Simple carbohydrates are associated with the enhanced risk of cardiovascular disease and adverse changes in lipoproteins in the organism. Conversely, sugars are known to exert a stabilizing effect on biological membranes, and this effect is widely exploited in medicine and industry for cryopreservation of tissues and materials. In view of elucidating molecular mechanisms involved in the interaction of mono- and disaccharides with biomimetic lipid systems, we study the alteration of dielectric properties, the degree of hydration, and the rotational order parameter and dipole potential of lipid bilayers in the presence of sugars. Frequency-dependent deformation of cell-size unilamellar lipid vesicles in alternating electric fields and fast Fourier transform electrochemical impedance spectroscopy are applied to measure the specific capacitance of phosphatidylcholine lipid bilayers in sucrose, glucose and fructose aqueous solutions. Alteration of membrane specific capacitance is reported in sucrose solutions, while preservation of membrane dielectric properties is established in the presence of glucose and fructose. We address the effect of sugars on the hydration and the rotational order parameter for 1-palmitoyl-2-oleoyl-sn-glycero-3- phosphocholine (POPC) and 1-stearoyl-2-oleoyl-sn-glycero-3- phosphocholine (SOPC). An increased degree of lipid packing is reported in sucrose solutions. The obtained results provide evidence that some small carbohydrates are able to change membrane dielectric properties, structure, and order related to membrane homeostasis. The reported data are also relevant to future developments based on the response of lipid bilayers to external physical stimuli such as electric fields and temperature changes.
Aluminum nitride (AlN) films were synthesized onto Si(100) substrates by pulsed laser deposition (PLD) in vacuum or nitrogen, at 0.1, 1, 5, or 10 Pa, and substrate temperatures ranging from RT to 800 °C. The laser parameters were set at: incident laser fluence of 3–10 J/cm2 and laser pulse repetition frequency of 3, 10, or 40 Hz, respectively. The films’ hardness was investigated by depth-sensing nanoindentation. The optical properties were studied by FTIR spectroscopy and UV-near IR ellipsometry. Hardness values within the range of 22–30 GPa and Young’s modulus values of 230–280 GPa have been inferred. These values were determined by the AlN film structure that consisted of nanocrystallite grains, strongly dependent on the deposition parameters. The values of optical constants, superior to amorphous AlN, support the presence of crystallites in the amorphous film matrix. They were visualized by TEM and evidenced by FTIR spectroscopy. The characteristic Reststrahlen band of the h-AlN lattice with component lines arising from IR active phonon vibrational modes in AlN nanocrystallites was well detectable within the spectral range of 950–500 cm−1. Control X-ray diffraction and atomic force microscopy data were introduced and discussed. All measurements delivered congruent results and have clearly shown a correlation between the films’ structure and the mechanical and optical properties dependent on the experimental conditions.
Homogeneous films from SiO1.3 (250 nm thick) were deposited on crystalline Si substrates by thermal evaporation of silicon monoxide. A part of the films was further annealed at 700 °C to grow amorphous Si (a-Si) nanoclusters in an oxide matrix, thus producing composite a-Si-SiO1.8 films. Homogeneous as well as composite films were irradiated by 20-MeV electrons at fluences of 7.2 × 1014 and 1.44 × 1015 el/cm2. The film thicknesses and optical constants were explored by spectroscopic ellipsometry. The development of the phase composition of the films caused by the electron-beam irradiation was studied by transmission electron microscopy. The ellipsometric and electron microscopy results have shown that the SiOx films are optically homogeneous and the electron irradiation with a fluence of 7.2 × 1014 el/cm2 has led to small changes in the optical constants and the formation of very small a-Si nanoclusters. The irradiation of the a-Si-SiOx composite films caused a decrease in the effective refractive index and, at the same time, an increase in the refractive index of the oxide matrix. Irradiation induced increase in the optical band gap and decrease in the absorption coefficient of the thermally grown amorphous Si nanoclusters have also been observed. The obtained results are discussed in terms of the formation of small amorphous silicon nanoclusters in the homogeneous layers and electron irradiation induced reduction in the nanocluster size in the composite films. The conclusion for the nanoparticle size reduction is supported by infrared transmittance results.
In the last decades, numerous dendrimers with a variety of potential biomedical applications have been developed and investigated. The aim of the present study was to evaluate the molecular mechanisms of interaction between two dendrimers with proven antibacterial activity (4-N,N-dimethylamino-1,8-naphthalimide (Dab) and 3-bromo-Dab (Dab-Br)) and POPC (1-palmitoyl-2-oleoylphosphatidylcholine) model membranes (monolayers and liposomes). The pressure-area isotherms and the compressional modulus of the monolayers revealed that Dab is likely to penetrate the hydrophobic region of POPC, whereas Dab-Br inserts mainly into the lipid headgroup area. This assumption was confirmed by FTIR-ATR of POPC liposomes containing Dab and Dab-Br dendrimers. In addition, Dab induced a higher lipid order in POPC large unilamellar vesicles (LUVs) compared to Dab-Br. Moreover, both dendrimers changed the negative zeta potential of POPC vesicles to positive values, with slightly higher effect of Dab-Br, indicating electrostatic interactions between the lipid headgroups and dendrimers. Furthermore, Dab was able to reduce the average POPC LUVs’ size, unlike Dab-Br. The visualization of giant unilamellar vesicles revealed that the increasing dendrimer concentration induced model membrane shrinking and complete disintegration, which was more prominent for Dab. Based on the experimental results, new fundamental knowledge about the destabilizing effect of dendrimers on model lipid membranes will be acquired with a focus on their application in pharmacology and clinical practice.
Background: Specifically designed peptide mimetics offer higher selectivity regarding their toxicity to mammalian cells. In addition to the α-helix conformation, the specific activity is related to the peptide’s ability to penetrate the cell membrane. The alterations in lipid membrane properties were addressed in the presence of the peptide KLAKLAK-NH2 and analogs containing β-alanine, strengthening the antibacterial activity and/or naphtalimide with proven anticancer properties. Methods: The molecular interactions of the peptide mimetics with POPC bilayers were studied using FTIR-ATR spectroscopy. The thermal shape fluctuation analysis of quasispherical unilamellar vesicles was applied to probe the membrane bending elasticity. The impedance characteristics of bilayer lipid membranes were measured using fast Fourier-transform electrochemical impedance spectroscopy. Results: A lateral peptide association with the membrane is reported for β-alanine-containing peptides. The most pronounced membrane softening is found for the NphtG-KLβAKLβAK-NH2 analog containing both active groups that corroborate with the indications for 1,8-naphthalimide penetration in the lipid hydrophobic area obtained from the FTIR-ATR spectra analysis. The β-alanine substitution induces strong membrane-rigidifying properties even at very low concentrations of both β-alanine-containing peptides. Conclusions: The reported results are expected to advance the progress in tailoring the pharmacokinetic properties of antimicrobial peptides with strengthened stability towards enzymatic degradation. The investigation of the nonspecific interactions of peptides with model lipid membranes is featured as a useful tool to assess the antitumor and antimicrobial potential of new peptide mimetics.