• 대한화학회지
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• 제29권2호
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• pp.151-157
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• 1985

클로로포름 용액에서 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane(cryptand 22), 1,7-diaza-4,10,13-trioxacyclopentadecane(cryptand 21), 1,12,15-triaza-5,8-dioxa-3,4:9,10-dibenzocycloheptadecane ($N_3O_2$) 및 1,12-diaza-5,8-dioxa-3,4:9,10-dibenzocyclotetradecane ($N_2O_2$)의 분자간 수소결합을 $^1H$-nmr 분광법으로 여러 온도에서 조사하였다. 묽은 용액에서 이 화합물들은 -NH기를 통한 수소결합에 의하여 이합체를 형성한다. 수소결합형성에 대한 평형상수 값의 크기는 cryptand 22 > cryptand 21 > $N_3O_2$ > $N_2O_2$의 순위이었다. 이 평형에는 분자구조의 대칭성과 분자내의 -NH기의 수와 위치가 영향을 미치고 있었다.

• 대한화학회지
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• 제32권3호
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• pp.233-242
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• 1988

디메틸술폭시드 용매 중에서 아직 밝혀진 바 없는 불포화계 $N_2O_2$형 거대고리 리간드들을 포함한 우라늄(VI)과 네오디움(III)착물, 그리고 cryptand 222와 DBC 거대고리 리간드를 가지는 네오디움(III)과 우라늄(VI)착물에 대한 직류폴라로그래프적 거동을 조사하였다. 직류폴라로그래피에 의하여 리간드와 착물의 산화 환원성, 가역성, 환원과정에 관여하는 전자수 및 산첨가에 따른 영향 및 산화-환원전극반응의 메카니즘을 알아 보았다. 그리고 착물들의 안정도 상수와 조성비를 알아보았다. immine계 거대고리 리간드를 가지는 네오디움(III)착물의 환원파는 나타나지 않았으나, 우라늄(VI)착물은 6전자 3단계 환원파를 DBC를 가지는 우라늄(VI)착물은 2전자 2단계 환원파를, 그리고 cryptand 222와 DBC를 가지는 네오디움(III)착물은 1전자 1단계 환원파를 각각 나타내었으며 이들 착물들은 확산지배적이며 가역성은 비교적 좋았다. uranyl(II)금속 착이온의 제 1,2단계 환원파는 1전자 환원반응이며 제 3단계 환원파에서는 4전자 환원반응, 그리고 neodymium(III)착물은 1전자 1단계 환원과정을 가진다. DBC와 imine계 거대고리 리간드를 가지는 우라늄(VI)착물은 pH=7.0이상에서, cryptand 222와 DBC를 리간드로 하는 네오디움(III)착물은 pH=4.0 이상에서 안정한 착물을 형성한다. imine계 거대고리 리간드를 가지는 $UO_2\;^{2+}$착물의 안정도 상수값은 $7.008{\sim}7.273$이라는 새로운 안정도 상수값들을 얻었고 이 값들은 Odien-Ntn > Trans Otn-Ntn = Cis Otn-Ntn > Oen-Ntn 순이었다. 그리고 $UO_2(II)$-cryptand 222 및 Nd(III)-DBC 착물의 안정도 상수값은 7.614, 12.669, 4.223이었고 DBC리간드 착물에서는 $UO_2\;^{2+}$착물의 안정도 상수값이 $Nd^{3+}$의 그것보다 크며 $Nd^{3+}-cryptand\;222$ 착물의 안정도 상수가 가장 크다.

• 환경위생공학
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• 제20권4호통권58호
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• pp.38-44
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• 2005

Cryptand resins were synthesized with 1-aza-15-crown-5 macrocyclic ligand attached to styrene divinylbenzene (DVB) copolymer with crosslink of $1\%,\;2\%,\;5\%\;and\;10\%$ by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time, dielectric constant of solvent and crosslink on adsorption of uranium$(UO_2^{2+})$ ion were investigated. The uranium ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in ethanol was in increasing order uranium$(UO_2^{2+})$ > zinc$(Zn^{2+})$ > samarium$(Sm^{3+})$ ion. The adsorption was in order of $1\%>2\%>5\%>10\%$ crosslink resin and adsorption of resin decreased in proportion to order of dielectric constant of solvents.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.645-651
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• 2005

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.130-137
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• 1991

The following new cryptand 221 complexes of lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate have been synthesized: $(Ln(C_{16}H_{32}N_2O_5)(H_2O)_2(NO_3)_3\ and \((UO_2)_2(C_{16}H_{32}N_2O_5)(H_2O)_4(NO_3)_4$. These complexes have been identified by elemental analysis, moisture titration, conductivity measurements and various spectroscopic techniques. The proton and carbon-13 NMR as well as calorimetric measurements were used to study the interaction of cryptand 221 with La(Ⅲ), Pr(Ⅲ ), Ho(Ⅲ) and $UO_2(Ⅱ)$ ions in nonaqueous solvents. The bands of metal-oxygen atoms, metal-nitrogen atoms and O-U-O in the IR spectra shift upon complexation to lower frequencies, and the vibrational spectra ({\delta}NMN$) of metal-amide complexes in the crystalline state exhibit lattice vibrations below 300 $cm^{-1}$. The NMR spectra of the lanthanides(Ⅲ) and dioxouranium(Ⅵ) nitrate complexes in nonaqueous solvents are quite different, indicating that the ligand exists in different conformation, and also the $^1H$ and $^{13}C-NMR$ studies indicated that the nitrogen atom of the ring has greater affinity to metal ions than does the oxygen atom, and the planalities of the ring are lost by complexation with metal ions. Calorimetric measurements show that cryptand 221 forms more stable complexes with $La^{3+}$ and $Pr^{3+}$ ions than with $UO^{22+}$ ion, and $La^{3+}/Pr^{3+}$ and $UO^{22+}/Pr^{3+}$ selectivity depends on the solvents. These changes on the stabilities are dependent on the basicity of the ligand and the size of the metal ions. The absorption band (230-260 nm) of the complex which arises from the direct interaction of macrocyclic donor atoms with the metal ion is due to n-{\delta}*$ transition and also that (640-675 nm) of $UO^{22+}$-cryptand 221 complex, which arises from interaction between two-dioxouranium(Ⅵ) ions in being out of cavity of the ligand ring is due to d-d* transition.

