Langmuir-Blodgett films of octadecanethiol--properties and potential applications

Octadecanethiol (ODT) is known to form self-assembled monolayer on noble metal surfaces which has potential technological applications. Langmuir-Blodgett (LB) technique is another useful method of obtaining highly ordered assembly of molecules. It is of interest to find whether ODT molecules can also form a stable Langmuir monolayer which facilitates the preparation of LB films. In literature, it has been reported that ODT molecules form an unstable Langmuir monolayer. We have studied the stability of the monolayer of the ODT molecules at air-water interface using surface manometry and microscopy techniques. We find the monolayer to be stable on ultrapure water of resistivity greater than 18MOmega cm. However, the behavior changes in the presence of even small amount of additives like NaOH or CdCl2 in the subphase. Our AFM studies on the LB films of ODT deposited from ion-free ultrapure water showed streak-like bilayer domains. The LB films of ODT deposited from CdCl2 containing aqueous subphase yield dendritic domains of the complexed unit grown over ODT monolayer. These nanostructures on surfaces may have potential applications in molecular electronics.     

Fabrication of densely packed titania nanosheet films on solid surface by use of Langmuir-Blodgett deposition method without amphiphilic additives

Densely packed exfoliated nanosheet films such as Ti0.91O2, Ti0.8M0.2O2 (M = Co, Ni), Ti0.6Fe0.4O2, and Ca2Nb3O10 on solid substrates were prepared by the LB transfer method without any amphiphilic additives at the air-water interface. Nanosheet crystallites covered nearly 95% on the solid surface with minimum overlapping of nanosheets. The LB transfer method of the Ti0.91O2 nanosheet monolayer film is applicable for not only hydrophilic substrates such as quartz, silicon, indium-tin oxide (ITO), and glass but also the hydrophobic Au surface. On the basis of these points, the LB transfer method has advantages compared to the alternating layer-by-layer method, which makes use of oppositely charged polyelectrolytes such as poly(ethylenimine) (PEI). Adsorption of hydrophobic Ti0.91O2 nanosheets at the air-water interface is responsible for this LB transfer deposition method. The addition of tetrabutylammonium bromide into the subphase assisted the adsorption, causing an increase in the adsorbed amount of Ti0.91O2 nanosheets at the air-water interface.     

Spectroscopic studies on molecular recognition capabilities of a nucleolipid bearing thymine headgroup to adenosine

The Langmuir-Blodgett (LB) films of octadecanoyl ester of 1-(2-carboxyethyl) thymine deposited from pure water and aqueous adenosine subphases were investigated by ultraviolet-visible (UV-vis), Fourier transform infrared-attenuated total reflection (FTIR-ATR), and Fourier transform surface-enhanced Raman scattering (FT-SERS) spectroscopy. The obtained spectral results indicate that the adenosine molecules in the subphase can be transferred onto solid substrates by LB techniques as a result of the formation of base pairs at the air/water interface. UV-vis spectra alternations indicated that, with increasing adenosine concentration in subphase, more adenosine molecules were recognized by nucleolipid monolayer and were transferred onto the quartz substrates. The closed-packing of the constituent molecules facilitates the photodimerization of the thymine moieties in the headgroup under ultraviolet irradiation. FTIR-ATR results suggest that the hydrocarbon chains of nucleolipid in the LB films deposited from pure water and aqueous adenosine take on a close-packed all trans conformation. By analyzing the FT-SERS spectra results, it can be deduced that the orientation of nucleobase in the headgroup is different before and after the recognition effect occurred. For LB film deposited from pure water, the nucleobases are lying flat on the silver substrates; whereas for LB film deposited from aqueous adenosine, the base pairs take an end-on adsorption on silver substrate.     

