Structure studies of langmuir-blodgett films

A method of small-angle X-ray investigation of the structure of Langmuir-Blodgett (L-B) films on substrates is developed. Experiments were carried out using a small-angle X-ray diffractometer with a position-sensitive detector. X-ray patterns contain 10–15 reflections with spacings from 50 Å up to 250 A and a number of ripples in the inner parts of the curves. An analysis of these ripples revealed integral parameters of L-B films (thickness 100 - 2000 A, a number of monolayers: 1–50). The Fourier-synthesis of the structural amplitudes gave electron density profiles across the films. These profiles demonstrated the successive realization of pre-programmed sequences of alternating bilayers in L-B superlattices.     

Langmuir and langmuir-blodgett films of metallosupramolecular polyelectrolyte-amphiphile complexes

A detailed analysis of a metallosupramolecular polyelectrolyte-amphiphile complex (PAC) at the air-water interface is presented. Langmuir isotherms, Brewster angle microscopy, and X-ray reflectance and diffraction methods are employed to investigate the structure of the Langmuir monolayers. The PAC is self-assembled from 1,3-bis[4'-oxa-(2,2':6',2' '-terpyridinyl)]propane, iron acetate, and dihexadecyl phosphate (DHP). Spreading the PAC at the air-water interface results in a monolayer that consists of two strata. DHP forms a monolayer at the top of the interface, while the metallosupramolecular polyelectrolyte is immersed in the aqueous subphase. Both strata are coupled to each other through electrostatic interactions. The monolayers can be transferred onto solid substrates, resulting in well-ordered multilayers. Such multilayers are model systems for well-ordered metal ions in two dimensions.     

Structure of valinomycin/fatty acid langmuir-blodgett films

We report on the structure of monolayer and multilayer Langmuir-Blodgett films of mixtures of arachidic acid and the ionophore valinomycin. Compressibility measurements on the floating layers and low angle x-ray diffraction experiments with multilayers indicate the possible miscibility of the two components at low concentrations of the ionophore. However, it would appear that the arachidic acid and valinomycin are insoluble in one another over most of the composition range.     

Preparation and characterization of poly-N-vinyl carbazole langmuir-blodgett films

Langmuir monolayers of poly-N-vinyl carbazole (PNVK) were obtained by dispensing PNVK dissolved in tetrahydrofuran onto an air-water interface. Surface pressure-area isotherms of mixed monolayer of the PNVK were studied under different subphase conditions such as temperature and pH of the subphase. It was demonstrated that the monolayer of PNVK remained stable over a temperature range of 10–40°C. The area per molecule of the solid phase was found to be 31Ų. These monolayers were transferred onto indium-tin-oxide-coated glass plates and characterized by spectroscopic and electrochemical techniques.     

液晶聚合物的单层与Langmuir-Blodgett膜

系统研究了手性液晶聚硅氧烷和光致变色液晶聚硅氧烷两个毓的侧链液晶聚合物在空气/水界面的单层行为和Langmuir-Blodgett(LB)膜沉积特性,对LB膜结构与存在的聚集现象进行了系统的表征,并初步探讨了LB膜中液晶聚合物表现的功能性。     

FT-Raman studies of langmuir-blodgett monolayer components containing absorbing chromophores

Structural studies of Langmuir-Blodgett monolayers and multilayers have revealed that both the hydrophilic and the hydrophobic parts of an amphiphilic molecule can influence the exent of 2-dimensional packing which occurs within a film. In particular, dye chromophores to which are appended long hydrocarbon tails will usually form films dominated by the interaction of the chromophores unless a small amount of hydrocarbon liquid is added. In this case the packing will be dominated by the intermolecular interaction of the hydrocarbon tails. FT-Raman studies of these amphiphilic molecules provides information about both parts of the molecule without resonance enhancement since the laser wavelength used for excitation is far removed from any absorption maxima of the dye chromophore. Specific examples of thiocyanine and merocyanine dyes will be discussed.     

