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Time-resolved spectroscopic studies of selected photoremovable protecting groupsAn, Huiying, 安慧颖 January 2010 (has links)
published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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Time-resolved absorption studies of chlorine dioxide photochemistry in solution /Bolinger, Joshua C. January 2006 (has links)
Thesis (Ph. D.)--University of Washington, 2006. / Includes bibliographical references (leaves 157-161).
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Time-resolved spectroscopic studies of the photophysics and photochemistry of selected benzoin and benzophenone compoundsDu, Yong, January 2008 (has links)
Thesis (Ph. D.)--University of Hong Kong, 2008. / Also available in print.
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Laser-induced breakdown spectroscopy as a diagnostic tool for coal finesAurelio, I. Andrew. January 2005 (has links)
Thesis (M.S.)--West Virginia University, 2005. / Title from document title page. Document formatted into pages; contains xii, 96 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 56-59).
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Time-resolved spectroscopic studies of Psoralens, Khellin, Visnagin and Lumichrome and derivativesFersi, Hannan 13 March 2006 (has links)
No description available.
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Ultrafast Dynamics of Flavin Cofactor in DNA Repair by Photolyase and in Signaling Formation of CryptochromeKao, Ya-Ting 30 July 2010 (has links)
No description available.
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Time-resolved spectroscopic studies of the photophysics and photochemistry of selected benzoin and benzophenone compoundsDu, Yong, 杜勇 January 2008 (has links)
published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy
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Polyyne rotaxanesMovsisyan, Levon January 2014 (has links)
This thesis describes the synthesis of polyyne rotaxanes and an investigation of their excited state photophysical properties. The threading of dumbbell-shaped carbon chains with macrocyclic components is a way to mechanically insulate and control the environment around the carbon chains. The resulting polyyne rotaxanes can serve as model compounds for insulated carbyne. Different strategies have been tested for the synthesis of polyyne rotaxanes with different topologies and structures. Study of rotaxanes in the excited states reveals strong electronic communication between an acetylenic thread and a macrocycle. Chapter 1 summarizes the field of acetylene scaffolding, introducing some recent achievements in acetylene chemistry. General synthetic methods for polyynes are discussed, and an introduction to active metal template synthesis of rotaxanes is given. Chapter 2 describes the synthesis of a family of polyyne rotaxanes with different axle lengths and macrocycles, prepared by homocoupling of terminal alkynes. Synthesis of hexayne rotaxane with functional pyridine end-group is presented and a number of crystal structures of polyyne rotaxanes are analyzed. Chapter 3 demonstrates the use of acetylene cross-coupling in the synthesis of rotaxanes. Synthesis of rotaxanes with different topological structure is provided. Chapter 4 details the excited state properties of polyynes studied by time -resolved spectroscopy. The complexes of rhenium(I) carbonyls with rotaxanes is presented and the excited state energy transfer in rotaxanes is studied. Chapter 5 explores new synthetic strategies for polyyne rotaxanes, using "masked" precursors. It also highlights the potential of carbenoid rearrangement of alkyliden es for the construction of linear and cyclic architectures. Chapter 6 is the summary of the project and general discussion of future directions. There are two appendices in the end of thesis: Appendix A covers the photophysics of rhenium tricarbonyl complex of the hexayne rotaxane with a small macrocycle and Appendix B reports work towards the synthesis of rotaxanes with platinum(II)-alkyne complexes.
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Resonance Raman and time-resolved spectroscopic studies of selected chlorobenzophenone and fluoroquinolonesLi, Wen, 李闻 January 2012 (has links)
Nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy was used in this thesis to
study the photoreduction reactions and the photochemistry of chloro-substituted benzophenone
(ClBP) triplets. The 3-chlorobenzophenone (3-ClBP), 4-chlorobenzophenone (4-ClBP) and
4,4′-dichlorobenzophenone (4,4′-diClBP) triplets exhibit similar properties to the parent BP
triplet. In isopropyl alcohol (IPA), the hydrogen abstraction reactions were observed for the
3-ClBP, 4-ClBP and 4,4′-diDlBP triplets. The diphenylketyl (DPK) radicals produced from the
hydrogen abstraction reactions were observed and the recombination of the DPK and
dimethylketyl radicals at the para-position was observed to form a light absorption transient
(LAT) species. In MeCN:H2O/1:1 aqueous solutions, these DPK radicals were also observed but
with a slower formation rate and the LAT species was produced by reaction with OH radicals.
