Aggregation and layering transitions in thin films of X-, T-, and anchor-shaped bolaamphiphiles at the air-water interface

Aggregation in Langmuir films is usually understood as being a disorderly grouping of molecules turning into chaotic three-dimensional aggregates and is considered an unwanted phenomenon causing irreversible changes. In this work we present the studies of 11 compounds from the group of specific surfactants, known as bolaamphiphiles, that exhibit reversible aggregation and, in many cases, transition to well-defined multilayers, which can be considered as a layering transition. These bolaamphiphiles incorporate rigid π-conjugated aromatics as hydrophobic cores, glycerol-based polar groups and hydrophobic lateral chains. Molecules of different shapes (X-, T-, and anchor) were studied and compared. The key property of these compounds is the partial fluorination of the lateral chains linked to the rigid cores of the molecules. The most interesting feature of the compounds is that, depending on their shape and degree of fluorination, they are able to resist aggregation and preserve a monolayer structure up to relatively high surface pressures (T-shaped and some X-shaped molecules), or create well-defined trilayers (X- and anchor-shaped molecules). Experimental studies were performed using Langmuir balance, surface potential and X-ray reflectivity measurements.     

Rigid Lipid Membranes and Nanometer Clefts: Motifs for the Creation of Molecular Landscapes

Amphiphilic lipids associate in water spontaneously to form micelles, vesicles, monolayers, or biological membranes. These aggregates are soft and their shape can be changed easily. They behave like complex fluids because they are merely held together by weak, nondirected forces. The most important characteristic of these monolayers is their ability to dissolve hydrophobic molecules in the form of freely movable monomers. The fluid molecular layers are not suitable to anchor the components of chain reactions. However, if the alkyl chains are replaced by rigid skeletons or if the head groups are connected through intermolecular interactions, the aggregates become rigid and their fluid solvent character is lost. The construction of chiral surfaces by synkinesis (synthesis of noncovalent compounds) and of enzyme‐type surface clefts of defined size can now be carried out by using rigid lipid membranes. Monolayers and nanometer pores on solid substrates attain sharp edges, and upright nanometer columns on smooth surfaces no longer dissipate. Five examples illustrate the advantages of using rigid molecular assemblies: 1) Cationic domains of rigid edge amphiphiles in fluid membranes act as manipulable ion channels. 2) Spherical micelles, micellar helical fibers, and vesicular tubes can be dried and stored as stable material. Molecular landscapes form on smooth surfaces. 3) α,ω‐Diamide bolaamphiphiles form rigid nanometer‐thick walls on smooth surfaces and these barriers cannot be penetrated by amines. Around steroids and porphyrins, they form rigid nanometer clefts whose walls and water‐filled centers can be functionalized. 4) The structure of rigid oligophenylene‐ and quinone monolayers on electrodes can be changed drastically and reversibly by changing the potential. 5) 10¹⁰ Porphyrin cones on a 1‐cm² gold electrode can be controlled individually by AFM‐ and STM‐tips and investigated by electrochemical, photochemical, and mechanical means. In summary, rigid monolayers and bilayers allow the formation of a great variety of membrane structures that cannot be obtained from classical fluid alkyl amphiphiles.     

Preparation of microscopic and planar oil-water interfaces that are decorated with prescribed densities of insoluble amphiphiles

