Influence of platelet-activating factor,lyso-platelet-activating factor and edelfosine on Langmuir monolayers imitating plasma membranes of cell lines differing in susceptibility to anti-cancer treatment: the effect of plasmalogen level

Three structurally related but differing in biological activities single-chained ether phospholipids (PAF (platelet-activating factor) and lyso-PAF) and an anti-cancer drug (edelfosine (ED)) were investigated in Langmuir monolayers imitating natural membranes. The aim of the undertaken experiments was to study the influence of these lipids on monolayers mimicking plasma membranes of cell lines differing in susceptibility to the anti-cancer activity of ED, i.e. promyelocytic leukaemia cells (HL-60) and promyeloblastic leukaemia cells (K-562). As these cells differ essentially in the cholesterol/phospholipid ratio and plasmalogen concentration in the membrane, we have carried out systematic investigations in artificial systems of various compositions. The results for model leukaemia cell membrane were compared with data acquired for systems imitating normal leucocytes. Our results show that the level of plasmalogens significantly modulates the influence of the single-chained phospholipids on the investigated systems. The experiments confirmed also that the interactions of ether lipids with a model membrane of HL-60 cells (in biological tests sensitive to ED) have opposite character when compared with K-562, being resistant to ED. Moreover, the values of the parameters characterizing monolayers serving as membrane models (strength of interactions, monolayers fluidity and morphology) proved both sensitivity of these cells to ED and lack of their susceptibility towards PAF. Interestingly, it has been found that lyso-PAF, which is usually described as an inactive precursor of PAF, displays a stronger effect on HL-60 model membranes than ED.     

Comparative study of porphyrin derivatives in monolayers at the air-water interface and in Langmuir-Blodgett films

The orientation and aggregation of various porphyrin derivatives at the air-water interface and in Langmuir-Blodgett films were investigated. Monolayer properties of these molecules, where long alkyl chain(s) were covalently bound through different functionality of varying hydrophilicity were studied by measuring surface pressure area isotherms. Such derivatives, where ether functionality (functionalities) was (were) used for linking long alkyl chain(s), did not form uniform monolayer; instead they were found to form multilayer clusters or aggregates on the water surface. On the other hand, porphyrin derivative functionalized at the four peripheral phenyl rings with eight hexadecyl ether chains formed stable spherical vesicles when deposited on mica. Tetra N-alkyl pyridinium porphyrins with long alkyl chain were found to form various phases on the water surface. Evidence of transition from horizontal orientation to vertical orientation of porphyrin rings of porphyrin molecules having C₁₄ chains was observed. This type of transition was lost with the porphyrin molecule with a relatively smaller chain (C₈).     

Morphology, defect evolutions and nano-mechanical anisotropy of behenic acid monolayer

Langmuir-Blodgett monolayers of behenic acid (BA) were prepared by the vertical deposition method and their morphological evolutions and nano-mechanical anisotropy were studied by atomic force microscopy (AFM) and lateral force microscopy. Results show that there are platforms in the differential surface pressure-area (π-A) isotherm presenting linear relations between the chain tilting angles and surface pressures. The reorganization, appearance and disappearance of defects such as pinholes and holes can strongly affect the profile of π-A isotherm; AFM images reflect evolution rules from pinholes to holes, and from monolayer to bilayers along with compression and relaxation of structures in BA monolayer. Due to higher molecule density and larger real contact area, the tip-monolayer contacts at 15 and 25 mN/m correspond to the Derjaguin-Muller-Toporov (DMT) model showing long-ranged interaction forces. But owing to more easily-deformed conformations, contacts at 5 and 35 mN/m accord with the Johnson-Kendall-Robert and DMT transition cases exhibiting short-ranged interface interactions. A little higher friction is proved in the direction perpendicular to the deposition.     

