A novel strategy to verification of adulteration in alcoholic beverages based on Schlieren effect measurements and chemometric techniques

A novel strategy to evaluation of adulteration in alcoholic beverages based on the measurement of the Schlieren effect using an automated FIA system with photometric detection is proposed. The assay is based on the Schlieren effect produced when beverage samples are injected in a single-line FIA system that uses water as carrier stream and a light-emitting diode-phototransistor photometer controlled by microcomputer as detector. The flow system presents limited mixing conditions which make possible to create gradients of refractive index (Schlieren effect) in the injected sample zone. These gradients are reproducible, characteristic of each alcoholic beverage and undergo specific modifications when adulterations with water or ethanol are imposed. Schlieren effect data of brandies, cachaças, rums, whiskies and vodkas were treated by SIMCA to elaborate class models applied in the evaluation of alcoholic beverages adulteration. Samples of the original matrix of each sort of beverages were adulterated in laboratory by adding water, methanol and ethanol in levels of 5% and 10% (v/v). These samples were used as test set to validate SIMCA class models. The verification of authenticity using Schlieren effect measurements presented good results making possible to identify 100% of the beverages samples adulterated in laboratory and 93% of the actual adulterated alcoholic beverages with confidence levels of 95%. As principal advantage, the automated system does not use reagents to carry out the analysis.     

Convergence analysis of time-point relaxation iterates for linear systems of differential equations

We study convergence properties of time-point relaxation (TR) Runge-Kutta methods for linear systems of ordinary differential equations. TR methods are implemented by decoupling systems in Gauss-Jacobi, Gauss-Seidel and successive overrelaxation modes (continuous-time iterations) and then solving the resulting subsystems by means of continuous extensions of Runge-Kutta (CRK) methods (discretized iterations). By iterating to convergence, these methods tend to the same limit called diagonally split Runge-Kutta (DSRK) method. We prove that TR methods are equivalent to decouple in the same modes the linear algebraic system obtained by applying DSRK limit method. This issue allows us to study the convergence of TR methods by using standard principles of convergence of iterative methods for linear algebraic systems. For a particular problem regions of convergence are plotted.     

Modification of surface properties of electrospun polyamide nanofibers by means of a perfluorinated acridine

Polyamide 6 (PA6) nanofibers were prepared from formic acid solutions by using electrospinning technique. The fibers were smooth, defects free and with diameters smaller than 200 nm. Small amounts of a perfluorinated acridine were added as dopant to the feed solution to modify the wettability of the fibers. The effect of doping on the contact angle values is well apparent. The contact angle values go from 50° of pure PA6 to 120° when 6% of acridine is added. A comparison between fibers and films of pure and doped polyamide 6 was carried out in order to determine the effect of morphology on wettability. Thermal annealing near the T_g of the polymer promoted the segregation of the molecules to the surface, reaching contact angles of 131° with smaller amounts (4%) of acridine. The surface segregation was also promoted by time aging.     

FTIR and WAXS analysis of periodate oxycellulose: Evidence for a cluster mechanism of oxidation

Cellulose paper (Whatman no.1, chromatographic grade) was oxidised with 0.1 M sodium metaperiodate at different oxidation levels (0–11 days at room temperature), and analysed with FTIR before and after chemical treatments (reduction, further oxidation, alkaline hydrolysis). The deconvolution of infrared data allowed us to verify that periodate oxidises cellulose in isolated domains, leading to the decrease of crystallinity, in agreement with the results of wide angle X-ray scattering (WAXS). In particular, the alkaline hydrolysis (β-alkoxy fragmentation) followed by mild acid treatment removed the oxidised groups and recovered most of the crystallinity of cellulose, as determined by the FTIR crystallinity index.     

Einkristalluntersuchungen an Fluoroperowskiten MPdF3 (M = Rb,K) und PdF2

Single Crystal Investigations on Fluoroperovskites MPdF₃ (M = Rb, K) and PdF₂ Single crystal investigations on PdF₂ (violet) confirm the tetragonale rutile structure [1, 2] with a = 495.44(3) pm, c = 338.48(3) pm, Z = 2, space group P4₂/mnm-D (No. 136) (x_F = 0.3058(8)). RbPdF₃ and KPdF₃ have been obtained. RbPdF₃ and KPdF₃ both ruby-red single crystals crystallize cubic (perovskite-structure), space group Pm3m-O (No. 221) with a = 429.41(8) pm (RbPdF₃) respectively a = 424.30(4) pm (KPdF₃).     

Synthesis of Glycosylrifamycins,a new type of semisynthetic rifamycins

Glycosylrifamycins, a new type of semisynthetic rifamycin derivatives, can be easily obtained by reaction of 3-(2-aminoethylthio)rifamycin SV ( 2 ) with a glycosyl compound carrying a coupling group, such as isothicyanate or carboxy. We prepared O-acetylated and free glucopyranosyl and arabinopyranosyl derivatives of rifamycin S and SV (see 3–10 ). Additionally, derivatives with D -saccharo-1,4-lactone and with shikimic acid were obtained (see 11–15 ). Glycosylrifamycins show an interesting inhibitory power on Gram-positive bacteria (Table).     

H2O−D2O solvent isotope effect in the volume behavior of some high-charge high-size electrolytes

The apparent molar volumes V of KCl, BaCl₂, K₂SO₄, LaCl₃, Co(en)₃Cl₃ [Tris(ethylenediamine)cobalt(III) chloride], K₃Co(CN)₆, K₃Fe(CN)₆, K₄Fe(CN)₆, and Ba₃[Co(CN)₆]₂ have been determined at 25°C in both light and heavy water. The V values in D₂O are systematically lower and increase more rapidly with salt concentration than the V in H₂O. The volume of transfer from H₂O to D₂O as well as the partial molar volume at infinite dilution in both solvents have also been calculated. These results together with literature values for other electrolytes were used to estimate both of these quantities for D₂O solutions of individual ions. The predictions of ion hydration models and ion-ion interactions are compared with experimental observations.     

Supramolecular adducts between macrocyclic Gd(iii) complexes and polyaromatic systems: a route to enhance the relaxivity through the formation of hydrophobic interactions

The set-up of reversible binding interactions between the hydrophobic region of macrocyclic GBCAs (Gadolinium Based Contrast Agents) and SO₃⁻/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancements of this class of MRI contrast agents. The strong binding affinity allows attaining relaxation enhancements up to 50% at pyrene/GBCA ratios of 3 : 1. High resolution NMR spectra of the Yb-HPDO3A/pyrene system fully support the formation of a supramolecular adduct based on the set-up of hydrophobic interactions. The relaxation enhancement may be accounted for in terms of the increase of the molecular reorientation time (τ_R) and the number of second sphere water molecules. This effect is maintained in blood serum and in vivo, as shown by the enhancement of contrast in T_1w-MR images obtained by simultaneous injection of GBCA and pyrene derivatives in mice.

The set-up of reversible binding interactions between the hydrophobic region of macrocyclic gadolinium based contrast agents and SO₃⁻/OH containing pyrene derivatives provides new insights for pursuing relaxivity enhancement of MRI contrast agents.