Ozonolysis Products Research Articles

Kinetics of Schiff base formation between the cholesterol ozonolysis product 3β-hydroxy-5-oxo-5,6-secocholestan-6-al and phosphatidylethanolamine

The kinetics of Schiff base formation between the cholesterol ozonolysis product 3β-hydroxy-5-oxo-5,6-secocholestan-6-al and dimyristoyl phosphatidylethanolamine was investigated. The activation energy of Schiff base formation at temperatures above and below the phase transition of the phospholipid was calculated. Increase in the activation energy derived from perturbation of the surface structure by the process of Schiff base formation was demonstrated. The presence of the Schiff base with the aldolization product of the oxysterol was also observed and its significance is discussed.

Solution ozonolysis of C70: stable products and chemiluminescence

For the first time the total and relative contents of the stable ozonolysis products of fullerene C70 solutions were identified by IR spectroscopy and elemental and chemical analyses. At the 100% conversion of C70 a mixture of products corresponding to the empirical formula C70O14.3H0.21 (epoxides: polyketones: polyesters: secondary fullerene ozonides (SFOZ): acids = 1.07: 6: 6: 0.21: 1.02) is formed. The content of polyketones, polyesters, acids, and SFOZ increases during the whole ozonolysis time (1 h). The number of oxygen atoms in epoxides C70On (n = 1–4) is lower than that in epoxides C60On (n = 1–6) formed by the ozonolysis of fullerene C60. The kinetic curve of accumulation of epoxides C70On (n = 1–4) passes through a maximum, which is observed 0.5 min after the beginning of ozonolysis. No epoxides were identified among the products 3.5 min after the ozonolysis. The photoluminescence (PL) (λmax = 645 and 685 nm) of fullerene polyketones in glassy EtO2/EtOH solutions frozen at 77 K was observed. This PL is much brighter, than that of polyketones formed upon the ozonolysis of fullerenes C60. For the first time the chemiluminescence (CL) was detected and studied upon the ozonolysis of C70 solutions at 300 K. The CL emitters are excited states of fullerene polyketones. The CL spectrum is partially overlapped with the known CL spectrum appeared upon the ozonolysis of C60 (λmax = 685 nm) but contains the greater number of maxima (λmax = 645 and 685 nm), which is related to a lower symmetry of the C70 oxidation products.

Hock Cleavage of Cholesterol 5α-Hydroperoxide: An Ozone-Free Pathway to the Cholesterol Ozonolysis Products Identified in Arterial Plaque and Brain Tissue

Cholesterol 5alpha-hydroperoxide, the major product of 1O2-oxidation of cholesterol, readily undergoes acid-catalyzed (Hock) cleavage of the C5-C6 bond to yield the 5,6-secosterol ketoaldehyde and the product of its intramolecular aldolization. These cholesterol oxidation products have long been thought to arise solely from ozonolysis of cholesterol, prompting the recent suggestion that ozone is produced in humans following their identification in arterial and brain tissue extracts.

The compaction of soot particles generated by spark discharge in the propene ozonolysis system

The compaction of soot aggregates generated by spark discharge is reported in the propene ozonolysis experiment. Since propene is not an organic aerosol precursor, the compaction cannot be explained by an earlier hypothesis attributing the compaction to the capillary forces of condensed organic matter in the small angle cavities of the aggregates [Saathoff, Naumann et al. (2003). Coating of soot and (NH 4) 2 SO 4 particles by ozonolysis products of alpha-pinene. Journal of Aerosol Science, 34, 1297–1321]. Several species among the gas-phase products from propene ozonolysis are proposed to contribute to the structural change of soot particles. As the compaction would directly change the morphology and the size distribution of soot particles, it is expected to induce important changes to the soot particles’ physical and chemical properties, which in turn would have significant atmospheric implications.

Detection of free amino acids in proxies of marine aerosol by photoelectron resonance capture ionization aerosol mass spectrometry

Photoelectron resonance capture ionization aerosol mass spectrometry (PERCI-AMS) has been applied to the analysis of proxies for marine aerosols with and without ozone; proxies used were mixed oleic acid–amino acid particles. The mechanism of ion formation for serine (104 m/z), glutamic acid (146 m/z), and phenylalanine (164 m/z) was dissociative electron attachment. This corresponds to loss of the hydrogen atom only, allowing for straightforward identification of the free amino acids. No ozonolysis products for the free amino acids were observed, even at high concentrations of ozone (500 ppm for 19 s). The direct detection of a novel gas-phase hydrated anion, [serine + H2O–H]–, is described. These preliminary results suggest that PERCI-AMS may provide an effective, simple and direct online method for the detection of organic nitrogen from free amino acids for future field studies of the marine troposphere.