Thermodynamic and spectroscopic studies on the nickel arachidate-RNA polymerase Langmuir-Blodgett monolayer

The Langmuir-Blodgett (LB) monolayers offer a unique system to study molecular interaction at the air-water interface with reduced dimensionality. In order to develop this further to follow macromolecular interactions at equilibrium, we first characterized the Ni (II)-arachidate (NiA) monolayer at varying conditions. Subsequently, the interaction between NiA and histidine-tagged RNA polymerase (HisRNAP) were also studied. LB films of arachidic acid-NiA and NiA-RNAP with different mole fractions were fabricated systematically. Surface pressure versus area per molecule (P-A) isotherms were registered, and the excess Gibbs energy of mixing was calculated. The LB films were then deposited on solid supports for Fourier transform infrared (FTIR) spectroscopic measurements. The FTIR spectra revealed the change in the amount of incorporated Ni (II) ions into the arachidic acid monolayer with the change in pH and the increasing mole fraction of RNAP in the NiA monolayer with its increasing concentration in the subphase. The system developed here seems to be robust and can be utilized to follow macromolecular interactions.     

Time-dependent complexation of glucose-reduced gold nanoparticles with octadecylamine Langmuir monolayers

We report on the reduction of aqueous chloroaurate ions by glucose to form gold nanoparticles of uniform size. We further demonstrate the complexation of these particles with octadecylamine (ODA) monolayers at the air-water interface. Pressure-area (pi-A) isotherms as a function of time of complexation revealed a significant expansion of the monolayer. Surface pressure variation with time for constant areas after spreading of the monolayer was carried out to observe the kinetics of complexation of the colloidal particles at the interface. The kinetics of complexation of the particles at the interface was also monitored by Brewster angle microscopy (BAM) measurements. Langmuir-Blodgett films of the particles complexed with ODA were formed at a subphase pH of 9 onto different substrates. Quartz crystal microgravimetry (QCM) was used to quantify the amount of particles deposited per immersion cycle of the quartz crystal. The LB films were further characterized by UV-vis and transmission electron microscopy (TEM) measurements. TEM measurements indicate a close packed and equidistant arrangement of colloidal particles in the LB film, probably due to hydrogen-bonding interactions.     

Deposition and photopolymerization of phase-separated perfluorotetradecanoic acid-10,12-pentacosadiynoic acid Langmuir-Blodgett monolayer films

Mixed monolayer surfactant films of perfluorotetradecanoic acid and the photopolymerizable diacetylene molecule 10,12-pentacosadiynoic acid were prepared at the air-water interface and transferred onto solid supports via Langmuir-Blodgett (LB) deposition. The addition of the perfluoroacid to the diacetylene surfactant results in enhanced stabilization of the monolayer in comparison with the pure diacetylene alone, allowing film transfer onto a solid substrate without resorting to addition of cations in the subphase or photopolymerization prior to deposition. The resulting LB films consisted of well-defined phase-separated domains of the two film components, and the films were characterized by a combination of atomic force microscope (AFM) imaging and fluorescence emission microscopy both before and after photopolymerization into the highly emissive "red form" of the polydiacetylene. Photopolymerization of the monolayer films resulted in the formation of diacetylene bilayers, which were highly fluorescent, with the apparent rate of photopolymerization and the fluorescence emission of the films being largely unaffected by the presence of the perfluoroacid.     

Directionally oriented LB films of an OPE derivative: assembly, characterization, and electrical properties

Langmuir films have been fabricated from 4-[4'-(4'-thioacetyl-phenyleneethynylene)-phenyleneethynylene]-aniline (NOPES) after cleavage of the thioacetyl protecting group. Characterization by surface pressure vs area per molecule isotherms and Brewster angle microscopy reveal the formation of a high quality monolayer at the air-water interface. One layer Langmuir-Blodgett (LB) films were readily fabricated by the transfer of the NOPES Langmuir film onto solid substrates. X-ray photoelectron spectroscopy (XPS), surface polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), and quartz crystal microbalance (QCM) experiments conclusively demonstrate the formation of one layer LB films in which the functional group associated with binding to the substrate can be tailored by the film transfer conditions. Using LB methods this molecule could be transferred to gold samples with either the amine or thiol group attached to the gold surface. The amine group is directly attached to the gold substrate (Au-NH(2)-OPE-SH) when the substrate is initially immersed in the subphase and withdrawn during the transfer process; in contrast, monomolecular films in which the thiolate group is attached to the gold substrate (Au-S-OPE-NH(2)) are obtained when the substrate is initially out of the subphase and immersed during the transfer process. The morphology of these films was analyzed by atomic force microscopy (AFM), showing the formation of homogeneous layers. Film homogeneity was confirmed by cyclic voltammetry, which revealed a large passivation of gold electrodes covered by NOPES monolayers. Electrical properties for both polar orientated junctions have been investigated by scanning tunnelling microscopy (STM), with both orientations featuring a nonrectifying behavior.     