Langmuir monolayers (monolayers of insoluble molecules formed at the surface of water), and associated Langmuir-Blodgett/Schaefer monolayers prepared by transfer of Langmuir films to the surfaces of solids, are widely used in studies aimed at understanding the physicochemical properties of biological and synthetic molecules at interfaces. In this article, we report a general and facile procedure that permits transfer of Langmuir monolayers from the surface of water onto microscopic and planar interfaces between oil and aqueous phases. In these experiments, a metallic grid supported on a hydrophobic solid is used to form oil films with thicknesses of 20 mum and interfacial areas of 280 mum x 280 mum. Passage of the supported oil films through a Langmuir monolayer is shown to lead to quantitative transfer of insoluble amphiphiles onto the oil-water interfaces. The amphiphile-decorated oil-water interfaces hosted within the metallic grids (i) are approximately planar, (ii) are sufficiently robust mechanically so as to permit further characterization of the interfaces outside of the Langmuir trough, (iii) can be prepared with prescribed and well-defined densities of amphiphiles, and (iv) require only approximately 200 nL of oil to prepare. The utility of this method is illustrated for the case of the liquid crystalline oil 4-pentyl-4'-cyanobiphenyl (5CB). Transfer of monolayers of either dilauroyl- or dipalmitoylphosphatidylcholine (DLPC and DPPC, respectively) to the nematic 5CB-aqueous interface is demonstrated by epifluorescence imaging of fluorescently labeled lipid and polarized light imaging of the orientational order within the thin film of nematic 5CB. Interfaces prepared in this manner are used to reveal key differences between the density-dependent phase properties of DLPC and DPPC monolayers formed at air-water as compared to that of nematic 5CB-aqueous interfaces. The methodology described in this article should be broadly useful in advancing studies of the interfacial behavior of synthetic and biological molecules at liquid-liquid interfaces.     

Synthesis of an Open‐Cage Structure POSS Containing Various Functional Groups and Their Effect on the Formation and Properties of Langmuir Monolayers

Recently, silsesquioxanes have been recognized as a new group of film‐forming materials. This study has been aimed at determining the effect of the kind of functional groups present in two different open‐cage structure POSS molecules on the possibility of the formation of Langmuir monolayers and their properties. To achieve this goal, two new POSS derivatives (of open‐cage structures) containing polyether and fluoroalkyl functional groups have been synthesized on the basis of a hydrosilylation process. An optimization of the process was performed, which makes it possible to obtain the above‐mentioned derivatives with high yields. In the next step, the Langmuir technique was applied to measurements of the surface pressure (π) ? the mean molecular area (A) isotherms during the compression of monolayers formed by molecules of the two POSS derivatives considered. Subsequently, the monolayers were transferred onto quartz plates according to the Langmuir–Blodgett technique. Both derivatives are able to form insoluble Langmuir films at the air–water interface, which can be transferred onto a solid substrate and effectively change its wetting properties.     

Thin films of discotic liquid crystals and their applications

ABSTRACT

Discotic liquid crystals (DLCs) are considered as fascinating systems due to their unique property of self-assembly to yield different columnar structures. DLCs are organic semiconductors and create pathways for the development of numerous optical and electrical devices. The thin films of DLCs can be considered as low dimensional system which can exhibit remarkable optical and physical properties. In this article, we present a review on ultrathin films of some interesting DLC molecules at air–water and air–solid interfaces. The Langmuir monolayer and Langmuir–Blodgett films of DLC molecules are extensively studied. The ultrathin films of DLC molecules can yield highly anisotropic layer wherein the molecular orientation and aggregation can have large impact on the physicochemical properties of the film. Different surface phases with different molecular orientations as function of surface density and temperature can be obtained by forming the Langmuir monolayer of the DLC molecules at the air–water interface. The Langmuir monolayer in a particular phase can be deposited onto the active area of a device layer-by-layer by employing a highly controlled Langmuir–Blodgett technique. Here, we report some interesting results related on molecular orientation of the DLC molecules at different interfaces. Such aggregation of DLC molecules in ultrathin films may find applications in thin film-based electro-optical devices.     

Molecular controlled nano-devices

In this perspective we present several examples of the ability to control electronic and magnetic properties of nano-devices by adsorbing on their surfaces organized self-assembled monolayers (SAM) of organic molecules. The work presented focuses on research in which we were involved and is aimed at demonstrating the ability to control physical properties of metal and semiconductor films by complementing them with the properties of a SAM. The organization of molecules on a surface produces a pseudo two-dimensional dipole layer, owing to the dipolar property of each of the molecules. The field confined in the layer could be enormous, however the molecules are either depolarized or charge is transferred between the substrate and the layer so as to reduce the energy of the dipole layer. This charge transfer process can be exploited for the use of hybrid-organic-inorganic devices as sensors, as wavelength specific light detectors, or for varying the critical temperature in semiconductor ferromagnets. The concept presented here, for combining electronic properties of organic molecules with those of the inorganic substrate, is another venue toward "molecular controlled electronics".     