Mass spectrometric characterization of β‐caryophyllene ozonolysis products in the aerosol studied using an electrospray triple quadrupole and time‐of‐flight analyzer hybrid system and density functional theory

The components of the organic aerosol formed due to gas-phase beta-caryophyllene ozonolysis were characterized by the use of a triple quadrupole and time-of-flight analyzer hybrid system coupled to an electrospray ionization source operated in the negative ion mode. A reversed-phase high-performance liquid chromatography (HPLC) column was used to achieve chromatographic separations at neutral pH which has been proved to induce ionization of organic compounds bearing aldehyde moieties. In addition to the detected oxo- and dicarboxylic acids, isomeric oxidation products, which bear multi-functional groups such as aldehyde, carbonyl and hydroxyl groups, could be differentiated by examining their corresponding collision-induced dissociation (CID) fragmentation pathways. Proposed fragmentation mechanisms were drawn for the experimentally observed fragmentation pathways in all the CID experiments. Cyclic oxidation products could also be discerned and their fragmentation behaviour under low energy collisional conditions was studied in detail. Gas-phase deprotonation potentials were calculated by the use of DFT B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d) + ZPVE to estimate the most thermodynamically favourable deprotonation site for efficient negative ion formation in the ion source. The optimized gas-phase geometries for the most prominent oxidation products reveal a strong intramolecular interaction between the upper and lower C4 carbon chains, which are formed after the decomposition of the primary ozonide generated by ozone attack of the reactive endocyclic C==C bond.

Quantum chemical and RRKM/master equation studies of isoprene ozonolysis: Methacrolein and methacrolein oxide

Methacrolein is a major product of isoprene ozonolysis, and methacrolein oxide is an important ozonolysis intermediate. We use CBS-QB3 and RRKM/master equation calculations to characterize all methacrolein formation pathways and all the unimolecular reactions of methacrolein oxide. Our predicted methacrolein yield agrees with experiment if we assume that all of the dioxirane formed from methacrolein oxide decomposes to methacrolein. The vinyl group of methacrolein oxide allows the species to cyclize to a dioxole with a reaction barrier lower than the barriers to either hydroperoxide or dioxirane formation. Two dioxole derivatives, 1,2-epoxy-2-methyl-3-propanal and 2-methyl-3-oxopropanal, should be measurable products of isoprene ozonolysis.

Synthesis and antiviral activity of lupane triterpenoids with modified cycle E

A reductive transformation of the peroxide products of ozonolysis of derivatives of 3beta-O-acetyl-22(17-->28)-abeo-lupa-17(28),20(29)-diene and the subsequent intramolecular ketalization led to a compound with a trioxane fragment. This is a new approach to a skeletal modification of triterpenoid cycle E. An activity of the synthesized compounds was found toward the viruses of type A influenza and herpes simplex.

Ozonolysis of alkenes and study of reactions of polyfunctional compounds: LXVIII. Investigation of transformations of peroxide products of olefins ozonolysis treated with hydroxylamine hydrochloride

Hydroxylamine hydrochloride efficiently reduces peroxide products of olefins ozonolysis into carbonyl compounds. Depending on the substrate character, solvent, and the treatment conditions the arising aldehydes transformed along the route aldehyde→aldoxime→nitrile→ester into individual compounds or their mixtures, or give the corresponding acetals.

