Polyoxometalate monolayers in Langmuir-Blodgett films

Langmuir and Langmuir-Blodgett (LB) films of a variety of polyoxometalates of different shapes, sizes, and charges were prepared by taking advantage of the adsorption properties of these polyanions on a positively charged monolayer of an organic surfactant spread on water. Three different aspects were investigated. 1) The electrochemical and electrochromic properties of LB films containing the easily reducible polyoxoanion [P2Mo18O62]6-. Absorbance changes of these LB films deposited onto an ITO substrate have been induced by repeated switching of the applied potential. These changes are due to the formation of the colored reduced forms of the polyanion. Coloration and bleaching of the LB film occur very quickly and are reversible. 2) The preparation of LB films based on magnetic polyoxometalates, such as the Keggin anions, [CoW12O40]6- and [SiMn(OH2)W11O39]6-, or containing magnetic clusters of increasing nuclearities such as [Co4(H2O)2(PW9O34)2]10- and [Co4(H2O)2(P2W15O62)2]16- based on a Co4O16 ferromagnetic cluster, and the polyoxometalates [Co9(OH)3(H2O)6(HPO4)2(PW9O34)3]16- and [Ni9(OH)3-(H2O)6(HPO4)2(PW9O34)3]16- based on a nonanuclear M9O36 cluster. 3) The preparation of LB films of the giant heteropolyoxomolybdate, [Na3(NH4)12][Mo57Fe6(NO)6O174(OH)3-(H2O)24]76 H2O.     

Langmuir and Langmuir-Blodgett monolayers of molecular tweezers and clips

Molecular clips and tweezers are able to selectively bind electron-deficient aromatic and aliphatic substrates. By means of pressure-area isotherms and Brewster angle microscopy (BAM), the self-association process and phase behavior of dimethylene-bridged molecular clips and tetramethylene-bridged molecular tweezers each substituted with two acetoxy groups as polar head groups were investigated. In a series of experiments, we observed that the molecular surface area of the clips and tweezers only depended on the skeletal structure and not on the polar groups. The measured areas agreed with the effective molecular diameters of the molecules if the aromatic side walls of the clips or tweezers were assumed to be aligned perpendicularly to the water surface. We compared the phase behavior of the pure molecular clips and tweezers with that of the host-guest complexes of these molecules, which were formed with 1,2,4,5-tetracyanobenzene (TCNB) as the guest molecule. For the clips with a central benzene (I) and naphthalene spacer unit (II), the complex formation with TCNB had no measurable influence on the phase diagrams of the films. We observed, however, a dramatic difference in the BAM images and pi-A isotherms between the pure molecular tweezers III and its complex with TCNB (TCNB@III). In addition to the pi-A isotherms, we used the surface potential (V)-area (A) isotherms to compare the pure tweezers III with the corresponding complex (TCNB@III). There was a strong difference in the maximum surface potential value for the pure tweezers (450 mV) and that for the complex (300 mV). In additional experiments, we prepared LB layers of such molecules, which were investigated by fluorescence spectroscopy. In comparison to the pure tweezers III, a luminescence emission of charge-transfer (CT) origin was observed for the host-guest complex (TCNB@III) fixed on the solid substrate. It turned out that the spectra were in good agreement with the results observed in chloroform solution.     

Phage Langmuir monolayers and Langmuir–Blodgett films

Stable, insoluble Langmuir monolayer films composed of Staphylococcus aureus-specific lytic bacteriophage were formed at an air–water interface and characterized. The phage monolayer was very strong, withstanding a surface pressure of ～40 mN/m at 20 °C. The surface pressure–area (Π–A) isotherm possessed a shoulder at ～7 × 10⁴ nm²/phage particle, attributed to a change in phage orientation at the air–water interface from horizontal to vertical capsid-down/tail-up orientation as surface pressure was increased. The Π–A-dependence was accurately described using the Volmer equation of state, assuming horizontal orientation to an air–water interface at low surface pressures with an excluded area per phage particle of 4.6 × 10⁴ nm². At high pressures phage particles followed the space-filling densely packed disks model with a specific area of 8.5 × 10³ nm²/phage particle. Lytic phage monolayers were transferred onto gold-coated silica substrates from the air–water interface at a constant surface pressure of 18 mN/m by Langmuir–Blodgett method, then dried and analyzed by scanning electron microscopy (SEM) and ellipsometry. Phage specific adsorption (Γ) in Langmuir–Blodgett (LB) films measured by SEM was consistent with that calculated independently from Π–A isotherms at the transfer surface pressure of 18 mN/m (Γ = 23 phage particles/μm²). The 50 nm-thickness of phage monolayer measured by ellipsometer agreed well with the horizontal phage average size estimated by SEM. Surface properties of phage Langmuir monolayer compare well with other monolayers formed from nano- and micro-particles at the air–water interface and similar to that of classic amphiphiles 1,2-diphytanoyl-sn-glycero-3-phosphocholine (phospholipid) and stearic acid.     

