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Synthesis, Structure, and Reactivity of the [Fe4S4(SR)4]2- (R = 2-, 3-, and 4-Pyridinemethane) Clusters

  • Kim, Yu-Jin;Han, Jae-Hong
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.48-54
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    • 2012
  • The $[Fe_4S_4]^{2+}$ clusters with 2-, 3-, and 4-pyridinemethanethiolate (S2-Pic, S3-Pic, and S4-Pic, respectively) terminal ligands have been synthesized from the ligand substitution reaction of the $(^nBu_4N)_2[Fe_4S_4Cl_4]$ (I) cluster. The new $(^nBu_4N)_2[Fe_4S_4(SR)_4]$ (R = 2-Pic; II, 3-Pic; III, 4-Pic; IV) clusters were characterized by FTIR and UV-Vis spectroscopy. Cluster II was crystallized in the monoclinic space group C2/c with a = 24.530 (5) $\AA$, b = 24.636(4) $\AA$, c = 21.762(4) $\AA$, ${\beta}=103.253(3)^{\circ}$, and Z = 8. The X-ray structure of II showed two unique 2:2 site-differentiated $[Fe_4S_4]^{2+}$ clusters due to the bidentate-mode coordination by 2-pyridinemethanethiolate ligands. Cluster III was crystallized in the same monoclinic space group C2/c with a = 26.0740(18) $\AA$, b = 23.3195(16) $\AA$, c = 22.3720(15) $\AA$, ${\beta}=100.467(2)^{\circ}$, and Z = 8. The 3-pyridinemethanethiolate ligand of III was coordinated to the $[Fe_4S_4]^{2+}$ core as a terminal mode. Cluster IV with 4-pyridinemethanethiolate ligands was found to have a similar structure to the cluster III. Fully reversible $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ redox waves were observed from all three clusters by cyclic voltammetry measurement. The electrochemical potentials for the $[Fe_4S_4]^{2+}/[Fe_4S_4]^+$ transition decreased in the order of II, III and IV, and the reduction potential changes by the ligands were explained based on the structural differences among the complexes. The complex III was reacted with sulfonium salt of $[PhMeSCH_2-p-C_6H_4CN](BF_4)$ in MeCN to test possible radical-involving reaction as a functional model of the [$Fe_4S_4$]-SAM (S-adenosylmethionine) cofactor. However, the isolated reaction products of 3-pyridinemethanethiolate-p-cyanobenzylsulfide and thioanisole suggested that the reaction followed an ionic mechanism and the products formed from the terminal ligand attack to the sulfonium.

Studies on the Manufacturing and Fermentation Characteristics of Soy-Sauce-Kimchi (장김치의 제조 및 발효특성에 관한 연구)

  • Kim, Eun-Jung;Hahn, Young-Sook
    • Korean journal of food and cookery science
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    • v.24 no.4
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    • pp.517-524
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    • 2008
  • This study made Soy-Sauce-Kimchi and investigated its pH, acidity, microorganism, salinity, chromaticity, viscosity and taste to revive traditional Soy-Sauce-Kimchi using Soy-Sauce instead of salt and to report its fermentation characteristics. As one of studies on traditional Kimchi, it tried for practical use of traditional Soy-Sauce-Kimchi which had been eaten in the middle region of Korea, especially in Seoul but currently has been prepared by only a few people and has disappeared gradually. According to the results of this study, among three groups of Soy-Sauce-Kimchi-I(s1), Soy- Sauce-Kimchi-II(s2) added by 2.5% sucrose and the control group(C), acidity of s2 was sharply increased after 24 hours and 72 hours at $20^{\circ}C$ and $10^{\circ}C$ respectively and there was few difference in salinity by temperature. In the case of s2 group, addition of 2.5% sucrose was considered to lead to increase of salinity. For chromaticity, while the L value and b value became larger after 48 hours, the a value tended to decline. Viscosity of s2 grew after 24 hours at all of $20^{\circ}C$, $10^{\circ}C$ and $1^{\circ}C$ and that was thought to be because propagation of bacteria such as Leuconostoc mesenteriodes following addition of 2.5% sucrose secreted dextransucrose so sucrose was transferred into dextran to increase viscosity. The total number of microorganisms was recorded to be largest after 48, 36 and 72 hours at $20^{\circ}C$, $10^{\circ}C$ and $1^{\circ}C$ respectively and the number of lactic acid bacteria was the largest at $1^{\circ}C$ after 72 hours compared to those at other temperatures. That was considered to be because microorganisms such as Leuconostoc mesenteriodes are psychrotropic lactic acid bacteria. For sensory evaluation, all appearance, chromaticity and odor of C were higher by $3{\sim}4$ points than those of s1 and s2(p < 0.001) and their feel also showed a similar tendency(p < 0.05). Considering the results of sensory evaluation, more researches were needed to overcome difference of taste for Soy-Sauce-Kimchi according to age due to characteristic flavor and smell of soy-source.

