Arrangement of trace metal contaminations in thin films of liquid crystals studied by X-ray standing wave technique

X-ray standing wave method has been applied to investigate the molecular organization in Langmuir–Blodgett films of liquid-crystalline lanthanide complex deposited on silicon substrates. The X-ray standing waves measurements were carried out at BESSY II on the beamline KMC-2. Energy spectra of characteristic fluorescence emitted from the samples have been recorded at each point in the X-ray reflectivity curve as the incident angle was scanned through the total external reflection region. The integrated intensity under selected peaks was analyzed as a function of the incident angle. Incorporation of metal ions (Fe, Zn, Cu, Ca) to the Langmuir monolayer from the triply distilled water subphase has been established. Owing to the element selectivity of X-ray standing wave technique the arrangement of several types of metal ions inside the Langmuir–Blodgett films was studied individually. The experimental data revealed that the shape of the fluorescence curves for the contamination metal ions is distinctly different indicating considerable differences in the lateral distribution of these ions in the film. These results may be attributed to the phase separation in Langmuir monolayer of liquid-crystalline lanthanide complex due to the incorporation of metal ions from the water subphase.     

Study on the Film Properties and Recognition for Metal Ions of Calix[4]arenes Derivative by Langmuir Monolayer

Calixarene molecules are very powerful ligand for ions and small molecules, and have been studied with several techniques as models for host‐guest systems. In this approach, the formation of Langmuir monolayer properties of three kinds calix[4]arene derivative were characterized and one of them, p‐tert‐butylthiacalix[4]arene (TCA), was chosen as object to study its Langmuir monolayer affected by different subphase conditions. The purpose of this study is to investigate the molecular recognition ability of TCA for metal ions at the water‐air interface. Changing the composition of aqueous subphase (containing various metal ion solutions respectively) produced strong variations on the monolayer parameters, indicating a different selectivity of the TCA ligand for the different metal cations. In particular, high selectivity for transition metal ions was found. Limiting area values are discussed in relation to the orientation of the cone‐shaped molecules at the water‐air interface.     

Study of the aggregation of human insulin Langmuir monolayer

The human insulin (HI) Langmuir monolayer at the air-water interface was systematically investigated in the presence and absence of Zn(II) ions in the subphase. HI samples were dissolved in acidic (pH 2) and basic (pH 9) aqueous solutions and then spread at the air-water interface. Spectroscopic data of aqueous solutions of HI show a difference in HI conformation at different pH values. Moreover, the dynamics of the insulin protein showed a dependence on the concentration of Zn(II) ions. In the absence of Zn(II) ions in the subphase, the acidic and basic solutions showed similar behavior at the air-water interface. In the presence of Zn(II) ions in the subphase, the surface pressure-area and surface potential-area isotherms suggest that HI may aggregate at the air-water interface. It was observed that increasing the concentration of Zn(II) ions in the acidic (pH 2) aqueous solution of HI led to an increase of the area at a specific surface pressure. It was also seen that the conformation of HI in the basic (pH 9) medium had a reverse effect (decrease in the surface area) with the increase of the concentration of Zn(II) ions in solution. From the compression-decompression cycles we can conclude that the aggregated HI film at air-water interface is not stable and tends to restore a monolayer of monomers. These results were confirmed from UV-vis and fluorescence spectroscopy analysis. Infrared reflection-absorption and circular dichroism spectroscopy techniques were used to determine the secondary structure and orientation changes of HI by zinc ions. Generally, the aggregation process leads to a conformation change from α-helix to β-strand and β-turn, and at the air-water interface, the aggregation process was likewise seen to induce specific orientations for HI in the acidic and basic media. A proposed surface orientation model is presented here as an explanation to the experimental data, shedding light for further research on the behavior of insulin as a Langmuir monolayer.     

Kinetics of Complexation in the Monolayers of Amphiphilic Dicetylcyclene on the Surface of Aqueous Copper(II) Chloride Solutions

The kinetics of complexation in monolayers of dicetycyclene at the surface of aqueous copper(II) chloride solutions was studied. It was shown that the changes in the phase state of monolayer related to the conformational transitions of macrocycle are responsible for the differences in the rate and binding mechanism of copper ions. It was concluded that the sterically more advantageous (for the coordination with the metal ion) conformation of macrocyclic polyamine is ensured in a monolayer. In addition, it was established that the rate and mechanism of complexation in such monolayers greatly depend on the degree of protonation of ligands, the latter being dependent on the subphase pH. It was also demonstrated that an increase in subphase pH to 7 and higher results in an almost total suppression of metal ion binding due to strong conformational distortion of dicetylcyclene macrocycles in a monolayer and the hydrogen bonding between macrocycles.     

