• Bulletin of the Korean Chemical Society
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• 제33권12호
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• pp.4015-4022
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• 2012

Manganese(III) 5-(4-carboxyphenyl)-10,15,20-triphenyl porphyrin chloride (Mn(TCPP)Cl) was grafted through amide bond on silica zeolite Y (HY), zeolite beta ($H{\beta}$) and hexagonal mesoporous silica (HMS). XRD, ICP-AES, $N_2$ physisorption, SEM, TEM, FTIR and thermal analysis were employed to analyse these novel heterogeneous materials. These silica supported catalysts were shown to be used for epoxidation and good shape selectivity was observed. The effect of support structure on catalytic performance was also discussed. The catalytic activity remained when the catalysts were recycled five times. The energy changes about epoxidation of alkenes by $NaIO_4$ and $H_2O_2$ were also computationally calculated to explain the different catalytic efficiency.

• 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.

• Bulletin of the Korean Chemical Society
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• 제15권12호
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• pp.1112-1118
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• 1994

Epoxidation of olefins has been studied using iodosylbenzene (PhIO) as the terminal oxidant and binuclear and mononuclear complexes of $Mn^{2+}$, $Co^{2+}$, and $Cu^{2+}$ as catalysts. Epoxides were the predominant products with trace amounts of allylic oxidation products, and the metal complexes were found to be effective catalysts in the epoxidation reactions. The reactivity of binuclear copper complexes was greater than that of the mononuclear copper complexes, whereas the binuclear and mononuclear complexes of $Mn^{2+}$ and $Co^{2+}$ showed similar reactivities. The nature of the ligands bound to copper did not influence the reactivity of the binuclear copper complexes so long as copper ions were held in close proximity. A metal-iodosylbenzene complex, such as suggested previously for Lewis acidic metal complex-catalyzed epoxidation by iodosylbenzene, is proposed as the active epoxidizing species. Some mechanistic aspects are discussed as well.

• Bulletin of the Korean Chemical Society
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• 제23권11호
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• pp.1635-1639
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• 2002

A new solvent polymeric membrane sensor based on tetra(p-chlorophenyl)porphyrinato manganese (III) acetate is described which demonstrates excellent selectivity toward the triiodide ion. The electrode has a linear dynamic range between 1.0 ${\times}$ $10^{-2}$ M and 7.0 ${\times}$$10^{-6}$M with a Nernstian slope of $-59.6{\pm}1$ mV per decade and a detection limit of 5.0 ${\times}$$10^{-6}$M. The proposed sensor revealed good selectivities for triiodide over a wide variety of other anions and could be used in a pH range 2-9. The electrode can be used for at least two months without any considerable divergence in potential. It was applied as indicator electrode in potentiometric titration of the triiodide and As(III) ions.

• 대한화학회지
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• 제36권5호
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• pp.744-752
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• 1992

철(III) protoporphyrin과 망간(II) tetrakis(4-N-carboxyphenyl) Porphyrin을 polystyrene divinylbenzene 공중합체 수지와 반응시켜 고분자결합 금속포피린을 합성하였다. 고분자와 결합된 포피린은 공명라만분광기를 이용, 합성과정에서 포피린과 중심금속의 산화상태 등 여러가지 화학적 성질이 변화되지 않았음으로 확인하였다. 합성된 고분자결합 금속포피린은 싸이토크롬 P-450과 같은 산화촉매효소의 모형화합물로서 과산화수소에 의한 olefin의 epoxidation과 alkane의 oxidation의 촉매로서 사용이 가능하였다. 그 효율은 고분자와 결합하지 않은 동종의 포피린에 비하여 현저히 증가되었으며, 특히 포피린이 산화제에 의해 분해되지 않아 재사용이 가능하였다. 실제 효소에서와 같이 imidazole 유도체와 같은 전자주게 배위자가 포피린 중심금속에 배위한 경우 촉매효과가 더욱 향상되었다.

• 분석과학
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• 제9권3호
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• pp.270-278
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• 1996

5, 10, 15, 20-tetraphenyl(porphyrinato)manganase(III) chloride(Mn(TPP)Cl)를 감응성 물질로 사용하는 염화이온 선택성 전극의 감응 메카니즘을 동일한 막 조성을 갖는 optode의 가시광선 스펙트럼 변화를 관찰하여 연구하였다. 고분자막 내에서 망간포르피린의 리간드인 염화이온은 물분자와 치환되며, 시료 용액의 할로겐족 음이온들은 고분자막으로 들어와 망간포르피린에 치환된 물분자 리간드를 다시 치환함으로써, 그리고 살리실산과 같은 지용성 음이온들은 포르피린 주변의 염화이온들과 이온 교환을 함으로써 감응전위를 발생하는 것으로 보인다. 또한 각 음이온들에 대한 선택성을 결정하는 중요한 요소는 망간포르피린-음이온 리간드의 결합상수와 음이온의 수화엔탈피의 균형에 의하여 결정되는 것임을 확인할 수 있었다.

