• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3173-3179
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• 2010

New complex $[Mn(II)H_{1.5}L]_2[Mn(II)H_3L]_2(ClO_4)_5{\cdot}3H_2O$ (1), where $H_3L$ is tris {2-(4-imidazolyl)methyliminoethyl} amine (imtren), has been prepared by reacting manganese(II) perchlorate hexahydrate with the imtren ligand in methanol. X-ray crystallographic study revealed that the imtren ligand hexadentately binds to Mn(II) ion through the three Schiff-base imine N atoms and three imidazole N atoms with a distorted octahedral geometry, and the apical tertiary amine N atom of the ligand pseudo-coordinates to Mn(II), forming overall a pseudo-seven coordination environment. The hydrogen-bonds between imidazole and imidazolate of $[Mn(II)H_{1.5}L]^{0.5+}$ complex ions are extended to build a 2D puckered network with trigonal voids. $[Mn(II)H_3L]^{2+}$ complex ions constitutes another extended 2D puckered layer without hydrogen bonds. Two layers are wedged each other to constitute overall stack of the crystal. Peroxidase activity of complex 1 was examined by observing the oxidation of 2,2'-azinobis(3-ethylbenzothiazoline)-6-sulfonic acid (ABTS) with hydrogen peroxide in the presence of complex 1. Generation of $ABTS^{+{\cdot}}$ was observed by UV-vis and EPR spectroscopies, indicating that the complex 1, a fully-coordinated mononuclear Mn(II) complex with nitrogen-only ligand, has a heme-independent peroxidase activity.

• 대한화학회지
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• 제27권5호
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• pp.368-375
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• 1983

5-아릴-1,3,4-옥시티아졸-2-온을 트리에틸포스파이트와 반응시키면 탈황반응에 의해 벤조니트릴과 에틸포스포로티오에이트가 66~94% 수득율로 얻어졌다. 다른 3가의 인화합물 즉, 트리메틸포스파이트, 트리에틸포스핀, 그리고 트리페닐포스핀들과도 같은 탈황반응이 관찰되었다. 그러나 트리페닐포스파이트와는 전혀 반응하지 않았다. 5-아릴-1,3,4-디티아졸-2-온을 트리페닐포스핀과 반응시키면 티오아실 이소시아네이트가 얻어졌다. 이것은 에테르에서 자체적으로 분해되어 벤조니트릴로 변하게 되나 클로로포름에서는 안정하다. 이 두 반응에서 관찰되는 탈황반응은 인이 고리속으로 들어가 고리를 늘인후 분자내에서의 자리옮김 반응에 의해 일어나는 것이라 생각된다. 클로로포름에서 안정한 티오아실 이소시아네이트는 이민과 1,4-고리화 첨가반응을 일으켜 티아다이아지논을 생성하였다.

• 청정기술
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• 제21권1호
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• pp.62-67
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• 2015

본 연구에서는 그래핀과 다중벽 탄소나노튜브를 포함하는 하이브리드 소재의 제조 및 슈퍼캐패시터 전극물질로의 활용에 관한 내용이 진행되었다. 이를 위하여 산화그래핀과 아민(-NH₂) 그룹이 치환된 다중벽 탄소나노튜브를 산 촉매 하에서 반응시켜, 새로운 이민(-C=N-) 결합이 도입된 하이브리드 복합체를 합성하였다. 상기 제조된 하이브리드 소재를 슈퍼캐패시터 전극 물질로 사용하고자 수산화칼륨 전해질 기반의 3상 전극 시스템을 활용하여 전기화학적 특성을 살펴보았다. 또한 하이브리드 소재에 존재하는 그래핀과 다중벽 탄소나노튜브의 비율 변화 실험을 통하여, 그래핀/탄소나노튜브의 질량비가 7.5/1일 때 그 특성이 최적화가 됨을 알 수 있었다. 최적화된 전극은 높은 비축천용량(132 F/g)을 나타내었을 뿐만 아니라, 반복된 충방전 실험에서 높은 안정성(95%, retention after 5000 cycles)을 나타내었다.

