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. 2024 Oct:76:103309.
doi: 10.1016/j.redox.2024.103309. Epub 2024 Aug 11.

Free radical fragmentation and oxidation in the polar part of lysophospholipids: Results of the study of blood serum of healthy donors and patients with acute surgical pathology

Alexey Fedoruk  1 , Oleg Shadyro  2 , Irina Edimecheva  3 , Dmitry Fedoruk  4 , Valery Khrutskin  5 , Leanid Kirkovsky  6 , Viktor Sorokin  7 , Halina Talkachova  8
Affiliations

Free radical fragmentation and oxidation in the polar part of lysophospholipids: Results of the study of blood serum of healthy donors and patients with acute surgical pathology

Alexey Fedoruk et al. Redox Biol. 2024 Oct.

Abstract

The interaction of reactive oxygen species with cell membrane lipids is usually considered in the context of lipid peroxidation in the nonpolar component of the membrane. In this work, for the first time, data were obtained indicating that damage to human cell membranes can occur in the polar part of lysophospholipids at the interface with the aqueous environment due to free radical fragmentation (FRF) processes. FRF products, namely 1-hexadecanoyloxyacetone (PAc) and 1-octadecanoyloxyacetone (SAc), were identified in human serum, and a GC-MS method was developed to quantify PAc and SAc. The content of FRF products in serum samples of 52 healthy donors was found to be in the range of 1.98-4.75 μmol/L. A linear regression equation, CPAc&SAc (μmol/L) = 0.51 + 0.064 × years, was derived to describe the relationship between age and content of FRF products. In 70 patients with acute surgical pathology in comparison with the control group of healthy donors, two distinct clusters with different concentration levels of FRF products were revealed. The first cluster: groups of 43 patients with various localized inflammatory-destructive lesions of hollow organ walls and bacterial translocation (septic inflammation) of abdominal cavity organs. These patients showed a 1.5-1.9-fold (p = 0.012) decrease in the total concentration of PAc and SAc in serum. In the second cluster: groups of 27 patients with ischemia-reperfusion tissue damage (aseptic inflammation), - a statistically significant increase in the concentration of FRF products was observed: in 2.2-4.0 times (p = 0.0001). The obtained data allow us to further understand the role of free-radical processes in the damage of lipid molecules. FRF products can potentially be used as markers of the degree of free-radical damage of hydroxyl containing phospholipids.

Keywords: Blood serum; Free radical fragmentation; Lysophosphatidylcholine; Palmitoxyacetone; Septic and aseptic inflammation; Stearoxyacetone.

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Conflict of interest statement

Declaration of competing interest We are sending the manuscript (original research article) by Alexey Fedoruk, Oleg Shadyro. Irina Edimecheva, Dmitry Fedoruk, Valery Khrutskin, Leanid Kirkovsky, Viktor Sorokin, Halina Talkachova entitled « Free radical fragmentation and oxidation in the polar part of lysophospholipids: results of the study of blood serum of healthy donors and patients with acute surgical pathology » to be evaluated for publication in «Redox Biology». The authors declare that there are no conflicts of interest. The authors alone are responsible for the content and writing of the paper. All authors have read the manuscript and concur with the submission, the work has not been published elsewhere, either completely, in part, or in another form, the manuscript has not been submitted to another journal and will not be published elsewhere.

Figures

Image 1
Graphical abstract
Fig. 1
Fig. 1
Scheme of homogeneous FRF of lysoglycerophospholipids with the formation of acyloxyacetones.
Fig. 2
Fig. 2
General chemical synthesis scheme for acyloxyacetones (R = C15H31 for PAc, C17H35 for SAc); DCC, N,N′-dicyclohexylcarbodiimide; DMAP, 4-dimethylaminopyridine.
Fig. 3
Fig. 3
The mass spectra of PAc (a), MAc (b) and SAc (c) in a calibration solution with a FRF products concentration of 10.0 μmol/L in the scan mode and the structures of the characteristic ionic fragments.
Fig. 4
Fig. 4
A – The chromatogram of a solution of PAc, MAc and SAc in SIM mode; B – The chromatogram of an authentic matrix sample in SIM mode; C – The chromatogram of an authentic matrix sample with the addition of MAc in SIM mode.
Fig. 5
Fig. 5
Calibration curves of PAc, SAc, MAc solutions in the concentration range of 1–10 μmol/L A – Calibration curve for PAc and SAc in surrogate and authentic matrix; B – Calibration curve for PAc, SAc and MAc in authentic matrix; C – Calibration curve for ratio of peak arears PAc to MAc and SAc to MAc.
Fig. 6
Fig. 6
A – Histogram of the distribution of the total concentration of PAc and SAc and Gaussian Kernel density estimation curve for the entire group of healthy donors aged 24–59 years (N = 52); B – Histograms of the data distribution frequencies for the total concentration of PAc and SAc and an estimation of the distribution density using the Gaussian smoothing method for two age groups: 24–40 years and 41–59 years.
Fig. 7
Fig. 7
A – Scatter plot of total PAc and SAc concentration data and regression lines for the group of healthy donors (N = 50); B – Dependence of the concentration of PAc, SAc and the sum of these FRF products on the age of patients СPAc (μmol/L) = 0.208 + 0.054 × years old, СSAc (μmol/L) = 0.011 + 0.021 × years old; СPAс&SAс (μmol/L) = 0.51 + 0.064 × years old.
Fig. 8
Fig. 8
A – The density distribution of data using the Gaussian smoothing method for the compared groups of patients with acute abdominal surgical pathology compared to healthy blood donors; B – Dependence of the sum of FRF products concentrations on the age of patients.
Fig. 9
Fig. 9
Scatter plot of total PAc and SAc concentration data for healthy donors, groups of patients with pancreonecrosis and intracranial hematomas against the age of patients.
Fig. 10
Fig. 10
Dendrogram of clustering of the studied groups using the method of centroid-weighted pair groups.
Fig. 11
Fig. 11
Suppression of the fragmentation reaction of alpha hydroxyl radicals of lysolipids by oxygen due to their oxidation.
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