Photoredox-Catalyzed Stereoselective Conversion of Alkynes into Tetrasubstituted Trifluoromethylated Alkenes.

Science.gov (United States)

Tomita, Ren; Koike, Takashi; Akita, Munetaka

2015-10-26

A regio- and stereoselective synthesis of trifluoromethylated alkenes bearing four different substituents has been developed. Stereocontrolled sulfonyloxytrifluoromethylation of unsymmetric internal alkynes with an electrophilic CF3 reagent, namely the triflate salt of the Yagupol'skii-Umemoto reagent, in the presence of an Ir photoredox catalyst under visible-light irradiation afforded trifluoromethylalkenyl triflates with well-predictable stereochemistry resulting from anti addition of the trifluoromethyl and triflate groups. Subsequent palladium-catalyzed cross-couplings led to tetrasubstituted trifluoromethylated alkenes in a highly stereoselective manner. The present method is the first example of a facile one-pot synthesis of tetrasubstituted trifluoromethylated alkenes from simple alkynes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereoselectivity of Mucorales lipases toward triradylglycerols--a simple solution to a complex problem.

Science.gov (United States)

Scheib, H.; Pleiss, J.; Kovac, A.; Paltauf, F.; Schmid, R. D.

1999-01-01

The lipases from Rhizopus and Rhizomucor are members of the family of Mucorales lipases. Although they display high sequence homology, their stereoselectivity toward triradylglycerols (sn-2 substituted triacylglycerols) varies. Four different triradylglycerols were investigated, which were classified into two groups: flexible substrates with rotatable O'-C1' ether or ester bonds adjacent to C2 of glycerol and rigid substrates with a rigid N'-C1' amide bond or a phenyl ring in sn-2. Although Rhizopus lipase shows opposite stereopreference for flexible and rigid substrates (hydrolysis in sn-1 and sn-3, respectively), Rhizomucor lipase hydrolyzes both groups of triradylglycerols preferably in sn-1. To explain these experimental observations, computer-aided molecular modeling was applied to study the molecular basis of stereoselectivity. A generalized model for both lipases of the Mucorales family highlights the residues mediating stereoselectivity: (1) L258, the C-terminal neighbor of the catalytic histidine, and (2) G266, which is located in a loop contacting the glycerol backbone of a bound substrate. Interactions with triradylglycerol substrates are dominated by van der Waals contacts. Stereoselectivity can be predicted by analyzing the value of a single substrate torsion angle that discriminates between sn-1 and sn-3 stereopreference for all substrates and lipases investigated here. This simple model can be easily applied in enzyme and substrate engineering to predict Mucorales lipase variants and synthetic substrates with desired stereoselectivity. PMID:10210199

Stereoselective sulfate conjugation of racemic 4-hydroxypropranolol by human and rat liver cytosol

Energy Technology Data Exchange (ETDEWEB)

Walle, T.; Walle, U.K. (Department of Cell and Molecular Pharmacology and Experimental Therapeutics, Medical University of South Carolina, Charleston (USA))

1991-03-01

The objective of this study was to determine the stereochemistry of sulfoconjugation of a chiral phenolic amine drug, 4-hydroxypropranolol (HOP), by the human liver. The reaction was catalyzed by the 100,000 g cytosol as the phenolsulfotransferase (PST) enzyme source with PAP35S as the co-substrate. The enantiomers of the intact sulfate conjugate formed, (+)-HOP35S and (-)-HOP35S, were separated by HPLC and measured by liquid scintillation spectrometry. Complex velocity vs. substrate concentration curves were obtained with two peaks of activity, one at 3 microM (high affinity) and one at 500 microM (low affinity). The high-affinity reaction demonstrated a high degree of stereoselectivity. Whereas the affinity of the enantiomers for this reaction was identical, with a very low apparent KM value of 0.59 microM, the apparent Vmax value for (+)-HOPS formation was 4.6-fold higher than for (-)-HOPS. In sharp contrast, the low-affinity reaction, with an apparent KM of 65 microM, was not stereoselective. Inhibition of the high-affinity reaction by elevated temperature, but not by dichloronitrophenol, indicated that this activity was due to a monoamine form of PST. Inhibition of the low-affinity reaction by dichloronitrophenol, but not by elevated temperature, indicated that this activity was due to a phenol form of PST. As a comparison, experiments with the rat liver cytosol demonstrated only one activity, with apparent KM values of 50 microM for both enantiomers and opposite stereoselectivity in maximum velocity compared to humans, {plus minus}-HOPS ratio 0.72. The results of this study demonstrate stereoselectivity in human hepatic sulfation of a chiral phenolic amine, with clear differences between PST isoenzymes.

Diversity-Oriented Syntheses by Combining CuAAC and Stereoselective INCIC Reactions with Peptides

DEFF Research Database (Denmark)

Wang, Yuanyuan; Madsen, Anders; Diness, Frederik

2017-01-01

Cascade reactions proceeding through peptide-derived N-carbamoyl iminium ions are reported. Two new reactions of N-carbamoyl iminium ions are described, including a stereoselective double cyclization generating N,N′-aminals and an acid-promoted auto-oxidation. Mechanistic investigations revealed...... that the N,N′-aminal formation is reversible under strongly acidic conditions. Both of these new reactions proved to be completely orthogonal to subsequent CuAAC chemistry. The reactions were performed in solution and on solid support. The robustness and high stereoselectivity of the methodology holds great...

Stereoselective separation of β-adrenergic blocking agents containing two chiral centers by countercurrent chromatography.

Science.gov (United States)

Lv, Liqiong; Bu, Zhisi; Lu, Mengxia; Wang, Xiaoping; Yan, Jizhong; Tong, Shengqiang

2017-09-01

Four β-adrenergic blocking agents, including 1-[(1-methylethyl)amino]-3-phenoxy-2-propanol (1), 1-[(1-methylethyl)amino]-3-(3-methylphenoxy)-2-propanol (2), 1,1'-[1,4-phenylenebis(oxy)]bis[3-[(1-methylethyl)amino]-2-propanol (3) and 1,1'-[(4-methyl-1,2-phenylene)bis(oxy)]bis[3-[(1-methylethyl)amino]-2-propanol (4), were stereoselectively separated by countercurrent chromatography using di-n-hexyl l-tartrate and boric acid as chiral selector. The compounds (3) and (4) have four optical isomers since they contained two chiral centers. A two-phase solvent system composed of chloroform-0.05molL -1 of acetate buffer containing 0.10molL -1 of boric acid (1:1, v/v) was selected, in which 0.10molL -1 of di-n-hexyl l-tartrate was added in the organic phase as chiral selector. 20-42mg of each racemate was stereoselectively separated by countercurrent chromatography in a single run with high purity of 96-98%, and the recovery of each separated compound reached around 87-93%. This is the first time report on successful stereoselective separation of optical isomeric compounds containing two chiral centers by countercurrent chromatography. At the same time, a chiral stationary phase was screened for analytical stereoselective separation of compounds (3) and (4) by high performance liquid chromatography. Copyright © 2017 Elsevier B.V. All rights reserved.

Stereoselective Hydrogenation and Ozonolysis of Iridoids. Conversion into Carbocyclic Nucleoside Analogues

DEFF Research Database (Denmark)

Franzyk, Henrik; Stermitz, Frank R.

1999-01-01

Stereoselective hydrogenation of the iridoids geniposide (9) and aucubin (19) was achieved by using the 1-methyl-1-methoxyethyl ether (MIP) as protecting group for the allylic alcohol, as it enhanced the stereoselectivity and prevented undesired hydrogenolysis. Ozonolysis of the hydrogenation...

Spiro(phosphoamidite) ligand (SIPHOS)/Cu(OTf)2-catalyzed highly regio-and stereo-selective hydroborations of internal alkynes with diborane in water

Institute of Scientific and Technical Information of China (English)

Qing-Qing Xuan; Ya-Hui Wei; Qiu-Ling Song

2017-01-01

The highly regio-and stereoselective hydroborations of unactivated internal alkynes with diboron compound catalyzed by Cu(OTf)2 with spiro(phosphoamidite) as ligand in the presence of Cs2CO3 in water was developed.This protocol was applied efficiently in the aqueous synthesis of multi-substituted vinylboranes.

CuI/Pd0 cooperative dual catalysis: tunable stereoselective construction of tetra-substituted alkenes.

Science.gov (United States)

Vercruysse, Sébastien; Cornelissen, Loïc; Nahra, Fady; Collard, Laurent; Riant, Olivier

2014-02-10

This paper describes a tunable and stereoselective dual catalytic system that uses copper and palladium reagents. This cooperative silylcupration and palladium-catalyzed allylation readily affords trisubstituted alkenylsilanes. Fine-tuning the reaction conditions allows selective access to one stereoisomer over the other. This new methodology tolerates different substituents on both coupling partners with high levels of stereoselectivity. The one-pot reaction involving a Cu(I)/Pd(0) cooperative dual catalyst directly addresses the need to develop more time-efficient and less-wasteful synthetic pathways. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereoselective synthesis of hernandulcin, peroxylippidulcine A, lippidulcines A, B and C and taste evaluation

Directory of Open Access Journals (Sweden)

Marco G. Rigamonti

2015-11-01

Full Text Available The first stereoselective synthesis of lippidulcines A, B and C has been accomplished starting from (+-hernandulcin, which has been prepared on a multigram scale. The previously assigned absolute configurations have been confirmed. The key steps of this synthesis are based on a modified version of the Kornblum–DeLaMare rearrangement, and on a highly regioselective and stereoselective ketone reduction with the MeCBS reagent. The taste evaluations indicate that none of these sesquiterpenes are sweet, instead the lippidulcine A is a cooling agent with a mint after taste.

An Expeditious Stereoselective Synthesis of (−)-Pinidinone from Ethyl Acetoacetate

International Nuclear Information System (INIS)

Damodar, Kongara; Jun, Jong-Gab

2016-01-01

An expeditious stereoselective synthesis of a naturally occurring 2,6-disubstituted piperidine alkaloid, (−)-pinidinone, has been accomplished with an overall yield of 31% in total eight steps. The synthesis involves ethyl acetoacetate as the starting material and the stereoselective α-aminoallylation of aldehyde with (S)-tert-butanesulfinamide, allyl bromide, and indium and Grubbs' olefin cross-metathesis as the pivotal steps.

Stereoselective Reduction of Imines with Trichlorosilane Using Solid-Supported Chiral Picolinamides

Directory of Open Access Journals (Sweden)

Sílvia D. Fernandes

2016-09-01

Full Text Available The stereoselective reduction of imines with trichlorosilane catalyzed by chiral Lewis bases is a well-established procedure for the synthesis of enantio-enriched amines. Five supported cinchona-based picolinamides have been prepared and their activity tested in a model reaction. The comparison of different supporting materials revealed that polystyrene gave better results than silica in terms of stereoselectivity. The applicability of the solid-supported catalyst of choice to the reduction of different imines was also demonstrated. Additionally, for the first time, a catalytic reactor containing a polymer-immobilized chiral picolinamide has been employed for the stereoselective reduction of imines with trichlorosilane under continuous flow conditions.

Stereocontrolled generation of nucleophilic (Z)- or (E)-α-fluoroalkenylchromium reagents via carbon-fluorine bond activation: highly stereoselective synthesis of (E)- or (Z)-β-fluoroallylic alcohols.

Science.gov (United States)

Nihei, Takashi; Yokotani, Saya; Ishihara, Takashi; Konno, Tsutomu

2014-02-14

Highly nucleophilic (Z)- or (E)-α-fluoroalkenylchromium species could be generated in a stereoselective manner via C-F bond activation of CBrF2-containing molecules, and they reacted smoothly with various aldehydes to give (E)- or (Z)-β-fluoroallylic alcohol derivatives in high yields, respectively.

Ionic liquids as precatalysts in the highly stereoselective conjugate addition of α,β-unsaturated aldehydes to chalcones.

Science.gov (United States)

Ta, Linda; Axelsson, Anton; Bijl, Joachim; Haukka, Matti; Sundén, Henrik

2014-10-20

Imidazolium-based ionic liquids (ILs) serve both as recyclable reaction media and as precatalysts for the N-heterocyclic carbene-catalyzed conjugate addition of α,β-unsaturated aldehydes to chalcones. The reaction produces a broad scope of 1,6-ketoesters incorporating an anti-diphenyl moiety in high yields and with high stereoselectivity. In recycling experiments, the IL can be reused up to five times with retained reactivity and selectivity. Moreover, the 1,6-ketoesters form self-assembled organogels in aliphatic hydrocarbons. The reaction protocol is robust, easily operated, scalable and highly functionalized compounds can be obtained from inexpensive and readily accessible starting materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereoselective Carbonyl Olefination with Fluorosulfoximines: Facile Access to Z or E Terminal Monofluoroalkenes.

Science.gov (United States)

Liu, Qinghe; Shen, Xiao; Ni, Chuanfa; Hu, Jinbo

2017-01-09

Terminal monofluoroalkenes are important structural motifs in the design of bioactive compounds, such as homeostasis regulators and mechanism-based enzyme inhibitors. However, it is difficult to control the stereoselectivity of known carbonyl olefination reactions, and olefin metathesis is limited to disubstituted terminal monofluoroalkenes. Although sulfoximines have been used extensively in organic synthesis, reports on their use in carbonyl olefination reactions have not appeared to date. Herein, we report highly stereoselective carbonyl monofluoroolefination with a fluorosulfoximine reagent. The potential of this method is demonstrated by the synthesis of MDL 72161 and by the late-stage monofluoromethylenation of complex molecules, such as haloperidol and steroid derivatives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Regio and stereoselectivity in ionic cycloadditions

Indian Academy of Sciences (India)

WINTEC

Though the reactions have both electrostatic control and frontier orbital control the former dominates in the initial stages of the reaction. Keywords. Stereoselectivity; ionic cycloaddition; density functional theory; acridizinium ion; methyl vinyl ether; 2,3-dimethylisoquinolinium ion. 1. Introduction. In polar or ionic cycloadditions ...

Mechanistic basis for high stereoselectivity and broad substrate scope in the (salen)Co(III)-catalyzed hydrolytic kinetic resolution.

Science.gov (United States)

Ford, David D; Nielsen, Lars P C; Zuend, Stephan J; Musgrave, Charles B; Jacobsen, Eric N

2013-10-16

In the (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides, the rate- and stereoselectivity-determining epoxide ring-opening step occurs by a cooperative bimetallic mechanism with one Co(III) complex acting as a Lewis acid and another serving to deliver the hydroxide nucleophile. In this paper, we analyze the basis for the extraordinarily high stereoselectivity and broad substrate scope observed in the HKR. We demonstrate that the stereochemistry of each of the two (salen)Co(III) complexes in the rate-determining transition structure is important for productive catalysis: a measurable rate of hydrolysis occurs only if the absolute stereochemistry of each of these (salen)Co(III) complexes is the same. Experimental and computational studies provide strong evidence that stereochemical communication in the HKR is mediated by the stepped conformation of the salen ligand, and not the shape of the chiral diamine backbone of the ligand. A detailed computational analysis reveals that the epoxide binds the Lewis acidic Co(III) complex in a well-defined geometry imposed by stereoelectronic rather than steric effects. This insight serves as the basis of a complete stereochemical and transition structure model that sheds light on the reasons for the broad substrate generality of the HKR.

Concepts for stereoselective acrylate insertion

KAUST Repository

Neuwald, Boris

2013-01-23

Various phosphinesulfonato ligands and the corresponding palladium complexes [{((PaO)PdMeCl)-μ-M}n] ([{( X1-Cl)-μ-M}n], (PaO) = κ2- P,O-Ar2PC6H4SO2O) with symmetric (Ar = 2-MeOC6H4, 2-CF3C6H4, 2,6-(MeO)2C6H3, 2,6-(iPrO)2C 6H3, 2-(2′,6′-(MeO)2C 6H3)C6H4) and asymmetric substituted phosphorus atoms (Ar1 = 2,6-(MeO)2C6H 3, Ar2 = 2′-(2,6-(MeO)2C 6H3)C6H4; Ar1 = 2,6-(MeO)2C6H3, Ar2 = 2-cHexOC 6H4) were synthesized. Analyses of molecular motions and dynamics by variable temperature NMR studies and line shape analysis were performed for the free ligands and the complexes. The highest barriers of ΔGa = 44-64 kJ/mol were assigned to an aryl rotation process, and the flexibility of the ligand framework was found to be a key obstacle to a more effective stereocontrol. An increase of steric bulk at the aryl substituents raises the motional barriers but diminishes insertion rates and regioselectivity. The stereoselectivity of the first and the second methyl acrylate (MA) insertion into the Pd-Me bond of in situ generated complexes X1 was investigated by NMR and DFT methods. The substitution pattern of the ligand clearly affects the first MA insertion, resulting in a stereoselectivity of up to 6:1 for complexes with an asymmetric substituted phosphorus. In the consecutive insertion, the stereoselectivity is diminished in all cases. DFT analysis of the corresponding insertion transition states revealed that a selectivity for the first insertion with asymmetric (P aO) complexes is diminished in the consecutive insertions due to uncooperatively working enantiomorphic and chain end stereocontrol. From these observations, further concepts are developed. © 2012 American Chemical Society.

Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

KAUST Repository

Brzozowska, Aleksandra; Azofra, Luis Miguel; Zubar, Viktoriia; Atodiresei, Iuliana; Cavallo, Luigi; Rueping, Magnus; El-Sepelgy, Osama

2018-01-01

The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

Highly Chemo- and Stereoselective Transfer Semihydrogenation of Alkynes Catalyzed by a Stable, Well-defined Manganese(II) Complex

KAUST Repository

Brzozowska, Aleksandra

2018-03-30

The first example of manganese catalyzed semihydrogenation of internal alkynes to (Z)-alkenes using ammonia borane as a hydrogen donor is reported. The reaction is catalyzed by a pincer complex of the earth abundant manganese(II) salt in the absence of any additives, base or super hydride. The ammonia borane smoothly reduces the manganese pre-catalyst [Mn(II)-PNP][Cl]2 to the catalytically active species [Mn(I)-PNP]-hydride in the triplet spin state. This manganese hydride is highly stabilized by complexation with the alkyne substrate. Computational DFT analysis studies of the reaction mechanism rationalizes the origin of stereoselectivity towards formation of (Z)-alkenes.

Marine Microorganisms as Source of Stereoselective Esterases and Ketoreductases: Kinetic Resolution of a Prostaglandin Intermediate

KAUST Repository

De Vitis, Valerio; Guidi, Benedetta; Contente, Martina Letizia; Granato, Tiziana Mariarita; Conti, Paola; Molinari, Francesco; Crotti, Elena; Mapelli, Francesca; Borin, Sara S.; Daffonchio, Daniele; Romano, Diego

2014-01-01

A screening among bacterial strains isolated from water-brine interface of the deep hypersaline anoxic basins (DHABs) of the Eastern Mediterranean was carried out for the biocatalytical resolution of racemic propyl ester of anti-2-oxotricyclo[2.2.1.0]heptan-7-carboxylic acid (R,S)-1, a key intermediate for the synthesis of d-cloprostenol. Bacillus horneckiae 15A gave highly stereoselective reduction of (R,S)-1, whereas Halomonas aquamarina 9B enantioselectively hydrolysed (R,S)-1; in both cases, enantiomerically pure unreacted (R)-1 could be easily recovered and purified at molar conversion below 57–58 %, showing the potential of DHAB extremophile microbiome and marine-derived enzymes in stereoselective biocatalysis.

Marine Microorganisms as Source of Stereoselective Esterases and Ketoreductases: Kinetic Resolution of a Prostaglandin Intermediate

KAUST Repository

De Vitis, Valerio

2014-09-30

A screening among bacterial strains isolated from water-brine interface of the deep hypersaline anoxic basins (DHABs) of the Eastern Mediterranean was carried out for the biocatalytical resolution of racemic propyl ester of anti-2-oxotricyclo[2.2.1.0]heptan-7-carboxylic acid (R,S)-1, a key intermediate for the synthesis of d-cloprostenol. Bacillus horneckiae 15A gave highly stereoselective reduction of (R,S)-1, whereas Halomonas aquamarina 9B enantioselectively hydrolysed (R,S)-1; in both cases, enantiomerically pure unreacted (R)-1 could be easily recovered and purified at molar conversion below 57–58 %, showing the potential of DHAB extremophile microbiome and marine-derived enzymes in stereoselective biocatalysis.

Synergistic Diazo-OH Insertion/Conia-Ene Cascade Catalysis for the Stereoselective Synthesis of γ-Butyrolactones and Tetrahydrofurans.

Science.gov (United States)

Hunter, Arianne C; Schlitzer, Steven C; Sharma, Indrajeet

2016-11-02

A novel and highly efficient diazo-OH insertion/Conia-ene cascade reaction of readily available homopropargylic acids and alcohols with diazo carbonyl compounds is described. The cascade reaction involves a synergistic Rh/Ag/Au catalyst cocktail and proceeds instantly with a variety of substituted diazo compounds and acids/alcohols to provide functionalized γ-butyrolactones and tetrahydrofurans with complete regio- and stereoselectivity. The unprecedented rate-enhancement, complete stereoselectivity, and the enabling of new Conia-ene cyclizations suggest a concerted [4+1]-cycloaddition reaction pathway under synergistic (Rh/Ag/Au)-catalysis conditions. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biological stereoselective reduction of 3,3,5-trimethylcyclohexanone by Glomerella cingulata.

Science.gov (United States)

Okamura, S; Kameoka, H; Miyazawa, M

2001-01-01

The microbial transformation of 3,3,5-trimethylcyclohexanone was investigated using the plant pathogenic fungus, Glomerella cingulata. With this organism 3,3,5-trimethylcyclohexanone gave the corresponding cis- and trans-3,3,5-trimethylcyclohexanols with the ratio of 20:1 forming the cis-isomer highly stereoselectively, upon 5 days incubation together with 3,3,5-trimethyl-2-cyclohexen-1-one (isophrone) as a minor product.

Stereoselectivity in bioaccumulation and excretion of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae.

Science.gov (United States)

Lv, Xiaotian; Liu, Chen; Li, Yaobin; Gao, Yongxin; Wang, Huili; Li, Jianzhong; Guo, Baoyuan

2014-09-01

Stereoselectivity in bioaccumulation and excretion of stereoisomers of epoxiconazole by mealworm beetle (Tenebrio molitor) larvae through dietary exposure was investigated. Liquid chromatography tandem mass spectrometry (HPLC-MS/MS) method that use a ChiralcelOD-3R[cellulosetris-Tris-(3, 5-dichlorophenyl-carbamate)] chromatography column was applied to carry out chiral separation of the stereoisomers. Wheat bran was spiked with racemic epoxiconazole at two dose levels of 20mg/kg and 2mg/kg (dry weight) to feed T. molitor larvae. The results showed that both the doses of epoxiconazole were taken up by Tenebrio molitor larvae rapidly at the initial stages. There was a significant trend of stereoselective bioaccumulation in the larvae with a preferential accumulation of (-)-epoxiconazole in the 20mg/kg dose. The stereoselectivity in bioaccumulation in the 2mg/kg dosage was not obvious compared to the 20mg/kg group. Results of excretion indicated an active excretion is an important pathway for the larvae to eliminate epoxiconazole which was a passive transport process with non stereoselectivity. The faster elimination might be the reason for the low accumulation of epoxiconazole, as measured by bioaccumulation factor (BAF). Copyright © 2014 Elsevier Inc. All rights reserved.

21 CFR 173.255 - Methylene chloride.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Methylene chloride. 173.255 Section 173.255 Food... Solvents, Lubricants, Release Agents and Related Substances § 173.255 Methylene chloride. Methylene chloride may be present in food under the following conditions: (a) In spice oleoresins as a residue from...

Electronic forces as descriptors of nucleophilic and electrophilic regioselectivity and stereoselectivity.

Science.gov (United States)

Liu, Shubin; Rong, Chunying; Lu, Tian

2017-01-04

One of the main tasks of theoretical chemistry is to rationalize computational results with chemical insights. Key concepts of such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While computational tools are available to predict barrier heights and other reactivity properties with acceptable accuracy, a conceptual framework to appreciate above quantities is still lacking. In this work, we introduce the electronic force as the fundamental driving force of chemical processes to understand and predict molecular reactivity. It has three components but only two are independent. These forces, electrostatic and steric, can be employed as reliable descriptors for nucleophilic and electrophilic regioselectivity and stereoselectivity. The advantages of using these forces to evaluate molecular reactivity are that electrophilic and nucleophilic attacks are featured by distinct characteristics in the electrostatic force and no knowledge of quantum effects included in the kinetic and exchange-correlation energies is required. Examples are provided to highlight the validity and general applicability of these reactivity descriptors. Possible applications in ambident reactivity, σ and π holes, frustrated Lewis pairs, and stereoselective reactions are also included in this work.

Regio- and stereoselective carbometallation reactions of N-alkynylamides and sulfonamides

Directory of Open Access Journals (Sweden)

Yury Minko

2013-03-01

Full Text Available The carbocupration reactions of heterosubstituted alkynes allow the regio- and stereoselective formation of vinyl organometallic species. N-Alkynylamides (ynamides are particularly useful substrates for the highly regioselective carbocupration reaction, as they lead to the stereodefined formation of vinylcopper species geminated to the amide moiety. The latter species are involved in numerous synthetically useful transformations leading to valuable building blocks in organic synthesis. Here we describe in full the results of our studies related to the carbometallation reactions of N-alkynylamides.

Stereoselective Synthesis of Tetrasubstituted Furylalkenes via Gold-Catalyzed Cross-Coupling of Enynones with Diazo Compounds.

Science.gov (United States)

Liu, Pei; Sun, Jiangtao

2017-07-07

A stereoselective, gold-catalyzed, cross-coupling reaction of enynones with diazo compounds has been developed, affording 2-alkenylfurans in moderate to good yields with excellent E-stereoselectivity. Upon using diazo compounds as nucleophiles to trap the in situ formed gold furyl carbene, this protocol provides a novel path toward the formation of unsymmetrical tetrasubstituted alkenes.

Regio- and stereoselective iodoacyloxylations of alkynes.

Science.gov (United States)

Priebbenow, Daniel L; Gable, Robert W; Baell, Jonathan

2015-05-01

A new method for the regioselective and stereoselective iodoacyloxylation of alkynes has been developed. This protocol utilizes a combination of an iodobenzene dicarboxylate and iodine to functionalize a series of activated and unactivated alkynes in an entirely selective and predictable fashion. The resultant iodo-enol esters were subsequently coupled with boronic acids to afford tetrasubstituted alkene derivatives, which could be further converted to the corresponding 1,1-disubstituted acetophenone.

Stereoselective handling of perhexiline: implications regarding accumulation within the human myocardium.

Science.gov (United States)

Chong, Cher-Rin; Drury, Nigel E; Licari, Giovanni; Frenneaux, Michael P; Horowitz, John D; Pagano, Domenico; Sallustio, Benedetta C

2015-12-01

Perhexiline is a prophylactic anti-ischaemic agent with weak calcium antagonist effect which has been increasingly utilised in the management of refractory angina. The metabolic clearance of perhexiline is modulated by CYP2D6 metaboliser status and stereoselectivity. The current study sought to (1) determine whether the acute accumulation of perhexiline in the myocardium is stereoselective and (2) investigate the relationship between duration of short-term therapy and the potential stereoselective effects of perhexiline within myocardium. Patients (n = 129) from the active arm of a randomised controlled trial of preoperative perhexiline in cardiac surgery were treated with oral perhexiline for a median of 9 days. Correlates of atrial and ventricular concentrations of enantiomers were sought via univariate followed by multivariate analyses. Myocardial uptake of both (+) and (-) perhexiline was greater in ventricles than in atria, and there was more rapid clearance of (-) than (+) perhexiline. The main determinants of atrial uptake of both (+) and (-) perhexiline were the plasma concentrations [(+) perhexiline: β = -0.256, p = 0.015; (-) perhexiline: β = -0.347, p = 0.001] and patients' age [(+) perhexiline: β = 0.300, p = 0.004; (-) perhexiline: β = 0.288, p = 0.005]. Atrial uptake of (+) enantiomer also varied directly with duration of therapy (β = 0.228, p = 0.025), while atrial uptake of (-) perhexiline varied inversely with simultaneous heart rate (β = -0.240, p = 0.015). (1) Uptake of both perhexiline enantiomers into atrium is greater with advanced age and displays evidence of both saturability and minor stereoselectivity. (2) Atrial uptake of (-) perhexiline may selectively modulate heart rate reduction.

Endophytic fungi as models for the stereoselective biotransformation of thioridazine.

Science.gov (United States)

Borges, Keyller Bastos; Borges, Warley De Souza; Pupo, Mônica Tallarico; Bonato, Pierina Sueli

2007-12-01

The stereoselective kinetic biotransformation of thioridazine, a phenothiazine neuroleptic drug, by endophytic fungi was investigated. In general, the sulfur of lateral chain (position 2) or the sulfur of phenothiazinic ring (position 5) were oxidated yielding the major human metabolites thioridazine-2-sulfoxide and thioridazine-5-sulfoxide. The quantity of metabolites biosynthesized varied among the 12 endophytic fungi evaluated. However, mono-2-sulfoxidation occurred in higher ratio and frequency. Among the 12 fungi evaluated, 4 of them deserve prominence for presenting an evidenced stereoselective biotransformation: Phomopsis sp. (TD2), Glomerella cingulata (VA1), Diaporthe phaseolorum (VR4), and Aspergillus fumigatus (VR12). Both enantiomers of thioridazine were consumed by the fungi; however, the 2-sulfoxidation yielded preferentially the R configuration at the sulfur atom.

A Large Scale Formal Synthesis of CoQ10: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

International Nuclear Information System (INIS)

Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik

2013-01-01

We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group

A sustainable process for gram-scale synthesis of stereoselective ...

Indian Academy of Sciences (India)

We have developed a new, simple and sustainable process for stereoselective synthesis of aryl substituted (E)-2-thiocyanatoacrylic acids by nucleophilic substitution and Knoevenagel condensation involving chloroacetic acid, ammonium thiocyanate and aromatic aldehydes at room temperature. The selectivity was ...

Regio- and stereoselective hydrosilylation of immobilized terminal alkynes

DEFF Research Database (Denmark)

Pedersen, Palle Jacob; Henriksen, Jonas; Gotfredsen, Charlotte Held

2008-01-01

Regio- and stereoselective hydrosilylation of terminal alkynes on solid support using diisopropyl hydrosilanes yielding b-(E)-vinyl silanes with excellent selectivity is reported. The hydrosilylation is catalyzed by Pt(DVDS)/P(iBuNCH2CH2)3N (DVDS = 1,3-divinyl-1,1,3,3-tetramethyl-disiloxane), in ...

A Large Scale Formal Synthesis of CoQ{sub 10}: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

Energy Technology Data Exchange (ETDEWEB)

Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik [LG Life Sciences, Ltd., Daejeon (Korea, Republic of)

2013-04-15

We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group.

Exploiting Synergistic Effects in Organozinc Chemistry for Direct Stereoselective C-Glycosylation Reactions at Room Temperature.

Science.gov (United States)

Hernan-Gomez, Alberto; Orr, Samantha; Uzelac, Marina; Kennedy, Alan; Barroso, Santiago; Jusseau, Xavier; Lemaire, Sebastien; Farina, Vittorio; Hevia, Eva

2018-06-01

Pairing a range of bis(aryl) zinc reagents ZnAr2 with the stronger Lewis acidic [(ZnArF2)] (ArF = C6F5), enables highly stereoselective cross-coupling between glycosyl bromides and ZnAr2 without the use of a transition metal. Reactions occur at room temperature with excellent levels of stereoselectivity, where ZnArF2 acts as a non-coupling partner although its presence is crucial for the execution of the C(sp2)-C(sp3) bond formation process. Mechanistic studies have uncovered a unique synergistic partnership between the two zinc reagents, which circumvents the need for transition-metal catalysis or forcing reaction conditions. Key to the success of the coupling is the avoidance of solvents that act as Lewis bases vs. diarylzinc compounds (e.g. THF. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

Energy Technology Data Exchange (ETDEWEB)

Dias, Luiz Carlos; Farina, Lui Strambi; Ferreira, Marco Antonio Barbosa, E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica

2013-02-15

A short and efficient stereoselective total synthesis of CMI-977 (LDP-977), a potent and orally active anti-asthmatic compound, was developed. The key steps involve a highly diastereoselective Mukaiyama oxidative cyclization, which provides the trans-THF (tetrahydrofuran) unit and a Seyferth-Gilbert homologation to construct the triple bond in the target molecule. The synthesis of the key chiral building block was performed using Jacobsen hydrolytic kinetic resolution. (author)

Stereoselective total synthesis of the potent anti-asthmatic compound CMI-977 (LDP-977)

International Nuclear Information System (INIS)

Dias, Luiz Carlos; Farina, Lui Strambi; Ferreira, Marco Antonio Barbosa

2013-01-01

A short and efficient stereoselective total synthesis of CMI-977 (LDP-977), a potent and orally active anti-asthmatic compound, was developed. The key steps involve a highly diastereoselective Mukaiyama oxidative cyclization, which provides the trans-THF (tetrahydrofuran) unit and a Seyferth-Gilbert homologation to construct the triple bond in the target molecule. The synthesis of the key chiral building block was performed using Jacobsen hydrolytic kinetic resolution. (author)

Compound list: methylene dianiline [Open TG-GATEs

Lifescience Database Archive (English)

Full Text Available methylene dianiline DAPM 00155 ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Human/in_vitro/methyle...es/LATEST/Rat/in_vivo/Liver/Single/methylene_dianiline.Rat.in_vivo.Liver.Single.zip ftp://ftp.biosciencedbc....jp/archive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/methylene_dianiline.Rat.in_vivo.Liver.Repeat.zip ... ...ne_dianiline.Human.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/open-tggat

Stereoselective synthesis of hydroxy stilbenoids and styrenes by atom-efficient olefination with thiophthalides.

