• Bulletin of the Korean Chemical Society
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• 제31권7호
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• pp.2031-2035
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• 2010

A triple-probe channel type chemosensor based on an $NO_2S_2$-macrocycle functionalized with phenyltricyanovinyl group was synthesized and its sensing characteristics were examined. The pink-red solution of L changed selectively to pale yellow upon addition of $Hg^{2+}$. The selective fluorometric response of L to all the tested metal ions was studied. The results showed that a large enhancement of the fluorescence of L was observed only in the case of $Hg^{2+}$. In addition, L showed large anodic shift (~ 0.3 V) for the addition of excess $Hg^{2+}$. Through above three observed results by the different techniques, we confirmed that the proposed chemosensor acts as the multiple-probe channel sensing material. The crystal structure of mercury(II) nitrate complexs of L which shows a 1-D polymer network with a formula $[Hg_2(L)_2(NO_3)_2({\mu}-NO_3)_2]_n$ was also reported.

• Bulletin of the Korean Chemical Society
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• 제34권5호
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• pp.1429-1434
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• 2013

A synthesis and cation-induced fluorescent behavior of the carbazole-attached $NO_2S_2$-macrocycle (L) is described and structurally characterized by single crystal X-ray analysis. The photoluminescence spectrum of L in 80% $CH_3CN/CH_2Cl_2$ displays a peak maximum at 431 nm (blue emission). In the metal-induced fluorometric experiment, L showed a drastic chelation-enhanced fluorescence quenching (CHEQ) effect only with $Hg^{2+}$ and $Cu^{2+}$. In ESI-mass study, a 1:1 stoichiometry for complexation of L with $Hg^{2+}$ was confirmed, suggesting the unique sensing behavior of the proposed ligand L due to the selective complexation affinity for $Hg^{2+}$. The observed results indicate that L is a promising turn-off type fluoroionophore for $Hg^{2+}$ and $Cu^{2+}$ detections. Additionally, the $Ag^+$ complex of the precursor macrocycle was prepared and its solid structure was crystallographically characterized.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3707-3710
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• 2010

A chromo/fluorogenic $NO_2S_2$-macrocycle L functionalized with nitrobenzofurazan unit as a dual-signaling probe was synthesized and structurally characterized by single crystal X-ray analysis. In a cation-induced color change experiment, L exhibited excellent $Hg^{2+}$ ion selectivity by showing the color change from orange-red to yellow. However, this hypochromic shift by $Hg^{2+}$ was observed for the weaker coordinating anion system such as ${NO_3}^-$ and ${ClO_4}^-$ ions. The observed anion effect is due to the strong coordination of anions inhibits the bond formation between $Hg^{2+}$ and the macrocyclic tert-N atom, which is sensitive to induce the color change. In the fluorometric experiment, L showed chelate-enhanced fluorescence change effect only with $Hg^{2+}$ ion, together with a change from yellow to green emission. The sensing ability for $Hg^{2+}$ with the proposed chemosensor L is due to the stable complexation with 1:1 stoichiometry (metal-to-ligand).

• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.474-477
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• 1991

The preferential transport phenomena of neutral cation-anion moieties in neutral macrocycle-facilitated emulsion liquid membrane were described in this study. Emulsion membrane systems consisting of (1) aqueous source phase containing 0.001 M M($NO_3$)$_2(M=Mn^{2+},\;Co^{2+},\;Ni^{2+},\;Cu^{2+},\;Zn^{2+},\;Sr^{2+},\;Cd^{2+},\;and\;Pb^{2+})$ (2) a toluene membrane containing 0.01 M ligand $(DBN_3O_2$, DA18C6, DT18C6, TT18C6, HT18C6) and the surfactant span 80 (sorbitan monooleate) (3% v/v) and (3) an aqueous receiving phase containing $Na_2S_2O_3$ or $NaNO_3$ were studied with respect to the disappearence of transition metal ions from the source phase as a function of time. Cation transports for various two component or three component equimolar mixture of transition metal and $Cu^{2+}$ in a emulsion membrane system incorporating macrocyclic ligand (HT18C6) as carrier were determinded. $Cu^{2+}$ was transported higher rates than the other $M^{2+}$ in the mixture solution. Equilibrium constants for cation-source phase co-anion, cation macrocycle and cation-receiving phase reagent interaction are examined as parameters for the prediction of cation transport selectivities.

