• Mass Spectrometry Letters
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• 제1권1호
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• pp.9-12
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• 2010

Trimethylboroxine (TMB) is a six-membered ring compound containing Lewis acidic boron and Lewis basic oxygen atoms that can bind halide anion and alkali metal cation, respectively. We employed Fourier transform ion cyclotron resonance spectroscopy to study the gas-phase binding of $LiBrLi^+$ and $F^-(KF)_2$ to TMB. TMB forms association complexes with both $LiBrLi^+$ and $F^-(KF)_2$ at room temperature, providing direct evidence for the ditopic binding. Interestingly, the $TMB{\cdot}F^-(KF)_2$ anion complex is formed 33 times faster than the $TMB{\cdot}Li^+BrLi$ cation complex. To gain insight into the ditopic binding of an ion pair, we examined the structures and energetics of $TMB{\cdot}Li^+$, $TMB{\cdot}F^-$, $TMB{\cdot}LiF$ (the contact ion pair), and $Li^+{\cdot}TMB{\cdot}F^-$ (the separated ion pair) using Hartree-Fock and density functional theory. Theory suggests that $F^-$ binds more strongly to TMB than $Li^+$ and the contact ion-pair binding ($TMB{\cdot}LiF$) is more stable than the separated ion-pair binding ($Li^+{\cdot}TMB{\cdot}F^-$).

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1525-1529
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• 2013

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reactions of 2-pyridyl thionobenzoate (5b) with alkali-metal ethoxides (EtOM, $M^+=Li^+$, $Na^+$, $K^+$, and 18-crown-6-ether complexed $K^+$) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. $[EtOM]_o$ curve upward regardless of the nature of the $M^+$ ions, while those of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ are linear with a positive intercept. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the ion-paired EtOM is more reactive than the dissociated $EtO^-$, and $M^+$ ions catalyze the reactions in the order $K^+$ < $Na^+$ < $Li^+$ < 18C6-complexed $K^+$. The plot of log $k_{EtOM}$ vs. $1/r_{Stokes}$ results in an excellent linear correlation, indicating that the reactions are catalyzed by the solvated $M^+$ ions but not by the bare $M^+$ ions. The reactions of 5b with EtOM have been concluded to proceed through a six-membered cyclic TS, in which the solvated $M^+$ ions increase the electrophilicity of the reaction center and the nucleofugality of the leaving group.

• 한국재료학회지
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• 제33권4호
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• pp.135-141
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• 2023

The volatilization of alkali ions in (K,Na)NbO₃ (KNN) ceramics was inhibited by doping them with alkaline earth metal ions. In addition, the grain growth behavior changed significantly as the sintering duration (t_s) increased. At 1,100 ℃, the volatilization of alkali ions in KNN ceramics was more suppressed when doped with alkaline earth metal ions with smaller ionic size. A Ca²⁺-doped KNN specimen with the least alkali ion volatilization exhibited a microstructure in which grain growth was completely suppressed, even under long-term sintering for t_s = 30 h. The grain growth in Sr²⁺-doped and Ba²⁺-doped KNN specimens was suppressed until t_s = 10 h. However, at t_s = 30 h, a heterogeneous microstructure with abnormal grains and small-sized matrix grains was observed. The size and number of abnormal grains and size distribution of matrix grains were considerably different between the Sr²⁺-doped and Ba²⁺-doped specimens. This microstructural diversity in KNN ceramics could be explained in terms of the crystal growth driving force required for two-dimensional nucleation, which was directly related to the number of vacancies in the material.

• 폴리머
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• 제24권6호
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• pp.802-809
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• 2000

Poly(L-glutamic acid) (PLGA)와 PVA 블렌드막을 제조한 후, ethanol 수용액중에서 막증의 polypeptide 사슬의 2차구조 전이거동에 미치는 용매조성 및 대이온종의 영향과 알칼리 금속 이온 (Li, na, K, Cs)에 대한 투과특성을 조사하였다. 막중 PLG 알칼리 금속염의 helix 형성거동에 있어 대이온 선택성은 Li>Na>K>Cs의 순으로 관찰되었고, 이와 같은 특이성은 탈용매화 에너지와 정전에너지의 감소에 따른 고분자 하전기와 대이온과의 contact ion-pair 형성에 의한 것으로 설명하였다. 또한 PLGA/PVA 블렌드막의 ethanol 수용액 중에서의 알칼리 금속이온의 투과거동을 살펴보면, ethanol 농도가 점차 증가함에 따라 K, Cs의 경우는 투고도가 증가한, Li, Na의 경우에는 감소하였다. K, Cs 이온의 경우 대이온과 염소이온간의 ion-pair (M$^{+}{\cdot}$Cl$^{-}$)형성에 의한 Donnan배제효과의 감소와 중성염 형태로의 분배량 증가때문인 것으로, Li, Na 이온의 경우 막중의 coil-helix 구조전이에 따른 자유체적의 감소와 고분자 하전기와의 상호작용이 증가하여 확산성이 크게 감소하였기 때문인 것으로 생각된다.

