• 대한화학회지
• /
• 제30권4호
• /
• pp.359-368
• /
• 1986

Crown ether (DC18C6, DC24C8)과 HDEHP로 알칼리 금속 이온을 용매 추출할 때의 추출평형을 연구하였다. 추출평형상수는 DC18C6계에서 $Na^+순으로 증가하였으며 DC24C8계에서는 $Rb^+순으로 증가하였다. 유기용매상으로 추출되는 추출종은 $M_1(crown ether)_1\;(HDEHP)_1$이며 추출평형상수의 크기는 crown ether의 유기용매상과 수용액상에서의 분배비와 crown ether-알칼리금속 착물의 안정도 상수에 의해서 결정된다.

• Bulletin of the Korean Chemical Society
• /
• 제11권4호
• /
• pp.276-281
• /
• 1990

The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

• 대한화학회지
• /
• 제39권9호
• /
• pp.698-704
• /
• 1995

33중량%의 PVC와 66중량%의 o-NPOE 가소제에 1중량%의 중성 전극물질인 4'-benzothiazolyl-benzo-15-crown-5를 사용하여 성형한 막전극은 다른 15-크라운-5난 18-크라운-6 유토체들에 비하여 나트륨에 대하여 보다 낮은 선택성을 갖는 칼륨선택성을 나타내었다. 이 막전극의 전기화학적 성질들(감응기울기, 선택성, 섬출한계 및 수명)을 잘 알려져 있는 칼륨선택성 전극물질인 발리노마이신, benzo-15-crown-5, 4'-aminobenzo-15-15-crown-5, benzo-18-crown-6, dibenzo-18-crown-6 및 bis[(benzo-15-crown-5)-4'-ylnethuyl]pimelate를 사용한 전극막들의 것과 동일한 실험 조건하에서 비교하였다. 이러한 비교연구를 통하여 벤조티아졸기가 치환된 벤조크라운에테르 화합물이 증가된 칼륨이온 선택성을 나타내게되는 이유를 치환기의 효과와 이온의 분배계수효과로 설명하였다.

• Bulletin of the Korean Chemical Society
• /
• 제27권10호
• /
• pp.1577-1580
• /
• 2006

The article reports the synthesis and enantiomeric recognition of a new chiral azophenolic pyridino-18-crown-6 ether, (S,S)-6, possessing diphenyl groups as chiral barriers. The association constants for the enantiomeric recognition of chiral primary amines (7-12) using chiral azophenolic pyridino-18-crown-6 ether, (S,S)-6, were determined by UV-visible titration method in acetonitrile at $25{^{\circ}C}$.

• Bulletin of the Korean Chemical Society
• /
• 제26권12호
• /
• pp.1969-1974
• /
• 2005

Composite systems of $Eu(phen)_2Cl_3{(H_2O)}_2$, Eu(DN-bpy)$(phen)Cl_3{(H_2O)}_2$ and Eu(DB-bpy)$(phen)Cl_3{(H_2O)}_2$ (DNbpy: $4,4^\prime$-Dinonyl-$2,2^\prime$-dipyridyl; DB-bpy: $4,4^\prime$-Di-tert-butyl-$2,2^\prime$-dipyridyl) with crown ethers of Benzo-15-crown-5 (B15C5), Benzo-18-crown-6 (B18C6), 18-crown-6 (18C6), Dibenzo-18-crown-6 (DB18C6) and Dibenzo-24-crown-8 (DB24C8) were fabricated successfully and characterized by using photoluminescent spectroscopy and luminescent lifetime measurements. All composites formed show high luminescence mainly in red region. It was found that the heterocyclic ligands such as phen, DN-bpy and DB-bpy as well as the crown ethers have great influences on the photoluminescent properties of $Eu^{3+}$ ion. The environment around $Eu^{3+}$ ion in the composite systems changes greatly,presumably the variation of the first coordination sphere. The $Eu^{3+}$ ion occupies higher symmetrical environment and in more than one kind of symmetrical site in the composite systems studied in this work.

