메틸렌블루와 바나듐을 활물질로 활용한 수계 유기 레독스 흐름 전지의 성능 평가

이원미,권용재 한국화학공학회 2018 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.56 No.6

In this study, methylene blue which is one of dye materials was introduced as active material for aqueous redox flow battery. The redox potential of methylene blue was shifted to negative direction as pH increased. The full-cell performance was evaluated by using methylene blue as the negative active material and vanadium as the positive active material with acid supporting electrolytes. The cell voltage of methylene blue/V4+ is very low (0.45 V). In addition, the maximum solubility of methylene blue in water is only 0.12 M. Therefore, the cell test was performed with very low concentration (0.0015 M methylene blue, 0.15 M V4+) at first time. Cut-off voltage range was 0 to 0.8 V and 1 mA·cm-2 current density was adopted during cycling. As a result, current efficiency (CE) was 99.67%, voltage efficiency (VE), 88.83% and energy efficiency (EE) was 85.87% and discharge capacity was (0.0500 Ah·L-1) at 4 cycle. In addition, the cell test was performed with increased concentration (0.1 M methylene blue, 0.15 M V4+) with 10 mA·cm-2 current density, leading to higher discharge capacity (3.8122 Ah·L-1) with similar efficiency (CE=99%, VE=85%, EE=85% at 4 cycle). 본 연구에서는 염료 물질 중 하나인 메틸렌 블루(methylene blue)를 수계 레독스 흐름 전지의 활물질로 처음으로 도입하였다. Methylene blue의 레독스 전위는 pH가 높아짐에 따라 음의 방향으로 이동하는 것을 확인할 수 있었다. 이methylene blue를 음극 활물질로 활용하고, 양극 활물질로는 바나듐(vanadium) 을 활용하여 산 전해질을 기반으로 셀성능 평가를 진행하였다. Methylene blue/V4+ 레독스 조합의 산 전해질에 대한 셀 전압은 0.45 V로 낮으며, Methylene blue의 물에 대한 용해도 또한 0.12 M로 굉장히 낮다. 이에 따라 0.0015 M의 낮은 농도로 단전지 셀 성능을 평가하였으며, Nafion 212 멤브레인을 사용하여 0~0.8 V 컷-오프 전압으로 1 mA/cm2 전류밀도 하에서 4 cycle에서 충방전 효율 96.67%, 전압효율 88.83%, 에너지효율 85.87%, 방전 용량(0.0500 Ah·L-1)의 성능을 보였으며, 낮은 방전용량은 활물질의 낮은 농도에 의한 것이므로 활물질인 메틸렌 블루의 농도를 0.1 M로, 전류밀도는 10 mA/cm2로 더 높였을 때4 cycle에서 CE 99%, VE 85%, EE 85%의 효율로 더 높은 방전 용량(3.8122 Ah·L-1)을 도출함을 확인할 수 있었다.

파라쿼트를 투여한 백서의 급성 폐 손상 모델에서 메틸렌블루 투여가 Inducible Nitric Oxide Synthase 유전자 발현에 미치는 효과에 관한 연구

박현수 ( Hyun Soo Park ),이창현 ( Chang Hyun Lee ),정성구 ( Sung Goo Jung ),서길준 ( Gil Joon Suh ),정성은 ( Sung Eun Jung ),윤여규 ( Yeo Kyu Youn ) 대한외상학회 2005 大韓外傷學會誌 Vol.18 No.1

