Antioxidant potential and authenticity of some commercial fruit juices studied by EPR and IRMS

Antioxidant status of foods, plant, or fruit products is generally characterized by means of spectroscopic methods. Methods like HPLC, UV-VIS, or MS spectroscopy are used to understand the chemical and physical properties of different samples, and also EPR spectroscopy seems to be a valuable tool to characterize antioxidant activity of juice beverages. In this technique, certain antioxidants present in fruit juices interact with free radicals interrupting the chain reaction that can possibly damage essential molecules. Recording the EPR signal decay caused by the reaction with a natural or artificial reducing agent, it is possible to draw conclusions about the antioxidant capability of materials. IRMS is a powerful tool to distinguish between an authentic fruit juice and a juice obtained by concentrate dilution. This technique allows also the detection of commercial C₄ cane or corn derived sugar syrups in C₃ fruit juices. In the present study, four commercial fruit juices were investigated using stable isotope measurements (oxygen, hydrogen, and carbon) and EPR measurements in order to check the correct labeling in the Romanian markets and to compare antioxidant activity of the studied juices and the reference. It was proven that the number of paramagnetic species decreases in time with different reaction rates and this was correlated with the antioxidant activity of the studied juices. Stable isotope ratio measurements have demonstrated that the fruit juices studied were reconstructed from concentrates with tap water, according to their label.     

Floer–Novikov homology and applications to Lagrangian submanifolds

We use a non-Hamiltonian version of Lagrangian Floer homology to prove that an exact Lagrangian submanifold in the cotangent bundle of the 3-torus T ³ must be diffeomorphic to T ³. This improves a previous result of Fukaya, Seidel and Smith.     

Mechanism of atmospheric CO2 fixation in the cavities of a dinuclear cryptate

Using density functional theory (DFT) methods, we have investigated two possible mechanisms for atmospheric CO(2) fixation in the cavity of the dinuclear zinc(II) octa-azacryptate, and the subsequent reaction with methanol whereby this latter reaction transforms the (essentially) chemically inert CO(2) into useful products. The first mechanism (I) was proposed by Chen et al. [Chem.-Asian J. 2007, 2, 710], and involves the attachment of one CO(2) molecule onto the hydroxyl-cryptate form, resulting in the formation of a bicarbonate-cryptate species and subsequent reaction with one methanol molecule. In addition, we suggest another mechanism that is initiated via the attachment of a methanol molecule onto one of the Zn-centers, yielding a methoxy-cryptate species. The product is used to activate a CO(2) molecule and generate a methoxycarbonate-cryptate. The energy profiles of both mechanisms were determined, and we conclude that, while both mechanisms are energetically feasible, free energy profiles suggest that the scheme proposed by Chen et al. is most likely.     

Effects of external electromagnetic fields on the conformational sampling of a short alanine peptide

Non‐equilibrium molecular dynamics simulations of a solvated 21‐residue polyalanine (A21) peptide, featuring a high propensity for helix formation, have been performed at 300 K and 1 bar in the presence of external electromagnetic (e/m) fields in the microwave region (2.45 GHz) and an r.m.s. electric field intensity range of 0.01–0.05 V/Å. To investigate how the field presence affects transitions between the conformational states of a protein, we report 16 independent 40 ns‐trajectories of A21 starting from both extended and fully folded states. We observe folding‐behavior of the peptide consistent with prior simulation and experimental studies. The peptide displays a natural tendency to form stable elements of secondary structure which are stabilized by tertiary interactions with proximate regions of the peptide. Consistent with our earlier work, the presence of external e/m fields disrupts this behavior, involving a mechanism of localized dipolar alignment which serves to enhance intra‐protein perturbations in hydrogen bonds (English, et al., J. Chem. Phys. 2010 , 133, 091105), leading to more frequent transitions between shorter‐lifetime states. © 2012 Wiley Periodicals, Inc.     

