Search

[Display omitted] • EE2 interacts with both SM and SM/Chol monolayers at the air/water interface. • The morphology and permeability was induced by EE2 only to SM/Chol GUVs. • The L o phase regulate the permeability of the vesicles in presence of EE2. Hormone treatments are frequently associated with cardiovascular diseases and cancers in women. Additionally, the detrimental effects of their presence as contaminants in water remain a concern. The transport of hormones through cell membranes is essential for their biological action, but investigating cell permeability is challenging owing to the experimental difficulty in dealing with whole cells. In this paper, we study the interaction of the synthetic hormone 17α-ethynylestradiol (EE2) with membrane models containing the key raft components sphingomyelin (SM) and cholesterol (Chol). The models consisted of Langmuir monolayers and giant unilamellar vesicles (GUVs) that represent bilayers. EE2 induced expansion of SM monolayers upon interacting with the non-hydrated amide group of SM head, but it had practically no effect on SM GUVs because these group are not available for interaction in bilayers. In contrast, EE2 interacted with hydrated phosphate group ( P O 2 -) and amide group of SM/Chol mixture monolayer, which could explain the loss in phase contrast of liquid-ordered GUVs suggesting pore formation. A comparison with reported EE2 effects on GUVs in the fluid phase, for which no loss in phase contrast was observed, indicates that the liquid-ordered phase consisting of lipid rafts is relevant to be associated with the changes on cell permeability caused by the hormones. [ABSTRACT FROM AUTHOR]

Cationic lipids are synthetic compounds of amphiphilic character used in Drug Delivery Systems (DDS), especially in gene therapy, as the carriers of genetic material. As it is known, the main limitation of the application of cationic lipids in DDS is their high cytotoxicity after in vivo administration and low bioactivity. This is probably related to not fully known the relationship between the lipid structure and its activity as well as the mechanism of lipofection or drug delivery. Therefore, in this work we determined the impact of a selected group of cationic lipids - triesters of phosphatidylcholine (Et-PCs) - differing in their hydrophobic structure on model mammalian membranes. In the research, as model systems, Langmuir monolayers and liposomes were applied. It was shown that the incorporation of Et-PCs into model mammalian membranes weakens interactions between lipids, causing the increase of fluidity, disordering degree and permeability of membrane. The destabilization of the membrane in this way can facilitate the entry of drugs, carried inside cationic liposomes, into the pathological cell. Moreover, the studies prove that the structure of the hydrophobic part of cationic lipids also affects the properties of lipid membranes. [Display omitted] • The interactions of Et-PCs with mammalian membranes depend on their composition. • The hydrophobic structure of Et-PCs effects on the properties of lipid membranes. • Et-PCs increase the disordering degree of molecules in model mammalian membranes. • Et-PC with unsaturated bonds in hydrophobic part fluidizes lipid membranes more. • EDOPC increases more the permeability of the model membrane than EDPPC. [ABSTRACT FROM AUTHOR]

The behavior of amphiphilic molecules such as lipids, peptides and their mixtures at the air/water interface allow us to evaluate and visualize the arrangement formed in a confined and controlled surface area. We have studied the surface properties of the zwitterionic DPPC lipid and Aβ(1–40) amyloid peptide in mixed films at different temperatures (from 15 to 40 °C). In this range of temperature the surface properties of pure Aβ(1–40) peptide remained unchanged, whereas DPPC undergoes its characteristic liquid-expanded → liquid-condensed bidimensional phase transition that depends on the temperature and lateral pressure. This particular property of DPPC makes it possible to dynamically study the influence of the lipid phase state on amyloid structure formation at the interface in a continuous, isothermal and abrupt change on the environmental condition. As the mixed film is compressed the fibril-like structure of Aβ(1–40) is triggered specifically in the liquid-expanded region , independently of temperature, and it is selectively excluded from the well-visible liquid condensed domains of DPPC. The Aβ amyloid fibers were visualized by using BAM and AFM and they were Thio T positive. In mixed DPPC/Aβ(1–40) films the condensed domains (in between 11 mN/m to 20 mN/m) become irregular probably due to the fibril-like structures is imposing additional lateral stress sequestering lipid molecules in the surrounding liquid-expanded phase to self-organize into amyloids. [Display omitted] • Βeta amyloid peptide forms fibril-like structures in phospholipid liquid phase. • Lipid phase acts as an amyloid inductor in biomembranes. • Fibril-like structures can be triggered by the interfacial condition. [ABSTRACT FROM AUTHOR]

Phosphatidic acid (PA) is one of the simplest membrane phospholipids, yet it plays a crucial role in various biologically relevant processes that take place in cells. Since PA generation may be triggered by a variety of factors, very often of antagonistic character, the specific nature of physiological responses driven by PA is not clear. In order to shed more light on these issues, we carried out a systematic characterization of membranes containing one of the three biologically significant PA molecular species. The effect of these molecules on the properties of membranes composed of phosphatidylcholine and/or cholesterol was assessed in a multidisciplinary approach, including molecular dynamic simulations, flicker noise spectroscopy, and Langmuir monolayer isotherms. The first enables the determination of various macroscopic and microscopic parameters such as lateral diffusion, membrane thickness, and defect analysis. The obtained data revealed a strong interaction between unsaturated PA species and phosphatidylcholine. On the other hand, the behavior of saturated PA was greatly influenced by cholesterol. Additionally, a strong effect on mechanical properties was observed in the case of three-component systems, which could not be explained by the simple extrapolation of parameters of the corresponding two-component systems. Our data show that various PA species are not equivalent in terms of their influence on lipid mono- and bilayers and that membrane composition/properties, particularly those related to the presence of cholesterol, may strongly modulate PA behavior.

The formation of ordered 2D nanostructures of double stranded DNA molecules at various interfaces attracts more and more focus in medical and engineering research, but the underlying intermolecular interactions still require elucidation. Recently, it has been revealed that mixtures of DNA with a series of hydrophobic cationic polyelectrolytes including poly(N,N-diallyl-N-hexyl-N-methylammonium) chloride (PDAHMAC) form a network of ribbonlike or threadlike aggregates at the solution—air interface. In the present work, we adopt a novel approach to confine the same polyelectrolyte at the solution—air interface by spreading it on a subphase with elevated ionic strength. A suite of techniques–rheology, microscopy, ellipsometry, and spectroscopy–are applied to gain insight into main steps of the adsorption layer formation, which results in non-monotonic kinetic dependencies of various surface properties. A long induction period of the kinetic dependencies after DNA is exposed to the surface film results only if the initial surface pressure corresponds to a quasiplateau region of the compression isotherm of a PDAHMAC monolayer. Despite the different aggregation mechanisms, the micromorphology of the mixed PDAHMAC/DNA does not depend noticeably on the initial surface pressure. The results provide new perspective on nanostructure formation involving nucleic acids building blocks.

Stimulus-responsive liposomes (L) for triggering drug release to the target site are particularly useful in cancer therapy. This research was focused on the evaluation of the effects of cholesterol levels in the performance of gold nanoparticles (AuNPs)-functionalized L for controlled doxorubicin (D) delivery. Their interfacial and morphological properties, drug release behavior against temperature changes and cytotoxic activity against breast and ovarian cancer cells were studied. Langmuir isotherms were performed to identify the most stable combination of lipid components. Two mole fractions of cholesterol (3.35 mol% and 40 mol%, L1 and L2 series, respectively) were evaluated. Thin-film hydration and transmembrane pH-gradient methods were used for preparing the L and for D loading, respectively. The cationic surface of L allowed the anchoring of negatively charged AuNPs by electrostatic interactions, even inducing a shift in the zeta potential of the L2 series. L exhibited nanometric sizes and spherical shape. The higher the proportion of cholesterol, the higher the drug loading. D was released in a controlled manner by diffusion-controlled mechanisms, and the proportions of cholesterol and temperature of release media influenced its release profiles. D-encapsulated L preserved its antiproliferative activity against cancer cells. The developed liposomal formulations exhibit promising properties for cancer treatment and potential for hyperthermia therapy.