Purpose: This study was designed to determine if methylene blue inhibited the lipid peroxidation, the production of NO, and the gene expression of iNOS in acute lung injury induced by paraquat and if the inhibitory effect was dose dependent. Methods: Female Sprague-Dawley rats were divided into four groups: the control group, the group treated with paraquat only, the group treated with paraquat and a low dose of methylene blue (2 mg/kg), and the group treated with paraquat and a high dose of methylene blue (20mg/kg). Methylene blue was administered via the jugular vein 1 h after paraquat administration, and animals were sacrificed 6 and 24 h after paraquat administration. Malondialdehyde (MDA) as lipid peroxidation, reduced glutathione (GSH) as an antioxidant defense, the plasma NO concentration, and the expression of iNOS mRNA in the lung tissue were measured Results: Lung MDA contents decreased, with no significant difference between the methylene-blue groups and the paraquat-only group. Lung GSH contents were significantly elevated at 24 h in the methylene-blue groups compared with the paraquat-only group. Plasma NO concentrations were significantly reduced at 6 and 24 h in the methylene-blue groups compared with the paraquat-only group. There was also a significant decrease in the plasma NO concentration at 6 h in the high-dose methylene-blue group compared with the low-dose methylene-blue group. The expression of iNOS mRNA in the lung tissue was slightly decreased in the methylene-blue groups. It was also markedly increased at 24 h in the paraquat-only group compared with the methylene-blue groups. The gene expression was relatively decreased in the high-dose methylene-blue group compared with the low-dose methylene-blue group. Conclusion: This study suggests that methylene blue has an inhibitory effect on the plasma NO concentration and the expression of iNOS mRNA in lung injury induced by paraquat. No inhibitory effect of methylene blue on lipid peroxidation or dose-dependent inhibitory effects were clearly shown.

Effect of Methylene Blue on Alpha-Adrenergic Agonists-Induced Vasoconstriction in Rat Aorta

Park, Jung Dae,Kim, In Kyeom,Kim, Choong Young 慶北大學校 醫科大學 1992 慶北醫大誌 Vol.33 No.1

흰쥐의 대동맥을 사용하여 methylene blue전처치가 아드레날린성 알파 효현제에 의한 혈관수축반응에 미치는 영향을 관찰하여 다음과 같은 결과를 얻었다 혈관내피세포가 존재할때는 혈관 내피세포를 제거했을 때에 비해 norepinephrine에 의한 최대수축에는 차이가 없었지만 adrenergic alpha-agonist인 phenylephrine에 의한 수축작용은 현저히 감소되었으며 adrenergic alpha2-agonist인 clonidine이나 guanabenz에 의한 수축작용은 나타나지 않았다. 한편, methylene blue전처치에 의해 혈관내피세포가 존재할때의 adrenergic alpha-agonists에 의한 수축작용은 methylene blue를 전처치 하지 않은 상태에서 혈관 내피세포를 제거했을때와 유사하였다. 그러나 혈관내피세포를 제거했을 때 methylene blue를 전처치하면 norepinephrine에 의한 최대수축은 감소되었고 clonidine과 guanabenz에 의한 최대수축은 증가되었으며 phenylephrine에 의한 최대수축은 별다른 차이가 없었다. 그러나 이러한 최대수축의 차이에도 불구하고 EC50에는 차이가 없었다. 이상의 결과로 미루어 보아 methylene blue는 혈관내피세포에서 유리되는 이완물질의 작용을 억제할 뿐 아니라, 평활근의 수축작용도 조절하는 것으로 생각된다. The effect of methylene blue on the contractile responses induced by some adrenergic alpha-agonists was examined in rat aortic ring preparations. In an intact endothelium, norepinephrine and phenylephrine to a much less extent produce increase in contraction dose-dependently in contrast to unresponsiveness to clonidine and guanabenz. By the removal of endothelium, EC_50 values for both drugs increased, and the unresponsiveness to clonidine and guanabenz unmasked. These phenomena were shown in intact endothelium with methylene blue pretreatment. In the denuded preparations, by pretreatment with methylene blue, the norepinephrine-induced contraction was diminished while the clonidine-and guanabenz-induced contractions were augmented. On the other hand, phenylephrine-induced contraction was not influenced. However, regardless of alteration of maximal contractions, methylene blue had no effect on the sensitivity of denuded tissues to all adrenergic agonists. These results suggest that methylene blue modulates the contractile responses of smooth muscle as well as inhibits the actions of endothelium-derived relaxing factors.

