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Stability Constants of First-row Transition Metal and Trivalent Lanthanide Metal Ion Complexes with Macrocyclic Tetraazatetraacetic and Tetraazatetramethylacetic Acids

  • 홍춘표;김동원;최기영;김창태;최용규
    • Bulletin of the Korean Chemical Society
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    • v.20 no.3
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    • pp.297-300
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    • 1999
  • The protonation constants of the macrocyclic ligands, 1,4-dioxa-7,10,13,16-tetraaza-cyclooctadecane-N,N',N",N"'-tetra(acetic acid) [N-ac4[18]aneN402] and 1,4-dioxa-7,10,13,16-tetraazacyclooctadecane-1,4-dioxa-7,10,13,16-N,N',N",N"'-tetra(methylacetic acid) [N-meac4[18]aneN4O2] have been determined by using potentiometric method. The protonation constants of the N-ac4[18]aneN4O2 were 9.31 for logK1H, 8.94 for logK2H, 7.82 for logK3H, 4.48 for logK4H and 2.94 for logK5H. And the protonation constants of the N-meac4[18]aneN4O2 were 9.34 for logK1H, 9.13 for logK2H, 8.05 for logK3H, 5.86 for logK4H, and 3.55 for logK5H. The stability constants of complexes on the divalent transition ions (Co2+, Ni2+, Cu2+, and Zn2+) and tiivalent metal ions (Ce3+, Eu3+, Gd3+, and Yb3+) with ligands N-ac4[18]-aneN4O2 and N-meac4[18]aneN4O2 have been obtained from the potentiometric data with the aid of the BEST program. The three higher values of the protonation constants for synthesized macrocyclic ligands correspond to the protonation of nitrogen atoms, and the fourth and fifth values correspond to the protonation of the carboxylate groups for the N-ac4[18]aneN4O2 and N-meac4[18]aneN4O2. The meatal ion affinities of the two tetra-azamacrocyclic ligands with four pendant acetate donor groups or methylacetate donor groups are compared. The effects of the metal ions on the stabilities are discussed, and the trends in stability constants resulting from changing the macrocyclic ring with pendant donor groups and acidity of the metal ions.

A Study on the Kinetics and Mechanism of the Hydrolysis of N-Benzylidenebenzenesulfonamide Derivatives (BBSA 유도체의 가수분해메카니즘과 반응속도론적 연구)

  • Suck-Woo Lee;Byung-Man Jang;Gwang Il Lee;Gi Chang Lee
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.919-924
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    • 1992
  • The kinetics of the hydrolysis of N-benzylidenebenzenesulfonamide derivatives have been investigated by ultraviolet spectrophotometry in $H_2O$ at $25^{\circ}C$. A rate equation which can be applied over a wide pH range was obtained. The substituent effect on the hydrolysis of N-benzylidenebenzenesulfonamide derivatives were studied and rate of hydrolysis is known to be accelerated by electron withdrowing group. Final product of the hydrolysis was benzenesulfonamide and benzaldehyde. Base on the rate equation, substituent effect, general base effect and final products, hydrolysis of N-benzylidenebenzenesulfonamide derivatives seemed to be initiated by the hydronium ion at the pH 0.2${\sim}$2.5 and proceeded by the neutral $H_2O$ molecule at pH 3.0${\sim}$8.0 but proceeded by the hydroxide ion at above pH 8.5.

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Assembly of Six-Membered Vanadium Borophosphate Cluster Anions: Synthesis and Structures of (NH4)2(C2H10N2)6[BaH2O)5]2[V2P2BO12]6.8H2O and (NH4)8(C3H12N2)4[Ba(H2O)7][V2P2BO12]6.17H2O

  • Yun, Ho-Seop;Do, Jung-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.26 no.1
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    • pp.146-150
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    • 2005
  • Two new barium vanadium borophosphate compounds, $(NH_4)_2(C_2H_{10}N_2)_6[Ba(H_2O)_5]_2[V_2P_2BO_{12}]_6{\cdot}8H_2O$, Ba- VBPO1 and $(NH_4)_8(C_3H_{12}N_2)_4[Ba(H_2O)_7][V_2P_2BO_{12}]_6{\cdot}17H_2O$, Ba-VBPO2 have been synthesized by interdiffusion methods in the presence of diprotonated ethylenediamine and 1,3-diaminopropane. Compound Ba-VBPO1 has an infinite chain anion (${[BaH_2O)_5]_2[V_2P_2BO_{12}]_6}$$^{14-}$, whereas Ba-VBPO2 has a discrete cluster anion {[$Ba(H_2O)_7][V_2P_2BO_{12}]_6$}$^{16-}$. Crystal Data: $(NH_4)_2(C_2H_{10}N_2)_6[Ba(H_2O)_5]_2[V_2P_2BO_{12}]_6{\cdot}8H_2O$, triclinic, space group P$\overline{1}$ (no. 2), a = 13.7252(7) $\AA$, b = 15.7548(8) $\AA$, c = 15.8609(8) $\AA$, α = 63.278(1)$^{\circ}$, $\beta$ = 75.707(1)$^{\circ}$, $\gamma$ = 65.881(1)$^{\circ}$, Z = 1; $(NH_4)_8(C_3H_{12}N_2)_4[Ba(H_2O)_7][V_2P_2BO_{12}]_6{\cdot}17H_2O$, monoclinic, space group C2/c (no. 15), a = 31.347(2) $\AA$, b = 17.1221(9) $\AA$, c = 22.3058(1) $\AA$, $\beta$ = 99.303(1)$^{\circ}$, Z = 4.

