Fatty Acid Ethyl Esters (FAEE): A New,Green and Renewable Solvent for the Extraction of Carotenoids from Tomato Waste Products

Currently there is a drive towards the minimisation and reclamation of valuable materials from the waste products of the food and beverage industry. This can be achieved through the extraction of residual nutraceuticals from such materials. Tomato pomace contains carotenoids and other chemicals which can be extracted directly into edible oils to improve the health-giving properties of such oils. We report here a novel green solvent, fatty acid ethyl esters (FAEE), which is significantly more effective than sunflower oil and hexane for the extraction of lycopene and beta-carotene from tomato skin waste. FAEE are a non-toxic renewable resource that is environmentally friendly and to our knowledge has never been used as a vegetal extraction fluid. The efficiency of FAEE extraction was significantly improved relative to both sunflower oil and hexane under ultrasound-assisted extraction (UAE) conditions. In addition, FAEE have the additional and significant advantage that once enriched with the extracted nutraceuticals can be used directly as a food additive.     

An intersection theorem for set-valued mappings

Given a nonempty convex set X in a locally convex Hausdorff topological vector space, a nonempty set Y and two set-valued mappings T: X ? X, S: Y ? X we prove that under suitable conditions one can find an x ∈ X which is simultaneously a fixed point for T and a common point for the family of values of S. Applying our intersection theorem, we establish a common fixed point theorem, a saddle point theorem, as well as existence results for the solutions of some equilibrium and complementarity problems.     

DFT study and quantitative detection by surface‐enhanced Raman scattering (SERS) of ethyl carbamate

Ethyl carbamate (EC), a potentially toxic compound, is found in alcoholic beverages and fermented foodstuff. A combined experimental and theoretical study of Raman on EC is reported in this work for the first time. The Raman bands observed for EC in solid phase are characteristic for the carbonyl group, C―C, C―H and N―H stretching and deformation vibrations. These spectral features coupled with a pKa study allowed establishing the neutral species of EC present in the aqueous solutions experimentally tested at different concentrations. In addition, by performing a density functional theory study in the gas phase, the calculated geometry, the harmonic vibrational modes, and the Raman scattering activities of EC were found to be in good agreement with our experimental data and helped establish the surface‐enhanced Raman scattering (SERS) behavior and EC adsorption geometry on the silver surfaces. The Raman peak at 1006 cm⁻¹, assigned to the υ_s(CC) + ω(CH) modes, the strongest and best reproducible peak in the SERS spectra, was used for a quantitative evaluation of EC. The limit of detection, which corresponds to a signal‐to‐noise ratio equal to 3, was found to be 2 × 10⁻⁷ M (17.8 µg l⁻¹). SERS spectra obtained by using hydroxylamine hydrochloride‐reduced silver nanoparticles provide a fast and reproducible qualitative and quantitative determination of EC in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.     

Polytriphenylamines synthesized by interfacial and microemulsion oxidative polymerization

Two triphenylamine-based polymers were successfully prepared by the interfacial and microemulsion oxidative polymerization of triphenylamine and 4-(diphenylamino)benzyl 2-bromo-2-methylpropanoate. Ammonium peroxodisulfate ((NH₄)₂S₂O₈) was used as a chemical oxidant and dichloromethane/water was used as a solvent. Sodium dodecyl benzene sulfonate was employed as a surfactant in the microemulsion system. Polytriphenylamines were characterized via Fourier transform infrared (FTIR) spectra and ¹H-NMR and UV–vis absorption spectroscopy. Molecular weights were determined by gel permeation chromatography and redox properties were studied by cyclic voltammetry. The surface morphology of thin polymer films was determined by atomic force microscopy.     

Joint seminormality and Dirac operators

In this article, an approach to joint seminormality based on the theory of Dirac and Laplace operators on Dirac vector bundles is presented. To eachn-tuple of bounded linear operators on a complex Hilbert space we first associate a Dirac bundle furnished with a metric-preserving linear connection defined in terms of thatn-tuple. Employing standard spin geometry techniques we next get a Bochner type and two Bochner-Kodaira type identities in multivariable operator theory. Further, four different classes of jointly seminormal tuples are introduced by imposing semidefiniteness conditions on the remainders in the corresponding Bochner-Kodaira identities. Thus we create a setting in which the classical Bochner's method can be put into action. In effect, we derive some vanishing theorems regarding various spectral sets associated with commuting tuples. In the last part of this article we investigate a rather general concept of seminormality for self-adjoint tuples with an even or odd number of entries.     

