• The Korean Journal of Pesticide Science
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• v.17 no.4
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• pp.264-270
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• 2013

Imidacloprid is a systemic insecticide which act as an insect neurotoxin. It used for control of pest such as aphids and other sucking insects in fruits and vegetables. Systemic pesticides move inside a crop following absorption by the plant, and these were converted into a variety of metabolites. Sometimes these metabolites make a problem about safety of agricultural products. So a simultaneous determination method of pesticide and its metabolites is needed, to monitor their presence in agricultural product and study on the fate of pesticide in a plant. This study's aim is to investigate simultaneous analysis method of imidacloprid and its metabolites, imidacloprid guanidine, imidacloprid olefin, imidacloprid urea, and 6-chloronicotinic acid in red pepper using QuEChERS method and LC-MS/MS systems. QuEChERS method was modifed beacuase $MgSO_4$ salts decreased the recoveries of 6-chloronicotinic acid in extraction procedure. Imidacloprid and its metabolites were extracted by acetonitrile with 1% glacial acetic acid and the extracts were purified through QuEChERS with primary secondary amine (PSA) and $C_{18}$ and analyzed with LC-MS/MS in ESI positive mode. Standard calibration curves were made by matrix matched standards and their correlation coefficients were higher than 0.999. Recovery studies were carried out on spiked pepper blank sample at four concentration levels (0.01, 0.04 and 0.1, 0.4 mg/kg). The average recoveries of imidacloprid and its metabolites were in the range of 70~120% with < 20% RSD. This result indicated that the method using QuEChERS and LC-MS/MS was suitable for the simultaneous determination of imidacloprid and its metabolites in red pepper.

• Proceedings of the Korean Society of Near Infrared Spectroscopy Conference
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• 2001.06a
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• pp.1031-1031
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• 2001

The mammary gland is made up of remarkably sensitive tissue, which has the capability of producing a large volume of secretion, milk, under normal or healthy conditions. When bacteria enter the gland and establish an infection (mastitis), inflammation is initiated accompanied by an influx of white cells from the blood stream, by altered secretory function, and changes in the volume and composition of secretion. Cell numbers in milk are closely associated with inflammation and udder health. These somatic cell counts (SCC) are accepted as the international standard measurement of milk quality in dairy and for mastitis diagnosis. NIR Spectra of unhomogenized composite milk samples from 14 cows (healthy and mastitic), 7days after parturition and during the next 30 days of lactation were measured. Different multivariate analysis techniques were used to diagnose the disease at very early stage and determine how the spectral properties of milk vary with its composition and animal health. PLS model for prediction of somatic cell count (SCC) based on NIR milk spectra was made. The best accuracy of determination for the 1100-2500nm range was found using smoothed absorbance data and 10 PLS factors. The standard error of prediction for independent validation set of samples was 0.382, correlation coefficient 0.854 and the variation coefficient 7.63%. It has been found that SCC determination by NIR milk spectra was indirect and based on the related changes in milk composition. From the spectral changes, we learned that when mastitis occurred, the most significant factors that simultaneously influenced milk spectra were alteration of milk proteins and changes in ionic concentration of milk. It was consistent with the results we obtained further when applied 2DCOS. Two-dimensional correlation analysis of NIR milk spectra was done to assess the changes in milk composition, which occur when somatic cell count (SCC) levels vary. The synchronous correlation map revealed that when SCC increases, protein levels increase while water and lactose levels decrease. Results from the analysis of the asynchronous plot indicated that changes in water and fat absorptions occur before other milk components. In addition, the technique was used to assess the changes in milk during a period when SCC levels do not vary appreciably. Results indicated that milk components are in equilibrium and no appreciable change in a given component was seen with respect to another. This was found in both healthy and mastitic animals. However, milk components were found to vary with SCC content regardless of the range considered. This important finding demonstrates that 2-D correlation analysis may be used to track even subtle changes in milk composition in individual cows. To find out the right threshold for SCC when used for mastitis diagnosis at cow level, classification of milk samples was performed using soft independent modeling of class analogy (SIMCA) and different spectral data pretreatment. Two levels of SCC - 200 000 cells/$m\ell$ and 300 000 cells/$m\ell$, respectively, were set up and compared as thresholds to discriminate between healthy and mastitic cows. The best detection accuracy was found with 200 000 cells/$m\ell$ as threshold for mastitis and smoothed absorbance data: - 98% of the milk samples in the calibration set and 87% of the samples in the independent test set were correctly classified. When the spectral information was studied it was found that the successful mastitis diagnosis was based on reviling the spectral changes related to the corresponding changes in milk composition. NIRS combined with different ways of spectral data ruining can provide faster and nondestructive alternative to current methods for mastitis diagnosis and a new inside into disease understanding at molecular level.

