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^..     

Selective oxidation of benzyl alcohol to benzaldehyde, 1‐phenylethanol to acetophenone and fluorene to fluorenol catalysed by iron (II) complexes supported by pincer‐type ligands: Studies on rapid degradation of organic dyes

Hexacoordinated non‐heme iron complexes [Fe^II(L¹)₂](ClO₄)₂ ( 1 ) and [Fe^II(L²)₂](PF₆)₂ ( 2 ) have been synthesized using ligands L¹ = (E)‐2‐chloro‐6‐(2‐(pyridin‐2ylmethylene) hydrazinyl)pyridine and L² = (E)‐2‐chloro‐6‐(2‐(1‐(pyridin‐2‐yl)ethylidene)hydrazinyl) pyridine]. These complexes are highly active non‐heme iron catalysts to catalyze the C (sp³)?H bonds of alkanes. These iron complexes have been characterized using ESI?MS analysis and molecular structures were determined by X‐ray crystallography. ESI ? MS analysis also helped to understand the generation of intermediate species like Fe^III?OOH and Fe^IV=O. DFT and TD?DFT calculations revealed that the oxidation reactions were performed through high‐valent iron center and a probable reaction mechanism was proposed. These complexes were also utilized for the degradation of orange II and methylene blue dyes.     

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.     

Flash Vacuum Pyrolysis: Techniques and Reactions

Flash vacuum pyrolysis (FVP) had its beginnings in the 1940s and 1950s, mainly through mass spectrometric detection of pyrolytically formed free radicals. In the 1960s many organic chemists started performing FVP experiments with the purpose of isolating new and interesting compounds and understanding pyrolysis processes. Meanwhile, many different types of apparatus and techniques have been developed, and it is the purpose of this review to present the most important methods as well as a survey of typical reactions and observations that can be achieved with the various techniques. This includes preparative FVP, chemical trapping reactions, matrix isolation, and low temperature spectroscopy of reactive intermediates and unstable molecules, the use of online mass, photoelectron, microwave, and millimeterwave spectroscopies, gas‐phase laser pyrolysis, pulsed pyrolysis with supersonic jet expansion, very low pressure pyrolysis for kinetic investigations, solution‐spray and falling‐solid FVP for involatile compounds, and pyrolysis over solid supports and reagents. Moreover, the combination of FVP with matrix isolation and photochemistry is a powerful tool for investigations of reaction mechanism.     

Computational modelling of multi-material energetic materials and systems

ABSTRACT

In this paper, we present a systematic roadmap for developing a robust and parallel multi-material reactive hydrodynamic solver that integrates historically stable algorithms with new and current modern methods to solve explosive system design problems. The Ghost Fluid Method and Riemann solvers were used to enforce appropriate interface boundary conditions. Improved performance in terms of computational work and convergence properties was achieved by modifying a local node sorting strategy that decouples ghost nodes, allowing us to set material boundary conditions via an explicit procedure, removing the need to solve a coupled system of equations numerically. The locality and explicit nature of the node sorting concept allows for greater levels of parallelism and lower computational cost when populating ghost nodes. Non-linear numerical issues endemic to the use of real Equations of State in hydro-codes were resolved by using more thermodynamically consistent forms allowing us to accurately resolve large density gradients associated with high energy detonation problems at material interfaces. Pre-computed volume tables were implemented adding to the robustness of the solver base.     

Crosslinking‐induced morphology change of latex nanoparticles: A study of RAFT‐mediated polymerization in aqueous dispersed media using amphiphilic double‐brush copolymers as reactive surfactants

Amphiphilic double‐brush copolymers (DBCs) with each graft site quantitatively carrying both a hydrophilic poly(ethylene oxide) (PEO) graft and a hydrophobic polystyrene (PSt) graft are synthesized by sequential reversible addition‐fragmentation chain transfer (RAFT) polymerization and ring‐opening metathesis polymerization (ROMP). These DBCs are used as both surfactants and polyfunctional RAFT agents in the radical polymerization of St in aqueous dispersed media. Miniemulsions with narrowly dispersed St‐based nanodroplets are readily obtained after ultrasonication of the reaction mixtures. Without the presence of crosslinker, chain‐extension polymerization of St from the DBCs yields well‐defined polymeric latexes with narrow size distributions. However, with the presence of divinylbenzene (DVB) as the crosslinker, vesicular polymeric nanoparticles are formed as the major product. Such crosslinking‐induced change in morphology of the resulting latex nanomaterials may be ascribed to the increase of interfacial curvature in the heterophase systems during crosslinking polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3250–3259     

