Targeted analytical methods for the determination of free fatty acids (FFAs) in human plasma are of high interest because they may help in identifying biomarkers for diseases and in monitoring the progress of a disease. The determination of FFAs is of particular importance in the case of metabolic disorders because FFAs have been associated with diabetes. We present a liquid chromatography-high resolution mass spectrometry (LC-HRMS) method, which allows the simultaneous determination of 74 FFAs in human plasma. The method is fast (10-min run) and straightforward, avoiding any derivatization step and tedious sample preparation. A total of 35 standard saturated and unsaturated FFAs, as well as 39 oxygenated (either hydroxy or oxo) saturated FFAs, were simultaneously detected and quantified in plasma samples from 29 subjects with type 2 diabetes mellitus (T2D), 14 with type 1 diabetes mellitus (T1D), and 28 healthy subjects. Alterations in the levels of medium-chain FFAs (C6:0 to C10:0) were observed between the control group and T2D and T1D patients.
25 March 2023 in European Journal of Organic Chemistry
A novel and easy‐to‐execute light‐driven protocol for the preparation of alkyl boronic acid pinacol esters from vinyl boronate usingN‐hydroxyphthalimide esters as the potential precursor is described. In this photochemical protocol, theN‐hydroxyphthalimide ester's fragmentation generates C‐centered radicals, which undergo a radical Michael addition to vinyl boronic pinacol ester furnishing the desired products. A good substrate scope having various functionalities is presented and good to high yields are obtained.
Synthetic photochemistry is an alternative, green and sustainable approach in organic synthesis, offering the possibility for the discovery of novel reactivities. Carboxylic acids are abundant and widely used as suitable radical precursors for light‐mediated processes, providing access to products that are not accessible via conventional methods. Herein, we report a green, cheap, metal‐free, photochemical decarboxylative protocol for the 1,4‐radical conjugate addition (Giese reaction) using thioxanthone, a commercially available organic molecule, or a thioxanthone‐triflic acid (TfOH) complex, as the photocatalyst, under LED 427 nm irradiation. A wide range of carboxylic acids, amino acids and Michael acceptors has been tested, affording the desired products in good to high yields.
Oxidized saturated fatty acids, containing a hydroxyl or an oxo functionality, have attracted little attention so far. Recent studies have shown that saturated hydroxy fatty acids, which exhibit cancer cell growth inhibition and may suppress β-cell apoptosis, are present in milk. Herein, we present the application of a liquid chromatography-high-resolution mass spectrometry (LC-HRMS) method for the detection and quantification of various saturated oxo fatty acids (SOFAs) previously unrecognized in milk. This robust and rapid analytical method, which involves simple sample preparation and a single 10-min run, revealed the presence of families of oxostearic acids (OSAs) and oxopalmitic acids (OPAs) in milk. 8OSA, 9OSA, 7OSA, 10OSA and 10OPA were found to be the most abundant SOFAs in both cow and goat milk. Higher contents of SOFAs were found in cow milk in comparison to goat milk. Together with SOFAs, ricinoleic acid, which is isobaric to OSA, was detected and quantified in all milk samples, following a “suspect” HRMS analysis approach. This unique natural fatty acid, which is the main component (>90%) of castor oil triglycerides, was estimated at mean content values of 534.3 ± 6.0 μg/mL and 460 ± 8.1 μg/mL in cow and goat milk samples, respectively.