Electrochemical Monitoring of ROS/RNS Homeostasis Within Individual Phagolysosomes Inside Single Macrophages

The existence of a homeostatic mechanism regulating reactive oxygen/nitrogen species (ROS/RNS) amounts inside phagolysosomes has been invoked to account for the efficiency of this process but could not be unambiguously documented. Now, intracellular electrochemical analysis with platinized nanowire electrodes (Pt‐NWEs) allowed monitoring ROS/RNS effluxes with sub‐millisecond resolution from individual phagolysosomes impacting onto the electrode inserted inside a living macrophage. This shows for the first time that the consumption of ROS/RNS by their oxidation at the nanoelectrode surface stimulates the production of significant ROS/RNS amounts inside phagolysosomes. These results establish the existence of the long‐postulated ROS/RNS homeostasis and allows its kinetics and efficiency to be quantified. ROS/RNS concentrations may then be maintained at sufficiently high levels for sustaining proper pathogen digestion rates without endangering the macrophage internal structures.     

Electron solvation by highly polar molecules: density functional theory study of atomic sodium interaction with water, ammonia, and methanol

This study further extends the scope of a previous paper [Y. Ferro and A. Allouche, J. Chem. Phys. 118, 10461 (2003)] on the reactivity of atomic Na with water to some other highly polar molecules known for their solvation properties connected to efficient hydrogen bonding. The solvation mechanisms of ammonia and methanol are compared to the hydration mechanism. It is shown that in the case of ammonia, the stability of the solvated system is only ensured by electrostatic interactions, whereas the methanol action is more similar to that of water. More specific attention is given to the solvation process of the valence 3s Na electron. The consequences on the chemical reactivity are analyzed: Whereas ammonia is nonreactive when interacting with atomic sodium, two chemical reactions are proposed for methanol. The first process is dehydrogenation and yields methoxy species and hydrogen. The other one is dehydration and the final products are methoxy species, but also methyl radical and water. The respective roles of electron solvation and hydrogen bonds network are analyzed in detail in view of the density of states of the reactive systems.     

Geometry changes of a Cu(I) phenanthroline complex on photoexcitation in a confining medium by time-resolved X-ray diffraction

Using a stroboscopic technique, in which the molecule is repeatedly excited and the structural change is probed more than 5000 times per second immediately after excitation, we performed a 16 K time-resolved single-crystal study of the microsecond lifetime triplet state of the Cu(I)phenanthroline derivative[Cu(I)(dmp)(dppe)][PF6] (dppe = 1,2-bis(diphenylphosphino)ethane). The geometry changes on excitation differ for the two symmetry-independent molecules, but are in the same direction as calculated for an isolated reference molecule, although the flattening distortion in the crystal is significantly smaller, implying that the reorganization energy is greatly affected by the confining medium.     

Intra- and intermolecular fluorescence quenching in 7-(pyridyl)indoles

Three isomeric 7-(pyridyl)indoles reveal very different, solvent-dependent photophysical properties. Due to rapid excited state depopulation involving intramolecular hydrogen bonding, 7-(2′-pyridyl)indole is practically nonfluorescent at room temperature. In nonpolar and polar aprotic solvents, 7-(3′-pyridyl)indole and 7-(4′-pyridyl)indole fluorescence strongly, but the emission is quenched in alcohols. Syn and anti rotameric forms of 7-(3′-pyridyl)indole are detected, each quenched to a different degree. This differential quenching is interpreted as evidence of enhanced S₁ → S₀ internal conversion being more efficient in cyclic solvates, with alcohol molecules forming a bridge between the proton donor and acceptor groups of an excited chromophore.     

Palladium‐Catalyzed Construction of Quaternary Stereocenters by Enantioselective Arylation of γ‐Lactams with Aryl Chlorides and Bromides

Herein, we report the first Pd‐catalyzed enantioselective arylation of α‐substituted γ‐lactams. Two sets of conditions were developed for this transformation, allowing for the use of either aryl chlorides or bromides as electrophiles. Utilizing a highly electron‐rich dialkylphosphine ligand we have been able to construct α‐quaternary centers in good yields (up to 91 % yield) and high enantioselectivities (up to 97 % ee).     

