The catalytic activity of theMFe2O4 spinel (M ¼ Mn, Co, Cu, Ni, Zn) was investigated for the oxidation of benzylic alcohols to respective carbonyls using tert-butyl hydroperoxide (TBHP) as an oxidant. The combination of CoFe2O4/TBHP in a dimethyl sulfoxide (DMSO) catalytic system was found to be most efficient for this catalytic conversion. A CoFe2O4 catalyst is magnetically separable and could be reusedwith no considerable loss in catalytic activity as proved for 5 consecutive cycles.

Reactive oxygen species (ROS) and reactive oxygen intermediates (ROI) play crucial roles in physiological processes. While excessive ROS damages cells, small fluctuations in ROS levels represent physiological signals important for vital functions. Despite the physiological importance of ROS, many fundamental questions remain unanswered, such as which types of ROS occur in cells, how they distribute inside cells, and how long they remain in an active form. The current study presents a ratiometric sensor of intracellular ROS levels based on genetically engineered voltage-gated sodium channels (roNaV). roNaV can be used for detecting oxidative modification that occurs near the plasma membrane with a sensitivity similar to existing fluorescence-based ROS sensors. Moreover, roNaV has several advantages over traditional sensors because it does not need excitation light for sensing, and thus, can be used to detect phototoxic cellular modifications. In addition, the ROS dynamic range of roNaV is easily manipulated in real time by means of the endogenous channel inactivation mechanism. Measurements on ROS liberated from intracellular Lucifer Yellow and genetically encoded KillerRed have revealed an assessment of ROS lifetime in individual mammalian cells. Flashlight-induced ROS concentration decayed with two major time constants of about 10 and 1000 ms.

Various cyclic systems containing active methylene sites are converted to ketones with a high level of selectivity under the optimized conditions

The catalytic activity of the manganese oxide was investigated for the oxidative functionalization of alkylaromatics to benzylic ketones using tert-butyl hydroperoxide (TBHP) as an oxidant. Manganese oxides of different types were tested for this reaction. Of all the oxides, the nano amorphous manganese dioxide exhibited significant catalytic activity and selectivity for the reaction. The nano amorphous MnO2/TBHP catalytic system could also be reused for six consecutive cycles with no considerable loss in catalytic activity.
Tetrahedron Letters 53 (2012) 2989–2992

Dimethyl- (DMD) and methyl(trifluoromethyl)-dioxiranes were used for oxyfunctionalization of spiro{1',7-cyclopropan-2-(E)-methyl-bicyclo[2.2.1]heptane} (1), tricyclo[3.2.2.0(2,4)]nonane (2), exo-endo-endo- (3) and exo-exo-exo-heptacyclo¬[9.3.1.0(2,10).0(3,8).0(4,6).0(5,9).0(12,14)]pentadecane (4), yielding tertiary alcohols as the main products. The rate constants for oxidation of 1-4 by DMD were measured and the Arrhenius parameters determined. The DFT theory (B3LYP and B3PW91) using restricted and unrestricted methods was employed to study the oxidation reaction of the C–H bond of cage hydrocarbons 1-4, adamantane, and acetone with DMD. The kinetic isotopic effect calculated using unrestricted methods agree with experiment. The reaction mechanism in terms of the concerted oxygen insertion vs the radical part is discussed.
2007, V.5, No.14, 2302 – 2310