• 대한화학회지
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• 제20권6호
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• pp.441-447
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• 1976

여러가지 양이온이 교환된 silicate 상에 pyridine, tertiary butylamine, ethylenediamine을 흡착시켜 IR spectra를 4000 ∼ 1200 $cm^{-1}$의 범위에서 그리고 여러 다른 탈기온도에서 얻었다. 이 결과 protonic 산 자리와 aprotonic 산 자리를 구별할 수 있었으며 양이온이 교환된 모든 silicate는 Bronsted 산과 Lewis 산을 모두 나타내었다. 그리고$ Na^+$이온이 교환된 silicate가 adsorbate와의 반응성이 가장 적게 나타났다. Tertiary butylamine의 band intensity의 상대적인 비는 교환된 양이온의 polarizing power와 비례하고 두개의 amino group을 가지고 있는 ethylenediamine은 tertiary butylamine에 비해서 silicate 표면으로부터 쉽게 탈착되지 않았으며 또한 Lewis 산 자리와 coordination bond를 이루는 경우와 Bronsted 산 자리와 $NH3^+$ 종을 만드는 경우외에 migrating proton을 떼어 냄으로 말미암아 표면산소와의 수소결합을 이루는 경우가 조사되었다.

• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.269-273
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• 2003

The synthesis and properties of 2,13-bis(3'-pyridylmethyl) $(L^3)$, 2,13-bis(4'-pyridylmethyl) $(L^4)$, and 2,13-bis(phenylmethyl) $(L^5)$ derivatives of 5,16-dimethyl-2,6,13,17-tetraazatrcyclo$[16.4.0.^{1.18}0^{7.12}]$docosane are reported. The 3- or 4-pyridylmethyl groups of $[ML^3](ClO_4)_2\;or\;[ML^4](ClO_4)_2$ (M = Ni(Ⅱ) or Cu(Ⅱ)) are not involved in coordination, and the coordination geometry (square-planar) and ligand field strength of the complexes are quite similar to those of $[ML^5](ClO_4)_2$, bearing two phenylmethyl pendant arms. However, the complex formation reactions of $L^3\;and\;L^4$ are strongly influenced by the pyridyl groups, which can interact with a proton or metal ion outside the macrocyclic ring. The macrocycle $L^5$ exhibits a high copper(Ⅱ) ion selectivity against nickel(Ⅱ) ion; the ligand readily reacts with copper(Ⅱ) ion to form $[CuL^5]^{2+}$ but does not react with hydrated nickel(Ⅱ) ion in methanol solutions. On the other hand, $L^3\;and\;L^4$ form their copper(Ⅱ) and nickel(Ⅱ) complexes under a similar condition, without showing any considerable metal ion selectivity. The ligands $L^3\;and\;L^4$ react with copper(Ⅱ) ion more rapidly than does $L^5$ at pH 6.4. At pH 5.0, however, the reaction rate of the former macrocycles is slower than that of the latter. The effects of the 3- or 4-pyridylmethyl pendant arms on the complex formation reaction of $L^3\;and\;L^4$ are discussed.

• 한국자기공명학회논문지
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• 제9권2호
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• pp.138-154
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• 2005

Vanadium-incorporated aluminophosphate molecular sieve $VO^{2+}-SAPO-5$ was studied by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies to determine the vanadium structure and interaction with various adsorbate molecules. It was found that the main species at low concentration of vanadium is a monomeric vanadium units in square pyramidal or distorted octahedral coordination, both in oxidation state (IV) for the calcined hydrated material and in oxidation state (V) for the calcined material. After calcinations in $O_2$ and exposure to moisture, only species A is observed with reduced intensities. It is suggested as a $VO(H_2O)_3^{2+}$ complex coordinated to two framework oxygen bonded aluminum. When calcined, hydrated $VO^{2+}-}SAPO-5$ is dehydrated at elevated temperature, a species loses its water ligands and transforms to $VO^{2+}$ ions coordinated to two framework oxygens (species B). Species B reduces its intensity, significantly after treatment with $O_2\;at\;600^{\circ}C$ for 5 h, thus suggesting oxidation of $V^{4+}\;to\;V^{5+}$. When dehydrated $VO^{2+}-SAPO-5$ contacts with $D_2O$ at room temperature, the EPR signal of species A is observed. Thus species assumed as a $VO^{2+}(O_f)_2(D_2O)_3$, by considering two framework oxygens. Adsorption of deuterated ethanol, propanol on dehydrated $VO^{2+}_{-}SAPO-5$ result in another new vanadium species E and F, respectively, which are identified as a $VO^{2+}-(CH_3CH_2OD)_3,\;VO^{2+}-(CH_3CH_2CH_2OD)_2$ complex. When deuterated benzene is adsorbed on dehydrated $VO^{2+}-SAPO-5$, another new vanadium species G, identified as a $VO^{2+}-(C_6D_6)$ is observed. Possible coordination geometries of these various complexes are discussed.