Anatomical Study on the Heart Meridian Muscle in Human

  • Park Kyoung-Sik
    • The Journal of Korean Medicine
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    • v.26 no.1 s.61
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    • pp.11-17
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    • 2005
  • This study was carried out to identify the components of the human heart meridian muscle, the regional muscle group being divided into outer, middle, and inner layers. The inner parts of the body surface were opened widely to demonstrate muscles, nerves, blood vessels and to expose the inner structure of the heart meridian muscle in the order of layers. We obtained the following results; $\cdot$ The heart meridian muscle is composed of muscles, nerves and blood vessels. $\cdot$ In human anatomy, the difference between terms is present (that is, between nerves or blood vessels which control the meridian muscle and those which pass near by). $\cdot$ The inner composition of the heart meridian muscle in the human arm is as follows: 1) Muscle H-l: latissimus dorsi muscle tendon, teres major muscle, coracobrachialis muscle H-2: biceps brachialis muscle, triceps brachialis muscle, brachialis muscle H-3: pronator teres muscle and brachialis muscle H-4: palmar carpal ligament and flexor ulnaris tendon H-5: palmar carpal ligament & flexor retinaculum, tissue between flexor carpi ulnaris tendon and flexor digitorum superficialis tendon, flexor digitorum profundus tendon H-6: palmar carpal ligament & flexor retinaculum, flexor carpi ulnaris tendon H-7: palmar carpal ligament & flexor retinaculum, tissue between flexor carpi ulnaris tendon and flexor digitorum superficial is tendon, flexor digitorum profundus tendon H-8: palmar aponeurosis, 4th lumbrical muscle, dorsal & palmar interrosseous muscle H-9: dorsal fascia, radiad of extensor digiti minimi tendon & extensor digitorum tendon 2) Blood vessel H-1: axillary artery, posterior circumflex humeral artery H-2: basilic vein, brachial artery H-3: basilic vein, inferior ulnar collateral artery, brachial artery H-4: ulnar artery H-5: ulnar artery H-6: ulnar artery H-7: ulnar artery H-8: palmar digital artery H-9: dorsal digital vein, the dorsal branch of palmar digital artery 3) Nerve H-1: medial antebrachial cutaneous nerve, median n., ulnar n., radial n., musculocutaneous n., axillary nerve H-2: median nerve, ulnar n., medial antebrachial cutaneous n., the branch of muscular cutaneous nerve H-3: median nerve, medial antebrachial cutaneous nerve H-4: medial antebrachial cutaneous nerve, ulnar nerve H-5: ulnar nerve H-6: ulnar nerve H-7: ulnar nerve H-8: superficial branch of ulnar nerve H-9: dorsal digital branch of ulnar nerve.

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NMR Investigation on the Intermolecular Hydrogen Bondings of the Macrocyclic Compounds Containing Nitrogen-Oxygen Donor Sets (질소-산소 주게 거대고리 화합물의 분자간 수소결합에 관한 NMR 연구)

  • Chang Ju Yoon;Jeong Kim;Si Joong Kim
    • Journal of the Korean Chemical Society
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    • v.29 no.2
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    • pp.151-157
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    • 1985
  • The intermolecular hydrogen bondings of 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane(cryptand 22), 1,7-diaza-4,10,13-trioxacyclopentadecane(cryptand 21), 1,12,15-triaza-5,8-dioxa-3,4:9,10-dibenzocycloheptadecane ($N_3O_2$) and 1,12-diaza-5,8-dioxa-3,4:9,10-dibenzocyclotetradecane ($N_2O_2$) have been studied in chloroform solutions by $^1H$-nmr spectrometry at various temperatures. The molecules dimerize each other with the hydrogen bonds through N-H groups in the dilute solutions. The formation constants of the hydrogen bonds are in the order of cryptand 22 > cryptand 21 > $N_3O_2$ > $N_2O_2$. It appears that the constants depend on the molecular symmetry, the number of N-H group, and the localization of N-H groups in the molecule.

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Synthesis of Some Novel N7-tetrazolo[5,1-f]-1,2,4-triazin-8-(7H)-one Compounds as Potential Antimicrobial Agents

  • El-Badry, Susan M.;Taha, Mamdouh A.M.
    • Journal of the Korean Chemical Society
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    • v.58 no.4
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    • pp.381-387
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    • 2014
  • A series of new $N^7$-tetrazolo[5,1-f ]-1,2,4-triazin-8-(7H)-one derivatives 4-16 were designed and synthesized from 3 with different reagents. The newly prepared compounds were characterized by spectral data and screened for their antimicrobial activities against various bacteria and fungi strains.

