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5SO 3 H-8-hydroxyquinoline coordinated to Europium (Eu-5SO 3 -HQ) was incorporated in biomembrane models using Langmuir monolayers. Dipalmitoyl phosphatidylcholine (DPPC) and dipalmitoyl phosphatidylserine (DPPS) were employed, representing mammalian cells and dioctadecyldimethylammonium bromide (DODAB) as a positively charged lipid to study the contrast with negatively charged lipids. Tensiometric, rheological and spectroscopic techniques were employed to characterize Eu-5SO 3 -HQ- lipid monolayer interactions. The complex condenses all the monolayer indicating interactions with the lipids' polar heads, but with distinctive effects on the mechanical and rheological properties. While the complex decreases the compression and elastic moduli of DPPC and DPPS monolayers, it increases for DODAB, also decreasing its lateral viscosity. Infrared spectroscopy shows that the interaction of Eu-5-SO 3 -HQ alters the ordering of the lipids' alkyl chains, impacting the monolayer's molecular packing. These results show that the interaction of Eu-5SO 3 -HQ with lipid monolayers at the air-water is modulated by the composition of the polar head, which can be supportive in the preparation of nanodevices for molecular probing. [Display omitted] • An Eu-hydroxyquinoline was incorporated in Langmuir monolayers. • Surface chemistry characterized molecular interactions. • Interactions with lipid polar heads depend on the charge. [ABSTRACT FROM AUTHOR]

Ceramide-1-phosphate (C1P) plays an important role in several biological processes, being identified as a key regulator of many protein functions. For instance, it acts as a mediator of inflammatory responses. The mediation of the inflammation process happens due to the interaction of C1P with the C2 domain of cPLA2α, an effector protein that needs the presence of submicromolar concentrations of calcium ions. The aim of this study was to determine the phase behaviour and structural properties of C1P in the presence and absence of millimolar quantities of calcium in a well-defined pH environment. For that purpose, we used monomolecular films of C1P at the soft air/liquid interface with calcium ions in the subphase. The pH was varied to change the protonation degree of the C1P head group. We used surface pressure versus molecular area isotherms coupled with other monolayer techniques as Brewster angle microscopy (BAM), infrared reflection–absorption spectroscopy (IRRAS) and grazing incidence X-ray diffraction (GIXD). The isotherms indicate that C1P monolayers are in a condensed state in the presence of calcium ions, regardless of the pH. At higher pH without calcium ions, the monolayer is in a liquid-expanded state due to repulsion between the negatively charged phosphate groups of the C1P molecules. When divalent calcium ions are added, they are able to bridge the highly charged phosphate groups, enhancing the regular arrangement of the head groups. Similar solidification of the monolayer structure can be seen in the presence of a 150 times larger concentration of monovalent sodium ions. Therefore, calcium ions have clearly a strong affinity for the phosphomonoester of C1P.

In order to form a nanostructured metallic layer below a Langmuir monolayer, radiolysis synthesis was carried out in an adapted geometry that we call surface X-ray radiolysis. In this procedure, an X-ray beam produced by a synchrotron beamline intercepts the surface of an aqueous metal-ion solution covered by a Langmuir monolayer at an angle of incidence below the critical angle for total internal reflection. Underneath the organic layer, the X-ray beam induces the radiolytic synthesis of a nanostructured metal–organic layer whose ultrathin thickness is defined by the vertical X-ray penetration depth. We have shown that increasing the X-ray flux on the surface, which considerably enhances the kinetics of the silver layer formation, results in a second growth regime of silver nanocrystals. Here the formation of the oriented thin layer is followed by the appearance of a 3D powder of silver clusters.

The use of reversible addition-fragmentation chain transfer (RAFT)-assisted encapsulating emulsion polymerization (REEP) has been explored to prepare diverse types of colloidal stable core–shell nanostructures. A major field of application of such nanoparticles is in emergent nanomedicines, which require effective biofunctionalization strategies, in which their response to bioanalytes needs to be firstly assessed. Herein, functional core–shell nanostructures were prepared via REEP and click chemistry. Thus, following the REEP strategy, colloidal gold nanoparticles (Au NPs, d = 15 nm) were coated with a poly(ethylene glycol) methyl ether acrylate (PEGA) macroRAFT agent containing an azide (N3) group to afford N3–macroRAFT@Au NPs. Then, chain extension was carried out from the NPs surface via REEP, at 44 °C under monomer-starved conditions, to yield N3–copolymer@Au NPs–core–shell type structures. Biotin was anchored to N3–copolymer@Au NPs via click chemistry using an alkynated biotin to yield biofunctionalized Au nanostructures. The response of the ensuing biotin–copolymer@Au NPs to avidin was followed by visible spectroscopy, and the copolymer–biotin–avidin interaction was further studied using the Langmuir–Blodgett technique. This research demonstrates that REEP is a promising strategy to prepare robust functional core–shell plasmonic nanostructures for bioapplications. Although the presence of azide moieties requires the use of low polymerization temperature, the overall strategy allows the preparation of tailor-made plasmonic nanostructures for applications of biosensors based on responsive polymer shells, such as pH, temperature, and photoluminescence quenching. Moreover, the interaction of biotin with avidin proved to be time dependent.

