Understanding the structure and dynamics of water's constituent ions, proton and hydroxide, has been a subject of numerous experimental and theoretical studies over the last century. Besides their obvious importance in acid-base chemistry, these ions play an important role in numerous applications ranging from enzyme catalysis to environmental chemistry. Despite a long history of research, many fundamental issues regarding their properties continue to be an active area of research. Here, we provide a review of the experimental and theoretical advances made in the last several decades in understanding the structure, dynamics, and transport of the proton and hydroxide ions in different aqueous environments, ranging from water clusters to the bulk liquid and its interfaces with hydrophobic surfaces. The propensity of these ions to accumulate at hydrophobic surfaces has been a subject of intense debate, and we highlight the open issues and challenges in this area. Biological applications reviewed include proton transport along the hydration layer of various membranes and through channel proteins, problems that are at the core of cellular bioenergetics.

Protons and Hydroxide Ions in Aqueous Systems

Thioflavin-T (ThT) can bind to amyloid fibrils and is frequently used as a fluorescent marker for in vitro biomedical assays of the potency of inhibitors for amyloid-related diseases, such as Alzheimer's disease, Parkinson's disease, and amyloidosis. Upon binding to amyloid fibrils, the steady-state (time-integrated) emission intensity of ThT increases by orders of magnitude. The simplicity of this type of measurement has made ThT a common fluorescent marker in biomedical research over the last 50 years. As a result of the remarkable development in ultrafast spectroscopy measurements, researchers have made substantial progress in understanding the photophysical nature of ThT. Both ab initio quantum-mechanical calculations and experimental evidence have shown that the electronically excited-state surface potential of ThT is composed of two regimes: a locally excited (LE) state and a charge-transfer (CT) state. The electronic wave function of the excited state changes from the initial LE state to the CT state as a result of the rotation around a single C-C bond in the middle of the molecule, which connects the benzothiazole moiety to the dimethylanilino ring. This twisted-internal-CT (TICT) is responsible for the molecular rotor behavior of ThT. This Account discusses several factors that can influence the LE-TICT dynamics of the excited state. Solvent, temperature, and hydrostatic pressure play roles in this process. In the context of biomedical assays, the binding to amyloid fibrils inhibits the internal rotation of the molecular segments and as a result, the electron cannot cross into the nonradiative "dark" CT state. The LE state has high oscillator strength that enables radiative excited-state relaxation to the ground state. This process makes the ThT molecule light up in the presence of amyloid fibrils. In the literature, researchers have suggested several models to explain nonradiative processes. We discuss the advantages and disadvantages of the various nonradiative models while focusing on the model that was initially proposed by Glasbeek and co-workers for auramine-O to be the best suited for ThT. We further discuss the computational fitting of the model for the nonradiative process of ThT.

Molecular rotors: what lies behind the high sensitivity of the thioflavin-T fluorescent marker.

Ultrafast photochemical reactions in liquids occur on similar or shorter time scales compared to the equilibration of the optically populated excited state. This equilibration involves the relaxation of intramolecular and/or solvent modes. As a consequence, the reaction dynamics are no longer exponential, cannot be quantified by rate constants, and may depend on the excitation wavelength contrary to slower photochemical processes occurring from equilibrated excited states. Such ultrafast photoinduced reactions do no longer obey the Kasha–Vavilov rule. Nonequilibrium effects are also observed in diffusion-controlled intermolecular processes directly after photoexcitation, and their proper description gives access to the intrinsic reaction dynamics that are normally hidden by diffusion. Here we discuss these topics in relation to ultrafast organic photochemical reactions in homogeneous liquids. Discussed reactions include intra- and intermolecular electron- and proton-transfer processes, as well as photochr...

Ultrafast Elementary Photochemical Processes of Organic Molecules in Liquid Solution

We present an overview of recent static and time-resolved vibrational spectroscopic studies of liquid water from ambient conditions to the supercooled state, as well as of crystalline and amorphous ice forms. The structure and dynamics of the complex hydrogen-bond network formed by water molecules in the bulk and interphases are discussed, as well as the dissipation mechanism of vibrational energy throughout this network. A broad range of water investigations are addressed, from conventional infrared and Raman spectroscopy to femtosecond pump–probe, photon-echo, optical Kerr effect, sum-frequency generation, and two-dimensional infrared spectroscopic studies. Additionally, we discuss novel approaches, such as two-dimensional sum-frequency generation, three-dimensional infrared, and two-dimensional Raman terahertz spectroscopy. By comparison of the complementary aspects probed by various linear and nonlinear spectroscopic techniques, a coherent picture of water dynamics and energetics emerges. Furthermore,...