Designing a Useful Lipid Raft Model Membrane for Electrochemical and Surface Analytical Studies

A model biomimetic system for the study of protein reconstitution or drug interactions should include lipid rafts in the mixed lipid monolayer, since they are usually the domains embedding membrane proteins and peptides. Four model lipid films composed of three components: 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC), cholesterol (Chol) and sphingomyelin (SM) mixed in different molar ratios were proposed and investigated using surface pressure measurements and thermodynamic analysis of the monolayers at the air–water interface and imaged by Brewster angle microscopy. The ternary monolayers were transferred from the air–water onto the gold electrodes to form bilayer films and were studied for the first time by electrochemical methods: alternative current voltammetry and electrochemical impedance spectroscopy and imaged by atomic force microscopy. In excess of DOPC, the ternary systems remained too liquid for the raft region to be stable, while in the excess of cholesterol the layers were too solid. The layers with SM in excess lead to the formation of Chol:SM complexes but the amount of the fluid matrix was very low. The equimolar content of the three components lead to the formation of a stable and well-organized assembly with well-developed raft microdomains of larger thickness, surrounded by the more fluid part of the bilayer. The latter is proposed as a convenient raft model membrane for further physicochemical studies of interactions with drugs or pollutants or incorporation of membrane proteins.     

A fixed point formula of Lefschetz type in Arakelov geometry I: statement and proof

We consider arithmetic varieties endowed with an action of the group scheme of n-th roots of unity and we define equivariant arithmetic K ₀-theory for these varieties. We use the equivariant analytic torsion to define direct image maps in this context and we prove a Riemann-Roch theorem for the natural transformation of equivariant arithmetic K ₀-theory induced by the restriction to the fixed point scheme; this theorem can be viewed as an analog, in the context of Arakelov geometry, of the regular case of the theorem proved by P. Baum, W. Fulton and G. Quart in [BaFQ]. We show that it implies an equivariant refinement of the arithmetic Riemann-Roch theorem, in a form conjectured by J.-M. Bismut (cf. [B2, Par. (l), p. 353] and also Ch. Soulé’s question in [SABK, 1.5, p. 162]). Oblatum 22-I-1999 & 20-II-2001?Published online: 4 May 2001     

Critical currents and the critical state in superconductors with magnetic ions

The critical state model is used to derive equations that relate the additional magnetic moment (ΔM) produced by the flux pinning to the critical current density (J_c) measured in transport measurements. The equations derived for conventional superconductors can be used for superconductors that contain magnetic ions, if ΔM is replaced by ΔM/(1 + χ′(H)) where χ′(H) is the differential susceptibility. In the critical state, the field gradient has contributions from both the macroscopic supercurrents and the Amperian currents from the magnetic ions. Magnetic measurements are sensitive to both contributions. Transport measurements only characterise the macroscopic supercurrents. For superconductors which contain rare-earth elements, the J_c values calculated using hysteretic magnetisation measurements without including the term χ′(H), can be in error by factors of 7.     

Compensation for depolarisation by a fibre coil in the presence of self-phase modulation

We report on the dependence of the degree of polarisation of an 80 fs pulsed laser beam propagating through a length of a single-mode birefringent fibre on the illumination power. Due to the birefringence and the nonlinear effect of self-phase modulation, the measured depolarisation dependence is oscillatory. It is, however, demonstrated that the oscillatory depolarisation can be compensated for by introducing a loop into the fibre geometry, which maintains the degree of polarisation of the pulsed beam as high as 90%.     

ESR study of some solvent effects of the Cu(II)-aspirinate complex

Powder ESR spectra of the [Cu₂(Asp)₄](H₂O)₂ complex show the existence of Cu(II) acetate like dimers characterized by a strong antiferromagnetic exchange interaction (J=?288 cm^?1). In pyridine-dimethylformamide solutions the monomeric species prevail. Two different monomeric species, the Cu(DMF)₄ of planar-distorted tetrahedral (T_d) symmetry and the Cu(Asp)₂(DMF)₂ with elongated tetrahedral-octahedral symmetry were evidenced in DMF solution adsorbed on NaY zeolite. In 40 % Py+60 % DMF solution two monomeric species were also identified. These are Cu(Asp)₂(DMF)₂ and Cu(Asp)₂(Py)₂, the last species having a CuN₂O₂ chromophore in atrans squareplanar arrangement. In pyridine Cu(II)-aspirinate solution only the Cu(Py)₄ monomeric species of CuN₄ chromophore was evidenced.