(1) Background: The study characterized barley mutants with brassinosteroid (BR) biosynthesis and signaling disturbances in terms of the physicochemical/structural properties of membranes to enrich the knowledge about the role of brassinosteroids for lipid metabolism and membrane functioning. (2) Methods: The Langmuir method was used to investigate the properties of the physicochemical membranes. Langmuir monolayers were formed from the lipid fractions isolated from the plants growing at 20 °C and then acclimated at 5 °C or 27 °C. The fatty acid composition of the lipids was estimated using gas chromatography. (3) Results: The BR-biosynthesis and BR-signaling mutants of barley were characterized by a temperature-dependent altered molar percentage of fatty acids (from 14:0 to 20:1) in their galactolipid and phospholipid fractions in comparison to wild-type (WT). For example, the mutants had a lower molar percentage of 18:3 in the phospholipid (PL) fraction. The same regularity was observed at 5 °C. It resulted in altered physicochemical parameters of the membranes (Alim, πcoll, Cs−1). (4) Conclusions: BR may be involved in regulating fatty acid biosynthesis or their transport/incorporation into the cell membranes. Mutants had altered physicochemical parameters of their membranes, compared to the WT, which suggests that BR may have a multidirectional impact on the membrane-dependent physiological processes.

Annexin A6 (AnxA6) is the largest member of the annexin family of proteins present in matrix vesicles (MVs). MVs are a special class of extracellular vesicles that serve as a nucleation site during cartilage, bone, and mantle dentin mineralization. In this study, we assessed the localization of AnxA6 in the MV membrane bilayer using native MVs and MV biomimetics. Biochemical analyses revealed that AnxA6 in MVs can be divided into three distinct groups. The first group corresponds to Ca2+-bound AnxA6 interacting with the inner leaflet of the MV membrane. The second group corresponds to AnxA6 localized on the surface of the outer leaflet. The third group corresponds to AnxA6 inserted in the membrane’s hydrophobic bilayer and co-localized with cholesterol (Chol). Using monolayers and proteoliposomes composed of either dipalmitoylphosphatidylcholine (DPPC) to mimic the outer leaflet of the MV membrane bilayer or a 9:1 DPPC:dipalmitoylphosphatidylserine (DPPS) mixture to mimic the inner leaflet, with and without Ca2+, we confirmed that, in agreement with the biochemical data, AnxA6 interacted differently with the MV membrane. Thermodynamic analyses based on the measurement of surface pressure exclusion (πexc), enthalpy (ΔH), and phase transition cooperativity (Δt1/2) showed that AnxA6 interacted with DPPC and 9:1 DPPC:DPPS systems and that this interaction increased in the presence of Chol. The selective recruitment of AnxA6 by Chol was observed in MVs as probed by the addition of methyl-β-cyclodextrin (MβCD). AnxA6-lipid interaction was also Ca2+-dependent, as evidenced by the increase in πexc in negatively charged 9:1 DPPC:DPPS monolayers and the decrease in ΔH in 9:1 DPPC:DPPS proteoliposomes caused by the addition of AnxA6 in the presence of Ca2+ compared to DPPC zwitterionic bilayers. The interaction of AnxA6 with DPPC and 9:1 DPPC:DPPS systems was distinct even in the absence of Ca2+ as observed by the larger change in Δt1/2 in 9:1 DPPC:DPPS vesicles as compared to DPPC vesicles. Protrusions on the surface of DPPC proteoliposomes observed by atomic force microscopy suggested that oligomeric AnxA6 interacted with the vesicle membrane. Further work is needed to delineate possible functions of AnxA6 at its different localizations and ways of interaction with lipids.

This review discusses recent progress in physicochemical understanding of the action of the saponin β -aescin (also called β -escin), the biologically active component in the seeds of the horse chestnut tree Aesculus hippocastanum. β -Aescin is used in pharmacological and cosmetic applications showing strong surface activity. In this review, we outline the most important findings describing the behavior of β -aescin in solution (e.g., critical micelle concentration ( c m c ) and micelle shape) and special physicochemical properties of adsorbed β -aescin monolayers at the air−water and oil−water interface. Such monolayers were found to posses very special viscoelastic properties. The presentation of the experimental findings is complemented by discussing recent molecular dynamics simulations. These simulations do not only quantify the predominant interactions in adsorbed monolayers but also highlight the different behavior of neutral and ionized β -aescin molecules. The review concludes on the interaction of β -aescin with phospholipid model membranes in the form of bilayers and Langmuir monolayers. The interaction of β -aescin with lipid bilayers was found to strongly depend on its c m c . At concentrations below the c m c , membrane parameters are modified whereas above the c m c , complete solubilization of the bilayers occurs, depending on lipid phase state and concentration. In the presence of gel-phase phospholipids, discoidal bicelles form; these are tunable in size by composition. The phase behavior of β -aescin with lipid membranes can also be modified by addition of other molecules such as cholesterol or drug molecules. The lipid phase state also determines the penetration rate of β -aescin molecules into lipid monolayers. The strongest interaction was always found in the presence of gel-phase phospholipid molecules.

