Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Synthesis of Diverse Functionalized Quinoxalines by Oxidative Tandem Dual C−H Amination of Tetrahydroquinoxalines with Amines

The tandem dual C−H amination of tetrahydroquinoxalines with free amines under aerobic copper catalysis conditions has been demonstrated. The synthetic protocol proceeds with good substrate and functional group compatibility, mild reaction conditions, short reaction time, the use of the naturally abundant [Cu]/O₂ catalyst system, excellent chemoselectivity and synthetic efficiency, and with no need for the pre-installation of specific aminating agents, which offers a practical platform for the rapid and diverse synthesis of diaminoquinoxalines. Moreover, this work has shown the potential of single-electron-oxidation-induced C−H functionalization of N-heterocycles, and its application in the development of optoelectronic materials.     

Mechanisms of Cobalt/Phosphine-Catalyzed Cross-Coupling Reactions

>The combination of CoCl₂ with bidentate phosphines is known to catalyze challenging cross-coupling and Heck-type reactions, but the mechanisms of these valuable transformations have not been established. Here, we use electrospray-ionization mass spectrometry to intercept the species formed in these reactions. Our results indicate that a sequence of transmetalation, reductive elimination, and redox disproportionation convert the cobalt(II) precatalyst into low-valent cobalt complexes. These species readily transfer single electrons to alkyl bromides, which thereupon dissociate into alkyl radicals and Br⁻. In cross-coupling reactions, the alkyl radicals add to the cobalt catalyst to form observable heteroleptic complexes, which release the coupling products through reductive eliminations. In the Heck-type reactions, the low abundance of newly formed ionic species renders the analysis more difficult. Nonetheless, our results also point to the occurrence of single-electron transfer processes and the involvement of radicals in these transformations.     

Inner-Sphere Oxygen Activation Promoting Outer-Sphere Nucleophilic Attack on Olefins

Alkoxylation and hydroxylation reactions of 1,5-cyclooctadiene (cod) in an iridium complex with alcohols and water promoted by the reduction of oxygen to hydrogen peroxide are described. The exo configuration of the OH/OR groups in the products agrees with nucleophilic attack at the external face of the olefin as the key step. The reactions also require the presence of a coordinating protic acid (such as picolinic acid (Hpic)) and involve the participation of a cationic diolefin iridium(III) complex, [Ir(cod)(pic)₂]⁺, which has been isolated. Independently, this cation is also involved in easy alkoxy group exchange reactions, which are very unusual for organic ethers. DFT studies on the mechanism of olefin alkoxylation mediated by oxygen show a low-energy proton-coupled electron-transfer step connecting a superoxide–iridium(II) complex with hydroperoxide–iridium(III) intermediates, rather than peroxide complexes. Accordingly, a more complex reaction, with up to four different products, occurred upon reacting the diolefin–peroxide iridium(III) complex with Hpic. Moreover, such hydroperoxide intermediates are the origin of the regio- and stereoselectivity of the hydroxylation/alkoxylation reactions. If this protocol is applied to the diolefin–rhodium(I) complex [Rh(pic)(cod)], free alkyl ethers ORC₈H₁₁ (R=Me, Et) resulted, and the reaction is enantioselective if a chiral amino acid, such as l -proline, is used instead of Hpic.     

A phenomenological model for hydrocarbon high-temperature autoignition

A four-step phenomenological chemical–kinetic model is presented that is believed to apply to many aspects of combustion of most hydrocarbons at temperatures above about 1000 K. The mechanism involves chain initiation through reactive collision of fuel and oxidizer molecules, fuel consumption in a step that removes radicals, oxidizer consumption in a step that produces radicals and a chain termination step. An expression for the autoignition time is derived on the basis of this model and is applied to describe the ignition of propane–air mixtures and a few other hydrocarbons. It is shown that excellent agreement with ignition times obtained from detailed chemistry can be achieved by this model.     

High-Molecular-Weight Polynucleotides by Transferase-Catalyzed Living Chain-Growth Polycondensation

We present terminal deoxynucleotidyl transferase-catalyzed enzymatic polymerization (TcEP) for the template-free synthesis of high-molecular-weight, single-stranded DNA (ssDNA) and demonstrate that it proceeds by a living chain-growth polycondensation mechanism. We show that the molecular weight of the reaction products is nearly monodisperse, and can be manipulated by the feed ratio of nucleotide (monomer) to oligonucleotide (initiator), as typically observed for living polymerization reactions. Understanding the synthesis mechanism and the reaction kinetics enables the rational, template-free synthesis of ssDNA that can be used for a range of biomedical and nanotechnology applications.