Interaction of silver(I) and copper(I) with an O₂S₂-macrocycle - A comparative structural study

Kim, S.,Lee, E.,Lee, S.Y.,Lee, S.S.,Lindoy, L.F. Elsevier Sequoia [etc.] 2014 Inorganica chimica acta Vol.417 No.-

The 14-membered O<SUB>2</SUB>S<SUB>2</SUB>-macrocycle L reacts with AgPF<SUB>6</SUB> in acetonitrile/dichloromethane (1:1) to yield the cyclic, double S-Ag-S bridged complex, [Ag<SUB>2</SUB>L<SUB>2</SUB>(CH<SUB>3</SUB>CN)<SUB>4</SUB>](PF<SUB>6</SUB>)<SUB>2</SUB> (2), in which each Ag(I) is bound to two exo-oriented S donors arising from different macrocycles to form a 12-membered, di-Ag metallacycle. Two PF<SUB>6</SUB><SUP>-</SUP> ions form weak intramolecular contacts [Ag...F, 2.925(2)A] between the Ag centres in a bridging bidentate fashion. The coordination sphere of each Ag is completed by two weakly bound acetonitrile molecules. The respective macrocyclic ligands are arranged trans to the mean plane through the metallacycle. When the above synthetic procedure was repeated employing methanol/dichloromethane (1:1) as solvent, a complex of type [Ag<SUB>2</SUB>L<SUB>2</SUB>](PF<SUB>6</SUB>)<SUB>2</SUB> (3) was obtained whose structure incorporates a similar 12-membered metallacycle but with the respective macrocyclic rings now oriented towards the same side of the metallacyclic plane. The reaction of L with AgCF<SUB>3</SUB>SO<SUB>3</SUB> yields [Ag<SUB>2</SUB>L<SUB>2</SUB>(CF<SUB>3</SUB>SO<SUB>3</SUB>)<SUB>2</SUB>].2CH<SUB>3</SUB>CN (4) whose structure resembles that of [Ag<SUB>2</SUB>L<SUB>2</SUB>(CH<SUB>3</SUB>CN)<SUB>4</SUB>](PF<SUB>6</SUB>)<SUB>2</SUB> (2); each complex unit incorporates a di-Ag(I) 12-membered metallacycle, with symmetrical bridging bidentate CF<SUB>3</SUB>SO<SUB>3</SUB><SUP>-</SUP> ions weakly linking Ag centres. Long Ag1...Ag1C contacts are present between pairs of complex units. Reaction of Cu(CH<SUB>3</SUB>CN)<SUB>4</SUB>PF<SUB>6</SUB> (one equiv.) with L in methanol/dichloromethane (1:1) resulted in isolation of [CuL<SUB>2</SUB>]PF<SUB>6</SUB> (5) incorporating a distorted tetrahedral S<SUB>4</SUB>-coordination sphere, with each macrocycle binding as a bidentate ligand via its two (exo-orientated) S atoms. In contrast, reaction of [Cu(CH<SUB>3</SUB>CN)<SUB>4</SUB>]PF<SUB>6</SUB> (two equiv.) with L in either acetonitrile/dichloromethane (1:1) or methanol/dichloromethane (1:1) yielded [Cu<SUB>2</SUB>L<SUB>3</SUB>]PF<SUB>6</SUB> (6) in which the Cu(I) centres are bound exo to the macrocyclic cavity by individual S-donors from one L, with the coordination sphere of each Cu(I) completed by out-of-plane binding of the S<SUB>2</SUB>O donors from a second L. Unsymmetrical F...Cu contacts from a PF<SUB>6</SUB><SUP>-</SUP> anion weakly link the pair of Cu centres in a bridging bidentate fashion.

