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Surface pressure (π)–molecular area (A) isotherms were gathered to characterize the packing of binary mixed Langmuir monolayers of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphoethanolamine (DOPE) and one of two Gemini surfactants (GS), N,N‐bis(dimethyloctadecyl)‐1,7‐nonanediammonium dibromide (18‐7‐18) or 1,9‐bis(octadecyl)‐1,1,9,9‐tetramethyl‐5‐amino‐1,9‐nonanediammonium dibromide (18‐7NH‐18) of varying molar fractions. Information about miscibility behavior was derived from the π–A curves by examining the excess free energy of mixing (ΔGexc) that was calculated through the surface area additivity rule. Surface compressibility modulus (Cs−1) was also used to characterize intermolecular interactions. Mutual interactions between GS and DOPE were analyzed in terms of excess Gibbs energy of mixing and the value of this parameter depended strongly on the composition of the mixed film. GS and DOPE are generally miscible as DOPE reduces intermolecular repulsion between highly charged GS molecules leading to the formation of more densely packed mixed monolayers. However, GS and DOPE are immiscible in equimolar mixtures due to tail group packing mismatch between saturated and unsaturated alkyl chains. The prevalence of attractive synergistic interactions in the monolayers studied differs from a previous finding of antagonistic mixing behavior in GS/DOPE micelles. These results contribute to the understanding of GS‐lipid interactions and packing that are critical to the in vitro and in vivo stability of liposomes composed of these molecules used for non‐viral gene therapy applications. [ABSTRACT FROM AUTHOR]

This study explored the effects of bisphenol A (BPA), a residual contaminant derived from plastic materials, on binary mixtures of the phospholipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and cholesterol (Chol). These mixtures were structured into bilayers, forming giant unilamellar vesicles (GUVs), and monolayers, forming Langmuir films, whose compositions and phases are relevant for mimicking the cell plasma membrane in eukaryotic cells. The composition of the binary mixture of DOPC/Chol 8:2, representing the proportion of the primary lipid groups found in cells, was effective in inducing inward buddings when exposed to BPA, in addition to the multiple shape transformations observed for DOPC vesicles. In monolayers, BPA induced the π–A isotherm expansion of DOPC, Chol, and the binary mixtures, also mainly in the DOPC/Chol 8:2 monolayers. Consistently, polarization-modulated infrared reflection absorption spectroscopy measurements revealed more pronounced interactions between BPA and the DOPC headgroup (hydrogen bonding from the hydrogen of the BPA phenol group and the nitrogen from the DOPC choline group, preferentially) in the DOPC/Chol 8:2 monolayer compared to that in individual DOPC monolayer. The presence of Chol appears to make the DOPC headgroups more accessible for interaction, even in bilayers. These results emphasize the substantial impact of BPA on the DOPC/Chol binary mixture, highlighting its critical role in predicting the potential damage to human cell membranes. [ABSTRACT FROM AUTHOR]

This study explores how the unsaturation patterns of three acetogenins from Porcelia macrocarpa (2S,3R,4R)-3-hydroxy-4-methyl-2-(eicos-11′-yn-19′-enyl)-butanolide (1), (2S,3R,4R)-3-hydroxy-4-methyl-2-(eicos-11′-ynyl)-butanolide (2), and (2S,3R,4R)-3-hydroxy-4-methyl-2-eicosyl-butanolide (3)—affect their interactions with lipid interfaces, using Langmuir monolayers of dipalmitoyl-phosphoethanolamine (DPPE) as a model for protozoal membranes. The hypothesis posits that unsaturated acetogenins (1 and 2) will exhibit distinct behaviors compared to the saturated acetogenin (3) due to structural differences. Experiments incorporated each acetogenin into DPPE monolayers, employing techniques like tensiometry, dilatational rheology, infrared spectroscopy, and Brewster angle microscopy (BAM) to assess interactions and changes in film properties. Results showed that unsaturated acetogenin 1, active against Leishmania infantum and Trypanosoma cruzi, destabilized the film and induced rapid molecular reorganization, while acetogenin 2, inactive against these parasites, uniquely increased the viscous contribution to viscoelasticity. Saturated acetogenin 3 did not integrate into the film. All acetogenins enhanced fluidity, reducing elasticity and viscosity, with BAM revealing phase separation only in acetogenin 2. Infrared spectroscopy underscored the impact of drug-lipid interactions, leading to the conclusion that unsaturated acetogenins 1 and 2 have a more significant influence on thermodynamic and structural properties than acetogenin 3, offering insights into their potential therapeutic mechanisms.

Phospholipids are the most important structural elements of the bacterial cell wall, participate in the adaptation of microorganisms to the environment and can act as biomarkers for environmental changes and one of the components of environmental monitoring. Native phospholipids are used to form models of cell membranes, the biophysical properties of which can be studied by the Langmuir-Blodgett method. The aim of this work was to isolate and characterize the phospholipids of the cell membranes of the bacteria Staphylococcus aureus and Bacillus cereus and the formation of Langmuir monolayers based on them. The composition and ratio of fatty acids were determined by gas-liquid chromatography of fatty acid methyl esters. Fatty acids, found in the extract of the bacteria S. aureus 209-P and B. cereus 8035, are: hexadecanoic, trans-9-octadecenoic, octadecanoic, tetradecanoic, 13-methyltetradecanoic, 14-methylpentadecanoic, 15-methylhexadecanoic, cis-9-octadecanoic. To form a monolayer, a working solution of native phospholipids in chloroform with a concentration of C = 10-3 М was used. The monolayer formed when a 50 μl solution of a phospholipid mixture is applied to the surface has a more perfect structure, which is manifested in the constancy of its mechanical properties. The analysis of the obtained data has not yet revealed a clear dependence of the monolayer parameters on temperature. The changes in the compression modulus and compressibility were very minor. With an increase in the salt concentration, both an increase and a decrease in the compression modulus, and, consequently, the rigidity of the monolayer, is observed.