• Biomolecules & Therapeutics
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• 제12권1호
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• pp.25-33
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• 2004

In this study we investigated whether ATP loss was involved in the potentiated death of immunostimulated rat primary astrocytes in glucose-deprived condition. Rat primary astrocytes immunostimulated with LPS plus IFN-${\gamma}$ for 48 h underwent death upon glucose deprivation, which dependent on the production of peroxynitrite. Intracellular ATP level synergistically decreased by glucose deprivation in immunostimulated astrocytes but not in control cells, and the loss of ATP occurred well ahead of the LDH release. The synergistic cell death and ATP loss by immunostimulation and glucose deprivation were inhibited by iNOS inhibitor (L-NAME and L-NNA) or peroxynitrite decomposition catalyst (also a superoxide anion scavenger), Mn(III)tetrakis(N-methyl-4'-pyridyl)porphyrin (MnTMPyP). Exogenous addition of peroxynitrite generator, SIN-l timedependently induced ATP loss and cell death in the glucose-deprived astrocytes. Depletion of intracellular glutathione (GSH) and dis겨ption of mitochondrial transmembrane potential (MTP) were also observed under same conditions. Supply cellular ATP by the addition of exogenous adenosine or ATP during glucose deprivation inhibited ATP depletion, GSH depletion, MTP disruption and cell death in SIN-l treated or immunostimulated astrocytes. This study showed that perturbation in the regulation of intracellular ATP level in immunostimulated astrocytes might make them more vulnerable to energy challenging stimuli.

• International Journal of Oral Biology
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• 제41권3호
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• pp.141-147
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• 2016

Reactive oxygen species (ROS) and nitrogen species (RNS) are both important signaling molecules involved in pain transmission in the dorsal horn of the spinal cord. Xanthine oxidase (XO) is a well-known enzyme for the generation of superoxide anions ($O_2^{\bullet-}$), while S-nitroso-N-acetyl-DL-penicillamine (SNAP) is a representative nitric oxide (NO) donor. In this study, we used patch clamp recording in spinal slices of rats to investigate the effects of $O_2^{\bullet-}$ and NO on the excitability of substantia gelatinosa (SG) neurons. We also used confocal scanning laser microscopy to measure XO- and SNAP-induced ROS and RNS production in live slices. We observed that the ROS level increased during the perfusion of xanthine and xanthine oxidase (X/XO) compound and SNAP after the loading of 2',7'-dichlorofluorescin diacetate ($H_2DCF-DA$), which is an indicator of intracellular ROS and RNS. Application of ROS donors such as X/XO, ${\beta}-nicotinamide$ adenine dinucleotide phosphate (NADPH), and 3-morpholinosydnomimine (SIN-1) induced a membrane depolarization and inward currents. SNAP, an RNS donor, also induced membrane depolarization and inward currents. X/XO-induced inward currents were significantly decreased by pretreatment with phenyl N-tert-butylnitrone (PBN; nonspecific ROS and RNS scavenger) and manganese(III) tetrakis(4-benzoic acid) porphyrin (MnTBAP; superoxide dismutase mimetics). Nitro-L-arginine methyl ester (NAME; NO scavenger) also slightly decreased X/XO-induced inward currents, suggesting that X/XO-induced responses can be involved in the generation of peroxynitrite ($ONOO^-$). Our data suggest that elevated ROS, especially $O_2^{\bullet-}$, NO and $ONOO^-$, in the spinal cord can increase the excitability of the SG neurons related to pain transmission.

• International Journal of Oral Biology
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• 제31권4호
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• pp.127-133
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• 2006

[ $H_2O_2$ ], a member of reactive oxygen species (ROS), is known to be involved in the mediation of physiological functions in a variety of cell types. However, little has been known about the physiological role of $H_2O_2$ in exocrine cells. Therefore, in the present study, the effect of $H_2O_2$ on cholecystokinin (CCK)-evoked $Ca^{2+}$ mobilization and amylase release was investigated in rat pancreatic acinar cells. Stimulation of the acinar cells with sulfated octapeptide form of CCK (CCK-8S) induced biphasic increase in amylase release. Addition of $30\;{\mu}M\;H_2O_2$ enhanced amylase release caused by 10 pM CCK-8S, but inhibited the amylase release induced by CCK-8S at concentrations higher than 100 pM. An ROS scavenger, $10\;{\mu}M$ Mn(III)tetrakis(4-benzoic acid)porphyrin chloride, increased amylase release caused by CCK-8S at concentrations higher than 100 pM, although lower concentrations of CCK-8S-induced amylase release was not affected. To examine whether the effect of $H_2O_2$ on CCK-8S-induced amylase release was exerted via modulation of intracellular $Ca^{2+}$ signaling, we measured the changes in intracellular $Ca^{2+}$ concentration $([Ca^{2+}]_i)$ in fura-2 loaded acinar cells. Although $30\;{\mu}M\;H_2O_2$ did not induce any increase in $[Ca^{2+}]_i$ by itself, it increased the frequency and amplitude of $[Ca^{2+}]_i$ oscillations caused by 10 pM CCK-8S. However, $30\;{\mu}M\;H_2O_2$ had little effect on 1 nM CCK-8S-induced increase in $[Ca^{2+}]_i$. ROS scavenger, 1 mM N-acetylcysteine, did not affect $[Ca^{2+}]_i$ changes induced by 10 pM or 1 nM CCK-8S. Therefore, it was concluded that $30\;{\mu}M\;H_2O_2$ enhanced low concentration of CCK-8S-induced amylase release probably by increasing $[Ca^{2+}]_i$ oscillations while it inhibited high concentration of CCK-8S-induced amylase release.