Oligofunctional amphiphiles featuring geometric core group preorganization: synthesis and study of Langmuir and Langmuir-Blodgett films

Based on the principle of supramolecular preorganization, a new type of oligofunctional amphiphile, of which compounds 1-4 are representative structures, has been designed and synthesized. The typical feature of their structure is a highly rigid and geometrically well-defined central unit composed of ethynylene substituted aromatic spacers with different numbers of amphiphilic segment groups (also of a rigid geometric design) attached to it. The molecules form well-defined Langmuir films when spread from a solution at the air/water interface or when a 10(-4) M aqueous CaCl2 solution was used as the subphase. By analysis of the surface pressure-surface area (pi-A) isotherms, information on the packing behavior and orientation of the amphiphilic molecules depending on the molecular structure could be obtained. Morphological characterization of the dynamic process of monolayer compression at the air/water interface was carried out by Brewster angle microscopy, illustrating several phase states visualized as snap shots. Thin monolayer films produced on a 10(-4) M aqueous CaCl2 subphase can be transferred to a mica solid support by the Langmuir-Blodgett technique. Tapping mode atomic force microscopy reveals a surface topography of the monofilms composed of 1 and 3 that differ in roughness and also in the properties of elasticity, hardness and adhesive strength. X-Ray crystal structure analysis of three relevant intermediate compounds of the synthesis were successfully determined giving an indication of the potential structural features inherent in the new amphiphiles.     

Synthesis and ordering of two-dimensional polymers

The work to be discussed in this lecture departs from the usual focus of polymer science on linear chains and explores the “bulk” synthesis and properties of polymer molecules that can be considered shape-persistent molecular objects. Shapes that are particularly interesting are those not common in the conformational space of linear chains, for example, two-dimensional polymers shaped as plates or discs and macromolecules shaped as cylinders or parallelepipeds. The lecture focuses on a molecular object which is a rigid and internally anisotropic two-dimensional polymer with planar dimensions greater than its thickness. The shape-granting skeleton of this two-dimensional polymer is built by covalent bonds. We have so far developed three different strategies for their bulk synthesis, all involving systems in which reactive oligomers organize spontaneously into the necessary planar assemblies to form the object. In one strategy molecular recognition events such as homochiral interactions play a key role in the formation of the two-dimensional flat polymers /1/. A different methodology relies on nanophase separation in rodcoil block molecules in which a rigid segment is covalently bonded to a flexible one sharing the same backbone. The third strategy involves the folding of oligomers into hairpin structures which self assemble into two-dimensional liquids. In these two last strategies the layered rodcoils or hairpins react to form the covalent backbones necessary to grant shape to the object. A computer simulation relevant to the experimental system suggests that large two-dimensional polymers can be formed by extremely short backbones. The lecture will also describe examples of unique properties in advanced materials that could emerge from these rigid two-dimensional objects. These examples include. materials with self-organized surfaces of high chemical definition and temporal stability, self assembling membranes, molecular reinforcement, and films with remarkably stable electrical or optical properties.     