The Langmuir monolayer technique has been successfully used for decades to model biological membranes and processes occurring at their interfaces. Classically, this method involves surface pressure measurements to study interactions within membrane components as well as between external bioactive molecules (e.g. drugs) and the membrane. In recent years, surface-sensitive techniques were developed to investigate monolayers in situ ; however, the obtained results are in many cases insufficient for a full characterization of biomolecule-membrane interactions. As result, description of systems using parameters such as mixing or excess thermodynamic functions is still relevant, valuable and irreplaceable in biophysical research. This review article summarizes the theory of thermodynamics of single- and multi-component Langmuir monolayers. In addition, recent applications of this approach to characterize surface behaviour and interactions (e.g. orientation of bipolar molecules, drug-membrane affinity, lateral membrane heterogeneity) are presented.

In this work the cosmetic preservative based on a Ribes Nigrum (blackcurrant) plant extract (PhytoCide Black Currant Powder abbr. BCE) was investigated to evaluate its antibacterial effect and to gain an insight into its mechanism of action. The influence of this commercially available formulation on model Escherichia coli and Staphylococcus aureus lipid membranes was studied to analyze its interactions with membrane lipids at a molecular level. The mixed lipid monolayers and one component bacteria lipid films were used to investigate the effect of BCE on condensation and morphology of model systems and to study the ability of BCE components to penetrate into the lipid environment. The in vitro tests were also done on different bacteria species (E. coli, Enterococcus faecalis, S. aureus, Salmonella enterica, Pseudomonas aeruginosa) to compare antimicrobial potency of the studied formulation. As evidenced the in vitro studies BCE formulation exerts very similar antibacterial activity against E. coli and S. aureus. Moreover, based on the collected data it is impossible to indicate which bacteria: Gram-positive or Gram-negative are more susceptible to this formulation. Model membrane experiments evidenced that the studied preservative affects organization of both E. coli and S. aureus model system by decreasing their condensation and altering their morphology. BCE components are able to penetrate into the lipid systems. However, all these effects depend on the lipid composition and monolayer organization. The collected results were analyzed from the point of view of the mechanism of action of blackcurrant extract and the factors, which may determine the activity of this formulation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Langmuir monolayers containing different amounts of cholesterol and cholesteryl stearate were studied at two different temperatures (24 °C and 35 °C). The main goal was to contribute towards the understanding of how the variations in the chemical composition may affect the physico-chemical properties of these specific lipid monolayers. The model mixture was chosen considering that cholesteryl esters are present in cell membranes and some other biological systems, including human tear lipids. Therefore, an investigation into the effect of the lipid monolayer composition on their interfacial properties may elucidate some of the fundamental reasons for the deficiencies in cell membranes and tear film functioning in vivo. The experimental results have shown that the molar ratio of the mixture plays a crucial role in the modulation of the Langmuir film properties. The condensing effects of the cholesterol and the interactions between the lipids in the monolayer were the main factors altering the monolayer response to dilatational deformation. The modification of the mixture compositions leads to significant changes in the Langmuir films and the mechanical performance, altering the ability of the monolayer to reduce the surface tension and the viscoelastic properties of the monolayers. This suggests that subtle modifications of the biomembrane composition may significantly alter its physiological function.

Three-finger toxins are naturally occurring proteins in Elapidae snake venoms. Nowadays, they are gaining popularity because of their therapeutic potential. On the other hand, these proteins may cause undesirable reactions inside the body′s cells. A full assessment of the safety of Naja ashei venom components for human cell application is still unknown. The aim of the study was to determine the effect of the exogenous application of three-finger toxins on the cells of monocytes (U-937) and promyelocytes (HL-60), with particular emphasis on the modification of their membranes under the influence of various doses of 3FTx protein fraction (0–120 ng/mL). The fraction exhibiting the highest proportion of 3FTx proteins after size exclusion chromatography (SEC) separation was used in the experiments. The structural response of cell membranes was described on the basis of single-component and multi-component Langmuir monolayers that mimicked the native membranes. The results show that the mechanism of protein–lipid interactions depends on both the presence of lipid polar parts (especially zwitterionic type of lipids) and the degree of membrane saturation (the greatest-for unsaturated lipids). The biochemical indicators reflecting the tested cells (MDA, LDH, cell survival, induction of inflammation, LD50) proved the results that were obtained for the model.

Understanding the interaction of ions with organic receptors in confined space is of fundamental importance and could advance nanoelectronics and sensor design. In this work, metal ion complexation of conformationally varied thiacalix[4]monocrowns bearing lower-rim hydroxy (type I), dodecyloxy (type II), or methoxy (type III) fragments was evaluated. At the liquid–liquid interface, alkylated thiacalixcrowns-5(6) selectively extract alkali metal ions according to the induced-fit concept, whereas crown-4 receptors were ineffective due to distortion of the crown-ether cavity, as predicted by quantum-chemical calculations. In type-I ligands, alkali-metal ion extraction by the solvent-accessible crown-ether cavity was prevented, which resulted in competitive Ag+ extraction by sulfide bridges. Surprisingly, amphiphilic type-I/II conjugates moderately extracted other metal ions, which was attributed to calixarene aggregation in salt aqueous phase and supported by dynamic light scattering measurements. Cation–monolayer interactions at the air–water interface were monitored by surface pressure/potential measurements and UV/visible reflection–absorption spectroscopy. Topology-varied selectivity was evidenced, towards Sr2+ (crown-4), K+ (crown-5), and Ag+ (crown-6) in type-I receptors and Na+ (crown-4), Ca2+ (crown-5), and Cs+ (crown-6) in type-II receptors. Nuclear magnetic resonance and electronic absorption spectroscopy revealed exocyclic coordination in type-I ligands and cation–π interactions in type-II ligands.

The work presents the results of a study of the negative photochromism and luminescent properties of 1',3'-dihydro-3',3'-dimethyl-6-nitro-1'-octadecyl-[1-benzopyran-2,2'-indole]-8-methyl pyridinium chloride (SP2) in solutions, Langmuir monolayers, and cast films. It has been demonstrated that the introduction of the pyridine substituent into the chromene part of the amphiphilic spiropyran leads to stabilization of the open form of the compound under dark conditions, both in the dissolved and in the ordered planar state. The kinetic characteristics of photoreactions occurring in organic solvents upon irradiation by visible light and during relaxation in darkness are determined. Negative solvatochromism of SP2, which consists in the hypsochromic shift of the maximum absorption of the merocyanine form of the compound upon increase of the solvent polarity, is revealed. The luminescent properties of solutions of negative spiropyran and its cast films are investigated. For the first time, SP2 monolayers are formed at the air/water interface and their properties are studied. It is established that SP2 retains its photochromic properties upon transition from solutions to a two-dimensional condensed state. The results obtained open up broad prospects for the development of switchable optoelectronic and information systems based on negative spiropyrans. [ABSTRACT FROM AUTHOR]

