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Abstract This study aimed to investigate the effect of selected compounds from the group of triterpene sapogenins on model phosphatidylcholine membranes. Two types of biological membrane model systems were used in the work, i.e., liposomes (microelectrophoresis method) and spherical bilayers (interfacial tension method). Each model was modified with the tested sapogenin compounds, and the change in their physicochemical and electrical parameters was analyzed. Parameters characterizing the equilibrium in the membrane of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC)-oleanolic acid (OA) and DPPC-asiatic acid (AA) were determined). Based on the Young-Laplace equation, the interfacial tensions of spherical lipid bilayers were measured. The formation of 1:1 complexes was assumed in the DPPC-OA and DPPC-AA membrane systems, and the parameters characterizing the interactions in the formed complexes were calculated. Microelectrophoresis was used to study the surface charge density of lipid membranes. These values were obtained from electrophoretic mobility data using Smoluchowsky’s equation. The influence of pH on the electrolyte solution and the composition of the membranes was investigated. The results indicate that modifying DPPC membranes with selected triterpene sapogenins, both OA and AA, causes changes in the surface charge density and shifts of the isoelectric point. Data presented in this work, obtained through mathematical derivation and confirmed experimentally, are of great importance for interpreting phenomena occurring in lipid membranes. A quantitative description of equilibria between phosphatidylcholine and sapogenins lets us understand the processes on the membrane surface. The equilibria are particularly significant from the standpoint of cell functioning. Phosphatidylcholine-sapogenin interactions modulate a range of physicochemical properties of membranes, and they are important in the course of the multiple processes involving membranes in the living cell (e.g., transport mechanism).

The influence of kaempferol (K), myricetin (M) and lipoic acid (LA) on the properties of natural erythrocytes, isolated from animal blood and biological membrane models (monolayers and liposomes) made of phosphatidylcholine (PC), cholesterol (CHOL), and sphingomyelin (SM), CHOL in a ratio of 10:9, was investigated. The Langmuir method, Brewster angle microscopy (BAM) and microelectrophoresis were used. The presented results showed that modification of liposomes with kaempferol, myricetin and lipoic acid caused changes in the surface charge density and the isoelectric point value. Comparing the tested systems, several conclusions were made. (1) The isoelectric point for the DPPC:Chol:M (~2.2) had lower pH values compared to lipoic acid (pH~2.5) and kaempferol (pH~2.6). (2) The isoelectric point for the SM-Chol with myricetin (~3.0) had lower pH values compared to kaempferol (pH~3.4) and lipoic acid (pH~4.7). (3) The surface charge density values for the DPPC:Chol:M system in the range of pH 2–9 showed values from 0.2 to −2.5 × 10−2 C m−2. Meanwhile, for the DPPC:Chol:K and DPPC:Chol:LA systems, these values were higher at pH~2 (0.7 × 10−2 C m−2 and 0.8 × 10−2 C m−2) and lower at pH~9 (−2.1 × 10−2 C m−2 and −1.8 × 10−2 C m−2), respectively. (4) The surface charge density values for the SM:Chol:M system in the range of pH 2–9 showed values from 0.5 to −2.3 × 10−2 C m−2. Meanwhile, for the DPPC:Chol:K and DPPC:Chol:LA systems, these values were higher at pH~2 (0.8 × 10−2 C m−2), and lower at pH~9 (−1.0 × 10−2 C m−2 and −1.8 × 10−2 C m−2), respectively. (5) The surface charge density values for the erythrocytes with myricetin in the range of pH 2–9 showed values from 1.0 to −1.8 × 10−2 C m−2. Meanwhile, for the erythrocytes:K and erythrocytes:LA systems, these values, at pH~2, were 1.3 × 10−2 C m−2 and 0.8 × 10−2 C m−2 and, at pH~9, −1.7 × 10−2 C m−2 and −1.0 × 10−2 C m−2, respectively.

