• Title/Summary/Keyword: Organic ligand

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$Hg^{2+}$-promoted Aquation and Chelation of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = Amines) Complexes ($Hg^{2+}$에 의한 cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = 아민류) 착물의 아쿠아화 및 킬레이트화 반응)

  • Chang Eon Oh;Doo Cheon Yoon;Bok Jo Kim;Myung Ki Doh
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.565-578
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    • 1992
  • It has been suggested that Hg$^{2+}$-promoted reaction of a series of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (en = 1,2-diaminoethane) with L = NH$_3$, NH$_2$CH$_3$, glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN proceeds by dissociative interchange(I$_d$) mechanism from kinetic data, circular dichroism spectra, analyses of products, and the values of m(Grunwald-Winstein plot) using Y (solvent ionizing power) in aqueous solution and in mixed aqueous-organic solvent. It has been found that chloride replacement by water (aquation) for the series with L = NH$_3$ and NH$_2$CH$_3$ and chelation of ligand L to Co(Ⅲ) for the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN occurs, respectively. The rate constants on Hg$^{2+}$-induced reaction of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were increased with increasing the contents of ethanol in mixed water-ethanol solvents. In mixed water-30${\%}$ organic solvents, the rate constants of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ have also been measured in the order 30${\%}$ 2-propanol-water > 30${\%}$ ethanol-water > water. However, the rate constants of cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were reversed. The rate constants of the series with L= NH$_3$ and NH$_2$CH$_3$ were related to ligand field parameter (${\Delta}$), but those of the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, NH$_2$CH$_2$CN were not. The reaction between the series and Hg2+ in aqueous media containing NO$_3^-$ has been investigated. The results for the reaction do not alter the mechanism, but the rate only was altered.

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Organotitanium Chemistry II. Solvolytic Reaction of Dichlorodiacetatotitanium (IV) with Various Alcohols (유기-티탄화학 (제2보). Dichlorodiacetatotitanium (IV) 여러 알콜과의 가용매반응)

  • Hoo Sung Lee;Young Sun Un;Sohn Youn Soo;Choi Q. Won
    • Journal of the Korean Chemical Society
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    • v.17 no.3
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    • pp.174-181
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    • 1973
  • Dichlorodiacetatotitanium(IV) dissolves in alcohols with chemical reaction. Such solvolytic reaction of $TiCl_2(OAc)_2$with various alcohols has been studied by means of solution NMR spectroscopy and chemical analysis of the isolated products. The reaction of $TiCl_2(OAc)_2$ with primary alcohols has shown to be a quantitative two-step ligand substitution process as shown in the following: $TiCl_2(OAc)_2+ROH{\to}TiCl_2(OAc)_2(OR)+AcOH$ $TiCl_2(OAc)_2(OR)+ROH{\to}TiCl_2(OAc)_2+AcOH$The molecular form initially soluble in organic solvents has been found to be the monosubstituted species $TiCl_2(OAc)(OR)$. Alcoholysis with t-butyl alcohol has shown remarkable differences. When the mole ratio of t-butyl alcohol to $TiCl_2(OAc)_2$ is less than 1/2, the following reaction is dominant. $TiCl_2(OAc)_2+t-ButOH{\to}TiCl_2(OAc)_2+t-ButCl$However, at higher mole ratio another substitution process resembling the first step reaction with primary alcohols is competitively accompanied. The reaction with t-butyl alcohol also differs from that with primary alcohols in that only one either of the two chloro-or acetato-ligands in $TiCl_2(OAc)_2$ is subjected to substitution.

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Development of High-specificity Antibodies against Renal Urate Transporters Using Genetic Immunization