• Macromolecular Research
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• 제14권2호
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• pp.199-204
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• 2006

Remarkably high and stable separation performance for olefin/paraffin mixtures was previously reported by facilitated olefin transport through ${\pi}$-complex membranes consisting of silver ions dissolved in poly(hexamethylenevinylene) (PHMV). In this study, the ${\pi}$-complex formation of $AgBF_4,\;AgClO_4\;and\;AgCF_{3}SO_3$ with PHMV and their ionic interactions were investigated. FT-Raman spectroscopy showed that the C=C stretching bands of PHMV shifted to a lower frequency upon incorporation of silver salt, but the degree of peak shift depended on the counter-anions of salt due to different complexation strengths. The symmetric stretching modes of anions indicated the presence of only free ions up to [C=C]:[Ag]=1:1, demonstrating the unusually high solubility of silver salt in PHMV. Above the solubility limit, the ion pairs and higher-order ionic aggregates started to form. The coordination number of silver ion for C=C of PHMV was in the order $AgBF_4$ > $AgClO_4$ > $AgCF_{3}SO_3$, but became similar at [C=C]:[Ag]=1:1. The different coordination number was interpreted in terms of the different transient crosslinks of silver cations in the complex, which may be related to both the interaction strength of the polymer/silver ion and the bulkiness of the counteranion.

• Bulletin of the Korean Chemical Society
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• 제30권4호
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• pp.803-809
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• 2009

Notable blue shifts of the ν2 $C{\equiv}N$ stretching, $_{v4}$ C-C stretching and $_{v8}$ CCN deformation bands of $CD_3CN$ are observed upon solvation of $InCl_3$, resulting from the donor-acceptor interaction. The Raman spectrum in the $_{v2}$ region shows further details; at least two new bands emerge on the blue side of the $_{v2}$ band of free $CD_3CN$, whose relative intensities vary with concentration, suggesting that there exist at least two different cationic species in the solution. The strong hydrogen bonds formed between the methyl group and ${InCl_4}^-$ result in a large band appearing on the red side of the ν1 $CD_3$ symmetric stretching band. The solvation number of $InCl_3$, determined from the Raman intensities of the $C{\equiv}N$ stretching bands for free and coordinated $CD_3CN$, increases from $\sim$1.5 to $\sim$1.8 with decreasing concentration.

• 한국환경보건학회지
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• 제44권6호
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• pp.515-523
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• 2018

Objectives: Based on the results of a chemical substance emissions survey, we investigated characteristics of chemical emissions in industrial complexes and used them as basic data for chemical management. Methods: The emissions and characteristics of chemicals by major industrial complexes from 2011 to 2015 were analyzed using the Pollutant Release and Transfer Register homepage. To understand the status of chemical accidents for major chemicals emitted from the industrial complexes, the Chemistry Safety Clearing-house system of the National Institute of Chemical Safety was used. Results: Emissions from the top five industrial complexes accounted for about 30% of total chemical emissions. The chemical emission was the highest in the order of Ulsan Mipo Industrial Complex and Okpo Industrial Complex. The main chemicals emitted were xylene, ethylbenzene, ethyl acetate, toluene, dichloromethane, and others. Carcinogen emissions differed by industrial complex, but ethylbenzene and dichloromethane were the major chemicals for this type of emissions. Conclusion: Recently, the use and emission of chemicals have been continuously increasing. A chemical management plan should be prepared considering the characteristics of industrial complexes and chemical substance emissions.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2803-2808
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• 2014

