Search Results (3)

Lipid hydroperoxides (LOOH) are the initial products of the peroxidation of unsaturated lipids and play a crucial role in lipid oxidation due to their ability to decompose into free radicals and cause adverse effects on human health. Thus, LOOHs are commonly considered biomarkers of oxidative stress-associated pathological conditions. Despite their importance, the sensitive and selective analytical method for determination is limited, due to their low abundance, poor stability, and low ionizing efficiency. To overcome these limitations, in this study, we chemically synthesized eight fatty acid hydroperoxides (FAOOH), including FA 18:1-OOH, FA 18:2-OOH, FA 18:3-OOH, FA 20:4-OOH, FA 20:5-OOH, FA 22:1-OOH, FA 22:6-OOH as analytes, and FA 19:1-OOH as internal standard. Then, they were chemically labeled with 2-methoxypropene (2-MxP) to obtain FAOOMxP by one-step derivatization (for 10 min). A selected reaction monitoring assisted targeted analytical method was developed using liquid chromatography/tandem mass spectrometry (LC-MS/MS). The MxP-labelling improved the stability and enhanced the ionization efficiency in positive mode. Application of reverse-phase chromatography allowed coelution of analytes and internal standards with a short analysis time of 6 min. The limit of detection and quantification for FAOOH ranged from 0.1–1 pmol/µL and 1–2.5 pmol/µL, respectively. The method was applied to profile total FAOOHs in chemically oxidized human serum samples (n = 5) and their fractions of low and high-density lipoproteins (n = 4). The linoleic acid hydroperoxide (FA 18:2-OOH) and oleic acid hydroperoxide (FA 18:1-OOH) were the most abundant FAOOHs in human serum and lipoproteins. Overall, our validated LC-MS/MS methodology features enhanced detection and rapid separation that enables facile quantitation of multiple FAOOHs, therefore providing a valuable tool for determining the level of lipid peroxidation with potential diagnostic applications. Full article

Rate coefficients at ambient temperature and atmospheric pressure for the reaction of ozone with 2-methoxypropene (2-MPE) and 2-ethoxypropene (2-EPE) were determined in an evacuable 100 L Teflon reaction chamber using absolute and relative rate methods. The product experiments were carried out using a 50 L Teflon reaction chamber in conjunction with FTIR as the detection technique. The rate coefficients (k in units of cm³ molecule⁻¹ s⁻¹) obtained are 1.18 ± 0.13 × 10⁻¹⁷ and 1.89 ± 0.23 × 10⁻¹⁷ for reactions with 2-MPE and 2-EPE, respectively. The effects of the alkoxy group on the gas-phase reactivity of alkyl vinyl ethers toward ozone are compared and discussed. The major ozonolysis products are methyl acetate, formaldehyde and CO₂ for 2-MPE, and ethyl acetate, formaldehyde and CO₂ for 2-EPE. Possible mechanisms for the two vinyl ethers are proposed based on the observed reaction products. Additionally, atmospheric lifetimes of 32 h and 21 h for 2-MPE and 2-EPE were estimated based on the measured rate constants and the ambient tropospheric concentration of ozone, respectively. The obtained values of the lifetimes indicate that the reaction with ozone is an important loss process for these vinyl ethers in the atmosphere, especially in polluted areas. Full article

A highly efficient, regioselective method for the direct 2,3-O-isopropylidenation of α-D-mannopyranosides is reported. Treatment of various α-D-mannopyranosides with 0.12 equiv of the TsOH·H₂O and 2-methoxypropene at 70 °C gave 2,3-O-isopropylidene-α-D-mannopyranosides directly in 80%~90% yields. Based on this method, a 3,6-branched α-D-mannosyl trisaccharide was prepared in 50.4% total yield using p-nitrophenyl 2,3-O-isopropylidene-α-D-mannopyranoside as the starting material. Full article