The effect of neutral helper lipids on the structure of cationic lipid monolayers

Successful drug delivery via lipid-based systems has often been aided by the incorporation of ‘helper lipids’. While these neutral lipids enhance the effectiveness of cationic lipid-based delivery formulations, many questions remain about the nature of their beneficial effects. The structure of monolayers of the cationic lipid dimethyldioctadecylammonium bromide (DODAB) alone, and mixed with a neutral helper lipid, either diolelyphosphatidylethanolamine or cholesterol at a 1 : 1 molar ratio was investigated at the air–water interface using a combination of surface pressure–area isotherms, Brewster angle microscopy (BAM) and specular neutron reflectivity in combination with contrast variation. BAM studies showed that while pure DODAB and DODAB with cholesterol monolayers showed fairly homogeneous surfaces, except in the regions of phase transition, monolayers of DODAB with diolelyphosphatidylethanolamine were, in contrast, inhomogeneous exhibiting irregular bean-shaped domains throughout. Neutron reflectivity data showed that while the thickness of the DODAB monolayer increased from 17 to 24 Å as it was compressed from a surface pressure of 5–40 mN m⁻¹, the thickness of the helper lipid-containing monolayers, over the same range of surface pressures, was relatively invariant at between 25 and 27 Å. In addition, the monolayers containing diolelyphosphatidylethanolamine were found to be more heavily hydrated than the monolayers of cationic lipid, alone or in combination with cholesterol, with hydration levels of 18 molecules of water per molecule of lipid being recorded for the diolelyphosphatidylethanolamine-containing monolayers at a surface pressure of 30 mN m⁻¹ compared with only six and eight molecules of water per molecule of lipid for the pure DODAB monolayer and the cholesterol-containing DODAB monolayer, respectively.     

Stability of dimethyldioctadecylammonium bromide Langmuir-Blodgett films on mica in aqueous salt solutions—implications for surface force measurements

Langmuir-Blodgett (LB) monolayer films of dimethyldioctadecylammonium bromide (DDOA) on muscovite mica have been studied using Wilhelmy plate type wetting measurements, surface force measurements, atomic force microscopy (AFM), and Brewster angle microscopy (BAM) on insoluble monolayers of DDOA before deposition. In particular, the effect of exposure to aqueous KBr salt solutions was investigated. BAM shows a heterogeneous monolayer with small condensed domains of dendritic shape under conditions normally used for deposition. A stick-jump behaviour of the meniscus is seen during deposition, leading to a large-scale heterogeneity measurable in wetting studies. These also show breakdown and hydrophilization of the LB film at the three-phase contact line (meniscus) and when exposed to salt solutions of approximately 10⁻² M concentration. The advancing contact angle against water is approximately 105°. Surface force measurements show long-range attraction in water, but also a surface charge which depends on salt concentration, and breakdown when surfaces are brought into contact in high salt concentrations. AFM images of untreated films show small holes, and breakdown when exposed to salt solution, especially at the three-phase line. The LB film is judged to be less suitable as a model hydrophobic surface owing to its heterogeneity and instability in salt solution.     

Direct imaging by atomic force microscopy of surface-localized self-assembled monolayers on a cuprate superconductor and surface X-ray scattering analysis of analogous monolayers on the surface of water

A self-assembled monolayer of CF₃(CF₂)₃(CH₂)₁₁NH₂ atop the (001) surface of the high-temperature superconductor YBa₂Cu₃O_7-x was imaged by atomic force microscopy (AFM). The AFM images provide direct 2D-structural evidence for the epitaxial 5.5 Å square √2 × √2R45° unit cell previously predicted for alkyl amines by molecular modeling [J.E. Ritchie, C.A. Wells, J.-P. Zhou, J. Zhao, J.T. McDevitt, C.R. Ankrum, L. Jean, D.R. Kanis, J. Am. Chem. Soc. 120 (1998) 2733]. Additionally, the 3D structure of an analogous Langmuir monolayer of CF₃(CF₂)₉(CH₂)₁₁NH₂ on water was studied by grazing-incidence X-ray diffraction and specular X-ray reflectivity. Structural differences and similarities between the water-supported and superconductor-localized monolayers are discussed.     

Reversible collapse of the Langmuir films of a series of triphenylsilyl ether-terminated amphiphiles

The Langmuir films of a series of triphenylsilyl ether (TPSE)-terminated amphiphiles were investigated in order to explore the bulge amphiphile model developed by Haycraft et al. [Thin Solid Films, 515 (2007) 2990]. The TPSE series was examined using surface pressure-surface area isotherms over a range of temperatures (287-298 K) with simultaneous acquisition of Brewster angle microscopy images. The Langmuir films of the TPSE series exhibit the reversible collapse process characteristic of bulge amphiphiles, including an observation consistent with the reversed cybotactic cluster model and increased entropy upon collapse. No solid-like monolayer phases were found over the temperature range studied. The reversed cybotactic clusters displayed for these films show domain growth and coalescence that differ from those observed by Haycraft et al.     

