PREPARATION OF THIN FILM OF 9-HYDROXY-OXA[9]HELICENE AND ITS APPLICATION IN ORGANIC PHOTOVOLTAIC DEVICES

Langmuir monolayers and Langmuir-Blodgett (LB) films of the decatungstoeuropate [Eu(W(5)O(18))(2)](9-) (EuW(10)) and the amphiphilic Ir complex 1 have been successfully fabricated by using the adsorption properties of the EuW(10) polyanion dissolved in the aqueous subphase onto a positively charged 1 monolayer at the air-water interface. The compression isotherms and Brewster angle microscopy (BAM) of monolayers of 1 on pure water (1 monolayer) and on a subphase containing 10(-6) M EuW(10) and 10(-3) M NaCl (1/EuW(10) monolayer) have been studied. Infrared and UV-vis spectroscopy of the transferred LB films indicate that EuW(10) and 1 molecules are incorporated within these LB films. X-ray reflectivity (SXR) and atomic force microscopy (AFM) experiments indicate that LB films of 1 present a heterogeneous morphology while 1/EuW(10) films show a flatter and more homogeneous surface as well as a layered structure with a periodicity of 4.1 nm. Mixed monolayers of 1 and DODA (dimethyldioctadecylammonium bromide) have been prepared with EuW(10) polyanions in the subphase to control the concentration of 1 and EuW(10) polyanions within the LB films. AFM and SXR experiments with the transferred LB films show that the dilution of 1 with DODA improves the layered structure. The luminescence of 1 is partially quenched by EuW(10) in the 1/EuW(10) LB films, while emission from EuW(10) is not detected. On the other hand, emission from both entities is preserved in the LB films prepared from mixed DODA/1 monolayers, in which the red and yellow emissions arise independently from EuW(10) and 1, respectively. The different DODA:1 ratios lead to changes in the emission color. Therefore, they constitute a promising color-tunable luminescent material.

Effect of water and air–water interface on the structural modification of Ni-arachidate Langmuir–Blodgett films

In the present communication we report the formation of nano dimensional complex films of eosin Y (EY), stearic acid (SA) and dodecyl trimethyl ammonium bromide (DTAB) using Langmuir - Blodgett (LB) technique. By spreading SA onto the DTAB - EY mixed aqueous sub phase a complex monolayer of SA-DTAB-EY was formed. The adsorption kinetics in the complex monolayer was investigated by recording increase in surface pressure with time (S-t) graph at air - water interface. Initially the (S-t) graph shows steep rise and becomes flat at the end of the adsorption kinetics. More than 300 minutes were required to complete the adsorption process. In situ Brewster Angle Microscopy investigation gives compelling visual evidence of complex Langmuir monolayer formation at air-water interface. After transfer onto solid substrate the films were characterized by UV-Vis absorption and Atomic Force Microscopy (AFM). In the complex LB films the EY absorption bands were shifted and broadened with respect to pure EY solution and microcrystal spectrum due to the formation of nano dimensional aggregates. This was also supported by AFM investigations of the complex LB films.

Characterization of Langmuir and Langmuir–Blodgett films of an octasubstituted zinc phthalocyanine

In this paper, graphene oxide was incorporated in penicillinase-lipid Langmuir monolayers and transferred to solid supports as Langmuir-Blodgett (LB) films so that the enzyme catalytic properties could be evaluated. Adsorption of penicillinase and graphene oxide on dimyristoylphosphatidic acid (DMPA) monolayers at the air-water interface was investigated by tensiometry, vibrational spectroscopy, and Brewster angle microscopy. The LB films were characterized by quartz crystal microbalance, infrared spectroscopy, luminescence spectroscopy, and atomic force microscopy. Enzyme activity was studied with UV-vis spectroscopy, and the feasibility of the supramolecular device nanostructured as ultrathin films was essayed as an optical sensor device. The presence of graphene oxide in the enzyme-lipid LB film not only tuned the catalytic activity of penicillinase but also helped conserve its enzyme activity after weeks. These results may be related not only to the molecular architecture provided by the film but also to the synergism between the compounds on the active layer, leading to a molecular architecture that allowed a fast analyte diffusion owing to a suitable molecular accommodation which also preserved the penicillinase activity. This work then demonstrates the feasibility of employing LB films composed of lipids, graphene oxide, and enzymes as optical devices for biosensing applications as a proof-of-concept experiment.

