• Clinical and Experimental Pediatrics
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• v.52 no.5
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• pp.567-575
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• 2009

Purpose : Epilepsy affects more than 0.5% of the world's population. It has a large genetic component and is caused by electrical hyperexcitability in the central nervous system. Despite its prevalence, the disease lacks definitive diagnostic serological biomarkers. To identify potential biomarkers for epilepsy by a convenient method, we analyzed the expression of serum proteins, reflecting alterations in the patient's proteomes. Methods : We compared two-dimensional electrophoretic band patterns of human sera from eight patients with temporal lobe epilepsy (TLE) with those of eight control subjects. The differentially expressed bands were identified using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and electrospray ionization quadrupole time-of-flight mass spectrometry. esults : Twelve proteins were differentially expressed in the TLE group, of which 6 were identified. Expression of haptoglobin Hp2, PRO2675, immunoglobulin heavy chain constant region gamma 2, an unnamed protein, and three unidentified proteins were upregulated in serum from the patients with TLE, whereas those of major histocompatibility complex (MHC) class I antigen, plasma retinol-binding protein precursor, and three unidentified proteins were downregulated in these patients. After resection of the epileptogenic zone, the expressions of MHC class I antigen, immunoglobulin heavy chain constant region gamma 2, two of the downregulated unidentified proteins, and one of the upregulated unidentified proteins returned to the normal range. Conclusion : The 12 serum proteins in this study are potentially useful biomarkers for the diagnosis and monitoring of TLE.

• Analytical Science and Technology
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• v.24 no.3
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• pp.183-192
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• 2011

This study was done for the determination and excretion profile of superdrol and its metabolites in human urine using both liquid chromatography with electrospray ionization mass spectrometry and gas chromatography with mass spectrometry after trimethylsilylation. Superdrol and its two metabolites were detected in human urine after administration of superdrol to healthy volunteers. The intra-day recovery ranged 89.7-113.2%, accuracy ranged 91.8-113.8% and reproducibility ranged 0.2-6.8% and inter-day recovery ranged 89.3-104.1%, accuracy ranged 95.2-103.0%, reproducibility ranged 0.7-7.8%. We found that superdrol M1 was a hydration at C-3 and superdrol M2 was a hydroxylation at D-ring. Superdrol and two metabolites were excreted as their glucuronided fractions. The glucuro-/sulfa-conjugated ratio of superdrol, superdrol M1 and superdrol M2 were 0.02, 0.02, 0.01, respectively. The excretion studies showed that superdrol and two metabolites were reached 4.3 h after oral administration and superdrol and superdrol M1 were detected until 48 h in human urine.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.26 no.2
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• pp.178-187
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• 2016

Objectives: Diisocyanates are a potent inducer of diseases of the airways, especially asthma. In this study, toluenediamine(TDA) and methylenedianiline(MDA) in urine were evaluated as biomarkers of exposure to tolunenediisocyanate(TDI) and methylenediphenyl diisocyanate(MDI), respectively. Methods: Workers exposed to TDI and MDI, as well as non-occupationally exposed subjects, were studied and pre- and post-shift urine samples were collected from 8 control subjects and 8 workers from a factory which manufactures polyurethane products for reducing noise and vibration in automobiles. Airborne TDI and MDI(n=8) were sampled on solvent-free glass filters impregnated with n-butylamine and detected by liquid chromatography atmospheric pressure ionization tandem mass spectrometry. Urinary TDA and MDA were detected as pentafluoropropionic acid anhydride(PFPA) derivatives by liquid chromatography electrospray ionization tandem mass spectrometry. Results: The median levels of urinary 2,6-TDA(p<0.001), 2,4-TDA(p=0.001), and MDA(p<0.001) of workers in post-shift samples were significantly higher than those of controls. The median levels of urinary 2,6-0TDA($0.63{\mu}g/g$ creatinine vs $0.34{\mu}g/g$ creatinine, p=0.017) and MDA($4.21{\mu}g/g$ creatinine vs $3.18{\mu}g/g$ creatinine, p=0.017) of workers in post-shift samples were significantly higher than those of the pre-shift samples. There were significant correlations between the urinary 2,6-TDA, 2,4-TDA, and MDA of workers in post-shift samples and the airborne 2,6-TDI(rho=0.952, p<0.001), 2,4-TDI(rho=0.833, p=0.001), and MDI(rho=0.952, p<0.001). Conclusions: These urinary diamines, metabolites of diisocyanates, in post-shift samples were useful biomarkers to assess occupational exposure to diisocyanates.

