The impact of sterol structure on the interactions with sphingomyelin in mixed langmuir monolayers

In this work, the Langmuir monolayer technique was applied to study the interactions between sphingomyelin and various sterols differing in the structure of the side chain (cholesterol, beta-sitosterol, stigmasterol). The mean area per molecule and the excess free energy of mixing values were analyzed in the context of sterol-induced condensing effect and interactions between molecules in the mixed monolayers. Moreover, the compression modulus values were calculated and widely discussed from the point of view of the ordering effect of sterols. It was found that all of the sterols investigated form the most stable monolayers with sphingomyelin at 2:1 sphingomyelin:sterol proportion and the strongest interactions exist between molecules in cholesterol-containing films. Moreover, cholesterol provokes the strongest area condensation and reveals the highest ordering properties, while plant sterols were found to differ only slightly with regards to their ordering properties. Additionally, the ordering effect of the sterols on dipalmitoylphosphatidylcholine (DPPC) films was analyzed and compared to that on sphingomyelin films.     

Two-dimensional miscibility studies of alamethicin and selected film-forming molecules

Alamethicin (ALM), a 20-amino acid antibiotic peptide (peptaibol) from fungal sources, was mixed in Langmuir monolayers with six different surfactants: semifluorinated (F6H18, F10H19, F8H10OH, F6H10SH) and hydrogenated (C18SH and DODAC), aimed at finding appropriate molecules for ALM incorporation for nanodevice construction. Alamethicin-containing mixed monolayers were investigated by means of surface manometry (pi-A isotherms) and Brewster angle microscopy (BAM). Our results show that only semifluorinated alkanes can serve as an appropriate material since they form miscible and homogeneous monolayers with ALM within the whole concentration range. All the remaining surfactants, possessing polar groups, were found to demix with ALM. This effect was explained as being due to the existence of strong polar interactions between vertically oriented surfactant molecules, which tend to separate from horizontally oriented alpha-helices of the peptide. On the contrary, semifluorinated alkanes, lacking any polar group in their structure and bearing a large dipole moment, interact with ALM, also possessing a huge cumulative dipole moment. These dipole-dipole interactions between ALM and SFAs are more attractive than those between SFA molecules in their pure monolayers, causing the large ALM molecule, situated parallel to the interface, to be surrounded by SFA molecules in perpendicular orientation, leading to the formation of a highly organized binary mixed monolayer. BAM images of the ALM monolayer indicate that this peptide collapses with the nucleation and growth mechanism, like the majority of surfactants, which contradicts the model of ALM collapse by desorption, previously published in the literature.     

The Comparison of Physicochemical Parameters,Antioxidant Activity and Proteins for the Raw Local Polish Honeys and Imported Honey Blends

Many imported honeys distributed on the Polish market compete with local products mainly by lower price, which can correspond to lower quality and widespread adulteration. The aim of the study was to compare honey samples (11 imported honey blends and 5 local honeys) based on their antioxidant activity (measured by DPPH, FRAP, and total phenolic content), protein profile obtained by native PAGE, soluble protein content, diastase, and acid phosphatase activities identified by zymography. These indicators were correlated with standard quality parameters (water, HMF, pH, free acidity, and electrical conductivity). It was found that raw local Polish honeys show higher antioxidant and enzymatic activity, as well as being more abundant in soluble protein. With the use of principal component analysis (PCA) and stepwise linear discriminant analysis (LDA) protein content and diastase number were found to be significant (p < 0.05) among all tested parameters to differentiate imported honey from raw local honeys.     

Nucleation and growth in the collapsed langmuir monolayers from semifluorinated alkanes

The 3D phase formation was monitored in relaxation experiments of the collapsed Langmuir monolayers of selected partially fluorinated tetracosanes, that is, F6H18, F8H16, and F10H14. To carry out these experiments, the classical method of surface manometry, such as pi-A isotherms registration and the molecular area-time dependencies, under quasi-static monitoring conditions were applied. The evolution of 3D structures at the water/air interface was observed with Brewster angle microscopy (BAM). The obtained data were interpreted according to the nucleation-growth-collision theory model. It occurred that, even though the investigated chemicals are not classical surfactants and do not possess any polar headgroup, their evolution from a 2D monolayer to 3D structures can be successfully modeled with the above-mentioned theory. The influence of the subphase temperature on the nucleation process is also discussed.     

Swelling effects in cross-linked polymers by thermogravimetry

A Brazilian coal power plant generates a waste composed by the fly and bottom ashes produced from coal combustion and by a spent sulfated lime generated after SO₂ capture from combustion gases. This work presents a study of the early stages of the hydration of composites formed by this waste and a type II Portland cement, which will be used for CO₂ capture. The cement substitution degrees in the evaluated composites were 10, 20, 30 and 40%, and the effect of the coal power unit waste on the hydration reaction was analyzed on real time by NCDTA, during the first 40 h of hydration. The results show that the higher is the substitution degree, the higher is the retarding effect on the cement hydration process. Actually, by respective thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis on initial cement mass basis, this effect is caused by double exchange reactions among Ca and Mg components of the waste, during the first 4 h of hydration, which promote a much higher exothermic effect in the NCDTA curve, simultaneously to respective induction periods. The pozzolanic reactions, due to the presence of the waste silica and alumina containing amorphous phases, consume part of the original Ca(OH)₂ content existent in the waste in the case of 30 and 40% substituted pastes, and also from part of the Ca(OH)₂ produced in cement hydration reactions, in the case of the 10 and 20% substituted pastes.     

