Synthesis of novel amphiphilic azobenzenes and X-ray scattering studies of their Langmuir monolayers

We report a simple synthetic route to novel symmetrical alkylated and acylated amphiphilic 4,4'-diaminoazobenzene dyes, with their optical axis perpendicular to the amphiphilic direction of the molecule. Three different substitution patterns are reported, two of which are highly amphiphilic. At the air-water interface, the amphiphilic azobenzenes form noncrystalline but stable Langmuir films that display an unusual reversible monolayer collapse close to 35 mN/m. The structures and phase transitions were studied by X-ray reflectivity (XR) and grazing-incidence X-ray diffraction, both utilizing synchrotron radiation. Compression beyond the collapse point does not change the XR data, showing that the film is unchanged at the molecular level, even at areas less than half of that of the collapse. This leads to the conclusion that few macroscopic collapse sites are responsible for reversibly removing large amounts of material from the interface.     

Enantiomeric recognition of amino acids by amphiphilic crown ethers in Langmuir monolayers

Four new chiral, amphiphilic crown ethers differing by the hydrophobic tailgroups were synthesized, and their capacity to recognize enantiomeric amino acids was examined using Langmuir films. Surface pressure and surface potential measurements performed on the subphases containing L or D enantiomers of alanine, valine, phenylglycine, and tryptophane indicate that the crown ethers forming the monolayer interact with the amino acids. The effects observed are ascribed to the formation of host-guest complexes. The differences in the magnitude of the effects measured show that the crown ethers are capable of discriminating between different amino acids as well as the enantiomers. Our results demonstrate that the structure of the monolayer plays a decisive role in the molecular recognition process including chiral recognition.     

Phase behavior of mixed Langmuir monolayers from amphiphilic block copolymers and an antimicrobial peptide

The behavior of binary monolayers from PMOXA-PDMS-PMOXA triblock copolymers and alamethicin, an antimicrobial peptide, was investigated in the context of formation of novel biocomposite nanostructured materials. The properties of mixed monolayers were studied by surface pressure-area isotherms and Brewster angle imaging. As reported previously, functionality of alamethicin relies on its aggregation properties in lipid mono- and bilayers. This is also the case in polymer matrixes, however, here the mixing properties differ from lipid-peptide systems due to the polymers' structural specificity. The peptide influence on the polymer films is provided in detail for the first time, and supported by the compressibility data to asses the elastic properties of such composite membranes.     

Subphase pH effect on the limiting molecular area of amphiphilic β-diketones in Langmuir monolayers

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Fabrication of metal nanoparticle monolayers on amphiphilic poly(amido amine) dendrimer Langmuir films

A newly designed 1.5th generation poly(amido amine) dendrimer with an azacrown core, hexylene spacers, and octyl terminals was spread on gold nanoparticle (Au-NP) suspension. The surface pressure-area isothermal curves indicated that the molecular area of dendrimer on Au-NP suspension was significantly smaller than that on water, indicating the formation of dendrimer/Au-NP composites. The dendrimer Langmuir films on the Au-NP suspension were transferred to copper grids at various surface pressures and observed by transmission electron microscopy. The transferred films consisted of a fractal-like network of nanoparticles at low surface pressure and of a defect-rich monolayer of nanoparticles at high surface pressure. From these results, it was suggested that the dendrimers bind Au-NPs, and dendrimer/Au-NP composites formed networks or monolayers at the interface. From the intensity decrease of the Au plasmon band of Au-NP suspension after the formation of composite, it was estimated that some (approximately 14) dendrimer molecules bind to one Au-NP. Furthermore, neutron reflectivity at the air/suspension interface and X-ray reflectivity of the film transferred on a silicon substrate revealed that the dendrimer molecules are localized on the upper-half surface of Au-NP. Metal affinity of azacrown, flexibility of hexylene spacer, and amphiphilicity of dendrimer with octyl terminals played important roles for the formation of dendrimer/Au-NP hybrid films. The present investigation proposed a new method to fabricate the self-assembled functional polymer/nanoparticle hybrid film.     

Flow-induced patterning of Langmuir monolayers

Insoluble monolayers on water have been patterned at the macroscopic scale (i.e., at the centimeter scale of the flow apparatus) as well as the mesoscopic scale (i.e., down to the micron scale resolvable via optical microscopy). The macroscopic patterning at the air/water interface results from a hydrodynamic instability leading to a steadily precessing flow pattern. The velocity field is measured, and the associated shear stress at the interface is shown to be locally amplified by the flow pattern. The resulting hydrodynamic effects on two different monolayer systems are explored: (1) the pattern in a model monolayer consisting of micron-size, surface-bound particles is visualized to show that the particles are concentrated into isolated regions of converging flow with high shear, and (2) Brewster angle microscopy of a Langmuir monolayer (vitamin K1) shows not only that the monolayer is patterned at the macroscopic scale but also that the localized high-shear flow further patterns the monolayer at the mesoscale.     