Metal ion-induced H-aggregation of a water-soluble anionic dye Congo red (CR) in Langmuir–Blodgett (LB) film

Present communication reports the preparation of Langmuir monolayer of water-soluble anionic dye Congo red (CR) by allowing it to adsorb from the aqueous subphase onto the preformed Langmuir monolayer of anionic stearic acid using divalent metal cations Mg²⁺ as mediator. Isotherm and compressibility studies of SA-Mg-CR hybrid monolayer gave valuable information about the molecular organisation in the Langmuir monolayer. Absorption spectroscopic studies revealed the formation of H-aggregates in the hybrid Langmuir–Blodgett (LB) films fabricated at lower salt concentration in the subphase. Atomic Force Microscopic image gave visual evidence of distinct nanocrystalline domains in the LB monolayer film.     

Langmuir–Blodgett Monolayers and Films of Alkylated Tetraazacrowns Containing Metal Ions and Nanoparticles

The behavior of individual 1,7-dicetyltetraaza-12-crown-4 and its mixture with 1,4,7,10-tetracetyltetraaza-12-crown-4 in the Langmuir monolayers at the subphases containing Cu(II) ions or colloidal gold particles is studied. Based on the compression isotherms, the complexing ability of these amphiphilic cyclenes in a monolayer at the surface of aqueous dilute solutions of copper salt is established. It was shown that the fraction of complexes in a monolayer is proportional to the copper ion concentration in the subphase. Using surface balance, atomic force microscopy, and electron microscopy methods, it was revealed that the monolayer of dicetylcyclene at the surface of gold hydrosol binds nanoparticles from the subphase; the number of particles bound by the monolayer is proportional to their content in the hydrosol. The Langmuir–Blodgett films (LBF) of dicetylcyclene are prepared; their ability to bind copper ions from solution was disclosed by quartz crystal microbalance. The LBFs of dicetylcyclene containing gold nanoparticles in each layer are assembled.     

Infrared reflection-absorption spectroscopy and polarization-modulated infrared reflection-absorption spectroscopy studies of the organophosphorus acid anhydrolase langmuir monolayer

The secondary structure of the organophosphorus acid anhydrolase (OPAA) Langmuir monolayer in the absence and presence of diisopropylfluorophosphate (DFP) in the subphase was studied by infrared reflection-absorption spectroscopy (IRRAS) and polarization-modulated IRRAS (PM-IRRAS). The results of both the IRRAS and the PM-IRRAS indicated that the alpha-helix and the beta-sheet conformations in OPAA were parallel to the air-water interface at a surface pressure of 0 mN.m-1 in the absence of DFP in the subphase. When the surface pressure increased, the alpha-helix and the beta-sheet conformations became tilted. When DFP was added to the subphase at a concentration of 1.1 x 10(-5) M, the alpha-helix conformation of OPAA was still parallel to the air-water interface, whereas the beta-sheet conformation was perpendicular at 0 mN.m-1. The orientations of both the alpha-helix and the beta-sheet conformations did not change with the increase of surface pressure. The shape of OPAA molecules is supposed to be elliptic, and the long axis of OPAA was parallel to the air-water interface in the absence of DFP in the subphase, whereas the long axis became perpendicular in the presence of DFP. This result explains the decrease of the limiting molecular area of the OPAA Langmuir monolayer when DFP was dissolved in the subphase.     

