• Analytical Science and Technology
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• v.7 no.2
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• pp.213-224
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• 1994

Several isotopomers of cyclooctanone were prepared by selective deuterium substitution. Intrinsic isotope effects on $^{13}C$ NMR chemical shifts of these isotopomers were investigated systematically at low temperature. These istope effects were discussed in relation to the preferred boat-chair conformation of cyclooctanone. Deuterium isotope effects on NMR chemical shifts have been known for a long time. Especially in a conformationally mobile molecule, isotope perturbation could affect NMR signals through a combination of isotope effects on equilibria and intrinsic effects. The distinction between intrinsic and nonintrinsic effects is quite difficult at ambient temperature due to involvement of both equilibrium and intrinsic isotope effects. However if equilibria between possible conformers of cyclooctanone are slowed down enough on the NMR time scale by lowering temperature, it should be possible to measure intrinsic isotope shifts from the separated signals at low temperature. $^{13}C$ NMR has been successfully utilized in the study on molecular conformation in solution when one deals with stable conformers or molecules were rapid interconversion occurs at ambient temperature. The study of dynamic processes in general requires analysis of spectra at several temperature. Anet et al. did $^1H$ NMR study of cyclooctanone at low temperature to freeze out a stable conformation, but were not able initially to deduce which conformation was stable because of the complexity of alkyl region in the $^1H$ NMR spectrum. They also reported the $^1H$ and $^{13}C$ NMR spectra of the $C_9-C_{16}$ cycloalkanones with changing temperature from $-80^{\circ}C$ to $-170^{\circ}C$, but they did not report a variable temperature $^{13}C$ NMR study of cyclooctanone. For the analysis of the intrinsic isotope effect with relation to cylooctanone conformation, $^{13}C$ NMR spectra are obtained in the present work at low temperatures (up to $-150^{\circ}C$) in order to find the chemical shifts at the temperature at which the dynamic process can be "frozen-out" on the NMR time scale and cyclooctanone can be observed as a stable conformation. Both the ring inversion and pseudorotational processes must be "frozen-out" in order to see separate resonances for all eight carbons in cyclooctanone. In contrast to $^1H$ spectra, slowing down just the ring inversion process has no apparent effects on the $^{13}C$ spectra because exchange of environments within the pairs of methylene carbons can still occur by the pseudorotational process. Several isotopomers of cyclooctanone were prepared by selective deuterium substitution (fig. 1) : complete deuterium labeling at C-2 and C-8 positions gave cyclooctanone-2, 2, 8, $8-D_4$ : complete labeling at C-2 and C-7 positions afforded the 2, 2, 7, $7-D_4$ isotopomer : di-deuteration at C-3 gave the 3, $3-D_2$ isotopomer : mono-deuteration provided cyclooctanone-2-D, 4-D and 5-D isotopomers : and partial deuteration on the C-2 and C-8 position, with a chiral and difunctional case catalyst, gave the trans-2, $8-D_2$ isotopomer. These isotopomer were investigated systematically in relation with cyclooctanone conformation and intrinsic isotope effects on $^{13}C$ NMR chemical shifts at low temperature. The determination of the intrinsic effects could help in the analysis of the more complex effects at higher temperature. For quantitative analysis of intrinsic isotope effects, the $^{13}C$ NMR spectrum has been obtained for a mixture of the labeled and unlabeled compounds because the signal separations are very small.

• Analytical Science and Technology
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• v.34 no.6
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• pp.259-266
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• 2021

Cannabis (Marijuana) is one of the most widely used drugs in the world, and its distribution has been controlled in South Korea since 1976. Identification of 11-nor-Δ⁹-carboxy-tetrahydrocannabinol (THCCOOH) in urine can provide important proof of cannabis use, and it is considered scientific evidence in the forensic field. In this study, we describe a simultaneous quantitative method for identifying THCCOOH and THCCOOH-glucuronide in urine, using simple liquid-liquid extraction (LLE), and liquid chromatography-tandem mass spectrometry (LC-MS/MS). THCCOOH-D₃ and THCCOOH-glucuronide-D₃ were used as internal standards. Validation results of the matrix effect, as well as recovery, linearity, precision, accuracy, process efficiency, and stability were all satisfactory. No carryover, endogenous or exogenous interferences were observed. The limit of detection (LOD) of THCCOOH and THCCOOH-glucuronide were 0.3 and 0.2 ng/mL, respectively. The developed method was applied to 28 authentic human urine samples that tested positive in immunoassay screening and gas chromatography/mass spectrometry (GC/MS) tests. The ranges of concentrations of THCCOOH and THCCOOH-glucuronide in the samples were less than LOQ~266.90 ng/mL and 6.43~2133.03 ng/mL, respectively. The concentrations of THCCOOH-glucuronide were higher than those of THCCOOH in all samples. This method can be effectively and successfully applied for the confirmation of cannabinoid use in human urine samples in the forensic field.