Vibrational Spectroscopy and Dynamics of Water

Bioluminescence is a phenomenon that has fascinated mankind for centuries. Today the phenomenon and its sibling, chemiluminescence, have impacted society with a number of useful applications in fields like analytical chemistry and medicine, just to mention two. In this review, a molecular-orbital perspective is adopted to explain the chemistry behind chemiexcitation in both chemi- and bioluminescence. First, the uncatalyzed thermal dissociation of 1,2-dioxetane is presented and analyzed to explain, for example, the preference for triplet excited product states and increased yield with larger nonreactive substituents. The catalyzed fragmentation reaction and related details are then exemplified with substituted 1,2-dioxetanone species. In particular, the preference for singlet excited product states in that case is explained. The review also examines the diversity of specific solutions both in Nature and in artificial systems and the difficulties in identifying the emitting species and unraveling the color...

Chemi- and Bioluminescence of Cyclic Peroxides.

Optical steady-state and time-resolved spectroscopic methods were used to study the photoprotolytic reaction of oxyluciferin, the active bioluminescence chromophore of the firefly’s luciferase-cata...

Comparative study of the photoprotolytic reactions of D-luciferin and oxyluciferin.

Steady-state and time-resolved techniques were employed to study the nonradiative process of curcumin dissolved in ethanol and 1-propanol in a wide range of temperatures. We found that the nonradiative rate constants at temperatures between 175–250 K qualitatively follow the same trend as the dielectric relaxation times of both neat solvents. We attribute the nonradiative process to solvent-controlled proton transfer. We also found a kinetic isotope effect on the nonradiative process rate constant of ∼2. We propose a model in which the excited-state proton transfer breaks the planar hexagonal structure of the keto–enol center of the molecule. This, in turn, enhances the nonradiative process driven by the twist angle between the two phenol moieties.

Temperature dependence of the fluorescence properties of curcumin.

The excited-state proton transfer (ESPT) reaction of the "super"photoacid N-methyl-6-hydroxyquinolinium (MHQ) was studied using both fluorescence upconversion and time-correlated single photon counting (TCSPC) techniques. The ultrafast ESPT kinetics were investigated in various alcohols and water and determined to be solvent-controlled. The ESPT temperature dependence of MHQ was also studied in various alcohols and compared to that observed for another "super"photoacid, 5,8-dicyano-2-naphthol (DCN2). A full set of kinetic and thermodynamic parameters describing the ESPT was obtained. The protolytic photodissociation rate constant for MHQ was higher than that for DCN2, while the ESPT activation energies of MHQ were smaller. These findings are attributed to the approximately 3 orders of magnitude differences in excited-state acidities of MHQ and DCN2.

https://www.rsc.org/suppdata/cp/c2/c2cp23891h/c2cp23891h.pdf

Excited-state proton transfer in N-methyl-6-hydroxyquinolinium salts: solvent and temperature effects

Steady-state and time-resolved emission spectroscopy techniques were employed to study the excited-state proton transfer (ESPT) to water and D2O from QCy7, a recently synthesized near-infrared (NIR)-emissive dye with a fluorescence band maximum at 700 nm. We found that the ESPT rate constant, kPT, of QCy7 excited from its protonated form, ROH, is ∼1.5 × 1012 s–1. This is the highest ever reported value in the literature thus far, and it is comparable to the reciprocal of the longest solvation dynamics time component in water, τS = 0.8 ps. We found a kinetic isotope effect (KIE) on the ESPT rate of ∼1.7. This value is lower than that of weaker photoacids, which usually have KIE value of ∼3, but comparable to the KIE on proton diffusion in water of ∼1.45, for which the average time of proton transfer between adjacent water molecules is similar to that of QCy7.

Ultrafast Excited-State Intermolecular Proton Transfer of Cyanine Fluorochrome Dyes

Quasi-elastic neutron scattering was employed on samples of HCl-doped polycrystalline ice Ih. The analysis of the scattering signal provides the excess proton hopping time, τhop, in the temperature range of 140–195 K. The hopping time strongly depends on the temperature of the sample, and the activation energy of a hopping step is 17 kJ/mol. The values of τhop of the current experiment are in good agreement with calculated values derived from previous photochemical experiments,(1) in which we found that the proton hopping time at T > 242 K is on the order of 200 fs, roughly 10 times shorter than in liquid water at room temperature.

Itay Presiado

Papers

Comparative study of the photoprotolytic reactions of D-luciferin and oxyluciferin.

Temperature dependence of the fluorescence properties of curcumin.

Excited-state proton transfer in N-methyl-6-hydroxyquinolinium salts: solvent and temperature effects

Ultrafast Excited-State Intermolecular Proton Transfer of Cyanine Fluorochrome Dyes

Fast Proton Hopping Detection in Ice Ih by Quasi-Elastic Neutron Scattering