• Korean Journal of Weed Science
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• v.14 no.1
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• pp.1-7
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• 1994

The effects of S-23142{N-(4-chloro-2-fluoro-5-propargyloxyphenyl)-3, 4, 5, 6-tetrahydrophtalimide}, on protoporphyrin IX(PPIX) biosynthesis in Spinacia oleracea L, leaf in vivo and in vitro condition were investigated by reversed-phase HPLC with fluorescence detector. The stroma and the membrane fraction of spinach chloroplast were isolated by osmotic regulation. The conversion of ${\delta}$-aminolevulinic acid(ALA) to PPIX occured more in the stroma than in the membrane fraction. It suggested that the enzymes that catalyse PPIX biosynthesis from ALA were localized in the stroma. Also, the synthesized PPIX content from ALA was completely inhibited by $10^{-8}M$ of S-23412 or $10^{-7}M$ of acifluorfen in the stroma but not in the membrane fractions. Therefore, these results suggested that the target site of S-23142 and acifluorfen may exist in the stroma fraction of spinach chloroplast.

• Korean Journal of Weed Science
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• v.16 no.2
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• pp.150-159
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• 1996

This study was conducted to investigate the inhibition of protox activity and the PPIX accumulation of the oxyfluorfen-tolerant and-susceptible rice cultivars with barnyardgrass, a typical susceptible weed in accordance by oxyfluorfen treatment. The susceptible rice cultivars and barnyardgrass showed more inhibition of protox activity due to the treatment of oxyfluorfen than the tolerant rice cultivars. Especially in the concentration at $10^{-6}$M treatment, protox activity of the susceptible rice cultivars and barnyardgrass were the completely inhibited but the tolerant rice cultivars kept 32~59% of activity compared to the control. As the treatment concentration increased, the content of PPIX accumulation increased and it increased untill four hours of light exposure but it tended to decrease these after. The content of PPIX accumulation by the treatment of oxyfluorfen was more pronounced in the light condition than in the dark. Under the light and dark conditions, the susceptible rice cultivars and barnyardgrass showed more PPIX accumulation than the tolerant rice cultivate. Especialiy the susceptible barnyardgrass had more than the rice. With the treatment of GC and DA, tetrapyrrole biosynthesis inhibitor, the herbicidal activity by oxyfluorfen was inhibited, and the susceptible rice cultivars and barnyardgrass tended to have less effective than the tolerant rice cultivars and the content of chlorophyll or PPS accumulation tended to be similar.

• Bulletin of the Korean Chemical Society
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• v.27 no.1
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• pp.77-81
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• 2006

The commercially available Amberlite XAD-2 and XAD-4 resins were modified with macrocyclic protoporphyrin IX (PPIX) or tetrakis(p-carboxyphenyl) porphyrin (TCPP) to enhance the adsorption capacity for phenol and chlorophenols. The chemically modified polymeric adsorbents (XAD-2+PPIX, XAD-2+TCPP, XAD-4+PPIX, and XAD-4+TCPP) were applied to the solid phase extraction as an adsorbent material for the preconcentration of phenol and chlorophenols in environmental waters. Generally, the synthesized adsorbents showed higher recoveries than underivatized adsorbents, XAD-2 and XAD-4, without matrix interferences. Especially, XAD-4+PPIX showed more than 90% recoveries for all compounds used in this study including hydrophilic phenol. The major factor for the increase of the adsorption capacity was the increase of $\pi$-$\pi$ interaction between adsorbents and samples due to the introduction of the porphyrin molecule. However, the breakthrough volumes and recovery values of the XADs+TCPP columns were slightly decreased for the bulky chlorophenols such as TCP and PCP. Using molecular mechanics methods, the structures of TCPP and PPIX were compared with that of porphine, the parent molecule of porphyrin. Four bulky p-carboxyphenyl groups of TCPP were torsional each other, thus the molecular plane of TCPP were not on the same level. In conclusion, the decrease of breakthrough volumes and recovery values of XADs+TCPP columns for bulky phenols can be explained by the steric hindrance of the $\pi$-$\pi$ interaction between porphyrin plane and the phenols.

