HPLC separation,NMR and QTOF/MS/MS structure elucidation of a prominent nitric oxide donor agent based on an isomeric composition of a nitrosyl ruthenium complex

A new and promising nitrosyl ruthenium complex, [Ru(NO)(bdqi-COOH)(terpy)](PF₆)₃, bdqi-COOH is 3,4-diiminebenzoic acid and terpy is 2,2′-terpyridine, has been synthesized as a NO donor agent. The procedure used for [Ru(NO)(bdqi-COOH)(terpy)](PF₆)₃ synthesis has, apparently, yielded the formation of two isomers in which the ligand bdqi-COOH appears to be coordinated in its reduced form (bdcat-COOH), which could have differences in their pharmacological properties. Therefore, it was intended to separate the two possible isomers by high-performance liquid chromatography (HPLC) and to characterize them by high resolution mass spectrometry (QTOF MS) and by magnetic nuclear resonance spectroscopy (NMR). The results obtained by MS showed that the ESI-MS mass spectra of both HPLC column fractions, e.g. peak 1 and peak 2, are essentially equal, showing that both isomers display nearly identical gas-phase behavior with clusters of isotopologue ions centered at m/z 573, m/z 543 and m/z 513. Regarding the NMR analysis, the results showed that the positional isomerism is located in the bdqi-COOH ligand. From the observed results it can be concluded that the synthesis procedure that has been used results in the formation of two [Ru(terpy)(bdqi-COOH)NO](PF₆)₃ isomers.     

Quantitative analysis of beta-blockers in pharmaceutical preparations by capillary electrophoresis

A simple capillary electrophoresis method was developed for the analysis of four β-blockers (atenolol, metoprolol, pindolol, and propranolol) in pharmaceutical preparations. The method was validated regarding accuracy, precision, linearity, and detection/quantification limits, and the obtained values were in accordance to those reported in the literature. The method was applied to the determination of the drugs in commercial tablet preparations and proved to be fast and reliable for the quantitative analysis of the β-blockers.     

Selected polycyclic aromatic hydrocarbons in smoked tuna, swordfish and Atlantic salmon fillets

The presence of polycyclic aromatic hydrocarbons (PAHs) in commercial smoked fillets of tuna, swordfish and Atlantic salmon was studied. In Europe, the smoking technique is widely used in fish processing and these species are the most representative of the taste of consumers for smoked products. Samples were purchased on the Italian market and analysed by HPLC. Mean concentrations (ng g⁻¹) of acenaphthene (4.4, 6.2, 11.2), phenanthrene (11.5, 18.5, 8.9), anthracene (2.4, 5.2, 1.8), fluoranthene (17.0, 9.4, 4.7), benzo( k )fluoranthene (0.3, 0.1, 0.2) and benzo( a )pyrene (1.3, 0.1, 0.4) were found in Atlantic salmon, tuna and swordfish respectively. Benzo( b )fluoranthene (1.2 ng g⁻¹) was detected only in Atlantic salmon whereas dibenz( a,h )anthracene was never detected in this species, but only in tuna (0.5 ng g⁻¹) and swordfish (1.1 ng g⁻¹). Atlantic salmon contained the highest level of benzo( a )pyrene (2.8 ng g⁻¹) which is below the European regulatory level of 5 ng g⁻¹.     

Nanostructured medical device coatings based on self-assembled poly(lactic-co-glycolic acid) nanoparticles

Here we present a new method for providing nanostructured drug-loaded polymer films which enable control of film surface morphology and delivery of therapeutic agents. Silicon wafers were employed as models for implanted biomaterials and poly(lactic-co-glycolic acid) (PLGA) nanoparticles were assembled onto the silicon surface by electrostatic interaction. Monolayers of the PLGA particles were deposited onto the silicon surface upon incubation in an aqueous particle suspension. Particle density and surface coverage of the silicon wafers were varied by altering particle concentration, incubation time in nanoparticle suspension and ionic strength of the suspension. Dye loaded nanoparticles were prepared and assembled to silicon surface to form nanoparticle films. Fluorescence intensity measurements showed diffusion-controlled release of the dye over two weeks and atomic force microscopy (AFM) analysis revealed that these particles remained attached to the surface during the incubation time. This work suggests that coating implants with PLGA nanoparticles is a versatile technique which allows drug release from the implant surface and modulation of surface morphology.     

Determination of aflatoxins,deoxynivalenol, ochratoxin A and zearalenone in organic wheat flour under different storage conditions

Samples of flour derived from an organic wheat seed cultivated in the region Abruzzo (Central Italy) were examined for the detection of aflatoxins, deoxynivalenol, ochratoxin A and zearalenone after storage in the presence of oxygen or under vacuum, for one year. They were analysed by high-performance liquid chromatography with fluorescence detection for aflatoxins, ochratoxin A and zearalenone and with diode array detector for deoxynivalenol. An immunoaffinity column clean-up was applied for all the compounds, except for aflatoxin determination, which required a solid-phase extraction. Recoveries (range: 76–107%) and within-laboratory reproducibility (RSD% < 10.3) met the performance criteria of Commission Regulation (EU) No. 519/2014 amending Commission Regulation (EC) No. 401/2006 for the detection of mycotoxins in foodstuffs. Analytes were below the detection limit of the method, and this result was probably due to the quality of organic seed and good agricultural practices performed for the prevention of mycotoxin formation.     

