• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.588-595
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• 1989

Log K, ${\Delta}$H and ${\Delta}$S for the complexation of $La^{3+},\;Ce^{3+}$ and $Eu^{3+}$with various multidentate ligand containing crown ether, diaza crown ether and diamine ether have been determined in methanol and acetonitril solutions at $25^{\circ}C$ by solution calorimetric titration method. The greater stability constant of $La^{3+}$-15C5 than those of 18C6 diaza [2.2] in methanol are discussed in terms of the size of metal ion and the ligand cavity and of metal ion solvation. The stabilities of $Ce^{3+}$ and $La^{3+}$ ion complexes with a various multidentate ligand in acetonitril are in the order of (diamine ether)<18C6<15C5$Ce^{3+}$, $La^{3+}$ and $Eu^{3+}$-diaza [2.2] complexes in acetonitril are increased with the following order: $Eu^{3+}$ < $La^{3+}$ < $Ce^{3+}$, that is increasing order of the optimum size and of the charge density of metal ion.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3681-3689
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• 2013

This study explored a direct SET-photochemical strategy to construct a new family of thioene conjugated-naphthalamide fluorophore based lariat-crown ethers which show strong binding properties towards heavy metal ions. Irradiations of designed nitrogen branched (trimethylsilyl)methylthio-terminated polyethylenoxy-tethered naphthalimides in acidic methanol solutions have led to highly efficient photocyclization reactions to generate naphthalamide based lariat type thiadiazacrown ethers directly in chemo- and regio-selective manners which undergo very facile secondary dehydration reactions during separation processes to produce their corresponding amidoenethio ether cyclic products tethered with electron donating diethyleneoxy- and diethyenethio-side arm chains. Fluorescence and metal cation binding properties of the lariat type enamidothio products were examined. The photocyclized amidoenethio products, thioene conjugated naphthalamide fluorophore containing lariat-thiadiazacrowns exhibited strong fluorescence emissions in region of 330-450 nm along with intramolecular exciplex emissions in region of 450-560 nm with their maxima at 508 nm. Divalent cation $Hg^{2+}$ and $Pb^{2+}$ showed strong binding to sulfur atom(s) in side arm chain and atoms in enethiadiazacrown ether rings which led to significant enhancement of fluorescence from its chromophore singlet excited state and concomitant quenching of exciplex emission. The dual fluorescence emission responses towards divalent cations might provide a new guide for design and development of fluorescence sensors for detecting those metals.

• Journal of the Korean Chemical Society
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• v.39 no.9
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• pp.698-704
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• 1995

The ion-selective membrane fabricated with 33 wt% PVC, 66 wt% o-NPOE and 1 wt% 4'-benzothiazolylbenzo-15-crown-5 (TB15C5) as a neutral carrier exhibited an enhanced selectivity to potassium ion over sodium ion compared to those prepared with other 15-crown-5 or 18-crown-6 derivatives. The potentiometric properties (response slope, selectivity, detection limits and lifetime) of TB15C5-based ISE membranes along with those based on valinomycin, benzo-15-crown-5 (B15C5), 4'-aminobenzo-15-crouwn-5 (AB15C5), benzo-18-crown-6 (B18C6), dibenzo-18-crown-6 (DB18C6) and bis[(benzo-15-crown-5)-4'-ylmethyl]pimelate (PI-Ⅱ) ionophores were carefully examined under the same experimental conditions. The enhanced selectivity of TB15C5-based membrane to potassium is explained in terms of the effect of the benzothiazol functional group and the distribution coefficients of metal ions.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.276-281
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• 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.

• Journal of Energy Engineering
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• v.23 no.4
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• pp.141-149
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• 2014

In the present study, pure RHO zeolite was hydrothermally synthesized by using 18-crown-6 ether as a structure directing agent(SDA), and the small gases adsorption was investigated. Synthesized RHO zeolite was a cube shape particle of which average edge length was around $1.2{\mu}m$ and composed of primary crystallites having a diameter of around 100 to 200 nm. RHO zeolite structure was stable under 3h calcination at $600^{\circ}C$. Water adsorption data announced that RHO zeolite has a specific surface area of 483.32 m2/g and its micropore diameter was about 4 A. Gas adsorption was studied in the pressure range of 50 to 500 kPa for $CO_2$, $N_2$, $O_2$ and $H_2$. It was evident that RHO zeolite showed a strong $CO_2$ adsorption behavior. Especially, RHO zeolite showed a transient $CO_2$ adsorption behavior. The 3h $CO_2$ up-take at 50 kPa and 500 kPa was 1.283 and 3.357 mmol/g, respectively. The $CO_2/H_2$ selectivity was around 16 at 500 kPa. Compared with gas adsorption data for some representative microporous adsorbents, it was certain that RHO zeolite is a beneficial adsorbent for $CO_2/H_2$ separation.

