Solute Dynamics in Liquid Systems: Experiments and Molecular Dynamics Simulations

Open Access
Rumble, Christopher Allen
Graduate Program:
Doctor of Philosophy
Document Type:
Date of Defense:
April 26, 2017
Committee Members:
  • Mark Maroncelli, Dissertation Advisor/Co-Advisor
  • Mark Maroncelli, Committee Chair/Co-Chair
  • John B Asbury, Committee Member
  • William George Noid, Committee Member
  • Michael Anthony Hickner, Outside Member
  • electron transfer
  • proton transfer
  • ionic liquids
  • ultrafast spectroscopy
  • rotational dynamics
  • solvation dynamics
  • T1 relaxation
  • G-quadruplexes
  • charge transfer
  • molecular rotors
  • fluorescence
  • molecular dynamics simulation
This work reports on explorations into the effect of the liquid environment on the dynamics and kinetics of a range solute processes. The first study (Chapter 3) explores the photoisomerization of the rotor probe 9-(2-carboxy-2-cyanovinyl)julolidine, or CCVJ. Rotor probes are a class of fluorophores that undergo photoinduced isomerization reactions resulting in non-radiative relaxation out of the excited state. Literature reports had suggested that CCVJ exhibited a ‘flow effect,’ in which the emission intensity of CCVJ increases when the fluorophore solution is flowed at modest rates. Using steady-state and time-resolved fluorescence and 1H-NMR spectroscopy we show that the flow effect can be attributed to creation of a mixture of fluorescent and non-fluorescent CCVJ isomers by the excitation. The next study, Chapter 4, examines the the fluorescence of DNA G-quadruplex structures (GQSs), non-helical single-stranded DNA structures that exhibit quantum yields significantly higher than helical DNA or its constituent bases. By using a constant GQS core sequence we show that the addition of ‘dangling’ nucleotides can modulate emission from the GQS whereas conventional quenchers do not. The emission can also be altered by changes in temperature and addition of crowding reagents such as poly(ethylene glycol). Using time-resolved emission spectroscopy we show that GQS emission can be approximately dissected into two emitting populations with distinct kinetics. Chapters 5 and 6 report on the effects of solvation on charge transfer reactions in conventional molecular solvents and ionic liquid/conventional solvent mixtures. In Chapter 5 the excited state intramolecular proton transfer reaction of 4′-N,N-diethylamino-3-hydroxyflavone (DEAHF) is studied using sub-picosecond Kerr-gated emission spectroscopy in mixtures of acetonitrile and propylene carbonate. Previous studies of DEAHF tautomerization had shown that the proton transfer rate and equilibrium constant are highly dependent on both solvation dynamics and solvent polarity. Using acetonitrile/propylene carbonate mixtures, which have nearly identical polarity but have solvation times that vary over an order of magnitude, we were able to demonstrate that fast solvation dynamics introduces a barrier to the reaction and slows down the proton transfer rate. In Chapter 6 the intramolecular electron transfer reaction of 9-(4-biphenyl)-10-methylacridinium (BPAc+) is studied in mixtures of an ionic liquid and acetonitrile. Using KGE and picosecond time-correlated single photon counting measurements we show that the BPAc+ electron transfer rate is highly correlated with the mixture solvation time, consistent with rates observed in conventional solvents. Finally, Chapters 7 and 8 are an exploration of solute rotational dynamics in ionic liquids (ILs). Solute rotations in these unique solvents have been shown to be non-diffusive and poorly predicted by hydrodynamic theories of friction. We set out to explore the mechanisms of solute rotation in ILs using a combination of experimental methods and molecular dynamics (MD) simulations. In Chapter 7 the rotational dynamics of benzene and the IL cation 1- ethyl-3-methylimidizolium are studied using a combination of 2H longitudinal spin relaxation (T1) measurements and MD simulations. Using the simulations for guidance, we were able to interpret T1 measurements outside of the extreme narrowing limit. After the realism of the simulations was validated, they were then used to show that benzene exhibits markedly different dynamics for ‘spinning’ about the C6 symmetry axis and ‘tumbling’ (rotation of the C6 axis), and that large amplitude jump motions and orientational caging are prominent features of benzene’s rotations in ILs. Chapter 8 extends the benzene work to examine the effect of molecular size and charge distribution on solute rotational dynamics in ILs. Combining fluorescence anisotropy and T1 relaxation measurements with MD simulations of a carefully chosen set of probe molecules we show that molecular charge has only a modest effect of friction experienced by a rotating solute, whereas an increase in molecular size results in a substantial increase in rotation times. After validation of the simulations, we showed that large amplitude jumps and orientational caging dynamics, similar to what was observed with benzene, are also present in these solutes.