• Bulletin of the Korean Chemical Society
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• 제32권3호
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• pp.768-778
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• 2011

Calixpyrroles and related macrocycles are non-planer synthetic anion receptors that have attracted considerable attentions in recent years. Although the synthesis of calix[4]pyrrole (known as meso-octamethylporphyrinogen) was reported more than 100 years ago, the anion binding properties were first discovered in 1996. The simple calix[4]pyrroles can be synthesized in single step in high yield by condensation of pyrrole with acetone. The compounds showed preferential binding for halide anions including fluoride, phosphate, carboxylate, and chloride in organic media. Efforts to improve the anion affinity of calix[4]pyrrole and to enhance its selectivity have led to the synthesis of a variety of new calixpyrrole derivatives. Among the various modifications, introduction of straps on one side of the calix[4]pyrroles are the most effective. Incorporation of aromatic rings other than pyrroles also exhibited interesting binding behaviour. Introduction of signalling units as part of the strapping element enable to detect the anions on chromogenic or fluorogenic fashion. Finding of the anion transport properties across the membrane and cytotoxic effects of the calix[4]pyrroles open new window for calixpyrrole-related research. The polymer-incorporated systems have also been employed as anion complexants in solvent-solvent extraction. These old, yet easy-to-make macrocycles have well advanced more recently with the discovery of the ion-pair complexation properties. In this review, the synthetic developments and anion binding properties of calixpyrroles for the last decades will be discussed and will cover the advances in calixpyrrole chemistry.

• 대한화학회지
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• 제67권4호
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• pp.222-225
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• 2023

Metallic salts of C10-18 aliphatic carboxylic acids were prepared and their scanning electron microscopic images were analyzed for the morphology dependency with the metal and the carboxylic acid. Regardless of metal ion, metal salts of dicarboxylic acids showed a high crystallinity with a fiber image (SuA-Na). The aromatic dicarboxylates also represented a morphology of a rectangular-rod or board shapes (IA-Li, IA-Ba). With Na ion, most aliphatic carboxylate (MA, PA, SA) showed a fiber-like crystallinity. However, other monovalent Li, K and multivalent Mg, especially Al ion resulted a glassy-amorphous in the metallic salts of acids (MA, PA, SA). With divalent Ba and Ca ions, the metal salt of aliphatic acids expressed a branched round cluster shape as in SA-Ca, SA-Ba. Both Li and Mg ions with a similar size showed a strong morphological similarity in the metallic salts of aliphatic acids MA, PA, SA. In the case of Na and Ca ions with a similar size (98, 106 pm), both ionic salts of stearic acid gave a branching effect for a fiber or round granular image. In the case of hydroxyl-aliphatic acids (HLA, HPA, HSA), the fiber images in HLA-Na and HSA-Na was appeared about 100 nm thicker than those of nonhydroxycarboxylates (LA-Na, SA-Na). The metallic salts of unsaturated C-18 carboxylic acids (OlA, LeA and LnA) showed an amorphous glassy image due to a kinked carbon chain.

• 접착 및 계면
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• 제16권3호
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• pp.95-100
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• 2015

본 연구에서는 실리카, 산화아연, 아연이온이 코팅된 실리카가 carboxylic acid로 변성된 스티렌계 열가소성 엘라스토머(m-TPS) film의 마찰시 표면 파괴에 미치는 영향을 관찰하였다. 일반 실리카를 첨가한 m-TPS film은 실리카 입자간의 강한 filler-filler interaction에 의한 낮은 분산성 때문에 기계적 강도, 내마모성과 마찰시 표면 파괴가 저하되는 것으로 나타났다. 산화아연 또는 아연이온이 코팅된 실리카를 첨가한 m-TPS는 zinc ion과 carboxylic acid group 간의 ionic cluster 형성을 통하여 기계적 강도, 내마모성과 마찰 시 표면 파괴가 개선되었다. Zinc ion과 carboxylic acid group 간의 ionic cluster 형성은 $1550{\sim}1650cm^{-1}$의 zinc carboxylate group stretch 피크의 FT-IR 분석 결과로 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1553-1558
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• 2009