Rhodanese incorporated in Langmuir and Langmuir–Blodgett films of dimyristoylphosphatidic acid: Physical chemical properties and improvement of the enzyme activity

In this paper, carbon nanotubes (CNTs) were incorporated in penicillinase-phospholipid Langmuir and Langmuir-Blodgett (LB) films to enhance the enzyme catalytic properties. Adsorption of the penicillinase and CNTs at dimyristoylphosphatidic acid (DMPA) monolayers at the air-water interface was investigated by surface pressure-area isotherms, vibrational spectroscopy, and Brewster angle microscopy. The floating monolayers were transferred to solid supports through the LB technique, forming mixed DMPA-CNTs-PEN films, which were investigated by quartz crystal microbalance, vibrational spectroscopy, and atomic force microscopy. Enzyme activity was studied with UV-vis spectroscopy and the feasibility of the supramolecular device nanostructured as ultrathin films were essayed in a capacitive electrolyte-insulator-semiconductor (EIS) sensor device. The presence of CNTs in the enzyme-lipid LB film not only tuned the catalytic activity of penicillinase but also helped conserve its enzyme activity after weeks, showing increased values of activity. Viability as penicillin sensor was demonstrated with capacitance/voltage and constant capacitance measurements, exhibiting regular and distinctive output signals over all concentrations used in this work. These results may be related not only to the nanostructured system provided by the film, but also to the synergism between the compounds on the active layer, leading to a surface morphology that allowed a fast analyte diffusion because of an adequate molecular accommodation, which also preserved the penicillinase activity. This work therefore demonstrates the feasibility of employing LB films composed of lipids, CNTs, and enzymes as EIS devices for biosensing applications.

Micellar effect of surfactant on the aggregation pattern of a fluorescent dye in ultra-thin film

Three derivatives of tris(bipyridyl)–ruthenium(II) complexes with different alkyl‐chain lengths (nC18H37 (1), nC14H29 (2) and nC10H21 (3)) were synthesised. All these complexes behaved as an amphiphile and their surface properties were studied at the air–water interface by measuring surface pressure–area (Π–A) isotherms. The surface morphology of the resulting films at the air–water interface was also studied by using Brewster angle microscopy. Mean molecular areas of these complexes were measured from the Π–A isotherms, which were approximately 200 Å2, thereby indicating a parallel arrangement of the Ru–bipyridyl moiety of the complexes. Mono‐ and multilayer Langmuir–Blodgett (LB) films were formed on different solid surfaces with transfer ratios close to one. Similarities in the absorption and fluorescence spectra of these amphiphiles in solution as well as in LB films deposited on a quartz surface confirmed the successful transfer of these films onto the substrates. The latter provided information about the arrangements of metallosurfactant molecules within the LB films. The two‐dimensional concentrations of these films were calculated from the Lambert–Beer law as well as from the Π–A isotherm, which confirmed regular and reproducible transfer of the complex monolayers from the air–water interface onto the quartz surface. The surface morphology of these films on various substrates was characterised by atomic force microscopy. Furthermore, by oxidising the monolayer of complex 3, a one‐input sequential logic gate was constructed.

Here, we report the mixing behaviour of diacetylene monomer 10, 12-tricosadiynoic acid (TCDA) and rhodamine-800 (Rh8) using Langmuir–Blodgett (LB) technique. The presence of Rh8 affected the structures, phase behaviour as well as colorimetric properties of TCDA in the mixed films at air–water interface and onto solid support. The mixed LB films having TCDA molefraction ≥ 0.5 leads to multilayer formation, whereas multilayer formation was hardly observed for the films containing TCDA molefraction less than 0.5. It was observed that polymerization as well as phase change (blue to red) was possible only for multilayered films. Brewster angle microscopy, atomic force microscopy, and fluorescence inverted microscopy studies confirmed the formation of definite structures in the polymerized TCDA/Rh8 mixed films at air–water interface and onto solid support. Structure of TCDA polymer strands was largely influenced by the presence of Rh8 in the mixed films. Interestingly, energy transfer occurred from TCDA in red phase to Rh8 in the mixed films with TCDA molefraction greater than 0.4. Maximum energy transfer efficiency was found to be 47.3% for the mixed LB film with TCDA molefraction 0.9.