• 대한화학회지
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• 제55권1호
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• pp.50-56
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• 2011

(2, 4-difluoro-phenyl)-(2-phenyl-1H-quinolin-4-ylidene)-amine의 전기화학적 환원에 대하여 실온에서 순환전압전류 기술을 사용한 유리탄소전극(GCE)에서 N,N-dimethylformamide 하에서 0.1 M tetrabutylammoniumbromide로 조사하였다. 이민의 환원은 각각 한 전자를 포함하면서 2단계의 성공적인 단계로 일어난다. 이 매개물에서 처음 피크는 유리탄소전극 표면에서 약 -0.793 V(vs Ag/$Ag^+$)로 관측되었다. 그리고 그것은 더욱 안정하고 2번째 피크와 비교하여 명확하게 설명된다. 연구된 용매 매개물에서 이민의 확산계수($D_0$)는 수정된 Randles-Sevcik 식을 이용해 계산되었다. 반응 종들의 전자 이동 계수($\alpha$) 또한 계산되었다.

• Bulletin of the Korean Chemical Society
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• 제15권10호
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• pp.873-881
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• 1994

The approximate rate and stoichiometry of the reaction of excess diisobutylaluminum hydride-dimethyl sulfide complex($DIBAH-SMe_2$) with organic compounds containing representative functional group under standardized conditions (toluene, $0{\circ}C$) were examined in order to define the reducing characterstics of the reagent and to compare the reducing power with DIBAH itself. In general, the reducing action of the complex is similar to that of DIBAH. However, the reducing power of the complex is weaker than that of DIBAH. All of the active hydrogen compounds including alcohols, amines, and thiols evolve hydrogen slowly. Aldehydes and ketones are reduced readily and quantitatively to give the corresponding alcohols. However, $DIBAH-SMe_2$ reduces carboxylic acids at a faster rate than DIBAH alone to the corresponding alcohols with a partial evolution of hydrogen. Similarly, acid chlorides, esters, and epoxides are readily reduced to the corresponding alcohols, but the reduction rate is much slower than that of DIBAH alone. Both primary aliphatic and aromatic amides examined evolve 1 equiv of hydrogen rapidly and are reduced slowly to the amines. Tertiary amides readily utilize 2 equiv of hydride for reduction. Nitriles consume 1 equiv of hydride rapidly but further hydride uptake is quite slow. Nitro compounds, azobenzene, and azoxybenzene are reduced moderately. Cyclohexanone oxime liberates ca. 0.8 equiv of hydrogen rapidly and is reduced to the N-hydroxylamine stage. Phenyl isocyanate is rapidly reduced to the imine stage, but further hydride uptake is quite sluggish. Pyridine reacts at a moderate rate with an uptake of one hydride in 48 h, while pyridine N-oxide reacts rapidly with consumption of 2 equiv of hydride for reduction in 6h. Similarly, disulfides and sulfoxide are readily reduced, whereas sulfide, sulfone, and sulfonic acid are inert to this reagent under these reaction conditions.

• Bulletin of the Korean Chemical Society
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• 제13권2호
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• pp.199-207
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• 1992