Poly(butyl cyanoacrylate) (PBCA) nanoparticles have numerous applications, including drug and gene delivery, molecular imaging, and cancer therapy. To uncover the molecular mechanisms underlying their interactions with cell membranes, we utilized a Langmuir monolayer as a model membrane system. This approach enabled us to investigate the processes of penetration and reorganization of PBCA nanoparticles when deposited in a phospholipid monolayer subphase. Atomic force microscopy (AFM) was employed to visualize Langmuir–Blodgett (LB) films of these nanoparticles. Additionally, we examined the state of a monolayer of Pluronic F68, a stabilizer of PBCA nanoparticles in suspension, by measuring the changes in relative surface area and surface potential over time in the barostatic regime following PBCA suspension spreading. Based on these findings, we propose a molecular mechanism for nanoparticle reorganization at the air–water interface.

LL-37 is the only member of the cathelicidin-type host defense peptide family in humans. It exhibits broad-spectrum bactericidal activity, which represents a distinctive advantage for future therapeutic targets. The presence of choline in the growth medium for bacteria changes the composition and physicochemical properties of their membranes, which affects LL-37's activity as an antimicrobial agent. In this study, the effect of the LL-37 peptide on the phospholipid monolayers at the liquid–air interface imitating the membranes of Legionella gormanii bacteria was determined. The Langmuir monolayer technique was employed to prepare model membranes composed of individual classes of phospholipids—phosphatidylcholine (PC), phosphatidylethanolamine (PE), phosphatidylglycerol (PG), cardiolipin (CL)—isolated from L. gormanii bacteria supplemented or non-supplemented with exogenous choline. Compression isotherms were obtained for the monolayers with or without the addition of the peptide to the subphase. Then, penetration tests were carried out for the phospholipid monolayers compressed to a surface pressure of 30 mN/m, followed by the insertion of the peptide into the subphase. Changes in the mean molecular area were observed over time. Our findings demonstrate the diversified effect of LL-37 on the phospholipid monolayers, depending on the bacteria growth conditions. The substantial changes in membrane properties due to its interactions with LL-37 enable us to propose a feasible mechanism of peptide action at a molecular level. This can be associated with the stable incorporation of the peptide inside the monolayer or with the disruption of the membrane leading to the removal (desorption) of molecules into the subphase. Understanding the role of antimicrobial peptides is crucial for the design and development of new strategies and routes for combating resistance to conventional antibiotics. [ABSTRACT FROM AUTHOR]

Influences of subphase pH and temperature on the interfacial aggregation behavior of two double hydrophilic hyperbranched copolymers of poly[oligo(ethylene glycol) methacrylate‐co‐(2‐diisopropylamino)ethyl methacrylate] (P(OEGMA‐co‐DIPAEMA)) at the air/water interface are studied by the Langmuir film balance technique. Morphologies of their Langmuir–Blodgett (LB) films are characterized by atomic force microscopy (AFM). At the interface, P(OEGMA‐co‐DIPAEMA) copolymers tend to form a dense network structure of circular micelles composed of branching agent‐connected carbon backbone cores and mixed shells of OEGMA and DIPAEMA segments (pendant groups). This network structure containing many honeycomb‐like holes with diameters of 6–8 nm is identified for the first time and clearly observed in the enlarged AFM images of their LB films. Under acidic conditions, surface pressure versus molecular area isotherms of the two copolymers in the low‐pressure region show larger mean molecular area than those under neutral and alkaline conditions due to the lack of impediment from DIPAEMA segments. Upon further compression, each isotherm exhibits a wide pseudo‐plateau, which corresponds to OEGMA segments being pressed into the subphase. Furthermore, the isotherms under neutral and alkaline conditions exhibit the lower critical solution temperature behavior of OEGMA segments, and the critical temperature is lower when the hyperbranched copolymer contains higher OEGMA content. [ABSTRACT FROM AUTHOR]

The results of a study of the physicochemical and photomechanical properties of mixed Langmuir monolayers based on palmitoyloleoylphosphatidylcholine (POPC), dipalmitoylphosphatidylcholine (DPPC) and amphiphillic spirocompounds are presented. For the first time mixed monolayers based on POPC, DPPC, spiropyran 1',3'-dihydro-1'-hexadecyl-3'3'-dimethyl-6-nitrospiro[2H-benzopyran-2,2'-(2H)indole] and spironaphtoxazine 3,3-dimethyl-1-hexadecyl-1,3-dihydrospiro[indoline-2,3'-naphtho[2,1-b][1,4]oxazine]-9'-ol were formed in various combinations and ratios, and their comparative study was carried out. It has been established that binary mixture of phospholipids and spirocompounds form stable monolayers in which phase transitions can be controlled by UV-light. It has been shown that irradiation of monomolecular phosphatidylcholine films containing small amounts of photosensitive compounds (up to 10% by weight) makes it possible to turn them into a liquid-condensed state at pressures above 10 mN/m. The results obtained open broad prospects for using photochromic spirocompounds to control the permeability of biological membranes using light stimuli. [ABSTRACT FROM AUTHOR]

The antimicrobial and antibiofilm properties of arginine-based surfactants have been evaluated. These two biological properties depend on both the alkyl chain length and the spacer chain nature. These gemini surfactants exhibit good activity against a wide range of bacteria, including some problematic resistant microorganisms such us methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa. Moreover, surfactants with a C10 alkyl chain and C3 spacer inhibit the (MRSA) and Pseudomonas aeruginosa biofilm formation at concentrations as low as 8 µg/mL and are able to eradicate established biofilms of these two bacteria at 32 µg/mL. The inhibitory activities of the surfactants over key enzymes enrolled in the skin repairing processes (collagenase, elastase and hyaluronidase) were evaluated. They exhibited moderate anti-collagenase activity while the activity of hyaluronidase was boosted by the presence of these surfactants. These biological properties render these gemini arginine-based surfactants as perfect promising candidates for pharmaceutical and biological properties. [ABSTRACT FROM AUTHOR]