• Korean Journal of Environmental Agriculture
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• v.15 no.3
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• pp.316-324
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• 1996

The four tolerant and one susceptible plant to oxyfluorfen were selected from 26 species and investigated for the inhibition of protox activity, the PPIX accumulation, and the activity of antioxidative enzymes by oxyfluorfen treatment. When treated, the oxyfluorfen-tolerant plant species showed a less decrease in fresh weight and height than the susceptible one. The susceptible barnyardgrass showed more inhibition of protox activity due to the treatment of oxyfluorfen than the tolerant species. Especially at the concentration of $10^{-6}M$, protox activity of the susceptible barnyardgrass was inhibited completely, but tolerant species maintained $25{\sim}45%$ of the activity. Under the light and dark condition, the susceptible barnyardgrass showed more PPIX accumulation than the tolerant.

• Korean Journal of Weed Science
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• v.16 no.4
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• pp.337-345
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• 1996

This study was conducted to investigate the protox activity, the PPIX accumulation and the activity of antioxidative enzymes of the oxyfluorfen-tolerant and -susceptible rice cultivars by oxyfluorfen and oxytluorfen-similar herbicides treatment. When treated with acifluorfen, bifenox or oxadiazon, the oxyfluorfen-tolerant rice cultivars showed less decreased in fresh weight than the susceptible rice cultivars. The inhibition of protox activity was in the order of acifluorfen > oxyfluorfen > bifenox > oxadiazon, and the PPIX accumulation was in the sequence of oxadiazon > acifluorfen > oxyfluorfen > bifenox. The inhibition of protox activity and the PPIX accumulation by the herbicide was greater in the susceptible rice cultivars than in the tolerant rice cultivars. The effect inhibiting the decrease of chlorophyll content resulting from the treatment of GC, tetrapyrrole biosynthesis inhibitor, was in the order of oxyfluorfen > acifluorfen > bifenox > oxadiazon, and the tolerant rice cultivar had more than the susceptible rice cultivar. In the treatment of DPE and oxadiazon, the activities of MDAR, POX and GR was higher in the tolerant rice cultivar than in the susceptible rice cultivar, and in the case of POX isozyme the activities of main D and E bands increased in the tolerant rice cultivars at tested herbicides but they didn't in the susceptible rice cultivar.

• Toxicological Research
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• v.20 no.4
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• pp.293-298
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• 2004

Background: Crohn's disease is characterized by a chronic relapsing inflammation of the bowel. Gliotoxin has been known to play strong immunosuppressive properties, while mechanisms for its anti-inflammatory actions are not completely understood. Here, we investigated the effects of gliotoxin in trinitrobenzene sulfonic acid (TNBS) induced mouse colitis, an animal model of Crohn's disease. Results: Gliotoxin dramatically improved clinical and histopathological symptoms in accompanied with reduced expression of TNF-$\alpha$, IL-1$\beta$, and ICAM-1 protein levels in TNBS induced colitis. Interestingly Gliotoxin induced Heme oxygenase-1 (HO-1) and the HO-1 inducer cobalt protoporphyrin IX (CoPPIX) completely mimicked the protective effects of gliotoxin in TNBS induced colitis mice. In contrast, the HO-1 inhibitor zinc protoporphyrin IX (ZnPPIX) could reverse the anti-inflammatory effects of gliotoxin and CoPPIX. Conclusions: Gliotoxin is a potential therapeutic agent targeting for the treatment of Crohn's disease by inducing HO-1.

• Journal of Physiology & Pathology in Korean Medicine
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• v.22 no.4
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• pp.871-877
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• 2008

