• Bulletin of the Korean Chemical Society
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• 제18권9호
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• pp.1014-1017
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• 1997

1,3-Dipropyloxycalix[4]arene dibenzocrown ethers were synthesized in the fixed 1,3-alternate conformation by the reaction of 1,3-dipropyloxycalix[4]arenes with a dibenzo dimesylates. Complexation toward alkali metal ions using ISEs showed a high cesium selectivity. Conformational flexibility of the corresponding 1,3-alternate calixcrown ether (4) with respect to the NMR time scale is found to depend on the temperature and polarity of the NMR solvent.

• Bulletin of the Korean Chemical Society
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• 제28권4호
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• pp.682-684
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• 2007

• Bulletin of the Korean Chemical Society
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• 제15권9호
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• pp.791-795
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• 1994

1,3-Dimethyl and dipropyl ethers of p-t-butylcalix[4]arene and calix[4]arenes have been converted to the corresponding diesters, acetate and propionate, and their conformations are inferred based on the $^1H$ and $^{13}C$ NMR spectra. The presence of t-butyl groups is effective in maintaining the cone conformation on derivatization.

• 대한화학회지
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• 제42권5호
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• pp.531-538
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• 1998

캘릭스[4]아렌 유도체(호스트 1)를 이온선택성 물질로 사용하고, 지지체로 poly(vinyl chloride)(PVC), 가소제로 dioctylsebacate(DOS)를 사용하여 이온 선택성 막전극을 제작하였다. 호스트 1 막전극을 지시전극으로 사용하여 알칼리, 알칼리 토금속 양이온 그리고 전이 금속 양이온에 대하여 각각의 감응전위를 측정한 결과, 바탕 전해질이 탈 이온수 일때 $Pb^{2+}$의 감응전위가 $1.0 \times10^-6M~1.0 \times 10^-1 M$ 농도 범위에서 이론적인 Nernstian 감응전위 기울기에 가까운 26.5mV/decade를 보여 주었다. 또한 pH 영향을 조사해 본 결과 pH 4.00∼12.00 범위에서 감응전위값이 일정하게 유지되었다. 따라서 본 연구에서 제작된 호스트 1 막전극은 탈이온수 상에서 $Pb^{2+}$에 친화성을 갖는 이온 막전극으로 나타났다.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1675-1677
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• 2009

• Bulletin of the Korean Chemical Society
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• 제33권7호
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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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• 제25권6호
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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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• 제32권3호
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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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• 제23권6호
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• pp.891-896
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• 2002

The structures and energies of p-tert-butylcalix[4]crown-6-ether(1) in various conformers and their alkyl ammonium complexes have been calculated by ab initio HF/6-31G quantum mechanics method. We have tried to obtain the relative affinity of partial-cone and 1,3-alternate conformers of 1 for alkyl ammonium guests by comparison with its cone-shaped analogue. We have also calculated the relative complexation efficiency of these host-guest complexes focusing on the binding sites of $crown-\sigma-enther$ moiety or benzene-rings pocket of the host molecule 1. These calculations revealed that the crown moiey has better complexation efficiency than upper rim part of calyx[4]arene that is in similar trend to the cone-shaped complexes.

• Bulletin of the Korean Chemical Society
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• 제22권11호
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• pp.1248-1254
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• 2001

The conformations and energies of p-tert-butylcalix[4]crown-6-ether (1) and its alkyl ammonium complexes have been calculated by ab initio HF/6-31G quantum mechanics method. The cone conformation was found to be most stable for free host 1. We hav e determined the binding site of these host-guest complexes focusing on the crown-6-ether or p-tert-butylcalix[4]arene pocket of the cone conformation of host molecule 1. The primary binding site of host 1 for the recognition of alkyl ammonium guests was confirmed to be the central part of the crown moiety of cone conformation. The complexation energy calculations revealed that the ammonium cation without alkyl group showed the highest complexation efficiency when combined with host 1, that is in satisfactory agreement with the experimental results.