Formation, structure, and morphology of triazole-based Langmuir-Blodgett films

The formation, morphology, and structure of two-dimensional Langmuir-Blodgett (LB) assemblies of octadecyltriazole (ODT)-based metal-containing oligomers presenting, in the case of iron, the spin-crossover phenomenon is studied with Brewster angle microscopy, IR dichroism, X-ray diffraction, and atomic force microscopy. Two processes occurring at the air-water interface are confirmed to dominate the mechanism of formation of these LB films, the instability of the coordination polymers at the air-water interface and recoordination of metal ions in the subphase at the interface during the LB deposition process. The Langmuir film allowing the LB film formation is mostly made of ODT. The films do present a lamellar structure in which the ODT molecules are tilted and incorporate coordinated isolated metal ions and oligomers of metal ions. The morphology of the LB films is globally flat but with a rather high roughness resulting from inhomogeneities related to phenomena occurring during the LB film formation. These observations are in agreement with the relative affinity of the metal ions with ODT and the relative stability of the coordination polymers at the air-water interface, which have been determined for the group Cu-Fe-Co-Ni.     

Macroscopic alignment of graphene stacks by Langmuir-Blodgett deposition of amphiphilic hexabenzocoronenes

We present structural studies of Langmuir (L) and Langmuir-Blodgett (LB) films of new amphiphilic hexa-peri-hexabenzocoronene (HBC) discotics, carrying five branched alkyl side chains and one polar group. The polar group is either a carboxylic acid moiety or an electron acceptor moiety (anthraquinone). Grazing-incidence X-ray diffraction (GIXD) and X-ray reflectivity, both utilizing synchrotron radiation, show that these amphiphilic HBCs form well-defined Langmuir monolayers at the air-water interface, with a pi-stacked columnar structure where the HBC cores are rotated around the surface normal and tilted relative to the water surface. The intercolumnar distance is 20 A. The HBCs are confined to a layer lying on top of the layer of polar groups that are in contact with the water subphase. Efficient transfer of the monolayer of the anthraquinone-substituted HBC derivative to hydrophobic quartz substrates by vertical dipping gave well-defined multilayer Y-type LB films. Polarized optical spectroscopy, GIXD, and X-ray reflectivity measurements show that the LB films consist of at least two phases. Heating the films results in an irreversible rearrangement to a single macroscopically aligned phase of hexagonally packed columns oriented along the dipping direction with disk planes perpendicular to the columnar axes and stacked in a cofacial manner. This phase transition is analogous to the reversible transition observed in the bulk material.     

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.     

A novel method for monolayer deposition: water seepage method

A method has been developed to deposit monolayers of a supramolecular assembly of amphiphiles onto solid substrates. A stable monolayer in a solid state is allowed to form at the air-water interface. The subphase is then allowed to seep out at a controlled rate and the monolayer descends and ultimately is deposited on the solid substrate. The quality of the films thus formed is comparable to that of the film deposited by the Langmuir-Blodgett technique. The method is simple, cost-effective and adaptable for scaling up for industrial application or scaling down for specialized use.     