Abstract In this study, the effect of polyols, erythritol, xylitol, mannitol, on a model membrane systems composed of DMPC was investigated using differential scanning calorimetry and Fourier transform infrared spectroscopy. Generally, it is considered that polyols possess strong hydrophilic properties, and either does not interact with the hydrophobic environment at all, or these interactions are very weak. To better understand the mutual interactions between polyols and the lipid system, the Langmuir technique was used to examine the molecular organization of monolayers and to calculate their thickness in the presence of polyols at the subphase. The detailed description of the interactions between polyols and DMPC molecules was complemented by the analysis of the morphology of monolayers with the application of Brewster angle microscopy. From ATR FTIR, the significant spectral shift is observed only for the PO 2 − stretching band, which correlates strongly with the polyol chain-length. The longer the polyol chain, the weaker the observed interactions with lipid molecules. The most important findings, obtained from thickness measurements, reveal that short-chain polyols may prevent the formation of bilayers by the DMPC molecules under high surface pressure. The changes in the organization of DMPC monolayers on the surface, as visualized by Brewster angle microscopy, showed that the domains observed for phospholipid film spread on pure water differ substantially from those containing polyols in the subphase. Graphical abstract Unlabelled Image Highlights • Effect of polyols on the DMPC liposomes and monolayers. • Influence of polyol chain length on the incorporation into lipid membrane. • Polyols stabilize the structure of DMPC monolayer. [ABSTRACT FROM AUTHOR]

Abstract 2-Hydroxyoleic acid (2OHOA, Minerval), a derivative of oleic acid, is the lipid used in Membrane Lipid Therapy. This compound is of confirmed anticancer effect, however its exact mechanism of action has not been fully elucidated. In this work the interactions of 2OHOA with cholesterol, sphingomyelin and phosphatidylcholine in Langmuir films were investigated. Moreover, the influence of this drug on SM/Chol and POPC/Chol films was studied. The collected results evidenced that 2OHOA substantially increases fluidity of lipid monolayers and modifies membrane organization, however, its influence depends on drug concentration and membrane properties. It was found that the condensation of model membrane is a critical factor determining the effect of 2OHOA. Moreover, the drug molecules added into SM/Chol film treated as model raft system drastically decrease molecular packing, weaken the interactions between raft components, destabilize the system and alter its morphology. This allows one to suggest that alterations made directly in membrane and microdomains architecture can be treated as one of the areas of Minerval activity. Graphical abstract Unlabelled Image Highlights • Minerval decreases the condensation, packing density and stability of lipid monolayers. • The shape of Minerval molecule determines its incorporation into model membrane. • Lipid/Minerval interactions become more favorable with increasing monolayer fluidity. • Anticancer activity of Minerval may include its influence on membrane architecture. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • The reaction between 1O 2 and unsaturated groups of DOPC and POPC leads to hydroperoxide formation. • The PM-IRRAS results confirm the migration of hydroperoxides from the hydrophobic core of the membrane toward the water/monolayer interface. • The decrease in membrane thickness inferred from GIXOS measurements is consistent with lipid hydroperoxidation for DOPC and POPC monolayers. Abstract Photodynamic therapy (PDT) efficiency depends on many factors including the incorporation of the photosensitizer (PS) in cell membranes and possible lipid hydroperoxidation. In this study, we show that hydroperoxidation may be photoinduced when eosin Y is incorporated into Langmuir monolayers that serve as cell membrane models. This occurs for Langmuir monolayers of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), which have unsaturation in their hydrophobic chains. In contrast, light irradiation had no effect on monolayers of saturated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). Evidence of hydroperoxidation was obtained from the area increase in eosin-containing DOPC and POPC monolayers upon irradiation, which was accompanied by a decrease in monolayer thickness according to grazing incidence X-ray off-specular scattering (GIXOS) data. Furthermore, the changes in polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) induced by irradiation were consistent with hydroperoxide migration toward the lipid hydrophilic heads.. In summary, this combination of experimental methods allowed us to determine the effects of eosin Y interaction with cell membrane models under irradiation, which may be associated with the underlying mechanisms of eosin Y as photosensitizer in PDT. [ABSTRACT FROM AUTHOR]

A novel series of amphiphilic cobalt-cage derivatives (ACCD), bearing a diaza-crown bridge and varying alkyl chains, facilitate ion transport across biomembrane models via self-aggregation. In this study, compression isotherm analyses and atomic force microscopy (AFM) were used to assess the interactions of these amphiphiles with Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC) in order to elucidate electrostatic and steric contributions to ion transport. The stability and compressibility of DPPC monolayers are disrupted by ACCD molecules with short (C 12 ) alkyl chains. These top-heavy amphiphiles (large cone angles) create voids at the interface of the hydrophobic/aqueous layer leading to monolayer expansion and packing efficiency of the aliphatic chains is disrupted. Long-tailed analogues (C 16 , C 18 ) are cohesively integrated into DPPC monolayers due to their smaller cone angles at the interfacial region and increased hydrocarbon compatibility in the hydrophobic region. Thermodynamic data indicate the formation of electrostatic complexes between DPPC and longer-tailed amphiphiles consistent with AFM observations of aggregate structures at the corresponding concentrations. [ABSTRACT FROM AUTHOR]

