• 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.

• Journal of Radiopharmaceuticals and Molecular Probes
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• v.3 no.2
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• pp.116-121
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• 2017

To overcome the low reactivity and solubility of alkali metal fluorides (MFs), various types of phase transfer catalysts (PTCs) have been developed over the last decades. However, since the fluoride activated by such PTC sometimes has a strong basicity, it may cause various side reactions such as elimination reaction or hydroxylation reaction in the nucleophilic fluorination reaction. Also, they may cause separation problems in the compound purification process. In recent advanced study, various PTCs have been developed to solve these problem of conventional catalyst. In this review, we would like to introduce three kinds of novel multifunctional organic catalysts such as bis-tert-alcohol-functionalized crown-6-calix[4]arene (BACCA), easy separable pyrene-tagged ionic liquid (PIL) by reduced graphene oxide (rGO), and tri-tert-butanolamine organic catalyst.

• Journal of the Korean Chemical Society
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• v.50 no.1
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• pp.7-13
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• 2006

infrared(IR) absorption spectra were calculated for the ethyl ester of p-tert-butylcalix[4]arene (1) in the cone conformer and its alkali-metal-ion complex. The vibrational spectra were obtained by restricted Hartree-Fock (RHF) calculations with the 6-31G basis set. The characteristic vibrational frequencies of various C-O and C=O stretching motions of the complexes show that the structure of 1+K+ complex is almost of C4v symmetry compared to 1+Na+ (C2v) analogue. The theoretical results for the host molecule 1 and complex (1+Na+) were compared with the experimental results, and the calculated vibrational frequencies agree well with the features of the experimental spectra.

• 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.29 no.7
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• pp.1374-1378
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• 2008

Using DFT B3LYP/6-31+G(d,p)//B3LYP/6-31G(d,p) calculation method, stable molecular structures were optimized for the p-tert-butylcalix[4]arene functionalized at lower rim by cage-annulated crown ether (1) in two different conformers and their potassium-ion complexes. Cone conformer of free host 1 was slightly more stable than partial-cone conformer. For two different kinds of complexation mode, the potassium ion in benzene-rings (bz) pocket showed comparable complexation efficiency with the cation in cage-annulated crown-ether (cr) for the cone and partial-cone conformers of 1. The complex (1${\bullet}K^+$) in the cr-binding mode for the partial-cone conformer was more stable than the cone conformer for B3LYP/6-31G(d,p) geometry optimization. However, $1_{(cone)}{\bullet}K^+$(cr) showed lower single-point energy than the $1_{(pc)}{\bullet}K^+$(cr) for B3LYP/6- 31+G(d,p) calculation method.

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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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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• 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.

• Journal of the Korean Electrochemical Society
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• v.1 no.1
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• pp.40-44
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• 1998

The LAPS device of fast response and high sensitivity, based on electrochemical potential difference, and its system were fabricated for the precise measurement of pH changes and its characteristic were investigated. The electrostatic variation characteristics of LAPS according to the pH changes and parameters in the device were verified through a simulation using LAPS equivalent circuit model. The LAPS device and its system were fabricated on the basis of the result of simulation. The fabricated LAPS system showed linear sensitivity (about 56 mV/pH within the range of pH 2 to pH 11. In order to overcome the defect of general urea sensor (especially slow response time), urease immobilized nitrocellulose membrane was attached on the LAPS and resulted in the very fast response time, 0.29 mV/sec, 0.86 mV/sec at urea concentration of $50{\mu}g/ml,\; 500{\mu}g/ml$, respectively. And also in order to measure the uranyl ion, the uranyl ion selective sensing membrane with calix[6]arene derivative was used and its sensitivity was 25mV/concentration decade in the wide uranyl ion concentration range of $10^{-11}M\;to\;10^{-4}M$.