Inelastic electron tunneling spectroscopy of alkane monolayers with dissimilar attachment chemistry to gold

We compare the low-temperature electron transport properties of alkyl monolayers which utilize different attachment strategies to gold. Inelastic electron tunneling spectroscopy (IETS) and current-voltage analysis were performed on molecular junctions incorporating alkyl-dithiocarbamate and alkanethiolate self-assembled monolayers of similar length. Alkyl-dithiocarbamate monolayers were formed by the condensation of dioctylamine or didecylamine with carbon disulfide in anhydrous ethanol and compared to alkanethiolate SAMs of 1-decanethiol and 1-dodecanethiol, respectively. The electron transport properties of each monolayer were examined using magnetically assembled microsphere junctions under high-vacuum conditions at low temperature. IETS was employed to differentiate the films on the basis of vibrational modes which are characteristic of each method of attachment. We use quantum chemical simulations of model compounds to calculate frequency and intensity of predicted signals arising from molecular vibrations to aid in the accurate assignment of the spectra. A qualitative comparison of our devices also reveals an increase in current density when utilizing dithiocarbamate attachment to gold compared to alkanethiolate molecules of similar length.     

On sub-T(g) dewetting of nanoconfined liquids and autophobic dewetting of crystallites

The glass transition temperature (T(g)) of thin films is reduced by nanoconfinement, but it is also influenced by the free surface and substrate interface. To gain more insights into their contributions, dewetting behaviors of n-pentane, 3-methylpentane, and toluene films are investigated on various substrates as functions of temperature and film thickness. It is found that monolayers of these molecules exhibit sub-T(g) dewetting on a perfluoro-alkyl modified Ni substrate, which is attributable to the evolution of a 2D liquid. The onset temperature of dewetting increases with film thickness because fluidity evolves via cooperative motion of many molecules; sub-T(g) dewetting is observed for films thinner than 5 monolayers. In contrast, monolayers wet substrates of graphite, silicon, and amorphous solid water until crystallization occurs. The crystallites exhibit autophobic dewetting on the substrate covered with a wetting monolayer. The presence of premelting layers is inferred from the fact that n-pentane crystallites disappear on amorphous solid water via intermixing. Thus, the properties of quasiliquid formed on the crystallite surface differ significantly from those of the 2D liquid formed before crystallization.     

Invited Lecture. Studies of liquid crystal monolayers and films by optical second harmonic generation

It is shown that optical second harmonic generation can be used to probe a number of important properties of liquid crystals: second order non-linearity of liquid crystal molecules, polar ordering and orientation of liquid crystal monolayers at various interfaces, and bulk alignment of molecules in supported and freely suspended films. Surface effects on bulk alignment can also be investigated.     

Critical influence of the alkane length in surface and liquid-crystalline properties of perfluorodecyl-n-alkanes

Differential scanning calorimetry (DSC) measurements together with texture observation with polarizing microscope revealed the presence of a smectic phase for shorter homologues. Film forming properties of all the perfluorodecyl-n-alkanes synthesized here at the air-water interface were thoroughly investigated. Nearly all the compounds investigated were found to be capable of Langmuir monolayer formation when spread at the water-air interface, apart from semifluorinated alkanes (SFA) containing short hydrogenated moiety (n < 10), which partially dissolve in the water subphase. The investigated homologous series of SFA can be divided into four groups, regarding their liquid-crystalline and surface properties. The first group includes molecules with n = 6-10, which form smectic phases in the bulk and do not form stable monolayers at the free water surface. SFA containing 11 or 12 hydrogenated carbons belong to the second group, forming smectic phases at elevated temperatures, which transform into 3D ordering upon cooling. These molecules are found to form Langmuir monolayers of intermediate stability. The remaining groups contain perfluorodecylalkanes with n > 12, which differ in their calorimetric properties; however, both form very stable films on the water surface and do not exhibit liquid-crystalline properties.     

Influence of monolayer state on spectroscopy and photoisomerization of an amphiphilic styryl-pyridinium dye on a solid substrate