Heme oxygenase-1 (HO-1), an inducible heme-degrading enzyme, is expressed by macrophages and endothelial cells in response to various stresses and mediators of inflammation. HO-1 has been recently implicated in regulation of angiogenesis via expression of VEGF. The purpose of this study was to determine the effects of HO-1 modulation on the collagen-induced arthritis (CIA) model and on angiogenesis via up- regulation of VEGF expression in human synovial fibroblast. DBA/1J mice were treated with an inhibitor of HO-1, tin protoporphyrin IX (SnPP), or with an inducer of HO-1, cobalt protoporphyrin IX (CoPP), from day 1 to day 35 after CIA induction. The clinical evolution of disease was monitored visually. At the end of the experiment, histopathologic changes were examined on the joints. VEGF expression in paws were measured by immunohistochemical stain. mRNA expression of HO-1 and VEGF stimulated with various concentration of $TNF-{\alpha}$, CoPP accessed on human synovial fibroblast by RT-PCR. Effects of pretreatment with SnPP on mRNA expression of HO-1 and VEGF in the presence of CoPP and $TNF-{\alpha}$ in synovial fibroblast was accessed by Real-time RT-PCR. Administration of cobalt protoporphyrin IX significantly induced the inflammatory response, with increased arthritis index and expression of VEGF in the paws of the arthritis models. Treatment with SnPP significantly reduced the severity of CIA through inhibition of joint inflammation and cartilage destruction. The expression of VEGF were also significantly reduced by SnPP treatment in the paw. CoPPIX as inducer of HO-1, increased HO-1 and VEGF expression dose dependently in synovial fibroblast. In contrast, inhibition of HO-1 activity by SnPPIX abrogated CoPPIX-induced HO-1 and VEGF production in synovial fibroblast. Stimulation with $TNF-{\alpha}$ increased HO-1 and VEGF expression itself and showed additive effect on HO-1 and VEGF expression when it treated with CoPP. When SnPP was treated with CoPP and $TNF-{\alpha}$, it abrogated the CoPP induced HO-1 and VEGF expression and also abrogated $TNF-{\alpha}$ induced HO-1 and VEGF expression in synovial fibroblast. The effects of HO-1 induction in rheumatoid arthritis results in aggravation of arthritis via up-regulation of VEGF. I concluded that inhibition of the expression or activity of HO-1 could be a therapeutic target of rheumatoid arthritis.

• Bulletin of the Korean Chemical Society
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• v.30 no.1
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• pp.177-182
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• 2009

We present the geminate rebinding kinetics measurements of CO to 2-methylimidazole (2-MeIm) bound ferrous protoporphyrin- IX (FePPIX) in alkaline glycerol/water mixtures at 293 K after photolysis. The kinetics was probed by monitoring the CO stretching mode using femtosecond vibrational spectroscopy. When 2-MeIm is used in excess, heme dimers that typically form in low viscosity solutions disappear as the viscosity of the solvent increases. Heme aggregates formed in low viscosity solutions turn monomeric as more 2-MeIm is added, suggesting that 6-coordinated heme, including a strong proximal histidine tends to be in the monomeric form. The vibrational band of CO in the 2-MeIM-FePPIX-CO is well described by a single Gaussian function centered at 1958 $cm^-1$ and 28 $cm^-1$ full width at half maximum. The efficiency and rate of the geminate rebinding of CO to the heme increase with viscosity of the solvent, suggesting that retention of the dissociated CO near the heme, for a longer period by the viscous solvent media, accelerates rebinding.

• KOREAN JOURNAL OF CROP SCIENCE
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• v.42 no.1
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• pp.79-88
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• 1997