• Journal of the Korean earth science society
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• v.36 no.1
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• pp.109-124
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• 2015

A novel approach, hybrid surface rainfall (KNU-HSR) technique developed by Kyungpook Natinal University, was utilized for improving the radar rainfall estimation. The KNU-HSR technique estimates radar rainfall at a 2D hybrid surface consistings of the lowest radar bins that is immune to ground clutter contaminations and significant beam blockage. Two HSR techniques, static and dynamic HSRs, were compared and evaluated in this study. Static HSR technique utilizes beam blockage map and ground clutter map to yield the hybrid surface whereas dynamic HSR technique additionally applies quality index map that are derived from the fuzzy logic algorithm for a quality control in real time. The performances of two HSRs were evaluated by correlation coefficient (CORR), total ratio (RATIO), mean bias (BIAS), normalized standard deviation (NSD), and mean relative error (MRE) for ten rain cases. Dynamic HSR (CORR=0.88, BIAS= $-0.24mm\;hr^{-1}$, NSD=0.41, MRE=37.6%) shows better performances than static HSR without correction of reflectivity calibration bias (CORR=0.87, BIAS= $-2.94mm\;hr^{-1}$, NSD=0.76, MRE=58.4%) for all skill scores. Dynamic HSR technique overestimates surface rainfall at near range whereas it underestimates rainfall at far ranges due to the effects of beam broadening and increasing the radar beam height. In terms of NSD and MRE, dynamic HSR shows the best results regardless of the distance from radar. Static HSR significantly overestimates a surface rainfall at weaker rainfall intensity. However, RATIO of dynamic HSR remains almost 1.0 for all ranges of rainfall intensity. After correcting system bias of reflectivity, NSD and MRE of dynamic HSR are improved by about 20 and 15%, respectively.

• Journal of Food Hygiene and Safety
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• v.32 no.4
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• pp.298-305
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• 2017

Benzovindiflupyr is a new pyrazole carboxamide fungicide that inhibits succinate dehydrogenase of mitochondrial respiratory chain. This study was carried out to develop an analytical method for the determination of benzovindiflupyr residues in agricultural commodities using LC-MS/MS. The benzovindiflupyr residues in samples were extracted by using acetonitrile, partitioned with dichloromethane, and then purified with silica solid phase extraction (SPE) cartridge. Correlation coefficient ($r^2$) of benzovindiflupyr standard solution was 0.99 over the calibration ranges ($0.001{\sim}0.5{\mu}g/mL$). Recovery tests were conducted on 5 representative agricultural commodities (mandarin, green pepper, potato, soybean, and hulled rice) to validate the analytical method. The recoveries ranged from 79.3% to 110.0% and then relative standard deviation (RSD) was less than 9.1%. Also the limit of detection (LOD) and limit of quantification (LOQ) were 0.0005 and 0.005 mg/kg, respectively. The recoveries of interlaboratory validation ranged from 83.4% to 117.3% and the coefficient of variation (CV) was 9.0%. All results were followed with Codex guideline (CAC/GL 40) and Ministry of Food and Safety guideline (MFDS, 2016). The proposed new analytical method proved to be accurate, effective, and sensitive for benzovindiflupyr determination and would be used as an official analytical method.

