Hydrogen Abstraction of Ketoprofen in the Excited Triplet State with Indole and Methylindoles.

Relaxation of excited states and reactivity of ketoprofen (KP), one of the most popular nonsteroidal anti-inflammatory drugs, with indole and methylindoles have been studied with transient absorption and quantum chemical calculations. KP in the excited triplet state, KP*, abstracted a hydrogen atom from indole and methylindoles to afford a ketyl radical and a counter radical. The bimolecular quenching rate constants of KP* by indole and methylindoles, , and the hydrogen atom abstraction rate constants, , were obtained.

Characteristics of the excited triplet states of thiolated guanosine derivatives and singlet oxygen generation.

Thioguanine is sensitive to UVA light and generates singlet molecular oxygen (1O2*) when exposed to UVA. Three thioguanosine derivatives, 2',3',5'-tri-O-acetyl-6-thioguanosine (ta6TGuo), 2',3',5'-tri-O-acetyl-8-thioguanosine (ta8TGuo), and 2',3',5'-tri-O-acetyl-6,8-dithioguanosine (taDTGuo) were explored photophysically and photochemically. Nanosecond transient absorption and time-resolved near-infrared emission measurements were carried out to investigate the characteristics of their excited triplet states in acetonitrile solution.

Absorption Characteristics and Quantum Yields of Singlet Oxygen Generation of Thioguanosine Derivatives.

6-Thioguanine (1a) is considered to be photochemotherapeutic due to its specific characteristics of photosensitivity to UVA light and singlet molecular oxygen generation. To extend its phototherapeutic ability, two related thioguanines, 8-thioguanine (2a) and 6,8-dithioguanine (3a), have been designed and explored. Since the solubility of these thioguanines in dehydrated organic solvents is too poor to study, their triacetyl-protected ribonucleosides, that is, 2',3',5'-tri-O-acetyl-6-thioguanosine (1c), 2',3',5'-tri-O-acetyl-8-thioguanosine (2c) and 2',3',5'-tri-O-acetyl-6,8-dithioguanosine (3c) were prepared and investigated.

Acid Dissociation Equilibrium and Singlet Molecular Oxygen Quantum Yield of Acetylated 6,8-Dithioguanosine in Aqueous Buffer Solution.

2',3',5'-Tri- O-acetyl-6,8-dithioguanosine (taDTGuo) is a nucleoside derivative of drug 6-thioguanine and under further development as a potential photochemotherapeutic agent due to its desirable properties of photosensitivity to UVA light and singlet molecular oxygen generation. The photochemical characteristics of taDTGuo under biological conditions (namely in aqueous solution) were intensively investigated by the steady-state absorption and emission, time-resolved near-infrared emission measurements, and quantum chemical calculations. taDTGuo was found to be held in sequential acid dissociation equilibria within pH 3.