감시림프절생검에서생체염료로써Isosulfan Blue와 Methylene Blue의 유용성 비교

양정현 한국유방암학회 2007 Journal of breast cancer Vol.10 No.2

Purpose: Isosulfan blue dye has been widely used for localizing sentinel lymph nodes (SLNs) in breast cancer patients. The use of methylene blue has recently been applied for localizing SLNs. We compared the use of each dye to investigate the effectiveness of methylene blue for the localization of SLNs. Methods: From January to December of 2005, 326 patients underwent surgery for breast cancer at Samsung Medical Center. In 86 patients, only a blue dye was used for SLN localization. Isosulfan blue and methylene blue were randomly given. Each dye (5 mL) was given by subareolar or peritumoral injection. The injection site was gently massaged with a warm gauze for 5 min. A frozen biopsy was performed for all SLNs, and an axillary dissection was done for positive frozen biopsy cases or cases in which axillary metastasis was clinically suspected. Results: Fifty-eight cases (61.1%) had been treated with isosulfan blue and 37 cases (38.9%) had been treated with methylene blue. Blue nodes were found in 96.6% of samples in the isosulfan blue group and 86.5% of samples in the methylene blue group. The mean number of SLNs was 2.10 in the isosulfan blue group and 2.27 in the methylene blue group (p>0.05). The frozen biopsy was positive for malignant cells in 16 of 56 cases in the isosulfan blue group and 4 of 32 cases in the methylene blue group. Axillary lymph node dissection was performed in 23 cases in the isosulfan blue group and 19 cases in the methylene blue group. Conclusion: There are no significant differences in the success rate, the mean number of SLNs found and the false negative rate between the use of isosulfan blue and methylene blue for localization of SLNs in breast cancer patients.

삼색도장버섯(Daedaleopsis tricolor TP3)에 의한 Methylene blue의 탈색과 분해

임형선,윤경하 순천향대학교 기초과학연구소 2000 순천향자연과학연구 논문집 Vol.6 No.1

Abstract In order to investigate the optimal conditions of decolorization and the degraded product of methylene blue by Daedaleopsis tricolor TP3 identified and isolatde from south korea, this study was performed. The effective medium for decolorization of methylene blue by the strain consisted Of 0.5% galactose, 0.12% yeast extract, 2.0% KH2PO4, 0.5% MgSO4 · 7H2O, 0.1% CaCl2ㆍ 2H2O, 0.002% thiamine-HCl, and 0.146% 2,2-dimethylsuccinate(DMS). The pH of the medium was adjusted to 5.5 with 1N NaOH solution. When the strain was grown in the above medium plus methylene blue at 30℃ for 7 days, a new product shown the maximum absorption at the region of 611nm wavelength and to be 0.67 of Rf with thin-layer chromatography was found. The new product was identified as azure C, tri-demethylated methylene blue derivative.

세균 내독소 유발 혈관 저반응성에 대한 NG-nitro-L-arginine methyl ester와 Methylene blue의 영향

손의동,이광윤,하정희,김원준,최형철 영남대학교 의과대학 1997 Yeungnam University Journal of Medicine Vol.14 No.2

