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Synthesis and Characterization of 14-Membered Tetraaza Macrocycles with N-Ethyl Groups and their Nickel(Ⅱ) and Copper(Ⅱ) Complexes

  • Kang Shin-Geol;Kweon Jae Keun
    • Bulletin of the Korean Chemical Society
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    • v.13 no.3
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    • pp.256-259
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    • 1992
  • The 14-membered tetraaza macrocyclic ligand 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradeca-4,11-diene(B) can be synthesized as its dihydroperchlorate salt by the one-pot reaction of 2-ethylaminoethylamine, methylvinyl ketone, and perchloric acid in absolute ethanol. The reaction of Ni(II) or Cu(II) ion and the salt yields $[M(B)]^{2+}$ (M = Ni(II) or Cu(II)), which reacts with $NaBH_4$ to produce $[M(D)]^{2+}$ (D = 1,8-diethyl-5,12-dimethyl-1,4,8,11-tetraazacyclote tradecane). The complexes $[M(L)]^{2+}$ (L = B or D) have planar geometry and contain two ethyl groups at the donor nitrogen atoms of the ligands. The red solids $[Cu(B)](X)_2(X)$ = $ClO_4-$ or $PF_6^-$) react with water molecules of atmospheric moisture to produce the purple solids in which water molecules are coordinated to the metal ion. Synthesis, characterization, and the properties of the new N-ethylated macrocyclic ligands and their Ni(II) and Cu(II) complexes are reported.

Changes of Oxidative Enzymes and Fatty Acid Composition of Bifidobacterium adolescentis and B. longum under Anaerobic and Aerated Conditions. (산소의 Stress에 따른 Bifidobacterium adolescentis와 Bifidobacterium longum의 산화효소의 활성과 세포 지방산 조성의 변화)

  • 신순영;박종현
    • Microbiology and Biotechnology Letters
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    • v.26 no.1
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    • pp.7-14
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    • 1998
  • To study the oxygen tolerance mechanism of bifidobacteria, we have studied the growth of cells, the activities of the enzymes which were related with oxygen, such as catalase, superoxide dismutase(SOD), NADH oxidase, and NADH peroxidase, and cellular fatty acid compositions of Bifidobacterium adolescentis and B. longum under anaerobic and aerated (microaerobic and aerobic) conditions. B. longum grew relatively well under the microaerobic conditions, whereas the growth of B. adolescentis was inhibited under the same aerated conditions. B. adolescentis had extremely low level of NADH oxidative enzymes while B. longum had the relatively high level of NADH oxidative enzymes, whose activities were dramatically increased from 3.7 to 11.4 times by microaerobic condition but not in B. adolescentis. The activity of SOD was unexpectedly high in B. adolescentis compared with in B. longum under anaerobic and aerated conditions. The activities of catalase were not detected in all samples tested in this study. We also found that normal $C_{l6:0}$ and $C_{18:1}$ were the major fatty acids in B. adolescentis and B. longum under anaerobic and aerated conditions. 2.2-14.1% $C_{l9:0}$ cyclo fatty acid was detected only in B. longum and the fatty acid was increased by the addition of the aeration. The $C_{l9:0}$ cyclic fatty acid was identified as a cis 9, 10-methylene octadecanoic acid, which was different from lactobacillic acid in the cyclized site. 6.6%-24.6% of dimethyl acetals (DMA) which came from plasmalogen were observed in the B. adolescentis and B. longum grown under anaerobic condition, and the components were notably decreased in the cells grown under the aerated conditions. It is believed that NADH oxidative enzymes play an important role to detoxify oxygen metabolites of Bifidobacteriurn spp. under anaerobic and microaerobic conditions. Independently from oxidative enzymes, it seems that oxygen stress may induce the change of the level of cellular fatty acids showing an increase of $C_{l9:0}$ cyclo in B. longum and a decrease of $C_{l8:1}$ of plasmalogen in B. longum and B. adolescentis to adapt in environment.

