• Biomolecules & Therapeutics
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• v.28 no.5
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• pp.443-455
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• 2020

The thioredoxin (Trx) system plays critical roles in regulating intracellular redox levels and defending organisms against oxidative stress. Recent studies indicated that Trx reductase (TrxR) was overexpressed in various types of human cancer cells indicating that the Trx-TrxR system may be a potential target for anti-cancer drug development. This study investigated the synergistic effect of auranofin, a TrxR-specific inhibitor, on sulforaphane-mediated apoptotic cell death using Hep3B cells. The results showed that sulforaphane significantly enhanced auranofin-induced apoptosis by inhibiting TrxR activity and cell proliferation compared to either single treatment. The synergistic effect of sulforaphane and auranofin on apoptosis was evidenced by an increased annexin-V-positive cells and Sub-G1 cells. The induction of apoptosis by the combined treatment caused the loss of mitochondrial membrane potential (ΔΨm) and upregulation of Bax. In addition, the proteolytic activities of caspases (-3, -8, and -9) and the degradation of poly (ADP-ribose) polymerase, a substrate protein of activated caspase-3, were also higher in the combined treatment. Moreover, combined treatment induced excessive generation of reactive oxygen species (ROS). However, treatment with N-acetyl-L-cysteine, a ROS scavenger, reduced combined treatment-induced ROS production and apoptosis. Thereby, these results deduce that ROS played a pivotal role in apoptosis induced by auranofin and sulforaphane. Furthermore, apoptosis induced by auranofin and sulforaphane was significantly increased through inhibition of the phosphoinositide 3-kinase (PI3K)/Akt pathway. Taken together, the present study demonstrated that down-regulation of TrxR activity contributed to the synergistic effect of auranofin and sulforaphane on apoptosis through ROS production and inhibition of PI3K/Akt signaling pathway.

• Applied Chemistry for Engineering
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• v.33 no.2
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• pp.188-194
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• 2022

This work presents a non-destructive and straightforward approach to assemble a large-scale conductive electronic film made of a pre-treated single-walled carbon nanotube (SWCNT) solution. For effective electron transfer between the immobilized enzyme and SWCNT electronic film, we optimized the pre-treatment step of SWCNT with p-terphenyl-4,4"-dithiol and dithiothreitol. Glucose oxidase (GOx, a model enzyme in this study) was immobilized on the SWCNT electronic film following the positively charged polyelectrolyte layer deposition. The glucose detection was realized through effective electron transfer between the immobilized GOx and SWCNT electronic film at the negative potential value (-0.45 V vs. Ag/AgCl). The SWCNT electronic film-based glucose biosensor exhibited a sensitivity of 98 ㎂/mM·cm². In addition, the SWCNT electronic film biosensor showed the excellent selectivity (less than 4 % change) against a variety of redox-active interfering substances, such as ascorbic acid, uric acid, dopamine, and acetaminophen, by avoiding co-oxidation of the interfering substances at the negative potential value.

• Journal of Life Science
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• v.33 no.10
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• pp.776-782
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• 2023

Silymarin, which is derived from dried Silybum marianum (milk thistle) seeds and fruits, possesses various beneficial properties, such as hepatoprotective, antioxidative, anti-inflammatory, and anticancer activity. This research aimed to explore the antioxidative activity of silymarin against oxidative stress and understand its molecular mechanism in RAW 264.7 cells. The study employed cell viability and reactive oxygen species (ROS) formation assays and western blot analysis. The results demonstrated that silymarin effectively reduced intracellular ROS levels induced by lipopolysaccharide (LPS) in a dose-dependent manner without causing any cytotoxic effects. Moreover, silymarin treatment significantly upregulated the expression of heme oxygenase (HO)-1, a phase II enzyme known for its potent antioxidative activity. Additionally, silymarin treatment significantly induced the expression of nuclear factor-erythroid 2 p45-related factor (Nrf) 2, a transcription factor responsible for regulating antioxidative enzymes, which was consistent with the upregulated HO-1 expression. To investigate the involvement of key signaling pathways in maintaining cellular redox homeostasis against oxidative stress, the phosphorylation status of mitogen-activated protein kinase (MAPK) and phosphoinositide 3-kinase (PI3K) was estimated by western blot analysis. The results showed that silymarin potently induced HO-1 expression, which was mediated by the phosphorylation of p38 MAPK. To further validate the antioxidative potential of silymarin-induced HO-1 expression, tert-butyl hydroperoxide (t-BHP)-induced oxidative damage was employed and attenuated by silymarin treatment, as identified by a selective inhibitor for each signaling molecule. In conclusion, silymarin robustly enhanced antioxidative activity by inducing HO-1 via the Nrf2/p38 MAPK signaling pathway in RAW 264.7 cells.