The approximate rates and stoichiometry of the reaction of excess sodium diethyldihydroaluminate (SDDA) with 68 selected organic compounds containing representative functional groups were examined under standard conditions (THF-toluene, $0^{\circ}C$ in order to compare its reducing characteristics with lithium aluminum hydride (LAH), aluminum hydride, and diisobutylaluminum hydride (DIBAH) previously examined, and enlarge the scope of its applicability as a reducing agent. Alcohols, phenol, thiols and amines evolve hydrogen rapidly and quantitatively. Aldehydes and ketones of diverse structure are reduced rapidly to the corresponding alcohols. Reduction of norcamphor gives 11% exo-and 89% endo-norborneol. Conjugated aldehydes such as cinnamaldehyde are rapidly and cleanly reduced to the corresponding allylic alcohols. p-Benzoquinone is mainly reduced to hydroquinone. Hexanoic acid and benzoic acid liberate hydrogen rapidly and quantitatively, however reduction proceeds very slowly. Acid chlorides and esters tested are all reduced rapidly to the corresponding alcohols. However cyclic acid anhydrides such as succinic anhydride are reduced to the lactone stage rapidly, but very slowly thereafter. Although alkyl chlorides are reduced very slowly alkyl bromides, alkyl iodides and epoxides are reduced rapidly with an uptake of 1 equiv of hydride. Styrene oxide is reduced to give 1-phenylethanol quantitatively. Primary amides are reduced very slowly; however, tertiary amides take up 1 equiv of hydride rapidly. Tertiary amides could be reduced to the corresponding aldehydes in very good yield ( > 90%) by reacting with equimolar SDDA at room temperature. Hexanenitrile is reduced moderately accompanying 0.6 equiv of hydrogen evolution, however the reduction of benzonitrile proceeds rapidly to the imine stage and very slowly thereafter. Benzonitrile was reduced to give 90% yield of benzaldehyde by reaction with 1.1 equiv of hydride. Nitro compounds, azobenzene and azoxybenzene are reduced moderately at $0^{\circ}C$, but nitrobenzene is rapidly reduced to hydrazobenzene stage at room temperature. Cyclohexanone oxime is reduced to the hydroxylamine stage in 12 h and no further reaction is apparent. Pyridine is reduced sluggishly at $0^{\circ}C$, but moderately at room temperature to 1,2-dihydropyridine stage in 6 h; however further reaction is very slow. Disulfides and sulfoxides are reduced rapidly, whereas sulfide, sulfone, sulfonic acid and sulfonate are inert under these reaction conditions.

• Natural Product Sciences
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• 제27권4호
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• pp.245-250
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• 2021

The methylglyoxal (MGO) trapping constituents from Malus baccata L. were investigated using incubation of MGO and crude extract under physiological conditions followed by HPLC analysis. The peak areas of MGO trapping compounds decreased, and their chemical structures were identified by HPLC-ESI/MS. Sieboldin was identified as a major active molecule representing MGO-trapping activity of the crude extract. After reaction of sieboldin and MGO, remaining MGO was calculated by microplate assay method using imine (Schiff base) formation of 2,4-dinitrophenylhydrazine (DNPH) and aldehyde group. After 4 h incubation, sieboldin trapped over 43.8% MGO at a concentration of 0.33 mM and showed MGO scavenging activity with an RC₅₀ value of 0.88 mM for the incubation of 30 min under physiological conditions. It was also confirmed that sieboldin inhibited the production of advanced glycation end products (AGE) produced by bovine serum albumins (BSA)/MGO. Additionally, MGO trapping mechanism of sieboldin was more specifically identified by ¹H-, ¹³C-, 2D NMR and, confirm to be attached to the position of C-3' (or 5').

• Advances in nano research
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• 제15권1호
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• pp.35-48
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• 2023

Nanoparticles are known for their outstanding properties such as particle size, surface area, optical and electrical properties. These properties have significantly boasted their applications in various surface phenomena. In this work, calcium oxide nanoparticles were synthesized from periwinkle shells as an approach towards waste management through resource recovery. The sol gel method was used for the synthesis. The nanoparticles were characterized using X-Ray diffractometer (XRD), Fourier Transformed Infra-Red Spectrophotometer (FTIR), Brunauer Emmett Teller (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultra violet visible spectrophotometer (UV-visible). While DLS and SEM underestimate the particle diameter, the BET analysis reveals surface area of 138.998 m²/g, pore volume = 0.167 m³/g and pore diameter of 2.47 nm. The nanoparticles were also employed as an adsorbent for the purification of dye (methyl orange) contaminated water. The adsorbent showed excellent removal efficiency (up to 97 %) for the dye through the mechanism of physical adsorption. The adsorption of the dye fitted the Langmuir and Temkin models. Analysis of FTIR spectrum after adsorption complemented with computational chemistry modelling to reveal the imine nitrogen group as the site for the adsorption of the dye unto the nanomaterials. The synthesized nanomaterials have an average particle size of 24 nm, showed a unique XRD peak and is thermally and mechanically stable within the investigated temperature range (30 to 70 ℃).