Cyclosporin A (CsA), a hydrophobic peptide, mainly known for its immunosuppressant properties, has shown a broad range of biological activities, including antimalarial action. Since CsA was found to be active on membrane level, it was subjected for investigations involving membrane models. Our former studies on interactions between CsA and different membrane lipids using Langmuir monolayer technique indicated its affinity for sphingomyelin (SM). Inspired by this finding we have extended our experiments on multicomponent systems and performed systematic investigations of CsA behavior towards artificial membranes containing different mutual proportion of sphingomyelin and cholesterol (Chol). Langmuir monolayer results have been complemented with in-situ films structure visualization applying Brewster angle microscopy (BAM) and, after films transfer onto solid support, atomic force microscopy (AFM). Our results show that cyclosporin A introduced to SM:Chol mixed monolayers distributes differently, depending on SM-to-Chol proportion. In raft-mimicking (2:1) stoichiometry, even distribution of the drug within SM:Chol matrix was observed. However, in SM:Chol model membranes of different proportion (3:1; 1:1; 1:2), containing either the excess of unbound sphingomyelin or cholesterol in addition to model lipid raft domains, introduction of CsA induced a phase separation. [ABSTRACT FROM AUTHOR]

The influence of surface coverage to the structural properties of 4-n-octyl-4´-cyanobiphenyl (8CB) monolayer at the air/water interface was studied by full atomistic molecular dynamics simulations. These properties include density profiles, interface thickness, monolayer width, orientational order parameters, and atom-pair radial distribution functions. The calculated tilt angles of the cyanobiphenyl and alkyl parts are in fairly good agreement with the experiments. The simulation results exhibit the general trends in the previous experimental and simulation data. [ABSTRACT FROM AUTHOR]

Lauryl gallate (LG) is an antioxidant agent. However, it exhibits poor solubility in water. Its interactions with the membrane result in structure evolution thus affecting the membrane functionality. In this paper the Brewster angle microscope coupled with the Langmuir trough was applied to determine the morphology, phase behaviour, thickness and miscibility of ternary Langmuir monolayers with equal mole fractions of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC); 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and an increasing mole fraction of LG. The results were discussed as regards analogous systems where cholesterol (Chol) was the third component. Moreover, the phosphatidylcholine-lauryl gallate (PC-LG) interactions were monitored by the attenuated total reflectance Fourier transform infrared spectroscopy and time-of-flight secondary ion mass spectrometry. Besides lipid composition, the addition of LG was found to be a significant factor to modulate the model membrane properties. The LG molecules adjust themselves to the PC monolayer structure. The hydrophobic fragment is dipped into the membrane interior while the hydroxyl groups of phenolic gallate moiety associate with the polar groups of PC mainly through hydrogen bonding inducing the compacting effect. LG is found to be deeply submerged within DOPC, closer to the double bonds, and its insertion practically does not affect the DPPC/DOPC membrane fluidity. This is crucial for getting more profound insight into the role of LG in stabilizing the non-raft domains, mostly exposed to oxidation in which LG can co-localize and serve its antioxidant function. [ABSTRACT FROM AUTHOR]

Drug delivery to the body via the inhaled route is dependent upon patient status, device use, and respirable formulation characteristics. Further to inhalation, drug‐containing particles interact and dissolve within pulmonary fluid leading to the desired pharmacological response. Pulmonary surfactant stabilises the alveolar air‐liquid interface and permits optimal respiratory mechanics. This material represents the initial contacting surface for all inhaled matter. On dissolution, the fate of a drug substance can include receptor activation, membrane partitioning and cellular penetration. Here, we consider the partitioning behaviour of salbutamol when located in proximity to a simulated pulmonary surfactant monolayer at pH 7. The administration of salbutamol to the underside of the surfactant film resulted in an expanded character for the 2‐dimensional ensemble and a decrease in the compressibility term. The rate of drug partitioning was greater when the monolayer was in the expanded state (ie, inhalation end‐point), which was ascribed to more accessible areas for molecular insertion. Quantum mechanics protocols, executed via Gaussian 09, indicated that constructive interactions between salbutamol and integral components of the model surfactant film took the form of electrostatic and hydrophobic associations. The favourable interactions are thought to promote drug insertion into the monolayer structure leading to the observed expanded character. The data presented herein confirm that drug partitioning into pulmonary surfactant monolayers is a likely prospect further to the inhalation of respirable formulations. As such, this process holds potential to reduce drug‐receptor activation and/or increase the residence time of drug within the pulmonary space. [ABSTRACT FROM AUTHOR]

The principal site for gaseous exchange within the lung is the alveolar space, which is bathed in a lipid‐protein blend called pulmonary surfactant. This material is the initial contacting site for orally inhaled products and environmental toxins. Using the lung biosimulator, this study investigates the influence of cannabis smoke on the activity of the lung surfactant replacement product, Curosurf. Initially, 50‐mg cannabis material was pyrolysed and the smoke collected. Cannabis smoke profiling was conducted via gas chromatography–mass spectroscopy, with a mean concentration of 1% Δ9‐tetrahydrocannabinol determined. The smoke aliquots were transferred to the lung biosimulator and expansion—contraction cycles were then initiated to mimic tidal breathing. Baseline data confirmed that Curosurf works effectively under physiologically relevant conditions. Exposure to cannabis smoke from 2 independent batches reduced the Langmuir maximum surface pressure values by approximately 20% and increased the compressibility term; interbatch variation was detected. Cannabis smoke impaired the ability of Curosurf to lower the surface tension term. This was ascribed to the penetration of the planar, hydrophobic drug into the two‐dimensional film, and destructive interaction with polar functionalities. The net effect would be increased work of breathing for the individual. [ABSTRACT FROM AUTHOR]