High potential and fast electron transfer of a cathode mediator are significant factors for improving the performance of biofuel cells. This paper reports the first synthesis of a cathode redox polymer that is a coordination complex of poly (acrylic acid-vinylpyridine-acryl amide) (PAA-PVP-PAA) and [Os(4,4'-dicarboxylic acid-2,2'-bipyridine)$_2Cl_2]^{/+}$ ($E^{\circ}=0.48V$ versus Ag/AgCl). Bilirubin oxidase can be easily incorporated into this polymer matrix, which carried out the four-electron oxygen under typical physiological conditions (pH 7.2, 0.14 M NaCl, and $37^{\circ}C$). This new polymer showed an approximately 0.1 V higher redox potential than existing cathode mediators such as PAA-PVI-$[Os(dCl-bpy)_2Cl]^{+/2+}$. In addition, we suggest increasing the polymer solubility with two hydrophilic groups present in the polymer skeleton to further improve fast electron transfer within the active sites of the enzyme. The maximum power density achieved was 60% higher than that of PAA-PVI-$[Os(dCl-bpy)_2Cl]^{+/2+}$. Furthermore, high current density and electrode stability were confirmed for this osmium polymer, which makes it a promising candidate for high-efficiency biofuel cells.

• Bulletin of the Korean Chemical Society
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• 제25권7호
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• pp.977-982
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• 2004

The reaction of $cis-[Cr([14]-decane)(OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = benzoate(bz) or chlorobenzoate(cbz)} leads to a new compound $[Cr([14]-decane)(bz)_2]ClO_4$ or $[Cr([14]-decane)(cbz)_2]ClO_4$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. The crystal structure of $[Cr([14]-decane)(cbz)_2]^+$ was determined. The complex shows a distorted octahedral coordination environment with the macrocycle adopting a folded cis-V conformation. The angle $N_{axial}-Cr-N_{axial}$ deviates by $14.5^{\circ}$ from the ideal value of $180^{\circ}$for a perfect octahedron. The bond angle cis-O-Cr-O between the Cr(III) ion and the two carboxylate oxygen atoms of the monodentate p-chlorobenzoate ligands is close to 90$^{\circ}$. The FAB mass spectra of the $cis-[Cr([14]-decane)(La)_2]ClO_4$ display peaks due to the molecular ions $[Cr([14]-decane)(bz)_2-H]^\;,\;[Cr([14]-decane)(cbz)_2-2H]^$ at m/z 578, 646, respectively.

• 한국자기공명학회논문지
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• 제10권1호
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• pp.115-125
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• 2006

Hippuryl-L-histidyl-L-leucine(HHL) is widely used as a substrate of angiotensin converting enzyme(ACE) cleaving the neurotransmitter angiotensin(I) to the octapeptide angiotensin(II). The structure of the substrate molecules should provide information regarding the geometric requirements of the ACE active site. For the purpose of determination of in vivo reaction, metallo(Cu, Zn)-HHL complexes were synthesized and the degree of complex formation were identified by MALDITOF, ESI mass spectrometric analysis. Tn addition, the pH-dependent species distribution curves were obtained by potentiometric titration. Nitrogen atoms of imidazole ring and oxygen atom of caboxylate groups in the peptide chain were observed to be participated in the metal complex formation. After purification of complexes further structural characterization were made by utilizing UV-Vis, electrochemical methods and NMR. Complete NMR signal assignments were carried out by using 2D-spectrum techniques COSY, TOCSY, NOESY, HETCOR. A complex that two imidazole and carboxylate groups are asymmetrically participating to coordination mode was predicted to the solution-state structure of $Cu(II)-HHL_2$ based on $^{13}C-NMR$ signal assignment and NOE information.

• 한국결정학회지
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• 제15권1호
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• pp.5-8
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• 2004

Copper(I) bromide(CuBr) 와 pyrazine($C_4H_4N_2$, pyz)의 수열 반응으로 2차원 배위 고분자 [CuBr(pyz)] (1)이 얻어졌다. X-ray 구조 결정 결과, 고분자 1은 4.0${\times}$5.7 ${\AA}$ 크기를 갖는 직사각형 격자들을 토대로 한 2차원 그물 망 구조를 갖고 있었다. 고분자 1은 b-축 방향으로 통로(channel)를 갖고 있다.