Investigations of the presence of caffeine in the Rudawa River, Kraków, Poland.

Caffeine concentration in surface water (Rudawa River, Kraków, Poland) has been being investigated since 2011. The method applied for investigations was developed in 2011, and the first series of measurements of caffeine concentration in surface water began in 2011. Caffeine concentration was determined by the gas chromatography-mass spectrometry (GC-MS) method. Solid phase extraction (SPE) was used to enrich the concentration of caffeine in water samples. As an internal standard, the caffeine isotope (13)C3 in methanol (Sigma Aldrich) was used. The values of four additional parameters (concentration of nitrates, biochemical oxygen demand after 7 days, number of Escherichia coli and number of Enterococcus faecalis) were determined for the water sample analyzed. Caffeine was detected in all studied samples. The control series of measurements during 2011-2014 confirmed that caffeine is present in Rudawa River water and that the concentration of this substance in Rudawa River ranges from 14.0 to 852.0 ng/dm(3). There is no correlation between the concentration of caffeine and the concentration of other anthropogenic contaminants determined in water.

Biodegradable polymer-lipid monolayers as templates for calcium phosphate mineralization.

A combination of poly([R]-3-hydroxy-10-undecenoate) (PHUE), a biodegradable polymer from the group of polyhydroxyalkanoates (PHAs), and lipids of different head groups was used to support the growth of calcium phosphate, the main component of mammalian bones. Crystallization took place under two-dimensional films (Langmuir monolayers). The addition of a negatively charged lipid, 1,2-dioleoyl-sn-glycero-3-phospho-l-serine, to a PHUE film led to the formation of lipid domains (rich in negative charge), and resulted in excellent mineralization control: crystals with uniform size and morphology were formed. The results show that carefully optimized combinations of materials can lead to better control of calcium phosphate crystallization compared to one-component organic scaffolds.

Interactions of biodegradable poly([R]-3-hydroxy-10-undecenoate) with 1,2-dioleoyl-sn-glycero-3-phosphocholine lipid: a monolayer study.

Polyhydroxyalkanoates (PHAs) are biodegradable, biocompatible polyesters and very attractive candidates for biomedical applications as materials for tissue engineering. They have a hydrophobic character, but some are able to spread at the air-water interface to form monomolecularly thin films (Langmuir monolayers). This is a very convenient model to analyze PHA self-assembly in two dimensions and to study their molecular interactions with other amphiphilic compounds, which is very important considering compatibility between biomaterials and cell membranes. We used the Langmuir monolayer technique and Brewster angle microscopy to study the properties of poly([R]-3-hydroxy-10-undecenoate) (PHUE) films on the free water surface in various experimental conditions. Moreover, we investigated the interactions between the polymer and one of the main biomembrane components, 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). The addition of lipid to a polymer film does not change the monolayer phase behavior; however, the interactions between these two materials are repulsive and fall in two composition-dependent regimes. In summary, this is the first systematic study of the monolayer behavior of PHUE, thus forming a solid basis for a thorough understanding of material interactions, in particular in the context of biomaterials and implants.

The influence of phospholipid structure on the interactions with nystatin, a polyene antifungal antibiotic A Langmuir monolayer study.

This work presents the investigations of the interactions between nystatin, a polyene antibiotic, and phospholipids with various head groups (phosphatidylcholine and phosphatidylethanolamine) and acyl chains of different length and saturation degree. The experiments were performed with the Langmuir monolayer technique. Among phosphatidylethanolamines, DMPE, DPPE and DSPE were studied, while phosphatidylcholines were represented by DSPC and DOPC. The influence of the antibiotic on the molecular organization of the phospholipid monolayer was analysed with the compression modulus values, while the strength of nystatin/phospholipid interactions and the stability of the mixed monolayers were examined on the basis of the excess free energy of mixing values. The results obtained proved a high affinity of nystatin towards phospholipids. Nystatin was found to interact more strongly with phosphatidylcholines than with phosphatidylethanolamines. The most negative values of the excess free energy of mixing observed for the antibiotic and DOPC mixtures prove that nystatin favors the phospholipid with two unsaturated acyl chains. The results imply that nystatin/phospholipid interactions compete in the natural membrane with nystatin/sterol interactions, thereby affecting the antifungal activity of nystatin and its toxicity towards mammalian cells.

The study on the interaction between phytosterols and phospholipids in model membranes.

Sterols are one of the major components of cellular membranes. Although in mammalian membranes cholesterol is a predominant sterol, in the human organism plant sterols (phytosterols) can also be found. Phytosterols, especially if present in concentrations higher than normal (phytosterolemia), may strongly affect membrane properties. In this work, we studied phytosterol-phospholipid interactions in mixed Langmuir monolayers serving as model membranes. Investigated were two phytosterols, beta-sitosterol and stigmasterol and a variety of phospholipids, both phosphatidylethanolamines and phosphatidylcholines. The phospholipids had different polar heads, different length and saturation of their hydrocarbon chains. The interactions between molecules in mixed sterol/phospholipid films were characterized with the mean area per molecule (A(12)) and the excess free energy of mixing (DeltaG(Exc)). The effect of the sterols on the molecular organization of the phospholipid monolayers was analyzed based on the compression modulus values. It was found that the incorporation of the phytosterols into the phospholipid monolayers increased their condensation. The plant sterols revealed higher affinity towards phosphatidylcholines as compared to phosphatidylethanolamines. The phytosterols interacted more strongly with phospholipids possessing longer and saturated chains. Moreover, both the length and the saturation of the phosphatidylcholines influenced the stoichiometry of the most stable complexes. Our results, compared with those presented previously for cholesterol/phospholipid monolayers, allowed us to draw a conclusion that the structure of sterol (cholesterol, beta-sitosterol, stigmasterol) does not affect the stoichiometry of the most stable complexes formed with particular phospholipids, but influences their stability. Namely, the strongest interactions were found for cholesterol/phospholipids mixtures, while the weakest for mixed systems containing stigmasterol.