The antimicrobial property of silver nanoparticles (AgNPs) is believed to be associated to their interaction with biointerfaces such as microbial cell membranes, encouraging research on the identification of membrane sites capable of AgNPs binding. Although significant progress has been made in that regard, the exact molecular mechanism of action is yet to be fully understood. In this study, AgNPs dispersed in aqueous media and stabilized with polyvinylpyrrolidone were incorporated in Langmuir monolayers of selected lipids that served as cell membrane models. Results from pressure-area isotherms, vibrational spectroscopy and Brewster angle microscopy revealed condensation of glycoside-free lipid monolayers, evidencing that the AgNPs interact mostly with the lipid hydrophilic head groups. In contrast, the monolayers of systems containing glycoside derivatives were found to expand upon AgNPs incorporation, indicating that the glycosidic compounds might facilitate the incorporation of these nanoparticles in cellular membranes. These data can be therefore correlated with the possible toxicity and microbicide effect of AgNPs in lipidic surfaces of mammalian and microbial membranes. [ABSTRACT FROM AUTHOR]

Investigating the mechanism of action of drugs whose pharmaceutical activity is associated with cell membranes is fundamental to comprehending the biochemical and biophysical processes that occur on membrane surfaces. In this work, we investigated the interaction of an ester-type derivative of uridine, 3′,4′,6′-trimyristoyl uridine, with models for cell membranes formed by lipid monolayers at the air-water interface. For that, selected lipids have been chosen in order to mimic tumorigenic and non-tumorigenic cells. For mixed monolayers with 2-dipalmitoyl- sn - glycero -3-phosphocholine (DPPC) or 1,2-dihexadecanoyl- sn - glycero -3-phospho- l -serine (DPPS), the surface pressure–area isotherms exhibited a noticeable shift to lower areas in relation to the areas predicted for ideal mixtures, indicating a condensation of the monolayer structure. Changes in the viscoelastic properties of the interfacial film could be inferred by analyzing the compressibility modulus of the monolayer. Structural and morphological changes were also evidenced by using vibrational spectroscopy and Brewster angle microscopy, respectively, with distinctive effects on DPPC and DPPS. As conclusion we can state that the lipid composition of the monolayer modulates the interaction with this lipophilic drug, which may have important implications in understanding how this drug acts on specific sites of the cellular membrane. [ABSTRACT FROM AUTHOR]

Mixed Langmuir monolayers of 10,12-Pentacosadiynoic acid (DA) monomer and an amphiphilic Hemicyanine dye derivative have been formed at the air/water interface. Two derivatives of docosylpyridinium have been used, with either one included in the monolayer in 1:1 molar ratio. The DA monomers within the mixed monolayers have been polymerized in situ at the air/water interface. The crystalline structure of the monolayer and the kinetics of polymerization have been probed by grazing incidence X-ray diffraction (GIXD). The polymerization of DA proceeds with no phase segregation, exclusively leading to the red polydiacetylene form. The kinetics of polymerization at the air/water interface has been monitored in situ by GIXD. The experimental results have been combined with Molecular Mechanics computer simulations, revealing that DA molecules are sequentially arranged with molecules of Hemicyanine dye in alternating rows. The hydrophobic chains of the dye molecules act as spacers between the DA monomers. Surprisingly, such molecular arrangement does not hinder the in situ photopolymerization of DA. The mechanism of polymerization of DA within the mixed Langmuir monolayers has been convincingly described in molecular detail. This approach for interfacial polymerization of DA holds great potential for optically active devices and nanostructures comprising self-assembled thin films based in polydiacetylene. [ABSTRACT FROM AUTHOR]

High molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) are persistent organic pollutants which due to their limited biodegradability accumulate in soils where their increased presence can lead to the impoverishment of the decomposer organisms. As very hydrophobic PAHs easily penetrate cellular membranes of soil bacteria and can be incorporated therein, changing the membrane fluidity and other functions which in consequence can lead to the death of the organism. The structure and size of PAH molecule can be crucial for its membrane activity; however the correlation between PAH structure and its interaction with phospholipids have not been investigated so far. In our studies we applied phospholipid Langmuir monolayers as model bacterial membranes and investigated how the incorporation of six structurally different PAH molecules change the membrane texture and physical properties. In our studies we registered surface pressure and surface potential isotherms upon the monolayer compression, visualized the monolayer texture with the application of Brewster angle microscopy and searched the ordering of the film-forming molecules with molecular resolution with the application of grazing incidence X-ray diffraction (GIXD) method. It turned out that the phospholipid-PAH interactions are strictly structure dependent. Four and five-ring PAHs of the angular or cluster geometry can be incorporated into the model membranes changing profoundly their textures and fluidity; whereas linear or large cluster PAHs cannot be incorporated and separate from the lipid matrix. The observed phenomena were explained based on structural similarities of the applied PAHs with membrane steroids and hopanoids. [ABSTRACT FROM AUTHOR]

