The purpose of this paper is to investigate the dynamics of the fluorescence mechanism of boradiazaindacene (BODIPY) dye molecules, which are covalently bound to a polyethylene glycol based hydrogel structure with different concentrations, using a picosecond time-resolved spectroscopic technique. Since the hydrogel structure is capable of absorbing a large amount of water, without dissolving and without losing its shape, upon swelling, the distance between the BODIPY azide dyes is controllably changed; it is observed that the intensity weighted fluorescence lifetime for the highly concentrated donor dye molecules embedded in the hydrogel cluster network changes from 2.03 to 7.14 ns. Calculations based on our experimental results suggest that the fluorescence dynamics of the BODIPY azide dye molecules confined within the hydrogel network obeys the Forster resonance energy transfer (FRET) rather than self (or contact) quenching. If the hydrogel is dry, in which the distance between donors and acceptors is minimum, the energy transfer efficiency is found to be about 72%, and the distance between the two dye molecules is calculated to be 4.59 nm. Such a close placement causes a significant reduction in the fluorescence intensity due to a strong dipole-dipole interaction of the dye molecules. As the separation increases upon hydrogel swelling, the FRET efficiency reduces to 2%, which corresponds to a separation of 10 nm between two BODIPY dyes and hence a considerable increase in the level of fluorescence intensity. For the dilute hydrogel samples, the distance between the dye molecules is larger than the critical Forster distance. Therefore, the energy transfer efficiency for this type of dilute samples is found to be much lower.
Humidity induced change in the refractive index and thickness of the polyethylene glycol (PEG) coatings are in situ investigated for a range from 10 to 95%, using an optical waveguide spectroscopic technique. It is experimentally demonstrated that, upon humidity change, the optical and swelling characteristics of the PEG coatings can be employed to build a plastic fibre optic humidity sensor. The sensing mechanism is based on the humidity induced change in the refractive index of the PEG film, which is directly coated onto a polished segment of a plastic optical fibre with dipcoating method. It is observed that PEG, which is a highly hydrophilic material, shows no monotonic linear response to humidity but gives different characteristics for various ranges of humidity levels both in index of refraction and in thickness. It undergoes a physical phase change from a semi-crystalline structure to a gel one at around 80% relative humidity. At this phase change point, a drastic decrease occurs in the index of refraction as well as a drastic increase in the swelling of the PEG film. In addition, PEG coatings are hydrogenated in a vacuum chamber. It is observed that the hydrogen has a preventing effect on the humidity induced phase change in PEG coatings. Finally, the possibility of using PEG coatings in construction of a real plastic fibre optic humidity sensor is discussed.
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Humidity induced changes in the refractive index and thickness of polyethylene glycol (PEG) thin films are in situ determined by optical waveguide spectroscopy. PEG brushes are covalently attached to the surface of a thin gold film on a borosilicate crown glass (BK7) using a grafting-from chemical synthesis technique. The measurements are carried out in an attenuated total internal reflection setup. At low humidity levels, both the refractive index and the thickness change gradually due to swelling of the PEG thin films upon water intake. At around 80% relative humidity, a steep decrease in the refractive index and a steep increase in the thickness are observed as a result of a phase change from a semicrystalline state to a physical gel state. The hydrogenation of PEG films causes a less pronounced phase change from a semicrystalline state to a gel state. Due to fewer ether oxygen atoms available for the water molecules to make hydrogen bonding, the polymer has a more stable structure than before and the phase change is observed to shift to higher humidity levels. It is discussed that such a humidity induced change in the index of refraction can be utilized in constructing of a PEG based humidity sensor.
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