• 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.

• Korean journal of food and cookery science
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• v.18 no.2
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• pp.216-224
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• 2002

Persimmon powder (PW), which was prepared by pulverizing freeze-dried persimmon with peels, was added to Maejakgwa up to 25% of wheat flour. Maejakgwa samples were prepared by the central composit experimental design for three independent variables: amount of PW, frying time, and frying temperature. The color of Maejakgwa was influenced more by the frying time and temperature than the content of added PW. Crispiness and adhesiveness were highly correlated with overall preference. Although the amount of PW affected the adhesiveness, the adhesiveness could be controlled by the frying temperature and time. Frying temperature was the most effective factor on the crispness and hardness. The addition of high amount of PW obviously increased the sweetness and aftertaste. However, at the low amount of PW, frying for longer time at high temperature also increased the sweetness and aftertaste. Center sample (15% PW, frying for 4 min at 145$\^{C}$) showed the best score at the overall preference. Overall preference was improved as the sample was fried at high temperature/short time or at low temperature/long time. Maejakwa prepared with high amount of PW at 20% showed no significant difference with the center sample for overall preference as prepared by frying for 3 min at 155$\^{C}$. The optimum condition obtained by superimposing color, crispiness and overall preference was frying for 5∼6 min at 131∼140$\^{C}$.

• Economic and Environmental Geology
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• v.43 no.6
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• pp.555-564
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• 2010

Remediation process by using the bio-carrier (beads) with dead Bacillus sp. B1 and polysulfone was investigated for heavy metal contaminated groundwater. Sorption batch experiments using the bio-carrier were performed to quantify the heavy metal removal efficiencies from the contaminated solution. The analyses using SEM/EDS and TEM for the structure and the characteristic of precipitates on/inside the beads were also conducted to understand the sorption mechanism by the bio-carrier. Various amounts of freeze-dried dead Bacillus sp. B1 were mixed with polysulfone + DMF(N,N-dimethylformamide) solution to produce the bio-carrier (beads; less than 2mm in diameter) and 5% of Bacillus sp. B1 in the bio-carrier was optimal for Pb removal in the solution. The removal efficiency ratings of the bio-carrier for Pb, Cu and Cd were greater than 80% after adding 2g of bio-carrier in 50ml of aqueous solution (<10mg/L of each heavy metal concentration). Reaction time of the bio-carrier was very fast and most of the sorption reaction for heavy metals were completed within few hours. Batch experiments were duplicated at various pH conditions of aqueous solutions and Cu and Pb removal efficiencies highly maintained at wide pH ranges (pH 2-12), suggesting that the bio-carrier can be useful to clean up the acidic waste water such as AMD. From SEM/EDS and TEM analyses, it was observed that the bio-carrier was spherical shape and was overlapped by many porous layers. During the sorption experiment, Pb was crystallized on the surface of porous layers and also was mainly concentrated at the boundary of Bacillus sp. B1 stroma and polysulfone substrate, showing that the main mechanism of the bio-carrier to remove heavy metals is the sorption on/inside of the bio-carriers and the bio-carriers are excellent biosorbents for the removal of heavy metal ions from groundwater.

• Journal of Nutrition and Health
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• v.50 no.3
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• pp.225-235
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• 2017

Purpose: This study aimed to investigate the potential of freeze-dried persimmon powder (Diospyros kaki Thumb.) to protect against dyslipidemia induced by a high-fat/cholesterol diet (HFD) in a rat model. Methods: Fifty Wistar rats were randomly divided into five groups: normal control (NC), high-fat/cholesterol control (HC), tannin in HFD (HT, 1% of diet), immature persimmon in HFD (HI, 7% of diet), and mature persimmon in HFD (HM, 7% of diet). Tannin was used as a positive control. Biochemical, molecular, and histopathological changes were observed in the blood and liver. Results: We confirmed that a high fat/cholesterol diet successfully induced dyslipidemia, which was characterized by significantly altered lipid profiles in the plasma and liver. However, oxidized low-density lipoprotein levels, histopathological damage in the liver, and hepatic triglyceride levels were significantly reduced in all HT, HI, and HM groups compared to those in the HF group. In contrast, plasma apolipoprotein B level was significantly reduced only in the HT and HM groups, whereas reduction of the LDL-C level was detected only in the HI group. Although HF-induced sterol regulatory element-binding protein (SREBP) gene expression was significantly reduced in all treated groups, downstream gene expression levels varied among the different groups; significant reduction of fatty acid synthase (FAS) and 3-hydroxy-3-methylglutaryl-CoA (HMGCR) gene expression was detected only in the HI group, whereas cholesterol $7{\alpha}$-hydroxylase (CYP7A1) gene expression was significantly elevated only in the HM group. Conclusion: Taken together, the data suggest that protection of LDL oxidation and hepatic lipogenesis might be, at least partly, attributed to tannin in persimmons. However, the identified mechanisms varied up to the maturation stage of persimmon. In the case of immature persimmon, modulation of FAS and HMGCR gene expression was prominent, whereas in the case of mature persimmon, modulation of CYP7A1 gene expression was prominent.

• Korean Journal of Agricultural Science
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• v.6 no.2
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• pp.166-184
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• 1979

In order to prevent the water loss in the irrigation canal constructed on the sandy gravel layer or on the other highly permeable ground layer, lining has been practiced. Many studies have been done so far on the lining method to prevent the water loss in the irrigation canal and recently studies on the lining with plastic film or polyethylene film were also reported. However, the plastic film or polyethylene film has low strength and is liable to break, and water loss from pin hole caused by contacting with sand or gravel is highly predicted. This study was then conducted to find proper lining and buring method in canal construction of polypropylene mat after coated with vinyl, as one way to overcome the shortcoming frequently observed when plastic or usual polyehtylene film were used. Eventhough rather longer periods of experiments are needed to attain reliable and accurate results on the variation of durability, the durability of asphalt coated area, or on the damage due to freeze after burial or exposure of polypropylene mat, the experiemental results obtained during one year of period are summarized as follows: 1. The curvature at the area between canal bottom and side slope had increased stability and saved consruction cost. The relationship among the variation of curvature, the reduction of polypropylene mat and the reduced amount of soil cutting at each side slope was presented in Fig. 7 through 9. 2. The depth of covering material to protect polypropylene mat was desired to be over 30cm, considering the water depth, side slope, canal cleaning practices, traffic, or back pressure of irrigation period. 3. In order to increase the canal stability and to prevent slope erosion, sandy soil was required, to be placed under ground, and coarse gravel should cover the surface area of canal. 4. The studies on the stability of side slope in the canal should consider the passive area on the bottom and the slope should be about 1 to 2, considering the slope stability, allowable velocity and tractive force. 5. When compared with earth lining, the lining with polypropylene mat coated with vinyl was responsible to save 28% and 37% of canal lining cost, when the soil carrying distances were 500 and 700m. respectively. 6. The water interception was almost completely attained when the polypropylene mat coated with vinyl was used for lining. But further studies were assumed to be necessary for the use of asphalt since the strength of polypropylene mat connected with asphalt will vary with duration.