The spectroscopy and photochromic properties of transferred monolayers of the amphiphilic styryl-pyridinium dye 4-(3',4'-dimethoxystyryl)-N-octadecylpyridinium perchlorate (DMPOP) were studied at different conditions during their transfer. The emission maxima of the monolayers transferred from the air-water interface in the liquid-expanded phase are strongly dependent on the surface pressure applied during the transfer process, even at values when the area per molecule is 2-3 times larger than the area occupied by a chromophore. In monolayers transferred from the liquid-condensed phase, the presence of a different kind of aggregates was observed. The fluorescence emission properties of the monolayers can be reversibly modulated by photoinduced E-Z isomerization. A blue shift up to 72 nm in the emission maximum, depending on the transfer conditions of the films, can be obtained by irradiation with blue light, and partially recovered (a red shift of up to 26 nm) with UV radiation. The rate at which the first process (E-->Z) takes place is drastically reduced in monolayers transferred from the liquid-condensed phase as compared to those transferred from the liquid-expanded one. However, the rate of the reverse reaction (Z-->E) is not significantly altered. These properties make DMPOP a promising material for the preparation of Langmuir-Blodgett films, whose properties can be effectively controlled by the transfer conditions and subsequently optically modulated, for potential applications as photonics devices for data storage.     

Interfacial rheology and structure of tiled graphene oxide sheets

The hydrophilic nature of graphene oxide sheets can be tailored by varying the carbon to oxygen ratio. Depending on this ratio, the particles can be deposited at either a water-air or a water-oil interface. Upon compression of thus-created Langmuir monolayers, the sheets cover the entire interface, assembling into a strong, compact layer of tiled graphene oxide sheets. With further compression, the particle layer forms wrinkles that are reversible upon expansion, resembling the behavior of an elastic membrane. In the present work, we investigate under which conditions the structure and properties of the interfacial layer are such that free-standing films can be obtained. The interfacial rheological properties of these films are investigated using both compressional experiments and shear rheometry. The role of surface rheology in potential applications of such tiled films is explored. The rheological properties are shown to be responsible for the efficiency of such layers in stabilizing water-oil emulsions. Moreover, because of the mechanical integrity, large-area monolayers can be deposited by, for example, Langmuir-Blodgett techniques using aqueous subphases. These films can be turned into transparent conductive films upon subsequent chemical reduction.     

Phase behavior and viscoelastic properties of trisilanolcyclohexyl-POSS at the air/water interface

A trisilanol polyhedral oligomeric silsesquioxane (POSS), trisilanolcyclohexyl-POSS (TCyP), has recently been reported to undergo a series of phase transitions from traditional Langmuir monolayers to unique rodlike hydrophobic aggregates in multilayer films that are different from "collapsed" morphologies seen in other systems at the air/water interface. This paper focuses on the phase transitions and morphology of films varying in average thickness from monolayers to trilayers and the corresponding viscoelastic properties of trisilanolcyclohexyl-POSS molecules at the air/water interface by means of surface pressure-area per molecule (Pi-A) isotherms, Brewster angle microscopy (BAM), and interfacial stress rheometry (ISR) measurements. The morphology studies by BAM reveal that the TCyP monolayer can collapse into different 3D structures by homogeneous or heterogeneous nucleation mechanisms. For homogeneous nucleation, analysis by Vollhardt et al.'s nucleation and growth model reveals that TCyP collapse is consistent with instantaneous nucleation with hemispherical edge growth at Pi = 3.7 mN.m(-1). Both surface storage (Gs') and loss (Gs") moduli obtained by ISR reveal three different non-Newtonian flow regimes that correlate with phase transitions in the Pi-A isotherms: (A) A viscous liquidlike "monolayer"; (B) a "biphasic regime"between a liquidlike viscous monolayer and a more rigid trilayer; and (C) an elastic solidlike "trilayer". These observations provide interesting insights into collapse mechanisms and structures in Langmuir films.     

