• Analytical Science and Technology
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• v.17 no.3
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• pp.282-288
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• 2004

Inclusion selectivities of the cyanocadmate host complexes with ammonium oniums, $[Cd_x(CN)_{2x}][onium{\cdot}zG]$ (onium = $NMe_3Et^+$, $NMeEt{_3}^+$ and $NEt{_4}^+$, G = guest), have been investigated for $C_6H_6$ (B), PhMe (T), PhEt (E), ortho (O), meta (M), and para (P) isomers of $C_6H_4Me_2$ as the aromatic guest molecules. From the binary, ternary, quaternary and quinary mixed guests of B, T, E, O, M and P, the order of preference in the $NMe_3Et+$-host is $B{\gg}$T>P${\fallingdotseq}O{\fallingdotseq}M$ and E>O${\gg}P{\fallingdotseq}M$; in the $NMeEt{_3}^+$-host is T>B>P${\gg}O{\fallingdotseq}M$ and E>P${\gg}$M>O; in the $NEt{_4}^+$-host is $B{\gg}T{\fallingdotseq}O{\fallingdotseq}M{\fallingdotseq}P$. However, the $NEt{_4}^+$-host complexes of E, O, M and P mixed-guests were not obtained. These inclusion selectivities were compared to our previous results of the $NMe{_4}^+$-host; T>B>P${\gg}$M>O and E>P${\gg}$M>O.

• Archives of Pharmacal Research
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• v.13 no.1
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• pp.82-96
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• 1990

Ten (E)-and (Z)-isomers of 2-phenylcyclopropylamine (PCA), 1-Me PCA, 2-Me-PCA, N-Me-PCA, and N, N-diMe PCA and fifteen o-. m-, p- isomers of (E) PCA with substituents of Me, Cl, F, OMe, OH were synthesized in this laboratory and tested for the inhibition of rat brain mitochondrial MAO-A and MAO-B. The effects of substituents, their positions, and stereochemistry on the inhibition were assessed for the compounds with substituents at cyclopropyl and amino groups and QSAR analyses were performed using the potency data of ring-substituted compounds. The best correlated QSAR equations are as follows : pI$_{50}$ = 0.804 $\pi^2$-0.834 Blo-1.069 Blm + 0.334 Lp-1.709 HDp +7.897 (r = 0.945, s =0.211, F = 16.691, p = 0.000) for the inhibition of MAO-A;PI$_{50}$= 1.815$\pi$-0.825 $\pi^2$-1.203R + 0.900 Es$^2$ + 0.869 Es$^3$ + 0.796 Es$^4$-0.992 HDp + 0.562 HAo + 3.893 (r = 0.982, s =0.178, F = 23.351, p = 0.000) for the inhibition of MAO-B. Based on the potency difference between stereoisomers of cyclopropylamine-modified compounds and an QSAR cavity near para position, two hydrophobic carities interacting with Me group, a hydrophobic site near para position, and an amino group binding site and that in addition to the same two hydrophotic cavities, hydrophotic area, steric boundaries, hydrogen-acceptor site, and amino group binding site, another steric boundary near para position and a hydrogen donating site near ortho position constitute active sites of MAO-B.

• Archives of Pharmacal Research
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• v.21 no.4
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• pp.452-457
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• 1998

Three compounds, 5-(acetoxymethyl)-5-(hydroxymethyl)-3-tetradecyl-2,5-dihydro-2-furanone (3), 5-(acetoxymethyl)-5-(hydroxymethyl)-3,3-dihexyltetrahydro-2-furanone (4) and 5-(acetoxymethyl)-5-(hydroxymethyl)-3,3-dioctyltetrahydro-2-furanone (5), were designed and synthesized as surrogates of the ultrapotent DAG analogue, 5-(acetoxymethyl)-5-(hydroxymethyl) 3-[(Z)-tetradecylideneltetrahydro-2-furanone (1), a compound that showed high affinity for PKC-$\alpha$ ($K_1$=35 nM) in a competition binding assay with [$^3H$-20]phorbol-12,13-dibutyrate (PDBU). In an attempt to overcome the problem of generating geometrical E- and Z- isomers, as encountered with 1, the double bond was moved to an endocyclic location as in 3, or an additional alkyl chain was appended to C3 to give the corresponding 3,3-dialkyl saturated lactones (4 and 5). The lactone was constructed from glycidyl-4-methoxyphenyl ether in 5 steps. The target compounds showed reduced binding affinities for PKC-.alpha. with $K_{i}$ values of 192 nM (3), 4,829 nM (4), and 2,812 nM (5), respectively. These results indicate that constrained DAG analogues having a tetrahydro-2-furanone template are effectively discriminated by PKC-(X in terms of the direction of the long alkyl chain connected to the 3-position.n.