Simulation chamber investigation of the reactions of ozone with short‐chained alkenes

Reaction rate coefficients and product yields in the gas phase reaction of O3 with the short‐chained alkenes ethene, propene, 1‐butene, isobutene, (E)‐butene, and (Z)‐butene were determined by Simulation of Atmospheric Photochemistry in a Large Reaction Chamber (SAPHIR). In a first set of experiments, reaction rate coefficients were acquired in an absolute reaction rate study from the measured concentration time profiles of ozone and the alkenes with side reactions being suppressed by adding a radical scavenger. The rate coefficients obtained agree well with literature data; for all but one alkene, the deviation was less than 10%. In a second set of experiments, OH yields were derived from the additional alkene turnover in the absence of a radical scavenger. In contrast to other studies, the OH yields determined in the dry chamber (propene, 0.10 ± 0.07; 1‐butene, 0.00 ± 0.08, isobutene, 0.30 ± 0.14; (Z)‐butene, 0.18 ± 0.09; and (E)‐butene, 0.70 ± 0.12) differed from the yields obtained under humid conditions (propene, 0.30 ± 0.08; 1‐butene, 0.30 ± 0.09; isobutene, 0.80 ± 0.10; (Z)‐butene, 0.40 ± 0.05; and (E)‐butene, 0.60 ± 0.12). The only exception was ethene ozonolysis, where no OH production was observed. HO2 yields (propene, 1.50 ± 0.75; 1‐butene, 1.60 ± 0.80; and isobutene, 2.00 ± 1.00) estimated from the additional ozone turnover compared to the experiments where radicals were not scavenged are reported here for the first time. Furthermore, the yields of the stable ozonolysis products CO, acetaldehyde, and formaldehyde were acquired by monitoring the concentration time profile of the respective compound.

On-line analysis of secondary ozonides from cyclohexene and d-limonene ozonolysis using atmospheric sampling townsend discharge ionization mass spectrometry

An on-line technique has been developed for analysis of gas-phase oxidation products formed in a reaction flow tube using different reaction times, concentrations and humidities. Products of ozonolysis, including thermally labile secondary ozonides (SOZ), were directly introduced into an atmospheric sampling townsend discharge ionization (ASTDI) source coupled to a triple quadrupole mass spectrometer (MS). Instant changes in the product composition were monitored in the total-ion chromatogram, or by fragment ions in the collision activated dissociation mass spectra by use of MS/MS scan techniques. Assignment of the individual ions was accomplished by inspection of the products’ mass spectra obtained by pre-concentration of the gas phase on a dedicated short column followed by chromatographic analysis. The observed reaction products correspond to those identified with other techniques. Of relevance for future mechanistic modelling, is the point that conditions of excess d-limonene favoured the formation of the d-limonene SOZ (major product), which was observed to be quite stable in dry and humid air, without oxidants. The d-limonene/ozone ratio was observed to be crucial for the stability of the SOZ, because it is prone to ozonolysis, and no SOZ could be detected in completely reacted 1:1 mixtures.

The catalytic ozonization of model lignin compounds in the presence of Fe(III) ions

The ozonization of several model lignin compounds (guaiacol, 2,6-dimethoxyphenol, phenol, and vanillin) was studied in acid media in the presence of iron(III) ions. It was found that Fe3+ did not influence the initial rate of the reactions between model phenols and ozone but accelerated the oxidation of intermediate ozonolysis products. The metal concentration dependences of the total ozone consumption and effective rate constants of catalytic reaction stages were determined. Data on reactions in the presence of oxalic acid as a competing chelate ligand showed that complex formation with Fe3+ was the principal factor that accelerated the ozonolysis of model phenols at the stage of the oxidation of carboxylic dibasic acids and C2 aldehydes formed as intermediate products.

Applications of CE‐ESI‐MS/MS analysis to structural elucidation of methylenecyclohexane ozonolysis products in the particle phase

The composition of secondary organic aerosol (SOA) from the gas phase ozonolysis of methylenecyclohexane was analyzed in a series of indoor aerosol chamber experiments. Capillary electrophoresis-electrospray ionization-ion trap mass spectrometry (CE/ESI-ITMS) was used for qualitative and quantitative analysis of SOA constituents. A number of dicarboxylic acids in the range of C(5)-C(6), such as adipic acid and glutaric acid, were found as major components of the organic products. Besides these smaller compounds, the formation of higher-molecular-weight compounds were observed under both neutral and acidic conditions. MS/MS experiments were carried out in order to obtain information on the monomer units and the structure of the dimers. MS(2) experiments of the two most prominent dimers with a mass-to-charge ratio (m/z) of 257 and m/z 273 yielded common fragments of m/z 83, 129 or 145. Based on the fragmentation patterns, these dimers are tentatively identified as carboxylate ester acids containing a unit of adipic acid in the structure. The dimer with m/z 257 was nearly 60% of the total detected compounds for both the neutral and acidic seed particle experiments.