• Sr-morin complex spontaneously forms at Langmuir monolayers. • Sr-morin complex formation change the lipid organization at the air-liquid interface. • Complexation was followed by UV–vis absorption and fluorescence techniques. • LB films harboring the Sr-morin complex support in vitro osteoblast growth. Flavonoid-metal complexes are widely studied because of their interesting luminescent behavior and biological activity. Despite the extensive exploration of flavonoid-metal coordination processes in solution, the formation of complexes using the flavonoid molecule inserted in a lipid membrane has been little investigated. This effect could provide important insight into the biological activity of flavonoids at lipid membranes and could represent an attractive strategy to design supramolecular structures. Here, we studied the complexation between Sr2+ and morin inserted in an octadecylphosphonic acid (OPA) Langmuir monolayer. This is a relevant system due to the synergism imposed by the association of the Sr2+ ability to control bone formation/resorption with the morin antioxidative effect. Morin incorporation into the OPA monolayers and further Sr2+ complexation were monitored by surface pressure isotherms. Electronic absorption spectroscopy and fluorescence techniques showed Sr-morin complexation both in solution and at the air-liquid interface. Although morin complexation has been described to occur only at basic pH, the specific thermodynamic properties at the air-liquid interface drove metal complexation. LB films were deposited on Ti surfaces, and the resulting OPA/Sr-morin coatings exhibited high surface free energy and increase on its polar component. This optimized surface feature supported further serum protein adsorption and osteoblast growth and differentiation, indicating that these lipid-based coatings are promising for bioactive coating design. This study paves the way for the use of this lipid-based coating in the design of implants for faster osteointegration. Moreover, flavonoid-metal complexation at membranes could also help to shed light on the biological role played by flavonoids. [ABSTRACT FROM AUTHOR]

Unsaturated fatty acids (UFAs) are known to lower the level of sterols in blood, which accounts for their cardioprotective effect. To understand the molecular basis of this effect, Langmuir monolayer studies have been performed. A series of UFAs differing in the length of the fatty acid chain and the number of double bonds (oleic acid, OA; linoleic acid, LA; stearidonic acid, SDA; eicosanoic acid, EA) were mixed with cholesterol and its more toxic oxidized derivative, 7‑ketocholesterol (7-KC), abundantly present in atheroma plaques. Strong attractive UFA-sterol interactions were attributed to the formation of "surface complexes", in which sterol molecules are bound, thereby reducing the amount of free sterol molecules. It has been found that strength of interactions increases with the degree of unsaturation of the acyl chain in UFA molecule. The most attractive interactions correspond to mixtures with SDA containing 70 mol% of 7-KC and 50 mol% of cholesterol. In both cases, the formation of high stability complexes of, respectively, 2:1 and 1:1 sterol/SDA stoichiometry has been proposed. Other complexes of lower stability and 1:2 stoichiometry were postulated for chol (or 7-KC)/LA systems. The complexes of the lowest stability correspond to chol (or 7-KC) mixtures with OA and EA of 1:1 stoichiometry. In all the cases, the interactions of 7-KC with UFAs are more energetically favorable versus cholesterol. The elongation of the hydrophobic chain of UFAs decreased the interactions with the studied sterols. The obtained results can be related to different conformations of the fatty acids chains. Unlabelled Image • Cholesterol and 7-ketocholesterol (7-KC) form surface complexes with unsaturated fatty acids (UFAs) • The formation of UFA-sterol complexes may account for lowering the blood level of sterols • The thermodynamic stability of sterol-UFA complexes increases with the number of double bonds in the UFA molecule • The elongation of the acyl chain of the UFA molecule reduces the interaction with sterols • The structure of UFA molecule determines the strength of interaction with sterols and the stiochiometry of complexes [ABSTRACT FROM AUTHOR]

Stereoselective interactions are pivotal for molecular recognition between biomolecules and lipid surfaces. The aim of this study was to determine factors differencing molecular interactions between 7-hydroxycholesterol epimers (oxysterols, which excessively appear in pathological processes in human body) and natural membrane phospholipids. Two-component systems of different mutual proportions of 7-hydroxycholesterol (7α-hydroxycholesterol or 7-β-hydroxycholesterol, in short 7α-OH or 7β-OH) and membrane lipids (POPC, DPPC, DPPE, DPPS, SM) were systematically analyzed in artificial membranes modeled as Langmuir monolayers. Classical surface pressure measurements were complemented with direct visualization of films texture both in situ (with Brewster angle microscopy, BAM) and after their transfer onto solid supports (with Atomic Force Microscopy, AFM). Our results clearly show striking differences in surface properties of the studied binary mixtures, emphasizing distinct effects of both 7-hydroxycholesterol epimers on the organization of lipid layers. Systematic study allowed to conclude that the structure of polar head group and interfacial region of the molecule play important role in oxysterol-phospholipid interactions, while the hydrophobic region is significantly less important in this respect. Unlabelled Image • 7-Hydroxycholesterol epimers interact differently with phospholipids in monolayers. • Phospholipids polar group region is crucial for interactions with studied epimers. • Saturation of phospholipid hydrophobic chains has little impact on interactions. • Interactions with sphingomyelin allow differentiating 7-hydroxycholesterol epimers. [ABSTRACT FROM AUTHOR]

Conditions were found for controlled reversible addition-fragmentation chain-transfer radical polymerization to obtain narrow-dispersity gradient methacrylic acid-methyl acrylate copolymer (Mn = 1.59 × 104). A copolymer of similar composition and molecular mass (Mn = 1.81 × 104) with random distribution of units was obtained by radical copolymerization in the presence of dodecyl mercaptan. The behavior of the gradient and random copolymers, each containing ∼14 mol % methacrylic acid units, was studied in solutions, Langmuir monolayers, and Langmuir-Blodgett films. Several ranges of the existence of associates and micelles, preserved upon transfer in a Langmuir-Blodgett film, were revealed for the narrow-dispersity copolymer at the water-air interface depending on pH of the subphase. Associates in the form of ribbon structures and molecular ensembles of nanometric size (network structure with loop-like fragments) are observed in the AFM images of Langmuir-Blodgett films of the gradient and random copolymers, respectively. [ABSTRACT FROM AUTHOR]

2-Hydroxyoleic acid (2OHOA, Minerval) is a Membrane Lipid Therapy drug with anti-cancer activity. Therapeutic effect of this substance is associated with its incorporation into cell membrane. However, despite its effectiveness in cancer treatment and the lack of the side effects, the molecular mechanism of Minerval action is not fully clarified. In this study the influence of 2OHOA on fluidity, permeability and molecular organization of artificial lipid membranes in the context of its membrane-related anticancer properties was investigated. The experiments were performed for raft-like model, composed of the equimolar mixture of sphingomyelin, palmitoyloleoylphosphatidylcholine and cholesterol, as well as for the systems with lower cholesterol content. As model membranes Langmuir films and liposomes were applied. The obtained findings reveal that the incorporation of 2OHOA into artificial lipid membranes leads to the alterations in the properties of the systems. It was found that 2OHOA provokes the chain-disordering, fluidization and the increase in permeability of the studied systems. Both the results of monolayers and bilayers studies show that the strongest 2OHOA effect is observed for raft like mixture. The latter may indicate that the molecular mechanism of action of this compound is closely related to its interactions with lipid rafts – domains that are responsible for the regulation of various cellular functions. • 2-Hydroxyoleic acid molecules disturb molecular organization of SM/POPC/Chol monolayers and bilayers. • The geometry of 2-hydroxyoleic acid molecules determined its effect on membrane. • 2-Hydroxyoleic acid increases chain-disordering, fluidization and permeability of model membranes. • The effect of 2-hydroxyoleic acid is the strongest on raft – imitating systems. [ABSTRACT FROM AUTHOR]