• Analytical Science and Technology
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• v.29 no.4
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• pp.170-178
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• 2016

Accuracy and precision of ID methods for different spike isotopes of ⁷⁶Se, ⁷⁷Se, and ⁷⁸Se were compared for the analysis of Selenium using quadrupole ICP/MS equipped with Octopole reaction cell. From the analysis of Se inorganic standard solution, all of three spikes showed less than 1 % error and 1 % RSD for both short-term (a day) and long-term (several months) periods. They showed similar results with each other and ⁷⁸Se showed was a bit better than ⁷⁶Se and ⁷⁷Se. However, different spikes showed different results when NIST SRM 1568a and SRM 2967 were analyzed because of the several interferences on the m/z measured and calculated. Interferences due to the generation of SeH from ORC was considered as well as As and Br in matrix. The results showed similar accuracy and precisions against SRM 1568a, which has a simple background matrix, for all three spikes and the recovery rate was about 80% with steadiness. The %RSD was a bit higher than inorganic standard (1.8 %, 8.6 %, and 6.3 % for ⁷⁸Se, ⁷⁶Se and ⁷⁷Se, respectively) but low enough to conclude that this experiment is reliable. However, mussel tissue has a complex matrix showed inaccurate results in case of ⁷⁸Se isotope spike (over 100 % RSD). ⁷⁶Se and ⁷⁷Se showd relatively good results of around 98.6 % and 104.2 % recovery rate. The errors were less than 5 % but the precision was a bit higher value of 15 % RSD. This clearly shows that Br interferences are so large that a simple mathematical calibration is not enough for a complex-matrixed sample. In conclusion, all three spikes show similar results when matrix is simple. However, ⁷⁸Se should be avoided when large amount of Br exists in matrix. Either ⁷⁶Se or ⁷⁷Se would provide accurate results.

• Journal of Food Hygiene and Safety
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• v.33 no.2
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• pp.124-130
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• 2018

The Ministry of Food and Drug Safety (MFDS) is amending its test methods for the use of health functional foods (dietary food supplement), in order to establish regulatory standards and specifications in Korea. In this regard, we continue to pursue and perform our research on the analytical method development for the items being researched and reviewed. In this study, we have developed a sensitive and selective test method that could simultaneously separate and determinate six major bioactive flavonolignans in silymarin, which are based on the use of a liquid chromatographic-tandem mass spectrometry (LC-MS/MS). The standard calibration curves presented a linearity effect with the correlation coefficient ($r^2$) > 0.999. The limits of detection (LODs) and limits of quantitation (LOQs) were in the range of $0.3{\sim}9.0{\mu}g/L$ and $0.8{\sim}27.3{\mu}g/L$, respectively. The recovery results ranged between 96.2~98.6% at 3 different concentration levels, and its relative standard deviations (RSDs) were less than 5% as noted in this study. The proposed analytical method was characterized with a noted high resolution of the individual silymarin constituents, and the assay was fully validated as well. Our research can provide a significant scientific evidence that can be useful to amend the silymarin test method for the Health Functional Food Code.

• Journal of Food Hygiene and Safety
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• v.34 no.1
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• pp.22-29
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• 2019

Validamycin A is an aminoglycoside fungicide produced by Streptomyces hygroscopicus that inhibits trehalase. The purpose of this study was to develop a method for detecting validamycin A in agricultural samples to establish MRL values for use in Korea. The validamycin A residues in samples were extracted using methanol/water (50/50, v/v) and purified with a hydrophilic-lipophilic balance (HLB) cartridges. The analyte was quantified and confirmed by liquid chromatograph-tandem mass spectrometer (LC-MS/MS) in positive ion mode using multiple reaction monitoring (MRM). Matrix-matched calibration curves were linear over the calibration ranges (0.005~0.5 ng) into a blank extract with $R^2$ > 0.99. The limits of detection and quantification were 0.005 and 0.01 mg/kg, respectively. For validation validamycin A, recovery studies were carried out three different concentration levels (LOQ, $LOQ{\times}10$, $LOQ{\times}50$, n = 5) with five replicates at each level. The average recovery range was from 72.5~118.3%, with relative standard deviation (RSD) less than 10.3%. All values were consistent with the criteria ranges requested in the Codex guidelines (CAC/GL 40-1993, 2003) and the NIFDS (National Institute of Food and Drug Safety) guideline (2016). Therefore, the proposed analytical method is accurate, effective and sensitive for validamycin A determination in agricultural commodities.