Contributions of chemical and mechanical surface properties and temperature effect on the adhesion at the nanoscale

The atomic force microscope (AFM) is a powerful tool to investigate surface properties of model systems at the nanoscale. However, to get semi-quantitative and reproducible data with the AFM, it is necessary to establish a rigorous experimental procedure. In particular, a systematic calibration procedure of AFM measurements is necessary before producing reliable semi-quantitative data. In this paper, we study the contributions of the chemical and mechanical surface properties or the temperature influence on the adhesion energy at a local scale. To reach this objective, two types of model systems were considered. The first one is composed of rigid substrates (silicon wafers or AFM tips covered with gold) which were chemically modified by molecular self-assembling monolayers to display different surface properties (methyl and hydroxyl functional groups). The second one consists of model polymer networks (cross-linked polydimethylsiloxane) of variable mechanical properties. The comparison of the force curves obtained from the two model systems shows that the viscoelastic contributions dominate for the adhesion with polymer substrates, whereas, chemical contributions dominate for the rigid substrates. The temperature effect on the adhesion energy is also reported. Finally, we propose a relation for the adhesion energy at the nanoscale. This relation relates the energy measured during the separation of the contact to the three parameters: the surface properties of the polymer, the energy dissipated within the contact zone and the temperature.     

The adhesive properties of pyridine-terminated self-assembled monolayers

The atomic force microscopy (AFM) adhesion force behaviour and contact angle titration behaviour of self-assembled monolayers (SAMs) presenting surface pyridine and substituted pyridine moieties has been investigated as a function of pH and electrolyte concentration. The pK_as of the pyridine moieties were modified through the incorporation of fluorine, chlorine and bromine substituents in the pyridyl ring. Contact angle titration and AFM adhesion force measurements were performed using aqueous phosphate buffered saline solutions over the pH range 3-9, and at concentrations of 150 mM and 0.1 mM. AFM adhesion force measurements were performed using a clean Si₃N₄ pyramidal-tipped AFM cantilever.     

The influence of the additives composition and concentration on the properties of SnOx thin films used in photocatalysis

The aim of this study is to investigate the influence of different organic additives on the surface properties of SnO_x thin films used for photocatalytic degradation of methylene blue. The films were obtained by anodic oxidation of tin substrate in electrolyte solutions containing green additives based on hydrophobic and hydrophilic maleic anhydride copolymers. The hydrophobic copolymer leads to the formation of thin films with increased specific area which generates a larger interfacial area between the layers and the dye solution. The consequence is an improvement in the photocatalytic efficiency: up to 16% compared to less than 5% for samples electrodeposited without polymer. The hydrophilic copolymer presence in the electrolyte solution leads to higher grain size and lower surface energy which significantly reduce the photocatalytic properties of the layers. The use of copolymers can be a tool for enhancing the surface roughness and film's wettability and thus the photodegradation efficiency.     

Atomic force microscopy studies of lateral phase separation in mixed monolayers of dipalmitoylphosphatidylcholine and dilauroylphosphatidylcholine

Atomic force microscopy imaging of dipalmitoylphosphatidylcholine (DPPC)/dilauroylphosphatidylcholine (DLPC) monolayers deposited onto alkanethiol modified-gold surfaces by the Langmuir–Schaefer technique was used to investigate domain formation in a binary system where phase separation arises from a difference in the alkyl chain lengths of the lipids. We have established how the condensed domain structure (shape and size) in DPPC/DLPC monolayers depends on the surface pressure and lipid composition. The mixed monolayers exhibit a positive deviation from an ideal mixing behavior at surface pressures of 32 mN/m. Lateral compression to pressures greater than the liquid-expanded-to-liquid-condensed (LE-to-LC) phase transition pressure of the mixed monolayer (8–16 mN/m) induces extensive separation into condensed DPPC-rich domains and a fluid DLPC matrix. The condensed structures observed at a few milliNeutons per meter above the LE-to-LC transition pressure resemble those reported for pure DPPC monolayers in the LE/LC co-existence region. At a bilayer equivalence pressure of 32 mN/m and 20 °C, condensed domains exist between x_DPPC 0.25 and 0.80, analogous to aqueous DPPC/DLPC dispersions. Compression from 32 to 40 mN/m results in either a striking distortion of the DPPC domain shape or a break-up of the microscopic DPPC domains into a network of nanoscopic islands (at higher DPPC mol fractions), possibly reflecting a critical mixing behavior. The results of this study provide a fundamental framework for understanding and controlling the formation of lateral domain structures in mixed phospholipid monolayers.     

