• Title/Summary/Keyword: molecular anions

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Photo-induced Isomerization and Polymerization of (Z,Z)-Muconate Anion in the Gallery Space of [LiAl2(OH)6]+ Layers

  • Rhee, Seog-Woo;Jung, Duk-Young
    • Bulletin of the Korean Chemical Society
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    • v.23 no.1
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    • pp.35-40
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    • 2002
  • Photoreaction of guest organic anions in layered organic-inorganic hybrid materials was investigated. The layered hybrids were synthesized by an anion-exchange reaction of $[LiAl_2(OH)_6]Cl{\cdot}yH_2O$ layered double hydroxide with aqueous (Z,Z)- and (E,E)-muconates under inert atmospheric condition, to give new organicinorganic hybrids of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$ and $[LiAl_2(OH)_6]_2[(E,E)-C_6H_4O_4]{\cdot}H_2O$, respectively. The basal spacings calculated by XRPD of intercalates indicate that muconate anions have almost vertical arrangements against the host $[LiAl_2(OH)_6]^+$ lattices in the interlayer of organic-inorganic hybrid materials. When UV light was irradiated on the suspension of $[LiAl_2(OH)_6]_2[(Z,Z)-C_6H_4O_4]{\cdot}zH_2O$, the (Z,Z)-muconate anions of the gallery space of hybrids were polymerized in the aqueous media while it was isomerized into more stable (E,E)-muconate in the methanollic suspension in the presence of catalytic amount of molecular iodine. All the products were characterized using elemental analysis, TGA, XRPD, FT-IR, $^1H$ NMR and $^{13}C$ CP-MAS NMR.

RIP3-Dependent Accumulation of Mitochondrial Superoxide Anions in TNF-α-Induced Necroptosis

  • Lee, Jiyoung;Lee, Sunmi;Min, Seongchun;Kang, Sang Won
    • Molecules and Cells
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    • v.45 no.4
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    • pp.193-201
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    • 2022
  • Excessive production of reactive oxygen species (ROS) is a key phenomenon in tumor necrosis factor (TNF)-α-induced cell death. However, the role of ROS in necroptosis remains mostly elusive. In this study, we show that TNF-α induces the mitochondrial accumulation of superoxide anions, not H2O2, in cancer cells undergoing necroptosis. TNF-α-induced mitochondrial superoxide anions production is strictly RIP3 expression-dependent. Unexpectedly, TNF-α stimulates NADPH oxidase (NOX), not mitochondrial energy metabolism, to activate superoxide production in the RIP3-positive cancer cells. In parallel, mitochondrial superoxide-metabolizing enzymes, such as manganese-superoxide dismutase (SOD2) and peroxiredoxin III, are not involved in the superoxide accumulation. Mitochondrial-targeted superoxide scavengers and a NOX inhibitor eliminate the accumulated superoxide without affecting TNF-α-induced necroptosis. Therefore, our study provides the first evidence that mitochondrial superoxide accumulation is a consequence of necroptosis.

Study on White Precipitate in Most of Waters after Thawing (물이 해동한 다음 발생하는 휜 침전물의 정성분석 및 이온의 변화)

  • 윤수철;박해룡;윤형식;김창수
    • Journal of Food Hygiene and Safety
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    • v.17 no.1
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    • pp.15-19
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    • 2002
  • The objectives of this study were to investigate the change of silicon, cations and anions dissolved in water before and after thawing, and analyzed what the white-colored precipitate (WP) farmed after thawing was composed of. The silicon concentration that has been changed might have been compared with the weight of WP under water-free state. The major component of WP has been approved to be a silicon, while calsium was only a little contained. As the weight of WP has been nearly equal to the reduced silicon concentration, the weight of its could be changeable calculated by silica (SiO$_2$) molecular weight. Therefore, WP could have been presumed to be a silica. The more silicon concentration was increased, the more weight of silicon was increased. Except for the sample "C", the amounts of cations and anions could be found to be unchangeable nearly. As a result of that, WP has been apparent to be silica itself while most of ions (excluded with Si) of any others were not changed.

