• Journal of the Korean Chemical Society
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• v.41 no.7
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• pp.366-370
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• 1997

• Bulletin of the Korean Chemical Society
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• v.25 no.5
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• pp.609-616
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• 2004

Complexation of cesium ion by p-tert-butylcalix[6]arene ethyl ester was studied by NMR spectroscopy in nonpolar $CDCl_3$ and polar acetone-$d_6$ and the results were compared with each other. Analysis of temperature dependent $^1H$ spectra and titration curves reveals that both solvents result in a 1 : 1 cone-form complex with nonpolar $CDCl_3$yielding a more tightly bound one than acetone-$d_6$. Unexpectedly, at very low temperature, we have found that two phenyl ring proton peaks of equal intensity appear both in $CDCl_3$and in acetone-$d_6$ solution which gradually collapse and eventually coalesce into a single line as temperature is raised. This observation could be interpreted in terms of the chemical exchange through direct and/or indirect interconversion between two equivalent conformations possible the complex in both solvents over the temperature range observed. And broadening of $^{133}Cs$ (I = 7/2) nmr line with increasing temperature has also been observed, indicating the exchange of $^{133}Cs$ ion between the complex and the solvent. From numerical fitting of lineshape changes for one-dimensional $^1H$ and $^{133}Cs$ spectra, the exchange rate constants and other relevant parameters for this conformational interconversion and the complex-solvent exchange were deduced.

• Bulletin of the Korean Chemical Society
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• v.30 no.6
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• pp.1247-1251
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• 2009

The recognition of neutral aromatic substrates by different neutral calix[4]arene receptors 1, 2, and 3 was studied by NMR spectroscopy. The stoichiometry is 1:1 in all cases as was confirmed by jobs plot. Owing to the deep cavity, 1 affords stronger binding abilities for substrate 4 and 5, while all receptors remained inert for substrates 6 and 7. The binding constants determined by $^1H$ NMR titration show that the recognition of substrate 4 by 1 gives strongest complexation ($K_a\;of\;9.8\;{\times}\;102\;M^{-1}$).

• Journal of the Korean Chemical Society
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• v.42 no.5
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• pp.531-538
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• 1998

The ion selective membrane electrode made of calix[4]arene-based host 1 as ionophore, poly (vinyl chloride) (PVC) as matrix and dioctylsebacate (DOS) as a plasticizer was studied. The potential responses of this membrane electrode to alkali, alkaline earth and transition metal cations were investigated. Especially this membrane electrode was turned out to be affinitive for $Pb^{2+}$ in the deionized water. It was observed that the response was linear in the concentration range from $1.0 \times 10^{-1} M to 1.0 \times 10^{-6} M of Pb^{2+}$ and its slope (26.5 mV/decade) was near to the sub-Nernstian response in deionized water. Also, the potential was maintained constantly in the range of pH $4.00 \sim 12.00$, which supports the potential usage as $Pb^{2+}$ affinitive electrode in the deionized water.

• Bulletin of the Korean Chemical Society
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• v.25 no.6
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• pp.847-851
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• 2004

The complexation characteristics of tetramethyl (1) and tetraethyl esters (2) of p-tert-butylcalix[4]arene with alkali metal cations have been investigated by ab initio calculation. The structures of endo- or exocomplexation of the hosts in cone conformation with alkali metal ions have been optimized using HF/6-31G method followed by B3LYP/6-31G(d) single point calculation. B3LYP/6-31G(d) calculations suggest that exo-complexation efficiencies of sodium ion to the cavity of lower rim of hosts 1 and 2 are 27.1 and 25.8 kcal/mol better than that of potassium ion, respectively. The exo-complexation efficiencies of potassium ion to the cavity of lower rim of hosts 1 and 2 are 33.3 and 31.5 kcal/mol better than the endo-complexation inside the upper rim (four aromatic rings) as expected from the experimental results. B3LYP/6-31G(d) calculation of the ethyl ester 2 shows 29.5 and 30.8 kcal/mol better exo-complexation efficiency for both sodium and potassium ions than the methyl ester 1.

• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2229-2237
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• 2012

The two chelates based on calix[4]arene and thiacalix[4]arene have been synthesized and used as neutral ionophores for preparing PVC based membrane sensor selective to $Ho^{3+}$ ion. The addition of potassium tetrakis(4-chlorophenyl)borate (KTpClPB) and various plasticizers, viz., NDPE, o-NPOE, DOP, TEP and DOS have been found to improve significantly the performance of the sensors. The best performance was obtained with the sensor no. 6 having membrane of $L_2$ with composition (w/w) ionophore (2%): KTpClPB (4%): PVC (37%): NDPE (57%). This sensor exhibits Nernatian response with slope $21.10{\pm}0.3mV/decade$ of activity in the concentration range $3.0{\times}10^{-8}-1.0{\times}10^{-2}M\;Ho^{3+}\;ion$, with a detection limit of $1.0{\times}10^{-8}M$. The proposed sensor performs satisfactorily over a wide pH range of 2.8-10, with a fast response time (5 s). The sensor was also found to work successfully in partially non-aqueous media up to 25% (v/v) content of methanol, ethanol and acetonitrile, and can be used for a period of 4 months without any significant drift in potential. The electrode was also used for the determination of $Ho^{3+}$ ions in synthetic mixtures of different ions and the determination of the arsenate ion in different water samples.