Some biological properties of violacein are believed to be associated with their interactions with lipid surfaces, encouraging research on the identification of membrane sites capable of drug binding. In this study, we investigated the interaction of violacein with cell membrane models represented by Langmuir monolayers of selected lipids: one representing healthy cellular membranes: dipalmitoylphosphatidylcholine, DPPC, and the other one representing tumorigenic cellular membranes, dipalmitoylphosphatidylserine, DPPS. It is shown that even small amounts of the compound affect the surface pressure-area isotherms as well as the surface vibrational spectra of the lipid monolayers, which points to a significant interaction. Such effects depend on the electrical charge of the monolayer-forming molecules, with the drug activity being particularly distinctive for negatively charged lipids in relation to zwitterionic lipids. Morphological analysis also suggests that violacein at the air-water interface is homogenized when incorporated in both lipids. Although the interaction of violacein with the lipids affects viscoelastic and structural properties of the Langmuir monolayer, it is not present permeability through lipid bilayers, as investigated using liposomes. These results therefore may have important implications in understanding how violacein acts on specific sites of the cellular membrane, and evidence the fact that the lipid composition of the monolayer modulates the interaction with the lipophilic drug. [ABSTRACT FROM AUTHOR]

The monolayer of CdSe/CdS/ZnS quantum dots was formed on the water surface at 11, 21, and 31 °C and studied by compression isotherms. Increasing subphase temperature increases the lift-off point of the monolayer and decreases the minimum area which can be reached on compression. Compression changes the monolayer state from LE to LC. The highest compression state can be reached at the lowest subphase temperatures. Increasing water subphase temperature leads to increasing homogeneity of the monolayers. Increasing subphase temperature leads to increasing quiescent layer thickness and diffusion rate. At the high subphase temperature, a duration of collective flowing of desorption processes from water interface to quiescent layer and from quiescent layer to turbulent layer is decreasing that connected with reaching a quiescent layer with which the saturation does not take a place at the achieved diffusion rate. [ABSTRACT FROM AUTHOR]

The outermost layer of skin, the stratum corneum (SC), contains a complex mixture of lipids, which controls the rate of cutaneous water loss (CWL) in reptiles, mammals, and birds. However, the molecular structure of SC lipids and how molecular configurations influence CWL is poorly understood. Here, the organization and structure of SC lipids extracted from birds were investigated by means of Langmuir films. Properties of lipids from the SC of arid and semi-arid adapted larks, known to have a low CWL, were compared with lipids extracted from the SC of mesic lark species with higher CWL to gain insight into how structure impacts CWL. Film properties were probed with surface pressure-area isotherms, Brewster angle microscopy (BAM), and vibrational sum frequency generation (VSFG). Results indicate organization and ordering of SC lipids in the arid-adapted hoopoe lark was vastly different from all other species, forming a miscible, rigid monolayer, whereas monolayers from semi-arid and mesic species were immiscible and disordered. Probing of interfacial water structure reveals that film morphology determines organization of water molecules near the monolayer; monolayers with a porous morphology had an increased population of water molecules that are weakly hydrogen-bonded. In general, CWL appears related to the miscibility and ordering of lipid components within the SC, as well as the ability of these lipids to interact with water molecules. From a broader perspective, CWL in larks appears linked to both the SC lipid composition and the aridity of the species’ environment. [ABSTRACT FROM AUTHOR]

Hexadecylphosphocholine (HePC, miltefosine) is an alkylphospholipid used clinically for the topical treatment of cancer and against leishmaniasis. The mechanism of action of HePC, not yet elucidated, involves its insertion into the plasma membrane, affecting lipid homeostasis. It has also been proposed that HePC directly affects lipid raft stability and function in cell membranes. The present work deals with two main questions in the understanding of the action of HePC: the bases for membrane selectivity and as a membrane perturbator agent. We explored the interaction of HePC with lipid monolayers and bilayer vesicles, combining monolayer penetration experiments, Brewster angle microscopy and differential scanning calorimetry. Several membrane compositions were tested to explore different rheological conditions, phase states and lateral structures. Additionally, the kinetics between the soluble and the membrane form of HePC was explored. Our results showed an increase in elasticity induced by HePC incorporation in all the membranes studied. Differential incorporation was found for membranes in different phase states, supporting a preferential partitioning and a higher dynamic kinetics of HePC incorporation into fluid membranes in comparison with condensed or liquid-ordered ones. This effect resulted in phase equilibrium displacement in phospholipids and membranes containing liquid-ordered domains. The presence of cholesterol or ergosterol induced a fast incorporation and slow desorption of HePC from sterol-containing monolayers, favoring a long residence period within the membrane. This contributes to a better understanding of the HePC regulation of membrane-mediated events and lipid homeostasis. [ABSTRACT FROM AUTHOR]