Selective nucleophilic additions to poly(methacrylate)s containing isothiocyanate moieties in the side chains and their application in cross‐linking

Reactivity of isothiocynate moieties in the side chain of polymethacrylate with amine, alcohol, or thiol was investigated, and the reactions were applied to preparation of networked polymers. Isothiocyanate of polymer side chain rapidly reacted with amines without a catalyst, to give the corresponding thioureas. However, it did not react with alcohols or thiols under the same conditions. Using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) as a catalyst, addition of alcohols or thiols to the isothiocyanate proceeded smoothly. Addition of amines, alcohols, and thiols to isothiocyanates moiety contained in the side chain of polymethacrylate also proceeded readily with or without the catalyst, respectively, to effectively give the corresponding side chain modified polymers. Occurrence of these additions was confirmed by ¹H NMR and IR measurements. Glass transition temperatures and thermal decomposition temperatures of the obtained polymers were investigated by differential scanning calorimetry and thermogravimetric analysis. Networked polymers were easily prepared by addition of 1,6‐hexamethylenediamine or hexamethylene glycol to the polymethacrylate having isothiocyanato groups. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1832–1842     

Aggregation-Induced Generation of Reactive Oxygen Species: Mechanism and Photosensitizer Construction

Luminogens with aggregation-induced emission (AIEgens) have been widely applied in the field of photodynamic therapy. Among them, aggregation-induced emission photosensitizers (AIE–PSs) are demonstrated with high capability in fluorescence and photoacoustic bimodal imaging, as well as in fluorescence imaging-guided photodynamic therapy. They not only improve diagnosis accuracy but also provide an efficient theranostic platform to accelerate preclinical translation as well. In this short review, we divide AIE–PSs into three categories. Through the analysis of such classification and construction methods, it will be helpful for scientists to further develop various types of AIE–PSs with superior performance.     

PhI(OTf)2 Does Not Exist (Yet)**

PhI(OTf)₂ has been used for the past 30 years as a strong I(III) oxidant for organic and inorganic transformations. It has been reported to be generated in situ from the reactions of either PhI(OAc)₂ or PhI=O with two equivalents of trimethylsilyl trifluoromethanesulfonate (TMS-OTf). In this report it is shown that neither of these reactions generate a solution with spectroscopic data consistent with PhI(OTf)₂, with supporting theoretical calculations, and thus this compound should not be invoked as the species acting as the oxidant for transformations that have been associated with its use.     

Synthesis of Aminopyridines and Aminopyridones by Cobalt‐Catalyzed [2+2+2] Cycloadditions Involving Yne‐Ynamides: Scope,Limitations, and Mechanistic Insights

An in‐depth study of the cobalt‐catalyzed [2+2+2] cycloaddition between yne‐ynamides and nitriles to afford aminopyridines has been carried out. About 30 nitriles exhibiting a broad range of steric demand and electronic properties have been evaluated, some of which open new perspectives in metal‐catalyzed arene formation. In particular, the use of [CpCo(CO)(dmfu)] (dmfu=dimethyl fumarate) as a precatalyst made possible the incorporation of electron‐deficient nitriles into the pyridine core. Modification of the substitution pattern at the yne‐ynamide allows the regioselectivity to be switched toward 3‐ or 4‐aminopyridines. Application of this synthetic methodology to the construction of the aminopyridone framework using a yne‐ynamide and an isocyanate was also briefly examined. DFT computations suggest that 3‐aminopyridines are formed by formal [4+2] cycloaddition between the nitrile and the intermediate cobaltacyclopentadiene, whereas 4‐aminopyridines arise from an insertion pathway.