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Vitamin D Dependent Rickets Type 1A Caused by CYP27B1 Mutation

  • Bak, Na Ry;Song, Eun Song;Yang, Eun Mi;Kim, Chan Jong
    • Childhood Kidney Diseases
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    • v.23 no.2
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    • pp.111-115
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    • 2019
  • Vitamin D dependent rickets type 1A (VDDR1A) is an autosomal recessive disorder caused by mutations in CYP27B1. Clinical findings are growth retardation, hypotonia, muscle weakness, hypocalcemic seizures, and radiological features of rickets. We aimed to present the VDDR1A case with a genetic study of CYP27B1. The 14-month-old boy was admitted to the hospital due to a seizure. Serum calcium, phosphorus, alkaline phosphatase, parathyroid hormone (PTH), 25(OH) vitamin D, and 1,25(OH)2 vitamin D values were 5.1 mg/dL, 3.7 mg/dL, 705 IU/L, 429 pg/mL, 24.9 ng/mL, and 8.8 pg/mL, respectively. Radiological study showed cupping and fraying of the distal ulna and radius. The molecular genetic study revealed that the patient had a compound heterozygous mutation, $Phe443Profs^*24$ and c.589+1G>A, in CYP27B1. Genetic analysis of the family members presented that the mother was heterozygous for the mutation c.589+1G>A, and that the father was heterozygous for $Phe443Profs^*24$. The patient was treated with calcium lactate and calcitriol. Until now, six Korean patients with VDDR1A have been studied. Including this case, Korean patients with VDDR1A were found to have only three different mutations in 14 alleles, indicating that the mutation in the CYP27B1 gene is homogeneous in the Korean population.

Protein Tyrosine Phosphatase 1B inhibitory Activity of Anthraquinones and Stilbenes

  • Na, Min-Kyun;Jin, Wen Yi;Min, Byung-Sun;Ahn, Jong-Seog;Bae, Ki-Hwan
    • Natural Product Sciences
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    • v.14 no.2
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    • pp.143-146
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    • 2008
  • Protein tyrosine phosphatase 1B (PTP1B) is emerging as a potential therapeutic target for the treatment of type-2 diabetes and obesity. To search for new types of PTP1B inhibitors, we have undertaken in vitro enzyme assay for some anthraquinones and stilbenes isolated from plants. Of the anthraquinones tested, physcion (1), 1-O-methylemodin (2), and emodin (3) showed high activities, with $IC_{50}$ values of 7.6, 7.0, and $3.8{\mu}g/mL$, respectively, while the anthraquinone glycosides, physcion-8-O-${\beta}$-D-glucopyranoside (4) and emodin-8- O-${\beta}$-D-glucopyranoside (5), were less active than their aglycones. All the stilbenens (6 - 15) slightly inhibited PTP1B activity at high concentration of $30{\mu}g/mL$. Our findings suggest that the hypoglycemic effect of anthraquinones may be associated with their PTP1B inhibitory activity.

Purification of Alginate Lyase from Streptomyces violaceoruber and the Growth Activity of Intestinal Bacteria by Degree of Polymerization of Alginate Hydrolysates (Streptomyces violaceoruber 유래 Alginate Lyase의 정제 및 Sodium Alginate 가수분해 올리고당의 중합도별 Bifidobacterium spp.과 Lactobacillus spp.에 대한 생육활성)

  • Yoon, Min;Park, Young-Seo;Park, Gwi-Gun
    • Food Engineering Progress
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    • v.21 no.2
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    • pp.103-109
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    • 2017
  • Alginate lyase from Streptomyces violaceoruber was purified by DEAE sephacel chromatography and SP sepharose chromatography. The specific activity of the purified enzyme was 14.6 units/mg protein, representing a 40.6-fold purification of the crude extract. The final preparation thus obtained showed a single band on Tricine-SDS polyacrylamide gel electrophoresis whose molecular weight was determined to be 23.3 kDa. The polyMG block of sodium alginate was hydrolyzed by the purified alginate lyase and then separated by activated carbon column chromatography and bio gel P-2 gel filtration. The main hydrolysates were composed of hetero type M/G-oligosaccharides with the degrees of polymerization (D.P.) being 6 and 8. To investigate the effects of hetero type M/G-oligosaccharides from the sodium alginate on the growth of some intestinal bacteria, cells were cultivated individually on the modified-MRS medium containing D.P. 6 and 8 M/G-oligosaccharides. B. longumgrew 4.25-fold and 6.44-fold more effectively by the treatment of D.P. 6 and 8 M/G-oligosaccharides compared with those of standard MRS medium. In addition, B. bifidumgrew 3.3-fold and 5.4-fold more effectively by the treatment of D.P. 6 and 8 M/G-oligosaccharides. In conclusion, D.P. 8 was more effective than D.P. 6 hetero M/G-oligosaccharides as regards the growth of Bifidobacteriumspp. and Lactobacillus spp.