Structural investigation of Langmuir and Langmuir-Blodgett monolayers of semifluorinated alkanes

The behavior of a semi-fluorinated alkane (C(10)F(21)C(19)H(39)) has been studied at the air-water interface by using surface pressure and surface potential-area isotherms as well as infrared spectroscopy for the Langmuir-Blodgett films. In addition, based on the quantum chemical PM3 semiempirical approach, the dimer structure was investigated, and the double helix was found to be the most stable conformation of the dimer. The obtained results allow us to imply that the phase transition observed in the course of the surface pressure/area isotherm is due to a conformational change originating from the double helix to a vertical, single helix configuration.     

Langmuir and Langmuir-Blodgett films of a novel tryptophan peptide lipid

A novel tryptophan peptide lipid, C18H35O (SA)-Gly-Trp-Gly-OH, was synthesized and studied for its surface chemistry and spectroscopic properties.     

Langmuir and Langmuir-Blodgett films of amphiphilic bistable rotaxanes

A series of amphiphilic bistable [2]rotaxanes--in which a ring-shaped component, the tetracationic cyclophane, cyclobis(paraquat-p-phenylene), has been assembled around two recognition sites, a tetrathia-fulvalene (TTF) unit and a 1,5-dioxynaphthalene (DNP) ring system, situated apart at different strategic locations within the central polyether section of an amphiphilic dumbbell component that is terminated by a hydrophobic tetraarylmethane-based stopper (near the TTF unit) at one end and by a hydrophilic tetraarylmethane-based stopper (near the DNP ring system) at the other end--has been designed and synthesized. The effects of systematic changes in the constitutions of the three ethylene glycol tails (diethylene or tetraethylene glycol) and end groups (hydroxyl or methoxyl functions) attached to the hydrophilic stoppers on Langmuir film balance and surface rheology experiments at 20 degreesC were examined to determine the monolayer stabilities and co-conformations of the [2] rotaxanes and their free dumbbell counterparts. These experiments allow us to propose a model for the rotaxane's structures at different surface pressures. All the [2]rotaxanes form stable Langmuir films. These films typically pass from a liquid-expanded region to a liquid-condensed region. The transition between the two regions was either directly observed or ascertained using film stability experiments. Film balance and surface rheology experiments showed that the addition of the tetracationic cyclophane component and hydroxyl end groups markedly increased the stabilities and viscoelasticity of the films.     

Photoreactions and lateral patterning in Langmuir and Langmuir-Blodgett films

Reversible morphological changes occur with photoisomerization of azobenzene in Langmuir-Blodgett (LB) films complexed with polycations, which contradicts an implicit assumption of the concept of free volume that two-dimensional film structures are preserved during the photoisomerization. J-aggregates of chromophores are formed by two processes. The first process is "light-induced J-aggregation" in which photoisomerized molecules form J-aggregates. The other process is "triggered J-aggregation," in which photoisomerization of one of the components triggers J-aggregation of another chemical species in the mixed films. Both processes of J-aggregation are in many cases accompanied by large morphological changes of the films. However, LB films fabricated using processes under isobaric conditions do not change their morphology during light-induced J-aggregation and are patterned with J-aggregates using ultraviolet illumination through a photomask. Phase separation in mixed LB films gives rise to two-dimensional patterns, which are used to fabricate templates by using an amphiphilic silane-coupling agent as one of the components in the mixed LB films. Nanopatterns are also fabricated.     