  • Xu, Guoshuang;Chen, Xiangmei;Wu, Di;Shi, Suozhu;Wang, Jianzhong;Ding, Rui;Hong, Quan;Feng, Zhe;Lin, Shupeng;Lu, Yang
    • BMB Reports
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    • v.39 no.6
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    • pp.696-702
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    • 2006
  • Recently three proteins, playing central roles in the bidirectional transport of urate in renal proximal tubules, were identified: two members of the organic anion transporter (OAT) family, OAT1 and OAT3, and a protein that designated renal urate-anion exchanger (URAT1). Antibodies against these transporters are very important for investigating their expressions and functions. With the cytokine gene as a molecular adjuvant, genetic immunization-based antibody production offers several advantages including high specificity and high recognition to the native protein compared with current methods. We fused high antigenicity fragments of the three transporters to the plasmids pBQAP-TT containing T-cell epitopes and flanking regions from tetanus toxin, respectively. Gene gun immunization with these recombinant plasmids and two other adjuvant plasmids, which express granulocyte/macrophage colony-stimulating factor and FMS-like tyrosine kinase 3 ligand, induced high level immunoglobulin G antibodies, respectively. The native corresponding proteins of URAT1, OAT1 and OAT3, in human kidney can be recognized by their specific antibodies, respectively, with Western blot analysis and immunohistochemistry. Besides, URAT1 expression in Xenopus oocytes can also be recognized by its corresponding antibody with immuno-fluorescence. The successful production of the antibodies has provided an important tool for the study of UA transporters.

Optical Resolution of Free Amino Acids with Addition of Copper(II) Chelates in a Reversed-Phase Liquid Chromatography (구리(II) 킬레이트의 첨가에 의한 자유아미노산 광학이성질체의 역상 액체크로마토그래피적 분리)

  • Sun Haing Lee;Tae Sub Oh;Hong Yeup An;Kyung Sug Park;Sang Oh OH
    • Journal of the Korean Chemical Society
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    • v.36 no.6
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    • pp.879-888
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    • 1992
  • Separation of the optical isomers of free amino acids by a reversed phase high performance liquid chromatography has been studied by adding a copper(II) complex of L-proline or L-proline derivatives (hydroxy-L-proline, N-benzyl-L-proline, p-xylenyl-L-proline, p-xylenyl-hydroxy-L-proline) in the mobile phase. An OPA postcolumn detection system was used for the detection of amino acids. The chromatographic properties for the free amino acids were discussed in terms of the pH, the kinds and concentration of chelate or organic modifier. The retention behaviors of the free amino acids were considerably different from, those of DNS-amino acids or DABS-amino acids. The enantioselectivity of the free amino acids was better than that of derivatized amino acids. The enantioselectivity between the optical isomers observed by use of the Cu(II)-p-xylenyl-L-proline chiral cheleate was the best among the several copper(II) chelate. A separation mechanism could be illustrated not only by the hydrophobic interaction of the diastereomer with stationary phase but also by the steric effect of the ligand exchange reaction between the free-amino acids and copper chelate.

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Solvent Extraction of Trace Amount of Ni(II) in Sea Water by using Salen[N,N'-bis(salicylidene)ethylenediamine] (Salen[N,N'-bis(salicylidene)ethylenediamine]을 이용한 해수 중 극미량 니켈의 용매추출)

  • In, Gyo;Choi, Jong-Moon;Kim, Young-Sang
    • Analytical Science and Technology
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    • v.17 no.6
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    • pp.481-488
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    • 2004
  • Solvent extraction of Ni(II) into a chloroform by using salen[N,N'-Bis (salicylidene)-ethylenediamine] as a ligand has been studied. Salen was synthesized from ethylenediamine and salicylaldehyde by simple condensation reaction in an ethanol. Salen formed a 1 : 1 complex with Ni(II) and its extraction constant was $10^{5.12}$. For the determination of Ni(II) in sea water samples, some experimental conditions such as pH of solution, amount of salen, acid type and concentration for back extraction, extraction time, and influence of foreign ions were optimized by using a synthetic sea water. The sea water of which the composition was similar to a natural sea water was synthesized in this laboratory. Trace Ni(II) was extracted into the chloroform in the weak basic solution above pH 8. And the nickel could be quantitatively extracted with the concentration of salen higher than $1.2{\times}10^{-4}mol/L$. This concentration was more than 180 times of Ni(II) in the solution with a mole ratio. Real samples of Korean coastal sea water were analyzed under optimized conditions. Even though Ni(II) was not detected in these samples. Recoveries more than 98% were obtained in the samples which 40 ng/mL of Ni(II) was spiked. And detection limit of proposed method was 1.3 ng/mL. From these results, it could be known that salen of this type would be applied for the determination of trace metals as an organic chelating reagent.

