• 제목/요약/키워드: ${\pi}$-complexation

검색결과 19건 처리시간 0.024초

Conductometric Behavior of Univalent Cation-Podand Complexes in Methanol

  • Kim, Dae-Yeon;Jung, Jong-Hwa;Chun, Jae-Sang;Lee, Shim-Sung
    • Bulletin of the Korean Chemical Society
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    • 제15권11호
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    • pp.967-971
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    • 1994
  • The stability constants, log K of the 1 : 1 complexation for IA ions, $Ag^+$, and $Tl^+$ with a series of podands having different aromatic end-groups (I-IV) have been determined conductometrically in methanol at 25.0 $^{\circ}$C. Exceptionally the equivalent conductivity, ${\lambda}_{eq}\;of\;Li^+\;and\;Na^+$ were increased by the addition of I, because the complexed ions are less mobile than solvated ions. The order of log K values for I was $Ag^+{\gg}Tl^+>K^+>Na^+>Rb^+>Cs6+>Li^+$. The log K sequence of the podands for the certain cations was I>II>III${\geq}$IV. And every podands except IV showed the maximum selectivity for $Ag^+$ among the cations. These results were discussed in terms of the aromatic end-group effects, such as hetero-donor atoms or conformational changes by ${\pi}-{\pi}$ stacking interactions. The detailed conformations of ${\pi}-{\pi}$ stacking were also discussed by the observations of upfield shifts of some aromatic protons upon complexation from $^1H$ NMR spectra.

Complexation of Co-contaminant Mixtures between Silver(I) and Polycyclic Aromatic Hydrocarbons

  • Yim, Soo-Bin
    • 한국환경과학회지
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    • 제12권8호
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    • pp.871-879
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    • 2003
  • The complexation of co-contaminant mixtures between Ag(I) and polycyclic aromatic hydrocarbon (PAH) molecules (naphthalene, pyrene, and perylene) were investigated to quantify the equilibrium constants of their complexes and elucidate the interactions between Ag(I) and PAH molecules. The apparent solubilities of PAHs in aqueous solutions increased with increasing Ag(I) ion concentration. The values, K$_1$ and K$_2$ of equilibrium constants of complexes of Ag(I)-PAHs, were 2.990 and 0.378, 3.615 and 1.261, and 4.034 and 1.255, for naphthalene, pyrene, and perylene, respectively, The K$_1$and K$_2$ values of PAHs for Ag(I) increased in the order of naphthalene < pyrene < perylene and naphthalene < pyrene ≒ perylene, respectively, indicating that a larger size of PAH molecule is likely to have more a richer concentration of electrons on the plane surfaces which can lead to stronger complexes with the Ag(I) ion. For the species of Ag(I)-PAH complexes, a 1:1 Ag(I) : the aromatic complex, AgAr$\^$+/, was found to be a predominant species over a 2:1 Ag(I) : aromatic complex, Ag$_2$Ar$\^$++/. The PAH molecules with four or more aromatic rings and/or bay regions were observed to have slightly less affinity with the Ag(I) ion than expected, which might result from inhibiting forces such as the spread of aromatic $\pi$ electrons over o wide molecular surface area and the intermolecular electronic repulsion in bay regions.

Novel-1,3-Alternate Calix[4]thiacrown Ethers

  • Sim, Won-Bo;Lee, Jai-Young;Kwon, Jong-Chul;Kim, Moon-Jib;Kim, Jong-Seung
    • Bulletin of the Korean Chemical Society
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    • 제23권6호
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    • pp.879-884
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    • 2002
  • A series of novel 1,3-alternate calix[4]-mono-thiacrown and -bis-thiacrowns were synhesized within good yields. The three dimensional 1,3-alternate conformation was confimed by X-ray crystal structure. From the results of two phase extraction and NMR studies on the ligand-metal complex, one can conclude that the calix[4]thiacrown ethers showed the very high selectivity for silver ion over other metal ions by an electrostatic interaction between sulfur atom and silver ion and by a $\pi-metal$ complexation.

FT-Raman Studies on Ionic Interactions in ${\pi}$-Complexes of Poly(hexamethylenevinylene) with Silver Salts

  • Kim Jong-Hak;Min Byoung-Ryul;Won Jong-Ok;Kang Yong-Soo
    • Macromolecular Research
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    • 제14권2호
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    • pp.199-204
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    • 2006
  • Remarkably high and stable separation performance for olefin/paraffin mixtures was previously reported by facilitated olefin transport through ${\pi}$-complex membranes consisting of silver ions dissolved in poly(hexamethylenevinylene) (PHMV). In this study, the ${\pi}$-complex formation of $AgBF_4,\;AgClO_4\;and\;AgCF_{3}SO_3$ with PHMV and their ionic interactions were investigated. FT-Raman spectroscopy showed that the C=C stretching bands of PHMV shifted to a lower frequency upon incorporation of silver salt, but the degree of peak shift depended on the counter-anions of salt due to different complexation strengths. The symmetric stretching modes of anions indicated the presence of only free ions up to [C=C]:[Ag]=1:1, demonstrating the unusually high solubility of silver salt in PHMV. Above the solubility limit, the ion pairs and higher-order ionic aggregates started to form. The coordination number of silver ion for C=C of PHMV was in the order $AgBF_4$ > $AgClO_4$ > $AgCF_{3}SO_3$, but became similar at [C=C]:[Ag]=1:1. The different coordination number was interpreted in terms of the different transient crosslinks of silver cations in the complex, which may be related to both the interaction strength of the polymer/silver ion and the bulkiness of the counteranion.