• Korean Journal of Environmental Agriculture
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• v.31 no.3
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• pp.248-254
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• 2012

BACKGROUND: In order to elucidate residual characteristics of difenoconazole and thiamethoxam by treatment to sweet persimmons for one year and to generate the data for the maximum residue limit (MRL) establishment for those pesticides in or on sweet persimmon. METHODS AND RESULTS: Systemic fungicide difenoconazole WP (10% a.i.) and systemic insecticide thiamethoxam WG (10% a.i.) were sprayed onto 12~25-years-old sweet persimmons according to its preharvest interval (PHI), respectively, and then fresh sweet persimmons were harvested at 0, 1, 3, 7, 14, 21 days after treatment from pesticide-sprayed plots at each 3 sites. The analytical methods were evaluated to limit of quantification, linearity, specificity, reproducibility and recoveries. The crop samples were extracted with acetone and performed dichloromethane partition process. The extracted samples of difenoconazole were analyzed by GC-ECD and the thiamethoxam extracted samples were analyzed by HPLC with good sensitivity and selectivity of the method. The average recoveries of difenoconazole ranged from 87.5 to 99.5% with the percentage of coefficient variation in the range 4.1~7.6% at three different spiking levels(0.02, 0.2 and 2.0 mg/kg). And the average recoveries of thiamethoxam and clothianidin ranged from 88.8 to 98.9% and 83.2 to 96.6% with the percentage of coefficient variation in the range 3.6~5.0% and 3.8~9.4% at three different spiking levels(0.02, 0.2 and 2.0 mg/kg), respectively. The residue amounts ranges of difenoconazole were 0.2~0.56 mg/kg and the residue amount was decreased below the MRL level, 1.0 mg/kg, after 1 day harvest. The residue amounts ranges of thiamethoxam were 0.08~0.28 mg/kg and the residue amount was decreased below the MRL level, 0.5 mg/kg, after 1 day harvest. And the residue amount of clothianidin was below then 0.03 mg/kg for only one test site of 14 and 28 day samples. CONCLUSION: As a result, the residual amounts of difenoconazole and thiamethoxam were not exceeded the MRL of established criteria for sweet persimmon. The biological half-lives of difenoconazole and thiamethoxam were 13.6, 19.4, 16.3 and 10.0, 15.3, 14.0 days at each three test sites, respectively.

• Applied Biological Chemistry
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• v.50 no.4
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• pp.245-252
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• 2007

FTA (fault tree analysis), an analytical method for system failure management, was employed in the management of faults in running PCR analysis. PCR is executed through several processes, in which the process of PCR machine operation was selected for the analysis by FTA. The reason for choosing the simplest process in the PCR analysis was to adopt it as a first trial to test a feasibility of the FTA approach. First, fault events-top event, intermediate event, basic events-were identified by survey on expert knowledge of PCR. Then those events were correlated deductively to build a fault tree in hierarchical structure. The fault tree was evaluated qualitatively and quantitatively, yielding minimal cut sets, structural importance, common cause vulnerability, simulation of probability of occurrence of top event, cut set importance, item importance and sensitivity. The top event was 'errors in the step of PCR machine operation in running PCR analysis'. The major intermediate events were 'failures in instrument' and 'errors in actions in experiment'. The basic events were four events, one event and one event based on human errors, instrument failure and energy source failure, respectively. Those events were combined with Boolean logic gates-AND or OR, constructing a fault tree. In the qualitative evaluation of the tree, the basic events-'errors in preparing the reaction mixture', 'errors in setting temperature and time of PCR machine', 'failure of electrical power during running PCR machine', 'errors in selecting adequate PCR machine'-proved the most critical in the occurrence of the fault of the top event. In the quantitative evaluation, the list of the critical events were not the same as that from the qualitative evaluation. It was because the probability value of PCR machine failure, not on the list above though, increased with used time, and the probability of the events of electricity failure and defective of PCR machine were given zero due to rare likelihood of the events in general. It was concluded that this feasibility study is worth being a means to introduce the novel technique, FTA, to the management of faults in running PCR analysis.