Phase II study of S-1 combined with oxaliplatin as therapy for patients with metastatic biliary tract cancer: influence of the <i>CYP2A6</i> polymorphism on pharmacokinetics and clinical activity

Kim, K-p,Jang, G,Hong, Y S,Lim, H-S,Bae, K-s,Kim, H-S,Lee, S S,Shin, J-G,Lee, J-L,Ryu, M-H,Chang, H-M,Kang, Y-K,Kim, T W Nature Publishing Group 2011 The British journal of cancer Vol.104 No.4

<P><B>Background:</B></P><P>Advanced biliary cancer is often treated with fluoropyrimidine-based chemotherapy. In this study, we evaluated the efficacy and tolerability of a combination of S-1, an oral fluoropyrimidine prodrug, and oxaliplatin in patients with metastatic biliary cancer.</P><P><B>Methods:</B></P><P>Patients with histologically confirmed metastatic biliary cancer and no history of radiotherapy or chemotherapy were enrolled. Oxaliplatin was administered intravenously (130 mg m<SUP>−2</SUP>), followed by 14-day administration of oral S-1 (40 mg m<SUP>−2</SUP> twice daily) with a subsequent 7-day rest period every 21 days. Pharmacokinetic analysis of S-1 was performed at cycle 1. Patients were genotyped for <I>CYP2A6</I> polymorphisms (<SUP>*</SUP>1, <SUP>*</SUP>4, <SUP>*</SUP>7, <SUP>*</SUP>9 or <SUP>*</SUP>10), and pharmacokinetic and clinical parameters compared according to the <I>CYP2A6</I> genotype.</P><P><B>Results:</B></P><P>In total, 49 patients were evaluated, who received a median of four cycles. The overall response rate was 24.5%. Median progression-free and overall survival was 3.7 and 8.7 months, respectively. The most common haematological grade 3 out of 4 toxicity was neutropenia (14%), while non-hematological grade 3 out of 4 toxicities included anorexia (14%), nausea (12%), asthenia (10%), vomiting (10%), and diarrhoea (4%). Biotransformation of S-1 (AUC<SUB>0−24 h</SUB> of 5-fluorouracil/AUC<SUB>0−24 h</SUB> of tegafur) was 1.85-fold higher for the <I>*1/*1</I> group than for the other groups (90% confidence interval 1.37–2.49). Diarrhoea (<I>P</I>=0.0740), neutropenia (<I>P</I>=0.396), and clinical efficacy (response rate, <I>P</I>=0.583; PFS, <I>P</I>=0.916) were not significantly associated with <I>CYP2A6</I> genotype, despite differences in 5-FU exposure.</P><P><B>Conclusion:</B></P><P>The combination of S-1 and oxaliplatin appears to be active and well tolerated in patients with metastatic biliary cancer, and thus is feasible as a therapeutic modality. <I>CYP2A6</I> genotypes are associated with differences in the biotransformation of S-1. However, the impact of the <I>CYP2A6</I> polymorphism on variations in clinical efficacy or toxicity requires further evaluation.</P>

Reduction of d-lactate content in sauerkraut using starter cultures of recombinant Leuconostoc mesenteroides expressing the ldhL gene

Jin, Q.,Li, L.,Moon, J.S.,Cho, S.K.,Kim, Y.J.,Lee, S.J.,Han, N.S. Society for Bioscience and Bioengineering, Japan ; 2016 Journal of bioscience and bioengineering Vol.121 No.5