The Effect of Extract of Cervi pantotrichum Cornu on Human Sperm Motility (녹용(Cervi pantotrichum cornu) 추출물이 인간 정자 운동성에 미치는 영향)

  • 신동혁;김지영;이창훈;정창진;조용선;최동희;고정재;윤태기
    • Journal of Embryo Transfer
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    • v.17 no.3
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    • pp.187-193
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    • 2002
  • This study was conducted to determine the effect of extract of Cervi pantotrichum cornu on human sperm motility, Four different types of media were prepared such as plain Ham's F-10 medium(control medium), control medium containing 0.3% bovine serum albumin(BSA)(medium A), control medium containing the extract of Cervi pantotrichum cornu aqua-acupuncture medium(medium B) and medium B containing 0.3% BSA(medium C). Human semen were washed and divided into 4 fractions and sperm were cultured in those medium for up to 72 hours at 37$^{\circ}C$ in a humidified atmosphere of 5% $CO_2$ in air. A total twenty eight semen samples including 14 normozoospermia and 14 asthenospermia were used for this study. In normozoospermia group, motility of control medium and medium A, B and C were 4.1%, 1.3%, 64.5%, and 77.1%, respectively after 24 hours of incubation, and were 0.0%, 0.0%. 8.8% and 44.9%, respectively after 48 hours of incubation. In asthenospermia group, motility of control medium and medium A, B and C were 2.0%, 2.2%, 58.3% and 85.1%, respectively after 24 hours of incubation, and decreased to 0.0%, 0.2%, 5.8% and 29.6%, respectively after 48 hours of incubation. In both groups, highest sperm motility was observed in medium C group when compared with other media. Furthermore motile sperm were found in medium C after 72 hours of incubation while no motile sperm was observed in the other media. Therefore it could be concluded that the extract of Cervi pantotrichum rornu affects on the human sperm motility.

Occurrence of Blue Mold on Tomato Caused by Penicillium oxalicum in Korea

  • Kwon, Jin-Hyeuk;Shen, Shun-Shan;Jee, Hyeong-Jin
    • The Plant Pathology Journal
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    • v.24 no.1
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    • pp.87-89
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    • 2008
  • A blue mold on tomato fruit caused by Penicillium oxalicum occurred sporadically in a greenhouse at Gyeongsangnam-do Agricultural Research and Extension Services. Infection usually occurred through wounds or cracks on the fruits. Symptoms began with water soaking lesions, then became watery and softened eventually. Colony of the causal fungus was white at the early growing stage, turned green on Czapek yeast extract agar and malt extract agar. Conidia were ellipsoidal in shape and $2-6{\times}2-4{\mu}m$ in size. Stipes were septate, smooth, thin walled, and $90-280{\times}3-4{\mu}m$ in size. Penicilli were mostly biverticillate. Ramuli were 1-3 groups, smooth, and $10-16{\times}2-3{\mu}m$ in size. Rami were 1-2 groups and $6-30{\times}2-4{\mu}m$ in size. Metulae were 2-3(5) verticils, smooth, and $12-20{\times}3-4{\mu}m$ in size. Phialides were 5-7 verticilate, ampulliform to cylindroidal, smooth, and $8-12{\times}2-3{\mu}m$ in size. Optimum temperature for growth was about $25^{\circ}C$. Pathogenicity of the fungus was proved on tomato fruit according to Koch's postulation. On the basis of mycological and pathological characteristics, the fungus was identified as P. oxalicum Currie & Thom. This is the first report of the blue mold on tomato fruit caused by P. oxalicum in Korea.