Improving the Chemical Stability of Al Alloy through the Densification of the Alumina Layer Assisted by SiF62- Anion Hydrolysis

  • Mosab Kaseem;Burak Dikici;Hongfei Liu
    • Nanomaterials
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    • v.12 no.8
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    • pp.1354-1365
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    • 2022
  • In this work, a high-density alumina layer with high chemical stability was successfully developed by controlling the hydrolysis of hexafluorosilicate (SiF62-) anions through the addition of various concentrations of sodium citrate (SCi) into the electrolyte of plasma electrolysis (PE). To achieve this aim, the substrate samples were anodized in alkaline aluminate-SiF62--based electrolytes with 0, 5, and 10 g/L of SCi. The presence of SCi anions in the electrolyte led to the formation of a thick adsorbed electrochemical double layer (EDL) on the substrate surface. The EDL not only affected the movement of SiF62- anions towards the anode but also influenced their hydrolysis reaction, which in turn led to a controllable sealing of structural defects with the hydrolysis products, namely SiO2 and AlF3. Among three different oxide layers, the oxide layer obtained from the electrolyte with 5 g/L SCi showed the highest chemical stability in a corrosive solution, which was linked to the fact that a considerable increase in the compactness of the oxide layers was obtained by the incorporation of SiO2 and AlF3. The mechanism underlying the effects of SCi on triggering the hydrolysis of SiF62- anions and factors affecting chemical stability are discussed based on the experimental data and computational analysis.

Analysis of Fatty Acyl Groups of Diacyl Galactolipid Molecular Species by HPLC/ESI-MS with In-source Fragmentation

  • Gil, Ji-Hye;Hong, Jong-Ki;Choe, Joong-Chul;Kim, Young-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.24 no.8
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    • pp.1163-1168
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    • 2003
  • The structures of molecular species of galactolipids, such as monogalactosyl diacylglycerol (MGDG) and digalactosyl diacylglycerol (DGDG), isolated from wheat flour have been investigated using negative-ion electrospray ionization (ESI) mass spectrometry interfaced with high performance liquid chromatography (HPLC). According to the result of HPLC analysis, MGDG and DGDG were found to consist of mixtures of five and four molecular species, respectively. The galactolipids have been also analyzed to determine their fatty acid compositions, using HPLC/ESI-MS combined with in-source (or cone voltage) fragmentation. HPLC/ ESI-MS is very useful for one-step analysis of mixtures of galactolipids with a small sample quantity. Especially, the carboxylate anions produced in in-source fragmentations of the negative-ion of each component separated by HPLC provide valuable information on the composition of its fatty acyl chains.

EPR Spectra of Spin-Labeled Cytochrome c Bound to Acidic Membranes: Implications for the Binding Site and Reversibility

  • Min, Tong-Pil;Park, Nan-Hyang;Park, Hee-Young;Hong, Sun-Joo;Han, Sang-Hwa
    • BMB Reports
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    • v.29 no.2
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    • pp.169-174
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    • 1996
  • Yeast cytochrome c (cyt c) was modified at cysteine-102 with a thiol-specific spin label and its interaction with liposomes containing acidic phospholipids was studied by electron paramagnetic resonance (EPR) spectroscopy. Association of cyt c with liposomes resulted in a significant reduction in the mobility of the spin label and a fraction of cyt c even seemed to be immobilized. Based on a large spectral change upon binding and the proximity of the spin-label to lysine-86 and -87, we propose these two residues to be the potential binding site at neutral pH. The interaction is electrostatic in nature because the spectral changes were reversed by addition of anions. Dissociation of the bound cyt c by anions, however, became less effective as the lipid/protein ratio increased. This suggests a repulsive lateral interaction among the bound cyt c. Unlabeled cyt c molecules added to preformed cyt c-liposome complex displaced the bound (spin labeled) cyt c and the process was competitive and reversible.

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Versatilities of Calix[4]pyrrole Based Anion Receptors

  • Lee, Chang-Hee
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.768-778
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    • 2011
  • Calixpyrroles and related macrocycles are non-planer synthetic anion receptors that have attracted considerable attentions in recent years. Although the synthesis of calix[4]pyrrole (known as meso-octamethylporphyrinogen) was reported more than 100 years ago, the anion binding properties were first discovered in 1996. The simple calix[4]pyrroles can be synthesized in single step in high yield by condensation of pyrrole with acetone. The compounds showed preferential binding for halide anions including fluoride, phosphate, carboxylate, and chloride in organic media. Efforts to improve the anion affinity of calix[4]pyrrole and to enhance its selectivity have led to the synthesis of a variety of new calixpyrrole derivatives. Among the various modifications, introduction of straps on one side of the calix[4]pyrroles are the most effective. Incorporation of aromatic rings other than pyrroles also exhibited interesting binding behaviour. Introduction of signalling units as part of the strapping element enable to detect the anions on chromogenic or fluorogenic fashion. Finding of the anion transport properties across the membrane and cytotoxic effects of the calix[4]pyrroles open new window for calixpyrrole-related research. The polymer-incorporated systems have also been employed as anion complexants in solvent-solvent extraction. These old, yet easy-to-make macrocycles have well advanced more recently with the discovery of the ion-pair complexation properties. In this review, the synthetic developments and anion binding properties of calixpyrroles for the last decades will be discussed and will cover the advances in calixpyrrole chemistry.