Among biodegradable polymers, polylactides (PLAs) have attracted considerable interest because the monomer can be produced from renewable resources. Since their initial degradability strongly affects commercial application fields, it is necessary to manage the degradation properties of PLAs to make them more commercially attractive. To control their degradability, poly(lactide-co-glycolide) (PLGA) copolymers of glycolide and isomer lactides (LAs) were synthesized, and their enzymatic and alkaline degradation rates of PLGA monolayers as functions of glycolide acid (GA) composition were systematically investigated by the Langmuir technique. The results showed that the alkaline and enzymatic degradations of PLGA monolayers were faster than those of l-polylactide (l-PLA), even though proteinase K is selectively effective in the l-lactide (l-LA) unit. Alkaline hydrolysis was strongly affected by their hydrophilicity, while the surface pressure of monolayers for enzymatic degradations was a major factor. [ABSTRACT FROM AUTHOR]

[Display omitted] • Comparative studies of planar and vesicular structures based on the same materials. • Characteristics of niosomes correlate with excess free energy of mixed monolayers. • Composition of shells determine morphology, polarity and microviscosity of niosomes. • Cholesterol increases the compatibility in monolayers and the stability of niosomes. In recent years, the study of niosomes as nanocarriers alternative to liposomes has received increasing attention. In contrast to well-studied liposome membranes, many aspects of the behavior of analogous niosome bilayers have not been studied. This paper considers one of these aspects related to the communication between the physicochemical properties of planar and vesicular objects. We present the first results of comparative studies of Langmuir monolayers of binary and ternary (with cholesterol) mixtures of non-ionic surfactants based on sorbitan esters and niosomal structures assembled from the same materials. The Thin-Film Hydration (TFH) method in the gentle shaking version was used to produce the particles of large sizes, while small unilamellar high quality vesicles with a unimodal distribution of particles were prepared by TFH using ultrasonic treatment and extrusion. An analysis of the structural organization and phase state of monolayers based on compression isotherms and supplemented by thermodynamic calculations, as well as the results of determining the particle morphology, polarity and microviscosity of niosome shells, made it possible to obtain fundamental data on the intermolecular interactions of the components and their packing in shells and to relate these data to the properties of niosomes. This relationship can be used to optimize the composition of niosome membranes and predict the behavior of these vesicular systems. It was shown that cholesterol excess creates regions of bilayers with increased rigidity (like "lipid rafts"), which hinders the process of folding film fragments into small niosomes. [ABSTRACT FROM AUTHOR]

In this work, a sensitive coating based on Langmuir–Blodgett (LB) films containing monolayers of 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE) with an immobilized glucose oxidase (GOx) enzyme was created. The immobilization of the enzyme in the LB film occurred during the formation of the monolayer. The effect of the immobilization of GOx enzyme molecules on the surface properties of a Langmuir DPPE monolayer was investigated. The sensory properties of the resulting LB DPPE film with an immobilized GOx enzyme in a glucose solution of various concentrations were studied. It has shown that the immobilization of GOx enzyme molecules into the LB DPPE film leads to a rising LB film conductivity with an increasing glucose concentration. Such an effect made it possible to conclude that acoustic methods can be used to determine the concentration of glucose molecules in an aqueous solution. It was found that for an aqueous glucose solution in the concentration range from 0 to 0.8 mg/mL the phase response of the acoustic mode at a frequency of 42.7 MHz has a linear form, and its maximum change is 55°. The maximum change in the insertion loss for this mode was 18 dB for a glucose concentration in the working solution of 0.4 mg/mL. The range of glucose concentrations measured using this method, from 0 to 0.9 mg/mL, corresponds to the corresponding range in the blood. The possibility of changing the conductivity range of a glucose solution depending on the concentration of the GOx enzyme in the LB film will make it possible to develop glucose sensors for higher concentrations. Such technological sensors would be in demand in the food and pharmaceutical industries. The developed technology can become the basis for creating a new generation of acoustoelectronic biosensors in the case of using other enzymatic reactions. [ABSTRACT FROM AUTHOR]

Understanding the mechanical behavior of biological membranes is of paramount importance in cell biophysics and in developing new biomaterials for medicine. In this study, we delve into the mechanical impact of β-escin, commonly referred to as escin, a naturally occurring biosurfactant derived from the seeds of the horse chestnut tree. To examine the modulable interaction between escin and dimyristoylphosphatidylcholine (DMPC), which is an archetypical fluid phospholipid and an essential constituent of the cellular fluid membrane, we have used artificial models based on the liquid crystal structure, such as bilayer vesicles and Langmuir monolayers. We have focused on the energetic and kinetic aspects of escin insertion when transversally adsorbed or longitudinally integrated within these model membranes. By employing surface microscopies of epifluorescence and Brewster angle reflectivity, we have elucidated the structural phase behavior of hybrid escin–phospholipid membranes, which exhibit dual mechanical properties characterized by high rigidity and reduced fluidity. Notably, at low temperatures, we observe a soft, glassy rheological behavior reminiscent of liquid crystalline ordered phases, which turns into a fluid-like viscoelasticity resembling more disordered phases at physiological temperatures. The hybrid membranes behave in one way or another as both are driven by an adsorption potential well imposed by escin cohesivity. These intriguing findings are discussed from a physicochemical perspective, highlighting their potential for future pharmacological designs and biomedical applications that exploit the dual mechanical impact of escin on biological membranes.

