• Mass Spectrometry Letters
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• 제2권2호
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• pp.37-40
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• 2011

Saccharin is a commonly used artificial sweetener in foodstuffs. However, for its carcinogenic dispute, it has been regulated by government bodies. In this study, isotope dilution mass spectrometry (ID-MS) was introduced for the accurate quantification of saccharin. To employ ID-LC/MS, we obtained its isotope analogue, $^{13}C_1$-sodium saccharin, by customized synthesis. Samples were spiked with $^{13}C_1$-sodium saccharin and analyzed with LC/MS in negative mode. Chromatographic conditions were optimized for the adequate chromatographic retention and separation of saccharin with a $C_{18}$ column. MS was operated with electrospray ionization by the selected ion monitoring (SIM) mode of $[M-H]^-$ for saccharin (m/z 182) and $[M-Na]^-$ for its isotope analogue (m/z 183). To validate the ID-LC/MS method for accurate measurement, we prepared a batch of a candidate material by sortifying quasi-tea-drinks with saccharin and analyzed samples gravimetrically fortified in various levels of concentration. The repeatability and reproducibility of this method was tested by analyzing the reference material. Result show that ID-LC/MS is a reliable method for the quantitative analysis of saccharin.

• Mass Spectrometry Letters
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• 제8권3호
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• pp.49-52
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• 2017

Ibuprofen is one of the most popular analgesic and antipyretic drugs. An isotope dilution mass spectrometry method based on LC/MS was developed as a candidate reference method for the accurate determination of ibuprofen in pharmaceutical tablets. Isotope labelled ibuprofen, $ibuprofen-d_3$, was added as an internal standard into sample extracts. Ibuprofen and $ibuprofen-d_3$, was analysed by LC/MS in a selected ion monitoring (SIM) mode to detect ions at m/z 205 and 208, respectively. The repeatability and reproducibility of the developed ID-LC/MS method were tested for the validation and assessment of metrological quality of the method.

• Mass Spectrometry Letters
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• 제5권2호
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• pp.52-56
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• 2014

Glycated hemoglobin (HbA1c) is used as an index of mean glycemia over prolonged periods. This study describes an optimization of enzyme digestion conditions for quantification of non-glycated hemoglobin (HbA0) and HbA1c as diagnostic markers of diabetes mellitus. Both HbA0 and HbA1c were quantitatively determined followed by enzyme digestion using isotope dilution liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) with synthesized N-terminal hexapeptides as standards and synthesized isotope labeled hexapeptides as internal standards. Prior to quantification, each peptide was additionally quantified by amino acid composition analysis using ID-LC-MS/MS via acid hydrolysis. Each parameter was considered strictly as a means to improve digestion efficiency and repeatability. Digestion of hemoglobin was optimized when using 100 mM ammonium acetate (pH 4.2) and a Glu-C-to-HbA1c ratio of 1:50 at $37^{\circ}C$ for 20 h. Quantification was satisfactorily reproducible with a 2.6% relative standard deviation. These conditions were recommended for a primary reference method of HbA1c quantification and for the certification of HbA1c reference material.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3228-3232
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• 2010

Malachite green (MG) has been used world-widely in aquaculture as a parasiticide or fungicide. Although MG performed successfully, it has not been permitted for use in aquaculture from European Union, USA, and Canada because of its carcinogenicity and mutagenicity. We developed a sensitive and specific method to determine MG and its principal metabolite, leucomalachite green (LMG), respectively by isotope dilution liquid chromatography mass spectrometry (ID-LC/MS). To enhance the extraction recovery of MG and LMG from fish tissue, an additional step, saponification, was introduced in sample preparation process to remove fat in sample extract, which hampered the performance of SPE columns. The residue of MG and LMG in fish was analyzed using liquid chromatography mass spectrometry in the selected ion monitoring (SIM) mode by monitoring at m/z 329 and 334 for MG and $d_5$-MG and at m/z 331 and 337 for LMG and $^{13}C_6$-LMG, respectively. This method was validated by comparing with the value of the reference material provided by Laboratory Government Chemistry (LGC). The results agreed within the measurement uncertainty and the accuracy was much improved than the provided reference value by LGC.

• Bulletin of the Korean Chemical Society
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• 제29권11호
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• pp.2125-2128
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• 2008

• Mass Spectrometry Letters
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• 제14권4호
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• pp.178-185
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• 2023

QuEChERS is used worldwide as a universal sample preparation method with many benefits, such as being quick, easy, cheap, effective, rugged and safe. This study examined whether QuEChERS can be employed in isotope dilution mass spectrometry (ID-MS) for accurate analysis of pesticides in food. The ratios of fortified values and measured values of malathion and fenitrothion using the QuEChERS method were compared with those using the solid phase extract (SPE) method which was previously used in this laboratory. The separations of the two pesticides on DB-5MS and VF-1701MS columns were compared. Malathion and fenitrothion were fortified into kimchi cabbage and pretreated with the QuEChERS method and the SPE method. The results obtained using the DB-5MS column varied according to the sample preparation method, column and pesticide level. Using the VF-1701 column, ratios were 98-102% by both QuEChERS and Carb/NH₂ SPE method for all fortification level. Malathion and fenitrothion were fortified into strawberry samples for comparison with kimchi cabbage. The results for the strawberry samples indicated that the ratios were not influenced by the sample preparation methods or GC column. The QuEChERS method could be acceptable in the ID-MS method for pesticide residue analysis in food, however other conditions should be carefully considered for accurate determination, such as the column, amount of analyte and food matrix.