Science.gov (United States)

Mitra, Prithiba; Shome, Brateen; De, Saroj Ranjan; Sarkar, Anindya; Mal, Dipakranjan

2012-04-14

The synthesis of stilbenoids and styryl carboxylic acids is accomplished with high E-stereoselectivity by olefination of aldehydes with thiophthalides under basic conditions. The olefination is highly atom-efficient as it only loses elemental sulfur during the reaction. This olefination, in conjunction with retro Kolbe-Schmitt reaction, allows facile synthesis of E-hydroxystilbenoids with minimal employment of protecting groups. This study also discloses two important findings: formation of i) 4-methylsulfanyl isocoumarins and ii) an 2-arylindenone. This journal is © The Royal Society of Chemistry 2012

29 CFR 1926.1152 - Methylene chloride.

Science.gov (United States)

2010-07-01

... 29 Labor 8 2010-07-01 2010-07-01 false Methylene chloride. 1926.1152 Section 1926.1152 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... Methylene chloride. Note: The requirements applicable to construction employment under this section are...

29 CFR 1915.1052 - Methylene chloride.

Science.gov (United States)

2010-07-01

... 29 Labor 7 2010-07-01 2010-07-01 false Methylene chloride. 1915.1052 Section 1915.1052 Labor Regulations Relating to Labor (Continued) OCCUPATIONAL SAFETY AND HEALTH ADMINISTRATION, DEPARTMENT OF LABOR... § 1915.1052 Methylene chloride. Note: The requirements applicable to shipyard employment under this...

Stereoselective synthesis of highly substituted bicyclic γ-lactones using homoaldol addition of 1-(1-cycloalkenyl)methyl carbamates

DEFF Research Database (Denmark)

Özlügedik, M.; Kristensen, Jesper Langgaard; Reuber, J.

2004-01-01

Stereoselective addition of aldehydes 4 to metallated 1-(1-cycloalkenyl) methyl N,N-diisopropylcarbamates 1 gave cyclic homoaldol adducts 6. By applying the (-)-sparteine method, enantiomerically enriched products were obtained. These were oxidatively cyclized to diastereomerically pure ¿-lactones...... 8 via the ¿-lactol ethers 7. After deprotonation of ¿-lactones 8 with lithium hexamethyldisilazide, a further substitution was achieved. By trapping the lactone enolates 11 with ß-naphthylmethyl bromide, single diastereomers of ¿-lactones 12 were produced....

Methylene Blue for Vasoplegia When on Cardiopulmonary Bypass During Double-Lung Transplantation.

Science.gov (United States)

Carley, Michelle; Schaff, Jacob; Lai, Terrance; Poppers, Jeremy

2015-10-15

Vasoplegia syndrome, characterized by hypotension refractory to fluid resuscitation or high-dose vasopressors, low systemic vascular resistance, and normal-to-increased cardiac index, is associated with increased morbidity and mortality after cardiothoracic surgery. Methylene blue inhibits inducible nitric oxide synthase and guanylyl cyclase, and has been used to treat vasoplegia during cardiopulmonary bypass. However, because methylene blue is associated with increased pulmonary vascular resistance, its use in patients undergoing lung transplantion has been limited. Herein, we report the use of methylene blue to treat refractory vasoplegia during cardiopulmonary bypass in a patient undergoing double-lung transplantation.

Stereoselective quantification of methadone and a d(6)-labeled isotopomer using high performance liquid chromatography-atmospheric pressure chemical ionization mass-spectrometry: application to a pharmacokinetic study in a methadone maintained subject.

Science.gov (United States)

Foster, David J R; Morton, Erin B; Heinkele, Georg; Mürdter, Thomas E; Somogyi, Andrew A

2006-08-01

There is evidence that the apparent oral clearance of rac-methadone is induced during the early phase of methadone maintenance treatment. However, it is not known if this is due to changes in bioavailability or if this phenomenon is stereoselective. This knowledge can be obtained by administering a dose of stable-labeled methadone at selected times during ongoing treatment. Therefore, the authors developed a stereoselective high performance liquid chromatography-atmospheric pressure chemical ionization mass-spectrometry assay for the quantification of the enantiomers of methadone and a d(6)-labeled isotopomer. The compounds were quantified in a single assay after liquid-liquid extraction and stereoselective high performance liquid chromatograph with atmospheric pressure chemical ionization-mass spectrometry detection. The following ions were monitored: m/z 310.15 for unlabeled methadone; m/z 316.15 for methadone-d(6); and m/z 313.15 for the methadone-d(3) (internal standard). Calibration curves ranged from 0.5 to 75 ng/mL for each compound. Extraction recovery was approximately 80% for all analytes, without evidence of differences between the unlabeled and stable-labeled compounds or concentration dependency. Minor ion promotion was observed (d(3)-labeled internal standard, with peak area ratios in extracted samples identical to control injections. The isotopomers did not alter each others' ionisation, even at 10:1 concentration ratios, and 10-fold diluted samples were within 10% of the nominal concentration. Assay performance was acceptable, with interassay and intra-assay bias and precision d(6) in a patient receiving chronic oral methadone maintenance therapy.

Stereoselective synthesis of unsaturated α-amino acids.

Science.gov (United States)

Fanelli, Roberto; Jeanne-Julien, Louis; René, Adeline; Martinez, Jean; Cavelier, Florine

2015-06-01

Stereoselective synthesis of unsaturated α-amino acids was performed by asymmetric alkylation. Two methods were investigated and their enantiomeric excess measured and compared. The first route consisted of an enantioselective approach induced by the Corey-Lygo catalyst under chiral phase transfer conditions while the second one involved the hydroxypinanone chiral auxiliary, both implicating Schiff bases as substrate. In all cases, the use of a prochiral Schiff base gave higher enantiomeric excess and yield in the final desired amino acid.

High-pressure homogenization associated hydrothermal process of palygorskite for enhanced adsorption of Methylene blue

Energy Technology Data Exchange (ETDEWEB)

Zhang, Zhifang [Center of Eco-materials and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Wang, Wenbo [Center of Eco-materials and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); R& D Center of Xuyi Attapulgite Applied Technology, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Xuyi 211700 (China); Wang, Aiqin, E-mail: aqwang@licp.cas.cn [Center of Eco-materials and Green Chemistry, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000 (China); R& D Center of Xuyi Attapulgite Applied Technology, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Xuyi 211700 (China)

2015-02-28

Graphical abstract: - Highlights: • Palygorskite was modified by a homogenization associated hydrothermal process. • The crystal bundles of PAL were disaggregated efficiently after modification. • The adsorption of palygorskite for Methylene blue was greatly enhanced. • MB-loaded palygorskite exhibits excellent resistance to acid and alkali solution. - Abstract: Palygorskite (PAL) was modified by a high-pressure homogenization assisted hydrothermal process. The effects of modification on the morphology, structure and physicochemical properties of PAL were systematically investigated by Field-emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FTIR), Brunauer–Emmett–Teller (BET) analysis, X-ray diffraction (XRD) and Zeta potential analysis techniques, and the adsorption properties were systematically evaluated using Methylene blue (MB) as the model dye. The results revealed that the crystal bundles were disaggregated and the PAL nanorods became more even after treated via associated high-pressure homogenization and hydrothermal process, and the crystal bundles were dispersed as nanorods. The intrinsic crystal structure of PAL was remained after hydrothermal treatment, and the pore size calculated by the BET method was increased. The adsorption properties of PAL for MB were evidently improved (from 119 mg/g to 171 mg/g) after modification, and the dispersion of PAL before hydrothermal reaction is favorable to the adsorption. The desorption evaluation confirms that the modified PAL has stronger affinity with MB, which is benefit to fabricate a stable organic–inorganic hybrid pigment.

Microbial Stereoselective One-Step Conversion of Diols to Chiral Lactones in Yeast Cultures

Directory of Open Access Journals (Sweden)

Filip Boratyński

2015-12-01

Full Text Available It has been shown that whole cells of different strains of yeast catalyze stereoselective oxidation of meso diols to the corresponding chiral lactones. Among screening-scale experiments, Candida pelliculosa ZP22 was selected as the most effective biocatalyst for the oxidation of monocyclic diols 3a–b with respect to the ratio of high conversion to stereoselectivity. This strain was used in the preparative oxidation, affording enantiomerically-enriched isomers of lactones: (+-(3aR,7aS-cis-hexahydro-1(3H -isobenzofuranone (2a and (+-(3aS,4,7,7aR-cis-tetrahydro-1(3H-isobenzofuranone (2b. Scaling up the culture growth, as well as biotransformation conditions has been successfully accomplished. Among more bulky substrates, bicyclic diol 3d was totally converted into enantiomerically-pure exo-bridged (+-(3aR,4S,7R,7aS-cis-tetrahydro-4,7-methanoisobenzofuran -1(3H-one (2d by Yarrovia lipolytica AR71. Microbial oxidation of diol 3f by Candida sake AM908 and Rhodotorula rubra AM4 afforded optically-pure cis-3-butylhexahydro-1(3H -isobenzofuranone (2f, however with low conversion.

Stereoselective hydrogenation of H-alkynes on boron-nickel catalysts

International Nuclear Information System (INIS)

Petrova, S.S.; Sijmer, Eh.Kh.; Amitan, I.I.

1992-01-01

It is ascertained that in the course of stereoselective hydrogenation of H-alkynes on boron-nickel catalysts the contact modified by 2-phenyl-1,5 dimethylpyrasol-2-anom in the ratio Ni(2+):BH 4 -=1:5 is the most active and selective one. Moreover, cis-alkane was prepared with the yield of 94.5% and selective of 79%

Methylene blue doped polymers: efficient media for optical recording

Science.gov (United States)

Ushamani, M.; Sreekumar, K.; Sudha Kartha, C.; Joseph, R.

2004-05-01

Polymer materials find application in optical storage technology, namely in the development of high information density and fast access type memories. A new polymer blend of methylene blue sensitized polyvinyl alcohol (PVA) and polyacrylic acid (PAA) in methanol is prepared and characterized and its comparison with methylene blue sensitized PVA in methanol and complexed methylene blue sensitized polyvinyl chloride (CMBPVC) is presented. The optical absorption spectra of the thin films of these polymers showed a strong and broad absorption region at 670-650 nm, matching the wavelength of the laser used. A very slow recovery of the dye on irradiation was observed when a 7:3 blend of polyvinyl alcohol/polyacrylic acid at a pH of 3.8 and a sensitizer concentration of 4.67 · 10-5 g/ml were used. A diffraction efficiency of up to 20% was observed for the MBPVA/alcohol system and an energetic sensitivity of 2000 mJ/cm2 was obtained in the photosensitive films with a spatial frequency of 588 lines/mm.

Combining multi-catalysis and multi-component systems for the development of one-pot asymmetric reactions: stereoselective synthesis of highly functionalized bicyclo[4.4.0]decane-1,6-diones.

Science.gov (United States)

Ramachary, Dhevalapally B; Sakthidevi, Rajasekar

2008-07-21

We have developed a direct amine/acid-catalyzed stereoselective hydrogenation of a variety of Wieland-Miescher (W-M) ketones, Hajos-Parrish (H-P) ketones and their analogs with organic hydrides (Hantzsch esters) as the hydrogen source. This astonishingly simple and biomimetic approach was used to construct highly functionalized chiral bicyclo[4.4.0]decane-1,6-diones in a diastereoselective fashion. This is an example of the development of a new technology by the combination of multiple catalysts and components in one pot to deliver highly functionalized chiral molecules.

DFT study of the mechanism and stereoselectivity of the 1,3-dipolar ...

Indian Academy of Sciences (India)

and methyl acrylate) using DFT method. An ana- lysis of ..... field (SCRF)30,46 model based on the polarizable con- tinuum model (PCM) of Tomasi's group47 have been applied. ... stereoselectivity relative to the gas-phase since the trends of ...

Stereo-controlled synthesis of polyheterocycles via the diene-transmissive hetero-Diels-Alder reaction of β,γ-unsaturated α-keto esters.

Science.gov (United States)

Otani, Takashi; Tamai, Yumiko; Seki, Kazunori; Kikuchi, Tomohiro; Miyazawa, Taiichiro; Saito, Takao

2015-06-07

We describe the stereoselective synthesis of polyring-fused heterocyclic compounds based on diene-transmissive hetero-Diels-Alder reactions utilizing β,γ-unsaturated α-keto esters. This protocol involves the initial endo- or exo-selective Diels-Alder (DA) reactions with electron-rich dienophiles, methylenation of the ester carbonyl groups with the Tebbe reagent, and a stereoselective second DA reaction with electron-deficient dienophiles. The use of enantioselective DA reactions in the initial reaction enables access to chiral polyring-fused heterocyclic compounds with multiple chiral centres.

The Blue Coma: The Role of Methylene Blue in Unexplained Coma After Cardiac Surgery.

Science.gov (United States)

Martino, Enrico Antonio; Winterton, Dario; Nardelli, Pasquale; Pasin, Laura; Calabrò, Maria Grazia; Bove, Tiziana; Fanelli, Giovanna; Zangrillo, Alberto; Landoni, Giovanni

2016-04-01

Methylene blue commonly is used as a dye or an antidote, but also can be used off label as a vasopressor. Serotonin toxicity is a potentially lethal and often misdiagnosed condition that can result from drug interaction. Mild serotonin toxicity previously was reported in settings in which methylene blue was used as a dye. The authors report 3 cases of life-threatening serotonin toxicity in patients undergoing chronic selective serotonin reuptake inhibitor (SSRI) therapy who also underwent cardiac surgery and received methylene blue to treat vasoplegic syndrome. An observational study. A cardiothoracic intensive care unit (ICU) in a teaching hospital. Three patients who received methylene blue after cardiac surgery, later discovered to be undergoing chronic SSRI therapy. None. All 3 patients received high doses of fentanyl during general anesthesia. They all developed vasoplegic syndrome and consequently were given methylene blue in the ICU. All 3 patients developed serotonin toxicity, including coma, after this administration and diagnostic tests were negative for acute intracranial pathology. Coma lasted between 1 and 5 days. Two patients were discharged from the ICU shortly after awakening, whereas the third patient experienced a complicated postoperative course for concomitant refractory low-cardiac-output syndrome. Patients undergoing chronic SSRI therapy should not be administered methylene blue to treat vasoplegic syndrome. Copyright © 2016 Elsevier Inc. All rights reserved.

Stereoselective Preparation of N-Alkyl Dipeptide Analogues via Dynamic Kinetic Resolution of α-Halo Acyl Amino Esters

International Nuclear Information System (INIS)

Shin, Eun Kyoung; Chang, Ji Yeon; Kim, Hyun Jung; Kim, Yong Tae; Park, Yong Sun

2006-01-01

We have shown that dynamic kinetic resolution of α-bromo and α-chloro amides in nucleophilic substitution reaction can be successfully applied towards the preparation of various N-terminal functionalized dipeptide analogues. The stereochemical aspects of the results showed that stereoselectivity depends critically on the structures of amine nucleophiles. This mild and practical method can be run on a multi-gram scale without any special precautions and should be applicable to stereoselective syntheses of various peptidomimetics. Extension of this synthetic methodology to dynamic resolution of N-(α-haloacetyl) peptides in the stereospecific nucleophilic substitution (S N 2) could be an attractive synthetic strategy for asymmetric syntheses of peptide analogues. Recently it has been shown from our group that the chiral information of adjacent amino acid residue is efficiently transferred to the new C-N bond formation at α-halo carbon center for asymmetric syntheses of di-, tri- and tetrapeptide analogues. The α-halo stereogenic center of undergoes rapid epimerization in the presence of diisopropylethylamine (DIEA) and tetrabutylammonium iodide (TBAI), and (αS) reacts with the nucleophile preferentially to provide the dipeptide analogue (αR). The mechanistic investigation showed that this is a case of dynamic kinetic resolution, in which the stereoselectivity is determined by the difference in the diastereomeric transition state energies for the reaction with the nucleophiles. Herein we describe our recent progress to extend the scope of the methodology to stereoselective preparation of N-terminal functionalized dipeptide analogues with various amine nucleophiles

Direct asymmetric allylic alkenylation of N-itaconimides with Morita-Baylis-Hillman carbonates

KAUST Repository

Yang, Wenguo; Tan, Davin; Li, Lixin; Han, Zhiqiang; Yan, Lin; Huang, Kuo-Wei; Tan, Choonhong; Jiang, Zhiyong

2012-01-01

-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various

A multi-enzymatic cascade reaction for the stereoselective production of γ-oxyfunctionalyzed amino acids

Directory of Open Access Journals (Sweden)

Junichi eEnoki

2016-04-01

Full Text Available A stereoselective three-enzyme cascade for synthesis of diasteromerically pure γ-oxyfunctionalized α-amino acids was developed. By coupling a dynamic kinetic resolution using an N-acylamino acid racemase and an L-selective aminoacylase from Geobacillus thermoglucosidasius with a stereoselective isoleucine dioxygenase from Bacillus thuringiensis, diastereomerically pure oxidized amino acids were produced from racemic N-acetylamino acids. The three enzymes differ in their optimal temperature and pH-spectra. Their different metal cofactor dependencies lead to inhibitory effects. Under optimized conditions, racemic N-acetylmethionine was quantitatively converted into L-methionine-(S-sulfoxide with 97% conversion and 95% de. The combination of these three different biocatalysts allows the direct synthesis of diastereopure oxyfunctionalized amino acids from inexpensive racemic starting material.

Adsorption of methylene blue onto treated activated carbon

International Nuclear Information System (INIS)

Yamin Yasin; Mohd Zobir Hussein; Faujan Ahmad

2007-01-01

The potential feasibility of treated and untreated activated carbon for removal of methylene blue from aqueous solution was investigated. The effects of various experimental parameters such as contact time, solution pH and adsorbent dosage were investigated. The extent of methylene blue removal increased with the increased in contact time, solution pH and amount of adsorbent used. Adsorption data was better fitted to the Langmuir isotherm. The results in this study indicated that the treated activated carbon was an attractive candidate for removing organic dye of methylene blue which shows great reduction of colour while reducing the time contact to achieve equilibrium. (author)

Stereoselective synthesis of a-hydroxy-b-amino acids: the chiral pool approach

Directory of Open Access Journals (Sweden)

RADOMIR N. SAICIC

2004-11-01

Full Text Available A method for the stereoselective homologation of a-amino acids into syn-a-hydroxy-b-amino acids is described, based on the conversion of stereoisomeric cyanohydrins into trans-oxazolines. The synthetic potential of the method is illustrated in the enantioselective formal synthesis of Bestatin.

Stereoselective and nonstereoselective effects of ibuprofen enantiomers on mitochondrial beta-oxidation of fatty acids

International Nuclear Information System (INIS)

Freneaux, E.; Fromenty, B.; Berson, A.; Labbe, G.; Degott, C.; Letteron, P.; Larrey, D.; Pessayre, D.

1990-01-01

The effects of the R-(-) and S-(+)ibuprofen enantiomers were first studied in vitro with mouse liver mitochondria incubated in the presence of various concentrations of exogenous coenzyme A. In the presence of a low concentration of coenzyme A (2.5 microM), the R-(-)enantiomer (which forms an acylcoenzyme A) inhibited stereoselectively the beta oxidation of [1- 14 C]palmitic acid but not that of [1- 14 C]palmitoyl-L-carnitine (which can directly enter the mitochondria). In the presence, however, of a concentration of coenzyme A (50 microM) reproducing that present in liver cell cytosol, both enantiomers (2 mM) slightly inhibited the beta oxidation of [1- 14 C]palmitic acid and markedly inhibited the beta oxidation of [1- 14 C]octanoic acid and [1- 14 C]butyric acid. In vivo, both enantiomers (1 mmol.kg-1) similarly inhibited the formation of [ 14 C]CO 2 from [1- 14 C]fatty acids. Both enantiomers similarly decreased plasma ketone bodies. Both similarly increased hepatic triglycerides, and both produced mild microvesicular steatosis of the liver. We conclude that both ibuprofen enantiomers inhibit beta oxidation of fatty acids in vitro and in vivo. In addition, the R-(-)enantiomer may stereoselectively sequester coenzyme A; at low concentrations of coenzyme A in vitro, this may stereoselectively inhibit the mitochondrial uptake and beta oxidation of long chain fatty acids

Zinc mediated activation of terminal alkynes: stereoselective synthesis of alkynyl glycosides.

Science.gov (United States)

Tatina, Madhu Babu; Kusunuru, Anil Kumar; Yousuf, Syed Khalid; Mukherjee, Debaraj

2014-10-28

Zinc mediated alkynylation reaction was studied for the preparation of C-glycosides from unactivated alkynes. Different glycosyl donors such as glycals and anomeric acetates were tested towards an alkynyl zinc reagent obtained from alkynes using zinc dust and ethyl bromoacetate as an additive. The method provides simple, mild and stereoselective access to alkynyl glycosides both from aromatic and aliphatic acetylenes.

Stereoselective and nonstereoselective effects of ibuprofen enantiomers on mitochondrial beta-oxidation of fatty acids

Energy Technology Data Exchange (ETDEWEB)

Freneaux, E.; Fromenty, B.; Berson, A.; Labbe, G.; Degott, C.; Letteron, P.; Larrey, D.; Pessayre, D. (Unite de Recherches de Physiolopathologie Hepatique (INSERM U-24), Hopital Beaujon, Clichy (France))

1990-11-01

The effects of the R-(-) and S-(+)ibuprofen enantiomers were first studied in vitro with mouse liver mitochondria incubated in the presence of various concentrations of exogenous coenzyme A. In the presence of a low concentration of coenzyme A (2.5 microM), the R-(-)enantiomer (which forms an acylcoenzyme A) inhibited stereoselectively the beta oxidation of (1-{sup 14}C)palmitic acid but not that of (1-{sup 14}C)palmitoyl-L-carnitine (which can directly enter the mitochondria). In the presence, however, of a concentration of coenzyme A (50 microM) reproducing that present in liver cell cytosol, both enantiomers (2 mM) slightly inhibited the beta oxidation of (1-{sup 14}C)palmitic acid and markedly inhibited the beta oxidation of (1-{sup 14}C)octanoic acid and (1-{sup 14}C)butyric acid. In vivo, both enantiomers (1 mmol.kg-1) similarly inhibited the formation of ({sup 14}C)CO{sub 2} from (1-{sup 14}C)fatty acids. Both enantiomers similarly decreased plasma ketone bodies. Both similarly increased hepatic triglycerides, and both produced mild microvesicular steatosis of the liver. We conclude that both ibuprofen enantiomers inhibit beta oxidation of fatty acids in vitro and in vivo. In addition, the R-(-)enantiomer may stereoselectively sequester coenzyme A; at low concentrations of coenzyme A in vitro, this may stereoselectively inhibit the mitochondrial uptake and beta oxidation of long chain fatty acids.

Stereoselective inhibition of thromboxane-induced coronary vasoconstriction by 1,4-dihydropyridine calcium channel antagonists

International Nuclear Information System (INIS)

Eltze, M.; Boer, R.; Sanders, K.H.; Boss, H.; Ulrich, W.R.; Flockerzi, D.

1990-01-01

The biological activity of the (+)-S- and (-)-R-enantiomers of niguldipine, of the (-)-S- and (+)-R-enantiomers of felodipine and nitrendipine, and of rac-nisoldipine and rac-nimodipine was investigated in vitro and in vivo. Inhibition of coronary vasoconstriction due to the thromboxane A2 (TxA2)-mimetic U-46619 in guinea pig Langendorff hearts, displacement of (+)-[ 3 H]isradipine from calcium channel binding sites of guinea pig skeletal muscle T-tubule membranes, and blood pressure reduction in spontaneously hypertensive rats were determined. The enantiomers were obtained by stereoselective synthesis. Cross-contamination was less than 0.5% for both S- and R-enantiomers of niguldipine and nitrendipine and less than 1% for those of felodipine. From the doses necessary for a 50% inhibition of coronary vasoconstriction, stereoselectivity ratios for (+)-(S)-/(-)-(R)-niguldipine, (-)-(S)-/(+)-(R)-felodipine, and (-)-(S)-/(+)-(R)-nitrendipine of 28, 13, and 7, respectively, were calculated. The potency ratio rac-nisoldipine/rac-nimodipine was 3.5. Ratios obtained from binding experiments and antihypertensive activity were (+)-(S)-/(-)-(R)-niguldipine = 45 and 35, (-)-(S)-/(+)-(R)-felodipine = 12 and 13, (-)-(S)-/(+)-(R)-nitrendipine = 8 and 8, and rac-nisoldipine/rac-nimodipine = 8 and 7, respectively. Highly significant correlations were found between the in vitro potency of the substances to prevent U-46619-induced coronary vasoconstriction and their affinity for calcium channel binding sites as well as their antihypertensive activity

Stereoselective synthesis of L-[4-13C]carnitine

International Nuclear Information System (INIS)

Unkefer, C.J.; Ehler, D.S.

1991-01-01

The stereoselective synthesis of L-[4- 13 C]carnitine was achieved in 5 steps. The label was introduced from K 13 CN into an easily separated diastereomeric pair of 3-deoxy-D-[1- 13 C]aldohexoses. Reductive amination of the labeled aldohexose yielded the corresponding D-1-(dimethylamino)[1- 13 C]alditol which was oxidized in two steps and alkylated with iodomethane to yield L-[4- 13 C]carnitine. The stereochemical integrity at C-2 of the 3-deoxy-D-[1- 13 C]glucose precursor was maintained throughout the synthesis of L-[4- 13 C]carnitine. (author)

Methylene blue microbubbles as a model dual-modality contrast agent for ultrasound and activatable photoacoustic imaging

Science.gov (United States)

Jeon, Mansik; Song, Wentao; Huynh, Elizabeth; Kim, Jungho; Kim, Jeesu; Helfield, Brandon L.; Leung, Ben Y. C.; Goertz, David E.; Zheng, Gang; Oh, Jungtaek; Lovell, Jonathan F.; Kim, Chulhong

2014-01-01

Ultrasound and photoacoustic imaging are highly complementary modalities since both use ultrasonic detection for operation. Increasingly, photoacoustic and ultrasound have been integrated in terms of hardware instrumentation. To generate a broadly accessible dual-modality contrast agent, we generated microbubbles (a standard ultrasound contrast agent) in a solution of methylene blue (a standard photoacoustic dye). This MB2 solution was formed effectively and was optimized as a dual-modality contrast solution. As microbubble concentration increased (with methylene blue concentration constant), photoacoustic signal was attenuated in the MB2 solution. When methylene blue concentration increased (with microbubble concentration held constant), no ultrasonic interference was observed. Using an MB2 solution that strongly attenuated all photoacoustic signal, high powered ultrasound could be used to burst the microbubbles and dramatically enhance photoacoustic contrast (>800-fold increase), providing a new method for spatiotemporal control of photoacoustic signal generation.

Palladium-catalyzed aerobic regio- and stereo-selective olefination reactions of phenols and acrylates via direct dehydrogenative C(sp2)-O cross-coupling.

Science.gov (United States)

Wu, Yun-Bin; Xie, Dan; Zang, Zhong-Lin; Zhou, Cheng-He; Cai, Gui-Xin

2018-04-26

An efficient olefination protocol for the oxidative dehydrogenation of phenols and acrylates has been achieved using a palladium catalyst and O2 as the sole oxidant. This reaction exhibits high regio- and stereo-selectivity (E-isomers) with moderate to excellent isolated yields and a wide substrate scope (32 examples) including ethyl vinyl ketone and endofolliculina.

Citrus pectin derived porous carbons as a superior adsorbent toward removal of methylene blue

International Nuclear Information System (INIS)

Zhang, Wenlin; Zhang, Lian Ying; Zhao, Xi Juan; Zhou, Zhiqin

2016-01-01

An adsorbent, citrus pectin derived porous carbons with ultra-high adsorption capacity, rapid adsorption rate and good reusability toward removal of methylene blue, was synthesized by a facile zinc chloride activation approach in this study. The materials hold a great potential for treatment of dye wastewater. - Graphical abstract: Citrus pectin derived porous carbons with ultra-high adsorption capacity, rapid adsorption rate and good reusability toward methylene blue removal. - Highlights: • Citrus pectin derived porous carbons (CPPCs) were synthesized a facile zinc chloride activation approach. • CPPCs had abundant macro/meso/micropores for trapping MB molecules. • CPPCs exhibited ultrahigh adsorption capacity, rapid adsorption rate and good reusability toward removal of MB.

Citrus pectin derived porous carbons as a superior adsorbent toward removal of methylene blue

Energy Technology Data Exchange (ETDEWEB)

Zhang, Wenlin [College of Horticulture and landscape Architecture, Southwest University, Chongqing 400716 (China); Zhang, Lian Ying [Institute for Clean Energy & Advanced Materials, Southwest University, Chongqing 400715 (China); Zhao, Xi Juan [College of Horticulture and landscape Architecture, Southwest University, Chongqing 400716 (China); Key Laboratory of Horticulture Science for Southern Mountainous Regions, Ministry of Education, Chongqing 400715 (China); Zhou, Zhiqin, E-mail: zhouzhiqin@swu.edu.cn [College of Horticulture and landscape Architecture, Southwest University, Chongqing 400716 (China); Key Laboratory of Horticulture Science for Southern Mountainous Regions, Ministry of Education, Chongqing 400715 (China)

2016-11-15

An adsorbent, citrus pectin derived porous carbons with ultra-high adsorption capacity, rapid adsorption rate and good reusability toward removal of methylene blue, was synthesized by a facile zinc chloride activation approach in this study. The materials hold a great potential for treatment of dye wastewater. - Graphical abstract: Citrus pectin derived porous carbons with ultra-high adsorption capacity, rapid adsorption rate and good reusability toward methylene blue removal. - Highlights: • Citrus pectin derived porous carbons (CPPCs) were synthesized a facile zinc chloride activation approach. • CPPCs had abundant macro/meso/micropores for trapping MB molecules. • CPPCs exhibited ultrahigh adsorption capacity, rapid adsorption rate and good reusability toward removal of MB.

Borax methylene blue: a spectroscopic and staining study.

Science.gov (United States)

Donaldson, P T; Russo, A; Reynolds, C; Lillie, R D

1978-07-01

Borax methylene blue is quite stable at room temperatures of 22-25 C. At 30 C polychroming is slow; during 50 days in a water bath at this temperature the absorption peak moves from 665 to 656 nm. At 35 C, the absorption peak reaches 660 nm in 7 days, 654 nm in 14. At 60 C polychroming is rapid, the absorption peak reaching 640-620 nm in 3 days. When the pH of the borax methylene blue solutions, normally about 9.0, is adjusted to pH 6.5, the absorption peak remains at 665 nm even when incubated at 60 C for extended periods. When used as a blood stain 0.4 ml borax methylene blue (1% methylene blue in 1% borax), 4 ml acetone, 2 ml borax-acid phosphate buffer to bring the solution to pH 6.5, and distilled water to make 40 ml, with 0.2 ml 1% eosin added just before using, an excellent Nocht-Giemsa type stain is achieved after 30 minutes staining. The material plasmodia P. falciparum, P. vivax, and P. berghei stain moderate blue with dark red chromatin and green to black pigment granules. The study confirms Malachowski's 1891 results and explains Gautier's 1896-98 failure to duplicate it.

Hexafluorobenzene: A powerful solvent for a noncovalent stereoselective organocatalytic Michael addition reaction

KAUST Repository

Lattanzi, Alessandra

2012-01-01

A dramatic enhancement of the diastereo- and enantioselectivity in the nitro-Michael addition reaction organocatalysed by a commercially available α,α-l-diaryl prolinol was disclosed when performing the reaction in unconventional hexafluorobenzene as a medium. DFT calculations were performed to clarify the origin of stereoselectivity and the role of C 6F 6. © The Royal Society of Chemistry 2012.

Modified methylene blue injection improves lymph node harvest in rectal cancer.

Science.gov (United States)

Liu, Jianpei; Huang, Pinjie; Zheng, Zongheng; Chen, Tufeng; Wei, Hongbo

2017-04-01

The presence of nodal metastases in rectal cancer plays an important role in accurate staging and prognosis, which depends on adequate lymph node harvest. The aim of this prospective study is to investigate the feasibility and survival benefit of improving lymph node harvest by a modified method with methylene blue injection in rectal cancer specimens. One hundred and thirty-one patients with rectal cancer were randomly assigned to the control group in which lymph nodes were harvested by palpation and sight, or to the methylene blue group using a modified method of injection into the superior rectal artery with methylene blue. Analysis of clinicopathologic records, including a long-term follow-up, was performed. In the methylene blue group, 678 lymph nodes were harvested by simple palpation and sight. Methylene blue injection added 853 lymph nodes to the total harvest as well as 32 additional metastatic lymph nodes, causing a shift to node-positive stage in four patients. The average number of lymph nodes harvested was 11.7 ± 3.4 in the control group and 23.2 ± 4.7 in the methylene blue group, respectively. The harvest of small lymph nodes (rectal cancer, especially small node and metastatic node retrieval, which provided more accurate staging. However, it was not associated with overall survival. © 2014 Royal Australasian College of Surgeons.

Preparation of Carbon-Chitosan-Polyvinyl Chloride (CC-PVC) Material and its Application to Electrochemical Degradation of Methylene Blue in Sodium Chloride Solution

Science.gov (United States)

Riyanto; Prawidha, A. D.

2018-01-01

Electrochemical degradation of methylene blue using Carbon-Chitosan-Polyvinyl Chloride (CC-PVC) electrode in sodium chloride have been done. The aim of this work was to degradation of methylene blue using Carbon-Chitosan-Polyvinyl Chloride (CC-PVC). Carbon chitosan composite electrode was preparing by Carbon and Chitosan powder and PVC in 4 mL tetrahydrofuran (THF) solvent and swirled flatly to homogeneous followed by drying in an oven at 100 °C for 3 h. The mixture was placed in stainless steel mould and pressed at 10 ton/cm2. Sodium chloride was used electrolyte solution. The effects of the current and electrolysis time were investigated using spectrophotometer UV-Visible. The experimental results showed that the carbon-chitosan composite electrode have higher effect in the electrochemical degradation of methylene blue in sodium chloride. Based on UV-visible spectra analysis shows current and electrolysis time has high effect to degradation of methylene blue in sodium chloride. Chitosan and polyvinyl chloride can strengthen the bond between the carbons so that the material has the high stability and conductivity. As conclusions is Carbon-Chitosan-Polyvinyl Chloride (CC-PVC) electrode have a high electrochemical activity for degradation of methylene blue in sodium chloride.

