• Bulletin of the Korean Chemical Society
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• v.33 no.1
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• pp.183-188
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• 2012

A blue phosphorescent $Ir(dfpypy)_3$ (dfpypy:fluorinated pyridine-pyridine ligand) complex with meridional configuration has been synthesized by newly developed effective method and its solid state structure and photoluminescence are characterized. For this complex, mer-$Ir(dfpypy)_3$, the glass-transition and decomposition temperatures appear at $160^{\circ}C$ and $384^{\circ}C$ respectively in TGA and DSC experiments, which indicates that this complex has high thermal stability. In a crystalline structure, an average Ir-C bond length of mer-$Ir(dfpypy)_3$ is slightly longer than that of fac-$Ir(dfpypy)_3$, which assumed to be due to the weak trans-influence. The absorption and emission spectra are observed more red-shifted in mer-$Ir(dfpypy)_3$ than fac-$Ir(dfpypy)_3$. In addition, the former is readily oxidized than the latter in electrochemical behavior.

• Journal of the Korean Society of Food Science and Nutrition
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• v.20 no.4
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• pp.401-407
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• 1991

Anticarcinogenic conjugated dienoic derivatives of linoleic acid (CLA) is present in grilled beef, cheese, and related foods, CLA is generated via isomerization of linoleic acid in the cow's rumen by anaerobic bacteria and food proceessing as well. Another source of CLA is its endogenous generation via the carbon centered free radical oxdation of linoleic acid. We propose that the formation and generation of CLA in vivo represents a previously unrecognized in situ "defense mechanism" against membrane attack by oxygen free radicals. The cis, 9-trans, 11 CLS isomer is selectively incorporated into cellular phospholipid, which exhibits a potent antioxidant, reduces the activation of 2-amino-3-methylimidazo, [4,5-f] quinoline (IQ) for baxterial mutagenesis, and inhibits ornithine decarboxylase(ODC) activity induced by 12-0-tetradecanoylphorbol-13-acetate (TPA). We believe that at least these biological activities of CLA explain the anticarcinogenic activity of CLA.

• Journal of Nutrition and Health
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• v.34 no.8
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• pp.896-904
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• 2001

Conjugated linoleic acid(CLA) is a group of positional and geometric isomers of linoleic acid(LA) and exhibits anticarcinogenic activity in multiple experimental animal models. Cis-9,trns-11(c9t11) and trans-10,cis-12(t10c12) CLA are the principal isomers found in foods. The present study was performed to determine whether CLA and the two isomers inhibits HT-29 cell proliferation and to assess whether such an effect was related to changes in secretion of eicosanoids. Cells were incubated in serum-free medium with various concentrations(0 to 20$\mu$M) of CLA or LA. CLA inhibited cell proliferation in a dose-dependent manner, with maximal inhibition(70 $\pm$ 1%) observed at 20$\mu$M concentration after 96 hours. However, LA had no effect at the same concentration range. To compare the ability of c9f11 and t10c12 to inhibit cell proliferation, cells were incubated with increasing concentrations(0 to 4$\mu$M) of these isomers. T10c12 inhibited cell proliferation in a dose-dependent manner. A 66 $\pm$ 2% decrease in cell number was observed within 96 hours after addition of 4$\mu$M t10c12. By contrast, c9t11 had no effect. The concentrations of CLA and the two isomers in the plasma membrane were increased when they were added to the incubation medium. However, they did not alter the levels of arachidonic acid in plasma membrane. To assess whether the proliferation inhibiting effect of CLA was related to changes in eicosanoid production, prostaglandin E$_2$(PGE$_2$) and leukotriene B$_4$(LTB$_4$) concentrations in conditioned media were estimated by a competitive enzyme immunoassay. Both CLA and t10c12 increased the production of materials reactive to PGE$_2$ and LTB$_4$ antibodies in a dose-dependent manner. By contrast, c9t11 had no effect. These results indicate that inhibition of HT-29 cell proliferation by CLA is attributed to the effect of the t10v12 isomer. The materials reactive to PGE$_2$ and LTB$_4$ antibodies may inhibit growth stimulatory effect of arachidonic acid-derived eicosanoids on HT-29 cell proliferation.

• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.633-643
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• 1989

The R$Rh_2(ap)_4$(2,2-trans) isomer (ap = 2-anilinopyridinate), which has two anilino nitrogens and two pyridyl nitrogens bound to each rhodium ion trans to their own kind, shows activation towards the one electron reduction of dioxygen at -0.40 V vs SCE. The ESR spectrum taken at 123 K proves the formation of a $[Rh_2(ap)_4(O_2)]$ ion with oxygen axially bound to one rhodium ion and the complex is at a RhⅡ2 oxidation state. The complex will form [$Rh_2(ap)_4(O_2)(CH_3CN)]^-$ in presence of $CH_3CN/CH_2Cl_2$ mixture without breaking the Rh-$O_2^-$ bond. When oxidized at -0.25 and 0.55 V, $[Rh_2(ap)_4(O_2)]$ will undergo two one electron oxidations to form $Rh_2(ap)_4(O_2)[Rh_2(ap)_4(O_2)]^+$. Both species have an axially bound superoxide ion but the former is at $Rh^{II}Rh^{III }$and the later at $Rh^{III}_2$ oxidation states. The ESR spetra and $CH_3CN$ addition study, on the other hand, show that the later complex is better described as $[Rh_{II}Rh^{III}(ap)_4(O_2)]^+$ with the odd electron localized on rhodium ion and the complex has an axially coordinated molecular oxygen. The electrochemical and ESR studies also show that the degree of dioxygen activation is a function of electrochemical redox potential.

• Korean Journal of Food Science and Technology
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• v.22 no.6
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• pp.681-685
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• 1990

Changes in the physicochemical characteristics and trans acid of cottonseed oil under the condition of selective hydrogenation, temperature$210^{\circ}C,\;H_2\;pressure\;0.3\;kg/cm^2$ Ni catalyst amount 0.12% (in oil), agitation speed 280 rpm, were investigated. The saturated fatty acid such as palmitic acid and stearic acid did not show any difference, while linoleic acid($50.03%{\rightarrow}9.38%$) were transformed to oleic acid ($20.65%{\rightarrow}60.35%$) during hydrogenation. In linoleic acid isomers, cc form were reduced significantly, but ct, tc, tt form showed little change, respectively. In oleic acid isomer, t form increased markedly, whereas there was no significant difference in c form. Meanwhile, melting point(MP) and solid fat content (SFC) were linearly increased, but iodine value(IV) linearly decreased as hydrogenation proceeded. From these results, linear regression equations were obtained as follows. MP & IV : Y= 1.59-2.36X(r=-0.96, p<0.05), SFC($at\;20^{\circ}C$) & MP : Y=2.81+2.01X(r=0.96, p<0.05), SFC($at\;20^{\circ}C$) & IV : Y=9.40-5.16X(r=-0.99, p<0.01), SFC($at\;20^{\circ}C$) & 18 : 1t : Y=6.25+8.48X(r=0.97, p<0.05)

• Journal of the Korean Chemical Society
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• v.37 no.6
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• pp.570-576
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• 1993

1-, 3-, 9-, and 21-Monolayer Langmuir-Blodgett(LB) films of stearic acid were deposited on silver-coated glass slides at the surface pressure of 30 mN/m. Fourier transform infrared(FTIR) reflection-absorption spectra (RAS) of these LB films were recorded at various temperatures from 31 to $72^{\circ}C.$ The spectra at $31^{\circ}C$ exhibited characteristic features of highly perpendicular orientation of the hydrocarbon chain. In the 1-monolayer LB film, the C=O stretching band was not observed, presumably due to the image dipole effect on the silver surface. In the 1-and 3-monolayer LB films, the trans isomer of stearic acid was prominent, but the cis isomer was dominant in the 21-monolayer LB film. FTIR-RAS measurements at an elevated temperature indicated that the chain melting temperature increases and approached to the bulk melting point with increasing the number of monolayer, except for the 1-monolayer LB film which has a higher melting temperature than the 3-monolayer film due to the strong interaction with the silver substrate.

• Journal of Nutrition and Health
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• v.35 no.2
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• pp.192-200
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• 2002

Conjugated linoleic acid (CLA) is a collective term for positional and geometric isomers of octadecadienoic acid in which the double bonds are conjugated. CLA has anticancer activity in a variety of animal cancer models, and cis-9, trans-11 (c9t11) and trans-10, cis-12(t10c12) CLA are the most predominant isomers present in the synthetic preparations utilized in these animal studies. To compare the ability of c9t11, t10c12 and an isomeric mixture of CLA to inhibit TSU-Prl cell growth, cells were incubated in a serum-free medium with various concentrations of these fatty acids. The isomeric mixture inhibited cell growth in a dose-dependent manner (1-3 $\mu$M) with a 41 $\pm$ 1% inhibition observed at 3 $\mu$M concentration after 48 hours. T10c12 also inhibited cell proliferation in a dote-dependent manner, However, the efficacy and potency of this isomer was much greater than that of the isomeric mixture with a 49 $\pm$ 2% inhibition observed at 0.3 $\mu$M concentration after 48 hours. By contrast, c9t11 slightly increased cell proliferation. To determine whether the growth-inhibiting effect of CLA is related to the changes in production of insulin-like growth factors (IGF) and IGF-binding proteins (IGFBP) by these cells, serum-free conditioned media were collected. Immunoblot analysis of conditioned media using a monoclonal anti-IGF-II antibody showed that both the isomeric mixture and t10c12 inhibited secretion of both mature 7,500 Mr and higher Mr forms of pro IGF-II, whereas c9t11 had no effect. Ligand blot analysis with 125I-IGF-II revealed the presence of two types of IGFBPs : 24,000 Mr IGFBP-4 and 30,000 Mr IGFBP-6. The production of IGFBP-4 slightly decreased at the highest concentrations of the isomeric mixture and t10c12. These results indicate that CLA inhibits human prostate cancer cell growth, an effect largely due to the action of t10c12. The growth inhibition may result, at least in part, from decreased production of IGF-II and IGFBP-4 by these cells.