This experiment was conducted to investigate the protoporphyrin Ⅸ (PPIX)accumulation, activity of antioxidative enzymes and contents of antioxidant in tolerant-wheat and susceptible-barley to protoporphyrinogen oxidase (Protox) inhibiting-herbicides [oxyfluorfen(2-chloro-l-(3-ethoxy-nitrophenoxy-4-(trifluoromethyl) benzene, acifluorfen (5-[2-chloro-4-(trifl-uoromethyl) phenoxy]-2-nitrobenzoic acid), bifenox(methyl-5-(2, 4-dichlorophenoxy) 2-nitroben-zoate), and oxadiazon (5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazol-2-one)]. The tolerant-wheat and susceptible-barley were soaked in these compounds at 10$^{-6}$ M for 2hrs and exposed to light for 2,4,6 or 8hrs to investigate change of the activity of antioxidative enzymes. The activities of monodehydroascorbate reductase(MDAR), catalase(CAL) and superoxide dismutase(SOD) were lower in the barley than in the wheat after the treatement of these compounds. The activity of peroxidase(POX) was lower in the barley than in the wheat at 8hrs after the treatment of oxyfluorfen but other compounds showed no difference in activity in wheat and barley. The activity of glutathione reductase(GR) was increased in wheat and barley according as hours of treatment of these compounds became increased but its activity was no difference between wheat and barley. In the case of the content of vitamin C due to the treatment of these compounds, the wheat decreased less than the barley. After the treatment of oxyfluorfen the content of vitamin E in the wheat was higher than in the barley but other compounds didn't have any difference between wheat and barley. And after the treatment of acifluorfen the content of carotenoid was greater in the wheat than in the barley but other compounds didn't have any difference between wheat and barley. The content of glutathione (GSH, GSSG) was greater in the barley than in the wheat. The content of protoporphyrin Ⅸ (PPIX) accumulation by the treatments of these compounds was more in the barley than in the wheat. Especially, the treatment of oxyfluorfen and acifluorfen were more accumulated 2.3 and 1.3 fold in the barley than in the wheat, respectively.

• Journal of Korean Society of Occupational and Environmental Hygiene
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• v.3 no.2
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• pp.141-151
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• 1993

Blood samples obtained from 200 adults who had visited the "S" general hospital were analyzed to compare the zinc protoporphyrin (ZPP) levels quantified by high performance liquid chromatograph (HPLC) and by hematofluorometer (HF) to investigate the methodological difference if any and the relationship between the levels of blood lead and ZPP among no-lead exposed adults. Also investigated were the distribution of ZPP and protoporphyrin IX (PPIX) concentrations, the establishment of normal levels of blood ZPP and blood lead, and the contribution of age and sex factors to these values. These subjects had no previous occupational exposure to lead. The results obtained were as follows : 1. The mean values of blood lead for male and female subjects were $9.46{\pm}2.44{\mu}g/dl$ and $8.09{\pm}2.17{\mu}g/dl$, respectively. The difference observed in the mean concentrations between male and female subjects was statistically very significant. 2. The mean values of blood ZPP by HPLC for male and female subjects were $15.94{\pm}4.55{\mu}g/dl$ and $22.26{\pm}6.61{\mu}g/dl$, respectively. The difference observed in the mean concentrations between male and female subjects was statistically not significant. The mean values of blood PPIX by HPLC for male and female subjects were $2.51{\pm}1.78{\mu}g/dl$ and $2.81{\pm}1.56{\mu}g/dl$, respectively. The difference observed in the mean concentrations between male and female subjects was statistically not significant. 3. The mean values of blood ZPP by HF for male and female subjects were $28.44{\pm}7.11{\mu}g/dl$ and $37.77{\pm}8.04{\mu}g/dl$, respectively. The difference observed in the mean concentrations between male and female subjects was statistically very significant. 4. No statistically significant correlation was found between the levels of blood ZPP and blood lead. 5. The ratio of ZPP and protoporphyrin IX (PPIX) concentration to erythrocyte protoporphyrin (EP, EP=ZPP+PPIX) concentration was 87.4% and 12.6%, respectively. 6. A statistically very significant correlation was found between the ZPP concentrations determined by HPLC and the values by HF (r=0.7565). The ZPP concentraitons quantified by HF were 1.75 times as high as the values obtained by HPLC. 7. The blood ZPP concentrations quantified by HPLC, HF, and spectrofluorometer (SF) from the blood samples obtained from 14 lead-exposed workers and from 16 no-lead exposed adults showed wide variations. The ZPP concentrations by HF were the highest followed by the levels obtained by SF and by HPLC. In the exposed group, no statistically significant difference was found among three methods of quantifying blood ZPP levels. In the no-lead exposed group, however, statistically significant difference was observed among these methods. The ZPP concentrations by HF were about twice as high as those of by HPLC or by SF. Among three methods of quantifying blood ZPP (HPLC, SF and HF), the results revealed significant difference. Therefore it is suggested that objective methods of quantifying blood ZPP and a system of correcting different ZPP levels be developed by the ministry of Labor.