The monoamine oxidase inhibition properties of selected structural analogues of methylene blue

International Nuclear Information System (INIS)

Delport, Anzelle; Harvey, Brian H.; Petzer, Anél; Petzer, Jacobus P.

2017-01-01

The thionine dye, methylene blue (MB), is a potent inhibitor of monoamine oxidase (MAO) A, a property that may, at least in part, mediate its antidepressant effects in humans and animals. The central inhibition of MAO-A by MB has also been linked to serotonin toxicity (ST) which may arise when MB is used in combination with serotonergic drugs. Structural analogues and the principal metabolite of MB, azure B, have also been reported to inhibit the MAO enzymes, with all compounds exhibiting specificity for the MAO-A isoform. To expand on the structure-activity relationships (SARs) of MAO inhibition by MB analogues, the present study investigates the human MAO inhibition properties of five MB analogues: neutral red, Nile blue, new methylene blue, cresyl violet and 1,9-dimethyl methylene blue. Similar to MB, these analogues also are specific MAO-A inhibitors with cresyl violet (IC 50 = 0.0037 μM), Nile blue (IC 50 = 0.0077 μM) and 1,9-dimethyl methylene blue (IC 50 = 0.018 μM) exhibiting higher potency inhibition compared to MB (IC 50 = 0.07 μM). Nile blue also represents a potent MAO-B inhibitor with an IC 50 value of 0.012 μM. From the results it may be concluded that non-thionine MB analogues (e.g. cresyl violet and Nile blue) also may exhibit potent MAO inhibition, a property which should be considered when using these compounds in pharmacological studies. Benzophenoxazines such as cresyl violet and Nile blue are, similar to phenothiazines (e.g. MB), representative of high potency MAO-A inhibitors with a potential risk of ST. - Highlights: • MB analogues, cresyl violet and Nile blue, are high potency MAO-A inhibitors. • Nile blue also represents a potent MAO-B inhibitor. • Potent MAO-A inhibition should alert to potential serotonin toxicity.

The monoamine oxidase inhibition properties of selected structural analogues of methylene blue

Energy Technology Data Exchange (ETDEWEB)

Delport, Anzelle [Pharmaceutical Chemistry, School of Pharmacy, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Centre of Excellence for Pharmaceutical Sciences, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Harvey, Brian H. [Centre of Excellence for Pharmaceutical Sciences, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Pharmacology, School of Pharmacy, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Petzer, Anél [Pharmaceutical Chemistry, School of Pharmacy, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Centre of Excellence for Pharmaceutical Sciences, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Petzer, Jacobus P., E-mail: jacques.petzer@nwu.ac.za [Pharmaceutical Chemistry, School of Pharmacy, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa); Centre of Excellence for Pharmaceutical Sciences, North-West University, Private Bag X6001, Potchefstroom 2520 (South Africa)

2017-06-15

The thionine dye, methylene blue (MB), is a potent inhibitor of monoamine oxidase (MAO) A, a property that may, at least in part, mediate its antidepressant effects in humans and animals. The central inhibition of MAO-A by MB has also been linked to serotonin toxicity (ST) which may arise when MB is used in combination with serotonergic drugs. Structural analogues and the principal metabolite of MB, azure B, have also been reported to inhibit the MAO enzymes, with all compounds exhibiting specificity for the MAO-A isoform. To expand on the structure-activity relationships (SARs) of MAO inhibition by MB analogues, the present study investigates the human MAO inhibition properties of five MB analogues: neutral red, Nile blue, new methylene blue, cresyl violet and 1,9-dimethyl methylene blue. Similar to MB, these analogues also are specific MAO-A inhibitors with cresyl violet (IC{sub 50} = 0.0037 μM), Nile blue (IC{sub 50} = 0.0077 μM) and 1,9-dimethyl methylene blue (IC{sub 50} = 0.018 μM) exhibiting higher potency inhibition compared to MB (IC{sub 50} = 0.07 μM). Nile blue also represents a potent MAO-B inhibitor with an IC{sub 50} value of 0.012 μM. From the results it may be concluded that non-thionine MB analogues (e.g. cresyl violet and Nile blue) also may exhibit potent MAO inhibition, a property which should be considered when using these compounds in pharmacological studies. Benzophenoxazines such as cresyl violet and Nile blue are, similar to phenothiazines (e.g. MB), representative of high potency MAO-A inhibitors with a potential risk of ST. - Highlights: • MB analogues, cresyl violet and Nile blue, are high potency MAO-A inhibitors. • Nile blue also represents a potent MAO-B inhibitor. • Potent MAO-A inhibition should alert to potential serotonin toxicity.

High-level Computational Study of the Site-, Facial- and Stereoselectivities for the Diels-Alder Reaction Between o-Benzoquinone and Norbornadiene

Directory of Open Access Journals (Sweden)

Ronald N. Warrener

2000-12-01

Full Text Available Ab initio and DFT quantum chemical calculations have been applied to a study of the Diels-Alder reaction of o-benzoquinone as diene and norbornadiene as dienophile. Transition states for the different reactions are located and activation energies estimated. The prefered exo-π-facial selectivity and exo,endo-stereoselectivity exhibited in this cycloaddition are readily predicted using RHF/3-21G or higher levels of calculations. Differences between experimentally observed results and calculations may be explained by the postulation of a second, nonconcerted biradical mechanism leading to formation of hetero Diels-Alder products.

Stereoselective inhibition of the hERG1 potassium channel

Directory of Open Access Journals (Sweden)

Liliana eSintra Grilo

2010-11-01

Full Text Available A growing number of drugs have been shown to prolong cardiac repolarization, predisposing individuals to life-threatening ventricular arrhythmias known as Torsades de Pointes. Most of these drugs are known to interfere with the human ether à-gogo related gene 1 (hERG1 channel, whose current is one of the main determinants of action potential duration. Prolonged repolarization is reflected by lengthening of the QT interval of the electrocardiogram, as seen in the suitably named drug-induced long QT syndrome. Chirality (presence of an asymmetric atom is a common feature of marketed drugs, which can therefore exist in at least two enantiomers with distinct three-dimensional structures and possibly distinct biological fates. Both the pharmacokinetic and pharmacodynamic properties can differ between enantiomers, as well as also between individuals who take the drug due to metabolic polymorphisms. Despite the large number of reports about drugs reducing the hERG1 current, potential stereoselective contributions have only been scarcely investigated. In this review, we present a non-exhaustive list of clinically important molecules which display chiral toxicity that may be related to hERG1-blocking properties. We particularly focus on methadone cardiotoxicity, which illustrates the importance of the stereoselective effect of drug chirality as well as individual variations resulting from pharmacogenetics. Furthermore, it seems likely that, during drug development, consideration of chirality in lead optimization and systematic assessment of the hERG1 current block with all enantiomers could contribute to the reduction of the risk of drug-induced LQTS.

Chemical composition effects of methylene containing polymers on gas emission under γ-irradiation

Energy Technology Data Exchange (ETDEWEB)

Ferry, M., E-mail: muriel.ferry@cea.fr [CEA, DEN, DPC, SECR, LRMO, F-91191 Gif-sur-Yvette (France); Dannoux-Papin, A. [CEA, DEN, DPC, SECR, LRMO, F-91191 Gif-sur-Yvette (France); Dély, N. [CEA, DSM, IRAMIS, LIDYL, PCR, F-91191 Gif-sur-Yvette (France); Legand, S.; Durand, D.; Roujou, J.L.; Lamouroux, C.; Dauvois, V. [CEA, DEN, DPC, SECR, LRMO, F-91191 Gif-sur-Yvette (France); Coignet, P.; Cochin, F. [AREVA NC DOR/RDP, 1 place Jean Millier, 92084 La Défense (France); Esnouf, S. [CEA, DEN, DPC, SECR, LRMO, F-91191 Gif-sur-Yvette (France); CEA, DSM, IRAMIS, LIDYL, PCR, F-91191 Gif-sur-Yvette (France)

2014-09-01

The presence of different chemical groups in methylene containing polymers can lead to very different behaviors under ionizing radiation. To better understand the effect of these groups on gas production under γ-irradiation, especially on hydrogen formation, and to study the efficiency of energy transfer between chemical groups, several methylene containing polymers with different controlled group concentrations were studied in inert atmosphere. We analyzed the influence of the nature and position of the chemical group using methylene containing copolymers with aliphatic side-chains (different lengths), ester groups in the side-chains (different concentrations) and ester groups in the polymer backbone (different concentrations). Radiation chemical yields of H{sub 2}, CO, CO{sub 2} and CH{sub 4} were determined at room temperature by high resolution mass spectrometry. On the basis of these results, we attempt to obtain a better understanding of the mechanisms involved. It can be observed that crystallinity and aliphatic side-chain have no effect on hydrogen formation. On contrary, esters on side-chain and in the backbone have an important influence on hydrogen formation, with the most important effect when esters groups are in the backbone. In these two kind of materials, energy fraction transferred from methylene to ester groups has been quantified and only 10 wt% (or less) of ester groups are sufficient to protect effectively the aliphatic moiety.

Stereoselective 1,3-Insertions of Rhodium(II) Azavinyl Carbenes

Science.gov (United States)

Chuprakov, Stepan; Worrell, Brady T.; Selander, Nicklas; Sit, Rakesh K.; Fokin, Valery V.

2014-01-01

Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild and convergent formal 1,3-insertion into N–H and O–H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bis-functionalized Z-olefins with perfect regio- and stereoselectively. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles. PMID:24295389

A stereoselective synthesis of (+)-physoperuvine using a tandem aza-Claisen rearrangement and ring closing metathesis reaction.

Science.gov (United States)

Zaed, Ahmed M; Swift, Michael D; Sutherland, Andrew

2009-07-07

A stereoselective synthesis of (+)-physoperuvine, a tropane alkaloid from Physalis peruviana Linne has been developed using a one-pot tandem aza-Claisen rearrangement and ring closing metathesis reaction to form the key amino-substituted cycloheptene ring.

Methylene blue improves mitochondrial respiration and decreases oxidative stress in a substrate-dependent manner in diabetic rat hearts.

Science.gov (United States)

Duicu, Oana M; Privistirescu, Andreea; Wolf, Adrian; Petruş, Alexandra; Dănilă, Maria D; Raţiu, Corina D; Muntean, Danina M; Sturza, Adrian

2017-11-01

Diabetic cardiomyopathy has been systematically associated with compromised mitochondrial energetics and increased generation of reactive oxygen species (ROS) that underlie its progression to heart failure. Methylene blue is a redox drug with reported protective effects mainly on brain mitochondria. The purpose of the present study was to characterize the effects of acute administration of methylene blue on mitochondrial respiration, H 2 O 2 production, and calcium sensitivity in rat heart mitochondria isolated from healthy and 2 months (streptozotocin-induced) diabetic rats. Mitochondrial respiratory function was assessed by high-resolution respirometry. H 2 O 2 production and calcium retention capacity were measured spectrofluorimetrically. The addition of methylene blue (0.1 μmol·L -1 ) elicited an increase in oxygen consumption of mitochondria energized with complex I and II substrates in both normal and diseased mitochondria. Interestingly, methylene blue elicited a significant increase in H 2 O 2 release in the presence of complex I substrates (glutamate and malate), but had an opposite effect in mitochondria energized with complex II substrate (succinate). No changes in the calcium retention capacity of healthy or diabetic mitochondria were found in the presence of methylene blue. In conclusion, in cardiac mitochondria isolated from diabetic and nondiabetic rat hearts, methylene blue improved respiratory function and elicited a dichotomic, substrate-dependent effect on ROS production.

Stereoselectivity of sodium borohydride reduction of saturated steroidal ketones utilizing conditions of Luche reduction

Czech Academy of Sciences Publication Activity Database

Šťastná, Eva; Černý, Ivan; Pouzar, Vladimír; Chodounská, Hana

2010-01-01

Roč. 75, č. 10 (2010), s. 721-725 ISSN 0039-128X R&D Projects: GA ČR(CZ) GA203/08/1498; GA MŠk(CZ) LC06077 Institutional research plan: CEZ:AV0Z40550506 Keywords : steroid * synthesis * stereoselectivity Subject RIV: CC - Organic Chemistry Impact factor: 3.106, year: 2010

Occupational methaemoglobinaemia. Mechanisms of production, features, diagnosis and management including the use of methylene blue.

Science.gov (United States)

Bradberry, Sally M

2003-01-01

unreliable in the presence of methaemoglobinaemia. Arterial blood gas analysis is mandatory in severe poisoning and reveals normal partial pressures of oxygen (pO2) and carbon dioxide (pCO2,), a normal 'calculated' haemoglobin oxygen saturation, an increased methaemoglobin concentration and possibly a metabolic acidosis. Following decontamination, high-flow oxygen should be given to maximise oxygen carriage by remaining ferrous haem. No controlled trial of the efficacy of methylene blue has been performed but clinical experience suggests that methylene blue can increase the rate of methaemoglobin conversion to haemoglobin some 6-fold. Patients with features and/or methaemoglobin concentrations of 30-50%, should be administered methylene blue 1-2 mg/kg/bodyweight intravenously (the dose depending on the severity of the features), whereas those with methaemoglobin concentrations exceeding 50% should be given methylene blue 2 mg/kg intravenously. Symptomatic improvement usually occurs within 30 minutes and a second dose of methylene blue will be required in only very severe cases or if there is evidence of ongoing methaemoglobin formation. Methylene blue is less effective or ineffective in the presence of glucose-6-phosphate dehydrogenase deficiency since its antidotal action is dependent on nicotinamide-adenine dinucleotide phosphate (NADP+). In addition, methylene blue is most effective in intact erythrocytes; efficacy is reduced in the presence of haemolysis. Moreover, in the presence of haemolysis, high dose methylene blue (20-30 mg/kg) can itself initiate methaemoglobin formation. Supplemental antioxidants such as ascorbic acid (vitamin C), N-acetylcysteine and tocopherol (vitamin E) have been used as adjuvants or alternatives to methylene blue with no confirmed benefit. Exchange transfusion may have a role in the management of severe haemolysis or in G-6-P-D deficiency associated with life-threatening methaemoglobinaemia where methylene blue is relatively contraindicated.

Preoperative Localization of Mediastinal Parathyroid Adenoma with Intra-arterial Methylene Blue

Energy Technology Data Exchange (ETDEWEB)

Salman, Rida; Sebaaly, Mikhael G. [American University of Beirut Medical Center, Department of Diagnostic Radiology (Lebanon); Wehbe, Mohammad Rachad; Sfeir, Pierre; Khalife, Mohamad [American University of Beirut Medical Center, Department of General Surgery (Lebanon); Al-Kutoubi, Aghiad, E-mail: mk00@aub.edu.lb [American University of Beirut Medical Center, Department of Diagnostic Radiology (Lebanon)

2017-06-15

Ectopic parathyroid is found in 16% of patients with hyperparathyroidism. 2% of ectopic parathyroid adenomas are not accessible to standard cervical excision. In such cases, video-assisted thoracoscopic resection is the recommended definitive treatment. We present a case of mediastinal parathyroid adenoma localized preoperatively by injecting methylene blue within a branch of the internal mammary artery that is supplying the adenoma. Intra-arterial methylene blue injection facilitated visualization and resection of the adenoma. The preoperative intra-arterial infusion of methylene blue appears to be an effective and safe method for localization of ectopic mediastinal parathyroid adenomas and allows rapid identification during thoracoscopic resection.

Insights into the Diels-Alder Reaction between 3-Vinylindoles and Methyleneindolinone without and with the Assistance of Hydrogen-Bonding Catalyst Bisthiourea: Mechanism, Origin of Stereoselectivity, and Role of Catalyst.

Science.gov (United States)

Yan, Chao-Xian; Yang, Fan; Yang, Xing; Zhou, Da-Gang; Zhou, Pan-Pan

2017-03-17

The Diels-Alder reaction between 3-vinylindoles and methyleneindolinone can proceed both under catalyst-free conditions and with bisthiourea as the catalyst. The reaction with bisthiourea is much faster and results in higher stereoselectivity of the product. The reaction mechanism, origin of stereoselectivity, and role of the catalyst were elaborated based on quantum mechanical calculations and theoretical methods of reactivity indices, NCI, QTAIM, and distortion/interaction models. In the uncatalyzed reaction, the two C-C bonds that are formed undergo conversion from noncovalent to covalent bonding via a concerted asynchronous mechanism. The weak intermolecular interactions formed in the transition state play important roles. The difference between the interaction and distortion energies is responsible for the stereoselectivity. In the catalyzed reaction, bisthiourea induces both the diene and dienophile to approach it via weak intermolecular interactions, which greatly lowers the energy barrier of the reaction and leads to the product with excellent stereoselectivity. The possible pathways of this reaction were explored, which suggested that the formation of the two C-C bonds goes through either a stepwise or concerted asynchronous mechanism. These results detail the reaction mechanism and shed light on both the significant role of the bisthiourea catalyst and the origin of stereoselectivity for this type of Diels-Alder reaction and related ones.

Novel management of methylene blue extravasation: A case report and review of literature

Directory of Open Access Journals (Sweden)

Rashid Saeed Khokhar

2015-01-01

Full Text Available Methylene blue is a highly irritant drug and has been used intraoperatively. Its accidental extravasation can lead to tissue necrosis. In this report, a unique management is described, and the patient recovered without any morbidity.

Products of the reaction between methylene iodide and tertiary arsines

International Nuclear Information System (INIS)

Gigauri, R.D.; Arabuli, L.G.; Machaidze, Z.I.; Rusiya, M.Sh.

2005-01-01

Iodides of iodomethylenetrialkyl(aryl) arsonium were synthesized with high yields as a result of interaction between methylene iodide and tertiary arsines. Exchange reactions of the iodides prepared with lead(II) nitrate in water-alcohol solutions gave rise to formation of iodomethylenetrialkyl(aryl) arsonium nitrates. All the products prepared were characterized by data of elementary analysis, IR spectroscopy, conductometry and melting points measurements [ru

Study of extraction-spectrophotometric micro-determination of boron with methylene blue and its application

International Nuclear Information System (INIS)

Zhu Daohong

1990-08-01

A sensitive extraction-spectrophotometric method for microdetermination of boron with methylene blue was investigated. The method was based on the extraction of a BF 4 - -methylene blue complex into dichloroethane. Boron was determined directly by measuring the absorbance at 658 nm. The calibration graph was linear over the range of 2.5 x 10 -9 to 8 x 10 -8 g/mL. The blank, mechanism of the reactions, interference of other ions and some optimum conditions of the method were studied in detail. The main source of the blank resulted from methylene blue and the complex of F - -methylene blue. In order to reduce the blank, the amounts of methylene blue, H 2 SO 4 and HF were used as less as possible. Only one to one complex BF 4 - -methylene blue was formed in the medium of H 2 SO 4 . About 90% of methylene blue and F - -methylene blue complex was removre with 5 ml of water and only a little amount of BF 4 -methylene blue complex was decomposed. The extraction-spectrophotometric method with methylene blue was first applied to the microdetermination of boron in sodium metal and UF 6 . The sample of sodium metal was taken and weighed in the glovebox filled with argon. Then sodium metal was oxidized, hydrolyzed, netralized and fluorizated with H 2 O, H 2 SO 4 and HF, respectively. The 0.5 ppm of boron in sodium metal was determined with a relative error about ±4%. This method can be applied to the determination of boron in sodium metal, sodium sulfate and sodium hydroxide at diffeent grades. The species of boron in the hydrolysate of UF 6 is BF 4 - anion, so the sample can be directly analyzed. Boron contents in the range of 0.1 to 0.5 ppm was determined with a relative error about ±3%. Six samples could be analysed in 2h

Probing the stereoselective interaction of ofloxacin enantiomers with corresponding monoclonal antibodies by multiple spectrometry

Science.gov (United States)

Mu, Hongtao; Xu, Zhenlin; Liu, Yingju; Sun, Yuanming; Wang, Baoling; Sun, Xiulan; Wang, Zhanhui; Eremin, Sergei; Zherdev, Anatoly V.; Dzantiev, Boris B.; Lei, Hongtao

2018-04-01

Although stereoselective antibody has immense potential in chiral compounds detection and separation, the interaction traits between stereoselective antibody and the corresponding antigenic enantiomers are not yet fully exploited. In this study, the stereospecific interactions between ofloxacin isomers and corresponding monoclonal antibodies (McAb-WR1 and McAb-MS1) were investigated using time-resolved fluorescence, steady-state fluorescence, and circular dichroism (CD) spectroscopic methods. The chiral recognition discrepancies of antibodies with ofloxacin isomers were reflected through binding constant, number of binding sites, driving forces and conformational changes. The major interacting forces of McAb-WR1 and McAb-MS1 chiral interaction systems were hydrophobic force and van der Waals forces joined up with hydrogen bonds, respectively. Synchronous fluorescence spectra and CD spectra results showed that the disturbing of tyrosine and tryptophan micro-environments were so slightly that no obvious secondary structure changes were found during the chiral hapten binding. Clarification of stereospecific interaction of antibody will facilitate the application of immunoassay to analyze chiral contaminants in food and other areas.

Stereoselective, nitro-Mannich/lactamisation cascades for the direct synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles

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Pavol Jakubec

2012-04-01

Full Text Available A versatile nitro-Mannich/lactamisation cascade for the direct stereoselective synthesis of heavily decorated 5-nitropiperidin-2-ones and related heterocycles has been developed. A highly enantioenriched substituted 5-nitropiperidin-2-one was synthesised in a four component one-pot reaction combining an enantioselective organocatalytic Michael addition with the diastereoselective nitro-Mannich/lactamisation cascade. Protodenitration and chemoselective reductive manipulation of the heterocycles was used to install contiguous and fully substituted stereocentres in the synthesis of substituted piperidines.

Carbon and TiO_2 synergistic effect on methylene blue adsorption

International Nuclear Information System (INIS)

Simonetti, Evelyn Alves Nunes; Simone Cividanes, Luciana de; Campos, Tiago Moreira Bastos; Rossi Canuto de Menezes, Beatriz; Brito, Felipe Sales; Thim, Gilmar Patrocínio

2016-01-01

Due to its high efficiency, low cost and a simple operation, the adsorption process is an important and widely used technique for industrial wastewater treatment. Recent studies on the removal of artificial dyes by adsorption include a large number of adsorbents, such as: activated carbon, silicates, carbon nanotube, graphene, fibers, titanates and doped titanates. The carbon insertion in the TiO_2 structure promotes a synergistic effect on the adsorbent composite, improving the adsorption and the charge-transfer efficiency rates. However, there are few studies regarding the adsorption capacity of TiO_2/Carbon composites with the carbon concentration. This study evaluates the effect of carbon (resorcinol/formaldehyde) insertion on TiO_2 structure through the adsorption process. Adsorbents were prepared by varying the carbon weight percentages using the sol-gel method. The physicochemical properties of the catalysts prepared, such as crystallinity, particle size, surface morphology, specific surface area and pore volume were investigated. The kinetic study, adsorption isotherm, pH effect and thermodynamic study were examined in batch experiments using methylene blue as organic molecule. In addition, the effect of carbon phase on the adsorption capacity of TiO_2-carbon composite was deeply investigated. SEM micrographs showed that TiO_2 phase grows along the carbon phase and FT-IR results showed the presence of Ti−O−C chemical bonding. The experiments indicate that the carbon phase acted as a nucleation agent for the growth of TiO_2 during the sol-gel step, with a TiO_2 structure suitable for blue methylene adsorption, resulting in a material with large surface area and slit-like or wedge-shaped pores. Further experiments will show the best carbon concentration for methylene blue adsorption using a TiO_2 based material. - Highlights: • This article deals with the adsorption of methylene blue onto TiO_2-Carbon composite. • The sol-gel synthesis was efficient

Methylene Blue to Treat Protamine-induced Anaphylaxis Reactions. An Experimental Study in Pigs

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Agnes Afrodite S. Albuquerque

Full Text Available ABSTRACT Objective: To examine if methylene blue (MB can counteract or prevent protamine (P cardiovascular effects. Methods: The protocol included five heparinized pig groups: Group Sham -without any drug; Group MB - MB 3 mg/kg infusion; Group P - protamine; Group P/MB - MB after protamine; Group MB/P - MB before protamine. Nitric oxide levels were obtained by the nitric oxide/ozone chemiluminescence method, performed using the Nitric Oxide Analizer 280i (Sievers, Boulder, CO, USA. Malondialdehyde plasma levels were estimated using the thiobarbiturate technique. Results: 1 Groups Sham and MB presented unchanged parameters; 2 Group P - a Intravenous protamine infusion caused mean arterial pressure decrease and recovery trend after 25-30 minutes, b Cardiac output decreased and remained stable until the end of protamine injection, and c Sustained systemic vascular resistance increased until the end of protamine injection; 3 Methylene blue infusion after protamine (Group P/MB - a Marked mean arterial pressure decreased after protamine, but recovery after methylene blue injection, b Cardiac output decreased after protamine infusion, recovering after methylene blue infusion, and c Sustained systemic vascular resistance increased after protamine infusion and methylene blue injections; 4 Methylene blue infusion before protamine (Group MB/P - a Mean arterial pressure decrease was less severe with rapid recovery, b After methylene blue, there was a progressive cardiac output increase up to protamine injection, when cardiac output decreased, and c Sustained systemic vascular resistance decreased after protamine, followed by immediate Sustained systemic vascular resistance increase; 5 Plasma nitrite/nitrate and malondialdehyde values did not differ among the experimental groups. Conclusion: Reviewing these experimental results and our clinical experience, we suggest methylene blue safely prevents and treats hemodynamic protamine complications, from the

Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

Science.gov (United States)

Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

1990-01-01

A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

Functional elastic hydrogel as recyclable membrane for the adsorption and degradation of methylene blue.

Directory of Open Access Journals (Sweden)

Song Bao

Full Text Available Developing the application of high-strength hydrogels has gained much attention in the fields of medical, pharmacy, and pollutant removal due to their versatility and stimulus-responsive properties. In this presentation, a high-strength freestanding elastic hydrogel membrane was constructed by clay nanosheets, N, N-dimethylacrylamide and 2-acrylamide-2-methylpropanesulfonic acid for adsorption of methylene blue and heavy metal ions. The maximum values of elongation and Young's modulus for 0.5% AMPSNa hydrogel were 1901% and 949.4 kPa, respectively, much higher than those of traditional hydrogels. The adsorptions were confirmed to follow pseudo-second kinetic equation and Langmuir isotherm model fits the data well. The maximum adsorption capacity of hydrogel towards methylene blue was 434.8 mg g(-1. The hydrogel also exhibited higher separation selectivity to Pb(2+ than Cu(2+. The methylene blue adsorbed onto the hydrogel membrane can be photocatalytically degraded by Fenton agent and the hydrogel membrane could be recycled at least five times without obvious loss in mechanical properties. In conclusion, this presentation demonstrates a convenient strategy to prepare tough and elastic clay nanocomposite hydrogel, which can not only be applied as recyclable membrane for the photocatalytic degradation of organic dye, but also for the recovery of valuables.

Effective photocatalytic decolorization of methylene blue utilizing ZnO/rectorite nanocomposite under simulated solar irradiation

Energy Technology Data Exchange (ETDEWEB)

Li, Shi-qian, E-mail: shiqianli04@tom.com [College of Resource and Environmental Science, Wuhan University, Hubei Key Laboratory of Biomass-resource Chemical and Environment Bio-technology, Wuhan 430079 (China); Department of Biology and Chemical Engineering, FuQing Branch of Fujian Normal University, Fuqing 350300 (China); Zhou, Pei-jiang; Zhang, Wan-shun [College of Resource and Environmental Science, Wuhan University, Hubei Key Laboratory of Biomass-resource Chemical and Environment Bio-technology, Wuhan 430079 (China); Chen, Sheng [Department of Biology and Chemical Engineering, FuQing Branch of Fujian Normal University, Fuqing 350300 (China); Peng, Hong [State Key Laboratory of Water Resources and Hydropower Engineering Science, Wuhan University, Hubei, Wuhan 430072 (China)

2014-12-15

Highlights: • Preparation of ZnO inserted in rectorite as photocatalyst in methylene blue photodegradation. • The ZnO/rectorite can be used as adsorbents and photocatalysts. • The ZnO/rectorite system was easy to be gathered and recycled. • Inferred ZnO/rectorite the photocatalytic degradation methylene blue of aqueous micro mechanism. - Abstract: Preparation of a nanometer zinc oxide/rectorite (ZnO/REC) composites photocatalyst based on natural rectorite was conducted using a hydrothermal intercalation method. The structure, thermal property, and surface morphology of ZnO/REC were characterized by X-ray diffractor (XRD), thermogravimetric analysis (TGA), high-resolution transmission electron microscope (HRTEM) and scanning electron microscope (SEM) techniques. The photocatalytic activity of ZnO/REC was evaluated by photocatalytic decolorization of methylene blue (MB) in aqueous solution as a model pollutant under simulated sunlight irradiation. The HRTEM results revealed that well-dispersed and uniform ZnO/REC nanocomposites with diameters of 10 nm were embedded in rectorite. The ZnO/REC nanocomposite exhibited high photocatalytic activity under simulated solar irradiation. After 2 h of irradiation by simulated solar light, over 99% of methylene blue solution (15 mg/L) was decolorized with 0.9 g/L of the photocatalyst. The ZnO/REC was reusable, which meant that the adsorption photocatalytic decolorization process could be operated at a relatively low cost. Since this process does not require the addition of hydrogen peroxide but uses sunlight, it can be developed as an economically feasible and environmentally friendly method to decolorize or treat dye wastewater using solar.

Stereoselective synthesis of functionalized cyclic amino acid derivatives via a [2,3]-Stevens rearrangement and ring-closing metathesis.

Science.gov (United States)

Nash, Aaron; Soheili, Arash; Tambar, Uttam K

2013-09-20

Unnatural cyclic amino acids are valuable tools in biomedical research and drug discovery. A two-step stereoselective strategy for converting simple glycine-derived aminoesters into unnatural cyclic amino acid derivatives has been developed. The process includes a palladium-catalyzed tandem allylic amination/[2,3]-Stevens rearrangement followed by a ruthenium-catalyzed ring-closing metathesis. The [2,3]-rearrangement proceeds with high diastereoselectivity through an exo transition state. Oppolzer's chiral auxiliary was utilized to access an enantiopure cyclic amino acid by this approach, which will enable future biological applications.

Azure B, a metabolite of methylene blue, is a high-potency, reversible inhibitor of monoamine oxidase

Energy Technology Data Exchange (ETDEWEB)

Petzer, Anél, E-mail: 12264954@nwu.ac.za [Unit for Drug Research and Development, School of Pharmacy, North-West University, Private Bag X6001, Potchefstroom, 2520 (South Africa); Harvey, Brian H. [Division of Pharmacology, School of Pharmacy, North-West University, Private Bag X6001, Potchefstroom, 2520 (South Africa); Wegener, Gregers [Centre for Psychiatric Research, Aarhus University Hospital-Risskov, Skovagervej 2, 8240 Risskov (Denmark); Petzer, Jacobus P. [Division of Pharmaceutical Chemistry, School of Pharmacy, North-West University, Private Bag X6001, Potchefstroom, 2520 (South Africa)

2012-02-01

Methylene blue (MB) has been shown to act at multiple cellular and molecular targets and as a result possesses diverse medical applications. Among these is a high potency reversible inhibition of monoamine oxidase A (MAO-A) that may, at least in part, underlie its adverse effects but also its psycho- and neuromodulatory actions. MB is metabolized to yield N-demethylated products of which azure B, the monodemethyl species, is the major metabolite. Similar to MB, azure B also displays a variety of biological activities and may therefore contribute to the pharmacological profile of MB. Based on these observations, the present study examines the interactions of azure B with recombinant human MAO-A and -B. The results show that azure B is a potent MAO-A inhibitor (IC{sub 50} = 11 nM), approximately 6-fold more potent than is MB (IC{sub 50} = 70 nM) under identical conditions. Measurements of the time-dependency of inhibition suggest that the interaction of azure B with MAO-A is reversible. Azure B also reversibly inhibits the MAO-B isozyme with an IC{sub 50} value of 968 nM. These results suggest that azure B may be a hitherto under recognized contributor to the pharmacology and toxicology of MB by blocking central and peripheral MAO-A activity and as such needs to be considered during its use in humans and animals. Highlights: ► Methylene blue (MB) is a known potent MAO-A inhibitor. ► Azure B, the major metabolite of MB, is more potent as a MAO-A inhibitor. ► Azure B may be a contributor to the CNS pharmacology and toxicology of MB.