Oxidized Cholesterol Metabolites Found in Human Atherosclerotic Lesions Promote Apolipoprotein C-II Amyloid Fibril Formation

Apolipoprotein amyloid deposits and lipid oxidation products are colocalized in human atherosclerotic tissue. In this study we show that the primary ozonolysis product of cholesterol, 3beta-hydroxy-5-oxo-5,6-secocholestan-6-al (KA), rapidly promotes human apolipoprotein (apo) C-II amyloid fibril formation in vitro. Previous studies show that hydrophobic aldehydes, including KA, modify proteins by the formation of a Schiff base with the lysine epsilon-amino group or N-terminal amino group. High-performance liquid chromatography, mass spectrometry, and proteolysis of KA-modified apoC-II revealed that KA randomly modified six different lysine residues, with primarily one KA attached per apoC-II molecule. Competition experiments showed that an aldehyde scavenging compound partially inhibited the ability of KA to hasten apoC-II fibril formation. Conversely, the acid derivative of KA, lacking the ability to form a Schiff base, accelerated apoC-II fibril formation, albeit to a lesser extent, suggesting that amyloidogenesis triggered by KA involves both covalent and noncovalent mechanisms. The viability of a noncovalent mechanism mediated by KA has been observed previously with alpha-synuclein aggregation, implicated in Parkinson's disease. Electron microscopy demonstrated that fibrils formed in the presence of KA had a similar morphology to native fibrils; however, the isolated KA-apoC-II covalent adducts in the absence of unmodified apoC-II formed fibrillar structures with altered ropelike morphologies. KA-mediated fibril formation by apoC-II was inhibited by the addition of the amine-containing compound hydralazine and the lipid-binding protein apoA-I. These in vitro studies suggest that the oxidized small molecule pool could trigger or hasten the aggregation of apoC-II to form amyloid deposits.

Synthesis, vibrational spectra and thermal stability of Ag 3O 4 and related Ag 7O 8X salts [formula omitted

The titled compounds were synthesized in high purity and yield by passing an ozone/oxygen mixture (5 vol% O 3 in O 2) through aqueous solutions of different Ag(I) salts at 273–298 K. Ag 3O 4 is obtained by ozonolysis of neutral or mildly acidic solutions of AgF (0.05 M) or AgBF 4 (0.05 M) at 273 K. Ozonolysis of aqueous solutions of AgNO 3, AgClO 4, Ag 2SO 4 and CH 3COOAg at 273–298 K afforded Ag 7O 8NO 3, Ag 7O 8ClO 4, Ag 7O 8HSO 4 and Ag 2O 2, respectively. Products were characterized by XRD, SEM, XPS, FT-IR, Raman spectroscopy and DSC. The spectroscopic data show that Ag 3O 4 and the Ag 7O 8X salts behave as metals at room temperature, due to overlap between valence and conduction bands in their electronic structure. The correct valence formulations for these compounds are (Ag 2.67+) 3O 4 and (Ag 2.67+) 6O 8 · Ag +X −, respectively. The thermal stability in air of the ozonolysis products was determined by DSC and also complementary XRD, FT-IR and Raman measurements. Ag 3O 4 was the least stable product, and thermally decomposed to 1.5Ag 2O 2(s) + 0.5O 2(g) within 20 h at 298 K. Thermal stabilities in air increased in the order Ag 3O 4 < Ag 7O 8ClO 4, Ag 7O 8HSO 4 < Ag 7O 8NO 3 < Ag 2O 2. This work resolves long-standing debate about the valence states of silver in Ag 3O 4 and Ag 7O 8X salts, and also provides valuable new spectroscopic information for these compounds. Attempts to prepare Ag 2O 3 by the ozonolysis route proved unsuccessful.

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system – a review

Abstract. The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation.