• Economic and Environmental Geology
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• v.51 no.3
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• pp.213-222
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• 2018

Metasediment-hosted Pb-Zn mineralized zone has been found in Dyusembay of Kazakhstan. Its petrological properties, metal index, alteration index and redox-sensitivity are compared with those of SEDEX type deposit. Mineralization is developed along foliation of host rock (graphitic phyllite) and controlled by folds and faults; major ore minerals including pyrite, pyrrhotite, sphalerite, and galena are disseminated or interlayered with fine-grained quartz. The margin of the mineralized zone is metamorphosed accompanying sericite and chlorite. Hydrothermal brecciation and Pb-Zn mineralization formed in quartz-calcite stockworks are confirmed at the around of Maytyubin granitoid intrusions. The mineralization is classified into three types according to those of occurrence, paragenesis, chemical composition and isotopic characteristics. Type 1 whose fine-grained pyrite, pyrrhotite and sphalerite are formed in parallel yet discontinuous to well-developed foliations of the host rock; its geochemistry is similar to those of the earlier stage in SEDEX-type mineralization. In case of type 2, the ore minerals of which are concentrated being parallel to a foliation by regional metamorphism, and most of them associated with quartz and muscovite (${\pm}$ biotite) paragenetically. Type 3 is formed in the hydrothermal breccia zone whose ore minerals are controlled by foliation and breccia and developed in quartz ${\pm}$ calcite veins having a form such as stratification, stockwork or veinlets. Host rocks in the mineralized zone indicate homogeneous metamorphic grade and there is no specific alteration zonation. Also, all types (type 1, type 2, and type 3) represent similar REEs patterns, it can be interpreted that these are originated from a same source. Sulphides occurred in mineralized zone indicate a limited range of sulphur isotope values (type 2, ${\delta}^{34}S=-13.3{\sim}-11.7$‰; type 3, ${\delta}^{34}S=-13.9{\sim}-8.2$‰), and a result of geothermometry presents different temperature ranges: type 2($251{\pm}38^{\circ}C{\sim}277{\pm}40^{\circ}C$); type 3($360{\pm}2^{\circ}C$ to $537{\pm}29^{\circ}C$). It is estimated to be due to the effect of metamorphism and Maytyubin granitoid intrusions, respectively. In addition, ternary chart of thorium, scandium, and zircon for discrimination of tectonic setting and redox sensitivity using V/Mo values indicate that hydrothermal sediments put on reduction environment after precipitation, before being affected by metamorphism and intrusion activity. Geochemical data are plotted on a distal trend of SEDEX-type with discrimination plot using SEDEX index. As a result, petrological-geochemical properties demonstrate that Dyusembay Pb-Zn mineralized zone is comparable to distal-type of SEDEX deposit.

• Tuberculosis and Respiratory Diseases
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• v.46 no.3
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• pp.327-337
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• 1999