Stereoselective uptake and distribution of the chiral neonicotinoid insecticide, Paichongding, in Chinese pak choi (Brassica campestris ssp. chinenesis)

International Nuclear Information System (INIS)

Wang, Haiyan; Yang, Zhen; Liu, Ruyang; Fu, Qiuguo; Zhang, Sufen; Cai, Zhiqiang; Li, Juying; Zhao, Xiaojun; Ye, Qingfu; Wang, Wei; Li, Zhong

2013-01-01

Highlights: • Absorption of foliar applied Paichongding by pak choi was not stereoselective. • Foliar uptake and downward transport of Paichongding were both found in pak choi. • Enantioselective and epimer-selective root uptake were observed for Paichongding. • Foliage/root uptake showed diastereoselective transport of Paichongding epimers. • The SR and RS are more easily taken up by roots and accumulated in edible parts. -- Abstract: Neonicotinoid chiral insecticidal Paichongding is a promising substitute for the widely used imidacloprid. Four stereoisomers of Paichongding, 5R,7R, 5S,7S, 5S,7R and 5R,7S, were employed in both foliage and roots of Chinese pak choi to investigate their stereoselective uptake and distribution in pak choi. Results showed that after foliar application, no stereoselective absorption into pak-choi plants was observed among the enantiomers. Total absorptions were 35.40% of the applied amount for 5R,7R, 36.66% for 5S,7S, 36.80% for 5S,7R and 38.20% for 5R,7S at 96 HAT. The translocation of the four absorbed stereoisomers within pak choi occurred both acropetally and basipetally and the transport of 14 C from enantiomers 5R,7R and 5S,7S were significantly higher than for 5R,7S and 5S,7R. Significant stereoselective translocation inside plants was observed between Paichongding epimers. Total root uptake reached 16.49–19.85% for 5R,7R and 5S,7S, and 24.57–28.82% for 5S,7R and 5R,7S at 144 HAT. Both enantioselective and diastereoselective root uptake into pak-choi occurred between the four stereoisomers. The 5R,7S and 5S,7R enantiomers were more readily uptaken by the roots than 5R,7R and 5S,7S and accumulated in the edible leaves. These results will help to develop an understanding of Paichongding using only the target-active enantiomer of pesticides

Stereoselective uptake and distribution of the chiral neonicotinoid insecticide, Paichongding, in Chinese pak choi (Brassica campestris ssp. chinenesis)

Energy Technology Data Exchange (ETDEWEB)

Wang, Haiyan; Yang, Zhen; Liu, Ruyang; Fu, Qiuguo; Zhang, Sufen; Cai, Zhiqiang; Li, Juying; Zhao, Xiaojun [Institute of Nuclear Agricultural Sciences, Key Laboratory of Nuclear Agricultural Sciences of Ministry of Agriculture and Zhejiang Province, Zhejiang University, Hangzhou 310029 (China); Ye, Qingfu, E-mail: qfye@zju.edu.cn [Institute of Nuclear Agricultural Sciences, Key Laboratory of Nuclear Agricultural Sciences of Ministry of Agriculture and Zhejiang Province, Zhejiang University, Hangzhou 310029 (China); Wang, Wei [Institute of Nuclear Agricultural Sciences, Key Laboratory of Nuclear Agricultural Sciences of Ministry of Agriculture and Zhejiang Province, Zhejiang University, Hangzhou 310029 (China); Li, Zhong, E-mail: lizhong@ecust.edu.cn [School of Pharmacy, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237 (China)

2013-11-15

Highlights: • Absorption of foliar applied Paichongding by pak choi was not stereoselective. • Foliar uptake and downward transport of Paichongding were both found in pak choi. • Enantioselective and epimer-selective root uptake were observed for Paichongding. • Foliage/root uptake showed diastereoselective transport of Paichongding epimers. • The SR and RS are more easily taken up by roots and accumulated in edible parts. -- Abstract: Neonicotinoid chiral insecticidal Paichongding is a promising substitute for the widely used imidacloprid. Four stereoisomers of Paichongding, 5R,7R, 5S,7S, 5S,7R and 5R,7S, were employed in both foliage and roots of Chinese pak choi to investigate their stereoselective uptake and distribution in pak choi. Results showed that after foliar application, no stereoselective absorption into pak-choi plants was observed among the enantiomers. Total absorptions were 35.40% of the applied amount for 5R,7R, 36.66% for 5S,7S, 36.80% for 5S,7R and 38.20% for 5R,7S at 96 HAT. The translocation of the four absorbed stereoisomers within pak choi occurred both acropetally and basipetally and the transport of {sup 14}C from enantiomers 5R,7R and 5S,7S were significantly higher than for 5R,7S and 5S,7R. Significant stereoselective translocation inside plants was observed between Paichongding epimers. Total root uptake reached 16.49–19.85% for 5R,7R and 5S,7S, and 24.57–28.82% for 5S,7R and 5R,7S at 144 HAT. Both enantioselective and diastereoselective root uptake into pak-choi occurred between the four stereoisomers. The 5R,7S and 5S,7R enantiomers were more readily uptaken by the roots than 5R,7R and 5S,7S and accumulated in the edible leaves. These results will help to develop an understanding of Paichongding using only the target-active enantiomer of pesticides.

High-pressure homogenization associated hydrothermal process of palygorskite for enhanced adsorption of Methylene blue

Science.gov (United States)

Zhang, Zhifang; Wang, Wenbo; Wang, Aiqin

2015-02-01

Palygorskite (PAL) was modified by a high-pressure homogenization assisted hydrothermal process. The effects of modification on the morphology, structure and physicochemical properties of PAL were systematically investigated by Field-emission scanning electron microscopy (FESEM), Transmission electron microscopy (TEM), Fourier transform infrared spectrometry (FTIR), Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD) and Zeta potential analysis techniques, and the adsorption properties were systematically evaluated using Methylene blue (MB) as the model dye. The results revealed that the crystal bundles were disaggregated and the PAL nanorods became more even after treated via associated high-pressure homogenization and hydrothermal process, and the crystal bundles were dispersed as nanorods. The intrinsic crystal structure of PAL was remained after hydrothermal treatment, and the pore size calculated by the BET method was increased. The adsorption properties of PAL for MB were evidently improved (from 119 mg/g to 171 mg/g) after modification, and the dispersion of PAL before hydrothermal reaction is favorable to the adsorption. The desorption evaluation confirms that the modified PAL has stronger affinity with MB, which is benefit to fabricate a stable organic-inorganic hybrid pigment.

Complications of Methylene Blue Dye in Breast Surgery: Case Reports and Review of the Literature

Directory of Open Access Journals (Sweden)

FJ Reyes, MB Noelck, C Valentino, L Grasso-LeBeau, JE Lang

2011-01-01

Full Text Available Introduction: Methylene blue dye has been used worldwide successfully with few complications in breast surgery. We present two different complications involving methylene blue: 1 skin and parenchymal necrosis when dye was injected in a subdermal fashion and 2 Mycoplasma infection caused by contaminated methylene blue in breast reduction surgery.Methods: We present two cases seen at the University of Arizona during 2008 and referred to a breast surgeon for management. We evaluated and managed complications of methylene blue dye injected by 2 referring surgeons for different indications. A review of the literature was performed.Results: The first case is a 67 year old female diagnosed with infiltrating ductal carcinoma of the left breast for which she was treated by her initial surgeon with left segmental mastectomy and sentinel node biopsy. The operating surgeon injected methylene blue in a subareolar subdermal fashion (distant from the primary tumor; unfortunately the patient suffered skin and breast necrosis requiring multiple surgical debridements and finally achieving delayed primary closure. The second case is a 45 year old female with infiltrating lobular carcinoma with a history of Mycoplasma infection secondary to methylene blue injected for breast reduction surgery. She required multiple debridements and had granulomas masquerading as cancer on MRI that confounded her extent of disease.Conclusions: The use of methylene blue dye in breast surgery is not without risk. In both cases methylene blue was responsible for complications requiring surgical debridement for local wound problems. In each case severe necrosis and infection were present. Methylene blue may cause not only significant morbidity, but may also produce cosmetically unsatisfactory results.

Gas-chromatographic resolution of enantiomeric secondary alcohols. Stereoselective reductive metabolism of ketones in rabbit-liver cytosol.

Science.gov (United States)

Gal, J; DeVito, D; Harper, T W

1981-01-01

Chiral secondary alcohols were treated with (S)-(-)-1-phenylethyl isocyanate. For each racemic alcohol, the resulting diastereomeric urethane derivatives were resolved on flexible fused-silica capillary GLC columns with retention times of 15 min or less. Derivatization of individual enantiomers showed that the urethane derivatives of (R)-(-)-2-octanol, (R)-(+)-1-phenylethyl alcohol, and (S)-(+)-2,2,2-trifluoro-1-phenylethanol are eluted before the corresponding diastereomers. The procedure is simple and rapid, and is suitable for the determination of the enantiomeric composition of chiral alcohols extracted from biological media. A series of aliphatic alcohols, aryl alkyl carbinols, and arylalkyl alkyl carbinols were resolved with the procedure, and the degree of resolution varied from good to excellent. Eight achiral ketones were incubated, individually, with rabbit-liver 90,000 g supernatant fractions, and the enantiomeric composition of the alcohol metabolites was determined with the GLC procedure. The reductions proceeded with high stereoselectivity to give alcohol products of 90% or greater enantiomeric purity. The reduction of 2-octanone and acetophenone gave predominant alcohols of (S)-configuration, in agreement with the Baumann-Prelog rule. The configuration of the predominant alcohols arising in the reduction of the remainder of the ketones could not be firmly established, but the evidence suggests that they are also of the (S)-configuration. Fluorine or methyl substitution in the ortho position of acetophenone produced an increase in the stereoselectivity, and the alcohol produced from ortho-methylacetophenone was enantiomerically greater than 99% pure.

Effect of buffer general acid-base catalysis on the stereoselectivity of ester and thioester H/D exchange in D2O.

Science.gov (United States)

Mohrig, Jerry R; Reiter, Nicholas J; Kirk, Randy; Zawadski, Michelle R; Lamarre-Vincent, Nathan

2011-04-06

As part of a comprehensive investigation on the stereochemistry of base-catalyzed 1,2-elimination and H/D exchange reactions of carbonyl compounds, we have found that the stereoselectivity of H/D exchange of 3-hydroxybutyryl N-acetylcysteamine (3) in D(2)O is strongly influenced by the presence of buffers. This buffer effect is also operative with a simple acyclic ester, ethyl 3-methoxybutanoate (7). Buffers whose general-acid components are cyclic tertiary ammonium ions are particularly effective in changing the stereoselectivity. (2)H NMR analysis showed that without buffer, H/D exchange of 3 produces 81-82% of the 2R*, 3R* diastereomer of 2-deuterio 3 (the anti product). In the presence of 0.33 M 3-quinuclidinone buffer, only 44% of the 2R*, 3R* diastereomer was formed. With ester 7, the stereoselectivity went from 93-94% in DO(-)/D(2)O to 60% in the presence of buffer. Phosphate buffer, as well as others, also showed substantial effects. The results are put into the context of what is known about the mechanism of H/D exchange of esters and thioesters, and the relevance of the buffer effect on the mechanism of the enoyl-CoA hydratase reaction is discussed. It is likely that hydrogen bonding in the enolate-buffer acid encounter complex is an important stereochemical determinant in producing a greater amount of the 2R*, 3S* diastereomer (the syn product). Studies that involve the protonation of enolate anions in D(2)O need to include the buffer general acid in any understanding of the stereoselectivity. © 2011 American Chemical Society

Synthesis and properties of Co-doped titanate nanotubes and their optical sensitization with methylene blue

International Nuclear Information System (INIS)

Ferreira, V.C.; Nunes, M.R.; Silvestre, A.J.; Monteiro, O.C.

2013-01-01

Here we report on a novel chemical route to synthesize homogenous cobalt-doped titanate nanotubes (CoTNT), using an amorphous Co-doped precursor. The influence of the synthesis temperature, autoclave dwell time and metal doping on the structural and microstructural as well as on the optical properties of the synthesized titanate nanotubes is studied and discussed. The optical band gaps of the CoTNT samples are red shifted in comparison with the values determined for the undoped samples, such red shifts bringing the absorption edge of the CoTNT samples into the visible region. CoTNT materials also demonstrate particular high adsorption ability for methylene blue, the amount of the adsorbed dye being higher than the one predictable for a monolayer formation. This suggests the possibility of intercalation of the dye molecule between the TiO 6 layers of the TNT structure. It is also shown that the methylene blue sensitized Co-doped nanostructures are highly stable under UV radiation and present a strong and broad absorption in the visible region. - Highlights: • New hydrothermal chemical route to synthesize cobalt-doped titanate nanotubes. • The Co-doping stabilizes the TNTs morphology in a temperature range of 160–200 °C. • Optical band gaps of CoTNTs are red shifted compared to the TNT samples. • Methylene blue sensitized CoTNTs are highly stable under UV–vis irradiation

Synthesis and properties of Co-doped titanate nanotubes and their optical sensitization with methylene blue

Energy Technology Data Exchange (ETDEWEB)

Ferreira, V.C. [University of Lisbon, Faculty of Sciences, Department of Chemistry and Biochemistry and CQB, Campo Grande, 1749-016 Lisboa (Portugal); Nunes, M.R. [University of Lisbon, Faculty of Sciences, Department of Chemistry and Biochemistry and CCMM, Campo Grande, 1749-016 Lisboa (Portugal); Silvestre, A.J. [Instituto Superior de Engenharia de Lisboa, Department of Physics and ICEMS, R. Conselheiro Emídio Navarro 1, 1959-007 Lisboa (Portugal); Monteiro, O.C., E-mail: ocmonteiro@fc.ul.pt [University of Lisbon, Faculty of Sciences, Department of Chemistry and Biochemistry and CQB, Campo Grande, 1749-016 Lisboa (Portugal)

2013-10-01

Here we report on a novel chemical route to synthesize homogenous cobalt-doped titanate nanotubes (CoTNT), using an amorphous Co-doped precursor. The influence of the synthesis temperature, autoclave dwell time and metal doping on the structural and microstructural as well as on the optical properties of the synthesized titanate nanotubes is studied and discussed. The optical band gaps of the CoTNT samples are red shifted in comparison with the values determined for the undoped samples, such red shifts bringing the absorption edge of the CoTNT samples into the visible region. CoTNT materials also demonstrate particular high adsorption ability for methylene blue, the amount of the adsorbed dye being higher than the one predictable for a monolayer formation. This suggests the possibility of intercalation of the dye molecule between the TiO{sub 6} layers of the TNT structure. It is also shown that the methylene blue sensitized Co-doped nanostructures are highly stable under UV radiation and present a strong and broad absorption in the visible region. - Highlights: • New hydrothermal chemical route to synthesize cobalt-doped titanate nanotubes. • The Co-doping stabilizes the TNTs morphology in a temperature range of 160–200 °C. • Optical band gaps of CoTNTs are red shifted compared to the TNT samples. • Methylene blue sensitized CoTNTs are highly stable under UV–vis irradiation.

Graphene-SnO2 composites for highly efficient photocatalytic degradation of methylene blue under sunlight.

Science.gov (United States)

Seema, Humaira; Christian Kemp, K; Chandra, Vimlesh; Kim, Kwang S

2012-09-07

Graphene sheets decorated with SnO(2) nanoparticles (RGO-SnO(2)) were prepared via a redox reaction between graphene oxide (GO) and SnCl(2). Graphene oxide (GO) was reduced to graphene (RGO) and Sn(2+) was oxidized to SnO(2) during the redox reaction, leading to a homogeneous distribution of SnO(2) nanoparticles on RGO sheets. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images show uniform distribution of the nanoparticles on the RGO surface and high-resolution transmission electron microscopy (HRTEM) shows an average particle size of 3-5 nm. The RGO-SnO(2) composite showed an enhanced photocatalytic degradation activity for the organic dye methylene blue under sunlight compared to bare SnO(2) nanoparticles. This result leads us to believe that the RGO-SnO(2) composite could be used in catalytic photodegradation of other organic dyes.

Enhanced Photocatalytic Performance of NiO-Decorated ZnO Nanowhiskers for Methylene Blue Degradation

Directory of Open Access Journals (Sweden)

I. Abdul Rahman

2014-01-01

Full Text Available ZnO nanowhiskers were used for photodecomposition of methylene blue in aqueous solution under UV irradiation. The rate of methylene blue degradation increased linearly with time of UV irradiation. 54% of degradation rate was observed when the ZnO nanowhiskers were used as photocatalysts for methylene blue degradation for 80 min under UV irradiation. The decoration of p-type NiO nanoparticles on n-type ZnO nanowhiskers significantly enhanced photocatalytic activity and reached 72% degradation rate of methylene blue by using the same method. NiO-decorated ZnO was recycled for second test and shows 66% degradation from maximal peak of methylene blue within the same period. The increment of photocatalytic activity of NiO-decorated ZnO nanowhiskers was explained by the extension of the electron depletion layer due to the formation of nanoscale p-n junctions between p-type NiO and n-type ZnO. Hence, these products provide new alternative proficient photocatalysts for wastewater treatment.

Stereoselective phytotoxicity of HCH mediated by photosynthetic and antioxidant defense systems in Arabidopsis thaliana.

Science.gov (United States)

Zhang, Qiong; Zhou, Cong; Zhang, Quan; Qian, Haifeng; Liu, Weiping; Zhao, Meirong

2013-01-01

Hexachlorocyclohexane (HCH) has been used for plant protection and sanitation world-widely, and its isomers have been detected in water, soil, and air as well as in vegetation. As a sink for lipophilic pollutants, vegetation is very important for the degradation and fate of organic contamination; however, little was known about their phytotoxicity and mechanisms of toxic effect. In this study, the stereoselective phototoxicity of four isomers (α, β, γ, and δ) of HCHs mediated by independent as well as interconnecting systems of photosynthesis and enzymatic antioxidant defense system in Arabidopsis thaliana were assessed. Our results revealed that all the HCHs not only stimulated the activities of catalase (CAT) and peroxidase (POD), but also inhibited the activity of superoxide dismutase (SOD). In photosynthesis system, the photosynthetic efficiency of PSI and PSII were all down regulated. Meanwhile, results from both systems showed that δ-HCH was the most toxic one, while α-HCH the least in Arabidopsis thaliana. For the first time, stereoselective effects of different isomers of HCH in plant were demonstrated. And the results suggest that it requires further research to fully elucidate the environmental toxicity and their mechanisms.

Stereoselective phytotoxicity of HCH mediated by photosynthetic and antioxidant defense systems in Arabidopsis thaliana.

Directory of Open Access Journals (Sweden)

Qiong Zhang

Full Text Available BACKGROUND: Hexachlorocyclohexane (HCH has been used for plant protection and sanitation world-widely, and its isomers have been detected in water, soil, and air as well as in vegetation. As a sink for lipophilic pollutants, vegetation is very important for the degradation and fate of organic contamination; however, little was known about their phytotoxicity and mechanisms of toxic effect. In this study, the stereoselective phototoxicity of four isomers (α, β, γ, and δ of HCHs mediated by independent as well as interconnecting systems of photosynthesis and enzymatic antioxidant defense system in Arabidopsis thaliana were assessed. PRINCIPAL FINDINGS: Our results revealed that all the HCHs not only stimulated the activities of catalase (CAT and peroxidase (POD, but also inhibited the activity of superoxide dismutase (SOD. In photosynthesis system, the photosynthetic efficiency of PSI and PSII were all down regulated. Meanwhile, results from both systems showed that δ-HCH was the most toxic one, while α-HCH the least in Arabidopsis thaliana. CONCLUSIONS: For the first time, stereoselective effects of different isomers of HCH in plant were demonstrated. And the results suggest that it requires further research to fully elucidate the environmental toxicity and their mechanisms.

Stereoselective bioaccumulation of chiral PCB 91 in earthworm and its metabolomic and lipidomic responses.

Science.gov (United States)

He, Zeying; Wang, Yuehua; Zhang, Yanwei; Cheng, Haiyan; Liu, Xiaowei

2018-07-01

Stereoselective bioaccumulation, elimination, metabolomic and lipidomic responses of earthworm Eisenia fetida exposed to chiral polychlorinated biphenyl (PCB) 91 in an earthworm-soil system were investigated. Preferential bioaccumulation of (-)-PCB 91 and elimination of (+)-PCB 91 were observed following 50 and 500 μg/kg dwt exposures. Enantiomer fraction (EF) values decreased over time during the uptake and elimination periods. Metabolomics and lipidomics techniques based on ultra-performance liquid chromatography/quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) revealed significant changes in 108 metabolites after earthworms exposure to (+)-, (-)-, and (±)-PCB 91, compared to control groups. Forty two of these metabolites were identified as amino acids, nucleosides, fatty acids, dicarboxylic acids, vitamins or others. Lysophospholipids including six lysophosphatidylcholines (LPC), six lysophosphatidylethanolamine (LPE), eight lysophosphatidylinositol (LPI) and five lysophosphatidylserine (LPS) were also differentially expressed between exposure and control groups. Alterations in the levels of metabolites and lipids indicated stereoselective effects of chiral PCB 91 on earthworm amino acid, energy, and nucleotide metabolism, neurodevelopment and gene expression. Overall, the effects of (+)-PCB 91 were more pronounced than that of (-)- and (±)-PCB 91. Copyright © 2018 Elsevier Ltd. All rights reserved.

Enhanced visible light photocatalytic degradation of methylene blue by F-doped TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Yu, Wei [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China); Liu, Xinjuan, E-mail: lxj669635@126.com [Shanghai Nanotechnlogy Promotion Center, Shanghai 200237 (China); Center for Coordination Bond and Electronic Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018 (China); Pan, Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China); Li, Jinliang; Liu, Junying [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China); Zhang, Jing; Li, Ping; Chen, Chen [Shanghai Nanotechnlogy Promotion Center, Shanghai 200237 (China); Sun, Zhuo [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai 200062 (China)

2014-11-15

Graphical abstract: F-doped TiO2 is synthesized using a modified sol–gel method for visible photocatalytic degradation of MB with a high degradation rate of 91%. - Highlights: • F-doped TiO{sub 2} are synthesized using a modified sol–gel method. • The photocatalytic degradation of methylene blue by F-doped TiO{sub 2} is investigated. • A high methylene blue degradation rate of 91% is achieved under visible light irradiation. - Abstract: F-doped TiO{sub 2} (F-TiO{sub 2}) were successfully synthesized using a modified sol–gel method. The morphologies, structures, and photocatalytic performance in the degradation of methylene blue (MB) were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV–vis absorption spectroscopy, and electrochemical impedance spectra, respectively. The results show that F-TiO{sub 2} exhibits an enhanced photocatalytic performance in the degradation of MB with a maximum degradation rate of 91% under visible light irradiation as compared with pure TiO{sub 2} (32%). The excellent photocatalytic activity is due to the contribution from the increased visible light absorption, promoted separation of photo-generated electrons and holes as well as enhanced photocatalytic oxidizing species with the doping of F in TiO{sub 2}.

Film dosimeters based on methylene blue and methyl orange in polyvinyl alcohol

DEFF Research Database (Denmark)

Chung, W.H.; Miller, A.

1994-01-01

Polyvinyl alcohol (PVA) films containing methylene blue and methyl orange are useful as gamma and electron radiation dosimeters. Absorbed doses should not exceed 40 kGy for methylene blue and 500 kGy for methyl orange. Because PVA is water-soluble, the films may be made without toxic solvents...

Stereoselective uptake and distribution of chiral neoniconoid insecticide paichongding in chinese pak choi (Brassica campestris ssp. Chinenesis)

International Nuclear Information System (INIS)

Wang Haiyan; Yang Zhen; Liu Ruyang; Fu Qiuguo; Zhang Sufen; Li Juying; Zhao Xiaojun; Ye Qingfu; Wang Wei; Li Zhong

2014-01-01

Paichongding, a neonicotinoid chiral insecticide containing two chiral centers, is a promising substitute for the widely used imidacloprid because it is effective against many imidacloprid-resistant insects. In this study, four optically-pure stereoisomers of Paichongding with 5R, 7R, 5S, 7S, 5S, 7R, and 5R, 7S were employed in both foliar and root of Chinese pak choi to investigate the stereoselective uptake and distribution of the insecticide in pak choi. The results showed, after foliar application, total absorption of individual "1"4C-Paichongding stereoisomers into pak-choi plants demonstrated no stereoselectivity between the enantiomers. The translocation of the four absorbed stereoisomers within pak choi occurred in both acropetal and basipetal directions and the transport of "1"4C from enantiomers 5R, 7R and 5S, 7S were significantly higher than enantiomers 5R, 7S and 5S, 7R. The statistically significant stereoselective translocation inside plants was observed between Paichongding epimers. Root treatment revealed that enantioselective and diastereoselective root uptake into pak-choi plants were both found between the four enantiomers. The enantiomers of 5R, 7S and 5S, 7R were more readily taken up by roots, and more readily accumulated in edible leaves than 5R, 7R and 5S, 7S. These results will help to develop an understanding of the proper application of Paichongding isomers in vegetables, and give useful information for food and environmental assessments of chiral pesticides. (authors)

Stereoselectivity in the salt-cocrystal products formed by phenylglycinol or phenylglycine with their respective sodium or hydrochloride salts.

Science.gov (United States)

Brittain, Harry G

2013-01-01

The salt and stereoselective cocrystal phenomena associated with 2-phenylglycinol and 2-phenylglycine have been studied using X-ray powder diffraction and differential scanning calorimetry. The chiral identities of the free acids and their sodium salts, or the free bases and their chloride salts, were found to play a determining role as to whether a salt-cocrystal product could or could not be formed. In particular, when cocrystallization of an enantiomerically pure basic or zwitterionic substance with its enantiomerically pure acid addition salt was attempted, a salt-cocrystal was only obtained when the absolute configuration of the two reactants is opposite. On the other hand, it has been found that no stereoselectivity in salt-cocrystal formation existed in the cocrystallization of an enantiomerically pure acidic or zwitterionic substance with its enantiomerically pure base addition salt. Copyright © 2012 Wiley Periodicals, Inc.

Retrograde Instillation of Methylene Blue in the Difficult Diagnosis of BPF

Directory of Open Access Journals (Sweden)

F. Ravenna

2012-01-01

Full Text Available We report two cases in which we were able to diagnose bronchopleural fistula through retrograde methylene blue instillation during bronchoscopy. In the first case, methylene blue was injected through an abdominal drain, followed by air instillation and detected in the left bronchial tree, demonstrating the presence of a fistula in the lingula’s bronchus. In the second case, methylene blue was injected into a pleural drain, through a breach on a surgical suture and detected in the right bronchial tree, demonstrating the presence of a fistula in the right inferior bronchus. The retrograde instillation of methylene blue, through a drain in the abdomen or the thoracic wall, is a safe, cheap, and practical method that allows the bronchoscopist to identify the presence of a fistula and, more importantly, to identify the exact point on the bronchial tree where a fistula is located. This provides the possibility of sealing the fistula with a variety of devices. It is our opinion that this procedure should be considered a primary method of diagnosis when a bronchopleural fistula is suspected and a drain on the thoracic or abdominal wall is positioned such that effusions are able to drain.

High-speed organocatalytic polymerization of a renewable methylene butyrolactone by a phosphazene superbase

KAUST Repository

Schmitt, Meghan L.; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

2014-01-01

The organic phosphazene superbase, 1-tert-butyl-4,4,4-tris(dimethylamino)- 2,2-bis[tris(dimethylamino)phosphoranylid-enamino]-2λ5, 4λ5-catenadi(phosphazene) (t-Bu-P4), is found to directly initiate high-speed polymerization of the biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL), in contrast to other polymerization systems using t-Bu-P4 which typically require addition of an organic acid or a nucleophile as a co-initiating component. This MMBL polymerization by t-Bu-P4 alone is extremely rapid; even with a low t-Bu-P4 loading of 0.1 mol% or 0.02 mol%, quantitative monomer conversion is achieved in 20 s or 1 min, respectively, affording medium to high molecular weight PMMBL bioplastics in a catalytic fashion. The combined experimental and theoretical/computational studies have yielded mechanisms of chain initiation through abstraction of a proton from a monomer by t-Bu-P 4, essentially barrier-less chain propagation through rapid conjugate addition of the enolate anion stabilized by the nano-size cation [t-Bu-P 4H]+ to the monomer, and chain termination through chain transfer to the monomer which generates a saturated termination chain end and the [t-Bu-P4H]+-stabilized anionic active species that starts a new chain. This journal is © the Partner Organisations 2014.

INTERACTION MODE BETWEEN METHYLENE BLUE-Sm(III ...

African Journals Online (AJOL)

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between methylene blue (MB)-Sm(III) complex and herring sperm DNA by using acridine orange .... the complex was recorded as KBr pellets on Spectrum One FTIR system (PE Company, USA), ..... mechanism of drugs and drug design.

Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

International Nuclear Information System (INIS)

Fernandes, Talita de A.; Universidade Federal do Rio de Janeiro; Silva, Alcides J.M. da; Costa, Paulo R.R.; Esteves, Pierre M.; Eberlin, Marcos N.; Vaz, Boniek G.; Universidade Federal de Goias

2013-01-01

The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc) 2 . The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag 2 CO 3 as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

Stereoselective virtual screening of the ZINC database using atom pair 3D-fingerprints.

Science.gov (United States)

Awale, Mahendra; Jin, Xian; Reymond, Jean-Louis

2015-01-01

Tools to explore large compound databases in search for analogs of query molecules provide a strategically important support in drug discovery to help identify available analogs of any given reference or hit compound by ligand based virtual screening (LBVS). We recently showed that large databases can be formatted for very fast searching with various 2D-fingerprints using the city-block distance as similarity measure, in particular a 2D-atom pair fingerprint (APfp) and the related category extended atom pair fingerprint (Xfp) which efficiently encode molecular shape and pharmacophores, but do not perceive stereochemistry. Here we investigated related 3D-atom pair fingerprints to enable rapid stereoselective searches in the ZINC database (23.2 million 3D structures). Molecular fingerprints counting atom pairs at increasing through-space distance intervals were designed using either all atoms (16-bit 3DAPfp) or different atom categories (80-bit 3DXfp). These 3D-fingerprints retrieved molecular shape and pharmacophore analogs (defined by OpenEye ROCS scoring functions) of 110,000 compounds from the Cambridge Structural Database with equal or better accuracy than the 2D-fingerprints APfp and Xfp, and showed comparable performance in recovering actives from decoys in the DUD database. LBVS by 3DXfp or 3DAPfp similarity was stereoselective and gave very different analogs when starting from different diastereomers of the same chiral drug. Results were also different from LBVS with the parent 2D-fingerprints Xfp or APfp. 3D- and 2D-fingerprints also gave very different results in LBVS of folded molecules where through-space distances between atom pairs are much shorter than topological distances. 3DAPfp and 3DXfp are suitable for stereoselective searches for shape and pharmacophore analogs of query molecules in large databases. Web-browsers for searching ZINC by 3DAPfp and 3DXfp similarity are accessible at www.gdb.unibe.ch and should provide useful assistance to drug

Continuous adsorption of methylene blue dye on the maize stem ground tissue

Directory of Open Access Journals (Sweden)

Kojić Predrag S.

2017-01-01

Full Text Available Continuous adsorption of methylene blue from aqueous solutions onto maize stem ground tissue in column mode was investigated. The study encompassed the effects of important parameters such as flow rate, initial concentration of methylene blue, and bed depth on methylene blue removal from model solutions. The maximum adsorption capacity of the maize stem was 45.9 mg/g at the initial methylene blue concentration of 20 mg/L, bed height of 6.5 cm and flow rate of 8 mL/min. It was found that the breakthrough time for reaching saturation increased with a decrease in the flow rate, and also occurred earlier for a higher influent concentration. The breakthrough times increased with the bed depth, thus allowing a larger volume to be treated. The Adams-Bohart, Yoon-Nelson, Clark and artificial neural network models were used to predict the breakthrough curves. These models gave excellent approximations of the experimental behavior.[Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172025

Studies in the stereoselective synthesis of 1,1-disubstituted 1,2,3,4-tetrahydroisoquinolines

OpenAIRE

Berg, Michael Arthur George

1992-01-01

Isoquinoline alkaloids and analogs play an important role in today's pharmaceutical industry. The need to synthesize single stereoisomers of these alkaloids is important. Many times only a single stereoisomer exhibits the desired activity, while other stereoisomers of the alkaloid exhibit undesired side effects. The stereoselective synthesis of 1, 1-disubstituted 1,2,3,4- tetrahydroisoquinolines using Reissert compound chemistry containing chiral acyl auxiliaries was studied with the ultimate...

Assessing Urinary Tract Junction Obstruction Defects by Methylene Blue Dye Injection.

Science.gov (United States)

Yun, Kangsun

2017-10-12

Urinary tract junction obstruction defects are congenital anomalies inducing hydronephrosis and hydroureter. Murine urinary tract junction obstruction defects can be assessed by tracking methylene blue dye flow within the urinary system. Methylene blue dye is injected into the renal pelvis of perinatal embryonic kidneys and dye flow is monitored from the renal pelvis of the kidney through the ureter and into the bladder lumen after applying hydrostatic pressure. Dye accumulation will be evident in the bladder lumen of the normal perinatal urinary tract, but will be constrained between the renal pelvis and the end point of an abnormal ureter, if urinary tract obstructions occur. This method facilitates the confirmation of urinary tract junction obstructions and visualization of hydronephrosis and hydroureter. This manuscript describes a protocol for methylene blue dye injection into the renal pelvis to confirm urinary tract junction obstructions.

Palladium-catalyzed arylation of enoates with iodobenzene: stereoselective synthesis of trisubstituted olefins

Energy Technology Data Exchange (ETDEWEB)

Fernandes, Talita de A. [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Silva, Alcides J.M. da; Costa, Paulo R.R., E-mail: prrcosta2011@gmail.com [Universidade Federal do Rio de Janeiro (UFRJ/LQB), RJ (Brazil). Nucleo de Pesquisas de Produtos Naturais. Laboratorio de Quimica Bioorganica; Esteves, Pierre M. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Interlab; Eberlin, Marcos N., E-mail: eberlin@iqm.unicamp.br [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Vaz, Boniek G. [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Instituto de Quimica. Laboratorio ThoMSon de Espectrometria de Massas; Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Instituto de QuImica

2013-03-15

The Heck reaction between E- and Z-enoates and iodobenzene was studied in the presence of Pd(OAc){sub 2}. The stereochemistry in resulting adducts was dependent on the enoate geometry (stereospecific reaction). Best yields were obtained from Z-isomers in acetone using Ag{sub 2} CO{sub 3} as base. The main cationic palladium intermediates possibly involved in the catalytic cycle could be intercepted and characterized by electrospray ionization mass spectrometry (ESI-MS). The stereoselectivity observed was rationalized through the classic mechanism of the Heck reaction. (author)

Graphene quantum dot synthesis using nanosecond laser pulses and its comparison to Methylene Blue

Science.gov (United States)

Kholikov, Khomidkhodza; Thomas, Zachary; Seyitliyev, Dovletgeldi; Smith, Skylar

A biocompatible photodynamic therapy agent that generates a high amount of singlet oxygen with high water dispersibility and excellent photostability is desirable. In this work, a graphene based biomaterial which is a promising alternative to a standard photosensitizers was produced. Methylene blue was used as a reference photosensitizer. Bacteria deactivation by methylene blue was shown to be inhibited inside human blood due to protein binding. Graphene quantum dots (GQD) were synthesized by irradiating benzene and nickel oxide mixture using nanosecond laser pulses. High resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, and nuclear magnetic resonance (NMR) were used for characterization of GQDs. Initial results show graphene quantum dots whose size less than 5 nm were successfully obtained. UV-VIS spectra shows absorption peak around 310 nm. The results of these studies can potentially be used to develop therapies for the eradication of pathogens in open wounds, burns, or skin cancers. New therapies for these conditions are particularly needed when antibiotic-resistant infections are present. NIH KBRIN.