• Bulletin of the Korean Chemical Society
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• 제32권5호
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• pp.1761-1764
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• 2011

• 대한화학회지
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• 제36권6호
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• pp.914-918
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• 1992

이 연구에서는 중성거대고리리간드를 운반체로 이용한 Emulsion 액체막에서 금속이온의 이동현상에 관하여 다루었다. Emulsion 막은 (1) 0.001M $M(NO_3)_2$ (M = $Mn^{2+}$, $Co^{2+}$, $Ni^{2+}$, $Cu^{2+}$, $Zn^{2+}$, $Sr^{2+}$, $Cd^{2+}$, $Pb^{2+}$)으로 된 수용액의 source phase와 (2)0.02M 거대고리리간드와 계면활성제인 span 80을 포함하는 toluene 막과 (3) $Na_2S_2O_3$ 또는 $NaNO_3$을 포함하는 receiving phase로 되어 있으며 시간에 따라 source phase로부터 금속이온들의 이동량을 연구하였다. 이성분계의 금속이온의 이동속도를 관찰하였다. 혼합용액에서의 $Cd^{2+}$이 다른 이온보다 높은 이동율을 나타내었다.

• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.525-529
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• 1991

A simple route is described for the selective functionalization of calixarene at the para positions of phenyl rings. Calix[4]arene tetraacetate 2, obtained from the treatment of calix[4]arene with acetic anhydride, undergoes Fries rearrangement to yield the diametrically para substituted p-diacetylcalix[4]arene 3 in 80% yield. The crystal and molecular strucutre has been determined by X-ray diffraction method. The crystals are orthorhombic, space group Pna21, with a = 11.121 (3), b = 10.374 (3), c = 21.690 (6) $\AA$ and Z = 4. The structure was solved by direct method and refined by full-matrix least-squares methods to final R of 0.036 for 1795 observed reflections. Each hydroxyl hydrogen atom is disordered over two positions. The macrocycle exists in the cone conformation which is determined by the strong circular intramolecular flip-flop type hydrogen bonds of phenolic OH, while crystal packing effects of the diametrically para-acetyl substituents seem to be responsible for the distortion of the cone conformation.

• 약학회지
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• 제41권5호
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• pp.554-558
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• 1997

Two alkaloidal components were isolated from the ether soluble part of the MeOH extract of the root bark of Euonymus japonica. Their structures were elucidated by the spe ctroscopic analylses as the sesquiterpene pyridine alkaloids derived from polyester sesquiterpenes which are characteristically detected in Celastraceae plants. These include macrocycle formed by two ester linkages between dihydro-${\beta}$-agarofuran nucleus and pyridinic dibasic acid(compound 1:evoninic acid, compound 2:wilfordic acid). The structure of compound $1[C_{47}H_{50}N_2O_{17},\;mp\;161{\sim}163^{circ}C$. $[{\alpha}]_D^{28}=+31.6^{\circ}$(c, 0.1 in EtOH)] was determined as novel structure named as euojaponine N, and compound $2[C_{48}H_{57}NO_{18},\;mp\;142{\sim}145^{circ}C,\;[{\alpha}_D^{27}=+27.0^{\circ}$(c, 0.1 in EtOH)] was identified as ebenifoline W-I reported from Maytenus ebenifolia.

• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.561-567
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• 1993

The twelve macrocycle (L) complexes of cadmium(II) nitrate have been synthesized: $CdL(NO_3)_2$. All the complexes have been indentified by elemental analysis, electric conductivity measurements, IR and NMR spectroscopic techniques. The molar electric conductivities of the complexes in water and acetonitrile solvent were in the range of 236.8-296.1 $cm^2{\cdot}mol^{-1}{\cdot}ohm^{-1}$ at 25$^{\circ}$C. The characteristic peaks of macrocycles affected from Cd(II) were shifted to lower frequencies as compared with uncomplexed macrocycles. A complex with 1,4,8,11-tetrakis(methylacetato)-1,4,8,11-tetraaza cyclodecane (L4) exhibited two characteristic bands such as strong stretching (1646 $cm^{-1})$, and weaker symmetric stretching band (1384 $cm^{-1})$. NMR studies indicated that all nitrogen donor atoms of macrocycles have greater affinity to cadmium(II) metal ion than do the oxygen atoms. The $^{13}$C-resonance lines of methylene groups neighboring the donor atom such as N and S were shifted to a direction of high magnetic field and the order of chemical shifts were $L_1 < L_2 < L_3 < L_6 < L_4$. Also the chemical shifts values were larger than those of methylene groups bridgeheaded in side-armed groups. This result seems due to not only the strong interaction of Cd(Ⅱ) with nitrogen donors according to the HSAB theory, but weak interaction of Cd(Ⅱ) and COO- ions or sulfur which is enhanced by the flexible methylene spacing group in side-armed groups. Thus, each additional gem-methyl pairs of L_3, L_4\;and\; L_6$ macrocycles relative to $L_1, L_2,\;and\;L_5$ leads to an large enhancement in Cd(II) affinity. ^{13}C$-NMR spectrum of the complex with $L_{12}$ (1,5,9,13-tetracyclothiacyclohexadecane-3,11-diol) reveals the presence of two sets of three resonance lines, and intensities of the each resonance line have the ratio of 1 : 2 : 2. This molecular conformation is predicted as structure of tetragonal complex to be formed by coordinating two sulfur atoms and the other two sulfur atoms which is affected by OH-groups.

• 대한화학회지
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• 제37권3호
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• pp.344-350
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• 1993

25,26,27,28-테트라아세트오키시[4]에렌·일수화물은 사방정계의 Pbca의 공간군을 갖고 있으며 a = 14.979(4), b = 15.154(4), c = 27.890(3) ${\AA}$, Z = 8, V = 6330.6 ${\AA}^{-3}$, D$_c$ = 1.28 $g{\cdot}cm^{-3}$, ${\lambda}$(Mo K${\alpha}$) = 0.71069 ${\AA}$, ${\mu}$ = 0.86 cm$^{-1}$, F(000) = 2600이고, 1.0 ${\sigma}$(I)보다 큰 강도를 가진 3376갱의 관측된 회절반점에 대하여 최종 R값은 0.069이다. 직접적에 의하여 구조를 풀었으며, 계단식 대각최소자승법에 의하여 정밀화하여, 모든 C-H 결합길이 (=0.96 ${\AA}$) 및 메칠기와 메칠렌기는 이상적인 기하학적 구조에 맞추어 계산하였다. 큰 고리는 1,3 alternate conformation을 하고 있으며 메칠렌기의 평균 평면으로부터 벤젠고리는 각각 110.7, 68.4, 113.7 및 60.8$^{\circ}$를 이루고 있으며, 4개의 각 아세트오키시기는 그들 자신의 벤젠고리와 각각 68.2, 97.6, 78.9 및 71.3$^{\circ}$의 각을 만들고 있다. 반대편에 마주 위치한 벤젠고리 (1)과 (3)은 135.6$^{\circ}$, (2)과 (4)는 135.2$^{\circ}$의 상대적 각을 이루고 있다. 물분자는 메칠렌기를 포한하고 잇는 큰고리의 평면의 z-좌표와 거의 같은 높이에 있으며, 분자내의 O(8)부터 2.942(5) ${\AA}$, 타분자의 O(2)(1/2-x, -1/2＋y, z)부터는 2.901 ${\AA}$의 거리에 있으며, 가장 짧은 분자간 거리는 O(4) 와 C(3)(1/2＋x, 1/2-y,-z)의 3.193 ${\AA}$이다.