<P>The n-form of lactate, which causes metabolic stress upon excessive dietary intake, is mainly produced by Leuconostoc sp., the predominant species in sauerkraut. To shift the metabolic flux of D-lactate from pyruvate to L-lactate, we expressed the L-lactate dehydrogenase (ldhL) gene in Leuconostoc mesenteroides ATCC 8293. The IdhL gene from Lactobacillus plantarum was introduced into L. mesenteroides using the shuttle vectors pLeuCM and pLeuCM42. To elevate the expression level of IdhL in L. mesenteroides, the nucleotides for pyruvate kinase promoter were fused to IdhL and cloned into above vectors to construct pLC18pkL and pLC42pkL. As results, introduction of pLC42pkL in L. mesenteroides significantly improved both L-LDH activity and L-lactate productivity during fermentation, decreasing the D-/L-lactate ratio. When used as a starter culture for sauerkraut fermentation, recombinant L. mesenteroides harboring pLC42pkL increased L-lactate concentration and decreased D-lactate concentration compared to the wild type strain. We newly developed a recombinant L. mesenteroides which has high L-lactate dehydrogenase activity and applied this strain to minimize the harmful effect of D-lactate during the sauerkraut fermentation. To the best of our knowledge, we demonstrate for the first time the effective use of recombinant Leuconostoc sp. for quality improvement of fermented foods. (C) 2015, The Society for Biotechnology, Japan. All rights reserved.</P>

Interaction of copper(II) with N-substituted bis(2-pyridylmethyl)amine derivatives

Kim, M.,Mora, C.,Lee, Y.H.,Clegg, J.K.,Lindoy, L.F.,Min, K.S.,Thuery, P.,Kim, Y. Elsevier 2010 Inorganic chemistry communications Vol.13 No.10

<P>Interaction of copper(II) with the N-substituted bis(2-pyridylmethyl)amine derivatives, (R)-N-1,N-1-bis (pyridine-2-ylmethyl)butane-1,2-diamine (L-1) and (R)-2-(bis(pyridin-2-ylmethyl)amino)butan-1-ol (L-2), has led to isolation of optically active [Cu(L-1)Cl]PF6 (1) and [Cu(L-2)Cl]ClO4 (2), respectively. The X-ray structures of (1) and (2) show that the copper is bound to all four heteroatoms of the respective ligands as well as to a chlorine atom in a distorted square pyramidal arrangement in which the three nitrogens of L-1 or L-2 occupy three positions of each basal plane while the fourth position is occupied by the chloro ligand; apical sites in each case are filled by the amine donor from the NH2-substituted butane arm in L-1 or the (protonated) alcohol oxygen of the 2-aminobutane-1-ol substituent in L-2. To a first approximation the coordination geometry in 2 is distorted square pyramidal; however, the remaining (axial) site on each copper centre is involved in a long contact (2.96 angstrom) with a bound chloro ligand from an adjacent complex which connects individual complex units in a zigzag 1-D polymeric chain, so that the coordination geometry could also be seen as pseudo-octahedral. A temperature-dependent magnetic study revealed the presence of ferromagnetic exchange coupling between copper centres in the chain reflecting the orthogonal structure between the chloro-bridged copper(II) ions; in contrast, and as expected, the discrete complex 1 is magnetically dilute. (C) 2010 Elsevier B.V. All rights reserved.</P>

Caspase-3 activation as a key factor for HBx-transformed cell death

Kim, A.,Kwon, O. S.,Kim, S. O.,He, L.,Bae, E. Y.,Lee, M. S.,Jeong, S. J.,Shim, J. H.,Yoon, D. Y.,Kim, C. H.,Moon, A.,Kim, K. E.,Ahn, J. S.,Kim, B. Y. Blackwell Publishing Ltd 2008 Cell proliferation Vol.41 No.5