Stereo-selective hydrolytic reaction of toxic compounds by enzyme immobilized on porous ceramics; Takoshitsu ceramics kotaika koso ni yoru dokusei kagobutsu no rittai sentakuteki kasui bunkai hanno

Energy Technology Data Exchange (ETDEWEB)

Kato, K.; Saito, T. [National Industrial Research Institute of Nagoya, Nagoya (Japan)

2000-08-25

Experiment was made on stereo-selective hydrolytic reaction of trifluoroethyl ester of ketoprophene by various kinds of lipase. In addition, study was made on the stability of lipase simply immobilized on porous ceramics under the existence of organic solvent. In the experiment, the hydrolytic activity of 8 kinds of lipase was studied for ketoprophene monochloroethyl ester (1a) and trifluoroethyl ester (1b). The experiment result showed that lipase M originating in mold (Mucor Javanicus) shows a high reactivity and stereo-selectivity for the compound (1a). The lipase immobilized on porous ceramics was easily obtained by a very simple method composed of only throwing carriers into enzyme suspension, agitation and refrigerated drying. The lipase immobilized on porous ceramics 'Toyonite 200-A' synthesized from kaolinite retained the residual activity of nearly 50%, original selectivity and considerable stability after 5 times of repetitive uses. This study result is useful for bio- reactors and bio-sensors for synthesis or decomposition of compounds. (NEDO)

Derivation of an occupational exposure limit (OEL) for methylene chloride based on acute CNS effects and relative potency analysis.

Science.gov (United States)

Storm, J E; Rozman, K K

1998-06-01

The Occupational Safety and Health Administration (OSHA) methylene chloride Permissible Exposure Level (PEL) or 25 ppm is quantitatively derived from mouse tumor results observed in a high-exposure National Toxicology Program bioassay. Because this approach depends on controversial interspecies and low-dose extrapolations, the PEL itself has stimulated heated debate. Here, an alternative safety assessment for methylene chloride is presented. It is based on an acute human lowest-observed-adverse-effect level (LOAEL) of 200 ppm for subtle central nervous system (CNS) depression. Steep, parallel exposure-response curves for anesthetic and subanesthetic CNS effects associated with compounds mechanistically and structurally related to methylene chloride are shown to support a safety factor of two to account for inter-individual variability in response. LOAEL/no-observed-adverse-effect ratios for subtle CNS effects associated with structurally related solvents are shown to support a safety factor range of two to four to account for uncertainty in identifying a subthreshold exposure level. Anesthetic relative potencies and anesthetic/subanesthetic effect level ratios are shown to be constant for the compounds evaluated, demonstrating that subanesthetic relative potencies are also constant. Relative potencies among similarly derived occupational exposure limits (OELs) for solvents structurally related to methylene chloride are therefore used to validate the derived methylene chloride OEL range of 25-50 ppm. Because this safety assessment is based on human (rather than rodent) data and empirical (rather than theoretical) exposure-response relationships and is supported by relative potency analysis, it is a defensible alternative to to the OSHA risk assessment and should positively contribute to the debate regarding the appropriate basis and value for a methylene chloride PEL.

Visualization of Stereoselective Supramolecular Polymers by Chirality-Controlled Energy Transfer.

Science.gov (United States)

Sarkar, Aritra; Dhiman, Shikha; Chalishazar, Aditya; George, Subi J

2017-10-23

Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereoselective Catalytic Synthesis of Active Pharmaceutical Ingredients in Homemade 3D-Printed Mesoreactors.

Science.gov (United States)

Rossi, Sergio; Porta, Riccardo; Brenna, Davide; Puglisi, Alessandra; Benaglia, Maurizio

2017-04-03

3D-printed flow reactors were designed, fabricated from different materials (PLA, HIPS, nylon), and used for a catalytic stereoselective Henry reaction. The use of readily prepared and tunable 3D-printed reactors enabled the rapid screening of devices with different sizes, shapes, and channel dimensions, aimed at the identification of the best-performing reactor setup. The optimized process afforded the products in high yields, moderate diastereoselectivity, and up to 90 % ee. The method was applied to the continuous-flow synthesis of biologically active chiral 1,2-amino alcohols (norephedrine, metaraminol, and methoxamine) through a two-step sequence combining the nitroaldol reaction with a hydrogenation. To highlight potential industrial applications of this method, a multistep continuous synthesis of norephedrine has been realized. The product was isolated without any intermediate purifications or solvent switches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon and TiO{sub 2} synergistic effect on methylene blue adsorption

Energy Technology Data Exchange (ETDEWEB)

Simonetti, Evelyn Alves Nunes, E-mail: evelynalvesnunes@yahoo.com.br; Simone Cividanes, Luciana de; Campos, Tiago Moreira Bastos; Rossi Canuto de Menezes, Beatriz; Brito, Felipe Sales; Thim, Gilmar Patrocínio

2016-07-01

Due to its high efficiency, low cost and a simple operation, the adsorption process is an important and widely used technique for industrial wastewater treatment. Recent studies on the removal of artificial dyes by adsorption include a large number of adsorbents, such as: activated carbon, silicates, carbon nanotube, graphene, fibers, titanates and doped titanates. The carbon insertion in the TiO{sub 2} structure promotes a synergistic effect on the adsorbent composite, improving the adsorption and the charge-transfer efficiency rates. However, there are few studies regarding the adsorption capacity of TiO{sub 2}/Carbon composites with the carbon concentration. This study evaluates the effect of carbon (resorcinol/formaldehyde) insertion on TiO{sub 2} structure through the adsorption process. Adsorbents were prepared by varying the carbon weight percentages using the sol-gel method. The physicochemical properties of the catalysts prepared, such as crystallinity, particle size, surface morphology, specific surface area and pore volume were investigated. The kinetic study, adsorption isotherm, pH effect and thermodynamic study were examined in batch experiments using methylene blue as organic molecule. In addition, the effect of carbon phase on the adsorption capacity of TiO{sub 2}-carbon composite was deeply investigated. SEM micrographs showed that TiO{sub 2} phase grows along the carbon phase and FT-IR results showed the presence of Ti−O−C chemical bonding. The experiments indicate that the carbon phase acted as a nucleation agent for the growth of TiO{sub 2} during the sol-gel step, with a TiO{sub 2} structure suitable for blue methylene adsorption, resulting in a material with large surface area and slit-like or wedge-shaped pores. Further experiments will show the best carbon concentration for methylene blue adsorption using a TiO{sub 2} based material. - Highlights: • This article deals with the adsorption of methylene blue onto TiO{sub 2}-Carbon

Stereoselective conjugate radical additions: application of a fluorous oxazolidinone chiral auxiliary for efficient tin removal.

Science.gov (United States)

Hein, Jason E; Zimmerman, Jake; Sibi, Mukund P; Hultin, Philip G

2005-06-23

[reaction: see text] A series of asymmetric free-radical-mediated intermolecular conjugate additions using a fluorous oxazolidinone chiral auxiliary has been completed. The fluorous auxiliary facilitated product isolation using fluorous solid phase extractions (FSPE), effectively removing excess organic and organometallic reagents. Parallel reactions carried out with a similar but nonfluorous norephedrine-derived oxazolidinone demonstrated the superior stereoselectivity and purification obtainable with the fluorous chiral auxiliary.

Degradation of methylene blue by radio frequency plasmas in water under ultraviolet irradiation

Energy Technology Data Exchange (ETDEWEB)

Maehara, Tsunehiro, E-mail: maehara@phys.sci.ehime-u.ac.jp [Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577 (Japan); Nishiyama, Kyohei; Onishi, Shingo; Mukasa, Shinobu; Toyota, Hiromichi [Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577 (Japan); Kuramoto, Makoto [Integrated Center for Science, Ehime University, Matsuyama 790-8577 (Japan); Nomura, Shinfuku [Graduate School of Science and Engineering, Ehime University, Matsuyama 790-8577 (Japan); Kawashima, Ayato [Faculty of Agriculture, Ehime University, Matsuyama 790-8566 (Japan)

2010-02-15

The degradation of methylene blue by radio frequency (RF) plasmas in water under ultraviolet (UV) irradiation was studied experimentally. When the methylene blue solution was exposed to RF plasma, UV irradiation from a mercury vapor lamp enhanced degradation significantly. A lamp without power supply also enhanced degradation since weak UV light was emitted weakly from the lamp due to the excitation of mercury vapor by stray RF power. Such an enhancement is explained by the fact that after hydrogen peroxide is produced via the recombination process of OH radicals around the plasma, OH radicals reproduced from hydrogen peroxide via the photolysis process degrade methylene blue.

Electrochemical preparation of poly(methylene blue)/graphene nanocomposite thin films

International Nuclear Information System (INIS)

Erçarıkcı, Elif; Dağcı, Kader; Topçu, Ezgi; Alanyalıoğlu, Murat

2014-01-01

Highlights: • Poly(MB)/graphene thin films are prepared by a simple electrochemical approach. • Graphene layers in the film show a broad band in visible region of absorbance spectra. • Morphology of composite films indicates both disordered and ordered regions. • XRD reveals that nanocomposite films include rGO layers after electropolymerization process. • Chemically prepared graphene is better than electrochemically prepared graphene for electrooxidation of nitrite. - Abstract: Poly(methylene blue)/graphene nanocomposite thin films were prepared by electropolymerization of methylene blue in the presence of graphene which have been synthesized by two different methods of a chemical oxidation process and an electrochemical approach. Synthesized nanocomposite thin films were characterized by using cyclic voltammetry, UV–vis. absorption spectroscopy, powder X-ray diffraction, and scanning tunneling microscopy techniques. Electrocatalytical properties of prepared poly(methylene blue)/graphene nanocomposite films were compared toward electrochemical oxidation of nitrite. Under optimized conditions, electrocatalytical effect of nanocomposite films of chemically prepared graphene through electrochemical oxidation of nitrite was better than that of electrochemically prepared graphene

Removal of congo red and methylene blue from waste water using coagulation

International Nuclear Information System (INIS)

Ghaffar, S.; Nosheen, S.; Ahmad, N.

2011-01-01

The textile industry has been condemned as being one of the world's worst offenders in terms of pollution Because of increasing population and industrial developments, a huge amount of wastewater is discharged to the environment above the level that the nature can eliminate. Many techniques like oxidation, reduction, physical treatment and biological method are available for removal of colored dyes from wastewater. The work presented here involved the decolorisation of wastewater containing congo red and methylene blue using various coagulants such as alum, bentonite and lime. The effect of various experimental factors such as dosage of coagulants, contact time between coagulant and dye and concentration of dyes and working environment like shaking and static was studied. Under static condition alum give almost 43% removal of congo red while with 10 minutes shaking 74 % removal of 80 dye was achieved with same coagulant. The highest removal of congo red was found to be 99.5 % by using alum after 30 minutes of shaking but in case of methylene blue it intensified the color and gave negative results. Lime gave only 33 % color removal of congo red under static conditions while 57% color was removed under shaking conditions. Maximum color removal achieved by lime was 89% at 40 minutes with shaking condition. Lime gave 60% removal of methylene blue in static condition and 90% removal in shaking condition and maximum absorbance at 80 ppm was 90%. Bentonite also used for the removal of methylene blue and gave 89% removal in shaking condition. By increasing shaking time %age removal increased to 100% at 40 min. And amount of coagulant increased the removal efficiency it attained 100% in both lime and bentonite coagulant for methylene blue Overall alum was found to be better coagulant for the removal of congo red from its aqueous solution. Lime and bentonite both proved better and economical for removal of methylene blue from aqueous solution at lab scale. (author)

21 CFR 558.76 - Bacitracin methylene disalicylate.

Science.gov (United States)

2010-04-01

...) ANIMAL DRUGS, FEEDS, AND RELATED PRODUCTS NEW ANIMAL DRUGS FOR USE IN ANIMAL FEEDS Specific New Animal Drugs for Use in Animal Feeds § 558.76 Bacitracin methylene disalicylate. (a) Approvals. Type A.... (b) Special considerations. The quantities of antibiotics are expressed in terms of the equivalent...

Metabolic stereoselectivity of cytochrome P450 3A4 towards deoxypodophyllotoxin : In silico predictions and experimental validation

NARCIS (Netherlands)

Julsing, Mattijs K.; Vasilev, Nikolay P.; Schneidman-Duhovny, Dina; Muntendarn, Remco; Woerdenbag, Herman J.; Quax, Wim J.; Wolfson, Haim J.; Ionkova, Iliana; Kayser, Oliver

Deoxypodophyllotoxin is stereoselectively converted into epipodophyllotoxin by recombinant human cytochrome P450 3A4 (CY-P3A4). Further kinetic analysis revealed that the Michaelis-Menten K(m) and V(max) for hydroxylation of deoxypodophyllotoxin by CYP3A4 at C7 position were 1.93 mu M and 1.48

High surface area mesoporous activated carbon-alginate beads for efficient removal of methylene blue.

Science.gov (United States)

Nasrullah, Asma; Bhat, A H; Naeem, Abdul; Isa, Mohamed Hasnain; Danish, Mohammed

2018-02-01

High surface area mesoporous activated carbon-alginate (AC-alginate) beads were successfully synthesized by entrapping activated carbon powder derived from Mangosteen fruit peel into calcium-alginate beads for methylene blue (MB) removal from aqueous solution. The structure and surface characteristics of AC-alginate beads were analyzed using Fourier transform infra-red (FTIR) spectroscopy, scanning electron microscopy (SEM) and surface area analysis (S BET ), while thermal properties were tested using thermogravimetric analysis (TGA). The effect of AC-alginate dose, pH of solution, contact time, initial concentration of MB solution and temperature on MB removal was elucidated. The results showed that the maximum adsorption capacity of 230mg/g was achieved for 100mg/L of MB solution at pH 9.5 and temperature 25°C. Furthermore, the adsorption of MB on AC-alginate beads followed well pseudo-second order equation and equilibrium adsorption data were better fitted by the Freundlich isotherm model. The findings reveal the feasibility of AC-alginate beads composite to be used as a potential and low cost adsorbent for removal of cationic dyes. Copyright © 2017 Elsevier B.V. All rights reserved.

Stereoselective Phytotoxicity of HCH Mediated by Photosynthetic and Antioxidant Defense Systems in Arabidopsis thaliana

OpenAIRE

Zhang, Qiong; Zhou, Cong; Zhang, Quan; Qian, Haifeng; Liu, Weiping; Zhao, Meirong

2013-01-01

BACKGROUND: Hexachlorocyclohexane (HCH) has been used for plant protection and sanitation world-widely, and its isomers have been detected in water, soil, and air as well as in vegetation. As a sink for lipophilic pollutants, vegetation is very important for the degradation and fate of organic contamination; however, little was known about their phytotoxicity and mechanisms of toxic effect. In this study, the stereoselective phototoxicity of four isomers (α, β, γ, and δ) of HCHs mediated by i...

Use of (S)-trans-gamma-monocyclofarnesol as a useful chiral building block for the stereoselective synthesis of diterpenic natural products.

Science.gov (United States)

Serra, Stefano; Cominetti, Alessandra A; Lissoni, Veronica

2014-03-01

A comprehensive study of the exploitation of (S)-trans-gamma-monocyclofarnesol as a useful chiral building block for the stereoselective synthesis of natural diterpene derivatives is here described. The farnesol derivative (+)-1 was used as starting material in the preparation of the diterpenes (S)-dehydroambliol-A and (S)-trixagol, as well as for the syntheses of the dinorditerpene (S)-dinortrixagone and of the guanidine-interrupted terpenoid (S)-dotofide. Key steps of the presented syntheses were the cross-coupling between an allyl acetate and a Grignard reagent, the Wittig reaction, the selective preparation ofa diacylguanidine derivative and the alkylation of a sulfone derivative, followed by the reductive removal of the same functional group. It is worth noting that the natural products (+)-8, (+)-12 and (+)-15 were prepared stereoselectively for the first time, thus allowing the unambiguous assignment of their absolute configuration.

Potential of metal nanoparticles in organic reactions

International Nuclear Information System (INIS)

Ranu, B C; Chattopadhyay, K; Saha, A; Adak, L; Jana, R; Bhadra, S; Dey, R; Saha, D

2008-01-01

Palladium(0) nanoparticle has been used as efficient catalyst for (a) the stereoselective synthesis of (E)- and (Z)-2-alkene-4-ynoates and -nitriles by a simple reaction of vic-diiodo-(E)-alkenes with acrylic esters and nitriles and (b) for the allylation of active methylene compounds by allylacetate and its derivatives. Copper(0) nanoparticle catalyzes aryl-sulfur bond formation very efficiently. All these reactions are ligand-free

21 CFR 700.19 - Use of methylene chloride as an ingredient of cosmetic products.

Science.gov (United States)

2010-04-01

... cosmetic products. 700.19 Section 700.19 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) COSMETICS GENERAL Requirements for Specific Cosmetic Products § 700.19 Use of methylene chloride as an ingredient of cosmetic products. (a) Methylene chloride has been used...

Stereoselective potencies and relative toxicities of coniine enantiomers.

Science.gov (United States)

Lee, Stephen T; Green, Benedict T; Welch, Kevin D; Pfister, James A; Panter, Kip E

2008-10-01

Coniine, one of the major toxic alkaloids present in poison hemlock ( Conium maculatum), occurs in two optically active forms. A comparison of the relative potencies of (+)- and (-)-coniine enantiomers has not been previously reported. In this study, we separated the enantiomers of coniine and determined the biological activity of each enantiomer in vitro and in vivo. The relative potencies of these enantiomers on TE-671 cells expressing human fetal nicotinic neuromuscular receptors had the rank order of (-)-coniine > (+/-)-coniine > (+)-coniine. A mouse bioassay was used to determine the relative lethalities of (-)-, (+/-)-, and (+)-coniine in vivo. The LD 50 values of the coniine enantiomers were 7.0, 7.7, and 12.1 mg/kg for the (-)-, (+/-)-, and (+)- forms of coniine, respectively. The results from this study demonstrate that there is a stereoselective difference in the in vitro potencies of the enantiomers of coniine that directly correlates with the relative toxicities of the enantiomers in vivo.

Microfluidics-based microbubbles in methylene blue solution for photoacoustic and ultrasound imaging

Science.gov (United States)

Das, Dhiman; Sivasubramanian, Kathyayini; Yang, Chun; Pramanik, Manojit

2018-02-01

Contrast agents which can be used for more than one bio-imaging technique has gained a lot of attention from researchers in recent years. In this work, a microfluidic device employing a flow-focusing junction, is used for the continuous generation of monodisperse nitrogen microbubbles in methylene blue, an optically absorbing organic dye, for dual-modal photoacoustic and ultrasound imaging. Using an external phase of polyoxyethylene glycol 40 stearate (PEG 40), a non-ionic surfactant, and 50% glycerol solution at a flow rate of 1 ml/hr and gas pressure at 1.75 bar, monodisperse nitrogen microbubbles of diameter 7 microns were obtained. The external phase also contained methylene blue hydrate at a concentration of 1 gm/litre. The monodisperse microbubbles produced a strong ultrasound signal as expected. It was observed that the signal-to-noise (SNR) ratio of the photoacoustic signal for the methylene blue solution in the presence of the monodisperse microbubbles was 68.6% lower than that of methylene blue solution in the absence of microbubbles. This work is of significance because using microfluidics, we can precisely control the bubbles' production rate and bubble size which increases ultrasound imaging efficiency. A uniform size distribution of the bubbles will have narrower resonance frequency bandwidth which will respond well to specific ultrasound frequencies.

Methylene Blue-Loaded Dissolving Microneedles: Potential Use in Photodynamic Antimicrobial Chemotherapy of Infected Wounds

Directory of Open Access Journals (Sweden)

Ester Caffarel-Salvador

2015-09-01

Full Text Available Photodynamic therapy involves delivery of a photosensitising drug that is activated by light of a specific wavelength, resulting in generation of highly reactive radicals. This activated species can cause destruction of targeted cells. Application of this process for treatment of microbial infections has been termed “photodynamic antimicrobial chemotherapy” (PACT. In the treatment of chronic wounds, the delivery of photosensitising agents is often impeded by the presence of a thick hyperkeratotic/necrotic tissue layer, reducing their therapeutic efficacy. Microneedles (MNs are an emerging drug delivery technology that have been demonstrated to successfully penetrate the outer layers of the skin, whilst minimising damage to skin barrier function. Delivering photosensitising drugs using this platform has been demonstrated to have several advantages over conventional photodynamic therapy, such as, painless application, reduced erythema, enhanced cosmetic results and improved intradermal delivery. The aim of this study was to physically characterise dissolving MNs loaded with the photosensitising agent, methylene blue and assess their photodynamic antimicrobial activity. Dissolving MNs were fabricated from aqueous blends of Gantrez® AN-139 co-polymer containing varying loadings of methylene blue. A height reduction of 29.8% was observed for MNs prepared from blends containing 0.5% w/w methylene blue following application of a total force of 70.56 N/array. A previously validated insertion test was used to assess the effect of drug loading on MN insertion into a wound model. Staphylococcus aureus, Escherichia coli and Candida albicans biofilms were incubated with various methylene blue concentrations within the range delivered by MNs in vitro (0.1–2.5 mg/mL and either irradiated at 635 nm using a Paterson Lamp or subjected to a dark period. Microbial susceptibility to PACT was determined by assessing the total viable count. Kill rates of >96

Stereoselective formation of a cholesterol ester conjugate from fenvalerate by mouse microsomal carboxyesterase(s).

Science.gov (United States)

Miyamoto, J; Kaneko, H; Takamatsu, Y

1986-06-01

In accordance with in vivo findings, of the four chiral isomers of fenvalerate (S-5602 Sumicidin, Pydrin, [RS]-alpha-cyano-3-phenoxybenzyl [RS]-2-(4-chlorophenyl)isovalerate), only the [2R, alpha S]-isomer (B-isomer) yielded cholesteryl [2R]-2-(4-chlorophenyl)isovalerate (CPIA-cholesterol ester) in the in vitro study using several tissue homogenates of mice, rats, dogs, and monkeys. There were species differences in the extent of CPIA-cholesterol-ester formation, with mouse tissues showing relatively higher activity than those of other animals. The kidney, brain, and spleen of mice showed relatively higher capacities to form this ester compared to other tissues, and the enzyme activity was mainly localized in microsomal fractions. The CPIA-cholesterol ester did not seem to be produced by three known biosynthetic pathways of endogenous cholesterol esters--acyl-CoA:cholesterol O-acyltransferase (ACAT), lecithin:cholesterol O-acyltransferase (LCAT), and cholesterol esterase. Carboxyesterase(s) of mouse kidney microsomes solubilized by digitonin hydrolyzed only the B alpha-isomer of fenvalerate, yielding CPIA, whereas they yielded the corresponding cholesterol ester in the presence of artificial liposomes containing cholesterol. Thus, it appears that the stereoselective formation of the CPIA-cholesterol ester results from the stereoselective formation of the CPIA-carboxyesterase complex only from the B alpha-isomer, which subsequently undergoes cleavage by cholesterol to yield the CPIA-cholesterol ester.

Allene functionalization via bicyclic methylene aziridines.

Science.gov (United States)

Boralsky, Luke A; Marston, Dagmara; Grigg, R David; Hershberger, John C; Schomaker, Jennifer M

2011-04-15

The oxidative functionalization of olefins is a common method for the formation of vicinal carbon-heteroatom bonds. However, oxidative methods to transform allenes into synthetic motifs containing three contiguous carbon-heteroatom bonds are much less developed. This paper describes the use of bicyclic methylene aziridines (MAs), prepared via intramolecular allene aziridination, as scaffolds for functionalization of all three allene carbons. © 2011 American Chemical Society

Easy Access to Evans’ Oxazolidinones. Stereoselective Synthesis and Antibacterial Activity of a New 2-Oxazolidinone Derivative

Directory of Open Access Journals (Sweden)

Gaspar Diaz

2014-06-01

Full Text Available An interesting new approach was developed for the synthesis of Evans’ chiral auxiliaries with excellent yields. In turn, another new stereoselective and efficient strategy has also allowed for the preparation of a 2-oxazolidinone derivative in 34% overall yield from the Morita-Baylis-Hillman adduct. The antibacterial activity of this oxazolidinone was tested against Staphylococcus aureus strains isolated from animals with mastitis infections.

Novel methylene-blue-sensitized photopolymers for holographic recording: a comparison

Science.gov (United States)

Ushamani, Mythili; Sreekumar, K.; Sudha Kartha, C.; Joseph, Rani

2004-06-01

Polymer matrices like PVC and a blend of PVA/PAA is introduced as new holographic media that cause red sensitivity with methylene blue. Unlike methylene blue sensitized polymers like PVA, PMMA, gelatin etc, the change of state occurring for methylene blue on laser irradiation on PVC matrix was found to be permanent. No recovery of dye on the irradiated spot was observed on storage. The outstanding properties of this material are its excellent optical clarity, insensitive to humidity, economical, ease of fabrication, absence of dark room storage etc. The recovery of dye in conventional MBPVA matrix can be delayed by blending PVA with PAA. Optimization of the ratio of PVA/PAA, the sensitizer concentration, pH, energy, diffraction efficiency measurements etc are done. pH is found to have a great influence on the recovery of the dye in this matrix. The effect of monomers in improving the diffraction efficiency on these dye doped polymer system is also evaluated. A comparative study is done on these polymer matrices and holographic gratings were recorded on these films from a He- Ne laser operating at 632.8 nm.

Methylene blue adsorption from aqueous solution by dehydrated peanut hull

Energy Technology Data Exchange (ETDEWEB)

Ozer, Dursun [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey); Dursun, Guelbeyi [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey)]. E-mail: gdursun@firat.edu.tr; Ozer, Ahmet [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey)

2007-06-01

Dyes are colour organic compounds which can colorize the other substances. These substances usually presents in the effluent water of many industries, such as textiles, leather, paper, printing and cosmetics. To observe the potential feasibility of removing colour, peanut hull as an agricultural by-product was dehydrated with sulphuric acid (DPH) and used for adsorption of methylene blue (MB) from aqueous solution. The effects of various parameters such as initial methylene blue concentrations, temperatures and particle sizes were examined and optimal experimental conditions were determined. Adsorption data were well described by the Langmuir model, although they could be modelled by the Freundlich model as well. The adsorption process followed the pseudo-second order kinetic model. The mass transfer model as intraparticle diffusion was applied to the experimental data to examine the mechanisms of rate controlling step. It was found that at the higher initial MB concentration, intraparticle diffusion is becoming significant controlling step. The thermodynamic constants of the adsorption process were also evaluated by using the Langmuir constants related to the equilibrium of adsorption at different temperatures. The results in this study indicated that dehydrated peanut hull was a good adsorbent for removing methylene blue.

ON THE CHEMISTRY AND STAINING PROPERTIES OF CERTAIN DERIVATIVES OF THE METHYLENE BLUE GROUP WHEN COMBINED WITH EOSIN

Science.gov (United States)

Wilson, Thomas M.

1907-01-01

1. Eosinate of thionin gives very satisfactory staining for blood smears. It is easily prepared and dissolves readily in methylated spirits. 2. In the methods heretofore employed for making mixtures of eosin and methylene blue derivatives, the eosinates of methylene violet and methylene azure are present in very small quantities or are altogether absent. 3. Thionol and thionin are probably formed in methylene blue which has been long boiled with dilute alkalies and silver oxide. 4. Good stains of eosin and methylene blue derivatives can be obtained by a variety of manipulations. 5. Methylated spirits is more economical as a solvent for this stain and better adapted for the simple technique above described than is methyl alcohol. There is some evidence that the staining act is of a chemical nature. PMID:19867116

Synthesis and highly visible-induced photocatalytic activity of CNT-CdSe composite for methylene blue solution

Directory of Open Access Journals (Sweden)

Chen Ming-Liang

2011-01-01

Full Text Available Abstract Carbon nanotube-cadmium selenide (CNT-CdSe composite was synthesized by a facile hydrothermal method derived from multi-walled carbon nanotubes as a stating material. The as-prepared products were characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, transmission electron microscopy (TEM, and UV-vis diffuse reflectance spectrophotometer. The as-synthesized CNT-CdSe composite efficiently catalyzed the photodegradation of methylene blue in aqueous solutions under visible-light irradiation, exhibiting higher photocatalytic activity.

Uniform Cu2Cl(OH)3 hierarchical microspheres: A novel adsorbent for methylene blue adsorptive removal from aqueous solution

International Nuclear Information System (INIS)

Wei, Wei; Gao, Pin; Xie, Jimin; Zong, Sekai; Cui, Henglv; Yue, Xuejie

2013-01-01

Using the solution phase method without any surfactants or templates, the hierarchical of Cu 2 Cl(OH) 3 microspheres were synthesized by freeze drying. The size and surface area of the microspheres are ca. 1–2 µm and 76.61 m 2 g −1 , respectively. A possible formation mechanism is presented based on the experimental results. Methylene blue was chosen to investigate the adsorption capacity of the as-prepared adsorbent. The effects of various experimental parameters, such as pH, initial dye concentration, and contact time were investigated. The results showed that the dye removal increased with the increasing in the initial concentration of the dye and also increased in the amount of microspheres used and initial pH. Adsorption data fitted well with the Freundlich adsorption isotherm. The thermodynamic analysis presented the exothermic, spontaneous and more ordered arrangement process. The microspheres could be employed effective for removal of dyes from aqueous solution. - Graphical abstract: The single-crystalline hierarchical Cu 2 Cl(OH) 3 spheres can be prepared for the first time by using a template-free process through freeze-drying. Meanwhile, the hierarchical spheres exhibited high adsorption capacity to methylene blue. Display Omitted - Highlights: • Cu 2 Cl(OH) 3 microspheres were successfully synthesized through a freeze drying process. • A possible formation mechanism of hierarchical microspheres was presented. • The Cu 2 Cl(OH) 3 microspheres have high methylene blue adsorption capacity. • Methylene blue adsorption is a spontaneous and exothermic process. • The adsorption mechanism of microspheres onto dye was proposed in detail

Efficient degradation of Methylene Blue dye over highly reactive Cu doped strontium titanate (SrTiO3) nanoparticles photocatalyst under visible light.

Science.gov (United States)

Rahman, Qazi Inamur; Ahmad, Musheer; Misra, Sunil Kumar; Lohani, Minaxi

2012-09-01

Visible light induced photocatalysts of Cu doped SrTiO3 (Cu/SrTiO3) nanoparticles with the size -60-75 nm were prepared via facile sol-gel method. The morphological, optical, crystalline properties and compositions of synthesized Cu/SrTiO3 nanoparticles were thoroughly characterized by field emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (XRD), ultra violet-visible spectroscopy (UV-Vis) and energy dispersive X-ray (EDX). A significant red shift in the UV-diffused reflectance spectrum was observed and the absorption edge shifted to visible region by the Cu doping. Surprisingly, the band gap of SrTiO3 was changed from 3.2 eV drop to 2.96 eV. The photocatalytic activity of the synthesized Cu/SrTiO3 nanoparticles was demonstrated for the degradation of Methylene Blue dye under visible light irradiation. The formation of new acceptor region in Cu/SrTiO3 was responsible for high photocatalytic activity of Cu/SrTiO3 nanoparticles. The results showed that the Methylene Blue dye was degraded by -66% within time span of 2 h over the Cu/SrTiO3 nanoparticles. This dye degradation reaction followed the Langmuir-Hinshelwood kinetics and also exhibited first order reaction rate. The calculated rate constant for the degradation reaction following first order kinetics was k = 0.0016 min(-1).

Stereoselectivity of presynaptic autoreceptors modulating dopamine release

International Nuclear Information System (INIS)

Arbilla, S.; Langer, S.Z.

1981-01-01

The effects of the (R)- and (S)-enantiomers of sulpiride and butaclamol were studied on the spontaneous and field stimulation-evoked release of total radioactivity from slices of rabbit caudate nucleus prelabelled with [ 3 H]dopamine. (S)-Sulpiride in concentrations ranging from 0.01-1μM enhanced the electrically evoked release of [ 3 H]dopamine while (R)-sulpiride was 10 times less potent than (S)-sulpiride. Exposure to (S)-butaclamol (0.1-1 μM) but not to (R)-butaclamol (0.1-10μM) enhanced the field-stimulated release of [ 3 H]dopamine. The facilitatory effects of (S)- and (R)-sulpiride and (S)-butaclamol on the stimulated release of the labelled neurotransmitter were observed under conditions in which these drugs did not modify the spontaneous outflow of radioactivity. Only the active enantiomers of sulpiride and butaclamol antagonized the inhibition by apomorphine (1μM) of the stimulated release of [ 3 H]dopamine. Our results indicate that the presynaptic inhibitory dopamine autoreceptors modulating the stimulation-evoked release of [ 3 H]dopamine in the caudate nucleus are, like the classical postsynaptic dopamine receptors, chemically stereoselective. (Auth.)

Corneal edema and permanent blue discoloration of a silicone intraocular lens by methylene blue.

Science.gov (United States)

Stevens, Scott; Werner, Liliana; Mamalis, Nick

2007-01-01

To report a silicone intraocular lens (IOL) stained blue by inadvertent intraoperative use of methylene blue instead of trypan blue and the results of experimental staining of various lens materials with different concentrations of the same dye. A "blue dye" was used to enhance visualization during capsulorhexis in a patient undergoing phacoemulsification with implantation of a three-piece silicone lens. Postoperatively, the patient presented with corneal edema and a discolored IOL. Various IOL materials were experimentally stained using methylene blue. Sixteen lenses (4 silicone, 4 hydrophobic acrylic, 4 hydrophilic acrylic, and 4 polymethylmethacrylate) were immersed in 0.5 mL of methylene blue at concentrations of 1%, 0.1%, 0.01%, and 0.001%. These lenses were grossly and microscopically evaluated for discoloration 6 and 24 hours after immersion. The corneal edema resolved within 1 month after the initial surgical procedure. After explantation, gross and microscopic analyses of the explanted silicone lens revealed that its surface and internal substance had been permanently stained blue. In the experimental study, all of the lenses except the polymethylmethacrylate lenses were permanently stained by methylene blue. The hydrophilic acrylic lenses showed the most intense blue staining in all dye concentrations. This is the first clinicopathological report of IOL discoloration due to intraocular use of methylene blue. This and other tissue dyes may be commonly found among surgical supplies in the operating room and due diligence is necessary to avoid mistaking these dyes for those commonly used during ocular surgery.