• Journal of Ginseng Research
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• v.20 no.4
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• pp.472-500
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• 1996

Researches on mineral nutrition, physiology and phyrsiological diseases, . cultivaction methods. brceding. pest control quality management and extension during 1976-1995 in Korea were reviewed Review in brceding and pest control was restricted to the researches directely related to cultivaction. Mineral nulrient up take. partion and varicos factors such as top dreasing. Light intersity etc. and interrelationship between minerals were investigated. Top dressing was not effective due to low minera1 requorement Physiological characteristics on tempelature light and water were well elucidated and applied to assess traditional cultivation method and its inovation. Photosyrnthetic pigments. light harvest proteins and activity of related enzymes were studied. In nitrogen metabolism arginine, praline, ammonium, threonine appeared to have important role in re growth of shoot Saponin metabolism was studied in relation to growth and new ginsenosides were found but physiological role of saponin was not clearly elucidated yet Endogenous growth regulators were reported and various erogenous growth regulators were studied for growth stimulation. short stem and seed pruning etc. Various physiological diseases were investigated for cause and control measures were established. Water culture was little studied Forest culture was studied but not retched the recommendable stage Drip irrigation straw mulching. seasonal shading and soil preparation method including soil fertility adjustment were established for practical application. Shading materials completely changed to polyethylene net and materials of polymers The research on ginseng cultivation in paddy field opened the way to establish the permanent ginseng cultivation plantation Ginseng harvester and seeder were developed in the late 1950s. Transplanted and many other machines were developed in the early 1990s. In ginseng breeding only pure line selection was of practical significance several verities were at the stage of seed propagation at ginseng plantations. Mutation breeding (${\gamma}$-ray. X-ray chemicals) was not successful. The research on plantlet formation through tissue culture was a little progressed but still far behind to vegetative propagation. Disease control research was concentrated in the isolation and identification of pathogans. their ecological charactelistics and biological control and soil humigation. Potato root rot nematodes was found and control method was established. Insect and small animal control research was greatly progresses in identification, ecological investigation, and ecological and physical control. Weed control was less important due to the development of mulching method of ridge and ditch. Quality factors of raw ginseng in relation to red ginseng process were extensively studied. Traditional quality measures were elucidated in accordance with modern analytical chemistry resulting in the importance of peptides in the centrat part rather than ginsenosides For large root production growth promoting rootzone micrcorganisms (PGPRM) were isolated and active compounds were identified. Field test on PGPRM was on going. Varictus methods formality improvement through cultivation were developed. Management research of ginseng production was rare Extension was active throuch official and private organizations and through workshop for the extension specialists, and direct lectures to grower's. Extension services made the researcher to understand the existing problems at grower's fields. Research environment for ginseng production was in prime time only for three years when Korea Ginseng Research Institute was established then gradually aggravated.

• Korean Journal of Food Science and Technology
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• v.46 no.4
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• pp.432-437
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• 2014

This study was carried out to examine the quality properties of honey in Korean commercial markets. The moisture content, stable carbon isotope ratio, invert sugar, cane sugar, and hydroxy-methylfurfural (HMF) contents of honey were measured according to the Korea Food Code and AOAC's (Association of Official Analytical Chemists) official methods. The stable carbon isotope ratio ranged from -25.18‰ to -12.60‰, which clearly differed between honey of $C_3$ origin (flower) and $C_4$ origin (artificial). Results of quality measurements revealed a moisture content of 18.12 to 19.70%, fructose content of 36.10 to 43.94%, glucose content of 22.61 to 31.91%, sucrose content of 1.56 to 4.75%, invert sugar content of 64.89 to 72.79%, and HMF content of 4.10 to 78.66 mg/kg. These values demonstrate that the quality of the tested honey meets the standard criteria of the Korean Food Code and Codex. However, it is necessary to reconsider the appropriate criteria for imported honey because it is circulated in the market through a long distribution process.

