Investigation of dioctadecyl bilirubinamide in monolayers and Langmuir–Blodgett films

A new amphiphilic ligand, dioctadecyl bilirubinamide [B(CONHR)₂, R=C₁₈H₃₇] form stable monolayers at the air–water interface on neutral, acidic and basic subphases as well as on subphases containing metal ions. Changes in the pH of the subphase do not produce remarkable effects on monomolecular films. The interactions between metal ions and B(CONHR)₂ molecules were investigated by means of various techniques in monolayers and Langmuir–Blodgett (LB) films. B(CONHR)₂ with its complexing head group in contact with the aqueous phase can form metal complexes with many metal ions present in the aqueous phase. The formation of B(CONHR)₂–metal complexes leads to large changes in the area per B(CONHR)₂ molecule. LB films transferred from pure water and metal ions containing subphases were characterized by XPS and low-angle X-ray diffraction.     

Langmuir–Blodgett multilayers of imidazoles

Langmuir–Blodgett (LB) multilayers have been formed from a wide variety of compounds but the basic studies from which others have developed have involved a long hydrocarbon chain terminated at one end by a hydrophilic group. The quaternary ammonium ion has a greater attraction for water than do the other groups which have been used and is so hydrophilic as to preclude the formation of LB layers of straight chain molecules terminated by this group. Certainly all such molecules up to and including octadecyl trimethyl ammonium bromide form micelles in preference to monolayers at the air/water interface though metastable monolayers of this compound have been reported. Quaternized imidazoles have, like quaternary ammonium ions, a positive charge but seem more likely to form LB films. We have thus explored the properties of several of these compounds with a view to producing one which has the desired properties. In order to combat the highly hydrophilic nature of the imidazole group it is necessary to employ a highly hydrophobic ‘tail group’. Thus our most successful compound contains two octadecyl alkyl chains. We have studied the behaviour of this compound at the air/water interface and have found that the nature of the subphase has a very marked influence on the shape of the isotherms. With nitric acid added to the subphase to bring about a pH of 3.5 it is possible to obtain good Y deposition with deposition ratios equal to one in both the upward and downward directions. However we have not been able to achieve LB deposition using any other acid. On heating, the compound in question it changes from a crystalline structure to a smectic structure at 55°C.     

The gas sensitivity of a metal-insulator-semiconductor field-effect-transistor based on Langmuir–Blodgett films of a new asymmetrically substituted phthalocyanine

Langmuir–Blodgett (LB) films of an amino-tri-tert-butyl-phthalocyanine (AmBuPc) were fabricated as the semiconductor thin layer for a metal-insulator-semiconductor field-effect-transistor (MISFET). The gas sensitivity of the low-conducting LB films MISFET was measured in a NO₂ atmosphere at different concentration. The results showed that the gas concentration and the drain-source current of the AmBuPc gas sensor satisfy Langmuir adsorption isotherm.     

An air-stable biomimetic Langmuir–Blodgett bilayer

The long-chain amphiphiles in biomembranes have their hydrophilic headgroups oriented outwards towards the aqueous environment, and their long aliphatic chains innermost. In Langmuir–Blodgett (LB) films the hydrophobic chains are normally outermost. LB films of long-chain derivatives can be prepared under water with the headgroups outermost and are stable while kept there, but the act of removing them from the aqueous environment removes the top monolayer. We demonstrate an adaptation of the LB technique which is appropriate for the preparation of biocompatible surfaces. It produces essentially bilayer films of long-chain derivatives on standard substrates with a hydrophilic outer surface. The films are stable in air. The films show large contact angle hysteresis with water, but the receding angle is in most cases less than 10°. The films can be immersed and withdrawn from water many times before wettability or average thickness change significantly. Compared to previously reported air-stable surfaces with a structure mimicking biological membranes, the substrate for the present surface is experimentally more convenient.     

Near-field microscopy of collapsed Langmuir–Blodgett films

Fluorescence near-field scanning optical microscopy (FL-NSOM) is used to probe the nanoscale structure in stained phospholipid monolayers deposited on glass substrates at moderate surface pressures. The FL-NSOM images reveal new liquid-expanded (LE) and liquid-condensed (LC) domains, including one-to-one correlation between fluorescence contrast and film topography. In particular, films of the phospholipid DPPC stained with DiIC₁₂ exhibit multilayer structures that are observed within the solid phase domains and have LE-like fluorescence signals. These features are attributed to clusters of dye molecules resulting from the localized collapse of the film upon compression. Such collapsed features are also observed in supported films of 100% DiIC₁₂ deposited at high surface pressure. In these films, spatially-resolved spectroscopy shows that the collapsed structures are amorphous based on the fluorescence spectrum while the molecules within the solid phase of the film have a fluorescence spectrum indicative of molecular aggregates.     