Batch Adsorption Study of Methylene Blue in Aqueous Solution ...

African Journals Online (AJOL)

PROF HORSFALL

of methylene blue (azo dye) from the synthetic industrial wastewater was investigated in a batch system. Rice husk and coconut shell were ... the textiles, rubber, paper, plastics, cosmetic, and .... wastewater by. Fenton's oxidation: Kinetic study.

Removal of Methylene Blue from aqueous solution using spent bleaching earth

Science.gov (United States)

Saputra, E.; Saputra, R.; Nugraha, M. W.; Irianty, R. S.; Utama, P. S.

2018-04-01

The waste from industrial textile waste is one of the environmental problems, it is required effective and efficient processing. In this study spent bleaching earth was used as absorbent. It was found that the absorbent was effective to remove methylene blue from aqueous solution with removal efficiency 99.97 % in 120 min. Several parameters such as pH, amount of absorbent loading, stirring speed are found as key factor influencing removal of methylene blue. The mechanism of adsorption was also studied, and it was found that Langmuir isotherm fitted to data of experiment with adsorption capacity 0.5 mg/g.

Protective effect of methanol-methylene chloride extract of ...

African Journals Online (AJOL)

Purpose: Terminalia glaucescens (Combretaceae) is traditionally used in Cameroon in the treatment of diabetes. The anti-hyperglycemic effect of the methanol-methylene chloride extract of the leaves of this plant was investigated in streptozotocin (STZ)-induced diabetic mice. Methods: Diabetes was induced in mice by a ...

Potential adsorption of methylene blue from aqueous solution using green macroalgaePosidonia oceanica.

Science.gov (United States)

Allouche, F.-N.; Yassaa, N.

2018-03-01

The use of inexpensive biological materials, such as marine algae for removing dyes from contaminated industrial effluents appears as a potential alternative method. The aim of this study is to investigate the aptitude of marine macroalgae Posidonia Oceanica local biomass abundant on the coasts of Algeria for selective sorption of methylene blue (MB) from an aqueous solution in batch experiments at 20 °C. A maximum percentage removal of Posidonia oceanica occurs at pH 5. Equilibrium isotherm data were analyzed using the Langmuir and the Freundlich isotherms. The adsorption equilibrium of methylene blue was best describe by Langmuir model than the Freundlich model. The maximum sorption capacity was 357 mgg-1at pH 5. The sorption data were very well described by the pseudo-second-order model. Keywords: Posidonia oceanica, Methylene blue (MB), Biosorption, Isotherm Equilibrium, Kinetics; Modelling.

Stereoselectivity and substrate specificity in the kinetic resolution of methyl-substituted 1-oxaspiro[2.5]octanes by Rhodotorula glutinis epoxide hydrolase

NARCIS (Netherlands)

Weijers, C.A.G.M.; Meeuwse, P.; Herpers, R.L.J.M.; Franssen, M.C.R.; Sudhölter, E.J.R.

2005-01-01

[GRAPHICS] The kinetic resolution of a range of methyl-substituted 1-oxaspiro[2.5]octanes by yeast epoxide hydrolase (YEH) from Rhodotorula glutinis has been investigated. The structural determinants of substrate specificity and stereoselectivity of YEH toward these substrates appeared to be the

A nonradioactive assay for poly(a)-specific ribonuclease activity by methylene blue colorimetry.

Science.gov (United States)

Cheng, Yuan; Liu, Wei-Feng; Yan, Yong-Bin; Zhou, Hai-Meng

2006-01-01

A simple nonradioactive assay, which was based on the specific shift of the absorbance maximum of methylene blue induced by its intercalation into poly(A) molecules, was developed for poly(A)-specific ribonuclease (PARN). A good linear relationship was found between the absorbance at 662 nm and the poly(A) concentration. The assay conditions, including the concentration of methylene blue, the incubation temperature and time, and the poly(A) concentration were evaluated and optimized.

Methylene blue (cationic dye) adsorption into Salvadora persica ...

African Journals Online (AJOL)

Methylene blue (MB) is the most commonly used substance for dyeing cotton, wood and silk. On inhalation, it can cause difficulty in breathing, while on direct contact, it may cause permanent injury of the eyes of human and animals, burning sensations, nausea, worming, profuse sweating, mental confusion and ...

Magnetic graphene sponge for the removal of methylene blue

International Nuclear Information System (INIS)

Yu, Baowei; Zhang, Xiaoliang; Xie, Jingru; Wu, Ruihan; Liu, Xiaoyang; Li, Hongliang; Chen, Fang; Yang, Hua; Ming, Zhu; Yang, Sheng-Tao

2015-01-01

Graphical abstract: - Highlights: • Magnetic graphene sponge is prepared for dye removal in aqueous solution. • Magnetic graphene sponge has an adsorption capacity of 526 mg/g for methylene blue. • Adsorption behaviors of methylene blue on magnetic graphene sponge are investigated. • Magnetic graphene sponge could be partially regenerated by washing with acidic ethanol. - Abstract: Magnetic carbon nanomaterials have been widely adopted as adsorbents in water treatment, but the low adsorption capacities largely limit their practical applications. In this study, magnetic graphene sponge (Fe 3 O 4 -GS) was prepared by lyophilization for the adsorption of dye pollutant. The incorporation of Fe 3 O 4 enabled the magnetic separation of Fe 3 O 4 -GS after the adsorption of methylene blue (MB). The adsorption capacity of Fe 3 O 4 -GS for MB was 526 mg/g, much higher than those of the magnetic carbon nanoadsorbents in the literature. The adsorption kinetics of MB on Fe 3 O 4 -GS was moderately fast, which could be analyzed by the pseudo-second-order model and intraparticle diffusion model. The thermodynamics study revealed that the adsorption was driven by the increased randomness on the interface. The pH and ionic strength had meaningful influences on the adsorption capacity of Fe 3 O 4 -GS. The facile regeneration of Fe 3 O 4 -GS would definitely reduce its operating cost. The implications to the environmental applications of magnetic carbon nanoadsorbents are discussed

Free energy calculations give insight into the stereoselective hydroxylation of α-ionones by engineered cytochrome P450 BM3 mutants.

Science.gov (United States)

de Beer, Stephanie B A; Venkataraman, Harini; Geerke, Daan P; Oostenbrink, Chris; Vermeulen, Nico P E

2012-08-27

Previously, stereoselective hydroxylation of α-ionone by Cytochrome P450 BM3 mutants M01 A82W and M11 L437N was observed. While both mutants hydroxylate α-ionone in a regioselective manner at the C3 position, M01 A82W catalyzes formation of trans-3-OH-α-ionone products whereas M11 L437N exhibits opposite stereoselectivity, producing trans-(3S,6S)-OH-α-ionone and cis-(3S,6R)-OH-α-ionone. Here, we explore the stereoselective C3 hydroxylation of α-ionone by Cytochrome P450 BM3 mutants M01 A82W and M11 L437N using molecular dynamics-based free energy calculations to study the interaction between the enzyme and both the substrates and the products. The one-step perturbation approach is applied using an optimized reference state for substrates and products. While the free energy differences between the substrates free in solution amount to ~0 kJ mol(-1), the differences in mutant M01 A82W agree with the experimentally obtained dissociation constants K(d). Moreover, a correlation with experimentally observed trends in product formation is found in both mutants. The trans isomers show the most favorable relative binding free energy in the range of all four possible hydroxylated diastereomers for mutant M01 A82W, while the trans product from (6S)-α-ionone and the cis product from (6R)-α-ionone show highest affinity for mutant M11 L437N. Marcus theory is subsequently used to relate the thermodynamic stability to transition state energies and rates of formation.

Photodynamic action of the methylene blue: mutagenesis and sinergism

International Nuclear Information System (INIS)

Capella, M.A.M.

1988-01-01

Two aspects of photodynamic therapy were studied: the associated mutagenesis and the interactions with physical agents, in order to increase its biological effects. The photodynamic action with methylene blue in the mutagenesis and sinergism is studied. (L.M.J.)

Sunlight-Induced Photochemical Degradation of Methylene Blue by Water-Soluble Carbon Nanorods

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Anshu Bhati

2016-01-01

Full Text Available Water-soluble graphitic hollow carbon nanorods (wsCNRs are exploited for their light-driven photochemical activities under outdoor sunlight. wsCNRs were synthesized by a simple pyrolysis method from castor seed oil, without using any metal catalyst or template. wsCNRs exhibited the light-induced photochemical degradation of methylene blue used as a model pollutant by the generation of singlet oxygen species. Herein, we described a possible degradation mechanism of methylene blue under the irradiation of visible photons via the singlet oxygen-superoxide anion pathway.

[Sensitive determination of Bi3+ by spectrofluorimetry based on graphene oxide-methylene blue system].

Science.gov (United States)

Zhai, Qiu-ge; Guo, Peng; Zhou, Lin; Liu, Yan-ming

2014-08-01

Graphene oxide was prepared by the modified Hummers method and characterized by field emission scanning electron microscopy. The interaction of graphene with methylene blue was studied by UV absorption, the intensity of two main absorption peaks of methylene blue decreased significantly after the fluorescence was quenched, and the energy transfer didn't occur because the overlap of the absorption spectrum of GO and the emission spectrum of MB is too small. Therefore, the fluorescence quenching of MB and GO was static. When adding a certain amount of Bi3+ in the graphene-methylene blue system, Bi3+ replaces the methylene blue from the graphene-methylene blue complexes because Bi3+ has the smaller volume and is more positively charged. The methylene blue therefore dissociates from the GO-MB complexes, resulting in the recovery of fluorescence of the system. Furthermore, the fluorescence of the system increases with the increase in the amount of Bi3+ due to the enhanced amount of MB in the system. A novel spectrofluorimetric method was therefore developed for the sensitive determination of Bi3+. Some parameters including the concentration of methylene blue, the amount of graphene oxide, the amount of nitric acid and the sequence of reagent adding were optimized to obtain higher sensitivity. The fluorescence of the system was detected at an emission wavelength of 667 nm with excitation at 690 nm. Under the optimized conditions, the concentration of Bi3+ showed good linear relationships with the fluorescence intensity in the range of 0.5-100 micromol x L(-1), with correlation coefficients of r = 0.9955. The limits of detection for Bi3+ was 1.0 x 10(-8) mol x L(-1) (S/N=3). The selectivity of the proposed method was evaluated and the results showed that 1000-fold K+, Ca+, Na+, Mg2+, Cu2+; 100-fold Fe3+, Be2+, SiO2- Al3+, Ni2+, Sb3+, NO3-, Cl-, F-, and 20-fold Pb2+, Hg2+, Cd2+ had negligible interference with the determination of Bi3+. The method has advantages of

Graphene oxide (rGO)-metal oxide (TiO2/Fe3O4) based nanocomposites for the removal of methylene blue

Science.gov (United States)

Banerjee, Soma; Benjwal, Poonam; Singh, Milan; Kar, Kamal K.

2018-05-01

Herein, ternary nanocomposites based on titanium dioxide, ferric oxide and reduced graphene oxide (GO) have been developed for photocatalytic degradation of methylene blue. The nanocomposites are prepared by simple sol-gel and wet assembly methods with varying weight ratio of each components to obtain efficient photocatalytic degradation. Due to the synergistic effect among the three components, a swift removal of methylene blue becomes possible under visible and UV light. The rGO-Fe3O4-TiO2 nanocomposite having composition 1:1:2 has achieved maximum degradation of methylene blue from the aqueous solution. About 99% of the dye has been removed within 6 min under UV irradiation, while in presence of visible light, 94% has been degraded from the wastewater. The enhancement of photocatalytic activity in this ternary system is attributed to the efficient separation of charge carriers from TiO2 to rGO under the exposure of light and the initiation of photo-Fenton reaction due to the incorporated Fe3O4 nanoparticles in presence of H2O2, which provides highly reactive hydroxyl ions that mineralize the pollutants. All these results indicate that these ternary nanocomposites possess great potential for both UV and visible light driven methylene blue destruction from the wastewater.

In Vitro Antimicrobial Photodynamic Therapy Against Trichophyton mentagrophytes Using New Methylene Blue as the Photosensitizer.

Science.gov (United States)

López-Chicón, P; Gulías, Ò; Nonell, S; Agut, M

2016-11-01

Antimicrobial photodynamic therapy combines the use of a photosensitizing drug with light and oxygen to eradicate pathogens. Trichophyton mentagrophytes is a dermatophytic fungus able to invade the skin and keratinized tissues. We have investigated the use of new methylene blue as the photosensitizing agent for antimicrobial photodynamic therapy to produce the in vitro inactivation of T mentagrophytes. A full factorial design was employed to optimize the parameters for photoinactivation of the dermatophyte. The parameters studied were new methylene blue concentration, contact time between the photosensitizing agent and the fungus prior to light treatment, and the fluence of red light (wavelength, 620-645nm) applied. The minimum concentration of new methylene blue necessary to induce the death of all T. mentagrophytes cells in the initial suspension (approximate concentration, 10 6 colony forming units per milliliter) was 50μM for a fluence of 81J/cm 2 after a contact time of 10minutes with the photosensitizing-agent. Increasing the concentration to 100μM allowed the fluence to be decreased to 9J/cm 2 . Comparison of our data with other published data shows that the susceptibility of T. mentagrophytes to antimicrobial photodynamic therapy with new methylene blue is strain-dependent. New methylene blue is a photosensitizing agent that should be considered for the treatment of fungal skin infections caused by this dermatophyte. Copyright © 2016 AEDV. Publicado por Elsevier España, S.L.U. All rights reserved.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform

OpenAIRE

Lundberg, Pontus; Lee, Bongjae F.; van den Berg, Sebastiaan A.; Pressly, Eric D.; Lee, Annabelle; Hawker, Craig J.; Lynd, Nathaniel A.

2012-01-01

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxi...

Calixarene methylene bisphosphonic acids as promising effectors of biochemical processes

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S. V. Komisarenko

2013-12-01

Full Text Available This interdisciplinary study, performed with participation of research workers of Palladin Institute of Biochemistry and Institute of Organic Chemist­ry of NAS of Ukraine, is devoted to analysis of biochemical effects of some calixarene methylene bisphosphonic acids (cyclic phenol oligomers on two well-known biological phenomenons – Mg2+-dependent ATP hydrolysis (myosin subfragment-1 of myometrium smooth muscle was used as an example and fibrin polymerization. Calix[4]arene С-97 (calix[4]arene methylene bisphosphonic acids is a macrocyclic substance, which contains intramolecular highly ordered lipophilic cavity formed by four aromatic rings, one of which is functionalized at the upper rim with methylene bisphosphonic group. At concentration of 100 µM, this substance was shown to effectively inhibit ATPase activity of pig myometrium myosin subfragment-1 (inhibition coefficient І0.5 = 83 ± 7 µM. At the same time, this calix[4]arene causes significant (vs. control increase of myosin subfragment-1 hydrodynamic diameter, which may indicate formation of an intermolecular complex between calixa­rene and myosin head. Computer simulation methods (docking and molecular dynamics with addition of grid technologies enabled to elucidate the grounds of intermolecular interactions between calix[4]arene С-97 and myometrium myosin subfragment-1, that involve hydrophobic, electrostatic and π-π-stacking interactions, some of which are close to the ATPase active centre. In view of the ability of calixarenes to penetrate into the cell and their low toxicity, the results obtained may be used as a basis for further development of a new generation of supramolecular effectors (starting from the above mentioned substances, in particular calix[4]arene С-97 for regulation of smooth muscle contractile activity at the level of ATP dependent actin-myosin interaction. Calix[4]arenes bearing two or four methylenebisphosphonic acid groups at the macrocyclic upper

Hierarchically ordered macro-mesoporous ZnS microsphere with reduced graphene oxide supporter for a highly efficient photodegradation of methylene blue

Energy Technology Data Exchange (ETDEWEB)

Sookhakian, M., E-mail: m.sokhakian@gmail.com [Department of Physics, University of Malaya, Kuala Lumpur 50603 (Malaysia); Amin, Y.M. [Department of Physics, University of Malaya, Kuala Lumpur 50603 (Malaysia); Basirun, W.J. [Department of Chemistry, University of Malaya, Kuala Lumpur 50603 (Malaysia); Centre of Research in Nanotechnology and Catalysis (NanoCat), Institute of Postgraduate Studies, University Malaya, Kuala Lumpur 50603 (Malaysia)

2013-10-15

A facile one-pot method for the fabrication of high quality self-assembled hierarchically ordered macro-mesoporous ZnS microsphere–reduced graphene oxide (RGO) composite without the use of templates or surfactants is described. During the hydrothermal process, reduced graphene oxide (RGO) was loaded into the ZnS microsphere by in situ reduction of graphene oxide added in the self-assembly system. The morphology and structure of the as-prepared composites were confirmed by X-ray diffraction, high resolution transmission electron microscopy, energy dispersive X-ray analysis, Fourier transform infrared spectroscopy and Raman spectroscopy. Incorporation of reduced graphene oxide as an excellent electron-transporting material effectively suppresses the charge recombination. Hence, a significant enhancement in the photocatalytic efficiency for the photodegradation of methylene blue was observed with the ZnS–RGO composite, compared to the pure ZnS. Overall, this research results may lay down new vistas for the in situ fabrication of the ZnS–RGO composite as a highly efficient photocatalysis under visible-light irradiation and their applications in environmental protection.

Structural diversity through intramolecular cycloaddition and modulation of chemical reactivity in excited state. Synthesis and photoreactions of 3-oxa-tricyclo[5.2.2.0(1,5)]undecenones: novel stereoselective route to oxa-triquinanes and oxa-sterpuranes.

Science.gov (United States)

Singh, V; Alam, S Q

2000-11-20

Synthesis of 11-methyl-3-oxa-tricyclo[5.2.2.0(1,5)]undecenones by intramolecular Diels-Alder reaction of highly labile spiroepoxycyclohexa-2,4-dienones and its photochemical reactions upon triplet (3T) and singlet (1S) excitation leading to a stereoselective route to oxa-triquinane and oxa-sterpurane, respectively, is described.

Magnetic graphene sponge for the removal of methylene blue

Energy Technology Data Exchange (ETDEWEB)

Yu, Baowei; Zhang, Xiaoliang; Xie, Jingru; Wu, Ruihan; Liu, Xiaoyang; Li, Hongliang; Chen, Fang; Yang, Hua; Ming, Zhu; Yang, Sheng-Tao, E-mail: yangst@pku.edu.cn

2015-10-01

Graphical abstract: - Highlights: • Magnetic graphene sponge is prepared for dye removal in aqueous solution. • Magnetic graphene sponge has an adsorption capacity of 526 mg/g for methylene blue. • Adsorption behaviors of methylene blue on magnetic graphene sponge are investigated. • Magnetic graphene sponge could be partially regenerated by washing with acidic ethanol. - Abstract: Magnetic carbon nanomaterials have been widely adopted as adsorbents in water treatment, but the low adsorption capacities largely limit their practical applications. In this study, magnetic graphene sponge (Fe{sub 3}O{sub 4}-GS) was prepared by lyophilization for the adsorption of dye pollutant. The incorporation of Fe{sub 3}O{sub 4} enabled the magnetic separation of Fe{sub 3}O{sub 4}-GS after the adsorption of methylene blue (MB). The adsorption capacity of Fe{sub 3}O{sub 4}-GS for MB was 526 mg/g, much higher than those of the magnetic carbon nanoadsorbents in the literature. The adsorption kinetics of MB on Fe{sub 3}O{sub 4}-GS was moderately fast, which could be analyzed by the pseudo-second-order model and intraparticle diffusion model. The thermodynamics study revealed that the adsorption was driven by the increased randomness on the interface. The pH and ionic strength had meaningful influences on the adsorption capacity of Fe{sub 3}O{sub 4}-GS. The facile regeneration of Fe{sub 3}O{sub 4}-GS would definitely reduce its operating cost. The implications to the environmental applications of magnetic carbon nanoadsorbents are discussed.

NAA-modified DNA oligonucleotides with zwitterionic backbones: stereoselective synthesis of A-T phosphoramidite building blocks.

Science.gov (United States)

Schmidtgall, Boris; Höbartner, Claudia; Ducho, Christian

2015-01-01

Modifications of the nucleic acid backbone are essential for the development of oligonucleotide-derived bioactive agents. The NAA-modification represents a novel artificial internucleotide linkage which enables the site-specific introduction of positive charges into the otherwise polyanionic backbone of DNA oligonucleotides. Following initial studies with the introduction of the NAA-linkage at T-T sites, it is now envisioned to prepare NAA-modified oligonucleotides bearing the modification at X-T motifs (X = A, C, G). We have therefore developed the efficient and stereoselective synthesis of NAA-linked 'dimeric' A-T phosphoramidite building blocks for automated DNA synthesis. Both the (S)- and the (R)-configured NAA-motifs were constructed with high diastereoselectivities to furnish two different phosphoramidite reagents, which were employed for the solid phase-supported automated synthesis of two NAA-modified DNA oligonucleotides. This represents a significant step to further establish the NAA-linkage as a useful addition to the existing 'toolbox' of backbone modifications for the design of bioactive oligonucleotide analogues.

One-Pot Route towards Active TiO2 Doped Hierarchically Porous Cellulose: Highly Efficient Photocatalysts for Methylene Blue Degradation

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Xiaoxia Sun

2017-03-01

Full Text Available In this study, novel photocatalyst monolith materials were successfully fabricated by a non-solvent induced phase separation (NIPS technique. By adding a certain amount of ethyl acetate (as non-solvent into a cellulose/LiCl/N,N-dimethylacetamide (DMAc solution, and successively adding titanium dioxide (TiO2 nanoparticles (NPs, cellulose/TiO2 composite monoliths with hierarchically porous structures were easily formed. The obtained composite monoliths possessed mesopores, and two kinds of macropores. Scanning Electron Microscope (SEM, Energy Dispersive Spectroscopy (EDS, Fourier Transform Infrared Spectroscopy (FT-IR, X-ray Diffraction (XRD, Brunauer-Emmett-Teller (BET, and Ultraviolet-visible Spectroscopy (UV-Vis measurements were adopted to characterize the cellulose/TiO2 composite monolith. The cellulose/TiO2 composite monoliths showed high efficiency of photocatalytic activity in the decomposition of methylene blue dye, which was decomposed up to 99% within 60 min under UV light. Moreover, the composite monoliths could retain 90% of the photodegradation efficiency after 10 cycles. The novel NIPS technique has great potential for fabricating recyclable photocatalysts with highly efficiency.

Solvent mimicry with methylene carbene to probe protein topography.

Science.gov (United States)

Gómez, Gabriela Elena; Monti, José Luis E; Mundo, Mariana Rocío; Delfino, José María

2015-10-06

The solvent accessible surface area (SASA) of the polypeptide chain plays a key role in protein folding, conformational change, and interaction. This fundamental biophysical parameter is elusive in experimental measurement. Our approach to this problem relies on the reaction of the minimal photochemical reagent diazirine (DZN) with polypeptides. This reagent (i) exerts solvent mimicry because its size is comparable to water and (ii) shows scant chemical selectivity because it generates extremely reactive methylene carbene. Methylation gives rise to the EM (extent of modification) signal, which is useful for scrutinizing the conformational change triggered by Ca(2+) binding to calmodulin (CaM). The increased EM observed for the full protein is dominated by the enhanced exposure of hydrophobic area in Ca(2+)-CaM. Fragmentation allowed us to quantify the methylene incorporation at specific sites. Peptide 91-106 reveals a major reorganization around the calcium 151 binding site, resulting in local ordering and a greater exposure of the hydrophobic surface. Additionally, this technique shows a high sensitivity to probe recognition between CaM and melittin (Mel). The large decrease in EM indicates the occlusion of a significant hydrophobic area upon complexation. Protection from labeling reveals a larger involvement of the N-terminal and central regions of CaM in this interaction. Despite its smaller size, Mel's differential exposure can also be quantified. Moreover, MS/MS fragmentation realizes the goal of extending the resolution of labeled sites at the amino acid level. Overall, DZN labeling emerges as a useful footprinting method capable of shedding light on physiological conformational changes and interactions.

Methylene blue adsorption by algal biomass based materials: biosorbents characterization and process behaviour.

Science.gov (United States)

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2007-08-17

Dead algal biomass is a natural material that serves as a basis for developing a new family of sorbent materials potentially suitable for many industrial applications. In this work an algal industrial waste from agar extraction process, algae Gelidium and a composite material obtained by immobilization of the algal waste with polyacrylonitrile (PAN) were physical characterized and used as biosorbents for dyes removal using methylene blue as model. The apparent and real densities and the porosity of biosorbents particles were determined by mercury porosimetry and helium picnometry. The methylene blue adsorption in the liquid phase was the method chosen to calculate the specific surface area of biosorbent particles as it seems to reproduce better the surface area accessible to metal ions in the biosorption process than the N2 adsorption-desorption dry method. The porous texture of the biosorbents particles was also studied. Equilibrium isotherms are well described by the Langmuir equation, giving maximum uptake capacities of 171, 104 and 74 mg g(-1), respectively for algae, algal waste and composite material. Kinetic experiments at different initial methylene blue concentrations were performed to evaluate the equilibrium time and the importance of the driving force to overcome mass transfer resistances. The pseudo-first-order and pseudo-second-order kinetic models adequately describe the kinetic data. The biosorbents used in this work proved to be promising materials for removing methylene blue from aqueous solutions.

The Adsorption Efficiency of Chemically Prepared Activated Carbon from Cola Nut Shells by on Methylene Blue

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Julius Ndi Nsami

2013-01-01

Full Text Available The adsorption of methylene blue from aqueous solution onto activated carbon prepared from cola nut shell has been investigated under batch mode. The influence of major parameters governing the efficiency of the process such as, solution pH, sorbent dose, initial concentration, and contact time on the removal process was investigated. The time-dependent experimental studies showed that the adsorption quantity of methylene blue increases with initial concentration and decreasing adsorbent dosage. The equilibrium time of 180 min was observed and maximum adsorption was favoured at pH 3.5. The dye removal using 0.1 g of adsorbent was more than 90%. This dosage (0.1 g was considered as the optimum dosage to remove methylene blue from aqueous solutions. The equilibrium adsorption data were analyzed by the Freundlich, Langmuir adsorption isotherm models. The kinetics of methylene blue solution was discussed by pseudo-first-order, pseudo-second-order, and Elovich models. The adsorption process follows the Elovich rate kinetic model, having a correlation coefficient in the range between 0.9811 and 1.

Synthesis of co-polymer-grafted gum karaya and silica hybrid organic–inorganic hydrogel nanocomposite for the highly effective removal of methylene blue

CSIR Research Space (South Africa)

Mittal, H

2015-11-01

Full Text Available The aim of this work was to study the adsorption behavior of the nanosilica-containing hydrogel nanocomposite of gum karaya grafted with poly(acrylic acid-acrylamide) (GK-cl-P(AA-co-AAM)) in the adsorption of methylene blue (MB) from aqueous...

Sorption study of methylene blue on activated carbon prepared from Jatropha curcas and Terminalia catappa seed coats

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Ismaila Olalekan Saheed

2016-12-01

Full Text Available This research work targets the effectiveness of the prepared activated carbon from Jatropha curcas and Terminalia catappa seed coats for the sorption of methylene blue (MB from aqueous solution. The prepared Jatropha activated carbon (JAC and Terminalia activated carbon (TAC were characterised using Fourier transform infrared spectroscopy (FTIR, Scanning electron microscopy (SEM and Branauer- Emmett-Teller (BET surface area analysis. Effect of initial concentration, pH, contact time, adsorbent dose and temperature on the sorption experiments were studied and the adsorption capacity of these adsorbents were found to be 37.84 mg/g and 17.44 mg/g for methylene blue uptake by JAC and TAC respectively. The experimental data were analysed using Langmuir, Fruendlich, and Dubinin-Radushkevich isotherms. The data fitted best into Langmuir isotherm for Methylene blue-JAC and Methylene blue-TAC systems. The kinetic studies fitted into pseudo second order kinetics model. The process chemistry was exothermic.

Viability of the Fricke dosemeter doped with methylene blue

International Nuclear Information System (INIS)

Souza, V.L.B.; Santos, C.D.A.; Rodrigues, K.R.G.; Cunha, M.S.; Figueiredo, M.D.C.; Melo, R.T.

2009-01-01

This work aims to find the possible utilization of the Fricke dosemeter doped with methylene blue (FMB) for the dosimetry of photodynamic therapy. The FMB was irradiated wit X rays and light emitted diodes demonstrating positive answers to the stimulus, being probably to be used for dosimetric objectives

Sorption characteristics of methylene blue onto Nypa fruiticans lignin ...

African Journals Online (AJOL)

The sorption characteristics of soda lignin extracted from Nypa fruiticans for the removal of methylene blue dye from aqueous solution was investigated in this study, as an ethically sound way of utilizing this unexploited abundant natural resource. Equilibrium data were fitted to the Langmuir and Freundlich isotherm ...

IRIS Toxicological Review of Dichloromethane (Methylene ...

Science.gov (United States)

EPA has finalized the Toxicological Review of Dichloromethane (Methylene Chloride): In support of the Integrated Risk Information System (IRIS). Now final, this assessment may be used by EPA’s program and regional offices to inform decisions to protect human health. This document presents background information and justification for the Intergrated Risk Information System (IRIS) Summary of the hazard and dose-response assessment of dichloromethane. IRIS Summaries may include oral reference dose (RfD) and inhalation reference concentration (RfC) values for chronic and other exposure durations, and a carcinogencity assessment. Internet/NCEA web site

Interactions of the (R) Ru-BINAP Catalytic Complex with an Inorganic Matrix in Stereoselective Hydrogenation of Methylacetoacetate – Kinetic, XPS and DRIFT Studies.

Czech Academy of Sciences Publication Activity Database

Klusoň, Petr; Krystyník, Pavel; Dytrych, Pavel; Bártek, L.

2016-01-01

Roč. 119, č. 2 (2016), s. 393-413 ISSN 1878-5190 R&D Projects: GA ČR GA15-14228S Institutional support: RVO:67985858 Keywords : (R)-Ru-BINAP complex * stereoselective hydrogenation * montmorillonite Subject RIV: CC - Organic Chemistry Impact factor: 1.264, year: 2016

Visible Light-Induced Degradation of Methylene Blue in the Presence of Photocatalytic ZnS and CdS Nanoparticles

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Parisa Vaziri

2012-09-01

Full Text Available ZnS and CdS nanoparticles were prepared by a simple microwave irradiation method under mild conditions. The obtained nanoparticles were characterized by XRD, TEM and EDX. The results indicated that high purity of nanosized ZnS and CdS was successfully obtained with cubic and hexagonal crystalline structures, respectively. The band gap energies of ZnS and CdS nanoparticles were estimated using UV-visible absorption spectra to be about 4.22 and 2.64 eV, respectively. Photocatalytic degradation of methylene blue was carried out using physical mixtures of ZnS and CdS nanoparticles under a 500-W halogen lamp of visible light irradiation. The residual concentration of methylene blue solution was monitored using UV-visible absorption spectrometry. From the study of the variation in composition of ZnS:CdS, a composition of 1:4 (by weight was found to be very efficient for degradation of methylene blue. In this case the degradation efficiency of the photocatalyst nanoparticles after 6 h irradiation time was about 73% with a reaction rate of 3.61 × 10−3 min−1. Higher degradation efficiency and reaction rate were achieved by increasing the amount of photocatalyst and initial pH of the solution.

Radiolysis of methylene blue studied by ESR

International Nuclear Information System (INIS)

Contineau, M.; Iliescu, C.; Ciureanu, M.

1983-01-01

Electron spin resonance spectra have been used to gain information on the mechanism of radiolysis of aqueous solutions of methylene blue. The identity and behaviour of the semiquinone radicals formed as intermediate reduction products were discussed for strongly acid and for alcaline solutions. In order to obtain information on the radiolytic mechanism in strongly acidic media, irradiation was performed in the presence of various types of scavengers: sodium formate, glucose, succinic acid, hydroquinone and D,L-α alanine. (author)

Differences of first-pass effect in the liver and intestine contribute to the stereoselective pharmacokinetics of rhynchophylline and isorhynchophylline epimers in rats.

Science.gov (United States)

Wang, Xin; Zheng, Mei; Liu, Jia; Huang, Zhifeng; Bai, Yidan; Ren, Zhuoying; Wang, Ziwen; Tian, Yangli; Qiao, Zhou; Liu, Wenyuan; Feng, Feng

2017-09-14

Uncaria rhynchophylla (Miq.) Miq. ex Havil., is a plant species used in traditional Chinese medicine to treat cardiovascular and central nervous system diseases. Rhynchophylline (RIN) and isorhynchophylline (IRN), a pair of epimers, are major alkaloids isolated from U. rhynchophylla and exhibit diverse pharmacological effects. Our previous study demonstrated that the pharmacokinetics of these epimers existed stereoselectivity after oral administration; however, the specific mechanism remains unknown and merits investigation. In the present study, the aim was to elucidate the mechanism underlying stereoselective pharmacokinetic characteristics of RIN and IRN in rats. The total (F), hepatic (F h ) and intestinal (F a ·F g ) bioavailabilities of each epimer were measured using portal vein cannulated rats following different dosing routes (intravenous, intraportal and intraduodenal) to assess individual contributions of the liver and intestine in stereoselective pharmacokinetics. Then the differences of first-pass metabolism in the liver and intestine between two epimers were evaluated by in vitro incubation with rat liver microsomes, intestinal S9 and gastrointestinal (GI) content solutions, respectively. Meanwhile, the membrane permeability and efflux by P-glycoprotein (P-gp) were examined by in situ single-pass intestinal perfusion with and without P-gp inhibitor verapamil. The configurational interconversion at different pH values and the excretions via feces and urine were also examined. Pharmacokinetic data showed that the total bioavailability of RIN was 5.9 folds higher than that of IRN (23.4% vs. 4.0%). The hepatic availability of RIN was 4.6 folds higher than that of IRN (46.9% vs. 10.3%), whereas the intestinal availability of RIN (48.1%) was comparable to that of IRN (42.7%). In addition, intestinal perfusion showed that IRN possessed higher intestinal permeability than RIN and co-perfusion with verapamil could affect absorption process of RIN but not IRN

Evaluation of anticancer properties of a new α-methylene-δ-lactone DL-249 on two cancer cell lines

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Pomorska Dorota K.