Polychlorinated biphenyls (PCB) are persistent organic pollutants that due to their chemical resistivity and inflammability found multiple applications. In spite of the global ban for PCB production, due to their long half-lives periods, PCB accumulate in the soils, so effective bioremediation of the polluted lands is of crucial importance. Some of the 209 PCB congeners exhibit increased toxicity to soil bacteria and their presence impoverish the soil decomposer community and slows down the degradation of environmental pollutants in the soils. The exact mechanism of PCB antimicrobial activity is unknown, but it is strictly related with the membrane activity of PCB. Therefore, to shed light on these interactions we applied Langmuir monolayers formed by selected phospholipids as model bacterial membranes. In our studies we tested 5 PCB congeners differing in the degree of chlorination and the distribution of the chlorine substituents around the biphenyl frame. Special attention was paid to tetra-substituted PCB because of their increased presence in the environment and disubstituted PCB being their degradation products. To characterize the model membranes as Langmuir monolayers, we used surface pressure measurements, Brewster angle microscopy and Grazing Incidence X-ray Diffraction. It turned out that among the tetra-substituted PCB the ortho -substituted non-dioxin like compound was much more membrane destructive than the flat dioxin-like congener. On the contrary, among the di-substituted PCB the flat para -substituted 2,2′-dichlorobiphenyl turned out to exhibit high membrane activity. Unlabelled Image • Phospholipid Langmuir monolayers applied as model bacterial membranes. • The ortho -substituted PCB is more membrane destructive than the dioxin-like PCB. • Dichlorosubstituted PCB metabolites are more membrane active than the parent PCB. • Large quantities of flat dioxin-like dichloro-PCB can be incorporated in the membranes. • PCB can be incorporated both to Gram negative and Gram positive bacteria membranes. [ABSTRACT FROM AUTHOR]

Synthetic polymers mimicking antimicrobial peptides have drawn considerable interest as potential therapeutics. N-substituted glycines, or peptoids, are recognized by their in vivo stability and ease of synthesis. Peptoids are thought to act primarily on the negatively charged lipids that are abundant in bacterial cell membranes. A mechanistic understanding of lipid-peptoid interaction at the molecular level will provide insights for rational design and optimization of peptoids. Here, we highlight recent studies that utilize synchrotron liquid surface X-ray scattering to characterize the underlying peptoid interactions with bacterial and eukaryotic membranes. Cellular membranes are highly complex, and difficult to characterize at the molecular level. Model systems including Langmuir monolayers, are used in these studies to reduce system complexity. The general workflow of these systems and the corresponding data analysis techniques are presented alongside recent findings. These studies investigate the role of peptoid physicochemical characteristics on membrane activity. Specifically, the roles of cationic charge, conformational constraint via macrocyclization, and hydrophobicity are shown to correlate their membrane interactions to biological activities in vitro. These structure-activity relationships have led to new insights into the mechanism of action by peptoid antimicrobials, and suggest optimization strategies for future therapeutics based on peptoids. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract The interaction of hydrophobic silver nanoparticles with different phospholipids and stratum corneum mimic (SCM) membranes is studied in Langmuir monolayers. Thus, silver nanoparticles coated with oleic acid (AgNP-OA) were synthesized, characterized and incorporated in Langmuir monolayers of single phospholipids –having different chain length, saturation degree and phase state– or of a SCM mixture. The incorporation of AgNP-OA to the lipid monolayers generated an expansion of the monolayers and a decrease of the surface compressional modulus compared to the pure lipid. X-ray photoelectron spectroscopy (XPS) suggested that the zwitterionic choline-phospholipids can be adsorbed onto the nanoparticles' surface, which is relevant considering that phospholipids are the major constituents of the cell membrane. We also studied the changes in the topography at the mesoscale level using Brewster angle microscopy. We found the most prominent changes in the lipids with liquid-condensed phase, such as SCM, showing segregation of their components. This could have major implications in the barrier function of the membrane, affecting for example the skin permeability towards hydrophobic nanoparticles. Finally, the capability of hydrophobic AgNP-OA for delivering Ag+ ions was studied in aqueous media in the absence and presence of phospholipids. In both conditions, AgNP-OA released Ag+ at reported-bactericidal concentrations, being double in the presence of phospholipids. [ABSTRACT FROM AUTHOR]

The use of cannabis for medicinal/recreational purposes is widespread throughout the world. Smoke inhalation is known to cause airway irritation due to noxious substances (ie, benzene) within the mix. Thus, advanced vaporisation platforms (eg, Davinci IQ) have been developed to circumvent negative health implications. Here, we consider the impact that cannabis smoke and cannabis vapour have on simulated lung surfactant performance within a model pulmonary space (ie, 37°C, elevated humidity and related fluid hydrodynamics). In total, 50 mg of herbal material was ignited or placed within a Davinci IQ vaporiser with subsequent activation. The aliquots were collected and then analysed using gas chromatography‐mass spectroscopy for composition and cannabinoid (eg, Δ9‐tetrahydrocannabinol [Δ9‐THC]) concentration. The average content within cannabis smoke was 2.84% (0.07%, SD) Δ9‐THC, with the same for cannabis vapour being 0.88% (0.14%, SD). Aerosolised samples were transferred to the lung biosimulator. When compared with the pristine Curosurf system, challenge with cannabis smoke and cannabis vapour reduced the surface pressure term by 26% and 7% and increased film compressibility by 60% and 15% at 80% trough area, respectively. The net effect would be enhanced film elasticity and an increased work of breathing, being more pronounced on cannabis smoke inhalation. The trends noted were ascribed to two factors operating synergistically, namely the amount of Δ9‐THC (plus others) within the aerosolised samples and the associated toxicity profile. Further research is required to establish mass‐balance effects (ie, titrated outputs) along with detailed chemical profiling of material generated from the unrelated cannabis activation pathways. [ABSTRACT FROM AUTHOR]

Abstract An approach for forming Langmuir monolayers of proteins is described, with lysozyme serving as an example. The essence of this approach is the deposition of a lysozyme solution containing a precipitant, KCl, onto the water surface in a Langmuir trough. The results of small-angle X-ray scattering indicate that the precipitant in the protein solution causes a significant fraction (>10%) of the protein molecules to assemble into dimers and octamers. Studying the formation of these monolayers by grazing-incidence X-ray standing waves (or X-ray standing waves under total external reflection conditions) showed that the thickness of the resulting protein layer was twice the diameter of an individual lysozyme molecule and matched the diameter of the octamer. Thin layers of precipitant ions (K and Cl) formed directly under the protein monolayer. Our results indicate that adding precipitant to the solution caused the formation of octamers with a retained structure that participated in Langmuir monolayer formation when the solution was applied to the water-subphase surface. Thus, the precipitant ions interacted with the protein monolayer. The proposed approach could facilitate the formation of ordered protein films in hybrid system design and in developing transition methods for nature-like technologies. Highlights • Here, we describe an approach for forming Langmuir monolayers with lysozyme. • A lysozyme–precipitant (KCl) solution was deposited in a Langmuir trough. • SAXS data point to the formation of dimers and octamers upon addition of KCl. • The precipitant ions interact with the protein monolayer. • Our approach may enable ordered protein film formation during hybrid system design. [ABSTRACT FROM AUTHOR]