<P>Abstract. </P><P><I>Objectives</I>: Nuclear factor-kappa B (NF-&kgr;B) activation has been associated with the tumorigenic growth of hepatitis B virus X protein (HBx)-transformed cells. This study was aimed to find a key target for treatment of HBx-mediated cancers. <I>Materials and methods</I>: NF-&kgr;B activation, endoplasmic reticulum-stress (ER-stress), caspase-3 activation, and cell proliferation were evaluated after Chang/HBx cells permanently expressing HBx viral protein were treated with inhibitors of NF-&kgr;B, proteasome and DNA topoisomerase. <I>Results</I>: Inhibition of NF-&kgr;B transcriptional activity by transient transfection with mutant plasmids encoding Akt1 and glycogen synthase kinase-3&bgr; (GSK-3&bgr;), or by treatment with chemical inhibitors, wortmannin and LY294002, showed little effect on the survival of Chang/HBx cells. Furthermore, I&kgr;Bα (S32/36A) mutant plasmid or other NF-&kgr;B inhibitors, 1-pyrrolidinecarbonidithioic acid and sulphasalazine, were also shown to have little effect on the cell proliferation. By contrast, proteasome inhibitor-1 (Pro1) and MG132 enhanced the HBx-induced ER-stress response and the subsequent activation of caspase-12, -9 and -3 and reduced cell proliferation. Camptothecin (CPT), however, triggered activation of caspase-3 without induction of caspase-12, and reduced cell proliferation. In addition, CPT-induced cell death was reversed by pre-treatment with z-DEVD, a caspase-3-specific inhibitor. <I>Conclusions</I>: Detailed exploitation of the regulators of caspase-3 activation could open the gate for finding an efficient target for development of anticancer therapeutics against HBx-transformed hepatocellular carcinoma.</P>

Reduction of Salmonella enterica on the surface of eggshells by sequential treatment with aqueous chlorine dioxide and drying

Choi, S.,Park, S.,Kim, Y.,Kim, B.s.,Beuchat, L.R.,Hoikyung, K.,Ryu, J.H. Elsevier Science Publishers 2015 International journal of food microbiology Vol.210 No.-

The synergistic effects of sequential treatments with chlorine dioxide (ClO<SUB>2</SUB>) and drying in killing Salmonella enterica on the surface of chicken eggshells were investigated. Initial experiments were focused on comparing lethalities of sodium hypochlorite (NaOCl) and ClO<SUB>2</SUB>. Eggs surface-inoculated with S. enterica in chicken feces as a carrier were immersed in water, NaOCl (50 or 200μg/mL), or ClO<SUB>2</SUB> (50 or 200μg/mL) for 1 or 5min. For 1-min treatments, lethal activities of sanitizers were not significantly different (P>0.05). However, after treatment with ClO<SUB>2</SUB> for 5min, reductions of S. enterica were significantly greater (P@?0.05) than reductions after treatment with water or NaOCl. The effect of treatment of eggs with ClO<SUB>2</SUB> or NaOCl, followed by drying at 43% relative humidity and 25<SUP>o</SUP>C for 24 and 48h, were determined. Populations of S. enterica decreased during drying, regardless of the type of sanitizer treatment. ClO<SUB>2</SUB> treatment, compared to water or NaOCl treatments, resulted in additional reductions of ca. >1.3logCFU/egg during drying. This indicates that sequential treatments with ClO<SUB>2</SUB> and drying induced synergistic lethal effects against S. enterica on the surface of eggshells. These observations will be useful when selecting a sanitizer to control S. enterica on the surface of eggshells and designing an effective egg sanitization system exploiting the synergistic lethal effects of sanitizer and drying.

왕겨에 의한 신령버섯균사체 액체배양액의 생쥐 항복수암성 증가

Young S. Kim(김영숙),Wook J. Jang(장욱진),Md. A. Rakib(라키브),Jung M. Kwon(권정민),Chae R. Ahn(안채린),So Y. Kim(김소영),Yong U. Cho(조용운),Young K. Ha(하영권),Jeong O. Kim(김정옥),Yeong L. Ha(하영래) 한국생명과학회 2010 생명과학회지 Vol.20 No.9