• Korean Journal of Environmental Agriculture
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• v.10 no.2
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• pp.149-157
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• 1991

In order to elucidate the possible change in the non-extractable bound residue of TCAB(3,3' 4,4' - tetrachloroazobenzene) in soil as a function of aging period, uniformly ring-labelled $^{14}C-TCAB$ was treated to soil(organic matter : 1.8%), and aged for 3, 6, 9, 12 and 15 months at $21{\pm}1^{\circ}C$, respectively. $^{14}CO_2$ evolution and volatilization loss during the aging were negligible. The amounts of non-extractable bound residue of TCAB increased gradually from 7.55% in 3-month aging to 19.32% in 15-month aging. Partition data suggested no formation of polar groups in the chemical structure of TCAB. Most of $^{14}C-radioactivity$ of bound residues was present in humin in the range of 50.52 to 58.93%. The fact that the number of microorganisms in soil decreased relative to the control suggested no chance of their involvement in the formation of non-extractable bound residues. Accordingly, the increase in the non-extractable bound residue of TCAB in soil with aging period is believed to be due to the transformation of the trans isomer to the cis one which is more polar and more adsorptive than the former.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.119-130
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• 1993

The stereochemistry of 1,3-thiazolidine sulfoxides 1 in which 3 chiral centres are present in a molecule was elucidated by deuterium exchange and trapping reactions. 3-Acetoxy-1,3-thiazolidines 5 was oxidized to 6 and 8, corresponding $\alpha$-cis 10, $\alpha$-trans 11, $\beta$ -cis 12, and $\beta$ -trans 13 isomers were separated from their diasteromeric mixtures. Sulfoxide 10 was isomerized to more thermodynamically stable isomer 13 under neutral conditions in refluxing benzene or toluene. The methyl hydrogens of 2-methyl group in the sulfoxide 13 and those of the sulfoxide 11 were deuterated by the deuterium incorporation reactions. The intermediate sulfenic acids 25 and 26 derived from the sulfoxides 10 and 12 via sigmatropic rearrangement were trapped by 2-mercaptobenzothiazole (2-MBT) to give disufides 27 and 28 respectively. However, the sulfoxides 11 and 13 were transformed to ring expansion product dihydro-1,4-thiazine 29 under the same reaction conditions. In the presence of acid catalyst, the sulfoxides 10, 11, and 12 were converted to dihydro-1,4-thiazine 29 through the sulfoxide 13 quantitatively. The mechanisms of isomerization of sulfoxides and the formation of 29 were also discussed.

• Biomolecules & Therapeutics
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• v.23 no.2
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• pp.134-140
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• 2015

Conjugated linoleic acids (CLA) are a family of isomers of linoleic acid. CLA increases growth arrest and apoptosis of human colorectal cancer cells through an isomer-specific manner. ATF3 belongs to the ATF/CREB family of transcription factors and is associated with apoptosis in colorectal cancer. The present study was performed to investigate the molecular mechanism by which t10, c12-CLA stimulates ATF3 expression and apoptosis in human colorectal cancer cells. t10, c12-CLA increased an apoptosis in human colorectal cancer cells in dose dependent manner. t10, c12-CLA induced ATF3 mRNA and luciferase activity of ATF3 promoter in a dose-dependent manner. The responsible region for ATF3 transcriptional activation by t10, c12-CLA is located between -147 and -1850 of ATF3 promoter. mRNA stability of ATF3 was not affected by t10, c12-CLA treatment. t10, c12-CLA increases $GSK3{\beta}$ expression and suppresses IGF-1-stimulated phosphorylation of Akt. The knockdown of ATF3 suppressed expression of $GSK3{\beta}$ and NAG-1 and PARP cleavage. The results suggest that t10, c12-CLA induces apoptosis through ATF3-mediated pathway in human colorectal cancer cells.