[Display omitted] Unravelling the structural diversity of cellular membranes is a paramount challenge in life sciences. In particular, lipid composition affects the membrane collective behaviour, and its interactions with other biological molecules. Here, the relationship between membrane composition and resultant structural features was investigated by surface pressure-area isotherms, Brewster angle microscopy and neutron reflectometry on in vitro membrane models of the mammalian plasma and endoplasmic-reticulum-Golgi intermediate compartment membranes in the form of Langmuir monolayers. Natural extracted yeast lipids were used because, unlike synthetic lipids, the acyl chain saturation pattern of yeast and mammalian lipids are similar. The structure of the model membranes, orthogonal to the plane of the membrane, as well as their lateral packing, were found to depend strongly on their specific composition, with cholesterol having a major influence on the in-plane morphology, yielding a coexistence of liquid-order and liquid-disorder phases. [ABSTRACT FROM AUTHOR]

Oxysterols are interesting molecules due to their dual nature, reflecting beneficial and harmful effects on the body. An issue that still needs to be solved is how slight modification of their structure owing to the location of the additional polar group in the molecules affects their biological activity. With this in mind, we selected three side chain-hydroxylated oxysterols namely: 20(S)-hydroxycholesterol (20(S)-OH), 24(S)-hydroxycholesterol (24(S)-OH), and 27-hydroxycholesterol (27-OH), and examined their behavior in mixtures with the bioactive sphingolipid – sphingomyelin (SM). Our research was based on the Langmuir monolayer technique supplemented with molecular dynamics (MD) and microscopic observation of the films texture (Brewster angle microscopy, BAM, and atomic force microscopy, AFM). Additionally, since 20(S)-hydroxycholesterol has not been studied so far, we thoroughly characterized this oxysterol in one-component monolayers. Our studies showed differences in the interactions of the studied oxysterols and sphingomyelin. Namely, it was found that 20(S)-OH binds to SM, unlike 24(S)-OH and 27-OH, which both weakly interact with SM. This distinct behavior was interpreted within the molecular dynamics as being due to weak intermolecular interactions between 20(S)-OH molecules, which allowed easy incorporation of SM into the 20(S)-OH monolayer. In contrast, the strong oxysterol-oxysterol interactions occurring in monolayers with 24(S)-OH or 27-OH make this process more difficult. This may be important in the process of bone formation/resorption. Other aspects derived from our study are: (i) the tendency of oxysterols to incorporate into lipid rafts (leading to their modification in structure and function), as well as (ii) the formation of multilayer structures, in which oxysterols are arranged in the characteristic forms of "strings of beads", which may facilitate their transport across the membrane. • Position of side chain OH group determines interactions of studied oxysterols with SM. • 20(S)-OH binds SM with strictly defined stoichiometry. • 24(S)-OH and 27-OH interactions with SM are weak and depend slightly on stoichiometry. • In the presence of SM, investigated oxysterols form multilayer structures. • Interactions with SM may contribute to diverse bioactivity of studied oxysterols. [ABSTRACT FROM AUTHOR]

The components of blackcurrant extract are known for their antimicrobial properties and the lipid membrane is the important target in terms of the activity of these compounds. In this work, a commercially available product that is PhytoCide Black Currant Powder (BCE), which can be used as a soothing, conditioning and antimicrobial agent in cosmetics, was investigated. The aim of this study was to explore its effect on skin cells and gain insight into the mechanism of its selectivity. The influence of this formulation on keratinocyte and fibroblast cells in in vitro tests was studied and the effect of BCE on model keratinocyte and fibroblast membranes was investigated. As model systems, the lipid monolayers of different compositions were used. The experiments involved the surface pressure/area measurement, penetration studies and Brewster angle microscopy experiments. The BCE formulation was shown to be non-toxic to the skin cells at the concentrations applied. Model membrane experiments confirmed that BCE components do not incorporate into keratinocyte and fibroblast membranes at membrane-related conditions. However, they alter morphology of the studied systems by acting in the region of polar head. Significant differences were found in the affinity of the BCE formulation for bacteria compared to skin lipids, consistent with the proven antibacterial effect of the preservative while lacking toxicity to skin cells. Thus, the membrane of the cell may be critical to the selectivity of the chemicals being tested. [Display omitted] • Black Currant Fruit Extract (BCE) can be used as a cosmetic preservative. • BCE formulation is non-toxic to the skin cells at the concentrations applied. • The components of BCE do not incorporate into the skin cells model membranes. • BCE formulation has significantly different affinity for bacteria vs skin lipids. • Membrane lipids may be critical to the selectivity of BCE preservative. [ABSTRACT FROM AUTHOR]

The interactions of DNA with lysozyme in the surface layer were studied by performing infrared reflection–absorption spectroscopy (IRRAS), ellipsometry, surface tensiometry, surface dilational rheology, and atomic force microscopy (AFM). A concentrated DNA solution was injected into an aqueous subphase underneath a spread lysozyme layer. While the optical properties of the surface layer changed fast after DNA injection, the dynamic dilational surface elasticity almost did not change, thereby indicating no continuous network formation of DNA/lysozyme complexes, unlike the case of DNA interactions with a monolayer of a cationic synthetic polyelectrolyte. A relatively fast increase in optical signals after a DNA injection under a lysozyme layer indicates that DNA penetration is controlled by diffusion. At low surface pressures, the AFM images show the formation of long strands in the surface layer. Increased surface compression does not lead to the formation of a network of DNA/lysozyme aggregates as in the case of a mixed layer of DNA and synthetic polyelectrolytes, but to the appearance of some folds and ridges in the layer. The formation of more disordered aggregates is presumably a consequence of weaker interactions of lysozyme with duplex DNA and the stabilization, at the same time, of loops of unpaired nucleotides at high local lysozyme concentrations in the surface layer. [ABSTRACT FROM AUTHOR]