왕겨가 Agaricus blazei Murill (AB: 신령버섯)균사체 액체배양 추출물의 항암성을 증가시키는지에 관한 연구를 수행하였다. AB균사체를 대두박을 기본으로 한 액체배지에 다양한 조건으로 배양하여, β-glucan 함량, Brix, 균사체를 측정하여 적정 생육조건을 선정하고, 이들의 열수추출물의 S-180 cell로 유도한 mouse 복수암에 대한 항암성을 조사하였다. AB균사체는 25℃에서 5일간 배양하였을 때 최적 생육을 나타내었고, 이 배양물이 다른 조건에서 배양한 배양물보다 우수한 항암성을 나타내었다. AB균사체의 생육 및 항암성은 변온배양에 따른 효과는 없었다. 따라서 이 최적배양조건(25℃, 5일 배양)에서 AB균사체를 1% 왕겨분말이 함유된 액체배지에 배양하고, 이의 열수 추출물의 항암성을 검증하였다. 1% 왕겨가 함유된 액체배지에서 배양한 열수추출물의 항암성은 왕겨가 함유되지 않은 배지의 열수추출물보다 항암성이 유의성 있게 증가되었다(p<0.05). 왕겨의 첨가는 AB균사체의 생육을 오히려 촉진시켰다. 이 결과는 왕겨가 AB균사체 뿐 만 아니라 다른 버섯균사체 액체배양물의 항암성 증진을 위한 원료로 활용될 수 있을 것임을 의미한다. The effects of rice hull (RH) powder on the anticarcinogenic activity of submerged-liquid cultures of Agaricus blazei Murill (AB) were assessed for mouse ascites cancers induced by mouse Sarcoma S-180 (S-180) cancer cells. Optimal growth of AB mycelia in the basal liquid culture medium, containing soybean meal, was achieved by culturing at 25℃ for 5 days, when evaluated by β-glucan content, Brix, and mycelial weight, relative to other culture conditions. Hot-water extract (HWE) of the submergedliquid culture of AB mycelia grown at 25℃ for 5 days exhibited a stronger anticarcinogenic activity, relative to HWE from other culture conditions. No such effects were obtained from AB mycelial cultures by alternative temperature-controlling cultures. Both cytotoxicity for S-180 cells and anticarcinogenic potentials for mouse ascites cancer of the HWE from AB mycelia grown in the basal medium containing 1% RH powder for 5 days at 25℃ were significantly (p<0.05) enhanced, relative to HWE from the AB mycelia culture of the basal medium without RH powder. These results indicate that HWE of submerged-liquid culture of AB mycelia, incubated in media containing 1% RH powder at 25℃ for 5 days, enhanced anticarcinogenic activity against S-180 cell-induced mouse ascites cancer, and suggest that RH powder is an excellent ingredient for the improvement of the anticarcinogenic potentials of the submerged-liquid culture of mushroom mycelia.

Development of an experimental apparatus and protocol for determining antimicrobial activities of gaseous plant essential oils

Seo, H.S.,Beuchat, L.R.,Kim, H.,Ryu, J.H. Elsevier Science Publishers 2015 International journal of food microbiology Vol.215 No.-

There is a growing interest in the use of naturally-occurring antimicrobial agents such as plant essential oils (EOs) to inhibit the growth of hazardous and spoilage microorganisms in foods. Gaseous EOs (EO gases) have many potential applications in the food industry, including use as antimicrobial agents in food packaging materials and sanitizing agents for foods and food-contact surfaces, and in food processing environments. Despite the potentially beneficial applications of EO gases, there is no standard method to evaluate their antimicrobial activities. Thus, the present study was aimed at developing an experimental apparatus and protocol to determine the minimal inhibitory concentration (MIC) and minimal lethal concentration (MLC) of EO gases against microorganisms. A sealed experimental apparatus was constructed for simultaneous evaluation of antimicrobial activities of EO gases at different concentrations without creating concentration gradients. A differential medium was then evaluated in which a color change allowed for the determination of growth of glucose-fermenting microorganisms. Lastly, an experimental protocol for the assessment of MIC and MLC values of EO gases was developed, and these values were determined for 31 EO gases against Escherichia coli O157:H7 as a model bacterium. Results showed that cinnamon bark EO gas had the lowest MIC (0.0391μl/ml), followed by thyme-thymol EO gas (0.0781μl/ml), oregano EO gas (0.3125μl/ml), peppermint EO gas (0.6250μl/ml), and thyme-linalool EO gas (0.6250μl/ml). The order of the MLC values of the EO gases against the E. coli O157:H7 was thyme-thymol (0.0781μl/ml)<cinnamon bark (0.1563μl/ml)<oregano (0.3125μl/ml)<peppermint (0.6250μl/ml)=thyme-linalool (0.6250μl/ml). The experimental apparatus and protocol enable rapid and accurate determination of the MIC and MLC values of EO gases and perhaps other types of gaseous antimicrobial agents.

