In the present Article, a reversible transition behavior from Jaggregates to excimer of an indocarbocyanine dye 1,1′-dioctadecyl-3,3,3′,3′tetramethylindocarbocyanine perchlorate (DiI) in Langmuir−Blodgett (LB) films was reported. Surface pressure−area (π−A) isotherms, UV−vis, and fluorescence spectroscopies as well as atomic force microscopy (AFM) were used for characterizations of the films. π−A isotherms suggest a balance of interactions between DiI and fatty acids in the mixed monolayer at DiI mole fraction X DiI = 0.4, resulting in a stable and ideally mixed monolayer. It has been observed that pure DiI formed excimer in LB films, whereas both J aggregates and excimer were formed in LB films when DiI was mixed with long chain fatty acids, viz., stearic acid or arachidic acid. In fatty acid matrix at X DiI = 0.4, only J aggregates were formed in the LB films. This has been confirmed using deconvolution of spectroscopic results as well as using excitation spectroscopy. The coherent size of the J aggregate was found to be a maximum for the mixed film at the mole fraction 0.4 of DiI in fatty acid matrix. The J-aggregate domain in the LB film contains approximately (20 ± 5) coherent sizes. However, J aggregates were totally absent when DiI was mixed with cationic surfactant, polymer, or nanoclay.
Abstract:In this communication we investigate two dyes N N ′ , -dioctadecyl thiacyanine perchlorate (NK) and octadecyl rhodamine B chloride (RhB) in Langmuir and Langmuir-Blodgett (LB) films with or with out a synthetic clay laponite. Observed changes in isotherms of RhB in absence and presence of nano-clay platelets indicate the incorporation of clay platelets onto RhB-clay hybrid films. AFM image confirms the incorporation of clay in hybrid films. FRET was observed in clay dispersion and LB films with and without clay. Efficiency of energy transfer was maximum in LB films with clay.Keywords: Fluorescence Resonance Energy Transfer (FRET), Langmuir-Blodgett, pressure-area isotherm, clay, dyes, Atomic Force Microscope (AFM).
IntroductionFluorescence Resonance Energy Transfer (FRET) is a physical phenomenon first described over 50 years ago [1,2]. Due to its sensitivity to distance, FRET has been used to investigate molecular level interaction. Fluorescence emission rate of energy transfer has wide applications in biomedical, protein folding, RNA/DNA identification and their energy transfer process [3][4][5][6][7][8][9]. Another important application of energy transfer is in dye lasers. Dye lasers have some limitations as the dye solution used as an active medium absorbs energy from the excitation source in a very limited spectral range and so the emission band also has these limitations. If a dye laser has to be used as an ideal source its spectral range needs to be extended. In order to extend the spectral range of operation, mixtures of different dye solutions/dye molecules embedded in solid matrices are being used. The work on energy transfer between different dye molecules in such mixtures in various solvents and solid matrices is, therefore, of great importance. The use of such energy transfer in dye lasers is also helpful in minimizing the photo-quenching effects and thereby, increasing the laser efficiency.FRET is the relaxation of an excited donor molecule by transfer of its excited energy to an acceptor molecule
In this communication, we report the design and synthesis as well as the supramolecular assembly behavior of a 2,4,5-triaryl imidazole derivative (compound 1) at the air-water interface and in thin films using Langmuir-Blodgett (LB) technique. The main idea for such a chemical structure is that the long alkyl chain and N-H of the imidazole core may help to form supramolecular architecture through the hydrophobic-hydrophobic interaction and hydrogen bonding, respectively. Accordingly, the interfacial behavior as well as morphology of 1 in thin films were studied through a series of characterization methods such as surface pressure-area (π-A) isotherm, hysteresis analysis, ultraviolet-visible (UV-vis) absorption and steady-state fluorescence spectroscopies, Fourier transform infrared, X-ray diffraction, Brewster angle microscopy (BAM), and atomic force microscopy (AFM) measurements, and so forth. Pressure-area isotherm is an indication toward the formation of supramolecular nanostructures instead of an ideal monolayer at the air-water interface. This has been confirmed by the hysteresis analysis and BAM measurement at the air-water interface. AFM images of 1 in the LB monolayer exhibits the formation of supramolecular nanowires as well as nanorods. By controlling different film-forming parameters, it becomes possible to manipulate these nanostructures. With the passage of time, the nanowires come close to each other and become straight. Similarly, nanorods come close to each other and form bundles of several rods in the LB films. H-bonding, J-aggregation, as well as compression during film formation might play a key role in the formation of such nanostructures. Electrical switching behavior of compound 1 was also observed because of the presence of an electron donor-acceptor system in 1. This type of organic switching behavior may be promising for next-generation organic electronics.
Abstract:Fluorescence resonance energy transfer (FRET) between two dyes acriflavine (Acf) and rhodamine B (RhB) were investigated in solution and Layer-by-Layer (LbL) self assembled films in presence and absence of clay mineral laponite. UV-Vis absorption and fluorescence spectroscopy studies suggest both the dyes present mainly as monomer in solution and films.Energy transfer occurred from Acf to RhB in solution and LbL films. The energy transfer efficiency increases in presence of clay laponite and the maximum efficiency were 78.17% and 32.54% in clay dispersion and in LbL films respectively. Presence of laponite particles onto LbL film was confirmed by atomic force microscopy investigations with a surface coverage of more than 75%. Energy transfer efficiency was pH sensitive and the energy transfer efficiency varies from 4.5% to 44.45% in mixed dye solution for a change in pH from 3.0 to 12.0. With proper calibration it is possible to use the present system under investigation to sense pH over a wide range of pH from 3.0 to 12.0.
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