• Bulletin of the Korean Chemical Society
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• v.28 no.4
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• pp.596-600
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• 2007

The structures and energies of p-tert-butylcalix[5]crown-6-ether (1) and its alkylammonium complexes have been calculated by DFT B3LYP/6-31G(d,p) method. We have studied the binding sites of these host-guest complexes focusing on the p-tert-butylcalix[5]arene pocket (endo) or the crown-6-ether moiety (exo) of 1. The smaller alkylammonium cations have the better complexation efficiency with p-tert-butylcalix[5]crown-6- ether than the bulkier alkylammonium ions. For the sec- and tert-butylammonium ions, the hydrogen-bond distances of the exo-complexes are shorter, therefore, stronger than the endo-cases. This DFT calculated result is in parallel with the trend of the experimental association constants of the branched butylammonium ions.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.793-799
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• 2011

We report the complexation behavior of calix[4]arenemonoquinone-triacid (CTAQ), which is an electroactive and water-soluble receptor for calcium ion. UV-visible and NMR spectroscopic studies revealed that CTAQ in aqueous media forms 1:2 as well as 1:1 (metal ion:CTAQ) stoichiometric complexes with $Ca^{2+}$, $Sr^{2+}$, and $Ba^{2+}$ ions. The nonlinear fitting of titration curves based on UV-visible absorption spectra showed that the binding constants of CTAQ for $Ca^{2+}$ ion are 4 $({\pm}2){\times}10^6\;M^{-1}$ for 1:1 and 1.4 $({\pm}0.5){\times}10^{11}\;M^{-2}$ for 1:2 complex. NMR conformational studies and the titration curves corroborate that the $Ca^{2+}$:CTAQ complex in aqueous solution is not present in the form of merely 1:1 one, being consistent with UV-visible spectrophotometric results. The Monte Carlo simulation supports the presence of a stable conformer of 1:2 complexes in which a $Ca^{2+}$ ion is interposed between two CTAQs at the global minimum. This is the first model of 1:2 stoichiometric complex of calix[4]arene and alkaline earth ions in aqueous media.

• Bulletin of the Korean Chemical Society
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• v.32 no.11
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• pp.3979-3990
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• 2011

Eight ionizable nano-baskets of cone 25,26-di(carboxymethoxy)calix[4]arene-crown-3,4,5,6 were synthesized and were verified by $^1H$ and $^{13}C$ NMR spectroscopy, IR spectroscopy and elemental analysis. The competitive solvent extractions of alkali and alkaline earth metal cations were studied using such nano-baskets. The novelty of this study is including three binding units of calixarene's bowl, crown ether's ring and electron-donor ionizable moieties in a unique scaffold to assess the binding tendency towards the cations. The objective of this work is to study the extraction efficiency, selectivity and $pH_{1/2}$ of such complexes. The result of solvent extraction experiments indicated that these compounds were effective extractants of alkali and alkaline earth metal cations. Their selectivities were greatly influenced by the acidity of solution and the conformations of the calixcrown. One conformer was selective to $Na^+$ in pH ${\geq}$ 4, while the other was highly selective to $Ba^{2+}$ in pH 6 and upper.

• Bulletin of the Korean Chemical Society
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• v.27 no.5
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• pp.613-630
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• 2006

Nucleic acids are virtually omnipresent; they exist in every living being. These macromolecules constitute the most important genetic storage material: the genes. Genes are conserved throughout the evolution of all living beings; they are transmitted from the parents to their offspring. Many interdisciplinary research groups are interested in modifying nucleic acids for use in a wider variety of applications. These modified oligonucleotides are used in many diverse fields, including diagnostics, detection, and therapeutics. In this account, we summarize our research efforts related to modified nucleic acid systems. First, we discuss our syntheses of modified oligonucleotides containing fluorescent tags for use as molecular probes (molecular beacons) to detect single-nucleotide polymorphisim (SNP) in nucleic acids and to distinguish between the B and Z forms of DNA. We also describe our research efforts into oligonucleotides functionalized with steroid derivatives to enhance their cell permeability, and the synthesis of several calix[4]arene-oligonucleotide conjugates possessing the ability to form defined triplexes. In addition, we have performed systematic studies to have an understanding about the functional groups necessary for a given nucleoside to behave as an organo or hydrogelator. The aggregation properties of a number of nucleoside-based phospholipids have been examined in different solvents; some of these derivatives are potential candidates for use as nucleoside-based liposomes. Finally, we also describe our research efforts toward the preparation of isoxazole- and isoxazoline-containing nucleoside derivatives and the determination of their antiviral activities.