Peroxides. IV.² Aliphatic Diperacids

Two‐electron reduction and one‐electron oxidation of organic hydroperoxides by human myeloperoxidase

“…The pH profile of the reaction of ferric MPO with 3‐CPBA was similar (Fig. 2C), yielding a k int value of (3.6±0.2)×10 7 M −1 s −1 and p K 1 and p K 2 values of (3.5±0.2) and (7.1±0.7), respectively, indicating that the decrease in activity at basic pH could be due to deprotonation of 3‐CPBA (p K a is 7.8 [10]). These findings demonstrate that also with aliphatic and aromatic peroxy acids compound I formation is controlled by the protonation state of a distal ionizable group, most likely His 95 [11], as has been demonstrated for the reaction with hydrogen peroxide [6,8].…”

“…1 yielded a k int value of (2.2±0.1)×10 6 M −1 s −1 and p K 1 and p K 2 values of (3.7±0.6) and (8.4±0.6), respectively. Since the p K a of PAA is 8.2 [10], it is clear that p K 2 is due to the dissociation of PAA.…”

Synthesis and characterisation of peroxypinic acids as proxies for highly oxygenated molecules (HOMs) in secondary organic aerosol

“…However, there is currently a lack of suitable analytical methods, which is exacerbated by the lack of appropriate standards for method development and validation. One subgroup of peroxy compounds are peroxy acids, which, apart from their relevance for atmospheric chemistry, are widely used as chemical reagents, disinfectants and bleaching agents (Holah et al, 1990;Luukkonen and Pehkonen, 2017;Milne, 1998;Ramirez, 2008;Reinhardt and Borchers, 2009). Due to their widespread practical applications, several methods have been developed both for the quantification of the overall peracid content (Davies and Deary, 1988;Greenspan and MacKellar, 1948) and for the separation and detection of specific peracids (Cairns et al, 1975;Effkemann et al, 1998;Kirk et al, 1992).…”

The standard enthalpies of formation and thermal stability of diacyldiperoxides

“…Peroxides I, II, V, and VIII were synthesized by the reaction between peroxydecanoic acid and the corre sponding dicarboxylic acid dichlorides [1], and perox ides III, IV, VI, VII by the reaction between the corre sponding acid chlorides with dicarboxylic acids [2] in the presence of pyridine at 273 K. Preliminary purifi cation of the products was performed by multiple sequential recrystallization from acetone and hexane. Final purification involved preparative liquid column chromatography on alumina with activity grade II at 290-295 K. The chromatographic column length was 50 cm, and hexane was used as an eluent.…”