Magnetic properties of ferrocenylmethylacrylate-N-dodecylacryl-amide copolymer Langmuir–Blodgett films

Langmuir–Blodgett (LB) films of the copolymer with ferrocenyl-methyl-acrylate (FcMA) and N-dodecyl-acrylamide (DDA) were fabricated. The magnetic moment of these LB films became about twenty times larger than that of the powder. In addition, the LB films had a magnetic anisotropy depending on the dipping direction. The FTIR results suggested that the polymer chains in the LB films were preferably aligned with the perpendicular of the dipping direction. These results were discussed by the intermolecular electron transfer.     

Transition from split streamlines to dip-coating during Langmuir–Blodgett film deposition

Mono-molecular films of arachidic acid were deposited on glass slides using the Langmuir–Blodgett (LB) technique. The liquid subphases were dilute solutions of ZnSO₄ at different pH. Glass slides were treated to create contact angles (θ) ranging from approximately 15° for clean glass slides, to contact angles greater than 120° for slides treated with ferric stearate. Intermediate contact angles were created by immersing slides in solutions of Sigmacote^® of varying concentration. Very small contact angles, θ≈0° were obtained with clean glass slides at high pH values. LB deposition data and transfer ratios (TR) were recorded for up-stroke and down-stroke operation. During upstroke, TR increase with decreasing contact angles reaching a maximum TR close to 100% when the receding contact angle is approximately 15–20°. This is typical of the split-ejection flow pattern found during up-stroke. For very small contact angles, i.e. less than 10°, TR suddenly become zero indicating a transition to a dip-coating flow pattern. During down-stroke operation, TR is zero or negative for small contact angles, reaching a maximum TR approximately 100% for contact angles larger than 120°.     

Surface characterization of the monolayer and Langmuir–Blodgett films of tetra-tert-butyl-copper phthalocyanine

The relaxation and hysteresis phenomena of the tetra-tert-butyl-copper phthalocyanine (ttb-CuPc) monolayer were investigated. The monolayer was then transferred to a hydrophilic glass surface to prepare one monolayer of Langmuir–Blodgett (LB) films. The uniformity, stability and molecular arrangement of the LB films were studied by measurements of dynamic contact angle (DCA), and were compared with the information obtained by transmission electron microscopy (TEM) and atomic force microscopy (AFM). The results show that the monolayer of ttb-CuPc is generally stable. The limiting area of a molecule is smaller than those reported in the literature, which is attributed to the aggregation of ttb-CuPc molecules into multilayer domains. The advancing and receding contact angles of water on these LB films are much smaller than those on a homogeneous film prepared by vacuum deposition. The wettability analysis on the LB films suggests that ttb-CuPc molecules are not arranged uniformly and continuously, and the LB film of ttb-CuPc contains a high ratio of exposed glass substrate. The surface morphology inspected by TEM and AFM shows the formation of separated domains of ttb-CuPc molecules, which is consistent with the surface condition evaluated from the surface wettability.     

Photophysical investigations of Langmuir–Blodgett mono- and multilayer films of pheophorbide-a

Absorption, fluorescence and time-resolved fluorescence spectroscopy has been applied to quasi two-dimensional Langmuir–Blodgett monolayers and three-dimensional arrangements of Langmuir–Blodgett films with different numbers of layers. Pure dye films of pheophorbide-a and films in which pheophorbide-a molecules were embedded in a behenic acid matrix have been investigated. Optical spectroscopy is used in order to obtain evidence for intra- and interlayer interaction in the membrane-like environment and distinguish between these different types of interactions. Depending on how the dye molecule is embedded a broad range of π-system interactions occur. Optical band shifts as well as band shape changes and the formation of new bands are indicators for these molecular interactions [M.B. Grieve, A.J. Hudson, T. Richardson, Thin Solid Films, 1994, 243, 581.]. Among such interactions, exciton coupling and excimer formation are considered to be possible reasons for the observed major differences between spectra and kinetics of mono- and multilayer Langmuir–Blodgett films. Exciton coupling is indicated by red shifts of the Q-band of about 600 cm⁻¹ in the absorption spectra of monolayer films. The observed broad red shifted fluorescence in the near-infrared region and their short lifetimes (≤100 ps) are assigned to excimer formation. Time-resolved fluorescence spectra of bilayer films as well as polarization dependencies of the Langmuir–Blodgett film absorption are presented.     