官能团对自组装分子膜摩擦特性的影响

在原子力显微镜上,对分子链长相同、官能团不同的两种自组装分子膜的摩擦特性进行了研究,分析了载荷和滑动速度对自组装分子膜摩擦特性的影响.结果表明:自组装分子末端官能团的化学活性越强,形成的自组装分子膜的团簇特征越显著;对于两种短链自组装分子,摩擦力随着载荷的增大而增大,而滑动速度的影响在自组装分子末端官能团化学活性较大时才表现出来.形成结构稳定的自组装分子膜后,摩擦力比成膜初期的自组装分子膜显著降低,具有减摩效应.具有较强化学活性官能团的自组装分子膜,当载荷增加到一定值以后,会失去减摩效应,其化学活性越强,摩擦力越大.     

Langmuir-Blodgett films of C60 and C60O on Silicon: Islands, rings and grains

We show that monolayer-high islands of C₆₀ and C₆₀O can be transferred from Langmuir films on a water or phenol sub-phase to oxide-terminated Si(111) substrates. Faceted islands, in some cases incorporating a foam-like morphology reminscent of that previously observed for Langmuir films at the water-air interface using Brewster angle microscopy, are formed and transferred using small amounts (100-400 μl) of low concentration (of order 10^− 5M) solutions of C₆₀ (or C₆₀O) with low target pressures (~ 10 mN/m). However, worm-like monolayer domains are also observed under identical experimental conditions, indicating the key role that inhomogeneous solvent evaporation plays in the formation of two-dimensional fullerene aggregates on the subphase surface. While Langmuir-Blodgett multilayers of C₆₀ and C₆₀O are both granular, there are significant morphological differences observed between the molecular thin films. In particular, C₆₀O multilayers contain a relatively high density of ring (or “doughnut”) features with diameters in the 100-300 nm range which are not observed for C₆₀. We attribute the origin of these features to dipolar or hydrogen bonding-mediated interactions between the C₆₀O molecules at the water surface.     

Focused ion beam milled pattern structures induced by laser pulse on AgInSbTe phase change films

Uniform and regular pattern structure array were fabricated on carbon (20 nm) /AgInSbTe (200 nm) / glass film by laser direct-writing technology with green and blue laser, respectively. The focused ion beam was used to mill the patterned structures to obtain the morphology inside the structures. The microscopy results indicate that the interior of the structure is hollow and the material is resolidified. Many shrinkage cavities and pores, the main characteristics of rapid solidification, were found inside the structures. The strong convection flow from the center of the molten pool to its periphery was the main cause of microbump formation. Material volume expansion from solid to liquid, and even to gas, also contributed to bump formation.     

Optical properties of an octadecylphosphonic acid self-assembled monolayer on a silicon wafer

We report a study of a full-coverage octadecylphosphonic acid (OPA or ODPA) self-assembled monolayer (SAM) spin-coated on the native oxide layer (SiO₂) of a single crystalline silicon (c-Si) wafer using spectroscopic ellipsometry (SE) and reflectometry (SR). The OPA SAM showed characteristics of being a dielectric film in visible range and becoming absorbing in deep-UV range. By assuming an optical stack model of OPA/SiO₂/c-Si for the OPA monolayer system and adopting the parameterized Tauc-Lorentz dispersion model, we obtained an excellent fit of the model to the SE and SR data, from which dispersion of optical functions as well as thickness of the OPA film were deduced. The OPA film thickness measured by atomic force microscopy (AFM) on partial coverage OPA samples was used as the initial trial film thickness in the fitting processes. The deduced OPA film thickness from SE and SR data fitting was in good agreement with that obtained by AFM.     

