eicosapentaenoic acid on the biomembrane models thermotropic parameters (transition temperature and enthalpy variation). Furthermore, in order to detect the influence of the presence of hydrophilic or lipophilic media on the entity of the compound absorption by the biomembrane models, kinetic experiments were carried out.The results indicate that eicosapentaenoic acid strongly interacts with the biomembrane models depressing the transition temperature and the enthalpy variation. Eicosapentaenoic acid is absorbed by the biomembrane models and the absorption is affected by the used medium; in fact a bigger absorption happens in the presence of a lipophilic medium.     

Solubility of carbon dioxide in pentaerythritol tetraoctanoate

In this paper, solubility measurements of CO₂ in pure pentaerythritol tetraoctanoate (PEC8) between 273 and 343 K are presented. The experiments were performed according to the static, synthetic method. The data are represented using the Peng–Robinson equation of state with the Huron–Vidal mixing rules and the UNIQUAC equation for the excess Gibbs Energy (g^E) at infinite pressure. This system shows immiscibility in liquid phase, with lower critical end point (LCEP) at T = 268 ± 0.1 K and xCO₂=0.98±0.001$x_{\text{C}{\text{O}}_2}=0.98\pm 0.001$ and upper critical end point (UCEP) at the critical point of pure CO₂.     

Generating CuII–Oxyl/CuIII–Oxo Species from CuI–α‐Ketocarboxylate Complexes and O2: In Silico Studies on Ligand Effects and C?H‐Activation Reactivity

Theoretically speaking : The mechanistic details associated with the generation and reaction of [CuO]⁺ species from Cu^I–α‐ketocarboxylate complexes, especially with respect to modifications of the ligand supporting the copper center, were investigated (see scheme). Theoretical models were used to characterize the electronic structures of different [CuO]⁺ species and their reactivity in C? H activation and O‐atom transfer reactions.

     

Molecular Complexes of Simple Anions with Electron‐Deficient Arenes: Spectroscopic Evidence for Two Types of Structural Motifs for Anion–Arene Interactions

Anion–π interactions between a π‐acidic aromatic system and an anion are gaining increasing recognition in chemistry and biology. Herein, the binding features of an electron‐deficient aromatic system (1,3,5‐trinitrobenzene (TNB)) and selected anions (OH^?, Br^?, and I^?) are examined in the gas phase by using the combined information derived from collision‐induced dissociation experiments at variable energy, infrared multiple‐photon dissociation spectroscopy, and quantum chemical calculations. We provide spectroscopic evidence for two different structural motifs of anion–arene complexes depending on the nature of the anion. The TNB–OR^? complexes (R=H, or alkyl groups which were studied earlier) adopt an anionic σ‐complex structure whereby RO^? attacks the aromatic ring with covalent bond formation, and develops a tetrahedral ring carbon bound to H and OR. The halide complexes rather conform to a structure in which the TNB moiety is hardly altered, and the halogen is placed on an unsubstituted carbon atom over the periphery of the ring at a C–X distance that is appreciably longer than a typical covalent bond length. The ensuing structural motif, previously characterized in the solid state and named weak σ interaction, is now confirmed by an IR spectroscopic assay in the gas phase, in which the sampled species are unperturbed by crystal packing or solvation effects.     

Chirality in the Absence of Rigid Stereogenic Elements: The Absolute Configuration of Residual Enantiomers of C3‐Symmetric Propellers

Two new tris(aryl)phosphane oxides existing as configurationally stable residual enantiomers have been synthesised and their racemates resolved by semipreparative HPLC on a chiral stationary phase (CSP HPLC). One of them, recognised as a conglomerate, could be resolved by fractional crystallisation at a preparative scale level. In this case, the absolute configuration of the propeller‐shaped molecule was determined by anomalous X‐ray scattering. The problem of the correlative assignment of the absolute configuration to all known C₃‐symmetric three‐bladed propeller‐shaped molecules existing as stable residual enantiomers is discussed. The configurational stability of the new chiral phosphane oxides and of the corresponding phosphanes was evaluated by CD signal decay kinetics and dynamic ¹H NMR spectroscopy. The racemisation barriers in phosphanes were found about 10 kcal mol^?1 lower than those found for the corresponding oxides, though geometry and inter‐ring gearing would be very similar in the two series. Configurational stability of residual tris(aryl)phosphanes was found to be influenced by the electronic availability of the phosphorus centre, as evaluated by electrochemical CV experiments.     

