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A new determination of molecular mobility in amorphous materials
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Text
TitleInfo
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Title
A new determination of molecular mobility in amorphous materials
SubTitle
PartName
PartNumber
NonSort
Identifier
ETD_1083
Identifier
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http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000051222
Language
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eng
Genre
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theses
Subject
(ID = SBJ-1);
(authority = RUETD)
Topic
Food Science
Subject
(ID = SBJ-2);
(authority = ETD-LCSH)
Topic
Amorphous substances
Subject
(ID = SBJ-3);
(authority = ETD-LCSH)
Topic
Sucrose
Subject
(ID = SBJ-4);
(authority = ETD-LCSH)
Topic
Vanillin
Abstract
This research investigated how the steady-state and time-resolved emission and intensity of phosphorescence from vanillin (4-hydroxy-3-methoxy benzaldehyde), a commonly used flavor compound, can be used to probe molecular mobility when dispersed within amorphous pure sucrose films. The luminescence properties and photophysical events of vanillin as a triplet state probe in amorphous sucrose films as a function of temperature was successfully characterized. The peak energy, bandwidth and lifetime data suggest that it is sensitive to molecular mobility and can be used monitor molecular mobility in amorphous sucrose films. Time-resolved phosphorescence intensity decays from vanillin were multiexponential both below and above the glass transition temperature, indicating that the pure (single component) amorphous matrix was dynamically heterogeneous on the molecular level.
Vanillin analogs (hydroxy, dihydroxy and ethyl vanillin)) phosphorescence lifetime were found to be extremely sensitive to the local environment in the amorphous sucrose in the glassy state and at the glass-to-rubber transition into the melt, and provided useful insight about the mechanism of vanillin sensitivity to molecular mobility. Based on this the capability of movement of methoxyl group about the C-O bond is thought to be the contributor to sensitivity of vanillin to matrix molecular mobility. The other possibility is that the effect is not that of larger group but rather that of group (like methoxy and ethoxy) not able to hydrogen bond to matrix, which can have a coupling the probe vibrations to the matrix.
Vanillin phosphorescence demonstrated that the average rate of matrix molecular mobility rates increases with an increase in the molecular size and Tg of the sugar in the glucose homologous series. A comparative study of mobility in three excipients sucrose, trehalose and PVP, using vanillin phosphorescence provided useful insight about their stabilizing effect.
The phosphorescence from probes erythrosin B, vanillin and tryptophan was successfully utilized to measure molecular mobility on three different time scales corresponding to each probe in amorphous sucrose and protein film. Molecular mobility was successfully studied in amorphous sucrose films by monitoring phosphorescence from the dual probe combination of erythrosin B: vanillin, erythrosin B: tryptophan and vanillin:tryptophan.
Vanillin analogs (hydroxy, dihydroxy and ethyl vanillin)) phosphorescence lifetime were found to be extremely sensitive to the local environment in the amorphous sucrose in the glassy state and at the glass-to-rubber transition into the melt, and provided useful insight about the mechanism of vanillin sensitivity to molecular mobility. Based on this the capability of movement of methoxyl group about the C-O bond is thought to be the contributor to sensitivity of vanillin to matrix molecular mobility. The other possibility is that the effect is not that of larger group but rather that of group (like methoxy and ethoxy) not able to hydrogen bond to matrix, which can have a coupling the probe vibrations to the matrix.
Vanillin phosphorescence demonstrated that the average rate of matrix molecular mobility rates increases with an increase in the molecular size and Tg of the sugar in the glucose homologous series. A comparative study of mobility in three excipients sucrose, trehalose and PVP, using vanillin phosphorescence provided useful insight about their stabilizing effect.
The phosphorescence from probes erythrosin B, vanillin and tryptophan was successfully utilized to measure molecular mobility on three different time scales corresponding to each probe in amorphous sucrose and protein film. Molecular mobility was successfully studied in amorphous sucrose films by monitoring phosphorescence from the dual probe combination of erythrosin B: vanillin, erythrosin B: tryptophan and vanillin:tryptophan.
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electronic resource
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xlix, 690 p. : ill.
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Ph.D.
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Includes bibliographical references
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by Rashmi Satyanarayan Tiwari
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Tiwari
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Rashmi Satyanarayan
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Rashmi Satyanarayan Tiwari
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Ludescher
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Richard
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chair
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Advisory Committee
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Richard Ludescher
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Takhistov
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Paul
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Paul Takhistov
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Huang
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Qingrong
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Qingrong Huang
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Vanderkooi
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Jane
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outside member
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Advisory Committee
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Jane Vanderkooi
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Rutgers University
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Graduate School - New Brunswick
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2008
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2008-10
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xx
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NjNbRU
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Rutgers University Electronic Theses and Dissertations
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ETD
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Title
Graduate School - New Brunswick Electronic Theses and Dissertations
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rucore19991600001
Identifier
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doi:10.7282/T3WM1DN7
Genre
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ETD doctoral
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The author owns the copyright to this work.
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Non-exclusive ETD license
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Author Agreement License
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I hereby grant to the Rutgers University Libraries and to my school the non-exclusive right to archive, reproduce and distribute my thesis or dissertation, in whole or in part, and/or my abstract, in whole or in part, in and from an electronic format, subject to the release date subsequently stipulated in this submittal form and approved by my school. I represent and stipulate that the thesis or dissertation and its abstract are my original work, that they do not infringe or violate any rights of others, and that I make these grants as the sole owner of the rights to my thesis or dissertation and its abstract. I represent that I have obtained written permissions, when necessary, from the owner(s) of each third party copyrighted matter to be included in my thesis or dissertation and will supply copies of such upon request by my school. I acknowledge that RU ETD and my school will not distribute my thesis or dissertation or its abstract if, in their reasonable judgment, they believe all such rights have not been secured. I acknowledge that I retain ownership rights to the copyright of my work. I also retain the right to use all or part of this thesis or dissertation in future works, such as articles or books.
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