Langmuir monolayers of bent-core molecules

A systematic study of five different, symmetric bent-core liquid crystals in Langmuir thin films at the air/water interface is presented. Both the end chains (siloxane vs hydrocarbon) and the core (more or less amphiphilic) are varied, to allow an exploration of different possible layer structures at the interface. The characterization includes systematic surface pressure isotherms, Brewster angle microscopy, and surface potential measurements. The properties of these layers are strongly dependent on the individual type of molecule: the molecules with amphiphilic end chains lie quite flat on the surface, while the molecules with hydrophobic end chains construct multilayer structures. In both cases, the three-dimensional collapse structure is reversible.     

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.     

Flow-controlled phase boundaries in Langmuir monolayers

Flow-controlled fingering of the liquid expanded/liquid condensed phase boundary in a 2-d insoluble monolayer is investigated using a laser-induced thermocapillary pump. Spatially periodic perturbations of the initially smooth monolayer phase boundary between a liquid expanded and liquid condensed phase are shown to lead to the development of steady profile of one-dimensional fingers. The steady-state modulation wave vector and the transient growth rate increase with the flow velocity that drives the instability following power scaling laws consistent with a theory of Bruinsma, Rondelez, and Levine (Bruinsma, R.; Rondelez, F.; Levine, A. Eur. Phys. J. E. 2001, 6, 191) on flow rather than diffusion dominated instabilities in monolayers.     

Iso-branched semifluorinated alkanes in Langmuir monolayers

A series of semifluorinated n-alkanes (SFAs), of the general formula: (CF3)2CF(CF2)6(CH2)nH (in short iF9Hn), n = 11-20 have been synthesized and employed for Langmuir monolayer characterization. Surface pressure and electric surface potential measurements were performed in addition to Brewster angle microscopy results, which enabled both direct visualization of the monolayers structure and estimation of the monolayer thickness at different stages of compression. Our paper was aimed at investigating the influence of the iso-branching of the perfluorinated fragment of the SFA molecule on the surface behavior of these molecules at the air/water interface. It occurred that iF9 SFAs with the number of carbon atoms in the hydrogenated moiety from 11 to 20 are capable of Langmuir monolayer formation. Monolayers from iF9H11 to iF9H13 are instable, whereas those formed by iF9 SFAs with longer hydrogenated chains form stable films at the free surface of water. As compared to SFAs containing perfluorinated chain in a normal arrangement, iso-branched molecules have a greater tendency to aggregate. Lower stability of monolayers formed by iF9 SFAs as compared to F10 SFAs originated from the surface nucleation observed in BAM images, even at the very initial stages of compression. The dipole moment vector for iso-branched SFAs was found to be virtually aligned with the main axis of the molecule, contrary to F10 SFAs, where the dipole moment vector was calculated to be tilted with respect to the main molecular axis. Quantitative Brewster angle microscopy measurements (relative reflectivity experiments) enabled us to monitor the changes of monolayer thickness at different stages of monolayer compression.     

Solid-supported monolayers and bilayers of amphiphilic beta-cyclodextrins

This paper describes the adsorption and spreading of beta-cyclodextrin (CD) vesicles on hydrophobic and hydrophilic substrates, which involves a transition from bilayer vesicles to planar molecular monolayers or bilayers. On substrates that are patterned with self-assembled monolayers by microcontact printing (muCP), the CD vesicles preferentially adsorb on hydrophobic areas instead of hydrophilic (nonionic) areas, and on cationic areas instead of hydrophilic (nonionic) areas. Supported monolayers of amphiphilic cyclodextrins CD1 and CD2 were obtained by adsorption of CD vesicles to hydrophobic substrates, and supported bilayers of amphiphilic cyclodextrins CD1 and CD2 were prepared by adsorption of CD vesicles on cationic substrates. Contact angle goniometry, atomic force microscopy and confocal fluorescence microscopy (CFM) were used to analyze the supported CD layers. The fluidity of the supported CD layers was verified using fluorescence recovery after photobleaching experiments. The supported layers function as a supramolecular platform that can bind suitable guest molecules through inclusion in the CD host cavities. Additionally, the CD host layers were patterned with fluorescent guest molecules by supramolecular muCP on the supported CD layers. The host-guest interactions were investigated with CFM and fluorescence resonance energy transfer experiments.     

Interfacial polymerisation of anilinium at Langmuir monolayers

Anilinium is strongly adsorbed at monolayers of the phospholipid L-alpha-dimyristoylphosphatidic acid (DMPA) and hexadecanesulfonic acid (HDSA) at the air-water interface, and undergoes chemical polymerisation under conditions where bulk polymerisation does not occur.     

Langmuir monolayers of a photoisomerizable macrocycle surfactant

An amphiphilic photoisomerizable macrocycle has been prepared that forms stable Langmuir monolayers at the air-water interface. The hydrophilic core of the molecule switches between closed and open isomers upon irradiation by the appropriate wavelengths of light. Isotherm measurements, Brewster angle microscope images, and atomic force micrographs (of transferred Langmuir-Blodgett films) suggest a phase transition between a face-on to a tilted edge-on molecular orientation as a function of surface concentration. In the face-on phase, in situ photoisomerization results in a reversible increase in surface pressure due to greater molecular crowding in the open configuration.     