• Korean Journal of Food Science and Technology
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• v.35 no.6
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• pp.1039-1044
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• 2003

We investigated the changes in saponins during the cultivation of soybean sprout. Crude saponin content was 4.15mg/g in germinated soybean and reached its peark (5.33mg/g) in soybean sprout cultivated for six days. Saponin content in the cotyledon, stem, and root of the soybean sprout cultivated for six days were 4.17, 7.46, and 7.45mg/g, respectively. Soyasaponins extracted from the soybean sprout were analyzed with LC-electrospray ionization (ESI)-mass spectrometry, in which a reverse phase $C_18$ column was used for separation of saponins. In the soybeen sprout, group B saponin, I, II, III, IV, and V increased 7, 2, 1.4, 8.7, and 3.3 fold, respectively, compared to those in the soybean seed. Group B saponin I, II, III, IV, and V in the stem of the soybean sprout were 10.53, 1.45, 10.49, 5.72 and 8.14 fold the level of those in the cotyldon, respectively. In the root, the contents of group B saponin I, III, IV, and V were 5.54, 2.77, 4.86 and 9.73 fold, respectively, higher than those in cotyledon, but the content of group B saponin 2 was 2.96 fold less than that in cotyledon. These results indicate that the biosyntheses of group B saponins are differentially regulated in growing soybean sprout.

• Analytical Science and Technology
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• v.16 no.6
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• pp.488-498
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• 2003

By LC/MS/MS, the analytical method of sildenafil and its analogues (homosildenafil, vardenafil and tadalafil) used as used medical treatment of impotence was established. electrosprary ionization (ESI) and atmospheric pressure chemical ionization (APCI) as a ionization method were applied. Several parameter were varied and the sensitivity and reproducibility were compared. In LC/ESI-MS method, capillary voltage, cone voltage, extractor, entrance and RF lens to create appropriate productr ions for multiple reaction monitoring (MRM) were variable parameter, but the formation of the other product ions except the precursor ion could not detect. And the value of entrance, collision energy, exit, corona voltage, cone voltage, extractor, RF lens, cone gas, and desolvation gas in APCI mode were varied, only the creation pattern of fragment ions by the change of RF lens value were detected, and the limit of detection was decreased due to the increase of S/N. Ten millimole ammonium formate (pH 4.8):acetonitrile=70:30 by isocratic elution in HPLC system was shown the maximum sensitivity in MS, the detection limit of sildenafil, homosildenafil, vardenafil and tadalafil obtained by ESI-MRM were 0.10, 0.025, 0.025, and $0.25{\mu}g/mL$ at S/N>5, respectively.

• Analytical Science and Technology
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• v.31 no.1
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• pp.39-46
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• 2018

Carbaryl and seven organophosphorous pesticides were analyzed simultaneously using on-line solid phase extraction (on-line SPE) coupled with liquid chromatography tandem mass spectrometry (LC/MS/MS). The target pesticides are Carbaryl, Methyl demeton, Fenitrothion, Malathion, Parathion, Phenthoate, Diazinon, and EPN. This method includes the direct injection of $500{\mu}L$ in the water sample, a 15 min separation period using a rapid resolution liquid chromatography system with on-line SPE, and detection through electrospray ionization (ESI) positive mode. The percentage of recovery of all pesticides ranged from 85.3 % to 100 %. This method showed an accuracy of ${\geq}90.0%$, possessing limits of detection and quantification within 0.05 to $0.28{\mu}g/L$ and 0.16 to $0.89{\mu}g/L$, respectively. The correlation coefficients (r) for the calibration curves within a range of 0.5 to $8.0{\mu}g/L$ were higher than 0.99. The evaluation results showed the efficacy of the method for all contents, and no pesticides were detected in the water quality sample.

• Journal of Food Hygiene and Safety
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• v.27 no.1
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• pp.37-41
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• 2012

