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Indicating pressure and environmental effects by means of the spectral shift with rhodamine B and fluorescein
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See supplementary material at http://dx.doi.org/10.1063/1.4927687
for graphical user interfaces of control software (Fig. S1); example of wavelength range selection for peak fitting (Fig. S2); fitting parameters of the wavelength-pressure data (Tab. S3); wavelength and intensity shifts with pressure for FITC-melamine resin beads in ethanol (Fig. S4); rare example of reversible shift in wavelength with changing pressure for rhodamine B (1 ⋅ 10−5
M) in PDMS (Fig. S5); mathematical basis of ‘deviation from linearity (DL)’ plots (Eqs. S6); derivation of equation(2)
(Eqs. S7); DL vs. pressure plots for two more polarity functions different from those in the eqs. (1)-(3)
(Fig. S8); example of irreversible wavelength shift of rhodamine B in ethanol, when water is penetrating in the solution during pressure cycling (Fig. S9).[Supplementary Material]
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Fluorescence absorption and emission wavelengths can be influenced by environmental conditions, such as pressure, temperature and concentration. Here those effects are explored with an emphasis on determining the potential of rhodamine B and fluorescein as high-pressure indicators. The red shift of the emission peak maxima of rhodamine B and fluorescein are investigated in dependence of pressure up to 200 MPa using as the solvents water, ethanol and poly(dimethylsiloxane) (PDMS) with rhodamine B and water, polystyrene beads and melamine resin beads with fluorescein. Emission spectra recording and peak fitting is done automatically at time intervals of down to a second and with 0.3 nm wavelength resolution. The wavenumber-pressure relation for rhodamine B reveals increasing divergence from linear behavior in the sequence of the solvents water, ethanol and silicone rubber. Graphical correlation of the data diverging only slightly from linearity with a selection of polarity functions is enabled using the concept of ‘deviation from linearity (DL)’ plots. Using the example of rhodamine B dissolved in PDMS elastomer it is shown that there is a temperature induced irreversible molecular reordering, when scanning between 3 and ∼50°C, and a polarity change in the proximity of the embedded dye molecule. Swelling studies are performed with PDMS containing rhodamine B, where the elastomer is first put in water, then in ethanol and again in water. There a complex solvent exchange process is revealed in the elastomer demonstrating the feasibility of fluorescence spectroscopy, when observing variations in wavelength, to indicate and enlighten molecular rearrangements and swelling dynamics in the polymer, and polarity changes and solvent exchange processes in the dye solvation shell.
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