Bis[tetraruthenium(IV)]-containing polyoxometalates: [{Ru(IV)4O6(H2O)9}2Sb2W20O68(OH)2]4- and [{Ru(IV)4O6(H2O)9}2{Fe(H2O)2}2{β-TeW9O33}2H]-

The reaction of [Sb(2)W(22)O(74)(OH)(2)](12-) and [Fe(4)(H(2)O)(10)(β-TeW(9)O(33))(2)](4-) with (NH(4))(2)[RuCl(6)] in aqueous solution resulted in the novel ruthenium(IV)-containing polyanions [{Ru(IV)(4)O(6)(H(2)O)(9)}(2)Sb(2)W(20)O(68)(OH)(2)](4-) and [{Ru(IV)(4)O(6)(H(2)O)(9)}(2){Fe(H(2)O)(2)}(2){β-TeW(9)O(33)}(2)H](-), exhibiting two cationic, adamantane-like, tetraruthenium(IV) units {Ru(4)O(6)(H(2)O)(9)}(4+) bound to the respective polyanion in an external, highly accessible fashion.     

Nanoparticle morphology and aspect ratio effects in Ag/PVDF nanocomposites

Optical response in silver/polyvinylidene fluoride nanocomposite materials with nonspherical inclusions was examined using direct dipolar interband transitions, from density functional theory. We discuss here the dependence of the optical response of the material on the geometry, crystallographic makeup and end-cap morphology of the metallic inclusions, as well as on their orientation relative to the polarization direction of the applied electromagnetic field. Each periodic unit cell contained a single inclusion and a polymer matrix; thus, the composite behaved as a monodisperse, perfectly oriented material. Overall, the spectral location of the composite excitation spectrum was tied to that of the metallic inclusions and correlated well to quantum confinement models for the direction of polarization: As linear size of the inclusion increased in a given direction, the excitation spectrum of light polarized in that direction was red-shifted. The effect of the polymer matrix was also examined. Coulomb repulsion from matrix energy states led to splitting of nanoparticle-based energy levels, and the matrix conduction band became involved in high-energy transitions. These effects led to extensions of the spectra of nanocomposites with less stable {100}–basal plane inclusions to very low excitation energies. Attenuation or redshifting of nanoparticle peaks with high photon energies was also observed for materials with small linear sizes along the excitation direction. Comparisons with experimental and time-dependent density functional theory results suggest that estimating the complex dielectric constant from interband transition dipole moments, in a time-independent fashion, provides reliable qualitative spectra for these systems.     

Extraction Properties of Oligodentate Carbamoylmethylphosphine Oxides and β-Aminophosphine Oxides Toward Lanthanides and Rhenium(VII)

Abstract

The extraction properties of a series of carbamoylmethylphosphine oxides and β-aminophosphine oxides with lanthanide metal ions is presented. Tris[bis(2-diphenyl- phosphorylethyl)-aminoethyl]amine is shown to be highly effective for extraction of Re(VII).     

Selective Phosphorylation of α,β-Unsaturated Carbonyl Compounds

Abstract

Elaboration of effective methods of selective phosphorylation of α,β-unsaturated carbonyl compounds containing simultaneously C[dbnd]C and C[dbnd]O bonds, which may compete with each other or react consistently one after another, is one of the most complex problems in the modern organophosphorus synthesis. On the basis of our previous systematic investigations of kinetics and mechanism of the Pudovik and Abramov reactions in the series of α,β-unsaturated carbonyl compounds we have suggested three possible ways to solve this problem: a) soft reaction conditions, regulated by solvent, catalyst and temperature; b) interface catalysis; c) metallocomlex catalysis (reaction in the coordination sphere of transition metal).     

Competition of Different Addition and Cycloaddition Processes During Reaction of Phosphorus(II) and (III) Halides with Alkynes

Abstract

Addition of P-halogenophosphaalkenes to I-alkoxyalkynes provides either 2-phosphabutadienes 2 or P(II1)-substituted allenes 3. The reaction o f P-halogenophosphaalkenes I with I-aminoalkynes leads to the phosphetines 4 wa 5 - the product of 1,2-addition reaction.