Studies on the formation of Langmuir monolayer and Langmuir–Blodgett films of octadecyl amine-bromocresol purple dye complex

Properties of the monolayer of octadecyl amine (ODA) molecules on aqueous solution of bromocresol purple (Bcp) dye have been studied over a wide range of pH by measuring the surface pressure-area isotherms. A strong interaction of ODA molecule was observed with the dye molecule in the pH range of 4–9. Under the present study, the dye molecules were adsorbed on the ODA monolayer at the water surface and subsequently a Langmuir–Blodgett (LB) film of ODA–dye complex was transferred from the air–water interface onto a solid substrate. Alternatively, dye molecules were incorporated into LB film by immersing the predeposited LB film of pure ODA into the dye solution, i.e. by adsorption of dye molecule at the solid–liquid interface. The adsorption behavior of ODA–Bcp dye complexes obtained through these two different routes was characterised with the help of UV–Visible spectroscopy. The nature of the ODA–dye complex deposited from air–water interface using the LB technique was found to be quite different from that of the complex formed by the adsorption of the dye into the pure ODA LB film. The adsorption spectra of the ODA–dye complex obtained from the air–water interface did not change with pH, while those of the ODA–dye complex formed from the solid–liquid interface showed pH dependence.     

Information storage based on photochemical effects in mixed Langmuir–Blodgett films

Mixed Langmuir–Blodgett (LB) films of two novel thiophene-spaced N-alkylpyridinium malononitrile zwitterionic dyes have been prepared. The LB films present two sharp, non-overlapping charge-transfer absorption bands which can be selectively photobleached in a irreversible fashion. The former could have potential application in multifrequency optical data storage.     

Langmuir–Blodgett films of substituted bis(naphthalocyaninato) rare earth complexes: structure and interaction with nitrogen dioxide

Ordered molecular assemblies of novel alkylthio-substituted bis(naphthalocyaninato) rare earth complexes M[2,3-Nc(SC₁₂H₂₅)₈]₂ (M=Gd, Er) have been fabricated by Langmuir–Blodgett (LB) technique and characterized by surface pressure-area isotherm measurements, electronic absorption and polarized electronic absorption spectroscopy and low-angle X-ray diffractometry. The interaction between the thin films and NO₂ gas was investigated. The experimental results indicate that the bis(naphthalocyaninato) rare earth molecules form well-ordered stable monolayers with face-to-face orientation for the macrocycles and edge-on configuration for the molecules at the air–water interface and lamellar multilayers on solid substrates. The orientation angles of naphthalocyanine rings with respect to the quartz plate surface in the LB films for M[2,3-Nc(SC₁₂H₂₅)₈]₂ with M of Gd and Er have been determined based on the polarized absorbance and found to be 50° and 54°, respectively. The adsorption–desorption process of NO₂ on LB films of M[2,3-Nc(SC₁₂H₂₅)₈]₂ has been monitored by electronic absorption spectroscopy. A process of gas desorption was found to obey the Elovich equation.     

Study of the environment effect on the properties of BDN-SA Langmuir–Blodgett films

The chemical and electrical properties of BDN-SA Langmuir–Blodgett films in air and N₂H₄ gas respectively, were studied using X-ray Photoelectron Spectroscopy (XPS) and the electrical resistance measurement. The results indicate that the oxidation effect caused by air leads to the lost of N and partial oxidation of Ni and S in the LB films; while the reduction effect induced by N₂H₄ gas decreases the amount of O in the LB films. The electrical resistance of LB film decreases dramatically after the film being exposed to N₂H₄ gas while increases with the exposure time in air.     

Migration and transfer of excitation energy in homogeneously dispersed porphyrin monolayers prepared from amphiphilic copolymers

Photophysical processes of tetraphenylporphyrin (TPP) units incorporated into a polymer monolayer have been studied by fluorescence spectroscopy with emphasis on energy migration and aggregate formation of TPPs in the two-dimensional sheet. Although UV–VIS absorption spectra showed few of TPP aggregates, the fluorescence was largely quenched in the high-TPP samples due to efficient energy migration and following energy transfer to the aggregates. With the aid of computer simulation, time-resolving decay analysis revealed the large diffusion coefficient of excitation energy and a low concentration of aggregate, suggesting that the TPP moieties were placed in the plane not with a random distribution, but with an ordered arrangement, probably due to some mutual repulsive forces which prevented overlap of the TPP units at the air–water interface. These results suggest that the polymer monolayer containing TPP units can be utilized as a component of molecular assemblies for designing efficient energy harvesting systems.     

Structural characterization of Langmuir–Blodgett films by X-ray diffraction in transmission geometry

In this paper, we present a method which employs X-ray diffraction in transmission geometry for structural determination of Langmuir–Blodgett (LB) films. The LB multilayers are deposited on the outer surface of a thin glass capillary and diffraction pattern was recorded using a pin-hole flat camera. The remarkable advantage of this method is that both the multilayer reflections and in-plane reflections are recorded in one diffraction pattern which provides the following information about the film: layer thickness, electron density profile normal to the layers, in-plane packing of molecules and tilt angle of molecular chains with respect to the plane. As an example, we have determined the lattice parameters and the electron density profile of a lead stearate LB film according to one diffraction pattern where 15 orders of layer reflections and three in-plane reflections were recorded.     