Principal component and cluster analyses as supporting tools for co-crystals detection

The effects of super absorbent polymer (SAP) on the early hydration evolution of Portland cement within 72 h were investigated by isothermal calorimetry, thermal analysis and X-ray diffraction analysis. The results show that the SAP definitely affects the early hydration process of Portland cement, increases the hydration heat evolution rate during the acceleration period and during the main exothermic peak, promotes the earlier appearance of the main exothermic peak, but does not affect the lengths of the initial reaction period and the induction period and the onset of the acceleration period. The SAP can accelerate cement hydration to increase the hydration degree within 72 h. But the dosage variation of SAP has minor influence on the hydration heat evolution and hydration degree. The SAP enhances the formation of Ca(OH)₂ after 12 h to keep higher content than that in the reference paste. The SAP does not affect the maximum content of ettringite, but delays the conversion of ettringite to monosulphate to remain ettringite content higher at later hydration time. Besides, no new phases are found to have formed in cement paste with SAP.     

Effect of the degree of substitution on the rheology of sodium carboxymethylcellulose solutions in propylene glycol/water mixtures

The linear dynamic viscoelastic properties and non-linear transient rheology of sodium carboxymethylcellulose solutions (Na-CMC) in propylene glycol/water mixtures were investigated. Measurements were carried out for the solutions of Na-CMC with three different degrees of substitution (DS), namely 0.62, 0.79, 1.04, and the similar average molecular weight (M_w ≈ 250,000 g/mol). The strong synergism between the molecules of Na-CMC with DS of 0.62 and 0.79, and propylene glycol has been observed. The occurrence of the overshoot shear stress and the low loss tangent values indicate the physical cross-linking of the polymer chains. The increase of propylene glycol concentration over 80 wt% and sodium carboxymethylcellulose (DS = 0.7) over 1.6 wt% leads to the formation of a physical cross-link network. The absence of overshoot shear stress and terminal behaviour in SAOS flow of the Na-CMC_1.04 solutions in the PG/water mixture shows that no intermolecular cross-linking of polymer chains occurred in them.     

Studies on reaction of reduced lipoic acid with Mukaiyama reagent and its application for pharmaceutical and food analysis

A new sensitive method for the determination of lipoic acid (LA) in selected food items based on its reaction with Mukaiyama reagent (2-chloro-1-methylpyridinium iodide, CMPI) was developed. It was stated that CMPI reacts with reduced form of lipoic acid (dihydrolipoic acid, DHLA) and the stable product is produced. The spectrum of the labeled form of DHLA exhibits new band at 312?nm. Based on its spectral characteristics new spectrophotometric and UV–high-performance liquid chromatography (HPLC) methods of LA determination were elaborated. Both methods allowed determination of the analyte in the concentration range of 5?×?10^?6–1?×?10^?4?mol?L^?1 with limit of detection 0.39?×?10^?6 and 0.77?×?10^?6?mol?L^?1 for spectrophotometric and HPLC method, respectively. The practical usability of newly developed methods was checked by determination of lipoic acid contents in its pharmaceutical preparate Revitanerw. The proposed method was precise and accurate. The relative error of determination did not exceed ±0.067%. As chromatographic method allowed the determination of analyte in the presence of complex matrix, it was applied for assay of free fraction of α-lipoic acid in selected food items. A procedure of LA isolation from biological matrix was developed. The extraction with dichloromethane allowed quantitative recovery at 102.94?±?4.20%. The green barley appeared to be the richest source of LA.     

Amorphous Form of Carvedilol Phosphate—The Case of Divergent Properties

The amorphous form of carvedilol phosphate (CVD) was obtained as a result of grinding. The identity of the obtained amorphous form was confirmed by powder X-ray diffraction (PXRD), different scanning calorimetry (DSC), and FT-IR spectroscopy. The process was optimized in order to obtain the appropriate efficiency and time. The crystalline form of CVD was used as the reference standard. Solid dispersions of crystalline and amorphous CVD forms with hydrophilic polymers (hydroxypropyl-β-cyclodextrin, Pluronic^® F-127, and Soluplus^®) were obtained. Their solubility at pH 1.2 and 6.8 was carried out, as well as their permeation through a model system of biological membranes suitable for the gastrointestinal tract (PAMPA-GIT) was established. The influence of selected polymers on CVD properties was defined for the amorphous form regarding the crystalline form of CVD. As a result of grinding (four milling cycles lasting 15 min with 5 min breaks), amorphous CVD was obtained. Its presence was confirmed by the “halo effect” on the diffraction patterns, the disappearance of the peak at 160.5 °C in the thermograms, and the changes in position/disappearance of many characteristic bands on the FT-IR spectra. As a result of changes in the CVD structure, its lower solubility at pH 1.2 and pH 6.8 was noted. While the amorphous dispersions of CVD, especially with Pluronic^® F-127, achieved better solubility than combinations of crystalline forms with excipients. Using the PAMPA-GIT model, amorphous CVD was assessed as high permeable (Papp > 1 × 10⁻⁶ cm/s), similarly with its amorphous dispersions with excipients (hydroxypropyl-β-cyclodextrin, Pluronic^® F-127, and Soluplus^®), although in their cases, the values of apparent constants permeability were decreased.