A series of Eu(III) complexes with various neutral ligands (2,2’:6’,2"-terpyridine (T), diglyme (D), 1N-(2-dimethylamino) ethyl)-1N, 2N, 2N-trimethylethane-1,2-diamine (PT), di-(2-picolyl)-amine derivative (HT), and multidentate terpyridine derivative (DT)) were synthesized to investigate the effect of coordination environment on the sensitized luminescence of Eu(III) complexes. The nine coordination sites of the $Eu^{3+}$ ion are occupied by three bidentate carboxylate moieties and one neutral ligand. The highest emission intensity is obtained for $Eu^{3+}$- $[NA]_3$ (PT), due to the difference in energy transfer efficiency and symmetry of the first coordination sphere of $Eu^{3+}$ ion. But, the lowest emission intensity is obtained for $Eu^{3+}$-$[NA]_3$(T). Terpyridine may not play an important role antenna for photosensitizing $Eu^{3+}$ ion. It could be attributed to the weak spectral overlap integral J value between its phosphorescence band and $Eu^{3+}$ion absorption band. Therefore, different coordination environment of $Ln^{3+}$ ion play an important role in providing sensitization of lanthanide ion emission.

• 한국세라믹학회지
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• 제50권6호
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• pp.539-544
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• 2013

A simple synthetic process is demonstrated for the preparation of MnS/carbon nanotube (CNT) composites for Li ion battery electrodes. CNTs were initially treated using a strong acid solution to generate carboxylate ions ($-COO^-$) on their surfaces. The MnS/CNT composites were synthesized by a polyvinyl-pyrrolidone-assisted hydrothermal method in the presence of as-functionalized CNTs. The phase and morphology of the MnS/CNT composites and pure MnS microspheres were characterized using X-ray diffraction and high-resolution transmission electron microscopy. Furthermore, the Li electroactivity levels of the MnS/CNT composites and MnS microspheres were investigated using cyclic voltammetry and galvanostatic cycling. The MnS/CNT composite electrodes showed higher specific capacities exceeding 365 $mA\;h\;g^{-1}$ at a C/10 current rate and enhanced cyclic performance compared to pure MnS microspheres.

• Journal of Photoscience
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• 제9권3호
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• pp.51-55
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• 2002

The 77 K emission and excitation spectra, and 298 K infrared and absorption spectra of [Cr(progly)(2,2-tri)]CIO$_4$[progly=prolylglycinate,2,2-tri=N-(2-aminoethyl)-1,2-ethanediamine] have been measured. The vibrational intervals of the electronic ground state are extracted from emission and infrared spectra. The twelve electronic bands due to spin-allowed and spin-forbidden transitions were assigned. Using the observed electronic transitions, a ligand field analysis was performed to determine the metaligand bonding properties for the coordinated atoms. It is found that the carboxylate oxygen of the progly is a strong $\sigma$-and $\pi$-donor while the peptide nitrogen has weak $\pi$-donor property toward chromium(III) ion.

• Bulletin of the Korean Chemical Society
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• 제17권5호
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• pp.433-436
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• 1996

Cobalt(Ⅲ) complexes of trifunctional amino acid and N,N'-diethylethylenediamine-N,N'-di-α-butyrate(deedba), s-cis-[Co(deedba)(L-aa)] (L-aa=S-methyl-L-cysteine, L-aspartic acid, L-glutamic acid) have been prepared from the reaction between the s-cis-[Co(deedba)(Cl2)]- complex and the corresponding amino acid. The amino acids have been found to coordinate through the amine and carboxylate groups. The S-methyl-L-cystene is coordinated not by the sulfur donor atom, but by the nitrogen and oxgen donor atoms, and the L-aspartic and L-glutamic acids are coordinated to the cobalt(Ⅲ) ion via formation of the five-membered glycinate chelate ring. Relatively small optical activity shown by the complexes is due to the chiral center present in the amino acids.