Oxysterols are products of cholesterol oxidation. They can be formed endogenously (in both enzymatic and non-enzymatic reactions) as well as exogenously (delivered with food). Recent studies clearly demonstrate cytotoxic properties of these compounds, being mainly due to their incorporation into natural lipid bilayers. This process can influence mechanical and physicochemical properties of biomembrane-mainly by modifying the interactions between its components, which may result in the disruption of proper functioning of cell membrane and could lead to its degradation. Therefore, it can be assumed that oxysterols may affect the initiation of neurodegenerative diseases, including Alzheimer's disease. However, the mode of action of these molecules at the molecular level is not fully known. To get a better understanding of the role of oxysterols in neurodegeneration, it is of great importance to examine mutual interactions between oxysterols and neuronal membrane components. One of the most promising techniques that can be used to analyze such interactions is the Langmuir monolayer technique. In this work, we have prepared an artificial neuronal membrane modeled as multicomponent Langmuir monolayer built up with cholesterol, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and sphingomyelin (SM). To examine whether there are any changes in the membrane properties under oxidative stress, in this paper we have investigated the impact of the representative ring-oxidized oxysterol: 7-ketocholesterol (7-KC). Our results show that replacing cholesterol with 7-KC increases the interaction between molecules in the model membrane. [ABSTRACT FROM AUTHOR]

Uropathogenic strains of Escherichia coli produce virulence factors, such as the protein toxin alpha-hemolysin (HlyA), that enable the bacteria to colonize the host and establish an infection. HlyA is synthetized as a protoxin (ProHlyA) that is transformed into the active form in the bacterial cytosol by the covalent linkage of two fatty-acyl moieties to the polypeptide chain before the secretion of HlyA into the extracellular medium. The aim of this work was to investigate the effect of the fatty acylation of HlyA on protein conformation and protein-membrane interactions. Polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) experiments were performed at the air-water interface, and lipid monolayers mimicking the outer leaflet of red-blood-cell membranes were used as model systems for the study of protein-membrane interaction. According to surface-pressure measurements, incorporation of the acylated protein into the lipid films was faster than that of the nonacylated form. PM-IRRAS measurements revealed that the adsorption of the proteins to the lipid monolayers induced disorder in the lipid acyl chains and also changed the elastic properties of the films independently of protein acylation. No significant difference was observed between HlyA and ProHlyA in the interaction with the model lipid monolayers; but when these proteins became adsorbed on a bare air-water interface, they adopted different secondary structures. The assumption of the correct protein conformation at a hydrophobic-hydrophilic interface could constitute a critical condition for biologic activity. [ABSTRACT FROM AUTHOR]

The fluorophilicity of fluorinated rhodamine-based fluorescence dyes (F-rhodamines) functionalized with CH 2 -C 3 F 7 (Rh-CH 2 -C 3 F 7 ) or C 2 H 4 -C 10 F 21 (Rh-C 2 H 4 -C 10 F 21 ) at both amine groups was tested in mixed monolayers of stearic acid (SA) and perfluorostearic acid (FC18) on a Langmuir trough coupled with epifluorescence microscopy. The composition of the Langmuir monolayers was systematically changed from 100% FC18 to 100% SA in order to investigate the fluorophilicity and lipophilicity of the two F-rhodamines by observing their partitioning behavior within the different monolayers. The F-rhodamine bearing the longer perfluoroalkyl group and alkyl spacer (Rh-C 2 H 4 -C 10 F 21 ) showed a substantially higher affinity to the FC18 rich phases in contrast to the F-rhodamine having the shorter perfluoroalkyl chain and alkyl spacer (Rh-CH 2 -C 3 F 7 ) which was excluded from FC18 as well as from SA domains. The FC18, SA, and FC18/SA 50:50 (mol%) monolayers were further investigated by infrared reflection absorption spectroscopy (IRRAS) in order to investigate the phase behavior of FC18 and SA. It was observed that the orientations of FC18 and SA molecules in the pure and mixed monolayers do not change upon compression. Furthermore, a decrease in the order of the FC18 molecules in the mixed monolayer is observed upon the addition of SA. The opposite is not valid in a sense that no loss in order of the SA molecules was observed upon the addition of FC18. This shows that SA partitions more into FC18 phases than FC18 into SA domains. This is due to the weaker van der Waals forces present between the perfluoroalkyl chains in comparison with stronger ones existing between the alkyl chains. [ABSTRACT FROM AUTHOR]

Whereas most of lipids have viscous properties and they do not have significant elastic features, ceramides behave as very rigid solid assemblies, displaying viscoelastic behaviour at physiological temperatures. The present review addresses the surface rheology of lipid binary mixtures made of sphingomyelin and ceramide. However, ceramide is formed by the enzymatic cleavage of sphingomyelin in cell plasma membranes. The consequences of the enzymatically-driven ceramide formation involve mechanical alterations of the embedding membrane. Here, an increase on surface shear viscosity was evidenced upon enzymatic incubation of sphingomyelin monolayers. The overall rheological data are discussed in terms of the current knowledge of the thermotropic behaviour of ceramide-containing model membranes. [ABSTRACT FROM AUTHOR]