Supramolecular architecture in Langmuir and Langmuir-Blodgett films incorporating a chiral azobenzene

This article describes the synthesis and fabrication of Langmuir and Langmuir-Blodgett (LB) films incorporating a chiral azobenzene derivative, namely, ( S)-4- sec-butyloxy-4'-[5'-(methyloxycarbonyl)pentyl-1'-oxy]azobenzene, abbreviated as AZO-C4(S). Appropriate conditions for the fabrication of monolayers of AZO-C4(S) at the air-water interface have been established, and the resulting Langmuir films have been characterized by a combination of surface pressure and surface potential versus area per molecule isotherms, Brewster angle microscopy, and UV-vis reflection spectroscopy. The results indicate the formation of an ordered trilayer at the air-water interface with UV-vis reflection spectroscopy showing a new supramolecular architecture for multilayered films as well as the formation of J aggregates. Films were transferred onto solid substrates, with AFM revealing well-ordered multilayered films without 3D defects. Infrared and UV-vis absorption spectroscopy indicate that the supramolecular architecture may be favored by the formation of H bonds between acid groups in neighboring layers and pi-pi intermolecular interactions. Circular dichroism spectra reveal chiro-optical activity in multilayered LB films.     

Formation of complex Langmuir and Langmuir-Blodgett films of water soluble rosebengal

This communication reports the formation of complex Langmuir monolayer at the air-water interface by charge transfer types of interaction with the water soluble N-cetyl N,N,N-trimethyl ammonium bromide (CTAB) molecules doped with rosebengal (RB), with the stearic acid (SA) molecules of a preformed SA Langmuir monolayer. The reaction kinetics of the formation of RB-CTAB-SA complex monolayer was monitored by observing the increase in surface pressure with time while the barrier was kept fixed. Completion of interaction kinetics was confirmed by FTIR study. This complex Langmuir films at the air-water interface was transferred onto solid substrates at a desired surface pressure to form multilayered Langmuir-Blodgett films. Spectroscopic characterizations reveal some molecular level interactions as well as formation of microcrystalline aggregates depending upon the molar ratios of CTAB and RB within the complex LB films. Presence of two types of species in the complex LB films was confirmed by fluorescence spectroscopy.     

Langmuir and Langmuir-Blodgett films of proline-rich N-terminal domain peptide of gamma-zein

The proline-rich N-Terminal domain peptides of γ-zein (VHLPPP)_n with n = 1 and 3 (peptides I and II) are shown to form stable Langmuir films at air/water interface and the films have been characterized using surface pressure–molecular area (π–A), surface potential–molecular area (ΔV–A) isotherms, respectively. The longer peptide sequence does not show dramatic increase in surface or interfacial properties suggesting that the minimum length of n = 1 is sufficient to achieve the necessary surface properties. Brewster angle micrographs also agreed with these results. The high surface-active nature of the peptide suggests a fairly non-polar character at air/water interface and at solid/air interface when coated expresses a high surface energy.

Additives such as isopropyl alcohol (IPA) and polyvinyl alcohol (PVA) with the peptides showed more homogenous films at the air/water interface and also improved mechanical and tensile properties. The organized assembly of peptide I at the air/water and solid/air interface suggests that even thin layer of the peptide could play an important role in coating the inner surface of protein body membrane in storage proteins. Composite films of such short peptides with biocompatible polymers may find applications as surface coatings and in biomaterials.     

Amphiphilic diblock dendrimers: synthesis and incorporation in Langmuir and Langmuir-Blodgett films

A new dendron with peripheral long alkyl chains and containing five C(60) units in the branching shell has been prepared and attached to a Fréchet-type dendron functionalized with ethylene glycol chains. The peripheral substitution of the resulting globular dendrimer with hydrophobic chains on one hemisphere and hydrophilic groups on the other provides the perfect hydrophobic/hydrophilic balance allowing the formation of stable Langmuir films. Furthermore, a perfect reversibility has been observed in successive compression/decompression cycles. The diblock structure of the dendrimer has been also crucial for the efficient transfer of the Langmuir films in order to obtain well-ordered multilayered Langmuir-Blodgett films. This approach appears particularly interesting since functional groups not well adapted for the preparation of Langmuir and Langmuir-Blodgett films such as fullerenes can be attached into the branching shell of the dendritic structure and, thus, efficiently incorporated in thin ordered films.     