Formation of flat, homogeneous surfaces of organized molecular films of three-armed polymerizable amphiphiles with metal-scavenging properties

Surface complexing (i.e., metal-bridged polymerization in this study) of a three-armed amphiphilic compound with metal-scavenging properties has been investigated using the surface pressure-area (π-A) isotherms of a Langmuir monolayer from the subphase. Inductively coupled plasma mass spectrometry (ICP-MS) was also carried out on eluted solutions from corresponding multilayers of the solid. Furthermore, the molecular arrangement and surface morphology of organized molecular films of the resultant comb polymer were estimated by in-plane and out-of-plane X-ray diffraction (XRD) and by atomic force microscopy. From an analysis of the wide-angle X-ray diffraction of the corresponding monomer in the bulk, the long hydrocarbon chains are observed to pack hexagonally in the solid state. Compared to their monolayer on distilled water as the subphase, a polymerized monolayer on a buffer solution containing Cd(2+) ions is remarkably expanded at 15 °C. From ICP-MS and IR measurements, it is found that this monolayer stoichiometrically contains Cd(2+) ions on the -SH group. It is found by XRD that highly ordered layer structures and regular 2D lattices are constructed in the organized molecular films of the Cd-bridged comb polymer. Furthermore, the surface morphology of Langmuir-Blodgett films fabricated from the monolayers on a buffer solution containing Cd(2+) and Pd(2+) shows flat and smooth domains upon metal scavenging and polymerization.     

Supramolecular assemblies of a new series of gemini-type schiff base amphiphiles at the air/water interface: in situ coordination, interfacial nanoarchitectures, and spacer effect

Great interest has been devoted to the gemini amphiphiles because of their unique properties. In this article, we report some interesting properties of the interfacial films formed by a series of newly designed gemini amphiphiles containing the Schiff base moiety. This novel series of gemini amphiphiles with their Schiff base headgroups linked by a hydrophobic alkyl spacer (BisSBC18Cn, n = 2, 4, 6, 8, 10) could be spread to form stable monolayers and coordinated with Cu(Ac)(2) in situ in the monolayer. The alkyl spacer in the amphiphiles has a great effect on the regulation of the properties of the Langmuir monolayers. A maximum limiting molecular area was observed for the monolayers of the gemini amphiphile with the spacer length of hexa- or octamethylene groups. Both the monolayers on water and on the aqueous Cu(Ac)(2) subphase were transferred onto solid substrates, and different morphologies were observed for films with different spacers. Nanonail and tapelike morphologies were observed for amphiphile films with shorter spacers (n = 2 and 4) on the water surface. Wormlike morphologies were observed for gemini films with longer spacers of C(8) and C(10) when coordinated with Cu(Ac)(2). An interdigitated layer structure was supposed to form in the multilayer films transferred from water or the aqueous Cu(Ac)(2) subphase.     

Lignin from sugar cane bagasse: extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels through impedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.     

The interaction between G-quadruplex-forming oligonucleotide and cationic surfactant monolayer at the air/water interface

We report on the interactions between a 21-mer quadruplex-forming oligonucleotide bearing human telomere sequence of dG(3)(T(2)AG(3))(3) (G4 DNA) and a positively charged dioctadecyldimethylammonium bromide (DODAB) monolayer at the air-aqueous interface, studied by surface film balance measurements. In the presence of G4 DNA, the π-A isotherm of the cationic Langmuir film shifted to lower molecular areas when compared with the reference isotherm recorded on the subphase containing only 50 mM triethylamine-acetate (TEAA) buffer. The presence of quadruplex-stabilizing metal cations (K(+) or Na(+)) further affected profiles of π-A isotherms. Further insight into processes related to the G4 DNA-monolayer interactions was provided by recording time profiles of the surface pressure of monolayer at a constant mean molecular area. In these experiments G4 DNA and/or metal ions were sequentially injected under the monolayer surface. Results indicated that multistranded assemblies of G4 DNA were formed at the monolayer interface even in the absence of metal ions, which suggested that the charged cationic surface of Langmuir monolayer induced aggregation of guanine-rich DNA strands. The presence of sodium and potassium ions inhibited formation of multi-stranded assemblies through the competitive G-quadruplex formation but to different extent that might be related to the differences in stability and topology of both quadruplexes.     