Possessing unique physicochemical properties, phthalocyanines are widely used as active components of supramolecular ensembles and nanomaterials. The functional properties of phthalocyanine-based materials are governed by not only the structure of their discotic molecules, but also the character of their intermolecular interactions, which determine both the self-assembly mechanism and the structure of such systems. This review discusses the experimental approaches, which are based on the notions of colloid and coordination chemistry that enable one to control intermolecular interactions in low-dimensional supramolecular ensembles based on phthalocyanines and metallocomplexes thereof. Using double-decker crown-substituted lanthanide phthalocyaninates as an example, it is shown how one- and two-dimensional nanomaterials with different properties can be obtained from the same type of building blocks employing a set of colloid-chemical methods. Such materials are, in particular, capable for controlled absorption of visible light in ultrathin films and can be employed as conducting one-dimensional components of planar elements for organic electronics. [ABSTRACT FROM AUTHOR]

In this review, we present one of the main areas of the work of the Laboratory of Physical Chemistry of Supramolecular Systems, Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, devoted to studying monolayers and ultrathin films on liquid and solid surfaces. Numerous problems are discussed concerning the peculiarities of the supramolecular organization, behavior, and functional potential of these traditional colloidal systems. The article describes diverse examples of systems that form ultrathin organized films at different interfaces and the processes occurring in them, thereby reflecting the contemporary stage of the interconnection of related fields of science (colloid and supramolecular chemistry, nanotechnology, biomimetics, sensorics, etc.). Such a combination makes it possible to develop new intelligent nanostructured devices. Complexation in ultrathin layers of ligands on liquid and solid substrates is considered in connection with the use thereof as sensitive sensory elements in systems with reduced dimensionality. Substantial attention is focused on the aggregation behavior of diverse ligands and topochemical reactions in organized 2D ensembles, development of new methods for preparing two-dimensional organic networks, and creation of highly stable supramolecular devices based thereon. In the light of the features of 2D systems, several types of mechanochemical transformations occurring under the action of two-dimensional compression–expansion are considered: the phenomenon of redox isomerism in monolayers of lanthanide bis-phthalocyaninates, the phenomenon of forced axial coordination in tetrapyrrole complexes of nickel with a change in its spin number, and the phenomenon of the reversible formation of excimers. Especial attention is given to the problems concerning the behavior of organic photochromes at interfaces and the perspectives of developing molecular switches based on photosensitive compounds. [ABSTRACT FROM AUTHOR]

The mitochondrion is an essential organelle enclosed by two membranes whose functionalities depend on their very specific protein and lipid compositions. Proteins from the outer mitochondrial membrane (OMM) are specialized in mitochondrial dynamics and mitophagy, whereas proteins of the inner mitochondrial membrane (IMM) have dedicated functions in cellular respiration and apoptosis. As for lipids, the OMM is enriched in glycerophosphatidyl choline but cardiolipin is exclusively found within the IMM. Though the lipid topology and distribution of the OMM and IMM are known since more than four decades, little is known about the interfacial and dynamic properties of the IMM and OMM lipid extracts. Here we build monolayers, supported bilayers and giant unilamellar vesicles (GUVs) of native OMM and IMM lipids extracts from porcine heart. Additionally, we perform a comparative analysis on the interfacial, phase immiscibility and mechanical properties of both types of extract. Our results show that IMM lipids form more expanded and softer membranes than OMM lipids, allowing a better understanding of the physicochemical and biophysical properties of mitochondrial membranes.

Biodegradable polymers in bio-based and chemically synthesized polymers are good substitutes to reduce non-degradable massive waste plastics. Biodegradable and CO2-redcible polylactides are widely used in commercial fields. The biodegradability is one of the most important factors affecting their wide applications. The objective of this study was to investigate hydrolytic kinetics of enantiomeric polylactide mixture monolayers with different molecular weights using a Langmuir film balance. The π-A and kinetic behaviors of mixture monolayers were compared with each other to determine the stereocomplexation effect between enantiomeric polylactides as a function of molecular weight. [ABSTRACT FROM AUTHOR]

High oil ratio fat emulsion injections are prone to poor emulsification, rapid creaming, and other quality problems; therefore, the selection of emulsifiers with high emulsifying ability is crucial for the production of fat emulsions. The existing methods used to evaluate the emulsifying ability of emulsifier are to evaluate the emulsifying ability from the emulsifier itself. In the study, Langmuir monolayer selected the most miscible phospholipid with oil phase from the alternative three phospholipids by studying the molecular interaction between oil phase and phospholipid at the air/water interface. The miscibility and thermodynamic stability analyses of the different oil phase/phospholipid mixed monolayers were performed, and the data from Δ A exc and Δ G ex concluded that all three oil phases had the strongest molecular interaction with E80 and the best miscibility. The emulsions were then prepared and analyzed by the results of particle size, ζ-potential, and stability of the emulsions, where the surface free energy in the stability test echoed the results reflected by the Δ G ex values in the thermodynamic stability test. These results indicate that Langmuir monolayers can be used to study the interaction between oil phase and emulsifier, thus providing new ideas for evaluating the emulsifying ability of phospholipids. [ABSTRACT FROM AUTHOR]

The Fe(III) complexes of branched asymmetric dendrimers were obtained by a one-step reaction as the second-generation architectures. Mesomorphic behavior was found for complexes with PF6− and BF4− counter-ions. To obtain knowledge about the existence of HS and LS fractions of iron(III) ion and their evolution with temperature, EPR methods were used. It was demonstrated that compounds contain one low-spin (LS, S = 1/2) and two HS-spin (HS, S = 5/2) of Fe(III) centers and are packed into two magnetic sub-lattices. A floating layers of Fe(III) complexes and Langmuir–Blodgett films on their base were formed and investigated in the presence of a magnetic field. [ABSTRACT FROM AUTHOR]