Alkylamine sensing using langmuir-blodgett films of n-alkyl-N-phenylamide-substituted zinc porphyrins

Two porphyrin compounds, zinc(II) 5,10,15,20-tetrakis(3,5,5-trimethyl- N-phenylhexanamide)porphyrin and zinc(II) 5,10,15,20-tetrakis(2,2-dimethyl- N-phenylpropanamide)porphyrin, have been investigated as possible candidates for the detection of alkylamines. UV-visible spectroscopy has shown that their solution absorption spectra are significantly modified upon interaction with a range of organic analytes, including acetic acid, butanone, ethylacetate, hexanethiol, octanal, octanol, alkylamines, and trimethylphosphite. Large spectral changes are observed for the family of alkylamines as a result of the specific affinity between zinc and the amine moiety. Langmuir-Blodgett (LB) films of the porphyrins have been fabricated in order to assess their solid-state sensing capability toward amines. The surface pressure-area (Pi- A) isotherms reveal a clear three-phase Langmuir film behavior and show that these monolayer films may be compressed to a relatively high surface pressure ( approximately 40-50 mN m (-1)). The isotherm data alongside molecular modeling suggest a relatively flat orientation of the porphyrin rings of both compounds: that is, a mutually parallel alignment of the plane of the porphyrin ring and that of the water surface. LB films deposited at 15 mN m (-1) have been exposed to alkylamine vapor (carried by N 2). A red shift and increase in intensity of the Soret band absorbance is observed which can be reversed by flowing pure N 2 over the gently heated sample (60 degrees C) after exposure. Primary amines were expected to invoke the greatest sensing response due to (i) their larger association constants with these porphyrins compared to secondary and tertiary amines and (ii) the ease of diffusion of amines which is expected to follow the order primary > secondary > tertiary due to the steric hindrance arising from the bulky secondary and tertiary amines. However, the magnitude of the absorbance change is largest for exposure to the secondary amines, dipropylamine and dibutylamine, for both porphyrins, compared to primary and tertiary amines. This trend follows that observed when the amines were added to solutions of the porphyrins. The rate of response of the porphyrin LB films falls as the molecular weight of the diffusing alkylamine increases. Furthermore, a greater rate of response is observed for the phenylhexanamide porphyrin compared to the phenylpropanamide porphyrin due to its lower molecular density within the LB film and therefore more porous structure.     

Thermal disordering of langmuir-blodgett films of cadmium stearate on sapphire

The phase behavior of monolayer and multilayer Langmuir-Blodgett films of cadmium stearate on sapphire is studied using pulsed optoacoustic spectroscopy of the methyl and methylene stretching modes. Heating irreversibly disorders monolayer films but multilayers reach a stable configuration which undergoes reversible phase transitions.     

Nonlinear optical and structural properties of langmuir-blodgett films of thiohelicenebisquinones

We provide a detailed investigation of the second-order nonlinear optical and structural properties of Langmuir-Blodgett (LB) films of nonracemic thiohelicenebisquinone (THBQ). We prepare both X- and Y-type films of different thicknesses and characterize them using optical second-harmonic generation and atomic-force microscopy (AFM). We find that the overall nonlinear properties of the samples are essentially independent of the film thickness and the deposition type and arise from susceptibility tensor components associated with chirality. Both X- and Y-type films can be described by D2 symmetry, which is a higher symmetry than the previously assumed C2 of LB films of THBQ and a similar helicenebisquinone (HBQ). However, the two types of films are shown to differ significantly with respect to the orientation of the in-plane axis. For Y type, the axis follows the direction of vertical sample deposition, but for X type, the direction of the axis varies randomly and significantly between different samples. The Y-type samples are therefore more ordered than the X-type samples. This was confirmed by AFM measurements in which the Y type exhibits uniform ordering into columnar structures. Similar structures in X type, on the other hand, are shorter and more randomly oriented, like those earlier observed for racemic samples of HBQ [Verbiest, T., et al. Science 1998, 282, 913]. The common nonlinear properties and different high-level ordering observed here for two different types of nonracemic samples reinforces that the nonlinearity of THBQ (and probably HBQ, as well) originates from the low-level columnar aggregation of the molecules with the higher-level structures playing a lesser role. In addition, within the columns, the molecules likely assume fairly random azimuthal orientations so that the columns themselves exhibit approximate Dinfinity symmetry.     

Photothermal reaction kinetics and thermal desorption of diacetylene langmuir-blodgett films

Photopolymerization and thermal changes in Langmuir-Blodgett films of diacetylene fatty acids are studied by reflection measurements. The technique is highly sensitive and allows investigation of the kinetics of changes in thickness and real and imaginary parts of the refractive index. In quantitative agreement with absorption and X-ray data, the reflectivity can be described by two consecutive photoreactions. The faster process involves an absorption, but no structural change, and the slower reaction an absorption change and an immediately coupled thickness increase by 6%. Polymerization removes a solid/fluid phase transition at 62°C for the unpolymerized fatty acid. Thermodesorption measurements demonstrate the increased thermostability by polymerization: Desorption temperatures are increased by 150°C corresponding to increases in binding energy of 9 kcal/mol.     