Effects of the Coptidis Rhizoma Extract on the Membranous Nephropathy induced by Cationic Bovine Serum Albumin in Mice (황연(黃連)이 Cationic Bovine Serum Albumin 투여로 유발된 Membranous Nephropathy Mouse Model에 미치는 영향)

  • Chae, Eun-Young;Cho, Chung-Sik;Kim, Cheol-Jung
    • The Korea Journal of Herbology
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    • v.24 no.1
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    • pp.99-110
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    • 2009
  • Objectives : The current treatment regimens for patients with nephrotic syndrome due to membranous nephropathy(MN) are based on steroids or immunosuppressive therapy with the aim of reducing proteinuria and improving outcome. Although these treatments attenuate the deterioration of renal function in MN patients, it has been suggested that all are burdened by significant toxicity. Therefore, more specific and less toxic therapies are needed. This study was to evaluate the effects of Coptidis Rhizoma Extract(CRE) on the MN induced by cBSA in mice. Methods : Mice were divided into 4 groups. One group named for 'Normal' was injected with a saline solution not to be immunized. The rest groups were treated as follows; After mice were immunized with 0.2 mg of cBSA and Freund's complete adjuvant one time every two weeks for 6 weeks, they received intra-peritoneal injection of 10 mg/kg of cBSA daily for 4 weeks. Also, they were divided into 3 groups. The first named for 'Control' was not given CRE. The second for 'CRE-250' was given oral administration of 250 mg/kg of CRE daily for 4 weeks. The third for 'CRE-500' was given 500 mg/kg of CRE. All of mice were sacrificed 4 weeks after the first immunization. We measured a body weight and 24hrs proteinuria as well as serological analysis. The morphologic changes of renal glomeruli were also observed with a light microscope and an electron microscope. Results : The levels of 24 hrs proteinuria, triglyceride, IgG, IL-6 were significantly decreased in both CRE groups. And the level of IgM was significantly decreased in CRE-250 group. In histological findings of kidney tissue, thickening of GBM and deposition of electron-density were consideraly decreased in both CRE groups. Conclusions : The present study suggests that CRE is highly effective when treating mice with MN induced by cBSA. More clinical data and studies are to be done for efficient application.

Biodistribution of Iodine-131-Iodomisonidazole and Imaging of Tumor Hypoxia in Mice bearing CT-26 Adenocarcinoma (CT-26 선암을 접종한 마우스에서 Iodine-131-Iodomisonidazole의 생체분포 및 종양저산소증의 영상화)

  • Kim, Hye-Won;Kim, Chang-Guhn;Yoon, Kwon-Ha;Kim, Hyun-Jeong;Juhng Seon-Kwan;Roh, Byung-Suk;Yang, David J.;Kim, E.Edmund;Lee, Hyun-Chul
    • The Korean Journal of Nuclear Medicine
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    • v.33 no.3
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    • pp.289-297
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    • 1999
  • Purpose: Misonidazole is a radiosensitizer that binds in hypoxic cells. The purpose of this study was to find out the feasibility of I-131-Iodomisonidazole (IMISO) for imaging of tumor hypoxia. Materials and Methods: Tosyl precursor was dissolved in acetonitrile and I-131-NaI was added to synthesize IMISO. Balb/c mice inoculated with CT-26 adenocarcinoma were injected with IMISO. Mice were sacrificed at 1, 2, 4, 24 hr and % of injected dose per gram of tissue (%ID/g) was determined. For scintigraphy and MRI, mouse bearing CT-26 adenocarcinoma was administered with IMISO and imaging was performed 4 hr after. Then, mouse body was fixed and microtomized slice was placed on radiographic film for autoradiography Results: %ID/g of tumor was 1.64 (1h), 0.98 (2h), 0.85 (4h) and 0.20 (24h), respectively. At 24h, %ID/g of tumor was higher than that of all other tissues except thyroid. Tumor to muscle ratio increased with time and tumor to blood ratio also increased with time and reached 1.53 at 24 hr. On autoradiogram, tumor was well visualized as an increased activity in central hypoxic area of the tumor which corresponds to the area of high signal intensity on T2-weighted MR image. On scintigraphy, tumor uptake was visualized. Conclusion: This results suggest that IMISO may have a potential for tumor hypoxia imaging in mouse model. However, further study is needed to improve it's localization in tumor tissue and to achieve acceptable images of tumor hypoxia.