Iridium(III) Complexes with Sulfonyl and Fluorine Substituents: Synthesis,Stereochemistry and Effect of Functionalisation on their Photophysical Properties

The synthesis and photophysical and electrochemical characterisation of new heteroleptic iridium complexes with electron‐withdrawing sulfonyl groups and fluorine atoms bound to phenylpyridine ligands are reported. The emission energy of these materials strongly depends on the position of the sulfonyl groups and on the number of fluorine substituents. A 90 nm wide tuning range of photoluminescence from the blue‐green (λ_em=468 nm) of iridium(III)bis[2‐(4′‐benzylsulfonyl)phenylpyridinato‐N,C2′][3‐(pentafluorophenyl)‐pyridin‐2‐yl‐1,2,4‐triazolate] to the orange (λ_em=558 nm) of iridium(III)bis[2‐(3′‐benzylsulfonyl)phenylpyridinato‐N,C2′](2,4‐decanedionate) has been achieved. Emission quantum yields ranging from 47 to 71 % have also been found for degassed solutions of the complexes, and a surprisingly high value of 16 % was recorded for iridium(III)bis[2‐(5′‐benzylsulfonyl‐3′,6′‐difluoro)phenylpyridinato‐N,C2′](2,4‐decanedionate) in air‐equilibrated dichloromethane. A unusual stereochemistry of the benzylsulfonyl‐substituted dimer and heteroleptic complexes has been detected by ¹H NMR spectroscopy, and is characterised by the mutual cis disposition of the pyridyl nitrogen atoms of the phenylpyridine ligands, which differs from the most common trans arrangement reported in the literature.     

Novel copolyesters based on poly(alkylene dicarboxylate)s: 2. Thermal behavior and biodegradation of fully aliphatic random copolymers containing 1,4-cyclohexylene rings

Aliphatic poly(butylene 1,12-dodecanedioate) is an interesting biodegradable polyester characterized by high thermal stability and high crystallinity, but low melting temperature. In order to improve the performances of this polymer some novel fully aliphatic random copolyesters have been prepared starting from 1,4-butanediol and different molar ratio of 1,12-dodecanedioc acid and 1,4-cyclohexanedicarboxylic acid. The copolymers have a notable resistance to thermal degradation, thermal properties which vary as a function of the composition, and maintain the mechanical characteristics of the poly(alkylene dicarboxylate). In particular, the copolymer containing the 70 mol% of 1,4-cyclohexanedicarboxylate units improves the thermal properties of the poly(butylene 1,12-dodecanedioate) and presents a very high biodegradation rate, higher than those of the two parent homopolymers. This behavior has been correlated to the low level of crystallinity of the sample and to the composition of the amorphous phase. Therefore, these novel fully aliphatic copolymers represent an interesting new class of copolyesters which can balance good physical properties and high biodegradability.     

Analysis of pharmaceuticals in indirect potable reuse systems using solid-phase extraction and liquid chromatography–tandem mass spectrometry

A solid-phase extraction (SPE) LC–MS/MS method for 18 commercial drugs in secondary wastewater and product water from water recycling plants using microfiltration (MF) and reverse osmosis (RO) has been developed, optimised and validated. The method incorporates a range of multi-class pharmaceuticals including lipid lowering agents, analgesics, antipyretics, non-steroidal anti-inflammatory drugs, antidepressants, anticoagulants, tranquilizers, cytostatic agents, and antiepileptics. Method limits of quantitation (MLQs) in secondary wastewater ranged from 15 to 250 ng/L, while MLQs in post-RO water ranged from 1 to 25 ng/L. Results from analysis of secondary wastewater from Western Australia are presented, and represent the largest survey of non-antibiotic pharmaceuticals within Australia to date. Analysis of post-RO water from two MF/RO water recycling facilities also demonstrate that MF/RO treatment removes most pharmaceuticals to below the analytical limits of detection, and more importantly, up to seven orders of magnitude below health-based guideline values.     

Selective oxidation of ethanol to acetic acid in highly efficient polymer electrolyte membrane-direct ethanol fuel cells

The selective conversion of ethanol into potassium acetate with concomitant production of electrical energy has been achieved in both passive and active direct fuel cells containing platinum-free electrodes and an anion-exchange polymer membrane. The power densities supplied by the passive systems at r.t. can be as high as 55 mW cm^?2, while the active systems can deliver up to 170 mW cm^?2 at 80 °C. Such high values have never been reported for direct ethanol fuel cells with whatsoever electrocatalyst in either alkaline or acidic media.