세균 내독소에 의하여 발생하는 패혈성 쇼크와 혈관 반응성 감소의 원인을 관찰하였다. 혈관 절편이 고정된 실험조에 세균 내독소 0.2mg 투여한 경우 36±3.65 nM NO가 발생되었고, NO 발생에 의한 혈관 이완효과를 억제하기 위해 전처치한 L-NAME, methylene blue는 혈관 절편의 phenylephrine (PE) 유발 수축 반응을 증가시켰으며 methylene blue에 의해 더 강한 수축 반응의 증가가 관찰되었다. 이때 혈관 내피세포가 존재할 경우에 PE에 대한 혈관 반응성이 증가되는 경향을 나타내었다. 세균 내독소 투여에 의해 acetylcholine 유발 혈관 이완은 증가되는 경향을 나타내었고, 전처치한 L-NAME, methylene blue에 의해 혈관 절편의 acetylcholine (ACh) 유발 이완은 억제되었으며 methylene blue에 의해 현저히 억제되었다. 그러나 세균 내독소를 투여하지 않은 군의 ACh 유발 혈관 이완 반응은 methylene blue에 의해서만 억제되었다. 결론적으로 세균 내독소에 의한 혈관 반응성 감소와 혈관 이완 반응은 NO가 발생되어 guanylyl cyclass를 활성화하여 유발된다고 생각되며, 세균 내독소에 의한 효과는 L-arginine·NO pathway 보다는 cyclic GMP 신호전달계를 경유한 경로에서 더 많은 영향을 받는 것으로 사료된다. This study was undertaken to examine the intensity of involvement of inducible nitric oxide synthase (iNOS) and cyclic GMP signal transduction pathway as one of the mechanisms of vaso-relaxative action of bacterial lipopolysaccharide (LPS) on the canine femoral artery strips. Canine femoral arteries were isolated and spiral strips of 10 mm long and 2 mm wide were made in the Tyrode solution of 0-4℃. The strips were prepared for isometric myography in Biancani's isolated muscle chamber containing 1 ml of Tyrode solution, which was maintained with pH 7.4 by aeration with 95% O₂/5% CO₂ at 37℃ and nitric oxide (NO) production was measured simulltaneously with isolated nitric oxide meter. LPS induced NO production, suppressed the phenylephrine (PE) induced contraction and enhanced the acetylcholine (ACh) induced realxation. NG-intro-L-arginine methyl ester (L-NAME), an NOS inhibitor, methylene blue, a guanylyl cyclase inhibitor, potentiated PE induced contraction and suppressed ACh induced relaxation on the LPS treated strips. The inhibitory potency of methylene blue for LPS induced vascular hyporesponsiveness was stronger than that of L-NAME. These results suggest that in canine femoral artery, both iNOs and cyclic GMP signal trnasduction pathway are related with LPS induced vascular hyporeponsiveness, but in minor with iNOS and in major with cyclic GMP signal trnasduction pathway.

산 촉매에 따른 아나타제/브루카이트 혼성형 TiO₂ 광촉매의 메틸렌블루 광분해특성

윤석민,김진훈,정의경,임지선,이영석,Yun, Seok-Min,Kim, Jinhoon,Jeong, Euigyung,Im, Ji Sun,Lee, Young-Seak 한국공업화학회 2011 공업화학 Vol.22 No.1