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Studies on the Shrinkage of Silk Yarn by Neutral Salts (견의 중성염류에 의한 염축에 관한 연구)

  • 이용우;이광길
    • Journal of Sericultural and Entomological Science
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    • v.33 no.2
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    • pp.87-92
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    • 1991
  • The shrinkages and physical properties of silk yarn were studied on the effect of treatment concentration, time and temperature with various neutral salts. The degummed silk yarn was shrunk about 35 percent by highly concentrated solution of Ca(NO3)2 on conditions of S.G.(special gravity) 1.45 at 9$0^{\circ}C$ or S. G. 1.46 at 8$0^{\circ}C$. About 40 percent of silk yarn was contracted in length by the treatment of CaCl2 solution on conditions of S. G. 1.33 at 9$0^{\circ}C$ for 5 mins. or at 85$^{\circ}C$ for 10 mins. By treating the concentrated solution of LiBr the silk yarn showed about 40 percent of shrinkage on a conditions of S. G. 1.38, $25^{\circ}C$ 24hrs. The physical properties of salt-treated silk yarn could be significantly changed with shrinkage variations. There were some differences in shrinkages between different type of salts. However, it was observed that generally the tenacity was decreased and breaking elongation increased as the shrinkage increased. The bulkiness of salt-treated silk yarn was increased by 110 to 120 percent compared with untreated yarn.

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Analysis of Chemical Composition and Antioxidant Activity of Codonopsis lanceolata Skin (더덕껍질의 일반성분 분석과 항산화 활성)

  • Kim, Na-Young;Chae, Hyun-Seok;Lee, In-Sook;Kim, Dong-Soo;Seo, Kang-Tae;Park, Sung-Jin
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.39 no.11
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    • pp.1627-1633
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    • 2010
  • The purpose of this study is to determine the possibility of Codonopsis lanceolata skin as natural health food source. To accomplish this purpose, the contents of general and antioxidative nutrients of C. lanceolata skin were measured. On a dry weight basis the contents of carbohydrate, crude protein, crude lipid and ash are 24.74, 2.73, 2.96 and 4.84%, and the calories of skin was 266.00 kcal/100 g and total dietary fiber was 64.73%. The contents of essential and non-essential amino acids were 633.40 and 870.72 mg/100 g wet weight basis. The K was the largest mineral followed by Ca, Mg, and P, suggesting that C. lanceolata skin is alkali material. The EDA of water extract from C. lanceolata skin was 18.28~79.30%, and the activity was dependent on the sample concentration. Total phenolic and flavonoids contents of water extract from C. lanceolata skin were estimated as 24.65 and $6.19\;{\mu}g/g$. The C. lanceolata skin extract showed the highest reducing power (3.5) at the concentration of 25 mg/mL. Based on the above results, we deemed that the C. lanceolata skin might have potential antioxidant activities. The general nutrients and antioxidant bioactive materials in C. lanceolata skin were also potential materials for good health food.

SHEAR BOND STRENGTH OF DENTIN BONDING AGENTS ON DENTIN SURFACE TREATED WITH EUGENOL (유지놀 처리된 상아질 표면의 상아질 접착제의 전단결합강도에 관한 연구)

  • Yu, Hwa-Sung;Choi, Gi-Woon;Choi, Kyung-Kyu;Park, Sang-Jin
    • Restorative Dentistry and Endodontics
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    • v.25 no.4
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    • pp.550-560
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    • 2000
  • In this study, shear bond strength of two bonding systems were measured and appearance of dentin surfaces were observed with SEM according to the storage time of eugenol on dentin surface, thus evaluated the effect of eugenol on bond strength of two dentin bonding systems. Control groups were directly bonded to dentin surface with One Step, Prime & Bond 2.1. Experimental groups were divided into experimental I and II according to dentin bonding agents. After eugenol application, dentin surfaces were bonded with One Step and Prime & Bond 2.1 according to the each storage time of immediately, 3min, 24hour, 48hour and 1week, and then control and experimental groups were filled with light cured composite resin(Z-100). After 24 hours water storage at $37^{\circ}C$, all samples were subjected to a shear load to fracture at a cross head 1.0mm/min with Instron universal testing machine(No. 4467). Etched dentin surface storaged for each time of immediately, 3min, 24hour, 48hour and 1 week after eugenol application were observed under Scanning Electron Microscope(Hitachi S-2300) at 20kvp. The data were evaluated statistically with two-way ANOVA and Tukey's HSD. The results were as follows; 1. Shear bond strengths were higher in control groups than in the experimental groups. 2. As storage time was increased after eugenol application, the shear bond strengths were decreased in experimental groups. 3. In experimental I, II the shear bond strengths were the lowest in which storage time was 1 week after eugenol application. 4. As storage time was increased after eugenol application, etched dentin surfaces showed obstructed dentinal tubule.