Separation of chitosan oligomers by immobilized metal affinity chromatography

A novel approach for chitosan oligosaccharide (COS) separation by immobilized metal affinity chromatography (IMAC) based on the differences in the interactions of chelated copper (II) ions with various COS (dimers, trimers, tetramers) is described. Polyhydroxylic chromatographic supports (agarose CL-6B and silica) were functionalized with various chelating functions such as iminodiacetate (IDA), carboxymethyl-aspartate (CM-Asp) and tris(carboxymethyl)ethylenediamine (TED). The COS retention capacities of the columns were between 2 and 6 mg/cm(3), depending on the chelating group. The COS were separated and/or enriched up to 95% for dimer and trimer and 90% for the tetramer, with yields of 60-95%.     

A dinuclear Ni(I) system having a diradical Ni2N2 diamond core resting state: synthetic, structural, spectroscopic elucidation, and reductive bond splitting reactions

One-electron reduction of the square-planar nickel precursor (PNP)NiCl ( 1) (PNP (-) = N[2-P(CHMe 2) 2-4-methylphenyl] 2) with KC 8 effects ligand reorganization of the pincer ligand to assemble a Ni(I) dimer, [Ni(mu 2-PNP)] 2 ( 2), containing a Ni 2N 2 core structure, as inferred by its solid-state X-ray structure. Solution magnetization measurements are consistent with a paramagnetic Ni(I) system likely undergoing a monomer <--> dimer equilibrium. The room-temperature and 4 K solid-state X-band electron paramagnetic resonance (EPR) spectra display anisotropic signals. Low-temperature solid-state X-band EPR data at 4 K reveal rhombic values g z = 1.980(4), g x = 2. 380(4), and g y = 2.225(4), as well as a forbidden signal at g = 4.24 for the Delta M S = 2 half field transition, in accord with 2 having two weakly interacting metal centers. Utilizing an S = 1 model, full spin Hamiltonian simulation of the low-temperature EPR spectrum on the solid sample was achieved by applying a nonzero zero-field-splitting parameter ( D = 0.001 cm (-1)), which is consistent with an S = 0 ground state with a very closely lying S = 1 state. Solid-state magnetization data also corroborate well with our solid-state EPR data and reveal weak antiferromagnetic behavior ( J = -1.52(5) cm (-1)) over a 2-300 K temperature range at a field of 1 Tesla. Evidence for 2 being a masked "(PNP)Ni" scaffold originates from its reaction with N 2CPh 2, which traps the Ni(I) monomer in the form of a T-shaped species, Ni(PNPNNCPh 2), a system that has been structurally characterized. The radical nature of complex 2, or its monomer component, is well manifested through the plethora of cooperative H-X-type bond cleavage reactions, providing the nickel(II) hydride (PNP)NiH and the corresponding rare functionalities -OH, -OCH 3, -PHPh, and -B(catechol) integrated into the (PNP)Ni moiety in equal molar amounts. In addition to splitting H 2, compound 2 can also engage in homolytic X-X bond cleavage reactions of PhXXPh to form (PNP)Ni(XPh) (X = S or Se).     

Dynamic NMR study of the oxaphosphetane complexation with lithium during the Wittig reaction

Dynamic NMR spectroscopy at very low temperatures (148–182 K) reveal the dynamic behavior of the (2‐tri(3‐furyl)‐3‐methyl‐4‐cyclopropenyl‐oxaphosphetane) generated during a Wittig reaction between tri(3‐furyl)ethylphosphonium iodine and cyclopropylaldehyde. The possibility of formation of different adducts between Li⁺ ions and oxaphosphetane or betainic intermediates was checked calculating the formation enthalpies using the MNDO, AM1, and PM3 semiempirical MO methods. The observed species are interpreted as oxaphosphetane complexes with lithium ions present in solution. Quantum mechanical calculations confirm the spectroscopic results. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008