Thin film
nitrobenzene
Quartz cuvette
Figure 4-16. Schematics of the designed apparatus.
400 450 500 550 600 650
0
25 50 75 100 125 150
Intensity
wavelength (nm)
t=0 t=900 s
Figure 4-17. Fluorescence spectra of blend II thin film before and after being treated with nitrobenzene vapor.
400 450 500 550 600 650 0
20 40 60 80 100 120
Intensi ty
wavelength (nm)
t=0 t=900 s
Figure 4-18. Fluorescence spectra of blend III thin film before and after being treated with nitrobenzene vapor.
400 450 500 550 600 650 0
100 200 300 400 500 600
Intensi ty
wavelength (nm)
t=0 t=900 s
Figure 4-19. Fluorescence spectra of pure BPy-POSS thin film before and after being treated with nitrobenzene vapor.
0 200 400 600 800 0
15 30 45 60 75 90
PL quenching efficiency @ 470 mn (%)
Time (s)
blend II blend III
pure BPy-POSS
Figure 4-20. Quenching efficiency of nitrobenzene to the fluorescence emission of blend II, blend III and pure BPy-POSS thin films.
Chapter 5 Conclusion
In this study, a bispyrenyl-functional polyhedral oligomeric silsequioxanes (BPy-POSS) was successfully synthesized by hydrosilylation between hydride-monofunctional isobutyl-POSS (Si-H iBu-POSS) and vinyl-functional bispyrene (V-BPy) obtained by etherification of 1-pyrenemethanol (Py-OH) and methallyl dichloride. As characterized by MALDI-TOF mass spectrum, 1H NMR spectrum, DSC thermogram, and solution PL spectrum, as-synthesized BPy-POSS has a monodispersed molar mass distribution at 1441.4 m/z (a complex with Ag ions), only β-hydrosilylated bonds between bipyrenyl and POSS units, a semicrystalline solid composed of amorphous bipyrenyl domains and crystal POSS domains, and a mixture of butterfly-like microstructures with most close open forms.
The phase separation of blends of BPy-POSS and inert isobutyl-POSS (i-Bu POSS) was observed by two glass-transition-temperatures in DSC thermograms and a mixture of crystal and amorphous domains in XRD analyses. As shown in PL microscopic images, the BPy-POSS are well dispersed on the surface of i-Bu POSS crystals to form PL micropatterns closely similar to the fractals of pure i-Bu POSS crystals, which is inactive to the incident UV lights. For a PL sensor in detecting nitrobenzene vapor, the significant decay (20~40%) of pyrenyl excimer emission at 470 nm was observed within 100s. The efficiency of nitrobenzene-induced quenching process for 5% BPy-POSS is higher than that for 20% BPy-POSS. These results indicate the advantage of using i-Bu POSS crystals as a template to disperse BPy-POSS in the capacity improvement of pyrene-based chemical sensors.
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