본 연구에서는 난분해성 유기물질의 광분해능을 증가시키고자 다양한 산 촉매 및 마이크로웨이브법으로 아나타제/브루카이트 혼성형 $TiO_2$ 광촉매를 제조하였다. 또한 그에 따른 입자 및 결정크기와 브루카이트 분율에 따른 메틸렌블루의 광분해특성을 고찰하였다. 아나타제/브루카이트 혼성형 $TiO_2$ 광촉매의 표면특성 및 입자크기는 주사전자현미경과 레이저회절 입도분석기를 통하여 평가하였고, 결정구조는 X선 회절장치를 통하여 확인하였다. 메틸렌블루의 광분해 특성은 자외선 가시광선 분광광도계를 통하여 확인하였다. 주사전자현미경과 레이저회절 입도분석결과로부터 아나타제 및 아나타제/브루카이트 혼성형 $TiO_2$ 광촉매는 약 500 nm 이하의 클러스터 형태의 입자크기 나타내었고, 평균입자 크기는 $6.66{\sim}6.85{\mu}m$로 산 촉매 종류에 의한 영향은 크지 않음을 알 수 있었다. 산 촉매의 종류 및 마이크로웨이브법으로 제조된 $TiO_2$ 광촉매는 XRD 분석결과로부터 아나타제/브루카이트 혼성형 결정구조를 나타내었고 그 결정구조는 마이크로웨이브 조사시간의 증가에 따라서 변화하지 않았다. 메틸렌블루의 광분해능 실험결과로부터 광분해능은 브루카이트 분율 및 결정크기에 비례하지 않았으며, 브루카이트 분율 및 결정크기가 적정치 이상이 되면 오히려 촉매활성이 저하되는 경향성을 나타내었다. 본 연구결과에서는 브루카이트 분율 및 결정크기가 9.4%, 4.53 nm인 아나타제/브루카이트 혼성형 $TiO_2$ 광촉매가 가장 우수한 광분해능을 나타내었다. In this study, anatase/brookite hybrid $TiO_2$ was prepared using different acid catalysts and microwave to improve photodegradation of organic pollutants. The methylene blue photodegradation properties of the prepared photocatalysts with different particle/crystal size and brookite fractions were investigated. Surface characteristics and particle sizes of anatase/brookite hybrid $TiO_2$ were evaluated using scanning electron microscopy (SEM) and laser diffraction particle size analyzer, respectively and crystal structures were investigated with X-ray diffraction (XRD). Methylene blue photodegradation properties were evaluated with UV-vis spectrophotometer. Anatase and anatase/brookite hybrid $TiO_2$ had less than 500 nm size of clusters and the average particle size of $6.66{\sim}6.85{\mu}m$, suggesting that types of acid catalysts did not affect the size. XRD of the prepared $TiO_2$ showed that the photocatalysts had anatase/brookite hybrid crystal structure and applying microwave did not change their crystal structure. Photodegradation of methylene blue with the prepared photocatalyst did not increased proportionally to the fraction of brookite and the crystal size and decreased when brookite fraction and the crystal size increased further. Anatase/brookite hybrid $TiO_2$ with brookite fraction of 9.4% and crystal size of 4.53 nm shows the best photodegradation activity of methylene blue.

Microgel-Encapsulated Methylene Blue for the Treatment of Breast Cancer Cells by Photodynamic Therapy

Anil Khanal,Minh-Phuong Ngoc Bui,Seong S. Seo 한국유방암학회 2014 Journal of breast cancer Vol.17 No.1

Purpose: Photodynamic therapy (PDT) is gaining increasing recognitionfor breast cancer treatment because it offers local selectivityand reduced toxic side effects compared to radiotherapyand chemotherapy. In PDT, photosensitizer drugs are loaded indifferent nanomaterials and used in combination with light exposure. However, the most representative issue with PDT is the difficultyof nanomaterials to encapsulate anticancer drugs at highdoses, which results in low efficacy of the PDT treatment. Here,we proposed the development of the poly(N-isopropylacrylamide)(PNIPAM) microgel for the encapsulation of methylene blue, ananticancer drug, for its use as breast cancer treatment in MCF-7cell line. Methods: We developed biocompatible microgels basedon nonfunctionalized PNIPAM and its corresponding anionicallyfunctionalized PNIPAM and polyacrylic acid (PNIPAM-co-PAA)microgel. Methylene blue was used as the photosensitizer drugbecause of its ability to generate toxic reactive oxygen speciesupon exposure to light at 664 nm. Core PNIPAM and core/shellPNIPAM-co-PAA microgels were synthesized and characterizedusing ultraviolet-visible spectroscopy and dynamic light scattering. The effect of methylene blue was evaluated using the MCF-7cell line. Results: Loading of methylene blue in core PNIPAM microgelwas higher than that in the core/shell PNIPAM-co-PAA microgel,indicating that electrostatic interactions did not play animportant role in loading a cationic drug. This behavior is probablydue to the skin layer inhibiting the high uptake of drugs in thePNIPAM-co-PAA microgel. Core PNIPAM microgel effectively retainedthe cationic drug (i.e., methylene blue) for several hourscompared to core/shell PNIPAM-co-PAA and enhanced its photodynamicefficacy in vitro more than that of free methylene blue. Conclusion: Our results showed that the employment of core PNIPAMand core/shell PNIPAM-co-PAA microgels enhanced theencapsulation of methylene blue. Core PNIPAM microgel releasedthe drug more slowly than did core/shell PNIPAM-co-PAA, and iteffectively inhibited the growth of MCF-7 cells.