Abstract Under pathological conditions, cholesterol oxidation products (oxysterols) appear in enhanced concentration in blood and cerebrospinal fluid, which leads to cytotoxic effect, especially in central nervous system. However, the mode of action of oxysterols on the membrane level has not been fully resolved. In this paper we have investigated the interaction between 7α- hydroxycholesterol, 7α-OH (one of the most abundant oxysterol in human body) and two major membrane lipids: sphingomyelin, SM (basic component of lipid rafts and nerve membrane) and 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine, POPC (main phospholipid of mammalian cell membranes). 7α-OH/SM mixtures may mimic pathologically changed lipid raft (ordered phase, L O) while the SM/POPC system can model its surrounding (liquid-disordered phase, L α). For our study, the Langmuir monolayer technique (based on registration of the surface pressure/area, π/A isotherms), complemented with surface visualization technique (Brewster angle microscopy, BAM) and theoretical calculations, have been employed. The observed affinity of 7α-OH to SM, which appears to be stronger than in cholesterol/SM system, indicates that cholesterol might be partially replaced in lipid rafts by its oxidized derivative. Its incorporation significantly increases rigidity of the system in relation to normal (cholesterol-containing) raft, which can disturb its proper functioning. On the other hand, the poor effect of this oxysterol on the raft's environment was observed. Graphical abstract Unlabelled Image Highlights • The influence of 7α-OH on SM and SM/POPC mixture was investigated. • Interactions in SM/7α-OH system are more favorable as compared to SM/Chol. • 7α-OH increases packing density and stability of model lipid raft. • 7α-OH shows little effect on the raft's environment. [ABSTRACT FROM AUTHOR]

Abstract Tissue-nonspecific alkaline phosphatase (TNAP) is a key enzyme in the biomineralization process as it produces phosphate from a number of phospho-substrates stimulating mineralization while it also inactivates inorganic pyrophosphate, a potent mineralization inhibitor. We have previously reported on the reconstitution of TNAP on Langmuir monolayers as well as proteoliposomes. In the present study, thin films composed of dimyristoylphosphatidic acid (DMPA) were deposited on titanium supports by the Langmuir-Blodgett (LB) technique, and we determined preservation of TNAP's phosphohydrolytic activity after incorporation into the LB films. Increased mineralization was observed after exposing the supports containing the DMPA:TNAP LB films to solutions of phospho-substrates, thus evidencing the role of TNAP on the growth of calcium phosphates after immobilization. These coatings deposited on metallic supports can be potentially applied as osteoconductive materials, aiming at the optimization of bone-substitutes integration in vivo. Graphical abstract Image 1 [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Epi -polygodial is isolated and presents Antitrypanosomal activity. • Epi -polygodial is incorporated in biointerface models. • Epi -polygodial changed the thermodynamic and structural properties of DPPE monolayers. • Changes in the monolayers can be associated to the interaction with membranes. Abstract Epi -polygodial, a drimane sesquiterpene was isolated from Drimys brasiliensis (Winteraceae). This compound demonstrated high parasite selectivity towards Trypanosoma cruzi trypomastigotes (IC 50 = 5.01 μM) with a selectivity index higher than 40. These results were correlated with the effects observed when this compound was incorporated in cellular membrane models of protozoans, represented by Langmuir monolayers of dipalmitoylphosphoethanolamine (DPPE). Surface pressure-area isotherms showed that epi -polygodial expands DPPE monolayers at higher areas and condenses them at lower areas, which was attributed to the preferential interaction with the polar heads of the lipid. This mechanism of action could be corroborated with Polarization-Modulation Reflection-Absorption Spectroscopy and Brewster Angle Microscopy. These results pointed to the fact that the interaction of epi -polygodial with DPPE monolayers at the air-water interface affects the physical chemical properties of the mixed film, which may be important to comprehend the interaction of this drug with cellular membranes at the molecular level. [ABSTRACT FROM AUTHOR]

Abstract In this paper, γ-terpineol, a known monoterpene with biological activity, including in lipidic interfaces, was incorporated in Langmuir monolayers of selected phospholipids as a model for cellular membranes. Surface pressure-area isotherms showed that selected amounts of γ-terpineol expand DPPC and DPPE monolayers and decreased the monolayer elasticity, confirming the lipid/compound interaction. Characterization with vibrational spectroscopy and Brewster angle microscopy pointed that γ-terpineol adsorbs on the polar heads of the phospholipids, affecting the gauche conformations of the aliphatic chains, and different patterns were observed for DPPC and DPPE monolayers, indicating a characteristic molecular accommodation of γ-terpineol along the polar head of the phospholipids. Therefore, distinctive interactions with DPPC and DPPE could be observed regarding the incorporation of γ-terpineol with each lipid, leading to particular molecular arrangements at the air-water interface and pointing the modulation of the interaction according to the chemical composition of the monolayer. Graphical abstract Unlabelled Image Highlights • Gamma-terpineol is isolated. • Gamma-terpineol is incorporated in biointerface models. • Gamma-terpineol changed the thermodynamic and structural properties of DPPC and DPPE monolayers. • BAM and PM-IRRAS reveal that the lipid modulate the interaction with gamma-terpineol. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Oxysterols, which are products of cholesterol oxidation, are important biological molecules. For our investigations we have selected two epimers: 7α-hydroxycholesterol (7α-OH) and 7 β-hydroxycholesterol (7β-OH). Both molecules have been found to be capable of stable Langmuir monolayer formation, however, the characteristic of their monolayers were quite different. Contrary to 7β -OH, which isotherm devoid any transition, the π/A dependence for 7α-OH displayed a broad plateau. Temperature strongly affected this plateau transition – the lower the temperature, the higher the surface pressure of the transition. Such an inverse temperature dependence is uncommon for classical film-forming molecules. Film thickness results excluded multilayers as the probable cause for this plateau. Based on theoretical calculations it was possible to infer that the plateau can be attributed to the change of orientation upon film compression, from being anchored mainly with both polar groups in the pre-plateau region to that with one polar group being detached from the water surface in the post-plateau region. Differences in surface behavior of both diastereoisomers have been explained as being due to orientation of OH groups in their molecules; i.e. for 7β-OH both hydroxyl groups (at C3 and C7) are situated on the same side of the rings A and B, while for 7α-OH – on different sides, which induces the lifting off of one OH group from the water surface. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Hydroxymethyl and alkyl groups decrease IC 50 values and increase the selectivity. • Modifications modulate the interaction with the membrane at the air-water interface. • For tumorigenic cells models, the presence of the compounds expanded the monolayers. • For non-tumorigenic cells models, the compounds have condensed the monolayers. Abstract Twenty-one isovanillin derivatives were prepared in order to evaluate their cytotoxic properties against the cancer cell lines B16F10-Nex2, HL-60, MCF-7, A2058 and HeLa. Among them, seven derivatives exhibited cytotoxic activity. We observed that for obtaining smaller IC 50 values and for increasing the index of selectivity, two structural features are very important when compared with isovanillin (1); a hydroxymethyl group at C-1 and the replacement of the hydroxyl group at C-3 by different alkyl groups. As the lipophilicity of the compounds was changed, we decided to investigate the interaction of the cytotoxic isovallinin derivatives on cell membrane models through Langmuir monolayers by employing the lipids DPPC (1,2-diplamitoyl- sn - glycero -3-phosphocoline) and DPPS (1,2-diplamitoyl- sn - glycero -3-phosphoserine). The structural changes on the scaffold of the compounds modulated the interaction with the phospholipids at the air-water interface. These results were very important to understand the biophysical aspects related to the interaction of the cytotoxic compounds with the cancer cell membranes. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Thymol is incorporated in biointerface models. • Thymol changed the thermodynamic and structural properties of DPPS monolayers. • Thymol aggregates DPPS monolayers. • Changes in the monolayers can be associated to the interaction with membranes. Abstract The physical-chemical effects of drugs/lipidic interfaces interactions are still little known, justifying investigations using model systems. Here, we investigated a drug with potential biological activity against microbial and tumorigenic cells, thymol, using phosphatidylserine as cellular membrane models. Surface pressure-area isotherms showed that selected amounts of thymol expand the monolayers and decreased its elasticity. Vibrational spectroscopy and Brewster angle microscopy pointed that thymol adsorbs on the lipid polar heads, affecting the aliphatic chain gauche conformations, causing aggregation at the interface. This indicated distinctive molecular accommodations of thymol along the phospholipidic structures, which is associated to its biological effect in natural membranes. [ABSTRACT FROM AUTHOR]