Discogen-DNA complex films at air-water and air-solid interfaces

We have studied films of an ionic discogenic (discotic mesogenic) molecule (pyridinium salt tethered with hexaalkoxytriphenylene (PyTp)) and DNA complex at air-water (A-W) and air-solid interfaces. We have formed an PyTp monolayer on an aqueous subphase containing a small amount of DNA to obtain a PyTp-DNA complex at the A-W interface. Compared to the pure PyTp monolayer, the PyTp-DNA complex monolayer exhibits a higher collapse pressure and lower limiting area, indicating condensation and better stability. A Brewster angle microscope was used for in situ observation of the morphology of the film at the A-W interface. The PyTp-DNA complex films on silicon wafers were prepared using the Langmuir-Blodgett (LB) technique. We find that several tens of layers of the PyTp-DNA complex monolayer can be transferred with good efficiency. Fourier transform infrared spectroscopy studies confirm the presence of DNA in the LB films of the PyTp-DNA complex. Nanoindentation measurements using atomic force microscope reveal that the PyTp-DNA complex films are about two times harder as compared to the pure PyTp films.     

Equilibrium structure and dynamics of (2R, 3R)-(+)-bis(decyloxy)succinic acid at the air-water interface

A twin-tailed, twin-chiral fatty acid, (2R,3R)-(+)-bis(decyloxy)succinic acid was synthesized and its two dimensional behavior at the air-water interface was examined. The pH of the subphase had a profound effect on the monolayer formation. On acidic subphase, stable monolayers with increased area per molecule due to hydrogen bonding and bilayers at collapse pressures were observed. Highly compressible films were formed at 40 degrees C, while stable monolayers with increased area were observed at sub-room temperatures. Langmuir monolayers formed on subphases containing 1 mM ZnCl2 and CaCl2 revealed two dimensional metal complex formation with Zn2+ forming a chelate-type complex, while Ca2+ formed an ionic-type complex. Monolayers transferred from the condensed phase onto hydrophilic Si(100) and quartz substrates revealed the formation of bilayers through transfer-induced monolayer buckling. Compression induced crystallites in 2D from monolayers and vesicle-like supramolecular structures from multilayers were the noted LB film characteristics, adopting optical imaging and electron microscopy. The interfacial monolayer structure studied through molecular dynamics simulation revealed the order and packing at a molecular level; monolayers adsorbed at various simulated specific areas of the molecule corroborated the (pi-A) isotherm and the formation of a hexagonal lattice at the air-water interface.     

Subphase pH effect on composition and structure of Fe(III) arachidate monolayers

The arachidic acid monolayers on Fe(III) subphase surfaces with various pH values have been studied. The π–A isotherms of monolayers and Fourier transform infra-red (FTIR) spectra of Langmuir–Blodgett (LB) films show that the films obtained on different pH subphases with a concentration of Fe(III) 5×10⁻⁵ M have different compositions. At low pH (2.4), the film appears to be almost 100% acid. The content of Fe(III) arachidate increases with increasing pH, at pH 3.7, the film appears to be 100% salt; and the content of salt decreases with pH larger than 3.7. The transmission electron microscope (TEM) observations show that the monolayer structures changed from patch aggregates formed by Fe(III) arachidate at low pH to a network or dotted structures formed by hydrolysates of Fe(III) at high pH. The Brewster angle microscopy (BAM) experiments show the different monolayer behaviors at various pH. These results indicate that the subphase pH greatly influenced the arachidic acid monolayers.     

Fourier transform surface-enhanced Raman scattering of single-layer nucleolipid Langmuir-Blodgett films on silver island film substrates

Surface-enhanced Raman scattering (SERS) spectra of four amphiphilic nucleolipids in single-layer Langmuir-Blodgett (LB) films deposited on silver island film substrates from pure water and complementary nucleotide-containing subphase and corresponding powder normal Raman spectra were obtained. The analysis of these spectra indicates that the SERS effect is mainly caused by a charge-transfer mechanism, and only the nucleobase headgroup moieties and complementary bases combined with them through hydrogen bonds, which are directly in contact with the silver island film substrates, could be enhanced. For the amphiphilic nucleolipids with the identical nucleobase headgroups, the SERS spectra of the LB films are similar, implying that the orientations of these nucleobase moieties on the silver substrates are analogous. However, the nucleobase takes different orientations on the silver substrates before and after complementary binding. The nucleobases in the LB films deposited from pure water are nearly lying flat on the silver surface, while the complementary binding pairs transferred from the air/water interface tend to take an end-on orientation on the metal surface.     

