• 환경위생공학
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• 제21권3호
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• pp.52-60
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• 2006

The ion exchange resins have been synthesized from chlormethyl styrene-1,4-divinylbenzene(DVB) with 1%, 2%, and 20%-crosslinking and macrocyclic ligand of cryptand 21 by copolymerization method and the adsorption characteristics of uranium(VI), copper(II) and dysprosium(III) metallic ions have been investigated in various experimental conditions. The synthesis of these resins was confirmed by content of chlorine, element analysis, and IR-spectrum. The effects of pH, equilibrium time, dielectric constant of solvent and crosslink on adsorption of metallic ions 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 ethanol was in increasing order uranium$(UO^{2+}_2)\;>\;copper(Cu^{2+})\;>\;dysprosium(Dy^{3+})$ ion. The adsorption was in order of 1%, 2%, and 20% 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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• 제24권11호
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• pp.1585-1589
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• 2003

A PVC-based membrane electrode for thallium(I) ions based on 1,21,23,25-tetramethyl-2,20: 3,19-dimetheno-[H, 2] H, 23H, 25H-bis-[1,3] dioxocino[5,4-i:5',4'-i] benzo [1,2-d: 5.4-d'] bis [1,3] benzodioxocin(II) has been prepared. The electrode displays a linear dynamic range of $1.0{\times}10^{-1}-1.0{\times}10^{-5}$ M, with a Nernstian slope of $59.8{\pm}0.2\;mV\;{decad^-1}$, and a detection limit $5.0{\times}10^{-6}$ M. It has a very fast response time of<10 s and can be used for at least ten weeks without a considerable divergence in potentials. This electrode revealed comparatively good selectivity with respect to alkali, alkaline earth, and some transition and heavy metal ions and was effective in a pH range of 2.0-10.0. It was used as an indicator electrode in potentiometric titration of thallium ion with sulfide ion.

• 대한화학회지
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• 제34권4호
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• pp.345-351
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• 1990

역상 고성능 액체 크로마토그래피에 Cu (Ⅱ)-L-Proline 킬레이트를 이동상에 첨가하여 답실아미노산(DABS-AA)을 광학분리했다. DABS-아미노산에 관한 머무름거동을 이동상으로 아세토니트릴, 착물 및 완충용액의 농도와 pH에 따라 연구 검토했다. DABS-아미노산의 광학분리선택성은 이동상의 pH와 킬레이트의 농도가 증가하면 증가하나 유기용매의 농도에 따라 감소한다. 완충액의 농도에는 무관하다. DABS-아미노산과 구리 착물간의 리간드 교환반응의 입체효과에 따른 시스-트란스 생성으로 분리메카니즘을 설명할 수 있다.

• Bulletin of the Korean Chemical Society
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• 제28권4호
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• pp.538-542
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• 2007

Polymeric electrodes for lead ion based on N,N'-bis-thiophen-2-ylmethylene-pyridine-2,6-diamine as an ion carrier were prepared. The membrane electrode (m-3) containing o-NPOE as a plasticizer and 50 mol% additive of ionophore gives an excellent Nernstian response (29.59 mV/decade) and the limit of detection of ?log a (M) = 5.74 to Pb2+ in Pb(NO3)2 solution at room temperature. The prepared electrode provided good sensitivity and outstanding selectivity and response for Pb2+ over a wide variety of other metal ions in pH 7.0 buffer solutions. The good sensitivity and selectivity towards lead ion are attributed to the strong complexation of lead ion to N,N'-bis-thiophen-2-ylmethylene-pyridine-2,6-diamine which has geometrically the proper cavity to coordinate to the ligand.

• 대한화학회지
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• 제36권4호
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• pp.558-564
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• 1992

여러 가지 치환기를 가지는 망간 포피린착물을 촉매로 사용하여 CH$_2$Cl$_2$ 용매하에서 styrene과 NaOCl간의 반응에 대한 수율을 구하였다. ortho 위치에 치환기를 가지는 망간 포피린 착물과 전자받게성의 치환기를 가지는 망간 포피린착물일 때 반응속도와 에폭사이드에 대한 선택성이 증가했다. 또한 망간 포피린착물에 축상 리간드로서 이미다졸을 도입할 때 반응속도와 에폭사이드에 대한 선택성이 증가했다. Michealis-Menten식을 이용한 반응속도론적 연구에 의하면 착물의 촉매능에 더 큰 영향을 주는 요소는 $K_m$ 임을 알았다. $K_m$ 값이 작을수록 더 큰 결합친화도를 가진다. 이론적인 연구로 EHMO계산에 의해 나온 결과와 실험에 의해 나온 결과는 좋은 일치를 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제34권9호
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• pp.2577-2582
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• 2013