Ion-Sensitive Monolayers and Langmuir–Blodgett Films of Amphiphilic Cyclen: Selectivity and Regeneration

Complexation of dicetyl cyclen with transition metal ions in the monolayers on the surface of aqueous solutions of Cu(II), Ni(II), Zn(II), Ag(I) and their mixtures was studied. It was established that the selectivity of the interaction of the monolayer composed of this ligand with transition metal ions is determined by the subphase pH value. It is disclosed that, in the acidic region of subphase pH values, dicetyl cyclen in the monolayer bounds predominantly the Ni(II) ions from solutions containing Cu²⁺ and Ni²⁺ ions, although its complexes with Ni(II) in the bulk under these conditions are less stable than similar complexes with Cu(II). The effect of conformational and charge states of the ligand on the protonation of macrocycle and the stability of its complexes is discussed. The possibility of the reversible regeneration of the monolayers and the Langmuir–Blodgett films of the complexes of dicetyl cyclen and copper(II) ions is shown to occur with no changes in the structure and properties of this planar system. It is shown that the Langmuir–Blodgett films based on dicetyl cyclen can be used as a sensor element for the quantitative analysis of the content of Cu(II) ions in dilute solutions.     

Mixed monolayers of alkylated azacrown ethers and palmitic acid at the air-water surface

The Langmuir films of two alkylated azacrown ethers at the air-water surface were characterized using surface pressure-area isotherms, ellipsometry, Brewster angle microscopy, and constant-area surface pressure relaxation. The azacrown ether molecules aggregate in the monolayer, which significantly stabilizes the film against dissolution. Mixed azacrown ether-palmitic acid monolayers were also characterized; results suggest that at high compression the two molecules interact repulsively. The influence of Cu(II) ions present in the aqueous subphase on the single components and mixed monolayer characteristics was also studied.     

Langmuir膜及LB膜中的金属参与

本文主要介绍了金属离子与Langmuir膜及LB膜相互作用中静电、配位等作用方式及其对膜相态和分子二维排列的影响。在此基础上探讨了Langmuir膜对金属离子的识别与传感。以Langmuir膜和LB膜为二维模板诱导无机盐定向生长作为金属/单分子膜结合的重要应用在文中也进行了讨论。通过举例展示了金属离子参与的Langmuir膜和LB膜催化有机反应的特点。最后对金属参与的Langmuir膜和LB膜在功能化和器件化等方面的研究也作了论述， 并通过介绍金属螯合类脂分子的Langmuir膜在蛋白质等生物大分子界面定向聚集研究中的应用表明了金属参与的Langmuir膜及LB 膜在生命科学研究中的意义。全文贯穿了金属结合调节Langmuir膜和LB膜组装结构以及通过金属结合导入功能基团进行有序组装的思想。     

Effects of Calcium Ions on Thermodynamic Properties of Mixed Bilirubin/Cholesterol Monolayers

The mixed monolayer behavior of bilirubin/cholesterol was studied through surface pressure-area (?-A) isotherms on aqueous solutions containing various concentrations of calcium ions. Based on the data of ?-A isotherms, the mean area per molecule, collapse pressure, surface compressibility modulus, excess molecular areas, free energy of mixing, and excess free energy of mixing of the monolayers on different subphases were calculated. The results show an expansion in the structure of the mixed monolayer with Ca2+ in subphase, and non-ideal mixing of the components at the air/water interface is observed with positive deviation from the additivity rule in the excess molecular areas. The miscibility between the components is weakened with the increase of concentration of Ca2+ in subphase. The facts indicate the presence of coordination between Ca2+ and the two components. The mixed monolayer, in which the molar ratio of bilirubin to cholesterol is 3:2, is more stable from a thermodynamic point of view on pure water. But the stable 3:2 stoichiometry complex is destroyed with the increase of the concentration of Ca2+ in subphase. Otherwise, the mixed monolayers have more thermodynamic stability at lower surface pressure on Ca2+ subphase.     

The Influence of Macrocyclic Tetraamine Immobilization in Langmuir Monolayers on Complex Formation Selectivity

Selective complex formation in Langmuir dicetyl cyclene monolayers on the surface of aqueous solutions of Cu(II), Ni(II), and Zn(II) salts and their mixtures was studied. The effect of selectivity “inversion” of diphilic cyclene immobilized in monolayers on the surface of solutions of a mixture of copper(II) and nickel(II) salts was observed; the inversion was induced by a change in subphase pH. An analysis of the isotherms of monolayer compression and X-ray fluorescence spectra of the corresponding Langmuir-Blodgett films showed that subphase acidification caused a gradual transition from the selective formation of copper-containing macrocyclic complexes to selective complex formation between the ligand and nickel ions. The effect observed was not characteristic of complex formation with similar unsubstituted tetraamines in bulk solution. The phenomenon was interpreted from the point of view of specific conformational transitions of the diphilic macroring in the two-dimensional system organized at the interphase boundary.     

