Multiple headspace solid‐phase microextraction using a new fiber for avoiding matrix interferences in the quantitative determination of ethyl carbamate in pickles

Abstract

Multiple headspace solid-phase microextraction (HS-SPME) using a novel fiber coated with anilino-methyl triethoxy silicane-methacrylic acid/terminated silicone oil has been introduced as a useful pretreatment technique coupled to gas chromatography-flame ionization detector for the detection of ethyl carbamate in pickles. Anilino-methyl triethoxy silicane and methacrylic acid are put into use simultaneously with the aim to increase the hydrogen interaction strength between ethyl carbamate and the coating. In addition, the new fiber exhibits high thermal stability, good reproducibility, and long lifetime. Extraction temperature, extraction time, amount of desiccant, and amount of sample were well optimized to guarantee the suitability of multiple HS-SPME. Significant matrix interference was observed among various types of pickles and the multiple HS-SPME procedure was proved to be effective in avoiding the matrix effect by a complete recovery of the analyte. The method showed satisfactory linearity (0.1-100 mg kg(-1)), precision (4.25%, n = 5), and detection limit (0.038 mg kg(-1)). The accuracy of the method was evaluated by comparison with standard addition method and the results were statistically equivalent. The study indicates that the multiple HS-SPME procedure is simple, convenient, accurate, and low-cost, and most of all, can be used for quantitative analysis in complex matrix without matrix effect.

Matrix effects demystified: Strategies for resolving challenges in analytical separations of complex samples

“…The use of SPME biocompatible extraction devices enables DI in complex samples through a biocompatible polymer that acts as a barrier that prevents macromolecules from attaching to the extraction phase, hence extending the lifetime of the devices, allowing reusability and minimization of MEs. Polydimethylsiloxane (PDMS), polyacrylonitrile (PAN), and Teflon AF are common polymers used as biocompatible binders for sorptive particles in SPME devices [75,92,93].…”

“…PDMS is a hydrophobic polymer that prevents the sorption of water and macromolecules and is thermally stable [92,93]. For these reasons, PDMS is typically used for GC applications, while PAN is hydrophilic by nature and forms a hydration layer through hydrogen bonds with the water molecules in the sample matrix, preventing the attachment of matrix interferences and is typically used for LC analysis [89,90,93]. These biocompatible phases prevent matrix components such as proteins and lipids from adhering to the extraction phase while allowing target analytes to sorb.…”

“…Besides standard addition calibration methods, multiple HS SPME techniques can account for matrix interference. The principle of this technique consists of performing consecutive HS extractions-from the same vial and accounting for the sum of all obtained peak areas to obtain the total amount of analyte in the sample [74,75,88,92,93]. A significant difference between peak areas in the HS and DI analysis indicates the presence of a ME [89].…”

“…This characteristic eliminates artifacts that can lead to coating saturation, thereby reducing the extraction of unwanted matrix components alongside the target analytes [75,89]. The advantage of SPME as a sample preparation technique lies in its ability to selectively extract only the free concentration of the desired analytes, effectively isolating them from the complex sample mixture [92,93]. Furthermore, SPME offers the unique capability of extracting polar and non-polar analytes from biological matrices [91].…”

Simultaneous determination of methylcarbamate and ethylcarbamate in fermented foods and beverages by derivatization and GC-MS analysis

“…Many methods for detecting EC in beverages have been reported, such as high-performance liquid chromatography (HPLC) [10-12], liquid chromatography tandem mass spectrometry (LC-MS/MS) [13], gas chromatography (GC) [14-17], and gas chromatography mass spectrometry (GC–MS) [6,9,18-27]. …”