은이온이 담지된 메조포러스 MCM-41을 이용한 n-부탄과 1-부텐의 흡착 특성 연구 (Adsorption Characteristics of n-Butane and 1-Butene on Mesoporous MCM-41 Containing Silver Ions)

  • 강 민;이형익;윤달영;고창현;김종남;김지만
    • Korean Chemical Engineering Research
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    • 제44권4호
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    • pp.393-398
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    • 2006
  • 고농도의 1-부텐을 생산하기 위하여 흡착 분리제의 개발이 필수적인데, 본 연구에서는 메조포러스 실리케이트인 MCM-41을 지지체로 하여 $AgNO_3$를 함침시켜 흡착제를 제조한 후, 1-부텐과 n-부탄의 흡착 특성을 연구하였다. 또한, 열처리 조건에 따른 $Ag^+$ 이온의 형성 비율과 1-부텐의 결합 능력을 알아보았다. MCM-41 흡착제의 경우, 13X 제올라 이트에 비하여 매우 높은 흡착량을 보여주었으며, 은이 담지되었을 때, n-부탄의 흡착량은 감소하는 반면에 1-부텐의 흡착량은 증가함으로써 1-부텐과 n-부탄의 흡착 분리에 매우 좋은 성능을 갖음을 확인할 수 있었다. 또한, 진공 분위기에서 373 K로 열처리한 Ag/MCM-41의 경우 가장 높은 1-부텐/n-부탄 흡착비를 보였으며, 특히 저압에서 매우 높은흡착비를 보여주었다.

공중합체 LB막의 제작과 유기가스 반응 특성 (Fabrication and organic gas response characteristics of the copolymer LB films)

  • 신훈규;최용성;장정수;권영수
    • E2M - 전기 전자와 첨단 소재
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    • 제9권2호
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    • pp.180-187
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    • 1996
  • The use of preformed copolymers and their cross-linking have been attempted in order to improve the intrinsic fragility of monolayers and Langmuir-Blodgett (LB) films and to make their technological applications. It has shown that an imidization followed a polyion-complexation can stabilize the LB films against heat and solvents. And, when the polymer structure was properly designed, concurrent removal of the alkyl tails together with imide formation could be accomplished. In this paper, the monolayers of the polymers which were polyion-complexed with PAA at the air-water interface can be transferred onto solid substrates such as porous fluorocarbon membranes filter and quartz crystal microbalance. The properties of the monolayers and the LB films will be discussed by .pi.-A isotherms, FT-IR, DSC, deposition ratio, QCM, and SEM. In addition, it was attempted to investigate the response characteristics of polymer LB films to the organic gases by the use of QCM.

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Selective Coordination of Silver Ions to Poly(styrene-b-(ethylene-co-butylene)-b-styrene) and its Influence on Morphology and Facilitated Olefin Transport

  • Lee, Dong-Hoon;Kang, Yong-Soo;Kim, Jong-Hak;Kang, Sang-Wook
    • Macromolecular Research
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    • 제16권8호
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    • pp.676-681
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    • 2008
  • The $\pi$-complex membranes of poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) of two silver salts of $AgBF_4$ and $AgCF_3SO_3$ were prepared and tested for the separation of the propylene/propane mixtures. The Fourier-transform infrared (FT-IR) spectra of these complexes showed that the silver salts were dissolved in SEBS up to a silver mole fraction of 0.14, due to $\pi$-complexation between the aromatic C=C bonds of styrene blocks and silver ions. Above this solubility limit, ion pairs and high-order ionic aggregates began to form, so that silver salts were distributed unselectively in both the EB and PS blocks. The domain size of the PS blocks was enlarged up to this critical concentration with increasing silver concentration without structural transitions, as confirmed by small angle x-ray scattering (SAXS). These structural properties of the SEBS/silver salt complexes may explain the lower separation properties for propylene/propane mixtures compared to poly(styrene-b-butadiene-b-styrene)(SBS)/silver salt complex membranes.

고분자 LB막의 $\pi-A$ 특성 및 안정성 ($\pi-A$ Isotherms and Stability of Polymer LB Films)

  • 최용성;신훈규;권영수;장정수;배진호
    • 대한전기학회:학술대회논문집
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    • 대한전기학회 1993년도 하계학술대회 논문집 A
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    • pp.3-5
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    • 1993
  • The use of preformed polymers and their cross-linking have been attempted in order to improve the intrinsic fragility of monolayers and Langmuir-Blodgett (LB) films and to make their technological applications possible. It has shown that an imidization followed a polyion-complexation can stabilize the LB films against heat and solvents. And, when the polymer structure was property designed, concurrent removal of the alkyl tails together with imide formation could be accomplished. In this paper, we present a characteristic monolayer behavior of polymer with pendent polyethers and carboxyls, it's polyion-complexed LB film with subphase polymer PAA, and a possible skeletonization of the LB film by thermal imidization. Also, deposition status of LB films are evaluated by using QCM.

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고분자 LB막의 $\pi$-A 특성 및 안정성 ($\pi$-A Isotherms and Stability of Polymer LB Films)

  • 최용성;신훈규;권영수;장정수;배진호
    • 대한전기학회:학술대회논문집
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    • 대한전기학회 1993년도 하계학술대회 논문집 B
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    • pp.537-539
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    • 1993
  • The use of preformed polymers and their cross-linking have been attempted in order to improve the intrinsic fragility of monolayers and Langmuir-Blodgett(LB) films and to make their technological applications possible. It has shown that an imidization followed a polyion-complexation can stabilize the LB films against heat and solvents. And, when the polymer structure was properly designed, concurrent removal of the alkyl tails together with imide formation could be accomplished. In this paper, we present a characteristic monolayer behavior of polymer with pendent polyethers and carboxyls, it's polyion-complexed LB film with subphase polymer PAA, and a possible skeletonization of the LB film by thermal imidization. Also, deposition status of LB films are evaluated by using QCM.

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