• 대한화학회지
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• 제35권5호
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• pp.569-574
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• 1991

pyrrole과 benzaldehyde 및 그 유도체로부터 meso-tetraphenylporphyrin(TPP)과 그 유도체 다섯가지를 합성한 후 이를 Co(II), Cu(II), Zn(II)의 염화물과 반응시켜 각각의 metalloporphyrin 착화합물을 만들고, 이 중 meso-tetra(p-aminophenyl)porphyrin(TNPP)을 다공성 polystyrene 수지와 반응시킨 후 여기에 Cu(II)의 염화물을 작용시켜 고분자결합 metalloporphyrin 착화합물 : Cu(Res-NH-TPP-$NH_2$)을 만들었다. 합성한 porthyrin 화합물들은 가시광선, 적외선 및 전자스핀공명 스펙트럼으로 확인하였고, 금속함량은 원자흡광 분광광도법으로 측정하였다. 합성한 porphyrin 화합물을 benzoquinone 광환원반응에 촉매로 이용한 결과, 일반적으로 유리 porphyrin보다 metalloporphyrin이, metalloporphyrin 중에는 Cu-TNPP의 촉매효과가 높았으며, 이에 고분자를 결합시키는 경우 효과가 더욱 향상됨을 알 수 있었다.

• 분석과학
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• 제14권1호
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• pp.72-79
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• 2001

금속포르피린과 그들의 고분자결합 유도체를 산화촉매로 한 2, 4, 6-trichlorophenol(TCP)의 산화분해반응을 수행하였다. 산화제로는 $KHSO_5$와 tert-butylhydroperoxide(TBHP)가 사용되었다. 금속포르피린은 TCP의 산화분해반응에서 매우 낮은 촉매활성을 보인 반면, 금속포르피린이 새로이 합성된 고분자나 XAD2 수지에 화학결합 되어있는 고분자결합 금속포르피린을 촉매로 사용한 TCP의 산화 분해반응에서는 매우 높은 촉매활성을 보여주었다. 또한, 피리딘이나 이미다졸과 같은 전자 주개 리간드가 축방향에 놓여 있는 고분자의 경우에는 더 큰 활성을 나타내었다. Maleic acid와 chloromaleic acid는 생성물로서 ESI-MS로 확인되었다. 특히, XAD2 수지에 결합된 촉매의 경우 산화제에 대한 안정성과 용매에 대한 불용성으로 인해 촉매로서 재사용이 가능함을 확인하였다.

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3727-3732
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• 2013

The interaction between metalloporphyrins and diazine tautomers was investigated using quantum chemistry method. The results showed that the metal atom in the metalloporphyrin was not coplanar with porphin ring, and zinc porphyrin has the most extent of its non-coplanar nature. The most stable complex in nine complexes was iron porphyrin. NBO analysis indicated that the interaction between the lone pair of electrons on the nitrogen atom and the unoccupied lone pair orbital of metal contributes significantly to the stability of the complexes. Through the conceptual DFT parameter and Fukui dual descriptor, the thermodynamic stability and reactivity of complexes were analyzed. The density difference function (DDF) analyzes were performed to explore the rearrangement of electronic density after the coordination interaction. NICS calculation indicated that metalloporphyrin aromaticity was reduced after the coordination interaction, and aromaticity of diazine tautomer was increased along direction vector of the coordination interaction force.

• 한국염색가공학회지
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• 제13권6호
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• pp.367-373
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• 2001

The preparations of deodorizing fibers using metalloporphyrines hove been investigated. The three metalloporphyrin derivatives(MTCPP, M=Mn, Zn, Sn) were prepared in modest to good yields. The metalloporphyrin derivative as a deodorant material was Introduced to fibers by a dyeing method. The deodorant activity(D.A.) of these deodorizing fibers was measured by chromogenic gas detector tubes. In comparison with untreated fiber, these deodorizing fibers was remarkably effective against $NH_3$ and $CH_3$SH$. More than 98% of ammonia can be removed within 20 min.. The D.A.(%) of fiber adsorbed MTCPP was more than 80% after 90min..