• 대한핵의학회지
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• 제35권1호
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• pp.69-74
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• 2001

목적: $^{99m}Tc$-HMPAO는 뇌혈류영상에 사용되는 방사성의약품으로, HMPAO (RR,SS)-4,8-diaza-3,6,6,9-tetramethylundecan-2,10-dione bisoxime)는 3개의 입체이성체(meso-, d-, l-HMPAO)가 존재한다. $^{99m}Tc$표지 meso-HMAPO와 d,l-HMPAO는 체내에서 뇌섭취에 차이를 나타낸다. 이 연구에서는 d,l-HMPAO 입체이성체 혼합물을 d-형과 l-형으로 분리하여 각각을 $^{99m}Tc$으로 표지하여 생체내분포를 비교하고자 하였다. 대상및 방법: 2,3-Butanedione monooxime과 2,2-dimethyl-1,3-propanediamine을 반응시켜 imine 형태의 중간화합물(수율: 54%)을 얻었다. 이를 환원시켜 d,l-과 meso-HMAPO 혼합물을 얻었다(수율 : 31%). 이것을 4번 분별결정하여 miso-HMPAO를 분리하였다(수율: 11%). d,l-라세미 혼합불은 (+)-타르타르 산과 (-)-타르타르 산을 이용하여 d-형과 l-형을 분리하였다(수율 25%, 5%). 합성한 각 입체이성체 HMPAO를 환원제로 $SnCI_2{\cdot}2H_2O$를 이용하여 $^{99m}Tc$으로 표지한 후, 마우스에 투여하여 1 시간 후 생체내분포를 확인하였다. 결과: 우리는 각 입체이성체 HMAPO를 합성하고 핵자기공명분광기와 선광도측정기를 이용하여 구조를 확인하였다. $^{99m}Tc$ 표피후 지용성 $^{99m}Tc$HMPAO의 방사화학적 순도는 80% 이상이었다. 각 입체이성체(d,l-, d-, l- HMPAO)의 뇌섭취율은 1.34, 1.12, 1.67% ID/g으로, l-형이 d-형보다 1.5 배 더 높았다. 결론: 우리는 각 입체이성체 HMPAO를 성공적으로 합성하였다. l-HMPAO를 분리하여 사용할 경우 보다 나은 영상을 기대할 수 있을 것으로 생각한다.

• Journal of Periodontal and Implant Science
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• 제41권1호
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• pp.17-22
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• 2011

Purpose: Nitric oxide (NO) has been known as an important regulator of osteoblasts and periodontal ligament cell activity. This study was performed to investigate the relationship between NO-mediated cell death of human periodontal ligament fibroblasts (PDLFs) and N-methyl-D-aspartic acid (NMDA) receptor antagonist (+)-5-methyl-10, 11-dihydro-5H-dibenzo[a,d]cyclohepten-5, 10-imine hydrogen maleate (MK801). Methods: Human PDLFs were treated with various concentrations (0 to 4 mM) of sodium nitroprusside (SNP) with or without $200\;{\mu}M$ MK801 in culture media for 16 hours and the cell medium was then removed and replaced by fresh medium containing MTS reagent for cell proliferation assay. Western blot analysis was performed to investigate the effects of SNP on the expression of Bax, cytochrome c, and caspase-3 proteins. The differences for each value among the sample groups were compared using analysis of variance with 95% confidence intervals. Results: In the case of SNP treatment, as a NO donor, cell viability was significantly decreased in a concentration-dependent manner. In addition, a synergistic effect was shown when both SNP and NMDA receptor antagonist was added to the medium. SNP treated PDLFs exhibited a round shape in culture conditions and were dramatically reduced in cell number. SNP treatment also increased levels of apoptotic marker protein, such as Bax and cytochrome c, and reduced caspase-3 in PDLFs. Mitogen-activated protein kinase signaling was activated by treatment of SNP and NMDA receptor antagonist. Conclusions: These results suggest that excessive production of NO may induce apoptosis and that NMDA receptor may modulate NO-induced apoptosis in PDLFs.