Measuring surface (excess) entropies provides a bounty of valuable structural information that is hard to obtain otherwise. In the paper these quantities are defined and procedures of measurements discussed. Mostly they involve measurements at different temperatures. A review is given for interfaces with aqueous solutions in the absence of polymers. This review illustrates how, sometimes unanticipated, pieces of information are obtained, for example with cloud seeding and a possible explanation of the Jones-Ray effect. As a novel extension the procedure is applied to deposited, or Langmuir, monolayers of poly(ethylene oxide)-poly(propylene oxide) block copolymers. It will be shown how the various phase transitions and associated configurations of these polymers can be recognized and monitored. [ABSTRACT FROM AUTHOR]

Pain is a prevalent condition that can have a serious impact upon the socioeconomic function of a population. Numerous methods exist to administer analgesic medication (e.g. aspirin) to the body however inherent drawbacks limit patient acceptability. The inhaled route offers promise to facilitate the administration of medication to the body. Here, we consider the crystallisation behaviour of aspirin, our model therapeutic agent, when in contact with material of relevance to the lung. Thus, our approach aims to better understand the interaction between drug substances and the respiratory tract. Langmuir monolayers composed of a mixed surfactant system were supported on an aqueous subphase containing aspirin (7.5 mg/ml). The surfactant film was compressed to either 5mN/m (i.e. inhalation end point) or 50 mN/m (i.e. exhalation end point), whilst located within a humid environment for 16 h. Standard cooling crystallisation procedures were employed to produce control samples. Antisolvent crystallisation in the presence or absence of lung-specific additives was conducted. All samples were analysed via scanning electron microscopy and X-ray diffraction. Drug-surfactant interactions were confirmed via condensed Langmuir isotherms. Scanning electron microscopy analysis revealed plate-like morphology. The crystallisation route dictated both the crystal habit and particle size distribution. Dominant reflections were the (100) and (200) aspects. The main modes of interaction were hydrogen bonding, hydrophobic associations, and van der Waals forces. Here, we have demonstrated the potential of antisolvent crystallisation with lung-specific additives to achieve control over drug crystal morphology. The approach taken can be applied in respirable formulation engineering. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Pulmonary surfactant is an endogenous material that lines and stabilises the alveolar air-liquid interface. Respiratory mechanics can be compromised by exposure to environmental toxins such as cigarette smoke, which contains nicotine. This study aims to determine the influence of nicotine on the activity of simulated lung surfactant at pH 7 and pH 9. In all cases, the addition of nicotine to the test zone caused deviation in surfactant film performance. Importantly, the maximum surface pressure was reduced for each system. Computational modelling was applied to assess key interactions between each species, with the Gaussian 09 software platform used to calculate electrostatic potential surfaces. Modelling data confirmed either nicotine penetration into the two-dimensional structure or interfacial/electrostatic interactions across the underside. The results obtained from this study suggest that nicotine can impair the ability of pulmonary surfactant to reduce the surface tension term, which can increase the work of breathing. When extrapolated to gross lung function, alveolar collapse and respiratory disease (e.g. chronic airway obstruction) may result. The delivery of nicotine to the (deep) lung can cause a deterioration in lung function and lead to reduced quality of life. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

Deviation in pulmonary surfactant structure-function activity can impair airway patency and lead to respiratory disorders. This novel study aims to evaluate the influence cigarette/e-cigarette vapour has on model surfactant films located within a simulated pulmonary environment using a lung biosimulator. Chromatographic analysis confirmed that nicotine levels were consistent with the sampling regimen employed. On exposure to smoke vapour, Langmuir isotherms exhibited condensed character and a significant reduction in maximum surface pressure was noted in all cases. Langmuir isocycles, reflective of the human breathing cycle, demonstrated condensed character on smoke vapour delivery. A reduction in the maximum surface pressure was clear only in the case of cigarette vapour application. The components of cigarette vapour can cause oxidative damage to pulmonary surfactant and impair recycling. Neutral nicotine molecules can weaken the structure of the monolayer and cause destabilisation. A protective effect was evident in the case of repeated surfactant compression - relaxation cycles (i.e. the ability to reduce the surface tension term was impaired less), demonstrating a likely innate biological defensive mechanism of the lung. E-cigarette vapour appeared to have a reduced impact on surfactant performance, which may hold value in harm reduction over the longer term. Copyright © 2017 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

In this work, silver nanoparticles (AgNPs) dispersed in non-aqueous media and stabilized with polyether block polymers amide (PEBA) were incorporated in Langmuir monolayers of dipalmitoylphosphatidylcholine (DPPC), which served as a cell membrane model. The AgNPs presented surface activity, disturbing the viscoelastic properties of the floating film. They expanded the monolayers decreasing their surface elasticity as observed with surface pressure-area isotherms. Polarization modulation reflection-absorption spectroscopy showed that the permanence of AgNPs at the air-water interface is favored by PEBA, affecting both the hydrophilic and the hydrophobic groups of the phospholipid. Brewster angle microscopy showed that the AgNPs lead to the formation of aggregates at the air-water interface, establishing domains that shear with each other due to the low lateral viscosity of irregular and non-monomolecular domains. These data can be correlated to the possible toxicity and microbicide effect of AgNPs in lipidic surfaces such as in mammalian and microbial membranes. [ABSTRACT FROM AUTHOR]