• Korean Journal of Environmental Agriculture
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• v.41 no.4
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• pp.355-364
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• 2022

BACKGROUND: Pre-harvest interval and decline pattern of thiamethoxam were determined in kiwifruit using liquid chromatography-tandem mass spectrometry (LCMS/MS). The study was carried out to propose import tolerance using OECD maximum residue limit (MRL) calculator for the export promotion of kiwifruit to Taiwan. METHODS AND RESULTS: The thiamethoxam residue in kiwifruit was determined by using the LC-TriQ-MS/MS with the analytical process to set up the import tolerance under greenhouse conditions for Taiwan. Excellent linearity was observed for all of the analytes with a determination coefficient (R²)≥0.99. The limit of quantification was determined to be 0.01 mg/kg for both thiamethoxam and clothianidin in kiwifruit. Linearity was determined from the co-efficient of determinants (R²) obtained from the seven-point calibration curve. The standard calibration curve showed as follows; 1) Site 1 (Gimje): y = 944,406X + 1,583 (R²=0.9995), 2) Site 2 (Goheung): y = 1,356,205X + 934 (R²=0.9983), and 3) Site 3 (Jangheung): y = 1,239,937X - 3,090 (R²=0.9908). The residue of thiamethoxam in the kiwifruit for three decline trials showed the range of 0.35 to 0.56 mg/kg in site 1 (Gimje), 0.24 to 0.55 mg/kg in site 2 (Goheung), and 0.28 to 0.42 mg/kg in site 3 (Jangheung), respectively. However, clothianidin was not detected in all of the treatments. The maximum residual amounts (decline) in the samples, sprayed according to the safe-use standard for thiamethoxam 10% WG in kiwifruit (30 days before harvest, 3 sprays every 7 days) were 0.56 mg/kg in site 1, 0.55 mg/kg in site 2, and 0.42 mg/kg in site 3, respectively. CONCLUSION(S): The import tolerance (IT) of thiamethoxam for kiwifruit may be proposed to be 0.9 mg/kg by using the OECD MRL calculator.

• Applied Biological Chemistry
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• v.17 no.1
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• pp.63-80
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• 1974

The chemical components of Citrus junos produced in Korea were divided into two parts; common and special components respectively. In the former the relation between the physiological effects of the plant and its ripening process was observed periodically while the latter was analyzed the ripening fruits for their effective utilization as food. The results are summarized as follows: 1. The analytical result of seasonal change showed that the rind ratio was higher than the flesh ratio and on a regional basis, the rind ratio was higher in the islands than on land areas. 2. In the experiment the moisture was increased until the third period, but afterwards it was made constant. While the content of crude fat, cellulose, ash, total acid and soluble non-nitrogen material were decreased until the third period and the cotent of cellulose and total acid were continuousely redused until the last period. In con trast with the above the content of reducing sugars was increased but the content of crude fat, cellulose, ash, crude protein and soluble non-nitrogen material were increased until last period. 3. The content of vitamin C was richer in the rind than in the flesh, in the Korean species than in the Japanese. 4. Free sugars; xylose, fructose, glucose were richer in the rind than in the flesh. 5. The content of volatile organic acids was richer in the rind than in the flesh. Among them, volatile acids, acetic acid, formic and n-valeric acid were found in the rind and formic acid, acetic acid and propionic acid were deteceed in the flesh. 6. The total content of non-volatile acids was richer in the flesh than in the rind. In the kind of non-volatile acids, citric acid,glutaric acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid and an unknown acid were found in the rind and citric acid, malic acid, succinic acid, oxalic acid, glutaric acid and malonic acid in the flesh. 7. Three kinds of aromatic components: D-limonene, ${\alpha}-pinene$, p-cymene and seven other kinds of unknown aromatic components were detected in neutral essential oils. Among them, D-limonene seemed to be main aromatic component in the fruits. 8. From the above results it is confirmed that both rind and flesh of the ripened fruit could be utilized for food effectively, and unripened fruits are suitable for producing citric acid, ripened fruits are also useful for producing juice.

