Evaluation of Polycyclic Aromatic Hydrocarbons in Smoked Cheeses Made in Poland by HPLC Method

Smoked cheeses are particularly popular among consumers for their flavor and aroma. Of interest, therefore, is the health aspect related to the likelihood of polycyclic aromatic hydrocarbons (PAHs), which are known carcinogens found in smoked products. Thus, the purpose of this study was to evaluate the occurrence of 15 polycyclic aromatic hydrocarbons (PAHs) in smoked and non-smoked cheeses purchased in Poland to monitor their safety. The level of selected PAHs in cheese samples was determined using the HPLC-DAD-FLD method. Most of the cheeses tested met the maximum level of benzo[a]pyrene (2 μg/kg) and the sum of benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene (12 μg/kg) established for these products. However, all the cheeses studied in this work had relatively low amounts of the sum of these compounds compared to the information available in the cheese literature, ranging from <LOD to 24.5 μg/kg. This amount does not pose a health risk to consumers. The predominant PAHs found were naphthalene, phenanthrene, fluorene and acenaphthene. Benzo[a]pyrene, the marker compound representing carcinogenic PAHs, was found in 100% and 0% of Polish smoked and non-smoked cheeses, respectively. Although there are currently no regulations for smoked cheeses and maximum concentrations of PAHs in this type of food product, control of PAHs content in cheeses is important due to the mutagenic and carcinogenic potential of these chemicals.     

Preliminary study of mechanism of action of SN38 derivatives. Physicochemical data,evidence of interaction and alkylation of DNA octamer d(GCGATCGC)2

The synthesis of water‐soluble SN38 derivatives is presented, and their stability in solutions used during drug development studies has been investigated. A preliminary study of mechanism of action of 9‐aminomethyl SN38 is presented. Using NMR techniques, the interaction of the oligomer d(GCGATCGC)₂ is studied, showing that the terminal GC base pairs are the main site of interaction. Using pulsed field gradient spin echo and mass spectroscopy, evidence of a spontaneous alkylation reaction of the DNA oligomer with SN38 derivatives is presented. A proposed mechanism of reaction is suggested. Copyright © 2016 John Wiley & Sons, Ltd.     

Manganese-Catalyzed Sustainable Synthesis of Pyrroles from Alcohols and Amino Alcohols

The development of reactions that convert alcohols into important chemical compounds saves our fossil carbon resources as alcohols can be obtained from indigestible biomass such as lignocellulose. The conservation of our rare noble metals is of similar importance, and their replacement by abundantly available transition metals, such as Mn, Fe, or Co (base or nonprecious metals), in key technologies such as catalysis is a promising option. Herein, we report on the first base-metal-catalyzed synthesis of pyrroles from alcohols and amino alcohols. The most efficient catalysts are Mn complexes stabilized by PN₅P ligands whereas related Fe and Co complexes are inactive. The reaction proceeds under mild conditions at catalyst loadings as low as 0.5 mol %, and has a broad scope and attractive functional-group tolerance. These findings may inspire others to use Mn catalysts to replace Ir or Ru complexes in challenging dehydrogenation reactions.     

Partial Methane Oxidation to Methanol on Ru-Porphyrins – on the Role of Non-Innocent Ligands and Spin Crossover

The partial oxidation reaction of CH₄ led to the formation of CH₃OH in the presence of Ru-porphyrin oxo complexes (denoted as POR, POR-O and POR-OH where in the case of the last two, oxygen atom and the OH group were attached to the active site, respectively), in which Ru was present on different oxidation states. The simulations were performed based on Density Functional Theory (DFT) with extended geometric and electronic structure analyses of each reaction step. Moreover, the reaction pathways were investigated in different spin states. The Spin Crossover (SCO) phenomenon was found to play an important role in the kinetics of the reaction in the presence of POR and POR-O. Harmonic Oscillator Model of Aromaticity (HOMA) index was applied for different spin states to estimate the aromaticity changes of the pyrrole rings in the Ru-porphyrin complexes. In order to characterize the nature of bonding, the Natural Bond Orbitals (NBO) analysis including the Wiberg Bond Index (WBI) and Natural Population Analysis (NPA) was carried out. Finally, the Non-Covalent Interactions (NCI) index was employed to gain insight into interactions between the components of the reaction. It was found that the non-covalent interactions cannot be neglected in the studied reaction paths.     

A Comprehensive Study of the Impacts of Oat β-Glucan and Bacterial Curdlan on the Activity of Commercial Starter Culture in Yogurt

This study provides important information about the impacts of various levels of oat (OBG) and bacterial (curdlan) β-glucan and fat contents in milk on survivability and metabolism of yogurt starter cultures. The results show that addition of β-glucans in the concentration higher than 0.25% reduced starter bacterial counts during storage and prolonged the milk acidification process. A significant increase in lactose consumption by starter cultures was noted in the yogurt samples with OBG addition up to 0.75%. The highest (by 567% on average) increase in lactic acid content was noted in the control yogurts. Whereas the lowest (by 351%) increase in lactic acid content was noted in yogurts with OBG. After 28-day storage, the acetic aldehyde content was significantly influenced by fat content, type and addition level of polysaccharide. A higher increase in acetoin content was noted in samples with 0.25% than in samples with 1% of polysaccharides. In turn, significantly lower increases in diacetyl and 2,3-pentanedione contents were observed in the yogurt samples with OBG than in these with curdlan, with diacetyl production increase along with the higher concentration of the polysaccharide. The addition of OBG and curdlan to milk contributed to differences in the starter culture metabolism, consequently, in the milk acidification dynamics.     

New Electrochemical Sensor of Prolonged Application for Metformin Determination Based on Hydrated Ruthenium Dioxide‐Carbon Black‐Nafion Modified Glassy Carbon Electrode

Metformin (MET) is an antidiabetic drug most commonly used in treatment of diabetes mellitus type 2 (T2D). Adsorptive stripping voltammetric method using carbon black – hydrated ruthenium dioxide – Nafion modified glassy carbon electrode (CB‐RuO₂‐Nafion GC electrode) have been developed for metformin determination in pharmaceutical formulations. By using ruthenium dioxide, electrode's lifespan was extended to at least 3 weeks (change of metrological parameters estimated as 3–4 %) what is an excellent result concerning other solutions previously described in the literature. Moreover the fabrication of the sensor is simple and fast. Deposition step was carried out at the potential 0 mV for 15 s. The best results were obtained in 0.05 M acetate buffer (pH 4.6). Important aspect was fixed MET : Cu(II) ratio equal to 1 : 8, otherwise linear dependence between register current and MET concentration could not be obtained. In addition, a significant improvement in the parameters of the calibration curve was obtained. Limit of detection was equal to 0.7 μM. Developed method was successfully applied in analysis of 2 pharmaceuticals products and in wastewater and river water. Accuracy of the method was estimated using recoveries, which were in the range 101–110 %. In order to adapt developed system into hydrodynamic conditions, amperometry in hydrodynamic transport conditions and flow injection analysis (FIA) measurements have been conducted. Conducted FIA measurements prove that developed method has potential for application in automized flow systems without frequent calibration.