Density functional theory (DFT) calculations were employed to help identify the intermediates
seen in the TR3 spectra and to help provide information about the vibrational motions of the
molecules examined. The 2-Cl-DPK radical was also observed in the TR3 spectra obtained in an
IPA solvent. However, the yield of the 2-Cl-DPK radical and the hydrogen abstraction rate was
observed to be significantly lower than that of the other ClBP examined here under the same
experimental conditions. The results DFT calculations show that the 2-chloro substituent changes
the geometry and the electron density of the molecular orbitals of the BP triplet so that the
2-chloro substituent reduces the hydrogen abstraction ability the triplet state, which is different
the hypothesis put forward by some previous studies that an electron-withdrawing group should
increase the photoreduction ability of BP derivatives.
Norfloxacin (NF) and Enoxacin (EN) are representative derivatives of Fluoroquinolones (FQ).
There are four forms of NF and EN and these different forms can coexist in aqueous solutions.
The UV-vis absorption and resonance Raman (RR) spectra of NF and EN have been obtained in
neat acetonitrile (MeCN), MeCN:HClO4-H2O/1:1 (pH?1), MeCN:H2O/1:1 (pH?7.5) and
MeCN:NaOH-H2O/1:1 (pH?13) solutions. The species observed in the spectra are assigned by
comparison of the experimental spectra to the DFT calculated spectra and the vibrational modes
are also described from the results of the DFT calculations. The absorption spectra of NF and EN
obtained in MeCN:H2O/1:1 solutions show that some other species coexist with the tautomeric
forms in the neutral aqueous solution. The RR spectra of the tautomeric forms of NF and EN
were obtained by subtraction of the RR spectra of the neutral and anionic forms from the RR
spectra of NF and EN in neutral aqueous solutions. The results suggest that NF and EN exists in
neutral, anionic and tautomeric forms in neutral aqueous solutions. The time dependant DFT
calculation results suggest that the fluorine atom has little contribution to the lowest unoccupied
molecular orbitals of the different forms of NF and EN. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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Time-resolved spectroscopic studies of hydrogen abstraction and decarboxylation reactions of selected benzophenone derivativesLi, Mingde, 李明德 January 2012 (has links)
Nanosecond time-resolved resonance Raman spectroscopy (ns-TR3), nanosecond transient absorption (ns-TA) and femtosecond transient absorption (fs-TA) were utilized to investigate the photochemistry of ketoprofen (KP), ketoprofen-purine dyads, fenofebric acid (FA) in different solutions.
For KP, the rate constant and reaction mechanism of KP are strongly dependent on the concentration of water. In neat acetonitrile and acetonitrile-rich solutions (water:acetonitrile?1:1, v:v), KP exhibits mostly benzophenone-like photochemistry to give rise to triplet state which in turn transforms to ketyl radical intermediate by hydrogen abstraction reaction. However, in aqueous solutions with higher water ratios (water:acetonitrile?80%) or acidic solutions, fs-TA studies found that after the irradiation of KP the singlet state will transform into the triplet state with a high efficiency through an intersystem crossing and a triplet state mediated decarboxylation reaction of KP is confirmed in water-rich and acidic solutions as well as the triplet state KP- anion generating a KP carbanion through a decarboxylation reaction. Triplet state ketoprofen (3KP) is firstly observed by ns-TR3 experiments and then excited triplet state intramolecular proton transfer (ESIPT) induces 3KP to facilely undergo the decarboxylation reaction to generate a triplet protonated carbanion biradical (3BCH) species, this observation is also confirmed by the results from density functional theory (DFT) calculations. For solutions with higher water concentrations (such as between 50% and 90% water by volume), the hydrogen abstraction and decarboxylation processes are two competitive pathways with different rate constants.
For KP-purine dyads, intramolecular hydrogen abstraction has been proposed to form ketyl-C1 biradical in acetonitrile solvent. Fs-TA study on KP-purine nucleoside dyads reveals that 3KP of cisoid dyads decays faster than 3KP of transoid dyads obtained in acetonitrile-water mixtures. Ns-TR3 experiments and DFT calculations suggest that ketyl-C1 biradical intermediate is generated with a higher efficiency for the 5-KP-dG dyad than for the 5-KP-dA and 5-KPGly-dA dyads. There is no ketyl-C1 biradical observed in ns-TR3 experiments for the 3-KP-dA dyad with transoid structure due to a steric effect.
For FA, a solvent dependent photochemistry is observed. A typical nπ* triplet state FA (3FA) is evolved by a high efficient intersystem crossing in acetonitrile-rich solutions and subsequently 3FA promptly abstracts a hydrogen from water molecule to generate a ketyl radical intermediate. In contrast, an inversion of the hydrogen abstraction and decarboxylation reactions of nπ* 3FA is rationalized with the assistance of water molecules when going from acetonitrile-rich to water-rich mixtures. However, in 50% PBS solution, FA carbanion is observed from the picosecond to nanosecond times and the cleavage of FA carbanion gives rise to the enolate 3- anion at later nanosecond delay times. / published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy
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