• 대한화학회지
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• 제53권3호
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• pp.257-265
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• 2009

$Cu^{+}$ 및 $Cu^{2+}$와 proline의 결합형태에 따른 구조 및 금속 친화도를 DFT(Density Functional Theory) 방법으로 조사하였다. 금속-proline의 결합과 여러 결합형태에 따른 에너지 순서는 $Cu^{+}$-Proline및 $Cu^{2+}$-proline 착화합물에서 서로 매우 상이함을 알았다. $Cu^{+}$-Proline의 경우, 바닥상태의 구조는 $Cu^{+}$가 중성 proline의 카르보닐 산소 및 이미노기 질소에 배위된 두 자리 배위를 하며, 이에 비해 $Cu^{2+}$-Proline 의 바닥상태의 구조는 zwitter이온 형태 proline의 카르복시기의 두 산소 사이에 chelation을 형성하는 구조임을 확인하였다. 가장 안정한 $Cu^{+}$-Proline 착화합물에서 proline의 금속 이온 친화도는 6-311++G(d,p) 수준에서 76.0 kcal/mol로 계산되었으며, proline의 $Cu^{2+}$ 이온 친화도는 258.5 kcal/mol로 나타났다.

• 분석과학
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• 제24권4호
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• pp.275-281
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• 2011

세제 제조시설 폐수의 유기물을 틀로 하여 $Al(OH)_3$과 $H_3PO_4$의 반응으로 $AlPO_4$-계 물질을 합성하였다. 소성된 $AlPO_4$-계 물질을 APTMS, 석신산 무수물과 반응시켜 표면을 카르복실기로 바꾸었다. 분말 XRD 결과, 특징적인 $AlPO_4$-계 물질의 패턴을 얻었으며, 물질의 형태는 SEM으로 조사하였고, 작용기는 FT-IR 분석으로 확인하였다. 증류수에 분산시킨 고체의 표면 전위 측정 결과, $AlPO_4-NH_2$는 양의 표면 전하를 갖는 반면, $AlPO_4$-COOH는 음의 표면 전하를 갖는 것으로 나타났다. 합성된 $AlPO_4$-계 물질을 이용하여 수용액에서 유해 중금속의 제거 실험을 수행하였다. 납 이온은 표면에 존재하는 카르복실기와 착물을 형성하며 물질에 흡착되었고, 흡착 분배계수는 91.1 mL/g이었다. 결론적으로 본 연구에서 고찰한 $AlPO_4$-계 물질은 수환경에서 유해 중금속 이온의 제거에 활용될 수 있을 것이다.

• Elastomers and Composites
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• 제48권3호
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• pp.225-231
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• 2013

본 연구에서는 carboxylated SBR latex와 zinc oxide가 SBS 복합재의 내마모성과 debris 특성 개선에 미치는 영향을 관찰하였다. 실리카를 첨가한 SBS 복합재는 실리카 입자간의 수소 결합에 의한 강한 filler-filler interaction으로 인한 낮은 분산성 때문에 기계적 강도, NBS 내마모성, debris 특성이 전체적으로 감소하는 것으로 나타났다. carboxylated SBR latex를 첨가한 SBS 복합재는 carboxyl group과 실리카의 silanol group간의 결합을 통하여 filler-filler interaction이 감소하고 실리카의 분산성이 증가하기 때문에 기계적 강도, NBS 내마모성, debris 특성이 향상되는 것을 확인 하였다. carboxylated SBR latex와 zinc oxide를 동시에 첨가한 경우, carboxyl group에 의한 실리카의 분산성 향상과 더불어 zinc ion과 carboxyl group간의 ion cluster 형성을 통하여 물성이 크게 증가하였다. Zinc ion과 carboxyl group간의 ion cluster 형성은 $1550{\sim}1650cm^{-1}$의 zinc carboxylate group stretch 피크의 FT-IR 분석 결과로 확인하였다. carboxylated SBR latex와 zinc oxide를 첨가한(SC-4) 복합재의 경우, 인장강도 $156kgf/cm^2$, 신장율 936%, 인열강도 59.4kgf/cm의 우수한 기계적 강도를 나타내었으며, NBS 내마모성은 338%로 가장 우수한 특성을 나타내었다. 또한, 표면 마찰 시에 debris 발생 역시 크게 감소하며, 표면 마찰 저항의 증가로 파도 형태의 마모 특성을 나타내었다.