• 전기화학회지
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• 제7권1호
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• pp.16-20
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• 2004

플러렌 이온$(full^-)$으로 수식된 피를 고분자 피막을 전기화학법으로 중합하기 위하여 사용된 전지는 Au/5mM pyrrole, 1mM fullerene, 0.1M $TBABF_4,\; CH_2C1_2/Pt$이었으며 이 전지로 $electrode/ppy(full^-)ppy(full^-){\ldots}$와 같은 웨이퍼형의 전극을 제작하였다. 이 전극을 사용한 Au(quartz crystal analyzer; QCA)/ppy$(full^-)$, 0.01M metal ion(aq.)/Pt형의 전지로 알카리 금속이온을 포집하였다. $Li^+,\;Na^+,\;K^+,\;Rb^+$ 및 $Cs^+$이온의 포집에 대한 속도상수는 일차반응 속도식으로 계산한 결과 그 값이 각각 $1.60\times10^{-8},\;3.13\times10^{-11},\;1.38\times10^{-9},\;2.71\times10^{-11}$ 및 $2.98\times10^{-12}mo1.s^{-1}$이였다. 이 전극을 수정판 미량저울(QCM)을 적용하여 결정한 각 이온의 화학양론은 $Li_7C_{60},\;Na_4C_{60},\;K_3C_{60},\;Rb_1C_{60}$ 및 $Cs_1C_{60}$이었다.

• 대한방사성의약품학회지
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• 제7권2호
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• pp.141-146
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• 2021

With increasing interest in fluorinated compounds, nucleophilic fluorination reaction has been generally used for synthesizing fluorine-containing chemicals. However, alkali metal fluorides (MFs) generally have low solubility and reactivity in organic solvent. To overcome these problems, various phase transfer catalysts (PTCs) have been investigated. Calix-arene is known as to capture the metal cation(M⁺), and therefore in this review, we would like to introduce several kinds of calix-arene based PTCs, such as bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA), oligo-ethylene glycol linked bis-triethyleneglycol crown-5-calix[4]arene (BTC5A), and ionic liquid functionalized calix-arene based catalyst, as well as ion-pair receptor crown-6-calix[4]arene-capped calix[4]pyrrole.

• Bulletin of the Korean Chemical Society
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• 제29권3호
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• pp.620-622
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• 2008

A new thiacalix[4]arene diamide (TCAm) has been prepared and its electrochemical property and complexation behavior toward various metal ions have been investigated by voltammetry. p-tert-Butylthiacalix[4]arene diamide (TCAm) exhibited selectivity toward Sr2+ ion over alkali, alkaline earth and transition metal ions while conventional calix[4]arene diamides showed selective binding property with Ca2+ ion. This is probably due to the bigger size of thiacalix[4]arene than those of calix[4]arene.

• 대한의용생체공학회:의공학회지
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• 제8권2호
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• pp.123-134
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• 1987

The transport phenomena of alkali metal chlorides through poly(2 hydroxyethyl methacrylate) hydrogel membrane have been studied using electrodialysis. The hydrogel membranes were prepared by the polymerization of 2-hydroxvethyl methacrylate in the presence of 45%(V/V) H2O and ethyleneglycodimethacrylate. The initiator used in the polymerization was azobismethylisobutyrate (AMIB) prepared from azobisiobtyronitrile (AIBN) using Mortimer method. The permeability of alkali metal chlorides such LiCl, NaCl and KCI at 50 voltage was obtained. The permeability of NaCl was also observed at 30, 40, 50, and 60 voltages respectively. The concentration of solutes permeated through the membrane was measurer by flame photometry. The experimental results have been discussed with the comparison of apparent solute molecular size, the self-diffusion coefficient of solutes, the transport number of cations in aqueous solution. These indic aloes that poly(2 hydroxyethyl methacrylate) hydrogel membrane shows a specific selectivity for sodium ion.

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 1998년도 가을 학술발표회논문집
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• pp.232-235
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• 1998

ion conducting polymers have been extensively investigated because of their potential application as an electrolyte in solid state batteries [1]. Among the polymer electrolytes, solid polymer electrolytes (SPEs) composed of ion conducting polymer and alkali metal salt have many advantages such as high ionic conductivity, high energy density and light weight. This made them suitable replacement for liquid electrolytes. (omitted)

• Bulletin of the Korean Chemical Society
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• 제25권10호
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• pp.1465-1470
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• 2004

A short and efficient synthesis, solvent extraction and potentiometric measurements of new thiazole-containing naphtho-crown ethers are reported. The naphthalene moiety enhances the ammonium ion selectivity over potassium ion. The selectivity of ${NH_4}^+/K^+$ follows the trend $3\;{\approx}\;2\;>\;1$, indicating that the differences in conformational changes of 2 and 3 in forming ammonium complexes affect little on the resulting ammonium/potassium extraction selectivity ratio. The ammonium ion-selective electrodes were prepared with noctylphenyl ether plasticized poly(vinyl chloride) membranes containing 1-4 the effect of one naphthalene unit introduced on either right (2) or left (3) side of thiazolo-crown ether on their potentiometric properties (e.g., ammonium ion selectivity over other cations, response slopes, and detection limits) were not apparent. However, the ammonium ion selectivity of 1, 2 and 3 over other alkali metal and alkaline earth metal cations is 10-100 times higher than that of nonactin.