Hydrogen separation of $V_{99.8}B_{0.2}$ Alloy Membrane in Water-gas shift Reaction (수성 가스 전이반응에서 $V_{99.8}B_{0.2}$ 합금 분리막의 수소분리)

  • Jeon, Sung-Il;Jung, Yeong-Min;Park, Jung-Hoon;Lee, Yong-Taek
    • Membrane Journal
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    • v.22 no.1
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    • pp.16-22
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    • 2012
  • The influence of co-existing gases on the hydrogen permeation without sweep gas was studied through a Pd-coated $V_{99.8}B_{0.2}$ alloy membrane. Membranes have been investigated in the pressure range 1.5-8.0 bar under pure hydrogen, hydrogen-carbon dioxide and hydrogen-carbon monoxide gas mixture without sweep gas at $400^{\circ}C$. Preliminary hydrogen permeation experiments without sweep gas have been confirmed that hydrogen flux was $40.7mL/min/cm^2$ for a Pd-coated $V_{99.8}B_{0.2}$ alloy membrane (thick : 0.5 mm) using pure hydrogen as the feed gas. In addition, hydrogen flux was $21.4mL/min/cm^2$ for $V_{99.8}B_{0.2}$ alloy membrane using $H_2/CO_2$ as the feed gas. The hydrogen permeation flux decreased with decrease of hydrogen partial pressure irrespective of pressure when $H_2/CO_2$and $H_2/CO$mixture applied as feed gas respectively and permeation fluxes were satisfied with Sievert's law in different feed conditions. It was found from XRD, SEM/EDX results after permeation test that the Pd-coated $V_{99.8}B_{0.2}$ alloy membrane had good stability and durability for various mixtures feeding condition.

The Effectiveness of Overflow Improvement of Broad-Crested Side Weirs according to Installing a Hydraulic Structure (보 설치에 따른 광정횡월류위어의 월류량 개선 효과)

  • Kang, Ho Seon;Cho, Hong Je
    • Journal of Korea Water Resources Association
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    • v.48 no.7
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    • pp.523-533
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    • 2015
  • In this study, the effectiveness of overflow improvement of weir was tested by conducting hydraulic experiments at the designated spot for installment of side weir under the condition of installment of hydraulic structures such as small reservoir in mainstream. The height of the reservoir was set up as a third of that of the weir, accordingly the rate of the height of the weir and the distance of the reservoir from the weir($B_h/L_b$) were 0.05, 0.025, 0.0167 each. As a result, overflows per unit width increased by 8.1%, 5.4% and 3.9% perspectively. A new discharge coefficient that adds $B_h/L_b$ as parameter to the existing discharge coefficient of trapezoidal broad crested side weir was suggested and the application of the new formula of discharge coefficient by comparing measured overflow with calculated overflow was identified.

Synthesis and Cytotoxlcity of Thioureido MAPP Derivatives (치오우레이도 MAPP 유도체의 합성과 세포독성)

  • 전상철;김연숙;김미영;임채욱;임철부
    • YAKHAK HOEJI
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    • v.48 no.5
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    • pp.272-277
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    • 2004
  • The 2-amino-l-phenylpropanols 4∼7 were reacted with isothiocyanates to afford the 20 thioureido MAPP derivatives 8a∼11e, which were tested their cytotoxic activity by MTT assay. The cytotoxicity of alkylthioureido compounds were increased and decreased by alkyl chain length from $C_{8}$ to $C_{14}$ and of phenylthioureido compounds showed poor activity. The compounds (8b, 8c, 9b, 9c, l0b, 10c, 11b, 11c) with $C_{10}$ and $C_{12}$ alkyl chains gave stronger activity than reference compound B13. The $IC_{50}$/ of compound 8c was 1.05$\mu$M and 3 times stronger activity than B13. The stereochemistry of synthesized compounds affected very little to cytotoxic activity.

The Biodegradation Characteristics of the Mixtures of Bunker-A, B Oils with Dispersants in the Seawater