This study aims to investigate the interactions appearing when the beta-2-glycoprotein-1 binds to a lipid bilayer. The inter- and intra-molecular forces acting between the two macromolecular systems have been investigated using a molecular dynamics simulation method. The importance of water bridges has also been addressed. Additionally, the viscoelastic response of the bilayer has been studied. In detail, the (saturated-chain) 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and (unsaturated-chain) 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE) bilayers have been chosen to test their behavior near the protein. Both of the lipids have a polar head but different chemical structures and are similar to the main phospholipids present in the synovial fluid. This study is meaningful for further explaining the worsening friction properties in articular cartilage, as the inactivation of phospholipid bilayers by beta-2-glycoprotein-1 is believed to be a cause of the destruction of cartilage in most rheumatic diseases and osteoarthritis. It was found that the protein binds stronger to the DPPC bilayer than to the POPE, but in both cases, it has the potential to change the local bilayer stability. Nevertheless, the binding forces are placed within a small area (only a few lipids contribute to the binding, creating many interactions). However, together, they are not stronger than the covalent bonds between C–O, thus, potentially, it is possible to push the lipids into the bilayer but detaching the lipids’ heads from the tail is not possible. Additionally, the protein causes water displacement from the vicinity of the bilayer, and this may be a contributor to the instability of the bilayer (disrupting the water bridges needed for the stabilization of the bilayer, especially in the case of DPPC where the heads are not so well stabilized by H–bonds as they are in POPE). Moreover, it was found that the diffusivity of lipids in the DPPC bilayer bound to the protein is significantly different from the diffusivity of the ones which are not in contact with the protein. The POPE bilayer is stiffer due to intramolecular interactions, which are stronger than in the DPPC; thus, the viscous to elastic effects in the POPE case are more significant than in the case of the DPPC. It is, therefore, harder to destabilize the POPE bilayer than the DPPC one.

In this examination, we investigated the effect of lipoic acid (LA) on the properties of biological membrane models (monolayers, bilayers, and liposomes) formed from phosphatidylcholine (PC) or phosphatidylserine (PS) using the Langmuir, microelectrophoresis, and interfacial tension methods. The Langmuir technique allowed us to calculate the π–A isotherms and determine the molecular surface areas of pure and mixed monolayers. Using mathematical equations, we established that LA and the lipids formed complexes at a 1:1 ratio. The interfacial tension method was based on Young and Laplace’s equation. We assumed the formation of a 1:1 complex in the PC–LA system. Using the mathematical relationships, we derived the parameters characterizing the resulting complex, i.e., the surface occupied by the complex and the interfacial tension and stability constant of the formed complex. The microelectrophoretic method was used to determine the dependence of the zeta potential of the lipid membranes as a function of the pH (pH 2 to 10) of the electrolyte solution. The results indicate that modification of PC or PS membranes with LA affects changes in the zeta potential and the isoelectric point values.

This research is devoted to assessment methods used in different test systems, including e-learning systems. The methods considered here are based on classical test theory and item response theory (IRT). We propose a new approach for improving the quality of assessment by diversifying evaluation points.

In this paper, we explain the amphoteric character of the cartilage surface by studying a lipid bilayer model built from phospholipids. We examined the interfacial tension values and molecular dynamics simulation in solutions of varying pH. The effects of negative and positive charge density (or fixed charges) on the (cartilage/cartilage) friction coefficient were investigated. In physiological (or synovial) fluid, after the isoelectric point (pI), the curve of interfacial tension decreases rapidly as it reaches pH 7.4 and then approaches a constant value at higher pH. It was shown that the curve of the interfacial tension curve exhibits a maximum value at the isoelectric point with a Gaussian shape feature. The phospholipid bilayers facilitate an almost frictionless contact in the joint. Moreover, the slippage of the bilayer and the short-range repulsion between the surfaces of the negatively charged cartilage surfaces are the main determinants of the low frictional properties of the joint.