Document Type
Dissertation - University Access Only
Award Date
2008
Degree Name
Doctor of Philosophy (PhD)
Department / School
Chemistry
Abstract
Previous work on substituted 1,8-naphthalimides has demonstrated a capacity for tissue bonding. The chemistry responsible for this ability, however, remains elusive. Evidence indicates naphthalimides function through an initiation step involving oxide generation followed by propagation involving protein inter- and intra-molecular crosslinks resulting from oxide sensitization. There is additional evidence that naphthalimides incorporate into protein structure through an undetermined process thereby facilitating protein-protein linkages. Of these two the latter is the least understood. The electronic transitions observed in the naphthalimides are highly dependent upon the environment in which they are irradiated, the light by which they are irradiated and the structural motifs present in the naphthalimides themselves. Increasing solvent polarity results in a bathochromic shift of absorbance maximum. Additionally, inclusion of electron donating substituents on the naphthalene ring can result in a low level electronic state known as an internal charge-transfer (ICT) state. Further manipulations of the ICT state can be obtained through variation of the naphthalene ring substituents resulting in a twisted internal charge-transfer (TICT) state. Photochemical studies of 44 in various solvents and in the presence various substrates may provide clarification as to the electronic transitions resulting in tissue bonding. Development of naphthalimide technology would provide a benefit over current technology through its ease of application, its broad range of uses, its use of visible light, and its ability to affect strong stable bonds. It is therefore the purpose of this study to investigate the behavior of N-butyl-4-butylamino-1,8-naphthalimide (44) in a biological system upon exposure to visible light. The goal of this study is to better understand the fate of 44 in such a system. This study includes irradiation of 44 in phosphate buffered saline (PBS) using 400-500 nm radiation and the isolation and characterization of system products resulting from this irradiation. The naphthalimide was irradiated at steps within the 400-500 nm band to determine the wavelengths responsible for system product formation. Studies were conducted to determine the effect of solvent on system product formation. The naphthalimide was irradiated in the presence of biological substrates including gelatin and bovine Achilles tendon type I collagen to determine the effect on system products. Finally 44 was irradiated in the presence of compounds chosen for their ability to mimic structural motifs present in collagen in order to probe possible naphthalimide/collagen interactions. Irradiation of 44 in the full 400-500 nm band results in unreacted starting material and 3 system products: N-butyl-1,8-naphthalimide (N-butyl) , N-butyl-1,8-naphthalimide-4-ol ( 4-ol) and 4-amino-N-butyl-1,8-naphthalimide ( 4-amino ). System products result from instability of the TICT state and display a preference for formation at 460 nm. Irradiation of 44 in the presence of collagen results in the removal of the starting material and the 4-amino system product. A common structural component to both is a 4-position nitrogen resulting in a ground state molecular dipole and significant ionic system characteristics. This indicates potential for Schiff base formation between the naphthalimide and proteins. The naphthalimide/peptide interaction also displays a preference for 460 nm radiation. Potential excited states present in collagen have not been investigated; however the 44/protein interaction is a result of reactivity occurring from the naphthalimide ICT state.
Library of Congress Subject Headings
Wounds and injuries -- Treatment
Tissues
Photochemistry
Format
application/pdf
Number of Pages
152
Publisher
South Dakota State University
Recommended Citation
Ristow, Brent A., "Photochemistry of N-butyl-4-butylamino-1, 8-naphthalimide and its Behavior in a Biological Environment" (2008). Electronic Theses and Dissertations. 1470.
https://openprairie.sdstate.edu/etd2/1470