Studies on the Citric Acid Fermentation with Fungi (Part III) Citric Acid Fermentation with Selected Strains (사상균에 의한 구연산발효에 관한 연구 (제III보) 선정균에 의한 구연산발효)

  • 성낙계;김명찬;심기환;정덕화
    • Microbiology and Biotechnology Letters
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    • v.8 no.3
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    • pp.181-191
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    • 1980
  • For the purpose of studies on the citric acid production, some experiments were carried out with isolated strains. The results obtained were as follows. 1) The optimal culture media of the strain M-80 in surface culture contained 140g of sucrose, 3.0g of (N $H_4$)$_2$S $O_4$, 1.5g of K $H_2$P $O_4$, 0.2g of MgS $O_4$.7$H_2O$, 3.0mg of F $e^{++}$, 1.0mg of Z $n^{++}$, 0.5N HCI to a pH of 5.0 and distilled water to 1.0 liter; and that of the strain M-315 in surface culture contained 140g of sucrose, 2.0g of N $H_4$N $O_3$, 1.0g of K $H_2$P $O_4$, 0.25g of MgS $O_4$. 7$H_2O$, 2.0mg of F $e^{++}$, 2.0mg of Z $n^{++}$, 0.05mg of C $u^{++}$, 0.5N HCI to a pH of 4.5 and distilled water to 1.0 liter. While that of the strain M-315 in submerged culture contained 140g of sucrose, 2.5g of N $H_4$N $O_3$, 1.5g of K $H_2$P $O_4$, 0.3g of MgS $O_4$. 7$H_2O$, 3.0mg of F $e^{++}$, 0.1mg of C $u^{++}$, 0.5N HCI to a pH of 4.5 and distilled water to 1.0 liter. The optimal temperature and size of inoculum were mostly 28-3$0^{\circ}C$, 10$^{7}$ -10$^{8}$ spores/50ml, respectively. 2) Through the course of citric acid production, the growth of strains had nearly been completed, pH value was rapidly decreased below 2.0 and the content of sugar was also reduced, while the accumulation of citric acid in media was remarkably begun in about 3-4 days. The yields of citric acid generally reached the maximum level in 8-10 days in surface or submerged fermentation process. 3) Methanol was effective citric acid production when they were added to fermentation media. In the case of surface culture, by addition of 2% (strain M-80), 3% (strain M-315), the yields of citric acid was increased 6.5%, 20.6%, respectively and 5.0% yield was increased by addition of 3% methanol in submerged culture media of the strain M-315. 4) Chromatography analysis of culture broth after fermentation under optimal culture conditions detected that the majority of acid in media was citric acid. 72.1mg/ml, 98.1mg/ml, of citric acid were determined in surface culture media by strains of M-80, M-315, and 59.8 mg/ml of citric acid was contained in the submerged culture media by the strain M-315. strain M-315.

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Valproic Acid Induces Transcriptional Activation of Human GD3 Synthase (hST8Sia I) in SK-N-BE(2)-C Human Neuroblastoma Cells

  • Kwon, Haw-Young;Dae, Hyun-Mi;Song, Na-Ri;Kim, Kyoung-Sook;Kim, Cheorl-Ho;Lee, Young-Choon
    • Molecules and Cells
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    • v.27 no.1
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    • pp.113-118
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    • 2009
  • In this study, we have shown the transcriptional regulation of the human GD3 synthase (hST8Sia I) induced by valproic acid (VPA) in human neuroblastoma SK-N-BE(2)-C cells. To elucidate the mechanism underlying the regulation of hST8Sia I gene expression in VPA-stimulated SK-N-BE(2)-C cells, we characterized the promoter region of the hST8Sia I gene. Functional analysis of the 5'-flanking region of the hST8Sia I gene by the transient expression method showed that the -1146 to -646 region, which contains putative binding sites for transcription factors c-Ets-1, CREB, AP-1 and NF-${\kappa}B$, functions as the VPA-inducible promoter of hST8Sia I in SK-N-BE(2)-C cells. Site-directed mutagenesis and electrophoretic mobility shift assay indicated that the NF-${\kappa}B$ binding site at -731 to -722 was crucial for the VPA-induced expression of hST8Sia I in SK-N-BE(2)-C cells. In addition, the transcriptional activity of hST8Sia I induced by VPA in SK-N-BE(2)-C cells was strongly inhibited by SP600125, which is a c-Jun N-terminal kinase (JNK) inhibitor, and $G{\ddot{O}}6976$, which is a protein kinase C (PKC) inhibitor, as determined by RT-PCR (reverse transcription-polymerase chain reaction) and luciferase assays. These results suggest that VPA markedly modulated transcriptional regulation of hST8Sia I gene expression through PKC/JNK signal pathways in SK-N-BE(2)-C cells.