• The Korean Journal of Nuclear Medicine Technology
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• v.25 no.2
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• pp.15-24
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• 2021

Purpose SPECT/CT was noted for its excellent correction method and qualitative functions based on fusion images in the early stages of dissemination, and interest in and utilization of quantitative functions has been increasing with the recent introduction of companion diagnostic therapy(Theranostics). Unlike PET/CT, various conditions like the type of collimator and detector rotation are a challenging factor for image acquisition and reconstruction methods at absolute quantification of SPECT/CT. Therefore, in this study, We want to find out the effect on the radioactivity concentration estimate by the increase or decrease of the total acquisition time according to the number of projections and the acquisition time per projection among SPECT/CT imaging conditions. Materials and Methods After filling the 9,293 ml cylindrical phantom with sterile water and diluting 99mTc 91.76 MBq, the standard image was taken with a total acquisition time of 600 sec (10 sec/frame × 120 frames, matrix size 128 × 128) and also volume sensitivity and the calibration factor was verified. Based on the standard image, the comparative images were obtained by increasing or decreasing the total acquisition time. namely 60 (-90%), 150 (-75%), 300 (-50%), 450 (-25%), 900 (+50%), and 1200 (+100%) sec. For each image detail, the acquisition time(sec/frame) per projection was set to 1.0, 2.5, 5.0, 7.5, 15.0 and 20.0 sec (fixed number of projections: 120 frame) and the number of projection images was set to 12, 30, 60, 90, 180 and 240 frames(fixed time per projection:10 sec). Based on the coefficients measured through the volume of interest in each acquired image, the percentage of variation about the contrast to noise ratio (CNR) was determined as a qualitative assessment, and the quantitative assessment was conducted through the percentage of variation of the radioactivity concentration estimate. At this time, the relationship between the radioactivity concentration estimate (cps/ml) and the actual radioactivity concentration (Bq/ml) was compared and analyzed using the recovery coefficient (RC_Recovery Coefficients) as an indicator. Results The results [CNR, radioactivity Concentration, RC] by the change in the number of projections for each increase or decrease rate (-90%, -75%, -50%, -25%, +50%, +100%) of total acquisition time are as follows. [-89.5%, +3.90%, 1.04] at -90%, [-77.9%, +2.71%, 1.03] at -75%, [-55.6%, +1.85%, 1.02] at -50%, [-33.6%, +1.37%, 1.01] at -25%, [-33.7%, +0.71%, 1.01] at +50%, [+93.2%, +0.32%, 1.00] at +100%. and also The results [CNR, radioactivity Concentration, RC] by the acquisition time change for each increase or decrease rate (-90%, -75%, -50%, -25%, +50%, +100%) of total acquisition time are as follows. [-89.3%, -3.55%, 0.96] at - 90%, [-73.4%, -0.17%, 1.00] at -75%, [-49.6%, -0.34%, 1.00] at -50%, [-24.9%, 0.03%, 1.00] at -25%, [+49.3%, -0.04%, 1.00] at +50%, [+99.0%, +0.11%, 1.00] at +100%. Conclusion In SPECT/CT, the total coefficient obtained according to the increase or decrease of the total acquisition time and the resulting image quality (CNR) showed a pattern that changed proportionally. On the other hand, quantitative evaluations through absolute quantification showed a change of less than 5% (-3.55 to +3.90%) under all experimental conditions, maintaining quantitative accuracy (RC 0.96 to 1.04). Considering the reduction of the total acquisition time rather than the increasing of the image acquiring time, The reduction in total acquisition time is applicable to quantitative analysis without significant loss and is judged to be clinically effective. This study shows that when increasing or decreasing of total acquisition time, changes in acquisition time per projection have fewer fluctuations that occur in qualitative and quantitative condition changes than the change in the number of projections under the same scanning time conditions.