The application of surface rheology and Brewster angle microscopy on mixed monolayers of DPPC and polymeric nanoparticles (cationic and anionic) showed that the sign of the particle charge affects the dynamic properties of the monolayers less than the nanoparticles' ability to aggregate. Under almost physiological conditions, the effect of nanoparticles on the elasticity of DPPC monolayer is insignificant. However, the particles prevent the surface tension from decreasing to extremely low values. This effect could affect the functionality of pulmonary surfactants. [ABSTRACT FROM AUTHOR]

The study aimed to synthesize and characterize the magnetic drug carrier modified with terbium (III) ions. The addition of terbium extends the possibilities of their applications for targeted anticancer radiotherapy as well as for imaging techniques using radioisotopes emitting β+, β−, α, and γ radiation. The synthesis of iron oxide nanoparticles stabilized with citrates using the co-precipitation method (IONP @ CA) was carried out during the experimental work. The obtained nanoparticles were used to synthesize a conjugate containing terbium ions and guanosine-5′-monophosphate as an analog of drugs from the thiopurine group. Conjugates and their components were characterized using Transmission Electron Microscopy, infrared spectroscopy, X-ray microanalysis, spectrofluorimetry, and thermogravimetric analysis. The hybrid was also investigated with Langmuir layers to check the interaction with analogs of biological membranes. [ABSTRACT FROM AUTHOR]

[Display omitted] Lung surfactant protects lung tissue and reduces the surface tension in the alveoli during respiration. Particulate matter with an aerodynamic diameter of less than 2.5 μm (PM 2.5), which invades primely through inhalation, can deposit on and interact with the surfactant layer, leading to changes in the biophysical and morphological properties of the lung surfactant. Langmuir monolayers of 1,2-dipalmitoyl- sn - glycero -3-phosphatidylcholine (DPPC) and clinical surfactant Calsurf were investigated with a PM 2.5 model injected into the water subphase, which were characterized by surface pressure-area isotherms, Brewster angle microscopy, atomic force microscopy, fluorescent microscopy, and x-ray photoelectron spectroscopy. The binding between DPPC/Calsurf and PM 2.5 was studied using isothermal titration calorimetry. PM 2.5 induced the expansion of the monolayers at low surface pressure (п) and film condensation at high п. Aggregation of PM 2.5 mainly occurred at the interface of liquid expanded/liquid condensed (LE/LC) phases. PM 2.5 led to slimmer and ramified LC domains on DPPC and the reduction of nano-sized condensed domains on Calsurf. Both DPPC and Calsurf showed fast binding with PM 2.5 through complex binding modes attributed to the heterogeneity and amphiphilic property of PM 2.5. This study improves the fundamental understanding of PM 2.5 -lung surfactant interaction and shows useful implications of the toxicity of PM 2.5 through respiration process. [ABSTRACT FROM AUTHOR]

The results of a systematic study on the adsorption of polylysine molecules of different lengths on the surface of a 1,2-dimyristoyl-sn-glycero-3-phospho-L-serine (DMPS) monolayer in the liquid (LE) and condensed (LC) states are presented. A compressibility diagram and the Volta potential were recorded with the Langmuir monolayer technique and further analyzed with the empirical approach. The structure of the monolayer films with adsorbed polypeptides was studied with synchrotron X-ray reflectometry. Two- and three-layer slab models describe the reflectivity data fairly well and reveal both the significant structural changes and the dehydration of the polar groups induced by all polylysines used at the maximal coverage of the monolayer interface in both the LE and LC states. On the one hand, in the LE phase of the monolayer (area per molecule A ≅ 70 Ǻ2), the integrated electron density of the lipid headgroup region is approximately half the density contained in the clean monolayer. This indicates both significant compaction and dehydration in the polar groups of the lipids, caused by the adsorption of polypeptides. On the other hand, in the LC state (A ≅ 40 Ǻ2), the degree of the hydration of the polar region is similar to that for the initial DMPS monolayer. However, both the electron density and the thickness of the head group region differ significantly from the values of these parameters for the clean monolayer in the LC state.

1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1-palmitoyl-2-oleyl-sn-glycerol-3-phosphorcholine (POPC) are important components in pulmonary surfactants (PSs), of which the relative content is related to lung compliance. Herein, the phase behavior and thermodynamic structure of mixed DPPC/POPC monolayers were studied to elucidate the intermolecular interaction between DPPC and POPC molecules. Surface pressure–molecular area isotherms demonstrated that POPC significantly affected the phase behavior of the lipid domain structure as a function of its concentration. The compression modulus of the mixed monolayers reduced with the increase in POPC proportion, which can be attributed to the intermolecular repulsion between DPPC and POPC. Brewster angle microscopy analysis showed that the ordered structure of the monolayers trended toward fluidization in the presence of POPC. Raman spectroscopy results revealed that the change in C–C skeleton stretching vibration was the main cause of the decrease in the monolayer packing density. These findings provide new insights into the role of different phospholipid components in the function of PS film at a molecular level, which can help us to understand the synergy effects of the proportional relationship between DPPC and POPC on the formation and progression of lung disease and provide some references for the synthesis of lung surfactants.