Investigation of the protonation state of novel cationic lipids designed for gene transfection

In order to be used in versatile DNA delivery systems, novel cationic lipids were synthesized. The head groups of the new compounds represented by monoamines or oligoamines can be charged or uncharged depending on the environmental pH. Since their pK values are unknown, the protonation properties of these lipids have been studied in a wide pH range. In our experiments, the amphiphilic molecules were organized as a Langmuir monolayer at the air-water interface. Total reflection X-ray fluorescence (TRXF) was used to determine the 2D concentration of bromide counterions bound to a positively charged (protonated) Langmuir monolayer. The protonation rate of the novel cationic lipids was estimated by comparing the fluorescence intensity with that of dioctadecyldimethylammonium bromide monolayers as a reference. TRXF investigations were supplemented with results of film-balance measurements, grazing incidence X-ray diffraction, and X-ray reflectivity data. The results obtained display that the monolayers of all studied compounds are completely uncharged at pH values above 10. In the investigated pH region, the highest protonation rate of the monolayers is observed at pH 3. The influence of the monolayer packing density on the protonation properties is clearly shown.     

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.     

N,N,N＇,N＇-四苄基取代方块菁染料LB膜研究

方块菁染料在有机光导材料^[1,2]、有机太阳能存储^[2,3]、光记录^[4、有机光盘中红外吸收器^[4]以及光纤识别功能薄膜等领域中有着广泛应用前景.     

Compressibility study of quaternary phospholipid blend monolayers

The mechanical properties of liposome membranes are strongly dependent on type and ratio of lipid compounds, which can have important role in drug targeting and release processes when liposome is used as drug carrier. In this work we have used Brewster's angle microscopy to monitor the lateral compression process of lipid monolayers containing as helper lipids either distearoyl phosphatidylethanolamine (DSPE) or dioleoyl phophatidylethanolamine (DOPE) molecules on the Langmuir trough. The compressibility coefficient was determined for lipid blend monolayers containing the helper lipids above, cholesterol, distearoyl phosphatidylcholine (DSPC) and pegylated-DSPE at room temperature. Two variables, the cholesterol fraction and the ratio ρ between the helper lipid (either DSPE or DOPE) and the reference lipid DSPC, were studied by multivariate analysis to evaluate their impact on the compressibility coefficient of the monolayers. The cholesterol level was found to be the most significant variable for DSPE blends while the ratio ρ was the most significant one for DOPE blend monolayers. It was also found that these two variables can exhibit positive interaction and the same compressibility value can be obtained with different blend compositions.     

Cationic Gemini surfactant at the air/water interface

The surface properties and structures of a cationic Gemini surfactant with a rigid spacer, p-xylyl-bis(dimethyloctadecylammonium bromide) ([C(18)H(37)(CH(3))(2)N(+)CH(2)C(6)H(4)CH(2)N(+)(CH(3))(2)C(18)H(37)],2Br(-), abbreviated as 18-Ar-18,2Br(-1)), at the air/water interface were investigated. It is found that the surface pressure-molecular area isotherms observed at different temperatures do not exhibit a plateau region but display an unusual "kink" before collapse. The range of the corresponding minimum compressibility and maximum compressibility modulus indicates that the monolayer is in the liquid-expanded state. The monolayers were transferred onto mica and quartz plates by the Langmuir-Blodgett (LB) technique. The structures of monolayers at various surface pressures were studied by atomic force microscopy (AFM) and UV-vis spectroscopy, respectively. AFM measurements show that at lower surface pressures, unlike the structures of complex or hybrid films formed by Gemini amphiphiles with DNA, dye, or inorganic materials or the Langmuir film formed by the nonionic Gemini surfactant, in this case network-like labyrinthine interconnected ridges are formed. The formation of the structures can be interpreted in terms of the spinodal decomposition mechanism. With the increase of the surface pressure up to 35 mN/m, surface micelles dispersed in the network-like ridges gradually appear which might be caused by both the spinodal decomposition and dewetting. The UV-vis adsorption shows that over the whole range of surface pressures, the molecules form a J-aggregate in LB films, which implies that the spacers construct a pi-pi aromatic stacking. This pi-pi interaction between spacers and the van der Waals interaction between hydrophobic chains lead to the formation of both networks and micelles. The labyrinthine interconnected ridges are formed first because of the rapid evaporation of solvent during the spreading processes; with increasing surface pressure, some of the alkyl chains reorient from tilting to vertical, forming surface micelles dispersed in the network-like ridges due to the strong interaction among film molecules.