Effect of Methylene Blue-mediated Photodynamic Therapy on Wild-type and Ciprofloxacin-resistant Mycobacterium smegmatis

Shim, Insoo,Choi, Myungwon,Min, Yegee,Seok, Kwang Hyuk,Kim, Jiyeun Kate,Jeong, Jee-Yeong,Oak, Chul-Ho,Park, Indal 대한미생물학회 2016 Journal of Bacteriology and Virology Vol.46 No.1

Tuberculosis (TB) patients are normally treated with a combination of antibiotics. However, with improper or incomplete treatment of antibiotics, the disease may progress to multidrug-resistant TB (MDR-TB). The treatment of MDR-TB is very costly and inefficient. Therefore, there is a great demand of new therapeutic approaches for MDR-TB such as photodynamic therapy. In this study, we tried to optimize the conditions for photodynamic inactivation of TB using methylene blue as a photosensitizer. Different combinations of methylene blue concentrations and light doses were tested for their photodynamic effects to A549 cells or Mycobacterium smegmatis (M. smegmatis). We also tested the effect of photodynamic therapy on ciprofloxacin-resistant M. smegmatis. Methylene blue treatment alone did not affect the survival rates of A549 cells or bacteria up to $5{\mu}g/ml$. When the A549 and M. smegmatis cells treated with methylene blue were irradiated with laser light (wavelength, 630 nm), photodynamic inactivation of cells was increased in methylene blue concentration- and light dose-dependent manners. Interestingly, the ciprofloxacin-resistant M. smegmatis exhibited higher level of susceptibility to methylene blue-mediated photodynamic inactivation. This study suggests that photodynamic therapy at $3.6J/cm^2$ in the presence of $5{\mu}g/ml$ methylene blue may be an appropriate range for therapy due to the high bactericidal activity against high level of ciprofloxacin-resistant M. smegmatis and the low damaging effect to mammalian cells. This study demonstrates that photodynamic therapy could be a potential alternative for MDR-TB treatment.

Effect of Methylene Blue-mediated Photodynamic Therapy on Wild-type and Ciprofloxacin-resistant Mycobacterium smegmatis

심인수,최명원,민예지,석광혁,김지연,정지영,옥철호,박인달 대한미생물학회 2016 Journal of Bacteriology and Virology Vol.46 No.1

Tuberculosis (TB) patients are normally treated with a combination of antibiotics. However, with improper or incompletetreatment of antibiotics, the disease may progress to multidrug-resistant TB (MDR-TB). The treatment of MDR-TB is verycostly and inefficient. Therefore, there is a great demand of new therapeutic approaches for MDR-TB such as photodynamictherapy. In this study, we tried to optimize the conditions for photodynamic inactivation of TB using methylene blue as aphotosensitizer. Different combinations of methylene blue concentrations and light doses were tested for their photodynamiceffects to A549 cells or Mycobacterium smegmatis (M. smegmatis). We also tested the effect of photodynamic therapyon ciprofloxacin-resistant M. smegmatis. Methylene blue treatment alone did not affect the survival rates of A549 cellsor bacteria up to 5 μg/ml. When the A549 and M. smegmatis cells treated with methylene blue were irradiated with laserlight (wavelength, 630 nm), photodynamic inactivation of cells was increased in methylene blue concentration- and lightdose-dependent manners. Interestingly, the ciprofloxacin-resistant M. smegmatis exhibited higher level of susceptibilityto methylene blue-mediated photodynamic inactivation. This study suggests that photodynamic therapy at 3.6 J/cm2 inthe presence of 5 μg/ml methylene blue may be an appropriate range for therapy due to the high bactericidal activity againsthigh level of ciprofloxacin-resistant M. smegmatis and the low damaging effect to mammalian cells. This study demonstratesthat photodynamic therapy could be a potential alternative for MDR-TB treatment.