Effect of Na+ and Ca2+ Ions on a Lipid Langmuir Monolayer: An Atomistic Description by Molecular Dynamics Simulations

Studying the effect of alkali and alkaline‐earth metal cations on Langmuir monolayers is relevant from biophysical and nanotechnological points of view. In this work, the effect of Na⁺ and Ca²⁺ on a model of an anionic Langmuir lipid monolayer of dimyristoylphosphatidate (DMPA^?) is studied by molecular dynamics simulations. The influence of the type of cation on lipid structure, lipid–lipid interactions, and lipid ordering is analyzed in terms of electrostatic interactions. It is found that for a lipid monolayer in its solid phase, the effect of the cations on the properties of the lipid monolayer can be neglected. The influence of the cations is enhanced for the lipid monolayer in its gas phase, where sodium ions show a high degree of dehydration compared with calcium ions. This loss of hydration shell is partly compensated by the formation of lipid–ion–lipid bridges. This difference is ascribed to the higher charge‐to‐radius ratio q/r for Ca²⁺, which makes ion dehydration less favorable compared to Na⁺. Owing to the different dehydration behavior of sodium and calcium ions, diminished lipid–lipid coordination, lipid–ion coordination, and lipid ordering are observed for Ca²⁺ compared to Na⁺. Furthermore, for both gas and solid phases of the lipid Langmuir monolayers, lipid conformation and ion dehydration across the lipid/water interface are studied.     

Effect of metal ions on monolayer collapses

A Langmuir monolayer of stearic acid on pure water and in the presence of certain divalent metal ions such as Cd and Pb at pH approximately 6.5 of the subphase water collapses at constant area, while for other divalent ions such as Mg, Co, Zn, and Mn at the same subphase pH the monolayer collapses nearly at constant pressure. Films of stearic acid with Cd, Pb, Mn, and Co in the subphase (at pH approximately 6.5) have been transferred onto hydrophilic Si(001) using a horizontal deposition technique, just after and long after collapse. Electron density profiles obtained from X-ray reflectivity analysis show that a three-molecular-layer structure starts to form just after constant area collapse, where in the lowest molecular layer, in contact with the substrate, molecules are in asymmetric configuration, i.e., both hydrocarbon tails are on the same side of the metal-bearing headgroup that touches the substrate, while the molecules above the first layer are in symmetric conformation of the tails with respect to the headgroups. Further along collapse, when the surface pressure starts to rise again with a decrease in area, more layers with molecules in the symmetric configuration are added, but the coverage is poor. On the other hand, only bimolecular layers form after constant pressure collapse, with the lower and upper layers having molecules in asymmetric and symmetric configurations, respectively, and the upper molecular layer density increases with compression of the monolayer after collapse. A "Ries mechanism" for constant area collapse and a "folding and sliding mechanism" for constant pressure collapse have been proposed.     

Scanning electrochemical microscopy as a probe of Ag+ binding kinetics at Langmuir phospholipid monolayers

A new method has been developed for measuring local adsorption rates of metal ions at interfaces based on scanning electrochemical microscopy (SECM). The technique is illustrated with the example of Ag+ binding at Langmuir phospholipid monolayers formed at the water/air interface. Specifically, an inverted 25 microm diameter silver disc ultramicroelectrode (UME) was positioned in the subphase of a Langmuir trough, close to a dipalmitoyl phosphatidic acid (DPPA) monolayer, and used to generate Ag+ via Ag electro-oxidation. The method involved measuring the transient current-time response at the UME when the electrode was switched to a potential to electrogenerate Ag+. Since the Ag+/Ag couple is reversible, the response is highly sensitive to local mass transfer of Ag+ away from the electrode, which, in turn, is governed by the interaction of Ag+ with the monolayer. The methodology has been used to determine the influence of surface pressure on the adsorption of Ag+ ions at a phospholipid (dipalmitoyl phosphatidic acid) Langmuir monolayer. It is shown that the capacity for metal ion adsorption at the monolayer increased as the density of surface adsorption sites increased (by increasing the surface pressure). A model for mass transport and adsorption in this geometry has been developed to explain and characterise the adsorption process.