• Journal of Food Hygiene and Safety
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• v.37 no.2
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• pp.39-45
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• 2022

This study aimed to investigate the validation and modify the analytical method to determine quercetin-3-𝑜-gentiobioside and isoquercitrin in Abelmoschus esculentus L. Moench for the standardization of ingredients in development of functional health products. The analytical method was validated based on the ICH (International Conference for Harmonization) guidelines to verify the reliability and validity there of on the specificity, linearity, accuracy, precision, detection limit and quantification limit. For the HPLC analysis method, the peak retention time of the index component of the standard solution and the peak retention time of the index component of A. esculentus L. Moench powder sample were consistent with the spectra thereof, confirming the specificity. The calibration curves of quercetin-3-𝑜-gentiobioside and isoquercitrin showed a linearity with a near-one correlation coefficient (0.9999 and 0.9999), indicating the high suitability thereof for the analysis. A. esculentus L. Moench powder sample of a known concentration were prepared with low, medium, and high concentrations of standard substances and were calculated for the precision and accuracy. The precision of quercetin-3-𝑜-gentiobioside and isoquercitrin was confirmed for intra-day and daily. As a result, the intra-day precision was found to be 0.50-1.48% and 0.77-2.87%, and the daily precision to be 0.07-3.37% and 0.58-1.37%, implying an excellent precision at level below 5%. As a result of accuracy measurement, the intra-day accuracy of quercetin-3-𝑜-gentiobioside and isoquercitrin was found to be 104.87-109.64% and the daily accuracy thereof was found to be 106.85-109.06%, reflecting high level of accuracy. The detection limits of quercetin-3-𝑜-gentiobioside and isoquercitrin were 0.24 ㎍/mL and 0.16 ㎍/mL, respectively, whereas the quantitation limits were 0.71 ㎍/mL and 0.49 ㎍/mL, confirming that detection was valid at the low concentrations as well. From the analysis, the established analytical method was proven to be excellent with high level of results from the verification on the specificity, linearity, precision, accuracy, detection limit and quantitation limit thereof. In addition, as a result of analyzing the content of A. esculentus L. Moench powder samples using a validated analytical method, quercetin-3-𝑜-gentiobioside was analyzed to contain 1.49±0.01 mg/dry weight g, while isoquercitrin contained 1.39±0.01 mg/dry weight g. The study was conducted to verify that the simultaneous analysis on quercetin-3-𝑜-gentiobioside and isoquercitrin, the indicators of A. esculentus L. Moench, is a scientifically reliable and suitable analytical method.

• The Korean Journal of Pesticide Science
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• v.17 no.4
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• pp.314-334
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• 2013

This study explored an efficient modified Quick, Easy, Cheap, Effective, Rugged and safe (QuEChERS) method combined with liquid chromatography-electrospray ionization with tandem mass spectrometric detection for the analysis of residues of 76 pesticides in brown rice, barley and corn including acidic sulfonylurea herbicides. Formic acid (1%) acid in acetonitrile and dispersive solid phase extractions used for extraction of pesticides and clean-up of the extract respectively. Two fortified spikes at 50 and 200 ng $g^{-1}$ levels were performed for recovery test. Mean recoveries of majority of pesticides at two spike levels ranged from 73.2 to 132.2, 80.9 to 136.8, 66.6 to 143.5 for brown rice, barley and corn respectively with standard error (CV) less than 10%. Good linearity of calibration curves were achieved with $R^2$ > 0.9907 within the observed concentration ranged. The modified method also provided satisfactory results for sulfonylurea herbicides. The method was applied to the determination of residues of target pesticides in real samples. A total of 26 pesticides in 36 out of 98 tasted samples were observed. The highest concentration was observed for tricyclazole at 1.17 mg $kg^{-1}$ in brown rice. This pesticide in two brown rice samples exceeded their MRLs regulated for rice in republic of Korea. Except tricyclazole none of the observed pesticides' concentration was higher than their MRLs. The results reveal that the method is effectively applicable to routine analysis of residues of target pesticides in brown rice, barley and corn.