Ozonolysis of polybutadienes with different microstructure in solution

AbstractThe reaction of ozone with 1,4‐cis‐polybutadiene and polybutadiene having the following linking of the butadiene units: 1,4‐cis (47%), 1,4‐trans (42%), 1,2 (11%) was investigated in CCl4 solution. It was found out by means of IR‐spectroscopy and 1H‐NMR spectroscopy that the basic ozonolysis products of both elastomers are ozonides and aldehydes. The aldehyde:ozonide ratio was 11 : 89 and 27 : 73 for E‐BR and BR, respectively. In addition, epoxide groups were detected, only in the case of BR, and their yield was about 10% of that of the aldehydes. On the basis of BR ozonolysis it was established that the ozonide yield from 1,4‐trans units is about 50%. By using the aldehyde yields, an evaluation was made of the efficiency of ozone degradation of the two polybutadienes, according to which the respective value of BR is considerably higher than that of E‐BR. A reaction mechanism is proposed, which explains the formation of the identified functional groups and the differences in the ozone degradation of the studied elastomers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 427–433, 2007

Secondary organic aerosol from limona ketone: insights into terpene ozonolysis via synthesis of key intermediates

Limona ketone was synthesized to explore the secondary organic aerosol (SOA) formation mechanism from limonene ozonolysis and also to test group-additivity concepts describing the volatility distribution of ozonolysis products from similar precursors. Limona ketone SOA production is indistinguishable from alpha-pinene, confirming the expected similarity. However, limona ketone SOA production is significantly less intense than limonene SOA production. The very low vapor pressure of limonene ozonolysis products is consistent with full oxidation of both double bonds in limonene and furthermore with production of products other than ketones after oxidation of the exo double bond in limonene. Mass-balance constraints confirm that ketone products from exo double-bond ozonolysis have a minimal contribution to the ultimate product yield. These results serve as the foundation for an emerging framework to describe the effect on volatility of successive generations of organic compounds in the atmosphere.

Cytotoxic effects of oxysterols produced during ozonolysis of cholesterol in murine GT1-7 hypothalamic neurons

Ozone present in the photochemical smog or generated at the inflammatory sites is known to oxidize cholesterol and its 3-acyl esters. The oxidation results in the formation of multiple “ozone-specific” oxysterols, some of which are known to cause abnormalities in the metabolism of cholesterol and exert cytotoxicity. The ozone-specific oxysterols have been shown to favor the formation of atherosclerotic plaques and amyloid fibrils involving pro-oxidant processes. In the present communication, cultured murine GT1-7 hypothalamic neurons were studied in the context of cholesterol metabolism, formation of reactive oxygen species, intracellular Ca2 + levels and cytotoxicity using two most commonly occurring cholesterol ozonolysis products, 3β- hydroxy-5-oxo-5,6-secocholestan-6-al (ChSeco) and 5β, 6β-epoxy-cholesterol (ChEpo). It was found that ChSeco elicited cytotoxicity at lower concentration (IC50 = 21 ± 2.4 μM) than did ChEpo (IC50 = 43 ± 3.7 μM). When tested at their IC50 concentrations in GT1-7 cells, both ChSeco and ChEpo resulted in the generation of ROS, the magnitude of which was comparable. N-acetyl-l-cysteine and Trolox attenuated the cytotoxic effects of ChSeco and ChEpo. The intracellular Ca2 + levels were not altered by either ChSeco or ChEpo. Methyl-β-cyclodextrins, which cause depletion of cellular cholesterol, prevented ChSeco- but not ChEpo-induced cytotoxicity. The cell death caused by ChEpo, but not ChSeco, was prevented by exogenous cholesterol. Although oxidative stress plays a significant role, the results of the present study indicate differences in the pathways of cell death induced by ChSeco and ChEpo in murine GT1-7 hypothalamic neurons.

Heterogeneous SOA yield from ozonolysis of monoterpenes in the presence of inorganic acid

The secondary organic aerosol (SOA) yield of a series of montoerpenes was investigated to determine the relative amounts of organic mass, which can be attributed to mass produced by heterogeneous acid-catalyzed reactions. Five monoterpenes ( α-pinene, terpinolene, d-limonene, Δ 2-carene, β-pinene) were studied using a 2 m 3 indoor Teflon chamber and SOA was created in the presence of both acidic and neutral inorganic seed aerosol. The relative humidity was varied to create differing acidic seed environments. The heterogeneous aerosol production was influenced by the seed mass concentration, the acidity of the inorganic seed aerosol, and also molecular structure of the monoterpene ozonolysis products. This study also can be incorporated with our previously presented model of the kinetic expression for SOA mass production from heterogeneous acid-catalyzed reactions.