[Display omitted] Ionizable lipids are a class of pharmaceutical excipients with a main application in lipid nanoparticles for nucleic acid delivery. New ionizable lipids are needed to tune characteristics of lipid-based nucleic acid delivery systems, e.g. stability, nucleic acid loading capacity and binding strength, as well as bio-distribution. Herein, we present the synthesis of three novel ionizable lipids as putative excipients for lipid-based nucleic acid delivery systems. Langmuir monolayer experiments with classical surface pressure/area isotherm evaluation were used to understand the self-assembly behavior of the lipids. Additional experiments with surface sensitive techniques, namely grazing incidence x-ray scattering and infrared reflection–absorption spectroscopy (IRRAS), were performed to understand structural characteristics of lipid associates. The latter technique was also used to investigate the nucleic acid binding process between DNA and the ionizable lipids. Finally, first transfection experiments with the novel lipids formulated as cationic liposomes were performed providing first efficacy data. Although the alkyl chain pattern was comparable for all three ionizable lipids, the results demonstrated that with increasing head-group size the DNA binding capacity changed and the alkyl chain fluidity was increased. The lipid with the lowest phase transition temperature and the smallest packing parameter showed the highest DNA transfer efficiency. [ABSTRACT FROM AUTHOR]

The mechanism of chemotherapeutic action of Ru-based drugs involves plasma membrane disruption and valuable insights into this process may be gained using cell membrane models. The interactions of a series of cytotoxic η6- p -cymene ruthenium(II) complexes, [Ru(η6- p -cymene)P(3,5-C(CH 3) 3 -C 6 H 3) 3 Cl 2 ] (1) , [Ru(η6- p -cymene)P(3,5-CH 3 -C 6 H 3) 3 Cl 2 ] (2) , [Ru(η6- p -cymene)P(4-CH 3 O-3,5-CH 3 -C 6 H 2) 3 Cl 2 ] (3) , and [Ru(η6- p -cymene)P(4-CH 3 O-C 6 H 4) 3 Cl 2 ] (4) , were examined using Langmuir monolayers as simplified healthy and cancerous outer leaflet plasma membrane models. The cancerous membrane (CM1 and CM2) models contained either 40 % 1,2- dipalmitoyl- sn -glycero-3-phosphocholine (DPPC) or 1,2-dioleoyl- sn -glycero-3-phosphocholine (DOPC), 30 % cholesterol (Chol), 20 % 1,2-dipalmitoyl- sn -glycero-3-phosphoethanolamine (DPPE), and 10 % 1,2-dipalmitoyl- sn -glycero-3-phospho- l -serine (DPPS). Meanwhile, the healthy membrane (HM1 and HM2) models were composed of 60 % DPPC or DOPC, 30 % Chol and 10 % DPPE. The complexes affected surface pressure isotherms and decreased compressional moduli of cancerous and healthy membrane models, interacting with the monolayers headgroup and tails according to data from polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). However, the effects did not correlate with the toxicity of the complexes to cancerous and healthy cells. Multidimensional projection technique showed that the complex (1) induced significant changes in the CM1 and HM1 monolayers, though it had the lowest cytotoxicity against cancer cells and is not toxic to healthy cells. Moreover, the most toxic complexes (2) and (4) were those that least affected CM2 and HM2 monolayers. The findings here support that the ruthenium complexes interact with lipids and cholesterol in cell membrane models, and their cytotoxic activities involve a multifaceted mode of action beyond membrane disruption. [Display omitted] • Ru complexes interact with both healthy and cancer plasma membrane models. • The cytotoxicity of Ru complexes in unrelated to their effect on membrane models. • Ru complexes either cross or penetrate the cell membrane. • The mechanism of action of Ru complexes goes beyond simple cell membrane disruption. [ABSTRACT FROM AUTHOR]

One of the main known effects of cholesterol is to rigidify the cell membrane throughout the so-called condensing effect. Although many studies have been done in mixtures of cholesterol with different membrane lipids, there are not many studies in a wide concentration range of cholesterol or at physiological conditions. In this work, we studied mixtures of DMPC/Cholesterol monolayers to determine the effect of cholesterol, from very low to physiological concentrations and two pHs. We use a Langmuir balance and Brewster angle microscopy to study their thermodynamic behavior at 37.0 ± 0.1°C at the air/solution interface. From the analysis of the (π−A) isotherms, we determined the excess area and the compressibility elastic modulus to determine the monolayers mechanical properties. Surprisingly, we found three main effects of cholesterol: The first one is a fluidization effect of the monolayer at all cholesterol concentrations. The second effect is the so-called condensing effect that appears due to the non-ideality of the mixture. The third effect is a stiffness of the monolayer as the cholesterol concentration increases. These effects are stronger in pure water, pH ≈ 6.6, than on buffer at physiological pH = 7.4. We also found that all mixtures are thermodynamically stable at all concentrations at a surface pressure of 30.1 ± 1.6 and 27.4 ± 3.2 mN/m in pure water and buffer, respectively. Furthermore, we compared this stability with a fatty acid monolayer that shows a much lower surface pressure equilibrium value that DMPC or its mixtures with cholesterol, indicating a possibly reason why double chain lipids are better than single chain lipids to made up the cell membrane.

Dengue virus infection depends on its fusion with the host membrane, where the binding occurs through interaction between proteins on the virus cell surface and specific viral receptors on target membranes. This process is mediated by the fusion peptide located between residues 98 and 112 (DRGWGNGCGLFGKGG) that forms a loop in domain II of dengue E glycoprotein. In this study, we evaluated the role of fusion peptide surrounding regions (88–97 and 113–123) of the Dengue 2 subtype on its interaction with the membrane and fusion activity. These sequences are important to stabilize the fusion peptide loop and increase fusion activity. Three peptides, besides the fusion peptide, were synthesized by SPPS using the Fmoc chemical approach. The first contains the fusion peptide and the C-terminal region of the loop (sequence 98–123); another contains the N-terminal region (88–112) and the larger peptide contains both regions (88–123). The peptides were able to interact with a model membrane. Differences in morphology of the monolayer promoted by the peptides were assessed by Brewster Angle Microscopy (BAM). Our data indicated that the C-terminal region of fusion peptide loop is more efficient in promoting fusion and interacting with the membrane than the N-terminal sequence, which is responsible for the electrostatic initial interaction. We propose a 2-step mechanism for the interaction of the dengue virus fusion peptide with the host membrane, where the N-terminal sequence docks electrostatically on the headgroups and then the C-terminal interacts via hydrophobic forces in the acyl chains. [Display omitted] • 2-step mechanism for dengue virus fusion peptide. • N-terminal region can be related to the initial interaction in the membrane. • C-terminal is important for dengue virus fusion peptide. [ABSTRACT FROM AUTHOR]