Synthesis and supramolecular self-assembly study of a novel porphyrin molecule in Langmuir and Langmuir-Blodgett films

The self-assembly and supramolecular engineering of porphyrins into ordered arrays have recently attracted much interest because of their promising application potential in molecular and electronic devices, spintronics, energy harvesting and storage, catalysis, and sensor development. We herein report the synthesis and supramolecular self-assembly study of a novel porphyrin molecule, 2Por-TAZ, in Langmuir and Langmuir-Blodgett films. The 2Por-TAZ molecule contains two porphyrin macrocycles attached to a triaminotriazine headgroup. Triaminotriazines are known to form a highly ordered linear supramolecular self-assembly through complementary hydrogen bonding with barbituric acid molecules at the air-water interface. Surface pressure-area isotherm measurements and polarized UV-vis absorption spectroscopic studies indicate that the 2Por-TAZ molecules adopted an edge-on orientation at the air-water interface. Polarized UV-vis absorption study also revealed that the 2Por-TAZ molecules formed linear supramolecular networks on pure water and barbituric acid subphase with porphyrin flat planes facing toward the compression direction. The binding of barbituric acid with 2Por-TAZ molecules was observed from the expansion of the Langmuir monolayer film. Compared to the transferred LB film from pure water subphase, both the UV-vis absorbance and fluorescence emission intensity of the LB film transferred from barbituric acid subphase increased significantly.     

In-plane orientation controlled by a rotating disc in Langmuir and Langmuir-Blodgett films of a merocyanine dye

When a Langmuir film consists of mesoscopic domains having an elongated shape, stretching of the film due to Langmuir-Blodgett (LB) deposition and shearing due to a rotating disc can induce in-plane orientations of these domains. When the former governs the phenomenon, the domains are aligned perpendicular to the substrate surface (just before the transfer). When the latter governs the phenomenon, the domains are aligned along the concentric flow lines. We have studied the more complicated intermediate case by using two different molecular systems. It has been demonstrated that in LB films fabricated under such conditions, the orientation of the domains depends on the position on the substrate and the deposition type. Furthermore, monolayers deposited during the upward and downward strokes of the substrate become non-equivalent.     

Using phospholipid Langmuir and Langmuir-Blodgett films as matrix for urease immobilization

The immobilization of enzymes in organized two-dimensional matrices is a key requirement for many biotechnological applications. In this paper, we used the Langmuir-Blodgett (LB) technique to obtain controlled architectures of urease immobilized in solid supports, whose physicochemical properties were investigated in detail. Urease molecules were adsorbed at the air-water interface and incorporated into Langmuir monolayers of the phospholipid dipalmitoyl phosphatidyl glycerol (DPPG). Incorporation of urease made DPPG monolayers more flexible and caused the reduction of the equilibrium and dynamic elasticity of the film. Urease and DPPG-urease mixed monolayers could be transferred onto solid substrates, forming LB films. A close packing arrangement of urease was obtained, especially in the mixed LB films, which was inferred with nanogravimetry and electrochemistry measurements. From the blocking effect of the LB films deposited onto indium tin oxide (ITO) substrates, the electrochemical properties of the LB films pointed to a charge transport controlled by the lipid architecture.     

Structural characterization and properties of an azopolymer arranged in Langmuir and Langmuir-Blodgett films

The fabrication of Langmuir and Langmuir-Blodgett (LB) films of an acid-azopolymer (PAzCOOH) is reported. Several techniques were used in their characterization: surface pressure (pi) and surface potential (DeltaV) isotherms, UV-vis reflection spectroscopy, and Brewster angle microscopy (BAM) for the Langmuir films and contact angle measurements, UV-vis, fluorescence, IR and Raman spectroscopy and scanning electronic microscopy (SEM) for the LB films. Our study reveals that lateral chains of the polymer situate preferentially onto the water surface with the acid group in contact with the water, where aggregates are scarcely formed. Therefore, the lateral chains of PAzCOOH can be treated as individual monomers to determine structural properties of the fabricated Langmuir and LB films. Monomeric treatment has been used to interpret UV-vis reflection spectroscopy, and a monomer model has been performed to represent lateral chains using density functional theory at B3LYP 6-31G(d,p) level of theory to assign the observed vibrational spectra.     

Characterization of Langmuir and Langmuir-Blodgett films of a thiomacrocyclic ionophore by surface pressure and AFM

The new synthesized thiomacrocyclic ionophore 4-phenyl-4-sulfide-11-(1-oxodecyl)-1,7-dithia-11-aza-4-phosphacyclotetradecane has proven to form Langmuir and Langmuir-Blodgett (LB) films. This ionophore shows a large affinity for copper(II) ions. Thus, the influence of the subphase composition on the surface pressure-area isotherms has been studied. The LB films have been observed by AFM and the effect of the subphase composition and the deposition surface pressure on the LB films is discussed. AFM image morphology has been correlated to the ionophore molecular structure. Surface pressure-area isotherms and AFM images show that the presence of copper(II) ions has an important role in the film structure.     