Local anesthetics (LAs) are known to act on membrane level; however, the molecular mechanism of their activity is still not fully understood. One hypothesis holds that these drugs can incorporate into lipid membrane of nerve cells and in this way change conformation of channel proteins responsible for transport of sodium ions. However, the action of anesthetics is not limited to nerve cells. These drugs also affect other types of cells and organelles, causing severe side effects. In this paper, we applied Langmuir monolayers-as model of cellular membranes-and investigated interactions between selected amide-type local anesthetics (lidocaine prilocaine, mepivacaine and ropivacaine, in the form of hydrochlorides) and lipid components of natural membranes: cholesterol, POPC and cardiolipin (CL) and their mixtures (POPC/cholesterol and POPC/CL/cholesterol), which can serve as simplified models of nerve cell membranes, erythrocytes, and mitochondria. The influence of the drug was monitored by registering the surface pressure (π) as a function of surface area per molecule (A) in a monolayer in the presence of the drug in the subphase. The structure of lipid monolayers on subphases containing and devoid of the studied drugs were visualized with Brewster angle microscopy (BAM). Langmuir monolayer studies complemented with surface visualization technique reveal the expansion and fluidization of lipid monolayers, with the most pronounced effect observed for cardiolipin. In mixed systems, the effect of LAs was found to depend on cholesterol proportion. The observed fluidization of membranes by local anesthetics may negatively affect cells functioning and therefore can explain side effects of these drugs both on the cardiovascular and nervous systems. [ABSTRACT FROM AUTHOR]

The progressive contamination of food products by mycotoxins such as zearalenone (ZEN) has prompted the search for specific substances that can act as protectors against an accumulation of these toxins. This paper discusses the effect of selenium ions and 24-epibrassinolide (EBR) as non-organic and organic compounds that preserve human lymphoblastic cells U-937 under ZEN stressogenic conditions. Based on measurements of cell viability and a DAPI test, concentrations of ZEN at 30 μmol/l, Se at 2.5 μmol/l and EBR at 0.005 μmol/l were selected. The addition of both protectors resulted in an increase in the viability of ZEN-treated cells by about 16%. This effect was connected with a decrease in lipid peroxidation (a decrease in the malonyldialdehyde content) and the generation of reactive oxygen species, which were determined by a cellular ROS/superoxide detection assay and the SOD activity. The Se protection was observed as the blocking of the all excess ROS, while the EBR action was mainly concentrated on something other than the superoxide radical itself. The experiments on the model lipid membranes that mimic the environment of U-937 cells confirmed the affect of ZEN on the structure and physicochemical properties of human membranes. Although the presence of both Se and EBR reduced the effect of ZEN by blocking its interaction with a membrane, the action of Se was more evident. [ABSTRACT FROM AUTHOR]

Abstract The aim of the present work was to contribute for a deeper understanding of the intermolecular interactions present in ionic liquid (IL) tribofilms through the comparative study of the ILs behavior at water and at silica surfaces. Three hydrophobic ILs were investigated at the air/water interface (Langmuir trough) and at the water/silica interface (adsorption, friction and wear). The same experiments were repeated with aqueous solutions of ILs containing the anionic surfactant sodium n -hexadecylsulphate (SHS). The main conclusion was that ILs and IL + SHS solutions able to form Langmuir monolayers are those which adsorb more strongly on the silica surface and which provide better protection to surface wear. Highlights • Ionic liquids (ILs) based on the [P 6, 6, 6, 14 ] cation form Langmuir monolayers. • IL based on the [N 1, 8, 8, 8 ] cation does not form stable monolayers. • Addition of long-chained anionic surfactant (SHS) stabilizes the mixed monolayer. • ILs able to form Langmuir monolayers adsorb more strongly on the silica surface. • ILs able to form Langmuir monolayers reduce silica wear in water lubrication. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Sphingomyelin (SM) structure is a key factor on membrane domain formation. • PM-IRRAS spectra of 16:0 vs 24:1-SM and mixtures with DOPC and Chol were analyzed. • Acyl chains packing and orientation of polar head groups were affected by the unsaturation in 24:1-SM. • 24:1-SM amide groups remained mostly as non-H-bonded when mixed with DOPC and Chol. • These findings may play a key role in cell signaling and binding of biomolecules. Abstract Membrane structure is a key factor for the cell's physiology, pathology, and therapy. Evaluating the importance of lipid species such as N-nervonoyl sphingomyelin (24:1-SM) —able to prevent phase separation— to membrane structuring remains a formidable challenge. This is the first report in which polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) is applied to investigate the lipid-lipid interactions in 16:0 vs 24:1-SM monolayers and their mixtures with 1,2-Dioleoyl-sn-glycero-3-phosphocholine (DOPC) and cholesterol (Chol) (DOPC/SM/Chol 2:1:1). From the results we inferred that the cis double bond (Δ15) in 24:1-SM molecule diminishes intermolecular H-bonding and chain packing density compared to that of 16:0-SM. In ternary mixtures containing 16:0-SM, the relative intensity of the two components of the Amide I band reflected changes in the H-bonding network due to SM-Chol interactions. In contrast, the contribution of the main components of the Amide I band in DOPC/24:1-SM/Chol remained as in 24:1-SM monolayers, with a larger contribution of the non-H-bonded component. The most interesting feature in these ternary films is that the C O stretching mode of DOPC appeared with an intensity similar to that of SM Amide I band in DOPC/16:0-SM/Chol monolayers (a two-phase [ Lo / Le ] system), whereas an extremely low intensity of the C O band was detected in DOPC/24:1-SM/Chol monolayers (single Le phase). This is evidence that the unsaturation in 24:1-SM affected not only the conformational properties of acyl chains but also the orientation of the chemical groups at the air/water interface. The physical properties and overall H-bonding ability conferred by 24:1-SM may have implications in cell signaling and binding of biomolecules. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Efficient uptake of inorganic nanoparticles hinders their application biomedicine. • Fluorinated ligands are a promising strategy for enhancing the cell uptake. • Experimental and computational studies describe the interaction with membrane. • Hydrophobicity provided by the fluorine atoms is key in the uptake. Abstract Fluorescent inorganic quantum dots are highly promising for biomedical applications as sensing and imaging agents. However, the low internalization of the quantum dots, as well as for most of the nanoparticles, by living cells is a critical issue which should be solved for success in translational research. In order to increase the internalization rate of inorganic CdSe/ZnS quantum dots, they were functionalized with a fluorinated organic ligand. The fluorinated quantum dots displayed an enhanced surface activity, leading to a significant cell uptake as demonstrated by in vitro experiments with HeLa cells. We combined the experimental and computational results of Langmuir monolayers of the DPPC phospholipid as a model cell membrane with in vitro experiments for analyzing the mechanism of internalization of the fluorinated CdSe/ZnS quantum dots. Surface pressure-molecular area isotherms suggested that the physical state of the DPPC molecules was greatly affected by the quantum dots. UV–vis reflection spectroscopy and Brewster Angle Microscopy as in situ experimental techniques further confirmed the significant surface concentration of quantum dots. The disruption of the ordering of the DPPC molecules was assessed. Computer simulations offered detailed insights in the interaction between the quantum dots and the phospholipid, pointing to a significant modification of the physical state of the hydrophobic region of the phospholipid molecules. This phenomenon appeared as the most relevant step in the internalization mechanism of the fluorinated quantum dots by cells. Thus, this work sheds light on the role of fluorine on the surface of inorganic nanoparticles for enhancing their cellular uptake. [ABSTRACT FROM AUTHOR]