The current standard for testing tetrodotoxin (TTX) in foodstuffs is the mouse bioassay (MBA) in Korea as in many other countries. However, this test suffers from potential ethical concerns over the use of live animals. In addition, the mouse bioassay does not test for a specific toxin thus a sample resulting in mouse incapacitation would need further confirmatory testing to determine the exact source toxin (e.g., TTX, STX, brevotoxin, etc.). Furthermore, though the time of death is proportional to toxicity in this assay, the dynamic range for this proportional relationship is small thus many samples must be diluted and new mice be injected to yield a result that falls within the quantitative dynamic range. Therefore, in recent years, there have been many efforts in this field to develop alternative assays. High performance liquid chromatography (HPLC) coupled with mass spectrometry (MS) has been emerged as one of the most promising options. A LC-MS-MS method involves solid-phase extraction (SPE) and followed by analysis using an electrospray in the positive ionization mode and multiple reactions monitoring (MRM). To adopt LC-MS-MS method as alternative standard for testing TTX, we performed a validation study for the quantification of TTX in puffer fish. This LC-MS-MS method showed good sensitivity as limits of detection (LOD) of $0.03{\sim}0.08{\mu}g/g$ and limits of quantification (LOQ) of $0.10{\sim}0.25{\mu}g/g$. The linearity ($r^2$) of tetrodotoxin were 0.9986~0.9997, the recovery were 80.9~103.0% and the relative standard deviations (RSD) were 4.3~13.0%. The correlation coefficient between the mouse bioassay and LC/MS/MS method was higher than 0.95.

• Korean Journal of Food Science and Technology
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• v.43 no.6
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• pp.675-682
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• 2011

This study was conducted to monitor the concentrations of 24 anti-impotence drugs and their analogues in various foods and dietary supplements, with the aim of ensuring the safety of the foods and supplements. The measurements were done in 226 samples using high performance liquid chromatography/photodiode array detector (HPLC/PDA) and liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). Five male sexual function enhancing products have been detected as follows: acethylvardenafil (21,476 mg/kg; 15 mg/capsule from one sample), sildenafil (52,778 mg/kg, 29 mg/capsule in one sample; 71,535 mg/kg, 48 mg/capsule in one sample), and tadalafil (9,772-55,545 mg/kg, 6-33 mg/capsule in four samples). A sustainable monitoring of anti-impotence drugs and their analogues in various foods and dietary supplement is recommended.

• The Korean Journal of Food And Nutrition
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• v.27 no.3
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• pp.532-537
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• 2014

Cortex Phellodendri (CP) is derived from the dried bark of Phellodendron amurense. It has been widely used as a drug in traditional Korea medicine for treating diarrhea, jaundice, swelling pains in the knees and feet, urinary tract infections, and infections of the body surface. Many analytical methods have been used to study oriental herbal medicines, such as thin-layer chromatography, column liquid chromatography, and high performance liquid chromatography (HPLC). In this study, preparative centrifugal partition chromatography (CPC) was successfully carried out in order to separate pure compounds from a CP methanol extract. The optimum two-phase CPC solvent system was composed of n-butanol: acetic acid: water (4:1:5 v/v/v). The flow rate of the mobile phase was 3 mL/min in ascending mode with rotation at 1,000 rpm. The CPC-separated fraction and purification procedures were carried out by preparatory HPLC. The $^1H$ NMR spectrum revealed that the resonances at ${\delta}$ 4.10 and 4.20 ppm corresponded to three protons ($-OCH_3$), whereas those at ${\delta}$ 6.10 ppm corresponded to two protons ($-OCH_2O-$). Further, two aromatic protons (H-11 and H-12) conveys a doublet-doublet pattern. The H-11 doublet and H-12 doublet appear at ${\delta}$ 7.98 and 8.11, respectively. The $^{13}C$ NMR. spectrum showed a tetrasubstituted with a methylenedioxy group at C2 and C3, and two methoxy groups at C9 and C10. The chemical structure of the berberine was identified by $^1H$, $^{13}C$-nuclear magnetic resonance and electrospray ionization-mass spectroscopy spectral data analysis.

• Microbiology and Biotechnology Letters
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• v.38 no.1
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• pp.84-92
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• 2010

Antibacterial compound from Bacillus subtilis MJP1 was purified using C18 Sep-Pak cartridge, ion exchange chromatography, and gel filtration chromatography. The purified antibacterial compound showed antibacterial activity against Listeria monocytogenes, Bacillus subtilis, Staphylococcus aureus subsp. aureus, and Enterococcus faecalis. The purified antibacterial compound was found to be stable at $100^{\circ}C$ for 5 min and in the pH range of 3.0~9.0, but it was unstable at pH 10.0. It was inactivated by proteinase K and pronase E, and heat treatment at $121^{\circ}C$ for 15 min, but it was stable with lipase and $\alpha$-amylase treatment, which indicated its proteineous nature. Ultra performance liquid chromatography and electrospray ionization tandem mass spectrometry analysis were used to identify the purified antibacterial compound and confirmed the existence of two peptides (3356.54 Da, 3400.5244 Da).