一种新的具有给体-受体结构的有机分子的合成及LB膜研究

本工作合成了一种新的具有给体-受体结构的长碳链有机分子, 2, 3-二(十六烷硫基)-5-(4'-硝基苯亚甲基)-1, 4-二硫代-2-环戊烯, 对其单分子膜的成膜性能进行了研究。在适宜条件下制备了单层及多层LB膜。通过电子衍射、X射线衍射、紫外-可见吸收光谱等手段对LB膜的结构进行了表征。实验结果表明, 这种化合物的成膜性能很好。单分子层膜的二次谐波测试表明该发色团分子具有较好的二阶非线性光学性。     

Fluorescence lifetime of chlorophyll a in pure and mixed langmuir-blodgett films

Fluorescence lifetimes of pure chlorophyll a monolayers were determined by single-photon counting and by picosecond spectroscopy. Neither technique could resolve its very fast decay rate, attributed to a high aggregate concentration and rapid intermolecular energy transfer. The same experiments were performed on monolayers of chlorophyll a diluted with phospholipids at a molar ratio of 1 to 100. From the single-photon counting decay curves, two fluorescence lifetimes were deconvoluted, i.e. 4.9 and 2.3 ns, indicating the presence of monomeric and aggregated chlorophyll a, respectively. They differ somewhat from the picosecond spectroscopic result where only one lifetime at 3.3 ns was calculated. This is indicative of an exciton annihilation process since it is smaller than the average of the single-photon counting lifetimes. Fluorescence spectroscopy was also used to better understand the photophysics of the chlorophyll a monolayer.     

Influence of ion transfer kinetics on the composition of langmuir-blodgett films

The effect of ion transfer kinetics on the ionic composition of Langmuir-Blodgett (LB) films formed by charged monolayers is analyzed. The dynamic regimes of the LB deposition are considered by taking into account the competitive adsorption of several counterions having different diffusivities, valences, binding constants, and bulk concentrations. It is shown that the composition of deposited films should change with the deposition rate. At lower deposition rates, the ion with higher binding constant is more represented within the deposited monolayer in comparison to the higher deposition rates. At low deposition rates, the ratio of counterion amounts within the LB films is the same as that within the floating monolayer excluding the ions within the diffuse layer. At high deposition rates, the ratio of the counterion amounts is the same as that within the floating monolayer when the potential-determining counterions within the diffuse layer are taken into account.     

Direct measurements of the mechanical properties of polymerized and unpolymerized langmuir-blodgett films

Mechanical measurements can be made on Langmuir-Blodgett (LB) films that have been peeled from their substrates, and are floating on the surface of water, by compressing them between the moving barrier and the Langmuir balance float in a standard monolayer trough. We have used this technique, which utilizes apparatus commonly available where LB films are made, to study multilayers of lead 10,12-tricosadiynoate (a diacetylene carboxylic acid) that were first polymerized and then peeled from the substrate. For comparison we have performed the same measurements on pieces of mylar, on unpolymerized films, and on films of calcium octadecanoate (a saturated chain fatty acid). We found Young's modulus for films of the saturated chain material, the unpolymerized diynoate, and the polymerized films, to be 6 GPa (900 kpsi), 0.5 GPa, and 6 GPa, respectively.     

Patterned langmuir-blodgett films of monodisperse nanoparticles of iron oxide using soft lithography

Langmuir-Blodgett (LB) films of monodisperse iron oxide nanoparticles have been successfully deposited onto patterned poly(dimethylsiloxane) surfaces. These patterned LB films of iron oxide nanoparticles were transferred onto solid substrates using micro contact printing.     

Structural characterization of langmuir-blodgett films of a cellulose derivative by X-ray photoelectron spectroscopy

The method of variable angle x-ray photoelectron spectroscopy has been applied to transferred monolayers of a new cellulose derivative. The results support a model for the monolayer in which the cellulose backbone lies flat on the substrate and the sidechains extend perpendicular to the surface. Furthermore, a significant portion of the substrate surface is found to be bare, indicating that the transferred monolayer contains major defects in the form of holes.     

Comparative review of structural parameters of the nearest surrounding of monoatomic cations in water and methanol media

Literature data on structure of coordination sphere of selected monoatomic cations in aqueous and methanol solutions have been reviewed and compared. The following structural parameters have been considered: coordination number, interparticle distances, the second coordination sphere features, and ionic association type. It has been revealed that for doubly charged ions the parameters of the first coordination sphere are similar in the both solvents. The second coordination sphere of the same cation consists of fewer solvating molecules located farther from the ion in the case of methanol as compared to water.