Chiral recognition of dipeptides in Langmuir monolayers

The recognition of the enantiomeric couples of ditryptophan in Langmuir films of N-hexadecanoyl-l-proline was investigated by surface pressure–area (π–A) isotherm measurements and Brewster angle microscopy experiments. The π–A isotherms relative to the films including the enantiomeric dipeptides show small differences whereas an evident enantiodiscrimination is observed by Brewster angle microscopy images.     

Miscibility and segregated structures in mixed Langmuir monolayers

The phase behavior and morphology of segregated structures are considered for mixed Langmuir monolayers, which comprise a type of supramolecular polymer having a complex internal structure mixed with a long chain fatty acid. We fabricated two different series of mixed monolayers from a polyglutamate (PG) copolymer having 30% octadecyl ester side chains and 70% methyl ester side chains and fatty acids. These mixed monolayers deposited on a solid substrate were studied by pressure-area diagram measurements, X-ray analysis, and atomic force microscopy. Stearic acid (STA) and hexacosanoic acid (HCA) with alkyl chain lengths of 17 and 25 carbon atoms, respectively, were used as low molecular weight components. For the mixture PG:STA, where the length of the STA molecules is comparable to the length of the PG side chains, we observed the formation of partially miscible monolayers. These mixtures exhibit a nanometer scale domain morphology formed by the STA molecules dissolved in the outer shell of the PG monolayer. In contrast, for the PG:HCA mixture we observed a strong tendency for microphase separation and the formation of well-defined submicron segregated structures in the monolayers. Lateral compression of the mixed monolayers to a point close to the collapse pressure promotes microphase separation in both types of mixed monolayers with the formation of anisotropic surface morphology and oriented domains.     

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.     

Pattern formation and morphology evolution in Langmuir monolayers

We present a study of how patterns formed by Langmuir monolayer domains of a stable phase, usually solid or liquid condensed, propagate into a metastable one, usually liquid expanded. During this propagation, the interface between the two phases moves as the metastable phase is transformed into the more stable one. The interface becomes unstable and forms patterns as a result of the competition between a chemical potential gradient that destabilizes the interface on one hand and line tension that stabilizes the interface on the other. During domain growth, we found a morphology transition from tip splitting to side branching; doublons were also found. These morphological features were observed with Brewster angle microscopy in three different monolayers at the water/air interface: dioctadecylamine, ethyl palmitate, and ethyl stearate. In addition, we observed the onset of the instability in round domains when an abrupt lateral pressure jump is made on the monolayer. Frequency histograms of unstable wavelengths are consistent with the linear-instability dispersion relation of classical free-boundary models. For the case of dendritic morphologies, we measured the radius of the dendrite tip as a function of the dendrite length as well as the spacing of the side branches along a dendrite. Finally, a possible explanation of why Langmuir monolayers present this kind of nonequilibrium growth patterns is presented. In the steady state, the growth behavior is determined by Laplace's equation in the particle density with specific boundary conditions. These equations are equivalent to those used in the theory of morphology diagrams for two-dimensional diffusional growth, where morphological transitions of the kind observed here have been predicted.     

Mixed Langmuir monolayers of gramicidin A and fluorinated alcohols

Mixed monolayers of gramicidin A (GA) and three alcohols, differing in the degree of fluorination, namely C18OH, F18OH, and F8H10OH have been investigated by means of: surface manometry (pi-A isotherms) and Brewster angle microscopy (BAM) aiming at finding appropriate molecules for incorporating gramicidin A for a biosensor design. Our results proved that only the semifluorinated alcohol is appropriate material for this purpose since it forms miscible and homogeneous monolayers with GA within the whole concentration range. The experimental results have been supported by the calculations of van der Waals energy profiles using the Insight II program. Both the hydrogenated and perfluorinated alcohols were found to aggregate at higher surface pressures, which exclude their application for gramicidin-based biosensor construction.     

Langmuir monolayer and Langmuir–Blodgett films of amphiphilic triblock copolymers with water-soluble middle block

Langmuir monolayers and Langmuir–Blodgett (LB) film morphology of amphiphilic triblock copolymers are studied using surface pressure-area measurements and atomic force microscopy (AFM), respectively. The triblock copolymers are composed of long water-soluble poly(ethylene oxide) (PEO) chains as middle block with very short poly(perfluorohexylethyl methacrylate) (PFMA) end blocks. The surface pressure-area isotherms show phase transitions in the brush regime. This phase transition is due to a rearrangement of PFMA block at the air–water interface. It becomes more significant with increasing PFMA content in the copolymer. LB films transferred at low surface pressures from the air–water interface to hydrophilic silicon substrates show surface micelles in the size range of 50–100 nm. A typical crystalline morphology of the corresponding PEO homopolymer is observed in LB films of copolymers with very short PFMA blocks, transferred in the brush region at high surface pressure. This crystallization is hindered with increasing PFMA content in the copolymer.