• Bulletin of the Korean Chemical Society
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• 제35권3호
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• pp.821-827
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• 2014

An isotope dilution liquid chromatography tandem mass spectrometry (ID LC-MS/MS) method has been developed and applied to the determination of arsenobetaine (AsB, ${(CH_3)_3}^+AsCH_2COO^-$) from oyster candidate certified reference material (CRM). The exact matching isotope dilution approach was adopted for accurate determination of AsB using $^{13}C_2$-labeled AsB as an internal standard. Efficiencies of different AsB extraction methods were evaluated using a codfish reference material and a simple sonication method was selected as the method of choice for the certification of the oyster candidate CRM. The hydrophilic interaction liquid chromatography (HILIC) combined with electrospray ionization tandem mass spectrometry (ESI/MS/MS) in selected reaction monitoring (SRM) mode was optimized for adequate chromatographic retention and robust quantification of AsB from codfish and oyster samples. By analyzing 12 subsamples taken from each 12 bottles systematically selected from the whole oyster CRM batch, the certified value of AsB was determined as $6.60mg{\cdot}kg^{-1}{\pm}0.31mg{\cdot}kg^{-1}$ and it showed excellent between-bottle homogeneity of less than 0.42%, which is represented by relative standard deviation of 12 bottles from the CRM batch. The major source of uncertainty was the certified value of the AsB standard solution.

• Mass Spectrometry Letters
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• 제3권2호
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• pp.58-61
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• 2012

A method based on flow injection-isotope dilution-cold vapor-inductively coupled plasma mass spectrometry (FI-IDCV-ICP/MS) has been applied to determine trace level of mercury in fly ash. $^{200}Hg$ isotopic spike was added to 0.25 g of BCR176R fly ash and then decomposed by microwave digestion procedure with acid mixture A (8 mL $HNO_3$ + 2 mL HCl + 2 mL HF) and acid mixture B (8 mL $HNO_3$ + 2 mL $HClO_4$ + 2 mL HF) for applying IDMS. Mercury cold vapor was generated by using reductant solution of 0.2% (w/w) $NaBH_4$ and 0.05% (w/w) NaOH. The measurements of n($^{200}Hg$)/n($^{202}Hg$) isotope ratio was made using a quadrupole ICP/MS system. The accuracy in this method was verified by the analysis of certified reference material (CRM) of fly ash (BCR 176R). The indicative value of Hg in BCR 176R fly ash was $1.60{\pm}0.23$ mg/kg (k = 2). The determined values of Hg in BCR 176R fly ash by the method of FI-CV-ID-ICP/MS described in this paper were $1.60{\pm}0.24$ mg/kg (k = 3.18) and the analysis results were in well agreement with the indicative value within the range of uncertainty.

• Bulletin of the Korean Chemical Society
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• 제35권12호
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• pp.3482-3488
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• 2014

Matrix-induced mass bias and its effect on the accuracy of isotope ratio measurements have been examined for a quadrupole-based inductively coupled plasma-mass spectrometer (Q ICP-MS). Matrix-induced mass bias effect was directly proportional to % mass difference, and its magnitude varied for element and nebulizer flow rate. For a given element and conditions in a day, the effect was consistent. The isotope ratio of Cd106/Cd114 under $200{\mu}g\;g^{-1}$ U matrix deviated from the natural value significantly by 3.5%. When Cd 111 and Cd114 were used for the quantification of Cd with isotope dilution (ID) method, the average of differences between the calculated and measured concentrations was -0.034% for samples without matrix ($0.076{\mu}g\;g^{-1}$ to $0.21{\mu}g\;g^{-1}$ for the period of 6 months). However, the error was as large as 1.5% for samples with $200{\mu}g\;g^{-1}$ U. The error in ID caused by matrix could be larger when larger mass difference isotopes are used.

• Mass Spectrometry Letters
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• 제11권4호
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• pp.108-112
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• 2020

A certified reference material (CRM) for the analysis of nutrient elements in an edible mushroom (Ganoderma lyceum) powder has been developed (KRISS CRM 108-10-011). The mass fractions of calcium (Ca), iron (Fe), and zinc (Zn) were measured by isotope dilution inductively coupled plasma mass spectrometry (ID ICP/MS). To dissolve the fungi cell wall of mushroom consisted of chitin fibers, sample preparation method by single reaction chamber type microwave-assisted acid digestion with acid mixtures was optimized. The mean measurement results obtained from 12 sample bottles were used to assign as the certified values for the CRM and the between-bottle homogeneities were evaluated from the relative standard deviations. The certified values were metrologically traceable to the definition of the kilogram in the International System of Units (SI). This CRM is expected to be used for validation of analytical methods or quality control of measurement results in analytical laboratories when they determine the mass fractions of elements in mushroom or other similar samples.