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

Optical anisotropy and surface phases of cholesterol derivative monolayer at air–water interface

Photoisomerization of amphiphilic azobenzene derivatives in Langmuir Blodgett films prepared as polyion complexes, using ionic polymers

Monolayer Langmuir–Blodgett (LB) films of 1,4-bis(pyridin-4-ylethynyl)benzene (1) together with the “STM touch-to-contact” method have been used to study the nature of metal–monolayer–metal junctions in which the pyridyl group provides the contact at both molecule–surface interfaces. Surface pressure vs area per molecule isotherms and Brewster angle microscopy images indicate that 1 forms true monolayers at the air–water interface. LB films of 1 were fabricated by deposition of the Langmuir films onto solid supports resulting in monolayers with surface coverage of 0.98 × 10−9 mol·cm−2. The morphology of the LB films that incorporate compound 1 was studied using atomic force microscopy (AFM). AFM images indicate the formation of homogeneous, monomolecular films at a surface pressure of transference of 16 mN·m−1. The UV–vis spectra of the Langmuir and LB films reveal that 1 forms two dimensional J-aggregates. Scanning tunneling microscopy (STM), in particular the “STM touch-to-contact” method, was used to determine the electrical properties of LB films of 1. From these STM studies symmetrical I–V curves were obtained. A junction conductance of 5.17 × 10−5 G0 results from the analysis of the pseudolinear (ohmic) region of the I–V curves. This value is higher than that of the conductance values of LB films of phenylene-ethynylene derivatives contacted by amines, thiols, carboxylate, trimethylsilylethynyl or acetylide groups. In addition, the single molecule I–V curve of 1 determined using the I(s) method is in good agreement with the I–V curve obtained for the LB film, and both curves fit well with the Simmons model. Together, these results not only indicate that the mechanism of transport through these metal–molecule–metal junctions is non-resonant tunneling, but that lateral interactions between molecules within the LB film do not strongly influence the molecule conductance. The results presented here complement earlier studies of single molecule conductance of 1 using STM-BJ methods, and support the growing evidence that the pyridyl group is an efficient and effective anchoring group in sandwiched metal–monolayer–metal junctions prepared under a number of different conditions.

We have synthesized a novel mesogenic azobenzene molecule and studied its monolayer film properties at air-water interface (Langmuir film) and air-solid interface (Langmuir-Blodgett film). The material, H-shaped dimer bis[5-(4'-n-dodecyloxy benzoyloxy)-2-(4''-methylphenylazo)phenyl] adipate (12D1H) exhibits a smectic C phase between 51 and 48 degrees C on cooling. Surface manometry studies showed the formation of a stable monolayer at the air-water interface. Brewster angle microscopy (BAM) showed that liquid domains coexisting with the gas region at large area transformed to a uniform liquid phase with increasing surface density and finally to a collapsed state. We have carried out atomic force microscope (AFM) studies on Langmuir-Blodgett (LB) films transferred onto freshly cleaved hydrophilic mica substrate. The AFM images showed domains of height of about 3.8 nm, which corresponds to the estimated height of the molecule confirming the formation of monomolecular film. On a hydrophobic silicon substrate, the LB transfer yields a bilayer film, which dewets to form uniform nanodroplets of diameter of about 100 nm and height in the range 10-50 nm. Our analysis indicated that the mechanism involved in the formation of nanodroplets can be attributed to spinodal dewetting. The 12D1H molecule containing an azobenzene group undergoes a trans to cis transformation in the presence of ultraviolet light. Our surface manometry studies showed that the monolayer in the presence of ultraviolet light was more stable with a collapse pressure three times that of the monolayer in the dark.