• Journal of the Korean Chemical Society
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• v.53 no.5
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• pp.521-529
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• 2009

Molecular structures of the various conformers for the 1,3-dimethoxy-p-tert-butylthiacalix[4] crown-5-ether (3) were optimized by using DFT B3LYP/6 - 31 + G(d,p) and mPW1PW91/6 - 31 + G(d,p) (hybrid HF-DF) calculation methods. We have analyzed the energy differences and structures of eight in/out orientations (cone_oo, cone_oi, pc_oo, pc_io, pc_oi, pc_ii, 13a_oo, 13a_io) of two methoxy groups in three major conformations (cone, partial-cone and 1,3-alternate). The 13a_oo (out-out orientation of the 1,3-alternate conformer) is calculated to be the most stable among eight different conformations of 3, and in accord with the experimental result. The ordering of relative stability resulted from the mPW1PW91/6 - 31 + G(d,p) calculation method is following: 13a_oo > 13a_io$\sim$pc_io$\sim$cone_oo > cone_oi$\sim$pc_oo$\sim$pc_oi > pc_ii.

• Bulletin of the Korean Chemical Society
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• v.29 no.5
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• pp.1069-1072
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• 2008

• Archives of Pharmacal Research
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• v.10 no.4
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• pp.239-244
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• 1987

An efficient and inexpensive method for the substitution of allylic hydroxyl group with fluoride, without allylic rearrangement, and elimination was developed. This method consists of treating an allylic alcohol with methylithium, followed by p-toluene sulfonyl fluoride, lithium fluoride and 12-Crown-4. This methodology was proved to be efficient by preparting geranyl fluoride, neryl fluoride, cinnamyl fluoride, E, E-farnesyl fluoride, retinyl fluoride and 4-fluoro-2-methyl-6-(ptolyl)-2-heptene.

• Bulletin of the Korean Chemical Society
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• v.22 no.9
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• pp.958-962
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• 2001

The chiral amine auxiliary mediated stereoselective alkylation reactions of glycinamides 1-6 and 15-17 using phase transfer catalyst (PTC) for liquid-solid extraction are described. The secondary N-(diphenylmethylene) glycinamides 1, 2 and 3 give better selectivities and yields than tertiary N-(diphenylmethylene) glycinamides 4, 5 and 6. Alkylation of the glycinamide 1 and 2 using 18-Crown-6 as a PTC in toluene at $-40^{\circ}C$ gives best selectivities and yields. Alkylations of N-(4-chlorophenylmethylene)glycinamides 15, 16 and 17 under same PTC conditions give $\alpha$, $\alpha-disubstituted$ amino acid derivatives 18, 19 and 20 with low diastereoselectivities.

• Bulletin of the Korean Chemical Society
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• v.25 no.4
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• pp.529-532
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• 2004

Cesium-133 NMR spectra of a single crystal of tetragonal $Cs^+ (15-crown-5)_2I^-$ were obtained as a function of crystal orientation in an applied magnetic field of 9.40T and analyzed to provide the magnitudes and orientations of the $^{133}Cs$ chemical shift and quadrupolar tensors for two magnetically nonequivalent and symmetry related sites. Chemical shift tensor components and parameters of quadrupolar interactions are obtained as ${\delta}_{11}=46(1),\;{\delta}_{22}=60(1),\;{\delta}_{33}=-30(1)$ ppm, quadrupole coupling constant QCC = 581(1) kHz, and asymmetry parameter ${\eta}$ = 0.481(1), respectively. The nonaxially symmetric NMR parameters imply that the local environment of the cesium nuclei is nonaxially symmetric. The DANTE experiment burned holes in the $^{133}Cs$ NMR line of the title compound. The hole burning of the single crystal and powder $^{133}Cs$ NMR lines showed that the NMR lines are not homogeneously broadened.