A novel stick-shaped portable sensing device featuring a microhole array interface between the polyvinylchloride-2-nitrophenyloctylether (PVC-NPOE) gel and water phase was developed for in-situ sensing of perchlorate ions in real water samples. Perchlorate sensitive sensing responses were obtained based on measuring the current changes with respect to the assisted transfer reaction of perchlorate ions by a perchlorate selective ligand namely, bis(dibenzoylmethanato)Ni(II) (Ni(DBM)2) across the polarized microhole array interface. Cyclic voltammetry was used to characterize the assisted transfer reaction of perchlorate ions by the $Ni(DBM)_2$ ligand when using the portable sensing device. The current response for the transfer of perchlorate anions by $Ni(DBM)_2$ across the micro-water/gel interface linearly increased as a function of the perchlorate ion concentration. The technique of differential pulse stripping voltammetry was also utilized to improve the sensitivity of the perchlorate anion detection down to 10 ppb. This was acquired by preconcentrating perchlorate anions in the gel layer by means of holding the ion transfer potential at 0 mV (vs. Ag/AgCl) for 30 s followed by stripping the complexed perchlorate ion with the ligand. The effect of various potential interfering anions on the perchlorate sensor was also investigated and showed an excellent selectivity over $Br^-$, $NO_2{^-}$, $NO_3{^-}$, $CO{_3}^{2^-}$, $CH_3COO^-$ and $SO{_4}^{2^-}$ ions. As a final demonstration, some regional water samples from the Sincheon river in Daegu city were analyzed and the data was verified with that of ion chromatography (IC) analysis from one of the Korean-certified water quality evaluation centers.

• 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.

• 대한화학회지
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• 제40권6호
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• pp.445-452
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• 1996

Hydridonitrosyl complex의 촉매 활용 가능성과 반응 mechanism을 조사하기 위하여 $RuH(NO)(PPh_3)_3$와 RuH(NO)(etp)에 의한 ketone과 aldehyde의 수소화 반응을 연구하였다. 이 촉매들은 ketone과 aldehyde의 수소화 반응에 대하여 촉매 활성을 보이고 있으며, 활성은 기질의 입체장애 및 전자적 요인에 의존하고 있다. 즉, 입체 장애가 적을수록 촉매의 활성이 증가하며, 전자적 요인의 효과는 ketone의 경우 carbonyl carbon의 부분양전하의 양이 증가할수록, aldehyde의 경우는 carbonyl group의 double bond character가 강할수록 반응성이 증대되는 방향으로 나타나고 있다. 이러한 결과는 ketone과 aldehyde의 반응 mechanism이 다름을 반영하고 있다. 한편, RuH(NO)(etp)와 과잉의 $PPh_3$ 존재하에서 $RuH(NO)(PPh_3)_3$가 촉매 활성을 보이고 있음은 NO ligand의 결합방식의 변화를 통한 반응경로가 존재함을 확인하고 있다. 과잉의 $PPh_3$는 촉매와의 몰비가 변함에 따라 작용의 변화(ligand의 해리 방지 ${\rightarrow}$ 염기 ${\rightarrow}$ ligand)가 나타나며 촉매 활성에 영향을 미치고 있다. 이러한 결과를 이해하기 위하여 각 촉매에 대한 반응 mechanism을 제시하였다. 한편, 동일한 기질에 있어서 RuH(NO)(etp)의 활성은 항상 $RuH(NO)(PPh_3)_3$에 비하여 낮았으며 이는 주로 착물의 구조차이에 기인한 것으로 해석되며, 경쟁반응에 있어서는 olefin의 수소화 반응이 carbonyl group의 수소화 반응보다 선택적으로 진행되고 있다.

• 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.

• 통합자연과학논문집
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• 제6권3호
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• pp.151-157
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• 2013

The ion exchange resins were synthesized from 1-aza-18-crown-6 macrocyclic ligand attached to styrene (2th petroleum in 4th class hazardous material) divinylbenzene (DVB) copolymer with crosslinks of 1%, 6%, and 15% by substitution reaction. These synthetic resins were confirmed by chlorine content, elementary analysis, surface area, and IR-spectrum. The object of this study was to seperate the metal ion absorbed in reinforcement water fire extinguishing agent. As the results of the effects of pH, equilibrium arrival time, and crosslink of synthetic resin on metal ion adsorption for resin adsorbent, the metal ions were showed high adsorption at pH 3 or over and adsorption equilibrium of metal ions was about 2 hours. In addition, adsorption selectivity for the resin in water was the order of Al (III) > Ni (II) > Sm (III) ions, adsorbability of the metal ions was in the crosslinks order of 1%, 6%, and 15%.