Abstract Water soluble perfluorinated compounds (PFCs) as perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA) and their shorter chain homologues are persistent organic pollutants widely distributed in the environment. PFCs accumulate in soils and sediments and because of their toxicity endanger the decomposer organisms. PFCs are toxic to a wide spectrum of soil bacteria and their biocide activity was related with their membrane activity; however, the exact mechanism of PFCs – bacterial membrane interactions is unknown. Therefore, to shed light on these questions we applied phospholipid Langmuir monolayers as simplified models of bacterial membranes and studied their interactions with selected environmentally relevant PFCs. The mechanical properties of the monolayers were characterized by surface pressure-mean molecular area isotherms and the analysis of compression modulus. The effects of PFC on the texture of the model membranes were studied with Brewster angle microscopy, whereas their influence on molecular packing in the 2D crystal lattice was searched by the Grazing Incidence X-ray diffraction technique. The effects of PFCs on the phospholipid polar heargroup conformation were studied by PM-IRRAS spectroscopy, whereas the effectivenes of the incorporation of PFCs into the model membrane was monitored in penetration tests. It turned out that the membranes rich in phosphatidylethanolamine typical to Gram negative bacteria are much PFCs susceptible than the cardiolipin rich membranes imitating Gram positive species. Moreover, the studies indicated that the switch from eight‑carbon atom perfluorinated chains to shorter chain homologues is not necessarily environmentally benign as perfluorobutane sulfonate caused also significant structural changes in the model membranes. Graphical abstract Unlabelled Image Highlights • Phospholipid Langmuir monolayers applied as model bacterial membranes. • Perfluorinated chemicals built in easier to zwitterionic phospholipid monolayers. • Short chain perfluorinated compounds are also membrane active. • Cardiolipins are resistant to perfluorinated pollutants. [ABSTRACT FROM AUTHOR]

Abstract The photoisomerization and thermal relaxation processes of three amphiphilic azobenzene derivatives (LCA n) showing liquid-crystalline properties were studied in solutions and in monomolecular films formed using Langmuir and Langmuir-Blodgett techniques. The well-controlled isomeric state of LCA n in chloroform during the UV irradiation allowed to prepare spreading solutions containing trans isomers , cis isomers or their mixture and to investigate molecular organization in the Langmuir films made of them. Surface pressure-mean molecular area isotherms and compression modulus-surface pressure dependences delivered information on a thermodynamic state, phase transitions and intermolecular interaction in the monolayers. LCA n in the trans state create densely-packed films, in which the photoisomerization do not occur due to the lack of free volume for the change of the molecules conformation and their strong tendency for the H-type aggregation. However, the reversible switching of the LCA n conformation during cyclic photoisomerization and thermal relaxation processes was observed in the LB films initially deposited onto quartz substrates in the cis state, where molecules are loosely-packed and exist in the monomeric form. Kinetics and rate constants of the photoisomerization and thermal relaxation were determined based on the recorded absorption spectra in order to obtain information on their efficiency and on the impact of the replacement of the alkyl chain attached in the LCA n para position with the alkyloxy chain. Our research show that LCA n are promising materials for application in optical memories, logic gates and holographic gratings. [ABSTRACT FROM AUTHOR]

Glycosaminoglycans (GAGs) are essential components of the extracellular matrices (ECMs) located on the outer surface of cellular membranes. They belong to the group of polysaccharides involved in diverse biological processes acting on the surface and across natural lipid membranes. Recently, particular attention has been focused on possible role of GAGs in the amyloid deposits. The amyloid formation is related to a disorder in protein folding, causing that soluble-in normal conditions-peptides become deposited extracellularly as insoluble fibrils, impairing tissue structure and its function. One of the hypothesis holds that GAGs may inhibit amyloid formation by interacting with the lipid membrane by blocking the accumulation of protein aggregates on the membrane surface. Although the biophysical properties of GAGs are described rather well, little is known about the nature of association between these polysaccharides and components of natural cell membranes. Therefore, a study of GAGs influence on membrane lipids is of particular importance. The aim of the present work is to get insight into the effect of hydrophilic dextran sulfate (DS)-that can be considered as GAG analogue-on membrane lipids organization. This study was based on examining interactions between DS sodium salt of molecular weight equal to about 40 kDa (DS40), dissolved in water subphase, and a model membrane, mimicked as Langmuir monolayer, formed by representative natural membrane lipids: cholesterol and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) as well as their mixtures. Due to the fact that calcium ions in excess may accumulate in the lipid membrane, attracting high molecular weight molecules to their surface, the influence of calcium ions present in the subphase on the DS40 activity has also been examined. It has been found that negatively charged DS, forming a sublayer underneath the monolayer, barely interacts with membrane lipids; however, in the presence of calcium ions the electrostatic interactions between DS40 and lipid membrane are significantly enhanced, leading to the formation of network-like crystalline structures at the surface of model membrane, which can prevent incorporation and interaction with other extracellular molecules, e.g., proteins. [ABSTRACT FROM AUTHOR]

The results of a study of the photochromic properties of 1´-hexadecyl-3´,3´-dimethyl-6-nitro-1´,3´-dihydrospiro[chromene-2,2´-indole] (SP) are presented. The kinetic characteristics of photophysical processes occurring in acetonitrile solution of SP upon irradiation with UV light and during dark relaxation are determined. It is shown that spiropyran modified at the nitrogen atom by a long-chain hydrocarbon radical exhibits photochromic properties in the dissolved state, with the rate of the direct photocoloration exceeding the rate of dark relaxation by an order of magnitude. Comparative studies of SP photoreaction in dissolved and 2D states are carried out. The obtained results open up broad prospects for application of such photochromes in thin-film devices obtained using the Langmuir monolayer technique. [ABSTRACT FROM AUTHOR]

The efficiency of the Förster resonance energy transfer (FRET) in a monolayer film containing the energy donor and energy acceptor fluorophores is low since the energy transfer process occurs in one plane only. As the number of layers increases to five, the energy transfer efficiency increases due to the interlayer energy transfer occurring in three dimensions. Further increase in the number of layers (up to 10) causes no significant increase in the efficiency since in this case the total film thickness exceeds an optimum value for the FRET process. [ABSTRACT FROM AUTHOR]

Human bestrophin-1 protein (hBest1) is a transmembrane channel associated with the calcium-dependent transport of chloride ions in the retinal pigment epithelium as well as with the transport of glutamate and GABA in nerve cells. Interactions between hBest1, sphingomyelins, phosphatidylcholines and cholesterol are crucial for hBest1 association with cell membrane domains and its biological functions. As cholesterol plays a key role in the formation of lipid rafts, motional ordering of lipids and modeling/remodeling of the lateral membrane structure, we examined the effect of different cholesterol concentrations on the surface tension of hBest1/POPC (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine) and hBest1/SM Langmuir monolayers in the presence/absence of Ca2+ ions using surface pressure measurements and Brewster angle microscopy studies. Here, we report that cholesterol: (1) has negligible condensing effect on pure hBest1 monolayers detected mainly in the presence of Ca2+ ions, and; (2) induces a condensing effect on composite hBest1/POPC and hBest1/SM monolayers. These results offer evidence for the significance of intermolecular protein–lipid interactions for the conformational dynamics of hBest1 and its biological functions as multimeric ion channel.