Polycyclic aromatic hydrocarbons in fresh and cold-smoked Atlantic salmon fillets

The occurrence of polycyclic aromatic hydrocarbons (PAHs) in smoked fish as a consequence of cold smoking was studied. Raw fillets of Salmo salar from Norway or the Irish Sea were sampled in a modern smokehouse and examined for PAH content. The same fillets, labeled with an identification number, were sampled immediately after the smoking process and analyzed. Among the investigated compounds, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, and benzo[ghi]perylene were detected in both raw and smoked fillets. No significant difference (P < 0.01) was observed between raw and smoked samples in the concentrations of six PAHs, but significant differences were found for fluorene, anthracene, fluoranthene, benz[a]anthracene, and benzo[ghi]perylene. Results confirm that PAHs concentrations in smoked fish are the product of both sea pollution and the smoking process. A modern smoking plant with an external smoke generator and a mild treatment as described here will not add significantly to the concentration of PAHs, except for some compounds.     

Food supplier qualification by an Italian Large-scale-Distributor: Auditing system and non-conformances

Nowadays government and purchasers are constantly setting increasing stringent requirements for food quality and safety, this means that production and distribution companies in the food and beverage sector must have full control over all incoming and outgoing goods. In particular food suppliers for Large-scale-Distributors have to meet many specific requirements and to undergo audits in order to assure the hygienic and sanitary quality of their products. This study offers an example of a checklist used by an Italian Large-scale-Distributor for investigating the status of its food suppliers in order to detect non-conformances; it also provides information on HACCP system management in Italian food industries. Results collected during 85 audits are shown. Large food plants show a better application of HACCP principles than small sized enterprises.     

The Auction Technique for the Sensor Based Navigation Planning of an Autonomous Mobile Robot

The problem of finding a path for the motion of a small mobile robot from a starting point to a fixed target in a two dimensional domain is considered in the presence of arbitrary shaped obstacles. No a priori information is known in advance about the geometry and the dimensions of the workspace nor about the number, extension and location of obstacles. The robot has a sensing device that detects all obstacles or pieces of walls lying beyond a fixed view range. A discrete version of the problem is solved by an iterative algorithm that at any iteration step finds the smallest path length from the actual point to the target with respect to the actual knowledge about the obstacles, then the robot is steered along the path until a new obstacle point interfering with the path is found, at this point a new iteration is started. Such an algorithm stops in a number of steps depending on the geometry, finding a solution for the problem or detecting that the problem is unfeasible. Since the algorithm must be applied on line, the effectiveness of the method depends strongly on the efficiency of the optimization step. The use of the Auction method speeds up this step greatly both for the intrinsic properties of this method and because we fully exploit a property relating two successive optimizations, proved on paper, that in practical instances enables the mean computational cost requested by the optimization step to be greatly reduced. It is proved that the algorithm converges in a finite number of steps finding a solution when the problem is feasible or detecting the infeasibility condition otherwise. Moreover the worst case computational complexity of the whole algorithm is shown to be polynomial in the number of nodes of the discretization grid. Finally numerical examples are reported in order to show the effectiveness of this technique.     

Development and Validation of a Method for the Determination of Quinolones in Muscle and Eggs by Liquid Chromatography-Tandem Mass Spectrometry

In this study, the development and validation of a multiresidue method for the detection of 11 quinolones (marbofloxacin, norfloxacin, ciprofloxacin, danofloxacin, lomefloxacin, enrofloxacin, sarafloxacin, difloxacin, oxolinic acid, nalidixic acid, flumequine) in muscle and eggs were reported. The method involved an extraction with a methanol/metaphosphoric acid mixture and a clean up by Oasis hydrophilic-lipophilic balance (HLB) cartridge. The validation was performed according to the Commission Decision 2002/657/EC. Linearity, specificity, decision limit (CCα), detection capability (CCβ), recovery, precision (repeatability and within-laboratory reproducibility), and ruggedness were determined. Depending on the analytes, CCα and CCβ ranged from 113 to 234 μg/kg and from 126 to 282 μg/kg in muscle samples, whereas in eggs, these parameters were between 5.6 and 7.4 μg/kg and between 6.1 and 9.8 μg/kg, respectively. In both the examined matrices, the recovery values were always higher than 90 % and precision, calculated as relative standard deviation, was equal to or lower than 16 % for repeatability and 23 % for within-laboratory reproducibility. The described method can be considered adequate for the simultaneous determination and quantification of quinolones in the tested food matrices.