2017-06-01

Full Text Available The anticancer activity of a new synthetic α-methylene-δ-lactone DL-249 was reported in leukemia HL-60 and breast cancer MCF-7 cells and compared with the activity of a natural α-methylene-γ-lactone from Tanacetum parthenium, parthenolide.

A facile approach to prepare porous cup-stacked carbon nanotube with high performance in adsorption of methylene blue.

Science.gov (United States)

Gong, Jiang; Liu, Jie; Jiang, Zhiwei; Wen, Xin; Mijowska, Ewa; Tang, Tao; Chen, Xuecheng

2015-05-01

Novel porous cup-stacked carbon nanotube (P-CSCNT) with special stacked morphology consisting of many truncated conical graphene layers was synthesized by KOH activating CSCNT from polypropylene. The morphology, microstructure, textural property, phase structure, surface element composition and thermal stability of P-CSCNT were investigated by field-emission scanning electron microscope, transmission electron microscope (TEM), high-resolution TEM, N2 sorption, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy and thermal gravimetric analysis. A part of oblique graphitic layers were etched by KOH, and many holes with a diameter of several to a doze of nanometers connecting inner tube with outside were formed, which endowed P-CSCNT with high specific surface area (558.7 m(2)/g), large pore volume (1.993 cm(3)/g) and abundant surface functional groups. Subsequently, P-CSCNT was used for adsorption of methylene blue (MB) from wastewater. Langmuir model closely fitted the adsorption results, and the maximum adsorption capacity of P-CSCNT was as high as 319.1mg/g. This was ascribed to multiple adsorption mechanisms including pore filling, hydrogen bonding, π-π and electrostatic interactions. Pseudo second-order kinetic model was more valid to describe the adsorption behavior. Besides, P-CSCNT showed good recyclablity and reusability. These results demonstrated that P-CSCNT had potential application in wastewater treatment. Copyright © 2015 Elsevier Inc. All rights reserved.

Removal efficiency of methylene blue using activated carbon from waste banana stem: Study on pH influence

Science.gov (United States)

Misran, E.; Bani, O.; Situmeang, E. M.; Purba, A. S.

2018-02-01

The effort to remove methylene blue in artificial solution had been conducted using adsorption process. The abundant banana stem waste was utilized as activated carbon precursor. This study aimed to analyse the influence of solution pH to removal efficiency of methylene blue using activated carbon from banana stem as adsorbent. Activated carbon from banana stem was obtained by chemical activation using H3PO4 solution. Proximate analysis result showed that the activated carbon has 47.22% of fixed carbon. This value exhibited that banana stem was a potential adsorbent precursor. Methylene blue solutions were prepared at initial concentration of 50 ppm. The influence of solution pH was investigated with the use of 0.2 g adsorbent for 100 mL dye solution. The adsorption was conducted using shaker with at a constant rate of 100 rpm at room temperature for 90 minutes. The results showed that solution pH influenced the adsorption. The activated carbon from banana stem demonstrated satisfying performance since removal efficiencies of methylene blue were higher than 99%.

Desorption and photodegradation of methylene blue from modified sugarcane bagasse surface by acid TiO2 hydrosol

International Nuclear Information System (INIS)

Yu Junxia; Chi Ruan; Guo Jia; Zhang Yuefei; Xu Zhigao; Xiao Chunqiao

2012-01-01

Waste sugarcane bagasse (SCB) was modified by pyromellitic dianhydride to improve its adsorption capacity for cationic dyes. Results showed that the adsorption capacity of the modified SCB for methylene blue was 564 mg g -1 , which was about 12 times than that obtained on the unmodified SCB. Methylene blue loaded modified SCB was regenerated by a self-clean eluent: TiO 2 hydrosol with pH ranged from 1 to 4, and HNO 3 solution with the same pH range was tested at the same time for comparison. Results showed that desorption kinetics of methylene blue in the hydrosol systems fit two-step kinetic model and controlled mainly by the slow step. As a self-clean eluent, acid hydrosol could firstly desorb and then photodegrade methylene blue under sunlight irradiation. After five desorption-photodegradation cycles, 78.3% of the absorbed dyes could be desorbed by using hydrosol (pH 2) as eluent. The hydrosol could be continuously used in desorption and photodegradation process, which would economize large volume of the eluent and moreover it would not bring secondary pollution.

Interaction mode between methylene blue-Sm(III) complex and ...

African Journals Online (AJOL)

Spectroscopic and viscosity methods were applied to investigate the interaction between methylene blue (MB)-Sm(III) complex and herring sperm DNA by using acridine orange as a spectral probe in Tris-HCl buffer (pH 7.40). By means of molar ratio method, the binding ratios between MB-Sm(III)and DNA were determined ...

Breadnut peel as a highly effective low-cost biosorbent for methylene blue: Equilibrium, thermodynamic and kinetic studies

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Linda B.L. Lim

2017-05-01

Full Text Available This work reports the potential use of peel of breadnut, Artocarpus camansi, as an effective low-cost biosorbent for the removal of methylene blue (MB. Oven dried A. camansi peel (ACP, which had a point of zero charge at pH = 4.8, showed maximum biosorption capacity which was far superior to most literature reported fruit biomasses, including samples that have been activated. Isotherm studies on biosorption of MB onto ACP gave a maximum biosorption capacity of 409 mg g−1. The Langmuir model was found to give the best fit among various isotherm models investigated and error analyses performed. Kinetics studies were fast with 50% dye being removed in less than 8 min from a 50 mg L−1 dye solution and further, kinetics followed the pseudo second order. Thermodynamic studies indicated that the biosorption process was both spontaneous and exothermic. Fourier transform infrared (FT-IR of ACP before and after MB adsorption was investigated. It can be concluded that oven dried breadnut peel is a highly promising low-cost biosorbent with great potential for the removal of MB.

Methylene blue adsorption from glycerol solution onto the acicular ...

African Journals Online (AJOL)

The mechanism of methylene blue adsorption onto the surface of synthetic acicular habit of α-goethite from glycerol solution has been studied through batch experiment at 25, 30 and 35 0C in a glass cell of minimal dead volume. To describe the adsorption results, an attempt was made to fit the data to the Langmuir, ...

Direct asymmetric allylic alkenylation of N-itaconimides with Morita-Baylis-Hillman carbonates

KAUST Repository

Yang, Wenguo

2012-08-03

The asymmetric allylic alkenylation of Morita-Baylis-Hillman (MBH) carbonates with N-itaconimides as nucleophiles has been developed using a commercially available Cinchona alkaloid catalyst. A variety of multifunctional chiral α-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed regio- and enantioselectivity. © 2012 American Chemical Society.

Improved methylene blue two-phase titration method for determining cationic surfactant concentration in high-salinity brine.

Science.gov (United States)

Cui, Leyu; Puerto, Maura; López-Salinas, José L; Biswal, Sibani L; Hirasaki, George J

2014-11-18

The methylene blue (MB) two-phase titration method is a rapid and efficient method for determining the concentrations of anionic surfactants. The point at which the aqueous and chloroform phases appear equally blue is called Epton's end point. However, many inorganic anions, e.g., Cl(-), NO3(-), Br(-), and I(-), can form ion pairs with MB(+) and interfere with Epton's end point, resulting in the failure of the MB two-phase titration in high-salinity brine. Here we present a method to extend the MB two-phase titration method for determining the concentration of various cationic surfactants in both deionized water and high-salinity brine (22% total dissolved solid). A colorless end point, at which the blue color is completely transferred from the aqueous phase to the chloroform phase, is proposed as titration end point. Light absorbance at the characteristic wavelength of MB is measured using a spectrophotometer. When the absorbance falls below a threshold value of 0.04, the aqueous phase is considered colorless, indicating that the end point has been reached. By using this improved method, the overall error for the titration of a permanent cationic surfactant, e.g., dodecyltrimethylammonium bromide, in deionized (DI) water and high-salinity brine is 1.274% and 1.322% with limits of detection (LOD) of 0.149 and 0.215 mM, respectively. Compared to the traditional acid-base titration method, the error of this improved method for a switchable cationic surfactant, e.g., tertiary amine surfactant (Ethomeen C12), is 2.22% in DI water and 0.106% with LOD of 0.369 and 0.439 mM, respectively.

Sulfonamide antibiotic removal and nitrogen recovery from synthetic urine by the combination of rotating advanced oxidation contactor and methylene urea synthesis process.

Science.gov (United States)

Fukahori, S; Fujiwara, T; Ito, R; Funamizu, N

2015-01-01

The combination of nitrogen recovery and pharmaceutical removal processes for livestock urine treatment were investigated to suppress the discharge of pollutants and recover nitrogen as resources. We combined methylene urea synthesis from urea and adsorption and photocatalytic decomposition of sulfonamide antibiotic using rotating advanced oxidation contactor (RAOC) contained for obtaining both safe fertilizer and reclaimed water. The methylene urea synthesis could recover urea in synthetic urine, however, almost all sulfonamide antibiotic was also incorporated, which is unfavorable from a safety aspect if the methylene urea is to be used as fertilizer. Conversely, RAOC could remove sulfonamide antibiotic without consuming urea. It was also confirmed that the methylene urea could be synthesized from synthetic urine treated by RAOC. Thus, we concluded that RAOC should be inserted prior to the nitrogen recovery process for effective treatment of urine and safe use of methylene urea as fertilizer.

Effect of some pre-treatments on the adsorption of methylene blue by Balkaya lignite

International Nuclear Information System (INIS)

Karaca, S.; Guerses, A.; Bayrak, R.

2004-01-01

In this study, the effects of some pre-treatments, such as HCl treatment, demineralization and pyrolysis, under a CO 2 atmosphere at different temperatures on the adsorption of methylene blue by Balkaya lignite were investigated. The adsorption capacities of the samples were determined before and after these pre-treatments. In addition, the removals of pyritic and organic sulfur and ash contents for the same coal samples were also defined. It was found that the adsorption capacities of the samples decreased after these pre-treatments. The decrease in adsorption capacity with pyrolysis can be attributed to the changes in surface morphology and/or pore size distribution of the coal samples. On the other hand, the observed decrease in adsorption capacity with removal of carbonates and silicates shows that these minerals have an important effect on methylene blue adsorption, and the adsorption considerably occurs through electrostatic interactions. In addition, the obtained results showed that the organic sulfur presence in the coal matrix have a positive effect on the methylene blue adsorption

Isotope effects on chemical equilibria

International Nuclear Information System (INIS)

Golding, P.D.

1974-01-01

The thermodynamic equilibrium constants of three deuterated substituted acetic acids are reported. The calculation of secondary isotope effects of the second kind for the three isotopic acid pairs has been accomplished by the appropriate comparison of thermodynamic equilibrium constants, and by the comparison of isotopic slopes. The effect of substituent variation on the isotope effects reported here disqualifies the simple inductive model as a legitimate description of secondary isotope effects of the second kind. The correlation of diminishing isotope effect per deuterium atom with increasing acidity is also invalidated by the present results. The syntheses of 9-thia-9,10-dihydrophenanthrene-9-oxide and thioxanthene-10-oxide are described. These compounds have been partially deuterated at their respective methylene positions. Spectral evidence indicates stereoselectivity of the methylene protons in the exchange reactions of both compounds. (author)

Adsorption of methylene blue from aqueous solution on the surface ...

African Journals Online (AJOL)

Adsorption of dye methylene blue from aqueous solution on the surface of sheep wool and cotton fibers was accomplished under the optimize conditions of temperature, concentration, pH, stay time duration and quantity of adsorbent. Spectrometric technique was used for the measurements of concentration of dye before ...

Intrauterine Methylene Blue Injection Influences the Accuracy of Pulse Oximetry Readings

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Fuh-Cheng Yeh

2005-12-01

Conclusions: Intraoperative administration of methylene blue may induce false low readings on pulse oximetry. The patient was not hypoxemic. If there is any doubt, arterial blood gas analysis should be done to ensure that the patient is well oxygenated.

Photodynamic action of methylene blue: mutagenesis and synergism

International Nuclear Information System (INIS)

Capella, M.A.M.

1988-01-01

The associated mutagenesis and the interactions with physical agents in order to potencialize its biological effects are studied. The induction of mutation in bacterias due to photodynamic action of methylene blue is presented as well as the induction of single breaks in bacterial DNA and the relationship between the repair systems, especially the SOS one. The interaction of the photodynamic therapy with low intensity electric current is discussed. (M.A.C.) [pt

Photodynamic Therapy With Methylene Blue for Skin Ulcers Infected With Pseudomonas aeruginosa and Fusarium spp.

Science.gov (United States)

Aspiroz, C; Sevil, M; Toyas, C; Gilaberte, Y

Photodynamic therapy (PDT) is a therapeutic modality with significant antimicrobial activity. We present 2 cases of chronic lower limb ulcers in which fungal and bacterial superinfection complicated management. PDT with methylene blue as the photosensitizer led to clinical and microbiological cure with no significant adverse effects. PDT with methylene blue is a valid option for the management of superinfected chronic ulcers, reducing the use of antibiotics and the induction of resistance. Copyright © 2017 AEDV. Publicado por Elsevier España, S.L.U. All rights reserved.

Radioiodinated methylene blue for melanoma targeting: Chemical characterisation and tumour selectivity of labelled components

International Nuclear Information System (INIS)

Blower, Philip J.; Clark, Katherine; Link, Eva M.

1997-01-01

Radioiodinated methylene blue contains a mixture of components showing selective uptake in human pigmented melanoma, and it has potential for imaging and therapy. Nuclear magnetic resonance and mass spectroscopic studies show that the majority of the radioactivity (85%) is in the form of monoiodinated methylene blue, 4-iodo-3-methylamino-7-dimethylaminophenaza thionium chloride. The amino group ortho-to iodine has become demethylated to a mono-methylamino group. The remainder (15%) of the mixture is the doubly labelled 4,5-diiodo-3,7-bis(methylamino) phenazathionium chloride. The separated components show similar tumour selectivity in athymic mice bearing human pigmented melanomas

Removal of basic dye methylene blue by using bioabsorbents Ulva ...

African Journals Online (AJOL)

In the present study, the removal of textile dye methylene blue was studied by adsorption technique using adsorbents such as, alumina, Ulva lactuca and Sargassum (Maine algae). The batch technique was adopted under the optimize condition of amount of adsorbent, stay time, concentration, temperature and pH. By using ...

Use of Aspergillus wentii for biosorption of methylene blue from ...

African Journals Online (AJOL)

In this study, Aspergillus wentii was used as a biosorbent for the adsorption of methylene blue from aqueous solution. The effects of contact time, initial dye concentration, solution pH and temperature on biosorption were investigated. The contact time required (that is, the equilibrium time) for maximum dye biosorption was ...

An unprecedented chemospecific and stereoselective tandem nucleophilic addition/cycloaddition reaction of nucleophilic carbenes with ketenimines.

Science.gov (United States)

Cheng, Ying; Ma, Yang-Guang; Wang, Xiao-Rong; Mo, Jun-Ming

2009-01-16

The first study of the reaction between nucleophilic carbenes and ketenimines is reported. The interaction of thiazole and benzothiazole carbenes with ketenimines proceeded in a chemospecific and stereoselective manner to produce thiazole- and benzothiazole-spiro-pyrrole derivatives generally in good yields. The reaction was proposed to proceed via a tandem nucleophilic addition of carbene to the C=N bond of ketenimine followed by a stepwise [3+2] cycloaddition of the 1,3-dipolar intermediate with the C=C bond of ketenimine. This reaction provides a powerful protocol for the construction of novel polyfunctional thiazole-spiro-pyrrole or benzothiazole-spiro-pyrrole compounds that are not readily accessible by other methods.

Microfluidic Chip Reactor and the Stereoselective Hydrogenation of Methylacetoacetate over (R)-Ru-BINAP in the [N8222][Tf2N]/Methanol/ Water Mixed Phase.

Czech Academy of Sciences Publication Activity Database

Klusoň, Petr; Stavárek, Petr; Pěnkavová, Věra; Vychodilová, Hana; Hejda, Stanislav; Bendová, Magdalena

2017-01-01

Roč. 115, May (2017), s. 39-46 ISSN 0255-2701 R&D Projects: GA ČR GA15-04790S Institutional support: RVO:67985858 Keywords : stereoselectivity * microfluidic chip * ionic liquids Subject RIV: CI - Industrial Chemistry, Chemical Engineering OBOR OECD: Chemical process engineering Impact factor: 2.234, year: 2016

Stereoselective Synthesis of Functionalized 1,3-Disubstituted Isoindolines via Rh(III)-Catalyzed Tandem Oxidative Olefination-Cyclization of 4-Aryl-cyclic Sulfamidate-5-Carboxylates.

Science.gov (United States)

Achary, Raghavendra; Jung, In-A; Son, Se-Mi; Lee, Hyeon-Kyu

2017-07-21

A new method for the direct, stereoselective synthesis of highly functionalized 1,3-disubstituted isoindolines 6 from enantiomerically enriched cyclic 4-aryl-sulfamidate-5-carboxylates (5) is described. The process involves sulfamidate directed, Rh(III)-catalyzed tandem ortho C-H olefination of the 4-aryl-sulfamidate-5-carboxylates and subsequent cyclization by aza-Michael addition. In the reaction, which generates trans-1,3-disubstituted isoindolines exclusively, the configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained in the product. Examples are provided which show that the cyclic sulfamidate moiety not only serves as a chiral directing group but also as a versatile handle for further functionalization of the generated isoindoline ring system.

Application of Spent Li-Ion Batteries Cathode in Methylene Blue Dye Discoloration

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Eric M. Garcia

2017-01-01

Full Text Available This paper aims to present the mechanism study of methylene blue (MB discoloration using spent Li-ion battery cathode tape and hydrogen peroxide. The recycled cathode used in this work is composed of 72% of LiCoO2, 18% of carbon, and 10% of Al. The value found for surface area is 8.9 m2/g and the ZCP value occurs in pH = 2.95. Different from what is proposed in the literature, the most likely mechanism of methylene blue discoloration is the oxidation/delitiation of LiCoO2 and the reduction of H2O2 forming OH∙. Thus, in this paper, an important and promising alternative for discoloration of textile industry dyes using spent Li-ion battery cathode is presented.

Extraosseous uptake of 99sup(m)technetium methylene diphosphonate

International Nuclear Information System (INIS)

Sty, J.R.; Kun, L.; Casper, J.; Babbitt, D.P.

1980-01-01

A child with a ganglioneuroblastoma and tumor uptake of 99 sup(m)technetium methylene diphosphate ( 99 sup(m)Tc-MDP) is presented. After surgical removal of an encapsulated tumor and radiation therapy, an interval bone scan demonstrated the same presurgical abnormality. Awareness of abnormal uptake of 99 sup(m)Tc-MDP in irradiated renal tissue prevents interpreting radiation nephritis as recurrent tumor. (orig.) [de

Structural characteristics of mixed oxides MOx/SiO2 affecting photocatalytic decomposition of methylene blue

International Nuclear Information System (INIS)

Gun’ko, V.M.; Blitz, J.P.; Bandaranayake, B.; Pakhlov, E.M.; Zarko, V.I.; Sulym, I.Ya.; Kulyk, K.S.; Galaburda, M.V.; Bogatyrev, V.M.; Oranska, O.I.; Borysenko, M.V.; Leboda, R.; Skubiszewska-Zięba, J.; Janush, W.

2012-01-01

A series of photocatalysts based on silica (nanoparticulate) supported titania, ceria, and ceria/zirconia were synthesized and characterized by a variety of techniques including surface area measurements, X-ray diffraction, Fourier transform infrared spectroscopy, zeta potential, surface charge density, and photocatalytic behavior toward methylene blue decomposition. Thermal treatment at 600 °C increases the anatase content of the titania based catalysts detected by XRD. Changes in the infrared spectra before and after thermal treatment indicate that at low temperature there are more ≡Si-O-Ti≡ bonds than at high temperature. As these bonds break upon heating the SiO 2 and TiO 2 separate, allowing the TiO 2 anatase phase to form. This results in an increased catalytic activity for the thermally treated samples. Nearly all titania based samples exhibit a negative surface charge density at pH 7 (initial pH of photocatalytic studies) which aids adsorption of methylene blue. The crystallinity of ceria and ceria/zirconia based catalysts are in some cases limited, and in others non-existent. Even though the energy band gap (E g ) can be lower for these catalysts than for the titania based catalysts, their photocatalytic properties are inferior.

Stereoselective synthesis of 1,3-disubstituted isoindolines via Rh(III)-catalyzed tandem oxidative olefination-cyclization of 4-aryl cyclic sulfamidates.

Science.gov (United States)

Son, Se-Mi; Seo, Yeon Ji; Lee, Hyeon-Kyu

2016-03-21

Rh(III)-catalyzed tandem ortho C-H olefination of cyclic 4-aryl sulfamidates (1) and subsequent intramolecular cyclization are described. This reaction serves as a method for the direct and stereoselective synthesis of 1,3-disubstituted isoindolines (3) starting with enantiomerically enriched 4-aryl cyclic sulfamidates. In this process, the configurational integrity of the stereogenic center in the starting cyclic sulfamidate is completely retained. In addition, the process generates trans-1,3-disubstituted isoindolines exclusively.

Methylene blue protects against TDP-43 and FUS neuronal toxicity in C. elegans and D. rerio.

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Alexandra Vaccaro

Full Text Available The DNA/RNA-binding proteins TDP-43 and FUS are found in protein aggregates in a growing number of neurodegenerative diseases, including amyotrophic lateral sclerosis (ALS and related dementia, but little is known about the neurotoxic mechanisms. We have generated Caenorhabditis elegans and zebrafish animal models expressing mutant human TDP-43 (A315T or G348C or FUS (S57Δ or R521H that reflect certain aspects of ALS including motor neuron degeneration, axonal deficits, and progressive paralysis. To explore the potential of our humanized transgenic C. elegans and zebrafish in identifying chemical suppressors of mutant TDP-43 and FUS neuronal toxicity, we tested three compounds with potential neuroprotective properties: lithium chloride, methylene blue and riluzole. We identified methylene blue as a potent suppressor of TDP-43 and FUS toxicity in both our models. Our results indicate that methylene blue can rescue toxic phenotypes associated with mutant TDP-43 and FUS including neuronal dysfunction and oxidative stress.

Methylene blue protects against TDP-43 and FUS neuronal toxicity in C. elegans and D. rerio.

Science.gov (United States)

Vaccaro, Alexandra; Patten, Shunmoogum A; Ciura, Sorana; Maios, Claudia; Therrien, Martine; Drapeau, Pierre; Kabashi, Edor; Parker, J Alex

2012-01-01

The DNA/RNA-binding proteins TDP-43 and FUS are found in protein aggregates in a growing number of neurodegenerative diseases, including amyotrophic lateral sclerosis (ALS) and related dementia, but little is known about the neurotoxic mechanisms. We have generated Caenorhabditis elegans and zebrafish animal models expressing mutant human TDP-43 (A315T or G348C) or FUS (S57Δ or R521H) that reflect certain aspects of ALS including motor neuron degeneration, axonal deficits, and progressive paralysis. To explore the potential of our humanized transgenic C. elegans and zebrafish in identifying chemical suppressors of mutant TDP-43 and FUS neuronal toxicity, we tested three compounds with potential neuroprotective properties: lithium chloride, methylene blue and riluzole. We identified methylene blue as a potent suppressor of TDP-43 and FUS toxicity in both our models. Our results indicate that methylene blue can rescue toxic phenotypes associated with mutant TDP-43 and FUS including neuronal dysfunction and oxidative stress.

Extended Fenske-Hall LCAO MO Calculations for Mixed Methylene Dihalides

Science.gov (United States)

Ziemann, Hartmut; Paulun, Manfred

1988-10-01

The electronic structure of mixed methylene dihalides CH2XY (X, Y = F, Cl, Br. I) has been studied using extended Fenske-Hall LCAO MO method. The comparison with available photoelec­tron spectra confirmes previous assignments of all bands with binding energies <100 eV. The electronic structure changes occurring upon varying the halogen substituents are discussed.

Stereoselectivity of the distribution of labelled noradrenaline in rabbit aortic strips after inhibition of the noradrenaline-metabolizing enzymes

Energy Technology Data Exchange (ETDEWEB)

Eckert, E; Henseling, M; Gescher, A; Trendelenburg, U [Wuerzburg Univ. (Germany, F.R.). Inst. fuer Pharmakologie und Toxikologie

1976-01-01

Rabbit aortic strips (nerve-free, reserpinepretreated or normal) whose noradrenaline-metabolizing enzymes were inhibited (by in vitro treatment with 0.5 mM pargyline for 30 min and by the presence of 0.1 mM U-0521) were exposed to 1.18 ..mu..M labelled (-)- or (+)noradrenaline for 30 min. At the end of the incubation period some strips were used for analysis of radioactivity (i.e., of noradrenaline and its metabolites), while for others the efflux of radioactivity was determined during 250 min of washout with amine-free solution. An estimate of the original distribution of the amine into the various extraneuronal and neuronal compartments of the tissue was obtained by compartmental analysis of the efflux curves. The mechanisms responsible for the accumulation of radioactivity in extraneuronal and axoplasmic compartments lack stereoselectivity; the rate constants for the efflux of radioactivity from these compartments are the same for (-)- and (+)noradrenaline. Despite the use of enzyme inhibitors, the 'late neuronal efflux' of radioactivity (i.e., the efflux collected between the 200th and 250th min of wash out) contained a considerable proportion of metabolites of noradrenaline. The metabolism of noradrenaline was stereoselective: while dihydroxyphenylglycol (DOPEG) was the predominant metabolite in the efflux from strips incubated with (-)noradrenaline, a considerable part of the efflux from strips incubated with the (+)isomer consisted of dihydroxymandelic acid and 'O-methylated and deaminated' metabolites (in addition to DOPEG).

Stereoselectivity of the distribution of labelled noradrenaline in rabbit aortic strips after inhibition of the noradrenaline-metabolizing enzymes

International Nuclear Information System (INIS)

Eckert, E.; Henseling, M.; Gescher, A.; Trendelenburg, U.

1976-01-01

Rabbit aortic strips (nerve-free, reserpinepretreated or normal) whose noradrenaline-metabolizing enzymes were inhibited (by in vitro treatment with 0.5 mM pargyline for 30 min and by the presence of 0.1 mM U-0521) were exposed to 1.18 μM labelled (-)- or (+)noradrenaline for 30 min. At the end of the incubation period some strips were used for analysis of radioactivity (i.e., of noradrenaline and its metabolites), while for others the efflux of radioactivity was determined during 250 min of washout with amine-free solution. An estimate of the original distribution of the amine into the various extraneuronal and neuronal compartments of the tissue was obtained by compartmental analysis of the efflux curves. The mechanisms responsible for the accumulation of radioactivity in extraneuronal and axoplasmic compartments lack stereoselectivity; the rate constants for the efflux of radioactivity from these compartments are the same for (-)- and (+)noradrenaline. Despite the use of enzyme inhibitors, the 'late neuronal efflux' of radioactivity (i.e., the efflux collected between the 200th and 250th min of wash out) contained a considerable proportion of metabolites of noradrenaline. The metabolism of noradrenaline was stereoselective: while dihydroxyphenylglycol (DOPEG) was the predominant metabolite in the efflux from strips incubated with (-)noradrenaline, a considerable part of the efflux from strips incubated with the (+)isomer consisted of dihydroxymandelic acid and 'O-methylated and deaminated' metabolites (in addition to DOPEG). (orig/GSE) [de

Obtaining multifunctional composites using styrofoam recycling: methylene blue adsorption

International Nuclear Information System (INIS)

Silva, T.H. da; Ferreira, B.F.; Faria, E.H. de; Ciuffi, K.J.; Calefi, P.S.

2011-01-01

There is high risk of environmental contamination by the textile industry if the generated waste is disposed into water streams and rivers. Another sector responsible for the generation of large amounts of waste is the styrofoam industry, since styrofoam is employed in various areas for packaging production. Therefore, today there is constant search for sustainable economic growth by means of materials recycling and reduction of residual pollutants. In this context, the present work aims to promote styrofoam recycling with its further utilization in the production of a kaolin-styrofoam composite for application as adsorbent of methylene blue originated from textile industry effluents. This adsorption is investigated in a column system, by exploiting the adsorptive properties of kaolin, such as large surface area and chemical and structural characteristics. The obtained materials were characterized by thermogravimetric analysis, X-ray diffraction, and UV-visible absorption spectroscopy. (author)

Ag-ligand modified tungstovandates and their efficient catalysis degradation properties for methylene blue

Energy Technology Data Exchange (ETDEWEB)

Zheng, Ran; Zhang, Huixia; Liu, Yunping; Wang, Xiaoxiao; Han, Zhangang, E-mail: hanzg116@126.com

2017-02-15

Two polytungstovandates [Ag(mbpy){sub 2}][Ag{sub 2}(mbpy){sub 3}][VW{sub 5}O{sub 19}]·H{sub 2}O (1) and [Ag(mbpy)]{sub 2}[Ag(mbpy){sub 2}]{sub 4}[VW{sub 12}O{sub 40}] (2) (mbpy =4,4′-dimethyl-2,2′-bipyridyl), had been hydrothermally synthesized and characterized by IR, TG, and single-crystal X-ray diffraction techniques. Single-crystal structural analysis revealed that the polyanionic clusters in two compounds are different: Lindqvist-type in 1 and α-Keggin-type in 2, respectively, while the cationic moieties in them are Ag-mbpy units. The experiments showed that this kind of hybrid crystal materials possesses more efficiently catalytic performance for the degradation of organic dye methylene blue (MB) in water solution under the UV irradiation. The significant degradation rate of MB can reach 89.9%, 94.9% by crystals 1 and 2 (40 mg) in the course of about 5 min. - Graphical abstract: Two Ag-ligand modified polytungstovandates had been synthesized and characterized, which were active in the catalytic degradation of organic dye methylene blue under the UV irradiation. - Highlights: • Two Ag-ligand modified tungstovandates were synthesized and characterized. • Weak interactions play important roles in constructing crystal frameworks. • Compounds are active to catalyze the degradation of methylene blue.

Redox reactions of methylene blue: a pulse radiolysis study

International Nuclear Information System (INIS)

Kishore, K.; Guha, S.N.; Mahadevan, J.; Moorthy, P.N.; Mittal, J.P.

1989-01-01

One-electron oxidation of methylene blue (MB - has been studied using specific oxidizing radicals such as Cl 2 - , Br 2 - , N 3 and Tl(II) in acidic and neutral aqueous solutions). The transient spectrum showed absorption maxima at 525 nm and 360 nm in the acidic pH region. At neutral pH also the absorption maxima were at 525 and 360 nm but the extinction coefficients were lower by 30%. A pK a of ∼4.3 was observed for the equilibrium MBH 3+ MB 2+ + H + . In the case of N 3 radical as the oxidant, the equilibrium: N 3 + MB = N 3 - + MB 2+ was observed for which an equilibrium constant of 120 was estimated from the experimental data. From this as well as from cyclic voltammetric experiments, the redox potential for the MB 2+ /MB + couple was calculated as 1.25 V vs NHE. The transient species produced by the reaction of OH radicals with methylene blue gave a very different spectrum with λ m = 400nm and a pK a of ∼ 8.6, and hence it is inferred that OH radicals do not bring about one-electron oxidation of the molecule. (author)

Estimation of surface area and pore volume of activated carbons by methylene blue and iodine numbers

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Cleiton A. Nunes

2011-01-01

Full Text Available Data of methylene blue number and iodine number of activated carbons samples were calibrated against the respective surface area, micropore volume and total pore volume using multiple regression. The models obtained from the calibrations were used in predicting these physical properties of a test group of activated carbon samples produced from several raw materials. In all cases, the predicted values were in good agreement with the expected values. The method allows extracting more information from the methylene blue and iodine adsorption studies than normally obtained with this type of material.

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

Science.gov (United States)

Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

2012-11-20

A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

Breakdown of methylene blue and methyl orange by pulsed corona discharge

NARCIS (Netherlands)

Grabowski, L.R.; Veldhuizen, van E.M.; Pemen, A.J.M.; Rutgers, W.R.

2007-01-01

The recently developed corona above water technique is applied to water containing 10 mg l-1 methylene blue (MB) or methyl orange (MO). The corona discharge pulses are created with a spark gap switched capacitor followed by a transmission line transformer. The pulse amplitude is 40 kV; its duration

Source reduction for prevention of methylene chloride hazards: cases from four industrial sectors

Directory of Open Access Journals (Sweden)

Ellenbecker Michael J

2003-07-01

Full Text Available Abstract Background Source reduction, defined as chemical, equipment and process changes that intervene in an industrial process to eliminate or reduce hazards, has not figured as a front-line strategy for the protection of workers' health. Such initiatives are popular for environmental protection, but their feasibility and effectiveness as an industrial hygiene approach have not been well described. Methods We investigated four cases of source reduction as a hazard prevention strategy in Massachusetts companies that had used methylene chloride, an occupational carcinogen, for cleaning and adhesive thinning. Three cases were retrospective and one was prospective, where the researchers assisted with the source reduction process change. Data were collected using qualitative research methods, including in-depth interviews and site visits. Results Motivated by environmental restrictions, a new worker health standard, and opportunity for productivity improvements, three companies eliminated their use of methylene chloride by utilizing available technologies and drop-in substitutes. Aided by technical assistance from the investigators, a fourth case dramatically reduced its use of methylene chloride via process and chemistry changes. While the companies' evaluations of potential work environment impacts of substitutes were not extensive, and in two cases new potential hazards were introduced, the overall impact of the source reduction strategy was deemed beneficial, both from a worker health and a production standpoint. Conclusion The findings from these four cases suggest that source reduction should be considered potentially feasible and effective for reducing or eliminating the potential hazards of methylene chloride exposure. Especially when faced with a hazard that is both an environmental and worker health concern, companies may chose to change their processes rather than rely on local exhaust ventilation equipment or personal protective

Nuclear overhauser spectroscopy of chiral CHD methylene groups

Energy Technology Data Exchange (ETDEWEB)

Augustyniak, Rafal [Ecole Normale Supérieure – PSL Research University, Département de chimie (France); Stanek, Jan [University of Warsaw, Faculty of Chemistry (Poland); Colaux, Henri; Bodenhausen, Geoffrey [Ecole Normale Supérieure – PSL Research University, Département de chimie (France); Koźmiński, Wiktor [University of Warsaw, Faculty of Chemistry (Poland); Herrmann, Torsten [Université de Lyon/UMR 5280 CNRS/ENS Lyon/UCB Lyon 1, Institut des Sciences Analytiques, Centre de RMN à Très Hauts Champs (France); Ferrage, Fabien, E-mail: Fabien.Ferrage@ens.fr [Ecole Normale Supérieure – PSL Research University, Département de chimie (France)

2016-01-15

Nuclear magnetic resonance spectroscopy (NMR) can provide a great deal of information about structure and dynamics of biomolecules. The quality of an NMR structure strongly depends on the number of experimental observables and on their accurate conversion into geometric restraints. When distance restraints are derived from nuclear Overhauser effect spectroscopy (NOESY), stereo-specific assignments of prochiral atoms can contribute significantly to the accuracy of NMR structures of proteins and nucleic acids. Here we introduce a series of NOESY-based pulse sequences that can assist in the assignment of chiral CHD methylene protons in random fractionally deuterated proteins. Partial deuteration suppresses spin-diffusion between the two protons of CH{sub 2} groups that normally impedes the distinction of cross-relaxation networks for these two protons in NOESY spectra. Three and four-dimensional spectra allow one to distinguish cross-relaxation pathways involving either of the two methylene protons so that one can obtain stereospecific assignments. In addition, the analysis provides a large number of stereospecific distance restraints. Non-uniform sampling was used to ensure optimal signal resolution in 4D spectra and reduce ambiguities of the assignments. Automatic assignment procedures were modified for efficient and accurate stereospecific assignments during automated structure calculations based on 3D spectra. The protocol was applied to calcium-loaded calbindin D{sub 9k}. A large number of stereospecific assignments lead to a significant improvement of the accuracy of the structure.