Monolayers and multilayers of uranyl arachidate: in-plane structure of uranyl arachidate multilayers

The molecular in-plane structure of uranyl arachidate Langmuir-Blodgett (LB) films formed at different subphase pH values was analysed by means of X-ray grazing-incidence diffraction. For multilayers formed at low subphase pH a reorganisation of the arachidic acid film structure is confirmed. At appropriate subphase pH values, reorganisation of the film structure e.g. via the formation of three-dimensional crystallites, is prevented by the presence of the uranyl ions and by the subsequent introduction of conformational disorder (gauche defects) in the alkyl chains. The observation of a macroscopic flow-induced in-plane texture in these uranyl arachidate LB films has profound implications for the design of ordered, supramolecular structures by the Langmuir-Blodgett technique.     

Pure and mixed films of a nitrostilbene derivative at the air-water interface, Langmuir-Blodgett multilayer fabrication, and optical characterization

This paper reports the preparation and characterization of pure Langmuir and Langmuir-Blodgett (LB) films of a stilbene derivative containing two alkyl chains, namely 4-dioctadecylamino-4'-nitrostilbene. Mixed films incorporating docosanoic acid and the stilbene derivative are also studied. Brewster angle microscopy (BAM) analysis has revealed the existence of randomly oriented three-dimensional (3D) aggregates, spontaneously formed immediately after the spreading process of the stilbene derivative onto the water surface. These 3D aggregates coexist with a Langmuir film that shows the typical gas, liquid, and solid-like phases in the surface pressure and surface potential vs area per molecule isotherms, indicative of an average preferential orientation of the stilbene compound at the air-water interface, and a gradual molecular arrangement into a defined structure upon compression. A blue shift of 55 nm of the reflection spectrum of the Langmuir film with respect to the spectrum of a chloroform solution of the nitrostilbene indicates that two-dimensional (2D) H-aggregates are formed at the air-water interface. The monolayers are transferred undisturbed onto solid substrates with atomic force microscopy (AFM) revealing that the one layer LB films are constituted by a monolayer of the stilbene derivative together with some 3D aggregates. When the nitrostilbene compound is blended with docosanoic acid, the 3D aggregation is avoided in the Langmuir and Langmuir-Blodgett films, but does not limit the formation of 2D H-aggregates, desirable for second-order nonlinear optical response in the blue domain. The AFM images of the mixed LB films show that they are formed by a docosanoic acid monolayer and, on the top of it, a bilayer of the stilbene derivative.     

Langmuir-Blodgett films and chiroptical switch of an azobenzene-containing dendron regulated by the in situ host-guest reaction at the air/water interface

An amphiphilic dendron containing an azobenzene ring at the focal point and the l-glutamate peripheral groups was designed. Its monolayer formation and host-guest reaction with cyclodextrins at the air/water interface and the properties of the transferred Langmuir-Blodgett (LB) films were investigated. The individual dendron, although without any long alkyl chains, could still form a stable monolayer at the air/water interface because of the good balance between hydrophilic and hydrophobic parts within the molecule. When cyclodextrin (CyD) was added to the subphase, a host-guest reaction occurred in situ at the air/water interface. The inclusion of the focal azobenzene moiety into the cavity of cyclodextrin decreased the packing of the aromatic ring and also led to the diminishment of the molecular area. Both the films formed at the surface of pure water and aqueous cyclodextrins were transferred onto solid substrates. Nanofiber structures were obtained for the film from the water surface as a result of the packing of the azobenzene groups, and circular domains were obtained for the film transferred from the aqueous CyD phases. The film transferred from the water surface showed an exciton couplet in the absorption band of azobenzene, whereas a negative Cotton effect was obtained for the film from CyD subphases. It was found that the supramolecular chirality in the LB film transferred from water was due to the transfer of the molecular chirality to the assemblies whereas that from the CyD subphase was due to the inclusion of azobenzene into the chiral cavity. Interestingly, the film from the water surface was photoinactive, whereas a reversible optical and chiroptical switch could be obtained for the film from the α-CyD subphase. The work provided a way to regulate the assembly and functions of organized molecular films by taking advantage of the interfacial host-guest reaction.     