• 환경위생공학
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• 제11권1호
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• pp.17-25
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• 1996

Resins with cryptand 22 macrocyclic ligand attached to chloromethylated styrene-1,4-divinylbenzene by substitution reaction were prepared and the effect of pH, metal concentration and cross-linkage of the matrix on the adsorption for $UO_2^{2+}$, $Cd^{2+}$ and $Sm^{3+}$ was investigated. The metal ion was not adsorbed on the resins pH range below 3 but above pH 4 fast adsorption behavior was showed. The resin selectivity determined in ethanol matrix was in increasing order $UO_2^{2+}{\;}>Cd^{2+}{\;}Sm^{3+}$. In addition, these metal ion could be separated on the column packed with 1% crosslinked resin by pH 2.5 $HNO_3$ as an eluent.

• 분석과학
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• 제17권2호
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• pp.91-97
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• 2004

1%, 2%, 5% 및 10%의 가교도를 가진 스틸렌 디비닐벤젠 공중합체에 1-aza-15-crown-5 거대고리 리간드를 치환반응으로 결합시켜 cryptand 이온교환 수지들을 합성하였다. 이들 수지의 합성은 염소 함량과 원소 분석 그리고 IR-스펙트럼으로 확인하였다. 우라늄 ($UO{_2}^{2+}$) 이온의 흡착에 미치는 pH, 시간, 수지의 가교도 그리고 용매의 유전상수에 따른 영향들을 조사하였다. 우라늄 이온은 pH 3 이상에서 큰 흡착율을 보였으며, 금속 이온들의 흡착 평형은 2시간 정도였다. 한편, 에탄올 용매에서 수지에 대한 흡착 선택성은 우라늄 ($UO{_2}^{2+}$), 마그네슘 ($Mg^{2+}$), 네오디뮴 ($Nd^{3+}$) 이온이었고, 우라늄 이온의 흡착력은 1%, 2%, 5% 및 10%의 가교도순 이었으며, 용매의 유전상수 크기에 반비례하였다.

• 환경위생공학
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• 제18권2호
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• pp.9-15
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• 2003

Resins have been synthesized from chlormethyl styrene 1,4- divinylbenzene(DVB) with 1%, 4%, and 20%-crosslinked and macrocyclic ligand of cryptand type by copolymerization method and the adsorption of uranium(VI), nickel(II) and lutetium(III) ions have been investigated in various experimental conditions. The correlation between the adsorption characteristics of rare earths and transition metal on the resins and stability constants of complexes with macrocyclic ligand have been examined. The uranium ion was not adsorbed on the resins below pH 2.0, but the power of adsorption of uranium ion increased rapidly above pH 3.0. The adsorption power was in the order of 1%, 4% and 20%-crosslinked resin, but adsorptive characteristics of resins decreased in proportion to the order of dielectric constants of solvents.

• 통합자연과학논문집
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• 제10권4호
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• pp.225-231
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• 2017

Cryptand resins were synthesized by mixing 1-aza-18-crown-6 macrocyclic ligand with styrene divinylbenzene copolymer having 1%, 2%, 5%, and 10% crosslink by a substitution reaction. These synthetic resins were confirmed by chlorine content, elementary analysis, SEM, surface area, and IR-spectrum. As the results of the effects of pH, crosslink of synthetic resin, and dielectric constant of a solvent on uranium ion adsorption for resin adsorbent, the uranium ion showed high adsorption at pH 3 or over. Adsorption selectivity for the resin in methanol solvent was the order of uranium ($UO_2{^{2+}}$) > calcium ($Ca^{2+}$) > neodymium ($Nd^{3+}$) ion, adsorbability of the uranium ion was the crosslink in order of 1%, 2%, 5%, and 10% and it was increased with the lower dielectric constant.

• 환경위생공학
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• 제23권1호
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• pp.57-65
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• 2008

Resins were synthesized with 1-aza-15-crown-5 macrocyclic ligand attached to styrene(dangerous matter) divinylbenzene(DVB) copolymer with crosslink of 1, 2, 6 and 15% by substitution reaction. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, time and crosslink on adsorption of metal ion　from water fire extinguishing agent by the synthetic resin adsorbent were investigated. The metal ion was showed fast adsorption on the resins above pH 3. The optimum equilibrium time for adsorption of metallic ions was about two hours. The adsorption selectivity determined in water was in increasing order of $Mg^{2+}>Al^{3+}>Pb^{2+}$. The adsorption was in the order of 1, 2, 6, and 15% crosslink resin.