Experimental surface pressure (π) and electric surface potential (ΔV) isotherms were measured for membrane lipids, including the following phosphatidylcholines (PCs)—1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC); 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC); 1,2-diarachidoyl-sn-glycero-3-phosphocholine (DAPC); and 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC). In addition, other phospholipids, such as phosphatidylethanolamines (represented by 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE)) and sphingolipids (represented by N-(hexadecanoyl)-sphing-4-enine-1-phosphocholine (SM)) were also studied. The experimental apparent dipole moments (μAexp) of the abovementioned lipids were determined using the Helmholtz equation. The particular contributions to the apparent dipole moments of the investigated molecules connected with their polar (μ⊥p) and apolar parts (μ⊥a) were theoretically calculated for geometrically optimized systems. Using a three-layer capacitor model, introducing the group’s apparent dipole moments (calculated herein) and adopting values from other papers to account for the reorientation of water molecules (μ⊥w/εw), as well as the for the local dielectric permittivity in the vicinity of the polar (εp) and apolar (εa) groups, the apparent dipole moments of the investigated molecules were calculated (μAcalc). Since the comparison of the two values (experimental and calculated) resulted in large discrepancies, we developed a new methodology that correlates the results from density functional theory (DFT) molecular modeling with experimentally determined values using multiple linear regression. From the fitted model, the following contributions to the apparent dipole moments were determined: μ⊥w/εw=−1.8±1.4 D; εp=10.2±7.0 and εa=0.95±0.52). Local dielectric permittivity in the vicinity of apolar groups (εa) is much lower compared to that in the vicinity of polar moieties (εp), which is in line with the tendency observed by other authors studying simple molecules with small polar groups. A much higher value for the contributions from the reorientation of water molecules (μ⊥w/εw) has been interpreted as resulting from bulky and strongly hydrated polar groups of phospholipids.

[Display omitted] • Calixarene pyrazoles show low hemolysis, low mutagenicity, and low in vivo toxicity. • NH-pyrazolated phenol ether and calixarenes stereoisomers inhibit M-HeLa cell growth. • Internal pathway of caspase-9 activation in M-HeLa cell lines treated by pyrazoles. • Upregulated DNA damage markers and M-HeLa cell-cycle halt after pyrazole treatment. • Monolayers of calixarene pyrazoles expand at air–water interface in presence of DNA. Tumor selectivity is yet a challenge in chemotherapy-based cancer treatment. A series of calixarenes derivatized at the lower rim with 3-phenyl-1H-pyrazole units with variable upper-rim substituent and conformations of macrocyclic core, alkyl chain length between heterocycle and core, as well as phenolic monomer (5-(4- tert -butylphenyloxy)methoxy-3-phenyl-1H-pyrazole) have been synthesized and characterized in a range of therapeutically relevant cellular models (M-HeLa, MCF7, A-549, PC3, Chang liver, and Wi38) from different target organs/systems. Specific cytotoxicity for M-HeLa cells has been observed in tert -butylcalix[4]arene pyrazoles in 1,3-alternate (compound 7b) and partial cone (compound 7c) conformations with low mutagenicity and haemotoxicity and in vivo toxicity in mice. Compounds 7b,c have induced mitochondrial pathway of apoptosis of M-HeLa cells through caspase-9 activation preceded by the cell cycle arrest at G0/G1 phase. A concomitant overexpression of DNA damage markers in pyrazole-treated M-HeLa cells suggests that calixarene pyrazoles target DNA, which was supported by the presence of interactions between calixarenes and ctDNA at the air–water interface. [ABSTRACT FROM AUTHOR]

The membrane of Gram-negative bacteria (GNB) is especially robust due to the additional, unique, highly asymmetric outer membrane, with lipopolysaccharides (LPSs) as the main component. This LPS layer serves as a protective barrier against antibiotics, host immune responses, and other environmental stresses. However, constructing model membranes containing LPS that capture the structural asymmetry for fundamental studies of the GNB cell wall remains an open challenge. In this context, we discuss how recent physicochemical studies of Langmuir monolayers incorporating LPS help us better understand the elastic properties and structural integrity of model LPS bacterial membranes. The classic Langmuir–Blodgett trough has been used to reveal different lipid phase behaviors of monolayers containing LPS mutants with different molecular architectures to mimic the outer leaflet of the GNB outer membrane, shedding light on the underpinning molecular interactions. Permeation and penetration of antimicrobial peptides are shown to alter the viscoelastic properties of LPS monolayers. The LPS-containing Langmuir monolayer can also be transferred to a substrate as the outer leaflet of an asymmetric solid-supported bilayer, and we will discuss the limitations and potential optimization of this method. Finally, we highlight how different physicochemical methods can corroborate and contribute to unravelling the structural characteristics of model bacterial membranes. [Display omitted] [ABSTRACT FROM AUTHOR]

Curcumin, a plant polyphenol extracted from the Chinese herb turmeric, has gained widespread attention in recent years because of its multifunctional properties as antioxidant, antinflammatory, antimicrobial, and anticancer agent. Effects of the molecule on mitochondrial membranes properties have also been evidenced. In this work, the interaction of curcumin with models of mitochondrial membranes composed of dimyristoylphosphatidylcholine (DMPC) or mixtures of DMPC and 4 mol% tetramyristoylcardiolipin (TMCL) has been investigated by using biophysical techniques. Spectrophotometry and fluorescence allowed to determine the association constant and the binding energy of curcumin with pure DMPC and mixed DMPC/TMCL aqueous bilayers. The molecular organization of pure DMPC and cardiolipin-containing Langmuir monolayers at the air-water interface were investigated and the morphology of the monolayers transferred into mica substrates were characterized through atomic force microscopy (AFM). It is found that curcumin associates at the polar/apolar interface of the lipid bilayers and the binding is favored in the presence of cardiolipin. At 2 mol%, curcumin is well miscible with lipid monolayers, particularly with mixed DMPC/TMCL ones, where compact terraces formation characterized by a reduction of the surface roughness is observed in the AFM topographic images. At 10 mol%, curcumin perturbs the stability of DMPC monolayers and morphologically are evident terraces surrounded by cur aggregates. In the presence of TMCL, very few curcumin aggregates and larger compact terraces are observed. The overall results indicate that cardiolipin augments the incorporation of curcumin in model membranes highlighting the mutual interplay cardiolipin-curcumin in mitochondrial membranes. [Display omitted] • DMPC or DMPC/TMCL bilayers, monolayers and supported films were prepared. • The interaction between lipid assemblies and curcumin was investigated. • Curcumin binding to DMPC bilayers is favored in the presence of cardiolipin. • Cardiolipin augments the miscibility of curcumin with lipid monolayers. • Cardiolipin promotes terraces formation and curcumin insertion in lipid films. [ABSTRACT FROM AUTHOR]