Magnetic Langmuir-Blodgett films of ferritin with different iron contents

Magnetic Langmuir-Blodgett films of four ferritin derivatives with different iron contents containing 4220, 3062, 2200, and 1200 iron atoms, respectively, have been prepared by using the adsorption properties of a 6/1 mixed monolayer of methyl stearate (SME) and dioctadecyldimethylammonium bromide (DODA). The molecular organization of the mixed SME/DODA monolayer is strongly affected by the presence of the water-soluble protein in the subphase as shown by pi-A isotherms, BAM images, and imaging ellipsometry at the water-air interface. BAM images reveal the heterogeneity of this mixed monolayer at the air-water interface. We propose that the ferritin is located under the mixed matrix in those regions where the reflectivity is higher whereas the dark regions correspond to the matrix. Ellipsometric angle measurements performed in zones of different brightness of the mixed monolayer confirm such a heterogeneous distribution of the protein under the lipid matrix. Transfer of the monolayer onto different substrates allowed the preparation of multilayer LB films of ferritin. Both infrared and UV-vis spectroscopy indicate that ferritin molecules are incorporated within the LB films. AFM measurements show that the heterogeneous distribution of the ferritin at the water-air interface is maintained when it is transferred onto solid substrates. Magnetic measurements show that the superparamagnetic properties of these molecules are preserved. Thus, marked hysteresis loops of magnetization are obtained below 20 K with coercive fields that depend on the number of iron atoms of the ferritin derivative.     

Synthesis and characterization of monolayers and Langmuir-Blodgett films of an amphiphilic oligo(ethylene glycol)-C60-hexadecaaniline conjugate

A novel amphiphilic oligo(ethylene glycol)-C60-hexadecaaniline (A16) tricomponent conjugate, C60>(A16-EG43), possessing a well-defined number of repeating aniline donor units and a hydrophilic ethylene glycol oligomer chain was synthesized. The compound is composed of a covalently bound donor-acceptor chromophore structure. Molecular self-assembly of C60>(A16-EG43) at the air-water interface formed a densely packed Langmuir monolayer with all highly hydrophobic fullerene cages located above the liquid interface. The monolayer can then be transferred onto a glass substrate via Langmuir-Blodgett (LB) deposition. LB multilayered thin films formed by multiple deposition of the monolayer yielded broadened optical absorption peaks extending beyond 600 nm into the 950 nm region, suggesting strong intermolecular interactions among the C60 cages and the A16 moieties. An X-ray reflectometry study clearly reveals that the Langmuir film at the air-water interface consists of a C60 top layer and a bottom layer containing hexcadecaaniline and oligo(ethylene glycol) with gradually decreasing electron density over a distance of approximately 130 A above bulk water. The pressure isotherm shows that the packing density of the C60>(A16-EG43) monolayer, corresponding to a molecular area of approximately 95 A2/molecule, is similar to that of the surface area of the C60 monolayer. This result suggests that C60 packing plays a dominant role in guiding the formation of the monolayer structure. Further photoexcitation of hexadecaaniline moieties of aligned (C60>)-A16 layers by a flash light source induces cross linking between adjacent A16 segments forming an interlinked A16 array. Our results have demonstrated a unique fabrication method for preparing the aligned donor-acceptor array using strong intermolecular interactions between fullerenes as the molecular orientation guiding force in the Langmuir-Blodgett technique.