Protein thiyl radical reactions and product formation: a kinetic simulation

Protein thiyl radicals are important intermediates generated in redox processes of thiols and disulfides. Thiyl radicals efficiently react with glutathione and ascorbate, and the common notion is that these reactions serve to eliminate thiyl radicals before they can enter potentially hazardous processes. However, over the past years increasing evidence has been provided for rather efficient intramolecular hydrogen transfer processes of thiyl radicals in proteins and peptides. Based on rate constants published for these processes, we have performed kinetic simulations of protein thiyl radical reactivity. Our simulations suggest that protein thiyl radicals enter intramolecular hydrogen transfer reactions to a significant extent even under physiologic conditions, i.e. in the presence of 30 μM oxygen, 1 mM ascorbate and 10 mM glutathione. At lower concentrations of ascorbate and glutathione, frequently observed when tissue is exposed to oxidative stress, the extent of irreversible protein thiyl radical-dependent protein modification increases

How to name new chemical elements (IUPAC Recommendations 2016)

A procedure is proposed to name new chemical elements. After the discovery of a new element is established by the joint IUPAC-IUPAP Working Group, the discoverers are invited to propose a name and a symbol to the IUPAC Inorganic Chemistry Division. Elements can be named after a mythological concept, a mineral, a place or country, a property or a scientist. After examination and acceptance by the Inorganic Chemistry Division, the proposal follows the accepted IUPAC procedure and is then ratified by the Council of IUPAC. This document is a slightly amended version of the 2002 IUPAC Recommendations; the most important change is that the names of all new elements should have an ending that reflects and maintains historical and chemical consistency. This would be in general “-ium” for elements belonging to groups 1–16, i.e. including the f-block elements, “-ine” for elements of group 17 and “-on” for elements of group 18.This manuscript (PAC-REP-15-08-02) was prepared in the framework of IUPAC project 2015-031-1-200

How to name new chemical elements (IUPAC Recommendations 2016)

A procedure is proposed to name new chemical elements. After the discovery of a new element is established by the joint IUPAC-IUPAP Working Group, the discoverers are invited to propose a name and a symbol to the IUPAC Inorganic Chemistry Division. Elements can be named after a mythological concept, a mineral, a place or country, a property or a scientist. After examination and acceptance by the Inorganic Chemistry Division, the proposal follows the accepted IUPAC procedure and is then ratified by the Council of IUPAC. This document is a slightly amended version of the 2002 IUPAC Recommendations; the most important change is that the names of all new elements should have an ending that reflects and maintains historical and chemical consistency. This would be in general "-ium” for elements belonging to groups 1-16, i.e. including the f-block elements, "-ine” for elements of group 17 and "-on” for elements of group 18

Standard electrode potentials involving radicals in aqueous solution: inorganic radicals

Inorganic radicals, such as superoxide and hydroxyl, play an important role in biology. Their tendency to oxidize or to reduce other compounds has been studied by pulse radiolysis; electrode potentials can be derived when equilibrium is established with a well-known reference compound. An IUPAC Task Group has evaluated the literature and produced the recommended standard electrode potentials for such couples as (O2/O2·-), (HO·, H+/H2O), (O3/O3·-), (Cl2/Cl2·-), (Br2·-/2Br-), (NO2·/NO2-), and (CO3·-/CO32-

Rust never sleeps: the continuing story of the Iron Bolt

Since 1981, Gordon Research Conferences have been held on the topic of Oxygen Radicals on a biennial basis, to highlight and discuss the latest cutting edge research in this area. Since the first meeting, one special feature of this conference has been the awarding of the so-called Iron Bolt, an award that started in jest but has gained increasing reputation over the years. Since no written documentation exists for this Iron Bolt award, this perspective serves to overview the history of this unusual award, and highlights various experiences of previous winners of this “prestigious” award and other interesting anecdotes

Ferryl for real. The Fenton reaction near neutral pH

According to the literature, the Fenton reaction yields HO˙ and proceeds with 53 M−1 s−1 at 25 °C and low pH. Above pH 5, the reaction becomes first-order in HO−, and oxygen atom transfer has been detected, which indicates formation of oxidoiron(2+), FeO2+. These observations, and the assumption that the intermediate [FeHOO]+ decays approximately iso-energetically to FeO2+, allow one to estimate an Gibbs energy of formation FeO2+ of +15 ± 10 kJ mol−1, from which follows the one-electron E°′(FeO2+, H2O/[Fe(HO)2]+) = +2.5 ± 0.1 V and the two-electron E°′(FeO2+, 2H+/Fe2+, H2O) = +1.36 ± 0.05 V, both at pH 7. In the presence of HCO3−, formation of FeCO3(aq) occurs which may facilitate formation of the [FeHOO]+ intermediate, and leads to CO3˙−. At pH 7, the product of the Fenton reaction is thus FeO2+, or CO3˙− if HCO3− is present.ISSN:1477-9226ISSN:1477-923

A resurrection of the Haber-Weiss reaction

ISSN:2041-172