Features of photopolymerization of Langmiur–Blodgett thin films of acetylenic acids

UV-induced polymerization of thin (1–4 monolayers) Langmuir–Blodgett films of acetylenic carboxylic acids with triple bonds in different positions (terminal: 23-tetracosinic acid HC≡C(CH2)21COOH, and internal: 2-docosinic CH3(CH2)18C≡CCOOH) and their lead salts is investigated. It is shown by means of IR spectroscopy that the topochemical reaction proceeds with the participation of carboxylic groups. The differences in the structure of mono- and bilayers are demonstrated. The mechanism of the topochemical reaction depends on the method of film transfer onto the substrate. It is shown by means of UV spectroscopy that short conjugated polyenes (containing 7 to 9 carbon atoms) are formed as the product of polymerization. The mechanism of the formation of these polyene chains is proposed on the basis of the experimental data and semi-empirical calculations.     

X-ray photoelectron spectroscopy study of Langmuir–Blodgett films of N-octadecyl-8-hydroxy-2-quinoline carboxamide deposited from subphases containing metal ions

The Langmuir–Blodgett films of N-octadecyl-8-hydroxy-2-quinoline carboxamide (HOQ) deposited from subphase containing metal ions were investigated by X-ray photoelectron spectroscopy (XPS). The amphiphilic HOQ with its complexing head group in contact with the aqueous phase can form metal complexes with the metal ions present in the aqueous phase. The formation of HOQ–metal complexes leads to the appearance of new XPS peaks assigned to the metal ions. The information on stoichiometry provided by XPS indicates that a metal ion is coordinated by one HOQ molecule for transition metal ions of the fourth period, but by two HOQ molecules for the metal ions after the fourth period.     

The structure of multilayer films of DNA-aliphatic amine is preparation technique dependent

The structures of DNA-hexadecylamine and DNA-hexadecyltrimethylammonium bromide multilayer films obtained by two different approaches: layer-by-layer (LbL) adsorption and Langmuir–Blodgett (LB) technique were compared. Interlayer distance and DNA conformation in these films were determined by small-angle X-ray scattering, infrared and ultraviolet spectroscopy. The following results were obtained: (1) X-ray diffractrograms of the films indicated a distinct layer structure; (2) the interlayer distances for LbL films were less than for LB-films, made from the same components and (3) the double stranded DNA was included into the DNA-hexadecylamine film as a single-stranded formation, whereas DNA in the DNA-hexadecyltrimethylammonium film retained its double-stranded form. Structural models of LbL and LB films were created.     

Studies of casting and LB films of ferroelectric liquid crystalline polysiloxane

Monolayers of side chain ferroelectric liquid crystalline polysiloxane have been successively transferred onto appropriate substrates by vertical dipping method to study the morphology and the orientation of the mesogens and the side chains by UV spectra and polarized FT-IR spectra and X-ray diffraction. The spectra for casting film and LB film are compared. The molecules in LB films are found to be more orientated along the normal of the substrate at an angle of 37° for the mesogens as the side chain as found by polarized FT-IR spectra and transmitting FT-IR spectra than casting film. Layer structure is also confirmed by X-ray diffraction results. The mesogens are found to form H-aggregates structure in bulk phase and LB films from UV spectra. Temperature-dependent UV spectra have revealed the change of the tilt angle of the mesogens inside the layer of both bulk phase and LB films.     

Amperometric cholesterol biosensors based on hybrid organic–inorganic Langmuir–Blodgett films

Preparation and characterization of a thin-film cholesterol biosensor employing an organic–inorganic hybrid system of cholesterol oxidase (ChOx) and Prussian blue (PB) is described. ChOx was immobilized in Langmuir–Blodgett (LB) films consisting of positively charged octadecyltrimethylammonium (ODTA) and nano-sized PB clusters. Immobilization was performed by simple immersion of ODTA/PB LB films into an aqueous solution of ChOx. Subsequent ChOx absorption into LB films was confirmed by infrared reflection–absorption spectroscopy. Obtained ODTA/PB/ChOx LB films clearly exhibited a response current to cholesterol under an applied potential of 0.0 V (vs. Ag/AgCl). The linearity of current density versus cholesterol concentration was confirmed for the range 0.2–1.2 mmol/L. The present study indicates that simple immersion of ODTA/PB LB films into an enzyme solution is a promising method to produce many types of thin-film biosensors comprising a hybrid system of an oxidative enzyme and PB nano-clusters that work at a very low potential range.