• Bulletin of the Korean Chemical Society
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• v.15 no.9
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• pp.729-732
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• 1994

The acid-promoted cleavage of the E-and Z-isomers of 1-phenyl-6-neopentyl-1,3,4-trimethyl-1-silacyclohe x-3-ene(II) under various conditions gave clean and nearly quantitative formation of the ring-opened 2,3,7,7-tetramethyl-5-(X)silyl-1-octene products (X=OMe, Cl, OH). The possible mechanism for the formation of the ring-opened products was suggested that the initial protonation of II at C-4 would give a carbocation oriented so that they are ${\beta}$ to the silicon atom, and the subsequent nucleophilic attack at silicon would give rise to the observed products (VI, VII, VIII).

• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.418-424
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• 1984

Rate constants for the hydrolysis of cinnamonitrile in the concentration range of 1 ∼ 5M of perchloric acid at 25$^{\circ}$C have been determined by UV spectrophotometry and from the Bunnett equations, hydration parameters (${\omega}$ = 9.8, ${\omega}^*$ = 0.42 & ${\phi}$=1.6) were obtained. CNDO/2 MO calculations were performed to determine relative stability, net charges, and overlap population of various conformational isomers. The results show that the (E)-planar is more stable than the (Z)-planar and protonation is favored on the nitrogen atom. On the basis of above findings, the acid hydrolysis is initiated by the protonation of the nitrogen atom of cinnamonitrile and then water molecule acting as nucleophile and as a proton transfer agent in the rate determining step. In the transition state of the acid hydrolysis, nucleophilic addition of water molecule occurs by sigma approach to the positively charged $C_7({\alpha}$) atom of the conjugate acid. As the results, we may conclude that the hydrolysis of cinnamonitrile in the strong acidic media proceeds through the A-2 type mechanism.

• The Korean Journal of Nuclear Medicine
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• v.34 no.5
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• pp.403-409
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• 2000

Objectives: Due to the heterogeneous receptor distribution and changes of receptor status over time, the biochemical measurement of estrogen receptor status of biopsy specimens is not sufficient to diagnose breast cancer. As a result, I-123 labeled estradiols have been applied for the diagnosis. The purpose of this study was to develop a suitable radioligand for imaging estrogen receptor-positive human breast tumors. Methods: Among the various estradiol derivatives, $17{\alpha}-[^{123}I]$iodovinyl estradiol ($[^{123}I]$IVE) has been prepared from $17{\alpha}$-ethynyl estradiol. Labeling of $E-17{\alpha}-[^{123}I]$iodovinyl estradiol (E-$[^{123}I]$IVE) was carried out using peracetic acid with $[^{123}I]NaI\;and\;Z-[^{123}I]IVE$ labelling was archived using chloamine-T/HCl solution with $[^{123}I]$NaI. Labeling yield was determined by silica thin-layer chromatography (TLC) and radiochemical purity was measured by high performance liquid chromatography (HPLC). The biodistribution of E-$[^{123}I]$IVE was measured in immature female rats at 60 min, 120 min and 300 min after injection. Results: The labeling yield of two isomers was 92% and 94% ($E-[^{123}I]IVE\;and\;Z-[^{123}I]IVE$, respectively). The radiochemical purity was more than 98% after purification. The highest uptake was observed at 120 min in uterus (3.11% ID/g for E-$[^{123}I]$IVE). Conclusion: These results suggest the possibility of using E-$[^{123}I]$IVE as an imaging agent for the evaluation of the evaluation of the presence of estrogen receptor in patients with breast cancer.

• The Korean Journal of Nuclear Medicine
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• v.34 no.5
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• pp.410-417
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• 2000

Purpose: Idoxifene is currently entering phase II clinical trials for the treatment of advanced breast cancer. The radiolabeled idoxifene using $[^{123}I]$ provides an opportunity for clinical pharmacology with single photon emission computed tomography (SPECT). The purpose of this study was to prepare radiolabeled idoxifene using $[^{123}I]$ and to determine its cell uptake of breast cancer cell line. Materials and Methods: With a view to evaluating new anticancer drugs, we are investigating the novel antiestrogen pyrrolidino-4-iodotamoxifen (idoxifene). $[^{123}I]$Idoxifene has been prepared in no-carrier-added form using a tributyl stannylated precursor which has been synthesized by means of (2-chloroethoxy)benzene with (${\pm}$)-2-phenylbutanoic acid on the basis of previously reported standard methods. The biodistribution and dynamic behavior of the compound were investigated using the comparative breast cancer cell line, MCF-7 (estrogen receptor-positive) and MDA-MB-468 (non-estrogen receptor). Results and Conclusion: Acylation of (2-chloroethoxy)benzene with (${\pm}$)-2-phenylbutanoic acid gave the versatile ketone (81%) which reacted with 1,4-diiodobenzene to give triphenylethylene as a mixture of E and Z geometric isomers, which were separated by the recrystallization in ethanol. The E-isomer was treated with pyrrolidine to give idoxifene (67%). In order to incorporate radioactive iodine into the 4-position, the 4-stannylated precursor was prepared (30%). The yield of radioiodination was 90-92% with a high radiochemical purity greater than 98%. The ratio of tumor uptake of the breast cancer cell line between MCF-7 and MDA-MB-468 was about 1.7.