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The Factors Influencing the Systemic Action of Dimethoate (O.O-dimethyl-S-(N-methylcarbamoylmethyl) phosphorodithioate) to the Rice Seeds and Phytotoxic Effects (수도종자에의 Dimethoate 침투력 및 발아저해에 관여하는 요인에 관한 연구)

  • Choi Seung Yoon
    • Korean journal of applied entomology
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    • v.9 no.2
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    • pp.57-74
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    • 1970
  • These experiments were conducted to investigate the :actors influencing the systemic action of Dimethoate (O,O-dimethyl-S-(N-methylcarhamoylmethyl) photphorodithioate) to rice seeds and the phytotoxic effects on the seed germination. Dimethoate $(Roxion^{(R)})$ $40\%$ emulsion was used. The varieties tested were Jinheung. Nongkwang,Suwon #82, Norm #6, Paltal, Shirogane, Suseong, Pungkwang, Shin #2, Fujisaka #5, Kwanok, and Jaekeun. The permeated Dimethoate was extracted from the treated seeds by chloroform and quantities were determined by Spectrophotometer. The phytotoxicity was evaluated from the effects on the germination of the treated seeds which were kept in an incubator. The oxygen consumption was measured by Warburg Manometer at $30^{\circ}C$ for 60 minutes. Indices of KOH disintegration of seeds and chemical composition of the seeds were also determined. The results obtained were as followings; 1) The amount of permeated Dimethoate in the seeds showed remarkable differences with varieties. The amount of Dimethoate per 100 grains was greater as in the ascending order of Suseong, Kwanok, Nongkwang, Jinheung, Paltal, Fujisaka #5, Suwon #82, Norm #6, Shirogane, Shin #2, Pungkwang and Jaekeun. 2) It was observed that the total amount of Dimethoate in the seeds(mg./100 grains) were greater among the varieties with large grain than those with small grains, while reverse cases were true in the amount of Dimethoate in a gramme of seeds, probably because of the greater surface areas In a small grains for a gramme weight. 3) There was no significant correlation between the permeated amount of Dimethoate and amount of absorbed water by the seeds when the seeds were treated with $0.1\%$ Dimethoate for 24 and 48 hours. 4) The permeability of Dimethoate to seeds significantly increased in the prolonged soaking periods, higher concentration, and higher temperature. 5) When the seeds were treated with $0.1\%$ Dimethoate for 24 and 48 hours at $15^{\circ},\;20^{\circ},\; 20^{\circ},\; and \;30^{\circ}C$, the permeated amount of Dimethoate were increased at higher temperature. It seems to be that the more active penetration of Dimethoate was involved at the higher temperature. 6) The phytotoxic effects of Dinethoate on the seed germination varied with the varieties. An descending order of varietal tolerance of seeds was as followings: Jinheung, Fujisaka #5, Suwon #82, Paltal, Nongkwang, Jaekeun, Shin #2, Kwanok, Shirogane, Pungkwang, Suseong, and Norm #6. 7) There was a positive correlation between the amount of Dimethoate permeated into the seeds (mg./gram. of seeds) and phytotoxicity of seeds. 8) The Phytotoxic effects of Dimethoate showed close correlation with the degree of KOH disintegration of seeds, average germination periods, and oxygen respiration of seeds. 9) It was observed that higher protein contents of the seeds decreased the phytotoxic effects of Dimethoate. 10) Relatively high negative correlation between the degree of KOH disintegration of seeds and crude protein content of the seeds was observed. 11) The average germination period was delayed for about 2 days when the seeds were treated with $0.2\%$ Dimethoate for 24 hours at $30^{\circ}C$. 12) The oxygen consumption of the seeds treated with $0.2\%$ Dimethoate for 24 hours at $30^{\circ}C$ was greatly decreased when compared with that of the normal seeds. 13) The amount of oxygen consumption of the seeds (in 24 hours after 24 hours water soaking) was negatively correlated with the average germination periods of the seeds.

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