• 한국염색가공학회지
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• 제13권6호
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• pp.9-9
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• 2001

The preparations of deodorizing fibers using metalloporphyrines have been investigated. The three metalloporphyrin derivatives(MTCPP, M=Mn, Zn, Sn) were prepared in modest to good yields. The metalloporphyrin derivative as a deodorant material was introduced to fibers by a dyeing method. The deodorant activity(D.A.) of these deodorizing fibers was measured by chromogenic gas detector tubes. In comparison with untreated fiber, these deodorizing fibers was remarkably effective against NH₃ and CH₃SH. More than 98% of ammonia can be removed within 20 min.. The D.A.(%) of fiber adsorbed MTCPP was more than 80% after 90min..

• 한국응용과학기술학회지
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• 제19권3호
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• pp.206-212
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• 2002

The catalytic activities of several metalloporphyrin, wherein the porphyrins are TPP(5,lO,l5,20-Tetraphenyl-21H,23H-porphyrin) and (p-X)TPP (X =$CH_{3}O$, $CH_{3}$, F, Cl), are reported for the oxidation of styrene and it's derivatives. The electronic effects of substrates and porphyrins on the catalytic activity of metalloporphyrin containing the transition metal ion such as Mn(III) was discussed. Investigating the correlation between the Michaelis-Menten's rate parameters and the substituent constants, we are going to analyze the influences on the changes of catalytic activity or rate determining step during the processes of the formation and the dissociation of the M-oxo-olefin.

• 한국응용과학기술학회지
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• 제21권1호
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• pp.76-88
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• 2004

The catalytic oxidation reaction of several cycloolefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin(M = Ga(III), In(III) and TI(III) complexes as a catalyst and sodium hypochlorite as a terminal oxidant. Porphyrins were $(p-CH_3O)$TPP, $(p-CH_3)$TPP, TPP, (p-F)TPP, (p-Cl)TPP and $(F_{20})$TPP (TPP=5,10,15,20-tetraphenyl-21H,23H-porphyrin) and olefins were cyclopentene, cyclohexene, cycloheptene and cyclooctene, The substrate conversion yield(%) was investigated according to the radius effect of non-redox metal ion, substituent effect and hindrance effect of metalloporphyrin. The conversion yield of cycloolefin was in the following order : $C_5$ < $C_6$ < $C_7$ = $C_8$.

• Bulletin of the Korean Chemical Society
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• 제35권11호
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• pp.3313-3318
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• 2014

The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.

• Archives of Pharmacal Research
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• 제29권3호
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• pp.188-190
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• 2006

In this study, a newly-synthesized metalloporphyrin, Gd-chlorin (PB Chlorin), was investigated by using a simple tissue phantom to test its efficacy as an MRI contrast agent. This study demonstrated the potential activity of Gd-chlorin as not only a MRI contrast agent, but also as a PDT photosensitizer by using a simple tissue phantom and conducting a very brief MRI experiment.

• 대한화학회지
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• 제67권3호
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• pp.175-180
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• 2023

Tetra-aryl substituted A4-type porphyrins (TP, TD, TA) and trans-A2B2 porphyrins (DDP1, AAP1) with electron-donating or withdrawing groups were synthesized. The band gap energy of those porphyrins was calculated from their UV-Vis spectra and CV data. With an electron-withdrawing group, the band gap energy of porphyrin TA increased via the LUMO energy up. Meanwhile, the introduction of an electron-donating group decreased the band gap of porphyrin by HOMO level up as as in the case of porphyrin TD. The band gap (2.19-2.28 eV) of metalloporphyrin PP-Ni was greater than those (1.81-2.06 eV) of non-metalloporphyrins PP due to the LUMO level up.