2014
DOI: 10.2478/s11532-014-0544-0
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A multi-property fluorescent probe for the investigation of polymer dynamics near the glass transition

Abstract: In addition to the commonly observed single molecule fluorescence intensity fluctuations due to molecular reorientation dynamics, a perylene bisimide-calixarene compound (1) shows additional on-off fluctuations due to its ability to undergo intramolecular excited state electron transfer (PET). This quenching process is turned on rather sharply when a film of poly(vinylacetate) containing 1 is heated above its glass transition temperature (T g), which indicates that the electron transfer… Show more

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Cited by 3 publications
(5 citation statements)
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“…In addition to the different kinetics, a significant fraction of molecules did not switch off at all in the higher T g polymers (see the Supporting Information). This points towards a heterogeneous distribution of free volume, as previously discussed for single‐molecule rotation measurements as well as for polymers with different T g values through single‐molecule photoinduced electron‐transfer studies …”
Section: Figuresupporting
confidence: 64%
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“…In addition to the different kinetics, a significant fraction of molecules did not switch off at all in the higher T g polymers (see the Supporting Information). This points towards a heterogeneous distribution of free volume, as previously discussed for single‐molecule rotation measurements as well as for polymers with different T g values through single‐molecule photoinduced electron‐transfer studies …”
Section: Figuresupporting
confidence: 64%
“…This points towards a heterogeneous distribution of free volume, as previously discussed for single-molecule rotation measurements [31] as well as for polymers with different T g values through single-molecule photoinduced electron-transfer studies. [32,33] Besides the photoswitching kinetics, the photostability of the probes determines their suitability for super-resolution fluorescence microscopy techniques. As shown in Figure 3, our photoswitch can perform many on-off cycles before photobleaching.…”
mentioning
confidence: 99%
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“…Especially when labeling dense polymer phases, the photoswitching kinetics can be significantly influenced. One important parameter describing the polymer density and thus the free volume available for the photoswitch for its cyclization or cycloreversion is its glass transition temperature T g as has been demonstrated, e.g., by studies on photoinduced electron transfer . Irie and co‐workers describe the dependency of the DAE switching kinetics on the environment, and we previously observed a reduced switching behavior in highly viscous media as well .…”
Section: Resultsmentioning
confidence: 99%
“…Zusätzlich zur unterschiedlichen Kinetik konnte ein signifikanter Anteil an Molekülen in Polymeren mit hohem T g nicht ausgeschalten werden (siehe Hintergrundinformationen). Dies deutet auf eine heterogene Verteilung von freiem Volumen hin, wie es bereits über Messungen der Einzelmolekülrotation, und, für Polymere mit unterschiedlichen Glasübergangstemperaturen, mittels photoinduziertem Elektronentransfer auf Einzelmolekülebene beobachtet wurde …”
Section: Figureunclassified