Background: Reactive oxygen species are involved in multi-stage process of carcinogenesis. The moot of cancer cell lines and cancer cells in tumor tissue produce reactive oxygen species and on the other hand, the activities of catalase, Mn- and CuZn-superoxide dismutase in tumor cells are usually low. These persistent oxidative stress in tumor tissue facilitates tumor invasion and metastasis. 12-kDa thioredoxin, which regulates the intracellular redox potential with glutathione and glutaredoxin is involved in cell activation, proliferation, differentiation and redox-mediated apoptosis. It is also purified as 14-kDa and 10-kDa eooinophilic cytotoxic enhancing factor(ECEF) from human histiocytic cell(U937) and 10-kDa ECEF has more than 20 times eosinophilic stimulation activity than 14-kDa ECEF. It has been reported that adult T-cell leukemia, squamous cell carcinoma of uterine cervix, and hepatocellular carcinoma show increased amounts of human thioredoxin and thioredoxin mRNA is increased in lung cancer. In this study, we investigated the expression of conventional antioxidant enzymes such as catalase, CuZn-SOD, and glutathione peroxidase and thioredoxin in lung cancer tissue compared to adjacent normal lung tissue and the induction of thioredoxin in macrophage cells after treatment of oxidative stress and endotoxin Methods: We measured the amount of conventional antioxidant enzymes such as catalase, CuZn-SOD, and glutathione peroxidase and thioredoxin in lung cancer tissue compared to adjacent normal lung tissue by immunoblot analysis and the induction of thioredoxin in mouse monocyte-macrophage cells(RAW 264.7) by treatment of 5 ${\mu}M$ menadione and 1 ${\mu}g/ml$ endotoxin Results: On immunoblot analysis, the expression of 12-kDa thioredoxin was increased in lung cancer tissue compared to paired normal lung tissue. but the expression of catalase and CuZn-SOD were decreased in lung cancer tissue compared to paired normal tissue and the expression of glutathione peroxidase in lung cancer was variable. The expression of truncated thioredoxin was also increased in lung cancer. When mouse monocyte-macrophage cells were treated with 5 ${\mu}M$ menadione and 1 ${\mu}g/ml$ endotoxin, the expression of thioredoxin was peaked at 12 hrs and sustained to 48 hrs. Conclusion: In contrast with other conventional antioxidants, the expression of 12-kDa and truncated thioredoxin in lung cancer were increased and it is closely associated with persistent oxidative stress in tumor microenvironment. Considering especially the biological functions of truncated thioredoxin, the increased amount of truncated thioredoxin has significant role in tumor growth through cell proliferation.

• Korean Journal of Mineralogy and Petrology
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• v.36 no.4
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• pp.303-312
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• 2023

The determination of the oxidation states of metal elements in manganese nodules sheds light on the understanding of the formation mechanism of nodules, providing insights into the paleo-environmental conditions such as the redox potential of the aqueous system. This study aims to reveal the oxidation states and chemical bonding of manganese in the natural polymetallic nodules, utilizing conventional X-ray photoelectron spectroscopy (XPS). Specifically, shallow manganese nodules from the Siberian Arctic Sea, effectively recording mineralogical variations, were used in this study. Detailed analysis of XPS Mn 2p spectra showed changes in the manganese oxidation state from the center to the outer parts of the nodules. The central part of the nodules showed a higher Mn⁴⁺ content, approximately 67.9%, while the outermost part showed about 63% of Mn⁴⁺ due to an increase in the Mn³⁺+Mn²⁺. The decrease in the Mn oxidation state with the growth is consistent with the previously reported mineralogical variations from todorokite to birnessite with growth. Additionally, the O 1s spectra presented a predominance of Mn-O-H bonds in the outer layers compared to the center, suggesting hydration by water in the layered manganates of outer layers. The results of this study demonstrate that XPS can be directly applied to understand changes in paleo-environmental conditions such as the redox states during the growth of manganese nodules. Finally, future studies using high-resolution synchrotron-based XPS experiments could achieve details in oxidation states of manganese and trace metal elements.

• Journal of Environmental Health Sciences
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• v.33 no.2 s.95
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• pp.123-131
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• 2007

Many environmental contaminants including several metals, polycyclic aromatic hydrocarbons, and pharmaceuticals, have been identified to be phototoxic in the water environment. Concerns regarding photo-enhancement of toxicity of several environmental contaminants have been increasing because of the increased level of ultraviolet irradiation on the earth surface. However, there exist arguments that there might be certain defense mechanisms taking place in the aquatic ecosystem, which may include behavioral characteristics or genetic acclimation. This study was conducted to understand the potential responses of aquatic receptors to several phototoxic metals in the real environment, where long-term acclimation of such organisms to low dose UV-B may take place. For this purpose, water flea Daphnia magna was acclimated to environmentally relevant dose of UV-B (12 to $18uW/cm^2$) for >11 generations. The differences in developmental and life history characteristics, and toxicity responses were evaluated. Acclimation did not affect the daphnids' growth, longevity, and reproduction characteristics such as time to first brood, and brood size: After 21 d, survival of D. magna was not influenced by UV-B acclimation. When the number of young per female was compared. the daphnids acclimated for 11 generations tend to produce less number of neonates than the un-acclimated individuals but with no statistical significance (p>0.05). Four metals that were reported to be phototoxic elsewhere were employed in this evaluation, that include As, Cd. Cu, and Ni. UV-B level being applied in acclimation did increase the toxicity of Cd and Cu, significantly (p<0.05). However, the toxicities of As and Ni were not affected by irradiation of UV-B. Phototoxic responses were evaluated between the acclimated and the un-acclimated daphnids. For Cu, UV-B acclimation led to reduction of the photo-induced toxicity $(p\approx0.1)$ in daphnids. Non-acclimated Daphnia were affected by 50% at 4.18 ug/l Cu. but UV-B acclimated individuals exhibited $EC_{50}$ of 5.89 ug/l. With Cd, UV-B acclimation appeared to increase phototoxicity (p>0.05). With As and Ni, UV-B acclimation did not influence photo-induced toxicity. This observation may be in part explained by the type of reactive oxygen species that were generated by each metal. Similar to UV-B light, Cu is known to generate superoxide anion by acting as redox cycling toxicant. This is one of the first studies that employed_laboratory based UV-B acclimated test species for photoenhanced toxicity evaluation.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.89.1-89.1
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• 2010

Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline $TiO_2$ electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline $TiO_2$. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

• 한국신재생에너지학회:학술대회논문집
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• 2011.05a
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• pp.117.2-117.2
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• 2011

Since Gratzel and co-workers developed a new type of solar cell based on the nanocrystalline TiO2 electrode, dye-sensitized solar cells (DSSCs) have attracted considerable attention on account of their high solar energy-to-conversion efficiencies (11%), their easy manufacturing process with low cost production compared to conventional p-n junction solar cells. The mechanism of DSSC is based on the injection of electrons from the photoexcited dye into the conduction band of nanocrystalline TiO2. The oxidized dye is reduced by the hole injection process from either the hole counter or electrolyte. Thus, the electronic structures, such as HOMO, LUMO, and HOMO-LUMO gap, of dye molecule in DSSC are deeply related to the electron transfer by photoexcitation and redox potential. To date, high performance and good stability of DSSC based on Ru-dyes as a photosensitizer had been widely addressed in the literatures. DSSC with Ru-bipyridyl complexes (N3 and N719), and the black ruthenium dye have achieved power conversion efficiencies up to 11.2% and 10.4%, respectively. However, the Ru-dyes are facing the problem of manufacturing costs and environmental issues. In order to obtain even cheaper photosensitizers for DSSC, metal-free organic photosensitizers are strongly desired. Metal-free organic dyes offer superior molar extinction coefficients, low cost, and a diversity of molecular structures, compared to conventional Ru-dyes. Recently, novel photosensitizers such as coumarin, merocyanine, cyanine, indoline, hemicyanine, triphenylamine, dialkylaniline, bis(dimethylfluorenyl)-aminophenyl, phenothiazine, tetrahydroquinoline, and carbazole based dyes have achieved solar-to-electrical power conversion efficiencies up to 5-9%. On the other hand, organic dye molecules have large ${\pi}$-conjugated planner structures which would bring out strong molecular stacking in their solid-state and poor solubility in their media. It was well known that the molecular stacking of organic dyes could reduce the electron transfer pathway in opto-electronic devices, significantly. In this paper, we have studied on synthesis and characterization of dendritic organic dyes with different number of electron acceptor/anchoring moieties in the end of dendrimer. The photovoltaic performances and the incident photon-to-current (IPCE) of these dyes were measured to evaluate the effects of the dendritic strucuture on the open-circuit voltage and the short-circuit current.

• Journal of the Korea Organic Resources Recycling Association
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• v.14 no.3
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• pp.101-109
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• 2006

Earthworms(Eisenia fetida) were fed with paper mill sludge produced from P&G or Yuhan Kimberly paper manufacturing factory, or cow dung manure. Turnover rate of feed into earthworm biomass and excreting rate on each feed were investigated on dry weight base. Biomass of earthworm population was increased on paper mill sludge, but it was fallen to death on cow dung manure, which had high electrical conductivity and low redox potential. When P&G paper mill sludge was supplied to adult, elder juvenile or younger juvenile for 84 days, turnover rate of feed into earthworm biomass was 0.48, 0.40 and 0.76%, respectively, and on Yuhan Kimberly paper mill sludge 0.26, 0.45, 0.42%. When P&G paper mill sludge was supplied to adult, elder juvenile or younger juvenile, excreting rate was 49.02, 54.32 and 55.39%, respectively and on Yuhan Kimberly paper mill sludge 32.22, 41.86, 40.69%, and on cow dung manure, 73.73, 57.89. 76.38%.