Surface characterization of the monolayer and Langmuir–Blodgett films of tetra-tert-butyl-copper phthalocyanine

The relaxation and hysteresis phenomena of the tetra-tert-butyl-copper phthalocyanine (ttb-CuPc) monolayer were investigated. The monolayer was then transferred to a hydrophilic glass surface to prepare one monolayer of Langmuir–Blodgett (LB) films. The uniformity, stability and molecular arrangement of the LB films were studied by measurements of dynamic contact angle (DCA), and were compared with the information obtained by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The results show that the monolayer of ttb-CuPc is generally stable. The limiting area of a molecule is smaller than those reported in the literature, which is attributed to the aggregation of ttb-CuPc molecules into multilayer domains. The advancing and receding contact angles of water on these LB films are much smaller than those on a homogeneous film prepared by vacuum deposition. The wettability analysis on the LB films suggests that ttb-CuPc molecules are not arranged uniformly and continuously, and the LB film of ttb-CuPc contains a high ratio of exposed glass substrate. The surface morphology inspected by TEM and AFM shows the formation of separated domains of ttb-CuPc molecules, which is consistent with the surface condition evaluated from the surface wettability.     

Study on chemical vapor deposited copper films on cyano and carboxylic self-assembled monolayer diffusion barriers

Thin copper films were produced by chemical vapor deposition using the precursor Cu^IIbis-hexafluoroacetylacetonate on the SiO₂/Si substrate modified with cyano and carboxylic self-assembled monolayers (SAMs) as diffusion barriers. The characterizations of the deposited copper films were measured by various thin film analysis techniques, i.e., scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The comparison between copper deposited on SiO₂ and on the SAM-modified SiO₂ substrates indicates that the copper films tend to be deposited onto the SAM-modified substrate, which is further proved by the calculation results of the interaction energies of copper and the SAMs with density functional theory method.     

Langmuir-Blodgett films of palladium(II)-imidazole liquid crystals

The self-assembly of organic-inorganic compounds of palladium(II)-bis(N-long chain substituted imidazole) dichloride complexes has been investigated. The presence of a hydroxyl group at the 2-position of alkyl chain induced liquid crystal properties. Molecular ordering of Pd(II)-imidazole complexes upon mechanical compression at the air/water interface is studied by surface pressure-area (π-A) isotherms and Brewster angle microscope. Incorporation of lateral hydroxyl group in the alkyl chain enhances the stability of the films via intramolecular hydrogen bonding interactions. Langmuir-Blodgett (LB) films formed by these compounds were studied by various techniques to characterize their surface morphology, hydrophilic/hydrophobic property, surface functionalities and interlayer spacings. U-shaped interdigitated assembling, good crystallinity and in-air stability of these LB films were demonstrated.     

Ag and O ion irradiation induced improvement in dielectric properties of the Ba(Co1/3Nb2/3)O3 thin films

We present the preliminary results of temperature and frequency dependent dielectric measurements on Ba(Co_1/3Nb_2/3)O₃ (BCN) thin films. These films were prepared on indium tin oxide (ITO) coated glass substrates by the pulse laser deposition (PLD) technique. It exhibits single-phase hexagonal symmetry. These films were irradiated with Ag¹⁵⁺ (200 MeV) and O⁷⁺ (100 MeV) beams at the fluence 1 × 10¹¹, 1 × 10¹², and 1 × 10¹³ ions/cm². On irradiating these films, its dielectric constant (?′) and dielectric loss (tan δ) parameters improve compared to un-irradiated film. Compared to O⁷⁺ irradiation induced point/cluster defects Ag¹⁵⁺ induced columnar defects are more effective in reducing/pinning trapped charges within grains. The present paper highlights the role of swift heavy ion irradiation in engineering the dielectric properties of conductive samples to enable them to be useful for microwave device applications.     

Nanomechanical properties of polymer thin films measured by force-distance curves

Force-displacement curves have been acquired with a commercial atomic force microscope on thin films of poly(n-butyl methacrylate) on glass substrates. Different film thicknesses, from 10 up to 430 nm, were chosen to examine in detail the so called “mechanical double-layer” topic, i.e., the influence of the substrate on the determination of the mechanical properties of thin films. Taking advantage of the Hertz theory we calculated for all films the contact radius between tip and sample as a function of the applied load. Further Young's modulus of the samples was derived from the experimental data as a function of the applied load and, alternatively, of the deformation. The results of this analysis for 10 different film thicknesses were fitted with several half empirical equations proposed by several researchers. The focus of this work is to evaluate such existing half empirical theories for mechanical double-layers and to show the need for an alternative consistent approach.