• The Korean Journal of Quaternary Research
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• v.16 no.2
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• pp.9-21
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• 2002

In Korea, many open-air upper palaeolithic sites are located at the river valley, particularly exposed in gently rotting terrain along the river course. They are situated at an altitude less trail 30 m above present river bottom, and covered with the blankets of slope deposits of several meters in thickness. The purpose of this research is to eluridate depositional and vegetational environment of the alluvial upper palaeolithic Jangheung-ri sites on the basis of analytical properties of grain size population, chronology, palynology, soil chemistry and clay mineralogy and magnetic susceptibility of the Jangheung-ri Quaternary formations. The lithostratograpy of Jangheung-ri sit is subdivided into 3 layers based on the depositional sequence and radiocarbon ages. From bottom to top, they are composed of slope deposits with lower paleosol layers, young fluvial sand and gravel with backswamp organic muds, and upper paleosol layers. The upper paleosol was formed under rather dry climatic condition between each flooding period. Dessication cracks were prevalent in the soil solum which was filled with secondarily minuted fragments due to pedogenetic process. The soil structure shows typical braided-typed cracks in the root part of cracking texture, and more diversified pattern of crackings downward. The young fluvial sand gravel were formed by rather perennial streams after LGM. The main part of organic muds was particularly formed after 15Ka. Local backswamp were flourished with organic muds and graded suspension materials in the flooding muds were intermittently accumulated in the organic muds until ca. 11Ka. This episode was associated with migration of Nam River toward present course. Organic muds were formed in backswamp or local pond. Abies/Picea-Betula with Ranunculaceae, Compositae, Cyperaceae were prevalent. This period is characterized with B$\Phi$lling, Older Dryas, Allerod, and Younger Dryas (MIS-1). Stone artefacts were found in the lower paleosol layers formed as old as 18Ka-22Ka. Based on the artefacts and landscape settings of the Jangheung-ri site, it is presumed that settlement grounds of old people were buried by frequent floodings of old Nam River, the river-beds of which were heavily fluctuated laterally and river-bed erosions were activated from south to north in Jangheung-ri site until the terminal of LGM9ca 17Ka).

• Journal of the Korean Society of Food Science and Nutrition
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• v.46 no.2
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• pp.210-219
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• 2017

This study aimed to establish an optimal extraction process and high-performance liquid chromatography (HPLC)-photodiode array (PDA) analytical method for determination of marker compounds, dihydrokaempferol (DHK) and 3-O-methylquercetin (3-MeQ), as a part of materials standardization for the development of health functional foods from stems of Opuntia ficus-indica var. saboten (OFS). The quantitative determination method of marker compounds was optimized by HPLC analysis, and the correlation coefficient for the calibration curve showed very good linearity. The HPLC-PDA method was applied successfully to quantification of marker compounds in OFS after validation of the method in terms of linearity, accuracy, and precision. Ethanolic extracts from stems of O. ficus-indica var. saboten (OFSEs) were evaluated by reflux extraction at 70 and $80^{\circ}C$ with 50, 70, and 80% ethanol for 3, 4, 5, and 6 h. Among OFSEs, OFS70E at $80^{\circ}C$ showed the highest contents of DHK and 3-MeQ of $26.42{\pm}0.65$ and $3.88{\pm}0.29mg/OFS100g$, respectively. Furthermore, OFSEs were determined for their antioxidant activities by measuring 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging and lipid peroxidation (LPO) inhibitory activities in rat liver homogenate. OFS70E at $70^{\circ}C$ showed the most potent antioxidant activities with $IC_{50}$ values of $1.19{\pm}0.11$ and $0.89{\pm}0.09mg/mL$ in the DPPH radical scavenging and LPO inhibitory assays, respectively. To identify active components of OFS, various chromatographic separation of OFS70E led to isolation of 11 flavonoids: dihydrokaempferol, dihydroquercetin, 3-O-methylquercetin, quercetin, isorhamnetin 3-O-glucoside, isorhamnetin 3-O-galactoside, narcissin, kaempferol 7-O-glucoside, quercetin 3-O-galactoside, isorhamnetin, and kaempferol 3-O-rutinoside. The results suggest that standardization of DHK in OFSEs using HPLC-PDA analysis would be an acceptable method for the development of health functional foods.