Copolyesterurethanes (PDLCLs) based on oligo(ε‐caprolactone) (OCL) and oligo(ω‐pentadecalactone) (OPDL) segments are biodegradable thermoplastic temperature‐memory polymers. The temperature‐memory capability in these polymers with crystallizable control units is implemented by a thermomechanical programming process causing alterations in the crystallite arrangement and chain organization. These morphological changes can potentially affect degradation. Initial observations on the macroscopic level inspire the hypothesis that switching of the controlling units causes an accelerated degradation of the material, resulting in programmable degradation by sequential coupling of functions. Hence, detailed degradation studies on Langmuir films of a PDLCL with 40 wt% OPDL content are carried out under enzymatic catalysis. The temperature‐memory creation procedure is mimicked by compression at different temperatures. The evolution of the chain organization and mechanical properties during the degradation process is investigated by means of polarization‐modulated infrared reflection absorption spectroscopy, interfacial rheology and to some extend by X‐ray reflectivity. The experiments on PDLCL Langmuir films imply that degradability is not enhanced by thermal switching, as the former depends on the temperature during cold programming. Nevertheless, the thin film experiments show that the leaching of OCL segments does not induce further crystallization of the OPDL segments, which is beneficial for a controlled and predictable degradation. [ABSTRACT FROM AUTHOR]

Hypothesis: Amphotericin B (AmB) is a highly effective antimicrobial, with broad antimycotic and antiparasitic effect. However, AmB poor water-solubilisation and aggregation tendency limits its use for topical applications. We studied the capacity of nanostructures formed by alkyl esters of L-ascorbic acid (ASCn) to solubilise AmB and tested the relationship between the prevalence of the monomeric form of AmB and its effectiveness as antimicrobial agent. Experiments: We developed self-assembled nanostructures formed by the commercial compound, palmitoyl ascorbic acid, as well as the shorter chained myristoyl and lauroyl ascorbic acid. AmB loaded ASCn nanostructures were studied by a combination of spectroscopic techniques, together with particle analysis, differential scanning calorimetry, microbiological tests, and Langmuir monolayer visualisation. Findings: We found no direct relation between the antimicrobial capacity and the prevalence of the monomeric form of the drug. However, the later was related to chemical stability and colloidal robustness. Nanostructures formed by ASC16 in its anionic state provide an appropriate environment for AmB in its monomeric form, maintaining its antimicrobial capacity. Langmuir film visualisation supports spectrophotometric evidence, indicating that ASC16 allows the in-plane solubilisation of AmB. Coagels formed by ASC16 appear as promising for carrying AmB for dermal delivery.

The application of surface rheology and Brewster angle microscopy on mixed monolayers of DPPC and polymeric nanoparticles (cationic and anionic) showed that the sign of the particle charge affects the dynamic properties of the monolayers less than the nanoparticles’ ability to aggregate. Under almost physiological conditions, the effect of nanoparticles on the elasticity of DPPC monolayer is insignificant. However, the particles prevent the surface tension from decreasing to extremely low values. This effect could affect the functionality of pulmonary surfactants.

This work examines the specific features of interaction of betulin diphosphate (BDP), exhibiting antitumor and wound-healing properties, with zinc cations during its immobilization on ZnO nanoparticles. The properties of Langmuir and transferred BDP monolayers from an aqueous subphase of zinc sulfate onto the surface of a solid substrate (CaF2, quartz) by the Langmuir—Schaefer method are investigated using IR and UV spectroscopy. It is shown that there is a twofold increase of the molecular area in the immobilized layers, while the compressibility modulus decreases by a factor of 1.5. Zinc oxide nanoparticles with immobilized BDP 10–20 nm in size (surface concentration of BDP is 100 mg g−1) retain the original hexagonal wurtzite structure. The efficiency of betulin diphosphate immobilized on the surface of zinc oxide nanoparticles is demonstrated in in vivo experiments for burn wounds in rats. [ABSTRACT FROM AUTHOR]

β-Amyloid (Aβ) is a 39–43 residue peptide involved in the pathogenesis of Alzheimer's disease. Aβ deposits onto the cells and gives rise to the plaques that are characteristic of the disease. In an effort to understand the molecular mechanism of plaque formation, we have examined the interaction of Aβ42, considered to be the most pathogenic of the peptides, with lipid bilayers consisting of 1-palmitoyl-2-oleoyl phosphatidylcholine (POPC) to which small amounts of GM1 ganglioside (1–5 mol%) were incorporated. POPC bilayers exist in the fluid, or liquid-disordered state at room temperature, mimicking the fluidity of cell membranes. An Aβ42 preparation consisting essentially of peptide monomers was used. A combination of molecular dynamics (MD), isothermal calorimetry and Langmuir balance measurements was applied. Our results show that Aβ binds POPC bilayers, and that binding increases (ΔG of binding decreases) with GM1, but only up to 3 mol% of the ganglioside, larger concentrations appearing to have a lower effect. MD and Langmuir balance measurements concur in showing that the peptide adsorbs onto the bilayer surface, but does not become inserted into it at surface pressures compatible with the cell membrane conditions. Thioflavin T measurements agree with MD in revealing a very low degree of peptide oligomerization/aggregation under our conditions. This is in contrast with previous studies showing peptide aggregation and insertion when interacting with membranes in the liquid-ordered state. The present contribution underlines the importance of bilayer lipid composition and properties for Aβ plaque formation. [ABSTRACT FROM AUTHOR]