Joonhee Lee

Accurate determination of ochratoxin A in Korean fermented soybean paste by isotope dilution-liquid chromatography tandem mass spectrometry.

Ochratoxin A (OTA), a naturally occurring mycotoxin, has been frequently detected in doenjang, a traditional fermented soybean paste, when it is fermented under improper conditions. Reliable screening of OTA in traditional fermented soybean paste (doenjang) is a special food-safety issue in Korea. Our laboratory, the National Metrology Institute of Korea, established an isotope dilution-liquid chromatography tandem mass spectrometry (ID-LC/MS/MS) method as a higher-order reference method to be used for SI-traceable value-assignment of OTA in certified reference materials (CRMs). (13)C20-OTA was used as an internal standard. Sample preparation conditions and LC/MS measurement parameters were optimised for this purpose. The analytical method was validated by measuring samples fortified with OTA at various levels. Repeatability and reproducibility studies showed that the ID-LC/MS/MS method is reliable and reproducible within 2% relative standard deviation. The analytical method was applied to determine OTA in various commercial doenjang products and home-made doenjang products.

Development of isotope dilution-liquid chromatography/mass spectrometry combined with standard addition techniques for the accurate determination of tocopherols in infant formula

During the development of isotope dilution-liquid chromatography/mass spectrometry (ID-LC/MS) for tocopherol analysis in infant formula, biased measurement results were observed when deuterium-labeled tocopherols were used as internal standards. It turned out that the biases came from intermolecular H/D exchange and intramolecular H/D scrambling of internal standards in sample preparation processes. Degrees of H/D exchange and scrambling showed considerable dependence on sample matrix. Standard addition-isotope dilution mass spectrometry (SA-IDMS) based on LC/MS was developed in this study to overcome the shortcomings of using deuterium-labeled internal standards while the inherent advantage of isotope dilution techniques is utilized for the accurate recovery correction in sample preparation processes. Details of experimental scheme, calculation equation, and uncertainty evaluation scheme are described in this article. The proposed SA-IDMS method was applied to several infant formula samples to test its validity. The method was proven to have a higher-order metrological quality with providing very accurate and precise measurement results.

Investigation of isotope dilution mass spectrometric (ID-MS) method to determine niacin in infant formula, breakfast cereals and multivitamins.

An isotope dilution LC/mass spectrometric (ID-LC/MS) method was developed as a candidate reference method for the accurate determination of niacin in infant formula, breakfast cereals and multivitamin. After spiking nicotinamide-d(4) as an internal standard, infant formula and breakfast cereal samples were hydrolysed under alkaline condition. Samples were then analysed in SRM mode to detect nicotinic acid and nicotinic acid-d(4) at m/z 124→80 and 127→84, respectively. In the case of multivitamin sample that contains mainly free nicotinamide, LC/MS monitored nicotinamide and nicotinamide-d(4) at their SRM channels of m/z 123→80 and m/z 127→84, respectively, after simple extraction. The repeatability and reproducibility were tested for the validation of the developed ID/LC-MS method. Additionally, the developed analytical method was applied to determine total niacin contents in homogenised infant formula, homogenised multivitamin, and commercially available products including different types of infant formula, breakfast cereals, and multivitamin tablets.

Development of isotope dilution-liquid chromatography/tandem mass spectrometry for the accurate determination of trans- and cis-vitamin K1 isomers in infant formula

A method based on isotope dilution-liquid chromatography/tandem mass spectrometry (ID-LC/MS/MS) using a C30 column has been developed for the separate and accurate determination of trans- and cis-vitamin K1 in infant formula. Vitamin K1 and the deuterium-labeled internal standard eluted at slightly different retention times experiencing different matrix effects, and this possibly resulted in biased measurement. The matrix effect profiles obtained from post-column infusion experiments showed that atmospheric pressure chemical ionization (APCI) was less susceptible to matrix effects near the retention time than electrospray ionization (ESI); therefore, APCI was used in this study. The developed method was validated by measuring fortified samples, and the results agreed with the gravimetric values. Its repeatability and reproducibly were within 2% relative standard deviation. The relative expanded uncertainty was approximately 5%, indicating that the method was of higher-order metrological quality as a reference method.

Accurate determination of hexabromocyclododecane diastereomers in extruded high-impact polystyrene: Development of an analytical method as a candidate reference method

Herein, an isotope dilution-liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) method was developed as a candidate reference method for the accurate quantitation of hexabromocyclododecane (HBCDD) diastereomers in plastics. The repeatability, reproducibility, and uncertainty results showed that developed ID-LC/MS/MS method is reliable and reproducible. As homogeneous samples, HBCDD-containing extruded high-impact polystyrene (HIPS) pellets were fabricated via an extrusion process. Notably, we detected α-, β-, γ-, δ-, ε-, η-, and θ-HBCDDs in the extruded HIPS pellets, and then determined their exact mass fractions using the ID-LC-MS/MS method. The relative contents (averageu202f±u202fstandard deviation) of HBCDD diastereomers in HIPS obtained using the phenyl-hexyl column were 67.08u202f±u202f0.41% (α-HBCDD), 19.73u202f±u202f0.37% (β-HBCDD), 11.59u202f±u202f0.16% (γ-HBCDD), and 1.6u202f±u202f0.07% (sum of δ-, ε-, η-, and θ-HBCDDs). These values differed significantly from the ones determined for the technical HBCDD mixtures (10.42% α-HBCDD, 5.30% β-HBCDD, 82.13% γ-HBCDD, 2.15% minor HBCDDs) used to fabricate the HIPS pellets and thus demonstrating the HBCDD isomerization during the extrusion. The proportion of minor HBCDDs was smaller than the uncertainty of the total HBCDD and that the sum of α-, β-, and γ-HBCDDs was comparable to the total HBCDD in the investigated samples. Notably, a real-life sample (expanded polystyrene board obtained from a local construction site) also showed a similar HBCDD profile, being rich in α-HBCDD.

Optimization and Application of Paper-Based Spray Ionization Mass Spectrometry for Analysis of Natural Organic Matter

In this study, paper-based ionization techniques-paper spray ionization (PSI) and paper spray chemical ionization (PSCI)-were evaluated and applied for high-resolution mass spectrometry (MS)-based analysis of natural organic matter (NOM). Methanol:isopropyl alcohol (50:50, v/v) and ethanol emerged as good spray solvents for PSI, and hexane:dichloromethane (50:50, v/v) was a good spray solvent for PSCI. PSI-MS spectra could be obtained with NOM samples on the microgram scale, which is a critical advantage over conventional electrospray ionization (ESI)-MS when the amount of available sample is limited. In addition, PSI is more tolerant to salt contamination than ESI for NOM analysis. PSCI preferentially ionized less polar compounds, which may not be ionized well using ESI. Therefore, PSCI can be used as a complementary method to ESI or PSI. Comparison of the numbers of peaks obtained with ESI-, PSI-, and PSCI-MS showed that employing PSI and PSCI can increase the number of compounds that can be detected by high-resolution MS. In conclusion, the data presented in this study showed that PSI and PSCI are suitable ionization techniques for NOM analysis. To the best of our knowledge, this is the first study evaluating and applying PSI and PSCI for NOM analysis.