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Cholesterol surrogates incorporating a benzophenone as part of the sterol tetracycle.

Photoactivatable analogues 4-6 of cholesterol (1), having their cross-linking site in the ring D sterol region, have been synthesized starting from bromotetralone 14 via enantioselective Robinson annulation to enone 13 and Suzuki carbonylative coupling to the appropriate phenylboronic acid. Each of 4-6 was shown to substitute successfully for 1 in an assay of apo A-I-induced cellular cholesterol efflux, indicating that these analogues equilibrated with 1 in all major cellular pools.

Benzophenones↗

Photoinduced omega-bond dissociation in the higher excited singlet (S2) and lowest triplet (T1) states of a benzophenone derivative in solution.

Photochemical properties of photoinduced omega-bond dissociation in p-benzoylbenzyl phenyl sulfide (BBPS) in solution were investigated by time-resolved EPR and laser flash photolysis techniques. BBPS was shown to undergo photoinduced omega-bond cleavage to yield the p-benzoylbenzyl radical (BBR) and phenyl thiyl radical (PTR) at room temperature. The quantum yield (phi(rad)) for the radical formation was found to depend on the excitation wavelength, i.e., on the excitation to the excited singlet states, S2 and S1 of BBPS; phi(rad)(S2) = 0.65 and phi(rad)(S1) = 1.0. Based on the CIDEP data, these radicals were found to be produced via the triplet state independent of excitation wavelength. By using triplet sensitization of xanthone, the efficiency (alpha(rad)) of the C-S bond fission in the lowest triplet state (T1) of BBPS was determined to be unity. The agreement between phi(rad)(S1) and alpha(rad) values indicates that the C-S bond dissociation occurs in the T1 state via the S1 state due to a fast intersystem crossing from the S1 to the T1 state. In contrast, the wavelength dependence of the radical yields was interpreted in terms of the C-S bond cleavage in the S2 state competing with internal conversion from the S2 to the S1 state. The smaller value of phi(rad)(S2) than that of phi(rad)(S1) was proposed to originate from the geminate recombination of singlet radical pairs produced by the bond dissociation via the S2 state. Considering the electronic character of the excited and dissociative states in BBPS showed a schematic energy diagram for the omega-bond dissociation of BBPS.

Benzophenones↗

Determination of ionic liquids solvent properties using an unusual probe: the electron donor-acceptor complex between 4,4'-bis(dimethylamino)-benzophenone and tetracyanoethene.

Michler's ketone (MK) and tetracyanoethene (TCNE) may be used as a UV-vis probe to investigate the solvent properties of ionic liquids (ILs). In molecular solvents, MK and TCNE give an electron donor-acceptor (EDA) complex, a zwitterionic species or a radical ion pair, depending on the aprotic or protic nature of the solvent and on its ionizing power. In agreement with the behavior observed in aprotic solvents, only the EDA complex was detected in ILs bearing low donor anions (beta < 0.7). The formation constant determined in [bmim][Tf(2)N] (K(c) = 5.6 (0.5) M(-1)) is similar to that measured in 1,2-dichloroethane at 25 degrees C. The visible absorption maximum (nu(max,CTC)) of the EDA complex is quantitatively described by a multiple correlation using the Kamlet-Taft pi, beta, and alpha parameters of the solvents. The H-bond donating capacity of ILs is not sufficient to determine the transformation of the EDA complex into the zwitterionic species, but the Kamlet-Taft alpha parameter seems to affect the position of the absorption band. The high ionization power of ILs, moreover, favors the slow dissociation of the EDA complex into its corresponding radical ion pair; this behavior generally characterizes highly polar and highly ionizing protic solvents, such as TFE and HFI. Finally, since the formation of the EDA complex is strongly affected by the presence of impurities, traces of nucleophiles (chloride or amines) or water may be easily detected through the change of the solution color.

Benzophenones↗