• Bulletin of the Korean Chemical Society
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• 제24권6호
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• pp.757-762
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• 2003

Since theoretical investigations of gas phase clusters enable the evaluation of intrinsic molecular properties and intermolecular interactions, one can predict the macroscopic properties of bulk matter, from a microscopic determination of the properties of individual atoms, molecules, or clusters. Based on the insights obtained from theoretical investigations of the properties of a large number of cluster systems (ranging from simple water clusters to large π-systems), we have investigated the properties of various novel molecular systems including endo/exohedral fullerenes, nanotori, nonlinear optical materials, ionophores/receptors, polypeptides, enzymes, organic nanotubes, nanowires, and electronic and nano-mechanical molecular devices. The present minireview highlights some of the interesting results obtained in the course of our extensive theoretical investigations of clusters and nanomaterials.

• 약학회지
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• 제39권1호
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• pp.61-67
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• 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.

• Bulletin of the Korean Chemical Society
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• 제22권7호
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• pp.699-702
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• 2001

A series of cleft-type ionophores having two convergent hydroxamic acid functions are prepared and their selective ionophoric properties toward heavy metal and transition metal ions have been investigated. Hydroxamic acids 3 exhibited a prominent selectivity toward heavy metal ions of Hg2+ and Pb2+, and transition metal ions of Cu2+ over other transition metal and alkaline earth metal ions from slightly acidic source phase (pH 6) to an acidic receiving phase (pH 1). Selective ionophoric properties toward Pb2+ and Cu2+ ions over other surveyed metal ions are also confirmed by the FAB-MS measurements.

• Bulletin of the Korean Chemical Society
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• 제18권5호
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• pp.519-522
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• 1997

A series of new ligands having convergent dicarboxylic acid functions, based-upon Rebek's cleft-type ionophore, have been prepared and their ion binding properties were investigated by the competitive extraction and transport experiments. The main purpose of the modification was to increase the lipophilicity of the Rebek's ionophore, which was attempted by utilizing propyl analog of Kemp's triacid or by changing the bridging unit. Ionophores 5 and 6 were found to have a pronounced ion-binding property toward Ca2+ ion. The selectivity in competitive extraction of ionophore 5 at pH 9 for Ca2+ over Mg2+ and Sr2+ is 2.0 and 59.3, respectively. The selectivity in competitive transport of ionophore 5 for Ca2+ over Mg2+ and Sr2+ is 29.8 and 99.3, and that of ionophore 6 is 10.0 and 23.2, respectively.

• Bulletin of the Korean Chemical Society
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• 제22권12호
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• pp.1345-1349
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• 2001

New quadruply-bridged calix[6]arenes (I-V) have been studied as cesium selective ionophores in poly(vinyl chloride) (PVC) membrane electrodes. PVC membranes were prepared with dioctyl sebacate (DOS) or 2-nitrophenyl octyl ether (o-NPOE) as the sol vent mediator and potassium tetrakis(p-chlorophenyl)borate as the lipophilic salt additive. These ionophores produced electrodes with near-Nernstian slope. The selectivity coefficients for cesium ion with respect to alkali, alkaline earth and ammonium ions have been determined. The lowest detection limit (logaCs+ = -6.3) and the higher selectivity coefficient (logkpotCs+,Rb+ = -2.1 by SSM, -2.3 by FIM for calix[6]arene I) for Cs+ have been obtained for membranes containing quadruply-bridged calix[6]arenes (I, Ⅱ, Ⅲ), which have no para t-butyl substituents on the bridging benzene ring.

• Bulletin of the Korean Chemical Society
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• 제23권10호
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• pp.1420-1424
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• 2002

• Bulletin of the Korean Chemical Society
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• 제24권1호
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• pp.37-44
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• 2003

We examined the effect of polyether-type nonionic surfactants (Brij 35, Triton X-100, Tween 20 and Tween 80) on the potentiometric properties of sodium-, potassium- and calcium-selective membranes which are prepared with widely used ionophores and four kinds of polymer matrices [poly(vinyl chloride) (PVC), polyurethane (PU), PVC/PU blend, and silicone rubber (SR)]. It was found that the PVC-based membranes, which provide the best performance among all other matrix-based membranes in the absence of nonionic surfactants, exhibited larger change in their potentiometric properties when nonionic surfactants are added to the sample solution. On the other hand, the sodium-selective SR-based membrane with calix[4]arene, potassium-selective PVC/PU- or SR-based membrane with valinomycin, and the calcium-selective SR-based membrane with ETH 1001 provide almost identical analytical performance in the presence and absence of Tween 20 or Tween 80 surfactants. The origin of nonionic surfactants effect was also investigated by interpreting the experimental results obtained with various matrices and ionophores. The results suggest that the nonionic surfactant extracted into the membrane phase unselectively form complexes with the primary and interfering ions, resulting in increased background potential and lower binding ability for the ionophore. Such effects should result in deteriorated detection limits, reduced response slopes and lower selectivity for the primary ions.

• Bulletin of the Korean Chemical Society
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• 제24권12호
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• pp.1737-1741
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• 2003

Azo-functionalized calix[4]arenes as ionophores for chloride-selective electrode, 5,11,17,23-Tetra-tert-butyl-25,27-bis[(N,N-dimethyl-aniline-azo-phenylthioureido)ethyl]oxy-26,28-dihydroxycalix[4]arene (4a) and 5,11,17,23-Tetra-tert-butyl-25,27-bis[(N,N-dimethyl-aniline-azo-phenylthioureido)ethyl]oxy-26,28-dimethoxycalix[4]arene (4b) were synthesized. The PVC membrane electrode based on azo-functionalized calix[4]arene 4a with o-NPOE exhibits a linear stable response over a wide concentration range ($1.5{\times}10^{-4}-1.0{\times}10^{-1}$) with a slope of -52.0 mV/decade and a detection limit of log[$Cl^-$] = -4.02. This ionophore-based membrane exhibited improved selectivity for chloride anion compared with classical Hofmeister series.

• Bulletin of the Korean Chemical Society
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• 제23권11호
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• pp.1585-1589
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• 2002

Two novel calixarene-based fluoroionophores were synthesized. Their conformations were confirmed to 1,3-alternate by X-ray crystal structures. From CHEF by blocking the PET mechanism in fluorescence spectra, we observed $In^{3+}$ and $Pb^{2+}$ selectivity over other metal ions. For $In^{3+}$ion, calix[4]-bis-azacrown-5 showed about 20 times more sensitive than calix[4]-mono-azacrown-5 because the source of the binding selectivity comes from the calixarene framework and azacrown ligand by controlling the fluorescence and PET mechanisms as-sociated with the amine moiety.

• Bulletin of the Korean Chemical Society
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• 제20권2호
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• pp.179-186
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• 1999

Several cholic acid derivatives containing 1-3 trifluoroacetylbenzoyl (TFAB) moieties were synthesized using selective acetylations, hydrolysis and/or oxidation of cholic acid derivatives and tested as receptors for a carbonate ion through solvent extraction method. The compounds having two and three TFAB moieties exhibited enhanced binding affinities toward a carbonate ion in comparison with those with one TFAB croup and the extent of complex formation also depended on the position of TFAB group attached.