Expression of Toll-like Receptors, Pro-, and Anti-inflammatory Cytokines in Relation to Gut Microbiota in Irritable Bowel Syndrome: The Evidence for Its Micro-organic Basis

  • Shukla, Ratnakar;Ghoshal, Ujjala;Ranjan, Prabhat;Ghoshal, Uday C
    • Journal of Neurogastroenterology and Motility
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    • v.24 no.4
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    • pp.628-642
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    • 2018
  • Background/Aims A Subset of patients with irritable bowel syndrome (IBS) may have mild inflammation due to immune activation. Toll-like receptors (TLRs) and cytokines may cause intestinal inflammation. We studied their expression in relation to gut microbiota. Methods Expression of TLRs and cytokines was assessed in 47 IBS patients (Rome III) and 25 controls using quantitative real-time polymerase chain reaction. Immunohistochemistry was further performed to confirm the expression of TLR-4 and TLR-5. Results Of 47 patients with IBS, 20 had constipation (IBS-C), 20 diarrhea (IBS-D), and 7 unclassified (IBS-U). The mRNA levels of TLR-4 and TLR-5 were up-regulated in IBS patients than controls (P = 0.013 and P < 0.001, respectively). Expression of TLR-4 and TLR-5 at protein level was 4.2-folds and 6.6-folds higher in IBS-D than controls. The mRNA levels of IL-6 (P = 0.003), C-X-C motif chemokine ligand 11 (CXCL-11) (P < 0.001) and C-X-C motif chemokine receptor 3 (CXCR-3) (P < 0.001) were higher among IBS patients than controls. Expression of IL-6 (P = 0.002), CXCL-11 (P < 0.001), and CXCR-3 (P < 0.001) were up-regulated and IL-10 (P = 0.012) was down-regulated in IBS-D patients than controls. Positive correlation was seen between TLR-4 and IL-6 (P = 0.043), CXCR-3, and CXCL-11 (P = 0.047), and IL-6 and CXCR-3 (P = 0.003). Stool frequency per week showed positive correlation with mRNA levels of TLR-4 (P = 0.016) and CXCR-3 (P = 0.005), but inversely correlated with IL-10 (P = 0.002). Copy number of Lactobacillus (P = 0.045) and Bifidobacterium (P = 0.011) showed correlation with IL-10 in IBS-C, while Gram-positive (P = 0.031) and Gram-negative bacteria (P = 0.010) showed correlation with CXCL-11 in IBS-D patients. Conclusions Altered immune activation in response to dysbiotic microbiota may promote intestinal inflammation in a subset of patients with IBS.

Anti-inflammatory effects of DATS via suppression of cross talk between the TLR4/NF-κB and CXCL12/CXCR4 pathways in LSP-stimulated RAW 264.7 macrophages (LSP로 유도된 RAW 264.7 대식세포에서 TLR4/NF-κB와 CXCL12/CXCR4 경로 억제를 통한 DATS의 항염증 효과)

  • Jeong, Yong Tae;Hwang, Buyng Su;Kim, Min-Jin;Shin, Su Young;Oh, Young Taek;Kim, Chul Hwan;Eom, Jung Hye;Lee, Seung Young;Choi, Kyung Min;Jeong, Jin-Woo;Cho, Pyo Yun
    • Proceedings of the Plant Resources Society of Korea Conference
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    • 2019.04a
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    • pp.113-113
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    • 2019
  • Diallyl trisulfide (DATS) is an organic polysulfide compound found in garlic. Although certain studies have demonstrated that DATS possesses strong anti-inflammatory activity, the underlying molecular mechanisms remain largely unresolved. In this study, we examined whether DATS exerts anti-inflammatory activity and investigated the possible mechanisms. Our results indicated that DATS significantly suppressed the lipopolysaccharide (LPS)-induced release of nitric oxide (NO) and prostaglandin E2 by inhibiting inducible NO synthase and cyclooxygenase-2 expression at the transcriptional and post-transcriptional levels in RAW 264.7 macrophages. DATS also down-regulated Toll-like receptor 4 (TLR4) and myeloid differentiation factor 88 expression, and inhibited nuclear translocation of nuclear transcription factor-kappa B (NF-${\kappa}B$) in LPS-stimulated 264.7 macrophages. Furthermore, we found that these inhibitory effects of DATS were associated with the inhibition of chemokine receptor (CXCR4) and ligand (CXCL12) expression, and reactive oxygen species generation. Overall, the present data indicated that DATS had anti-inflammatory effects on LPS-activated macrophages, possibly via inhibiting the TLR4/NF-kB and/or chemokine signaling pathways, and DATS could be a potential drug therapy for inflammation and its associated diseases.