Local electronic structure of Mn dopants in ZnO probed by resonant inelastic x-ray scattering

Chang, G S,Kurmaev, E Z,Jung, S W,Kim, H-J,Yi, G-C,Lee, S-I,Yablonskikh, M V,Pedersen, T M,Moewes, A,Finkelstein, L D IOP Pub 2007 Journal of physics, an Institute of Physics journa Vol.19 No.27

<P>The electronic structure of Mn dopants in ZnO epitaxial thin films synthesized at different temperatures has been investigated using resonant inelastic x-ray scattering. The resulting Mn L<SUB>2,3</SUB> x-ray emission spectra of Zn<SUB>0.8</SUB>Mn<SUB>0.2</SUB>O (resonantly excited at L<SUB>2</SUB> and L<SUB>3</SUB> absorption edges) reveal different spectral features depending on the growth temperature of the films. The relative integral intensity ratio of Mn L<SUB>2</SUB> to Mn L<SUB>3</SUB> emission lines is greatly suppressed in the case of nonmagnetic Zn<SUB>0.8</SUB>Mn<SUB>0.2</SUB>O grown at 700 °C due to L<SUB>2</SUB>L<SUB>3</SUB>M<SUB>4,5</SUB> Coster–Kronig transitions. The ferromagnetic sample grown at 600 °C exhibits a normal oxide structure. The results suggest that a high growth temperature causes direct Mn–Mn bonds from the segregation of Mn atoms in ZnO. Therefore the disappearance of ferromagnetism in Mn-doped ZnO can be attributed to antiferromagnetic Mn–Mn exchange interactions due to the inhomogeneous local environment around the Mn impurities.</P>

여대생의 트라우마와 자존감, 가족지지 및 갈등, 우울의 상관관계 연구

경유래,김영서,김주영,박은서,윤예은,이수진,조성온,주서희,황선영,Tsang Lok Yi,김석선,길민지 이화여자대학교 간호과학대학 2019 이화간호학회지 Vol.- No.53

Purpose: Precedent studies about the relationship between trauma and other variables was focused on children and middle aged women. This study however, aims to study the female college student population who are exposed to depression and low self-esteem from traumatic events of childhood and adolescence Methods: Using a descriptive correlation study design, 205 female college students attending female colleges were recruited. The instruments Post-traumatic Diagnostic Scale by Jacoz&Perry(1997), Self-esteem Scale by Rosenberg(1979), Family Support &Conflict Scale by Kim, and Depression Scale by Radloff(1977) were used. The questionnaires were distributed with Google Survey online. The data w re analyzed by average, standard deviation, percentage, and t-test using the SPSS/WIN 21.0 program. Results: The degree of trauma and self-esteem, family support and conflict showed negative correlation, and the degree of trauma and depression showed positive correlation. In other words, female college students with higher trauma tend to have lower self-esteem, more cognizance of family conflict, less feeling of family support, and more depression. Conclusion: This study is different in that it analyzes correlation between the degree of trauma and other variables, not the absence or frequency of trauma. This study is also meaningful as it consider the psychological changes from traumatic experience and provides the basic data for the prevention and therapeutic intervention in clinical field.