Periodic solutions of nonlinear impulsive differential inclusions with constraints

In this paper we obtain the existence of periodic solutions for nonlinear ``invariance' problems monitored by impulsive differential inclusions subject to impulse effects.

     

Aroma composition of red wines by different extraction methods and Gas Chromatography-SIM/MASS spectrometry analysis

One hundred and one volatile compounds, reported in literature as powerful odorants of wine, were quantified by Gas Chromatography-Selective Ion Monitoring/Mass Spectrometry (GC-SIM/MS) in Primitivo, Aglianico, Merlot and Cabernet Sauvignon red wines. Wine samples were extracted by 3 different extraction methods: 1) separation of the alcoholic fraction from the aqueous phase by salting-out and subsequent extraction by liquid-liquid micro-extraction with 1,1,2-trichlorotrifluoroethane (Freon 113); 2) extraction by liquid-liquid micro-extraction with dichloromethane; 3) solid phase extraction (SPE cartridge: 800 mg of LiChrolut EN resin) with pentane-dichloromethane (20:1) and dichloromethane. The selection of the ion fragments used for quantification was directly performed on a red wine sample. For each compound the area of the corresponding peak was normalized respect to the peak of the internal standard and then interpolated in a calibration curve obtained analysing a model wine solution (water, ethanol, tartaric acid and known amounts of analytes and of internal standard). The methods showed a good linearity: r2>0.990, except for farnesol (isomer a and c), octanal, decanal, furaneol and phenylacetic acid with 0.966 < or = r2 < or = 0.990. The 7 most powerful odorants were: beta-damascenone, acetaldehyde, maltol, ethyl 2-methylbutanoate, ethyl 3-methylbutanoate, 3-methylbutanoic acid and acetal; 7 other slightly less important were: ethyl hexanoate, ethyl acetate, 1-octen-3-ol, butanoic acid, rose oxide, furaneol and sotolon. The Aglianico wines were characterised by the major fermentation compounds (esters, fatty acids and 2-phenylethanol), beta-damascenone, beta-ionone and linalool. The Primitivo wines were characterized by furaneol, methoxypyrazine, gamma-nonalactone and acetaldehyde, while Cabernet Sauvignon and Merlot wines principally by cask derivates (vanillin, (Z) 3-methyl-gamma-octalactone [(Z) wiskylactone], maltol and eugenol), some aldehydes and 3-isopropyl-2-methoxypyrazine.     

Affinity capillary electrophoresis study of the linkage existing between proton and zinc ion binding to bacitracin A1

Measurements by capillary electrophoresis (CE) of bacitracin A(1) effective mobility at different pH values permitted to estimate the five acidic dissociation constants and the Stokes radii at different protonation stages of the macrocyclic dodecapeptide. The pK(a) values were 3.6 and 4.4 for the two carboxylic groups of the lateral chains of D-Asp-11 and D-Glu-4, respectively, 6.4 for the aza-atom of the imidazole ring of His-10, 7.6 for the amino group of N-terminal Ile-1 and 9.7 for the delta-amino group of D-Orn-7, very close to the values obtained by other researchers by titration experiments. In agreement with a rigid macrocyclic structure the Stokes radii of different protonated forms ranged only between 14.3 and 14.8 A. Best fitting procedures performed on experimental mobility measured at two different pH values (5.50 and 6.72) in the presence of increasing Zn(+2) concentration allowed confirming the model that assumes the binding of Zn(+2) to P(0) peptide form with a 1.5 x 10(3) M(-1) intrinsic association constant. Following to Zn(+2) binding, the pK(a) of the amino group of N-terminal Ile-1 is shifted from 7.6 to 5.9 and the Stokes radius is reduced of about 3 A. The mean charge of the bacitracin A(1)-Zn(+2) complex resulted +1.67 and +1.12 at pH 5.50 and 6.72, respectively. These results suggest that the amino group of N-terminal Ile-1 is not essential for Zn(+2) binding.     

HPLC Enantioseparation of Rigid Chiral Probes with Central,Axial, Helical,and Planar Stereogenicity on an Amylose (3,5-Dimethylphenylcarbamate) Chiral Stationary Phase

The chiral resolving ability of the commercially available amylose (3,5-dimethylphenylcarbamate)-based chiral stationary phase (CSP) toward four chiral probes representative of four kinds of stereogenicity (central, axial, helical, and planar) was investigated. Besides chirality, the evident structural feature of selectands is an extremely limited conformational freedom. The chiral rigid analytes were analyzed by using pure short alcohols as mobile phases at different column temperatures. The enantioselectivity was found to be suitable for all compounds investigated. This evidence confirms that the use of the amylose-based CSP in HPLC is an effective strategy for obtaining the resolution of chiral compounds containing any kind of stereogenic element. In addition, the experimental retention and enantioselectivity behavior, as well as the established enantiomer elution order of the investigated chiral analytes, may be used as key information to track essential details on the enantiorecognition mechanism of the amylose-based chiral stationary phase.     

Differences in Salivary Proteins as a Function of PROP Taster Status and Gender in Normal Weight and Obese Subjects

Taste plays an important role in processes such as food choices, nutrition status and health. Salivary proteins contribute to taste sensitivity. Taste reduction has been associated with obesity. Gender influences the obesity predisposition and the genetic ability to perceive the bitterness of 6-n-propylthiouracil (PROP), oral marker for food preferences and consumption. We investigated variations in the profile of salivary proteome, analyzed by HPLC-ESI-MS, between sixty-one normal weight subjects (NW) and fifty-seven subjects with obesity (OB), based on gender and PROP sensitivity. Results showed variations of taste-related salivary proteins between NW and OB, which were differently associated with gender and PROP sensitivity. High levels of Ps-1, II-2 and IB-1 proteins belonging to basic proline rich proteins (bPRPs) and PRP-1 protein belonging to acid proline rich proteins (aPRPs) were found in OB males, who showed a lower body mass index (BMI) than OB females. High levels of Ps-1 protein and Cystatin SN (Cyst SN) were found in OB non-tasters, who had lower BMI than OB super-tasters. These new insights on the role of salivary proteins as a factor driving the specific weight gain of OB females and super-tasters, suggest the use of specific proteins as a strategic tool modifying taste responses related to eating behavior.     

Modulating the Enantiodiscrimination Features of Inherently Chiral Selectors by Molecular Design: A HPLC and Voltammetry Study Case with Atropisomeric 2,2’-Biindole-Based Monomers and Oligomer Films

A family of inherently chiral electroactive selectors based on the 2,2’-biindole atropisomeric scaffold, of easy synthesis and modulable functional properties, is studied in cascade in two enantioselection contexts. They are at first investigated as probes in enantioselective HPLC, studying molecular structure and temperature effects, and achieving very efficient semipreparative enantioseparation. The enantiomers thus obtained, of remarkable chiroptical features (optical rotation as well as circular dichroism), are successfully applied as selectors in chiral voltammetry in different media for discrimination of the enantiomers of chiral electroactive probes, either by conversion into enantiopure electroactive electrode surfaces by electrooligomerization on glassy carbon substrate (the two monomers with shorter alkyl chains), or as chiral additive in achiral ionic liquid (the monomer with longest alkyl chains). Discrimination is conveniently and reproducibly achieved in terms of significant potential differences for the two enantiomers, specularly inverting either probe or selector configuration. In one case successful discrimination is also observed with the two probe enantiomers concurrently present, either as racemate or with enantiomeric excesses, neatly accounted for by the peak current ratios.