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Analysis of Human Serum Amyloid A-1 Concentrations Using a Lateral Flow Immunoassay with CdSe/ZnS Quantum Dots (Human Serum Amyloid A-1 단백질 농도 분석을 위한 CdSe/ZnS 양자점 기반의 Lateral Flow Immunoassay 방법 개발)

  • Fajri, Aidil;Goh, Eunseo;Lee, Sanghyuk;Lee, Hye Jin
    • Applied Chemistry for Engineering
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    • v.30 no.4
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    • pp.429-434
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    • 2019
  • A lateral flow immunoassay platform utilizing antibody functionalized water soluble CdSe/ZnS semiconductor quantum dots (QDs) was developed for the analysis of human serum amyloid A-1 (hSAA1) in a buffer solution. hSAA1 was chosen as a target protein because it is regarded as a potential biomarker associated with early diagnosis and prognosis in patients of lung cancer. The immunoassay strip on a nitrocellulose membrane was fabricated by spraying two lines composed of a test line with a monoclonal antibody against hSAA1 (10G1) (anti hSAA1) and a control line of anti-chicken IgY. While the CdSe/ZnS QDs synthesized in an organic phase were transferred to a water phase by ligand exchange using carboxylic acid modified alkane thiol. The QDs was then conjugated to monoclonal antibody against hSAA1 (14F8) [anti hSAA1 (14F8)] and used as a fluorescent detection probe. The sequential lateral flow of hSAA1 in different concentration and QDs-anti hSAA1 (14F8) complex allowed to form the surface sandwich complex of anti hSAA1 (10G1)/hSAA1/QD-anti hSAA1 (14F8), which was then analyzed using fluorescence microscope. A 100 nM concentration of hSAA1 protein can be detected by naked eyes under an optimized lateral flow buffer condition with a sensing time of 5 mins.

Studies on Partition and Extraction Equilibria of Metal-Dithiocarbamate Complexes(II). Metal Complexes of Ammonium Pyrrolidine Dithiocarbamate (Dithiocarbamate 금속착물의 분배 및 추출평형(제2보). Ammonium Pyrrolidine Dithiocarbamate의 금속착물)

  • Lee, Jong-Sun;Choi, Jong-Moon;Choi, Hee-Seon;Kim, Young-Sang
    • Analytical Science and Technology
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    • v.8 no.3
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    • pp.321-334
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    • 1995
  • Basic studies for the effective extraction of ammonium pyrrolidine dithiocarbamate(APDC) complexes of Co(II), Ni(II) and Cu(II) into a solvent have been performed. The maximum distribution ratio was appeared (log D=1.3543) at pH 2.0 and the partition coefficient was 2.489 in the extraction of $4{\times}10^{-5}M$ APDC itself into chloroform. From the UV/visible spectra of metal-chelates in aqueous and organic solutions, the pH to form stable 1:2 metal-ligand complexes were Co(II):5.0, Ni(II):8.0 and Cu(II):8.0, respectively and only 1 minute was enough to be partitioned into the chloroform. Besides, the partition and extraction equilibria of the complexes were investigated by back-extracting $10.0{\mu}g/ml$ metal-chelates from the solvent into an aqueous solution beacuse of their slight solubilities in the aqueous solution. The distribution coefficients and extractabilities were as follows : at pH 6.5~8.5 of the aqueous solution, log D=2.834 : E(%)=99.9% for $Co(PDC)_2$, at pH 11, log D=5.699 E%=100 for $Ni( PDC)_2$, and at pH 6.0, log D=2.025 : E(%)=99.1% for $Cu(PDC)_2$. And the extraction and formation constants were log $K_{ex}=9.671$ : log ${\beta}_2=6.938$ for $Co(PDC)_2$, log $K_{ex}=9.646$ : log ${\beta}_2=7.071$ for $Ni( PDC)_2$, and log $K_{ex}=9.074$ : log ${\beta}_2=7.049$ for $Cu(PDC)_2$, respectively. From these results, an optimum extraction procedure can be constructed for the separative concentration of trace metallic ions, and the quantitative determination of them in advanced materials and environmental samples will be expected without any influence of sample matrixes.

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