• Bulletin of the Korean Chemical Society
• /
• 제21권7호
• /
• pp.685-689
• /
• 2000

The complexation reaction between Pb2+,TI and Cd2+ions and macrocyclic ligands, 18-crown-6 ( 18C6) and dibenzo- 18-crown-6 (DB 18C6), was studied in dimethylsulfoxide (DMSO)-nitromethane (NM) and dimethyl-formamide (DMF)-nitromethane binary system s by square wave polarography (SWP) technique. The stoichiometry and stability of the complexes were determined by monitoring the shifts in half-waves or peak potentials of the polarographic waves of metal ions against the Iigand concentration. In most cases, the stability constants of complexes increase with increasing amounts of the nitromethane in mixed binary solvents used in this study. The complexes formed between 18C6 and DB18C6 and these metal cations in all cases had a stoichiometry of 1 : 1. The results obtained show that there is an inverse relationship between the formation constant of complexes and the donor number of solvents based on a Gatmann donocity scale and the stability constants show a high sensitivity to the composition of the mixed solvent systems. A linear behavior was observed for variation of log Kf of I8C6 complexes vs the composition of the mixed solvent systems in NM/DMSO and NM/DMF,but a non-linear behavior was observed in the case of DB 18C6 complexes in these binary systems. In most of the systems investigated, the Pb2+ cation forms a more stable complex with the 18C6 than other two cations and the order of selectivity of this Iigand for cations is: Pb2+ > TI+,Cd2+.

• Bulletin of the Korean Chemical Society
• /
• 제27권12호
• /
• pp.2011-2018
• /
• 2006

We have investigated the solvent effects on $\Delta log\;K_s $(the difference of stability constant of binding) and the different free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, i.e., the selectivity of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 using a Monte Carlo simulation of statistical perturbation theory (SPT) in diverse solvents. The stability constant ($\Delta log\;K_s $) of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, in $CH_3OH$ was calculated in this study as -1.06 agrees well with the different experimental results of -0.44~-0.6, respectively. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6. From the calculated coefficients of QSPR, we have noted that solvent polarity (ET) and Kamlet -Tafts solvatochromic parameters (b ) dominate the differences in relative solvation Gibbs free energies of $Nd^{3+}$ and $Eu^{3+}$ ions but basicity (Bj) dominates the negative values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 and acidity (Aj) dominates the positive values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6.

• Mass Spectrometry Letters
• /
• 제7권4호
• /
• pp.96-101
• /
• 2016

To determine the influence of the cationization agent on the collision activated dissociation (CAD) fragmentation behavior of oligosaccharides, the CAD spectra of the singly protonated, sodiated oligosaccharides and singly sodiated and dibenzo-18-crown-6 ether conjugated oligosaccharides were carefully compared. Each of these three different species showed quite different fragmentation spectra. The comparison of singly protonated and sodiated oligosaccharide CAD spectra revealed that different cationization agents affected the cationization agent adduction sites as well as the fragmentation sites within the oligosaccharides. When the mobility of $Na^+$ was limited by the dibenzo-18-crown-6 ether encapsulation agent, the examined linear oligosaccharides showed fragmentation patterns quite different from the unmodified ones. For the dibenzo-18-crown-6 ether conjugated oligosaccharides, the charge-remote fragmentation pathways were more likely to be activated than the chargedirected pathways. This work demonstrates that dibenzo-18-crown-6 ether conjugation can potentially provide a route to selectively activate the charge-remote fragmentation pathways, albeit to a limited extent, in tandem mass spectrometry studies.

• 약학회지
• /
• 제39권1호
• /
• pp.61-67
• /
• 1995

PVC membrane electrodes based on the lipophilic neutral carrier, dibenzo-18-crown-6, cyclic oligomers of teit-butylphenol-formaidehyde condensates, calix[4]arenes as the active sensors for verapamil have been prepared and tested in a variety of plasticizers. At pH 5.0, the electrode exhibits a Nernstian response in the range of 10$^{-2}$~5$\times$10$^{-5}$ M verapamil with a slope of 49.1$\pm$0.5mV per concentration decade. The electrode constructed in this work can be used continuously for at least 1 month before any damage to the membrane occurs. And the analyses of the local anesthetic amine, which are good to select a specific compound in a mixed solution, were also accomplished by using of another neutral carrier, a DB18C6, for comparing with calix[4]arene.

• 분석과학
• /
• 제7권2호
• /
• pp.181-186
• /
• 1994

Poly(3-methylthiophene) 전도성 막전극을 이용해서 벗김 전압-전류법으로 Ag의 분석 가능성을 연구하였다. 막전극 표면에 존재하는 18-crown-6은 수용액에서 Ag(I)을 착화에 의해서 흡수하고 이 Ag(I)은 제한된 전위 범위의 순환 전압-전류법에 의해서 막전극 속으로 이동하여 유리질 탄소전극에서 산화-환원된다. 따라서 막전극은 Ag(I)의 침투를 용이하게 하기 위해서 적당한 두께의 다공성으로 제조되어야 한다. 이러한 실험 결과를 바탕으로 수용액에서 $5.0{\times}10^{-6}M$의 Ag(I)을 검출할 수 있었다.