Langmuir and Langmuir-Blodgett films of multifunctional, amphiphilic polyethers with cholesterol moieties

Langmuir films of multifunctional, hydrophilic polyethers containing a hydrophobic cholesterol group (Ch) were studied by surface pressure-mean molecular area (π-mmA) measurements and Brewster angle microscopy (BAM). The polyethers were either homopolymers or diblock copolymers of linear poly(glycerol) (lPG), linear poly(glyceryl glycidyl ether) (lPGG), linear poly(ethylene glycol) (lPEG), or hyperbranched poly(glycerol) (hbPG). Surface pressure measurements revealed that the homopolymers lPG and hbPG did not stay at the water surface after spreading and solvent evaporation, in contrast to lPEG. Because of the incorporation of the Ch group in the polymer structure, stable Langmuir films were formed by Ch-lPG(n), Ch-lPGG(n), and Ch-hbPG(n). The Ch-hbPG(n), Ch-lPEG(n), Ch-lPEG(n)-b-lPG(m), Ch-lPEG(n)-b-lPGG(m), and Ch-lPEG(n)-b-hbPG(m) systems showed an extended plateau region assigned to a phase transition involving the Ch groups. Typical hierarchically ordered morphologies of the LB films on hydrophilic substrates were observed for all Ch-initiated polymers. All LB films showed that Ch of the Ch-initiated homopolymers is able to crystallize. This strong tendency of self-aggregation then triggers further dewetting effects of the respective polyether entities. Fingerlike morphologies are observed for Ch-lPEG(69), since the lPEG(69) entity is able to undergo crystallization after transfer onto the silicon substrate.     

Phthalocyanines in Langmuir and Langmuir-Blodgett films: from molecular design to supramolecular architecture

A short review is given on Langmuir and Langmuir-Blodgett films containing phthalocyanine derivatives. A particular emphasis is directed towards the molecular parameters that can be clearly related to the supramolecular architecture observed at the air-water interface and within the LB multilayers. Several examples concerning both edge-on and flat-lying phthalocyanine derivatives are discussed.     

Alignment of liquid crystal and dichroic dye molecules in mixed Langmuir and Langmuir-Blodgett films

A study of dichroic dye-liquid crystal mixtures (guest-host systems) in monolayers formed at a gas-liquid interface (Langmuir films) and at a solid surface (Langmuir-Blodgett films) has been made. As a host 4- n -octyl-4′-cyanobiphenyl (8CB) or 4- n -pentyl-4″-cyano- p -terphenyl (5CT) were chosen, while three dichroic azo dyes with various molecular structures were used as guest species. The dyes were added to the liquid crystal matrices at a concentration corresponding to the whole range of molar fractions and the surface pressure-mean molecular area isotherms for Langmuir films were recorded. On the basis of the isotherms, conclusions about the molecular organization and the miscibility of the components in the ultrathin films were drawn. The Langmuir films were transferred onto the quartz plates at surface pressures below the collapse point. The polarized absorption spectra of the Langmuir-Blodgett films were recorded and information about the alignment and intermolecular interactions in the mixtures of the non-amphiphilic dichroic dyes and the liquid crystals with strongly polar terminal groups were obtained.     

Alignment of liquid crystal and dichroic dye molecules in mixed Langmuir and Langmuir-Blodgett films

A study of dichroic dye-liquid crystal mixtures (guest-host systems) in monolayers formed at a gas-liquid interface (Langmuir films) and at a solid surface (Langmuir-Blodgett films) has been made. As a host 4- n -octyl-4'-cyanobiphenyl (8CB) or 4- n -pentyl-4"-cyano- p -terphenyl (5CT) were chosen, while three dichroic azo dyes with various molecular structures were used as guest species. The dyes were added to the liquid crystal matrices at a concentration corresponding to the whole range of molar fractions and the surface pressure-mean molecular area isotherms for Langmuir films were recorded. On the basis of the isotherms, conclusions about the molecular organization and the miscibility of the components in the ultrathin films were drawn. The Langmuir films were transferred onto the quartz plates at surface pressures below the collapse point. The polarized absorption spectra of the Langmuir-Blodgett films were recorded and information about the alignment and intermolecular interactions in the mixtures of the non-amphiphilic dichroic dyes and the liquid crystals with strongly polar terminal groups were obtained.