Viscoelastic behavior of aqueous surfactant micellar solutions

  • Toshiyuki Shikata;Mamoru Shiokawa;Shyuji Itatani;Imai, Shin-ichiro
    • Korea-Australia Rheology Journal
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    • v.14 no.3
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    • pp.129-138
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    • 2002
  • A cationic surfactant, cetyltrimethylammonium $\rho$-toluenesufonate (CTA$\rho$TS), forms long threadlike micelles in aqueous solution. The threadlike micelles make concentrated entanglement networks, so that the solution shows pronounced viscoelastic behavior as concentrated polymer systems do. However, a mechanism for a process responsible for the longest relaxation time of the threadlike micellar system is different from that of semi-dilute to concentrated polymer systems. The threadlike micellar system exhibits unique viscoelasticity described by a Maxwell model. The longest relaxation time of the threadlike micellar system is not a function of the concentration of CTA$\rho$TS, but changes with that of $\rho$-toluenesufonate ($\rho$$TS^{-}$) ions in the bulk aqueous phase supplied by adding sodium $\rho$-toluenesulfonate (NapTS). The rates of molecular motions in the threadlike micelles are not influenced by the concentration of $\rho$$TS^{-}$ anions, therefore, molecular motions in the threadlike micelles (micro-dynamics) are independent of the longest relaxation mechanism (macro-dynamics). A nonionic surfactant, oleyldimethylamineoxide (ODAO), forms long threadlike micelles in aqueous solution without any additives. The aqueous threadlike micellar system of ODAO also shows Maxwell type viscoelastic behavior. However, the relaxation mechanism for the longest relaxation process in the system should be different from that in the threadlike micellar systems of CTA$\rho$TS, since the system of ODAO does not contain additive anions. Because increase in the average degree of protonation of head groups of ODAO molecules in micelles due to adding hydrogen bromide causes the relaxation time remarkably longer, changes in micro-structure and micro-dynamics in the threadlike micelle are closely related to macro-dynamics in contrast with the threadlike micellar system of CTA$\rho$TS.

Synthesis of Facial Amphiphile 3,7-Diamino-5α-cholestane Derivatives as a Molecular Receptor

  • Ahmad, Md. Wasi;Jung, Young-Mee;Khan, Sharaf Nawaz;Kim, Hong-Seok
    • Bulletin of the Korean Chemical Society
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    • v.30 no.9
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    • pp.2101-2106
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    • 2009
  • A series of facial amphiphiles 3,7-diaminocholestane were synthesized from 3,7-diketocholestane via 2 sequential reductive aminations and anion recognition was evaluated with acetate, chloride, bromide, fluoride and phosphate anions. The stereo-selective reductive amination protocol was utilized to synthesized facial amphiphiles afforded receptors in high yields. The molecular receptor 2 showed the highest binding constant with acetate in a 1:1 ratio.

Antioxidant and Anti-hyperglycemic Activity of Polysaccharide Isolated from Dendrobium chrysotoxum Lindl

  • Zhao, Yaping;Son, Young-Ok;Kim, So-Soon;Jang, Yong-Suk;Lee, Jeong-Chae
    • BMB Reports
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    • v.40 no.5
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    • pp.670-677
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    • 2007
  • Although polysaccharide is believed to play an important role in the medicinal effect of Dendrobium chrysotoxum Lindl (DCL), its role as an antioxidant and in anti-hyperglycemic induction was not reported. In this study, polysaccharide with molecular weight of approximately 150 kDa, herein named DCLP, was isolated from the stem of DCL, and its antioxidative, hypoglycemic and immune stimulating effects were evaluated using various in vitro and in vivo assay systems. DCLP inhibited hydroxyl radicals ($^{\cdot}$OH)-mediated deoxyribose degradation by scavenging hydroxyl radicals directly as well as by chelating iron ions. DCLP also showed dose-dependent scavenging activity on superoxide anions ($O_2^{{\cdot}-}$) and offered significant protection (p < 0.001) against glucose oxidase-mediated cytotoxicity in Jurkat cells. DCLP had immune stimulating effects, as evidenced by the DCLP-mediated increases in the level of DNA synthesis, viability, and cytokine secretion in mouse lymphocytes. Moreover, oral administration of DCLP produced a significant reduction in blood glucose level in alloxan-induced diabetic mice. These findings suggest that DCLP has a potential utility in treating patients who require enhanced antioxidation, immune function and/or hypoglycemic activity.