  • BAEK Joong-Soo;KIM Gwang-Su;CHO Eun-il
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.29 no.6
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    • pp.787-796
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    • 1996
  • The biodegradation experiment, the TOD analysis and the element analysis for dispersant, Bunker-A oil and Bunker-B oil were conducted to study the biodegradation characteristics of a mixture of Bunker-A oil with dispersant and a mixture of Bunker-B oil with dispersant in the seawater. The results of biodegradation experiment showed 1mg of dispersant to be equivalent to 0.26 mg of $BOD_5$ and to 0.60 mg of $BOD_{20}$ in the natural seawater. The results of TOD analysis showed each 1 mg of dispersant, Bunker-A oil and Bunker-B oil to be equivalent to 2.37 mg, 2.94 mg and 2.74 mg of TOD, respectively. The results of element analysis showed carbon, hydrogen, nitrogen and phosphorus contents of dispersant to be $82.1\%,\;13.8\%,\;1.8\%\;and\;2.2\%$, respectively. Carbon and hydrogen contents of Bunker-A oil were found to be $73.3\%\;and\;13.5\%$, respectively, and carbon, hydrogen and nitrogen contents of Bunker-B oil to be $80.4\%,\;12.3\%\;and\;0.7\%$, respectively. Accordingly, the detection of nitrogen and phosphorus in dispersant shows that dispersants should be used with caution in coastal waters, with relation to eutrophication. The biodegradability of dispersant expressed as the ratio of $BOD_5/TOD$ was found to be $11.0\%$. As the mix ratios of dispersant to Bunker-A oil (3 mg/l) and a mixture of Bunker-B oil (3mg/l) were changed from 1 : 10 to 5 : 10, the biodegradabilities of a mixture of Bunker-A oil with dispersant and Bunker-B oil with dispersant increased from $2.1\%\;to\;7.2\%$ and from $1.0\%\;to\;4.4\%$, respectively. Accordingly, the dispersant belongs to the organic matter group of middle-biodegradability while mixtures in the mix ratio range of $1:10\~5:10$ belong to the organic matter group of low-biodegradability. The deoxygenation rate constant $(K_1)$ and ultimate biochemical oxygen demand $(L_0)$ obtained from the biodegradation experiment and Thomas slope method were found to be 0.125/day and 2.487 mg/l for dispersant (4 mg/l), respectively. $K_1\;and\;L_0$, were found to be $0.079\~0.131/day$ and $0.318\~2.052\;mg/l$ for a mixture of Bunker-A oil with dispersant and to be $0.106\~0.371/day$ and $0.262\~1.106\;mg/l$ for a mixture of Bunker-B oil with dispersant, respectively, having $1:10\~5:10$ mix ratios of dispersant to Bunker-A oil and Bunker-B oil. The ultimate biochemical oxygen demands of the mixtures increased as the mix ratio of dispersant to Bunker-A, B oils changed from 1 : 10 to 5 : 10. This suggests that the more dispersants are applied to the sea for the cleanup of Bunker-A oil or Bunker-B oil, the more decreases the dissolved oxygen level in the seawater.

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A Study on the Eutrophication in Artificial Lakes in Chonnam Area (全南地方의 一部 人工湖水의 富營養化에 관한 조사연구)

  • Kim, Seung Ho
    • Journal of Environmental Health Sciences
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    • v.11 no.1
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    • pp.15-28
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    • 1985
  • In order to analyze the water quality in artificial lakes in Chonnam area, a chemical and biological examination of Dongbock Lake and Changsung Lake was conducted from September to December 1983 and May 1984. A summary of the surveyed results is as follows 1. In Dongbock Lake, pH ranged from 7.2-8.1, D.O.: 8.2-12.6mg/l, B.O.D.: 4.4-22.1 mg/l, C.O.D.: 1.0-3.4rag/l, Cl$^-$: 5.9-11.9mg/l, Total-P: 0.001-0.071 mg/l, and Total -N: 0.016-0.697 mg/l, respectively. 2. In Changsung Lake, pH ranged from 7.2-8.1, D.O.: 8.1-9.8mg/l, B.O.D.: 0.9-2.9mg/l, C.O.D.: 1.9-3.4mg/l. Total- P: 0.006-0.016mg/l and Total -N:0.006-0.033mg/l, respectively. 3. The Phytoplankton identified in this investigation were distributed in a total of 46 genera and 76 spedes in Dongbock Lake 37 genera and 45 species in Changsung Lake. 4. In Dongbock Lake, it was found that the dominant algae were Melosira sp., Microcystis sp. and Synedra sp. in September Melosira sp. and Microcytis sp. in October, but Cymbella sp., Naviculla sp. and Nitzschis sp. were also observed in OctoberAsterionella sp., Melosira sp. and Microsystis sp. in November and Melosira sp., Asterionella sp sp. and Synedra sp. in December 1983. 5. In Changsung Lake, it was found that the dominant algae were Melosira sp., Lyngrbya sp. and Microcystis in September Melosira sp. and Synedra sp. in October and November and Melosira sp., Lyngbya sp. and Asterionella sp. in December 1983. The dominant algae were Melosira sp., Lyngbya sp. and Euglena sp. in May 1984. 6. It was found that the dominant algae in both Dongbock and Changsung Lakes were Microcystis sp., Melosira sp. and Asterionella sp.. Which are strongly related with water-bloom. Therefore, it could be suggested that the eutrophication phenomena is going to occur very easily in Dongbock Lake and possibly in Changsung Lake.

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