Stereoselective analysis of thioridazine-2-sulfoxide and thioridazine-5-sulfoxide: an investigation of rac-thioridazine biotransformation by some endophytic fungi.

Science.gov (United States)

Borges, Keyller Bastos; De Souza Borges, Warley; Pupo, Mônica Tallarico; Bonato, Pierina Sueli

2008-04-14

The purpose of this study was to develop a method for the stereoselective analysis of thioridazine-2-sulfoxide (THD-2-SO) and thioridazine-5-sulfoxide (THD-5-SO) in culture medium and to study the biotransformation of rac-thioridazine (THD) by some endophytic fungi. The simultaneous resolution of THD-2-SO and THD-5-SO diastereoisomers was performed on a CHIRALPAK AS column using a mobile phase of hexane:ethanol:methanol (92:6:2, v/v/v)+0.5% diethylamine; UV detection was carried out at 262 nm. Diethyl ether was used as extractor solvent. The validated method was used to evaluate the biotransformation of THD by 12 endophytic fungi isolated from Tithonia diversifolia, Viguiera arenaria and Viguiera robusta. Among the 12 fungi evaluated, 4 of them deserve prominence for presenting an evidenced stereoselective biotransformation potential: Phomopsis sp. (TD2) presented greater mono-2-sulfoxidation to the form (S)-(SE) (12.1%); Glomerella cingulata (VA1) presented greater mono-5-sulfoxidation to the forms (S)-(SE)+(R)-(FE) (10.5%); Diaporthe phaseolorum (VR4) presented greater mono-2-sulfoxidation to the forms (S)-(SE) and (R)-(FE) (84.4% and 82.5%, respectively) and Aspergillus fumigatus (VR12) presented greater mono-2-sulfoxidation to the forms (S)-(SE) and (R)-(SE) (31.5% and 34.4%, respectively).

Synergistic effect of pulsed corona discharges and ozonation on decolourization of methylene blue in water

CERN Document Server

Malik, M A; Ghaffar, A; Ahmed, K

2002-01-01

The effect of O sub 2 and O sub 3 bubbling on decolourization of methylene blue by pulsed corona discharges in water was studied. The pulsed corona discharges were produced by charging an 80 pF capacitor with a 40 kV DC source, through a 100 M OMEGA resistor, and discharging it into a needle-plate type reactor at 60 Hz through a rotating spark gap switch. A 20 ml sample of 13.25 mg l sup - sup 1 methylene blue in distilled water was decolourized in 120 min. Bubbling O sub 2 at 10 ml min sup - sup 1 through the discharge region reduced the decolourization time to 25 min. Bubbling O sub 2 containing 1500 mu mol O sub 3 l sup - sup 1 at 10 ml min sup - sup 1 reduced the decolourization time to 8 min. The O sub 3 was produced by fractionating input energy between a water treatment reactor and a O sub 3 generator, i.e. no additional energy was consumed for O sub 3 production. Under the same experimental conditions methylene blue solution in tap water was decolourized in >210 min by corona discharge in solution, in...

Conformational analysis of the chemical shifts for molecules containing diastereotopic methylene protons

Science.gov (United States)

Borowski, Piotr

2012-01-01

Quantum chemistry SCF/GIAO calculations were carried out on a set of compounds containing diastereotopic protons. Five molecules, including recently synthesized 1,3-di(2,3-epoxypropoxy)benzene, containing the chiral or pro-chiral center and the neighboring methylene group, were chosen. The rotational averages (i.e. normalized averages with respect to the rotation about the torsional angle τ with the exponential energy weight at temperature T) calculated individually for each of the methylene protons in 1,3-di(2,3-epoxypropoxy)benzene differ by ca. 0.6 ppm, which is significantly less than the value calculated for the lowest energy conformer. This value turned out to be low enough to guarantee the proper ordering of theoretical chemical shifts, supporting the interpretation of the 1H NMR spectrum of this important compound. The rotational averages of chemical shifts for methylene protons for a given type of conformer are shown to be essentially equal to the Boltzmann averages (here, the population-weighted averages for the individual conformers representing minima on the E( τ) cross-section). The calculated Boltzmann averages in the representative conformational space may exhibit completely different ordering as compared to the chemical shifts calculated for the lowest-energy conformer. This is especially true in the case of molecules, for which no significant steric effects are present. In this case, only Boltzmann averages account for the experimental pattern of proton signals. In addition, better overall agreement with experiment (lower value of the root-mean-square deviation between calculated and measured chemical shifts) is typically obtained when Boltzmann averages are used.

Comparing toxicologic and epidemiologic studies: methylene chloride--a case study.

Science.gov (United States)

Stayner, L T; Bailer, A J

1993-12-01

Exposure to methylene chloride induces lung and liver cancers in mice. The mouse bioassay data have been used as the basis for several cancer risk assessments. The results from epidemiologic studies of workers exposed to methylene chloride have been mixed with respect to demonstrating an increased cancer risk. The results from a negative epidemiologic study of Kodak workers have been used by two groups of investigators to test the predictions from the EPA risk assessment models. These two groups used very different approaches to this problem, which resulted in opposite conclusions regarding the consistency between the animal model predictions and the Kodak study results. The results from the Kodak study are used to test the predictions from OSHA's multistage models of liver and lung cancer risk. Confidence intervals for the standardized mortality ratios (SMRs) from the Kodak study are compared with the predicted confidence intervals derived from OSHA's risk assessment models. Adjustments for the "healthy worker effect," differences in length of follow-up, and dosimetry between animals and humans were incorporated into these comparisons. Based on these comparisons, we conclude that the negative results from the Kodak study are not inconsistent with the predictions from OSHA's risk assessment model.

Methylene-Cycloalkylacetate (MCA) Scaffold-Based Compounds as Novel Neurotropic Agents.

Science.gov (United States)

Lankri, David; Haham, Dikla; Lahiani, Adi; Lazarovici, Philip; Tsvelikhovsky, Dmitry

2018-04-18

One of the main symptoms in degenerative diseases is death of neuronal cell followed by the loss of neuronal pathways. In neuronal cultures, neurite outgrowths are cell sprouts capable of transforming into either axons or dendrites, to further form functional neuronal synaptic connections. Such connections have an important role in brain cognition, neuronal plasticity, neuronal survival, and regeneration. Therefore, drugs that stimulate neurite outgrowth may be found beneficial in ameliorating neural degeneration. Here, we establish the existence of a unique family of methylene-cycloalkylacetate-based molecules (MCAs) that interface with neuronal cell properties and operate as acceptable pharmacophores for a novel neurotropic (neurite outgrowth inducing) lead compounds. Using an established PC12 cell bioassay, we investigated the neurotropic effect of methylene-cycloalkylacetate compounds by comparison to NGF, a known neurotropic factor. Micrographs of the cells were collected by using a light microscope camera, and digitized photographs were analyzed for compound-induced neurotropic activity using an NIH image protocol. The results indicate that the alkene element, integrated within the cycloalkylacetate core, is indispensable for neurotropic activity. The discovered lead compounds need further mechanistic investigation and may be improved toward development of a neurotropic drug.

Methylene blue adsorption in clay mineral dealt with organic cation

International Nuclear Information System (INIS)

Silva, T.L.; Lemos, V.P.

2011-01-01

The interaction among organic cations, as the methylene blue (AM) and benzyltrimethylammonium (BTMA), and clay minerals of the group of the smectite they result in the formation of applied materials in the adsorption of organic pollutant presents in waters, soils and you cultivate. In this work they were prepared the adsorbents (organic-clays) smectite - AM and smectite-BTMA. The precursory sample of smectite was collected in Rio Branco-Acre. We were also used an smectite sample collected in Sena Madureira (SM)-Acre already characterized in previous work and a sample of standard smectite Swy-2-Na-Montmorillonite (SWy-2) of Wymong - USA. The organic agents selected for this study they were: Blue of Methylene, denominated AM and Benzyltrimethylammonium, denominated BTMA. They were appraised the capacities adsorptive of the treated samples with BTMA being used AM as adsorbate. The results of these evaluations detected that ran total adsorption of AM (concentrations varying from 1 to 10 ppm) for the treated samples with BTMA. The organic cation, BTMA, interacting with the surfaces of the natural clay was more efficient in the adsorption of AM than the clay without the previous treatment with this salt. (author)

SERS-active Ag, Au and Ag–Au alloy nanoparticles obtained by laser ablation in liquids for sensing methylene blue

Energy Technology Data Exchange (ETDEWEB)

Olea-Mejía, Oscar, E-mail: oleaoscar@yahoo.com.mx [Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Universidad Autónoma del Estado de México, km 14.5 Carretera Toluca-Atlacomulco, San Cayetano 50200, México (Mexico); Fernández-Mondragón, Mariana; Rodríguez-de la Concha, Gabriela [Centro Conjunto de Investigación en Química Sustentable UAEM-UNAM, Universidad Autónoma del Estado de México, km 14.5 Carretera Toluca-Atlacomulco, San Cayetano 50200, México (Mexico); Camacho-López, Marco [Laboratorio de Investigación y Desarrollo de Materiales Avanzados, Universidad Autónoma del Estado de México, Km 14.5 Carretera Toluca-Atlacomulco, San Cayetano 50925, México (Mexico)

2015-09-01

Highlights: • We synthesized Ag/Au nanoparticles by laser ablation in liquids. • We characterized such particles by UV–vis, TEM and EDS/STEM. • The SERS effect was studied for the obtained nanoparticles. • Pure silver nanoparticles showed the highest SERS signals. • We can sense methylene blue at a concentration of 10{sup −10} mole/L. - Abstract: We have synthesized Ag–Au nanoparticles by laser ablation in liquids using five different targets: 100% Ag, 80%Ag/20%Au, 50%Ag/50%Au, 20%Ag/80%Au and 100% Au (weight percentages). We used ethanol and methylene blue solutions in ethanol as the liquid media. The nanoparticles were mostly spherical with diameters 15, 19, 18, 23 and 11 nm, respectively. When alloyed targets were used, the resulting nanoparticles were completely alloyed forming solid solutions as evidenced by UV–vis Spectroscopy and Scanning Transmission Electron Microscopy. The obtained nanoparticles were employed to study the SERS effect of the methylene blue molecule. All the samples showed good SERS activity, however the ones composed of pure silver showed the greatest Raman signal enhancement. Finally, pure Ag nanoparticles were used for sensing methylene blue at different concentrations. While almost no signal can be discerned from the Raman spectrum when no particles are used at a concentration of methylene blue of 1 × 10{sup −2} M (∼3000 ppm), when Ag nanoparticles are used one can observe the characteristic peak of the molecule at concentrations as low as 1 × 10{sup −10} M (∼3 × 10{sup −5} ppm)

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando

2016-07-07

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

2016-01-01

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

Capillary gas chromatography of alkylbenzenes II. Correlations between the structures and methylene group increments and differences in retention indices of isomers

NARCIS (Netherlands)

Sojak, L.; Janak, J.; Rijks, J.A.

1977-01-01

The contribution to gas chromatographic retention behaviour of methylene group increments and differences in the retention indices (dI) of isomers of alkylbenzenes up to C16 on squalane and acetyltri-n-butyl citrate was studied. The methylene group increments appear to vary over a wide range (60–100

Decolorization of methylene blue in layered manganese oxide suspension with H2O2

International Nuclear Information System (INIS)

Zhang Lili; Nie Yulun; Hu Chun; Hu Xuexiang

2011-01-01

Highlights: → Layered birnessite-type manganese oxides exhibited a well-crystallized octahedral layer (OL) structure with β-MnOOH, α-MnOOH and γ-Mn 3 O 4 . → The catalyst was highly effective for the decolorization and degradation of methylene blue in the presence of H 2 O 2 at neutral pH. → The 1 O 2 and O 2 · - were the main reactive oxygen species in the reaction. - Abstract: Layered birnessite-type manganese oxides (Na-OL-1) were prepared via a redox reaction involving MnO 4 - and Mn 2+ under markedly alkaline conditions. According to the XRD analysis, the resulting material exhibited a well-crystallized octahedral layer (OL) structure with several different phases, including β-MnOOH, α-MnOOH and γ-Mn 3 O 4 . The catalyst was highly effective for the decolorization and degradation of methylene blue (MB) in the presence of H 2 O 2 at neutral pH. The tested MB was completely decolorized in Na-OL-1 suspension by the fraction dosing of H 2 O 2 (556.5 mM at the beginning and then 183.8 mM at 40 min). Based on the studies of electron spin resonance and the effect of radical scavengers, the 1 O 2 and O 2 · - were the main reactive oxygen species (ROS) in the reaction. It was found that both oxygen and ROS were generated from the decomposition of H 2 O 2 in Na-OL-1 suspension, wherein the decomposition pathways were proposed. The generation of H 2 O 2 in Na-OL-1 suspension at air atmosphere indicated that the existence of multivalent manganese oxides greatly enhanced the interfacial electron transfer, leading to the high activity of Na-OL-1.

Radioprotective effect against gamma-irradiation of methylene blue in the rat with reference to serum enzymes and pancreatic protein fractions examined by isoelectric focussing

Energy Technology Data Exchange (ETDEWEB)

Chung, S O; Nam, S Y [Kyung Hee Univ., Seoul (Korea). Dept. of Biology

1975-12-01

The Sprague-Dawley male rats were given 360 rads of single whole-body gamma-irradiation following an intraperitoneal injection of methylene blue (40 mg/kg). Serum glutamic oxaloacetic transaminase (SGOT), serum glutamic pyruvic transaminase (SGPT), serum amylase, serum lipase, and serum lecithinase A activities, and isoelectric focussing pattern of pancreatic juice proteins were determined at various time intervals after exposure. Methylene blue reduced generally the rise of SGOT, sGPT, amylase, and lipase activities. Methylene blue delayed also the serum lecithinase A fall after exposure. Mean number of protein bands as revealed by isoelectric focussing of pancreatic juice were significantly altered in both the control and the methylene blue-treated group after exposure. Especially methylene blue-treated group showed a marked delay in the decrease in number of protein bands after exposure. The possibility of using the SGOT, the SGPT, the serum amylase, the serum lipase, and the serum lecithinase A levels, and the number of protein bands in isoelectric focussing pattern of pancreatic juice as an early index of radiation injury is suggested.

Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

Directory of Open Access Journals (Sweden)

Jakub Saadi

2016-06-01

Full Text Available Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II back to palladium(0 which is apparently achieved by the present triethylamine.

Removal of methylene blue dye from wastewater by using supported liquid memberane technology

Directory of Open Access Journals (Sweden)

Ashraf Muhammad Waqar

2016-06-01

Full Text Available The present work describes the application of Supported Liquid Membrane (SLM technology towards the removal and recovery of a cationic dye (Methylene Blue from aqueous solutions. Natural and non-toxic vegetable oils have been impregnated on microporous polymeric films of polyvinylidene fluoride (PVDF to constitute a liquid membrane. Different parameters affecting the transport, like pH of feed solution, acid concentration in the strip solution, initial dye concentration, oil types and stirring speeds have been investigated. Highest value of flux (1.7 × 10−5 mg/cm2/sec1 for methylene blue dye was achieved with sunflower oil impregnated on the PVDF support, with pH maintained at 12 in the feed solution and 0.3 M hydrochloric acid concentration in the strip solution. It took 6 hours to transport maximum amount of dye under optimum conditions.

Kinetics analysis for development of a rate constant estimation model for ultrasonic degradation reaction of methylene blue.

Science.gov (United States)

Kobayashi, Daisuke; Honma, Chiemi; Matsumoto, Hideyuki; Takahashi, Tomoki; Kuroda, Chiaki; Otake, Katsuto; Shono, Atsushi

2014-07-01

Ultrasound has been used as an advanced oxidation method for wastewater treatment. Sonochemical degradation of organic compounds in aqueous solution occurs by pyrolysis and/or reaction with hydroxyl radicals. Moreover, kinetics of sonochemical degradation has been proposed. However, the effect of ultrasonic frequency on degradation rate has not been investigated. In our previous study, a simple model for estimating the apparent degradation rate of methylene blue was proposed. In this study, sonochemical degradation of methylene blue was performed at various frequencies. Apparent degradation rate constant was evaluated assuming that sonochemical degradation of methylene blue was a first-order reaction. Specifically, we focused on effects of ultrasonic frequency and power on rate constant, and the applicability of our proposed model was demonstrated. Using this approach, maximum sonochemical degradation rate was observed at 490 kHz, which agrees with a previous investigation into the effect of frequency on the sonochemical efficiency value evaluated by KI oxidation dosimetry. Degradation rate increased with ultrasonic power at every frequency. It was also observed that threshold power must be reached for the degradation reaction to progress. The initial methylene blue concentration and the apparent degradation rate constant have a relation of an inverse proportion. Our proposed model for estimating the apparent degradation rate constant using ultrasonic power and sonochemical efficiency value can apply to this study which extended the frequency and initial concentration range. Copyright © 2013 Elsevier B.V. All rights reserved.

ELECTROCHEMICAL BEHAVIOUR OF METHYLENE BLUE IN NON-AQUEOUS SOLVENTS

International Nuclear Information System (INIS)

Caram, J.A.; Suárez, J.F. Martínez; Gennaro, A.M.; Mirífico, M.V.

2015-01-01

Graphical abstract: Display Omitted - Highlights: • The dye is electro-reduced in two separated monoelectronic charge transfers. • Solvent/supporting electrolyte/acid/base modifies the electrochemical parameters. • A dissociation equilibrium of the dye in non-aqueous solvent is proposed. • The electro-generated and stable dye-radical is also chemically produced in EDA or KOH/DMF. • A new species is reversibly formed in KOH/EtOH or ACN. - Abstract: The electrochemical behaviour of methylene blue in solution of non-aqueous solvents with different supporting electrolytes was studied by cyclic voltammetry. Dye electro-reduction presents two well-defined processes of monoelectronic charge transfer yielding a free radical in the first process and an anion in the second electron transfer. Free radical and anion are long living species in some of the studied media. Effects of supporting electrolyte and solvent on the peak potentials, the peak current functions and the reversibility of the charge transfer processes are reported. A dissociation equilibrium of the dye in solution of non-aqueous solvents and the acid or base added determine markedly the electrochemical responses. In the particular cases of KOH/DMF or EDA basic media the chemical formation of the stable methylene blue radical was detected and it was characterized by EPR spectroscopy. A general reaction scheme is proposed

Determine the Intensity of UV Radiation and H2O2 on the Removal of Methylene Blue from Synthetic Wastewater

Directory of Open Access Journals (Sweden)

Mehdi Hosseini

2015-03-01

Full Text Available Background: There is a tremendous amount of color in textile wastewater that discharge it to the environment can cause a lot of environmental problems. The aim of this study is to evaluate the photocatalytic process UV/H2O2 to remove methylene blue dye from synthetic wastewater. Methods: UVC lamp was used as light source. In this study the effect of UV light intensity, irradiation distance, hydrogen peroxide concentration, and reaction time on the removal of methylene blue from aqueous solutions were studied. Data was analyzed by SPSS 18 and excel software. Results: The result showed that with increasing concentration of hydrogen peroxide, the color removal increases. Color removal changes were negligible at H2O2 concentration more than 5 mM. After 10 minutes reaction time at H2O2 concentration of 1 mm, efficiency of UVC/H2O2 is equal to 36.6%. Whilst at 5 mM concentration, removal efficiency is 89.2%. By increasing intensity of UV radiation, dye removal measure is also was increased, as the highest percentage of dye removal was obtained at 24 W radiation intensity. Conclusion: in present study, type of radiation and measure of hydrogen peroxide were the main factors in removal of methylene blue. Due to high efficiency of UVC/H2O2 process in removal of dye from aqueous solution, this method can use as an efficient process for removal of dye.

Enhanced removal of Methylene Blue by electrocoagulation using iron electrodes

OpenAIRE

Mohamed S. Mahmoud; Joseph Y. Farah; Taha E. Farrag

2013-01-01

The removal of pollutants from effluents by electrocoagulation has become an attractive method in recent years. The study deals with the enhancement of removal of Methylene Blue dye by using an electromagnetic field during the electrocoagulation process. Effects of electrolyte concentration, dye concentration, intensity and the direction of the electromagnet on the decolorization efficiency have been investigated. The formed ferric hydroxide flocs trap colloidal particles and make solid–liqui...

Synergistic effect of pulsed corona discharges and ozonation on decolourization of methylene blue in water

International Nuclear Information System (INIS)

Malik, Muhammad Arif; Ubaid-ur-Rehman; Ghaffar, Abdul; Ahmed, Kurshid

2002-01-01

The effect of O 2 and O 3 bubbling on decolourization of methylene blue by pulsed corona discharges in water was studied. The pulsed corona discharges were produced by charging an 80 pF capacitor with a 40 kV DC source, through a 100 MΩ resistor, and discharging it into a needle-plate type reactor at 60 Hz through a rotating spark gap switch. A 20 ml sample of 13.25 mg l -1 methylene blue in distilled water was decolourized in 120 min. Bubbling O 2 at 10 ml min -1 through the discharge region reduced the decolourization time to 25 min. Bubbling O 2 containing 1500 μmol O 3 l -1 at 10 ml min -1 reduced the decolourization time to 8 min. The O 3 was produced by fractionating input energy between a water treatment reactor and a O 3 generator, i.e. no additional energy was consumed for O 3 production. Under the same experimental conditions methylene blue solution in tap water was decolourized in >210 min by corona discharge in solution, in 30 min by corona discharge with O 2 bubbling, and in 11 min by corona discharge with bubbling of O 2 containing 1500 μmol O 3 l -1

Hydrothermal Synthesized and Alkaline Activated Carbons Prepared from Glucose and Fructose—Detailed Characterization and Testing in Heavy Metals and Methylene Blue Removal

Directory of Open Access Journals (Sweden)

Sanja Krstić

2018-06-01

Full Text Available In the presented paper, activated carbons were prepared from fructose and glucose, and activating agents (KOH, NaOH, LiOH by hydrothermal treatment (HTC treatment. After preparation, samples were characterized in details. Different techniques were used: x-ray powder diffraction analysis, Raman spectral analysis, elemental analysis, and determination of textural and morphological properties. Obtained results showed dependence of investigated properties and the nature of precursors (glucose or fructose as well as the type of hydroxides used as activating agents. After characterization, samples were tested as materials for heavy metals (Pb2+, Cd2+ and Zn2+ and methylene blue removal. Also, adsorption experiments were performed on wastewaters taken from tailings of the lead and zinc mine and kinetic of the methylene blue removal was studied. The factors which distinguished the KOH activated samples were high yield (~14%, content of organic carbon (63–74%, porosity and specific surface area (SBET ~700–1360 m2/g, a low degree of the crystal phase, indications that potassium ions may be included in heavy metals removal, good removal of the heavy metal ions (~47–59 mg/g for Pb2+, ~21–27 mg/g for Cd2+ and ~6–10 mg/g for Zn2+ and fast (~10–30 min and good methylene blue (~60–200 mg/g removal.

Experimental and kinetic studies on methylene blue adsorption by coir pith carbon.

Science.gov (United States)

Kavitha, D; Namasivayam, C

2007-01-01

Varying the parameters such as agitation time, dye concentration, adsorbent dose, pH and temperature carried out the potential feasibility of thermally activated coir pith carbon prepared from coconut husk for removal of methylene blue. Greater percentage of dye was removed with decrease in the initial concentration of dye and increase in amount of adsorbent used. Kinetic study showed that the adsorption of dye on coir pith carbon was a gradual process. Lagergren first-order, second-order, intra particle diffusion model and Bangham were used to fit the experimental data. Equilibrium isotherms were analysed by Langmuir, Freundlich, Dubnin-Radushkevich, and Tempkin isotherm. The adsorption capacity was found to be 5.87 mg/g by Langmuir isotherm for the particle size 250-500 microm. The equilibrium time was found to be 30 and 60 min for 10 and 20 mg/L and 100 min for 30, 40 mg/L dye concentrations, respectively. A maximum removal of 97% was obtained at natural pH 6.9 for an adsorbent dose of 100 mg/50 mL and 100% removal was obtained for an adsorbent dose of 600 mg/50 mL of 10 mg/L dye concentration. The pH effect and desorption studies suggest that chemisorption might be the major mode of the adsorption process. The change in entropy (DeltaS0) and heat of adsorption (DeltaH0) of coir pith carbon was estimated as 117.20 J/mol/K and 30.88 kJ/mol, respectively. The high negative value of change in Gibbs free energy indicates the feasible and spontaneous adsorption of methylene blue on coir pith carbon.

Stereoselective syntheses of (+- isoretronecanol and (+-5-epi-tashiromine via addition of chiral titanium (iv enolates to cyclic n-acyliminium ions

Directory of Open Access Journals (Sweden)

Elaine Pereira

2008-01-01

Full Text Available The stereoselective addition of the titanium (IV enolates derived from (S-4-isopropyl-N-4-chlorobutyryl-1,3-thiazolidine-2-thione (8 and from (S-4-isopropyl-N-4-chloropentanoyl-1,3-thiazolidine-2-thione (9 to N-Boc-2-methoxypyrrolidine (5b afforded the addition products (+-10 and (+-11 in 84% yield in both cases, as 8.6:1 and 10:1 diastereoisomeric mixtures, respectively. A three-step sequence allowed to convert these adducts to (+-isoretronecanol (1 and (+-5-epi-tashiromine (2 in 43% and 49% overall yield, respectively.

Stereoselective syntheses of (+)- isoretronecanol and (+)-5-epi-tashiromine via addition of chiral titanium (IV) enolates to cyclic n-acyliminium ions

Energy Technology Data Exchange (ETDEWEB)

Pereira, Elaine; Alves, Conceicao de Fatima; Boeckelmann, Maria Alice; Pilli, Ronaldo A [Universidade Estadual de Campinas (UNICAMP), Campinas, SP (Brazil). Inst. de Quimica

2008-07-01

The stereoselective addition of the titanium (IV) enolates derived from (S)-4-isopropyl-N-4-chlorobutyryl-1,3-thiazolidine-2-thione (8) and from (S)-4-isopropyl-N-4-chloropentanoyl-1,3-thiazolidine-2-thione (9) to N-Boc-2-methoxypyrrolidine (5b) afforded the addition products (+)-10 and (+)-11 in 84% yield in both cases, as 8.6:1 and 10:1 diastereoisomeric mixtures, respectively. A three-step sequence allowed to convert these adducts to (+)-isoretronecanol (1) and (+)-5-epi-tashiromine (2) in 43% and 49% overall yield, respectively. (author)

The tobacco carcinogen NNK is stereoselectively reduced by human pancreatic microsomes and cytosols.

Science.gov (United States)

Trushin, Neil; Leder, Gerhard; El-Bayoumy, Karam; Hoffmann, Dietrich; Beger, Hans G; Henne-Bruns, Doris; Ramadani, Marco; Prokopczyk, Bogdan

2008-07-01

Cigarette smoking increases the risk of cancer of the pancreas. The tobacco-specific nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) is the only known environmental compound that induces pancreatic cancer in laboratory animals. Concentrations of NNK are significantly higher in the pancreatic juice of smokers than in that of nonsmokers. The chiral NNK metabolite, (R,S)-4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) is itself a potent pancreatic carcinogen in rats. The carcinogenicity of NNAL is related to its stereochemistry; (S)-NNAL is a more potent lung tumorigen in the A/J mouse than is (R)-NNAL. In this study, we determined the potential of the human pancreas to convert NNK into NNAL. Human pancreatic microsomes and cytosols were incubated with [5-(3)H]NNK, and the metabolic products were determined by high-performance liquid chromatography (HPLC). (S)-NNAL was the predominant isomer formed in all cytosolic incubations. In ten microsomal samples, NNAL was formed at an average rate of 3.8 +/- 1.6 pmol/mg/min; (R)-NNAL was the predominant isomer in this group. The average rate of NNAL formation in 18 other microsomal samples was significantly lower, 0.13 +/- 0.12 pmol/mg/min (p < 0.001); (S)-NNAL was the predominant isomer formed in this group. In human pancreatic tissues, there is intraindividual variability regarding the capacity for, and stereoselectivity of, carbonyl reduction of NNK.

Stereoselective potencies and relative toxicities of γ-coniceine and N-methylconiine enantiomers.

Science.gov (United States)

Lee, Stephen T; Green, Benedict T; Welch, Kevin D; Jordan, Glenn T; Zhang, Qian; Panter, Kip E; Hughes, David; Chang, Cheng-Wei Tom; Pfister, James A; Gardner, Dale R

2013-04-15

γ-Coniceine, coniine, and N-methylconiine are toxic alkaloids present in poison hemlock (Conium maculatum). We previously reported the comparison of the relative potencies of (+)- and (-)-coniine enantiomers. In this study, we synthesized γ-coniceine and the enantiomers of N-methylconiine and determined the biological activity of γ-coniceine and each of the N-methylconiine enantiomers in vitro and in vivo. The relative potencies of these piperidine alkaloids on cells expressing human fetal muscle-type nicotinic acetylcholine receptors had the rank order of γ-coniceine > (-)-N-methylconiine > (±)-N-methylconiine > (+)-N-methylconiine. The relative lethalities of γ-coniceine and (-)-, (±)-, and (+)-N-methylconiine in vivo using a mouse bioassay were 4.4, 16.1, 17.8, and 19.2 mg/kg, respectively. The results from this study suggest γ-coniceine is a more potent agonist than the enantiomers of N-methylconiine and that there is a stereoselective difference in the in vitro potencies of the enantiomers of N-methylconiine that correlates with the relative toxicities of the enantiomers in vivo.

Adsorption capacity of methylene blue, an organic pollutant, by montmorillonite clay

KAUST Repository

Feddal, I.; Ramdani, Amina; Taleb, Safia; Gaigneaux, E. M.; Batis, Narjè s Harrouch; Ghaffour, NorEddine

2013-01-01

The isotherms and kinetics of the adsorption of a cationic dye in aqueous solution, methylene blue, on a local Algerian montmorillonite clay mineral (raw, sodium and thermally activated at 300 and 500°C) were determined experimentally. Various parameters influencing the adsorption were optimized, mainly solid-liquid contact time, mass of adsorbent, initial concentration of dye, pH of the solution and temperature. Results showed that the adsorption kinetics were fast: 30 min for the raw clay mineral, and 20 min for sodium clay mineral (SC) and thermally activated at 300°C, whereas with the clay mineral calcined at 500°C, the equilibrium was reached after 150 min only. The maximum adsorption capacity was reached at pH 6.6. Results deducted from the adsorption isotherms also showed that the retention follows the Langmuir model. In addition, it was found that the kinetics were in the order of 2 (K = 2.457 × 106 g/mg.h) for sodium clay and were limited by an intra-particle diffusion. SC was found to be a better adsorbent to remove methylene blue from industrial wastewater. © 2013 Balaban Desalination Publications. All rights reserved.

Adsorption capacity of methylene blue, an organic pollutant, by montmorillonite clay

KAUST Repository

Feddal, I.

2013-11-19

The isotherms and kinetics of the adsorption of a cationic dye in aqueous solution, methylene blue, on a local Algerian montmorillonite clay mineral (raw, sodium and thermally activated at 300 and 500°C) were determined experimentally. Various parameters influencing the adsorption were optimized, mainly solid-liquid contact time, mass of adsorbent, initial concentration of dye, pH of the solution and temperature. Results showed that the adsorption kinetics were fast: 30 min for the raw clay mineral, and 20 min for sodium clay mineral (SC) and thermally activated at 300°C, whereas with the clay mineral calcined at 500°C, the equilibrium was reached after 150 min only. The maximum adsorption capacity was reached at pH 6.6. Results deducted from the adsorption isotherms also showed that the retention follows the Langmuir model. In addition, it was found that the kinetics were in the order of 2 (K = 2.457 × 106 g/mg.h) for sodium clay and were limited by an intra-particle diffusion. SC was found to be a better adsorbent to remove methylene blue from industrial wastewater. © 2013 Balaban Desalination Publications. All rights reserved.

A Novel ZnO-Methylene Blue Nanocomposite Matrix for Biosensing Application

Directory of Open Access Journals (Sweden)

Shibu Saha

2011-01-01

Full Text Available A novel hybrid matrix of zinc oxide-methylene blue (ZnO-MB has been successfully developed for biosensing application. The introduction of methylene blue into the ZnO thin film leads to reduction in the charge transfer resistance and suggests an increase in the electron transfer capacity of the composite. Glucose oxidase (GOx was chosen as the model enzyme and effectively immobilized on the surface of hybrid ZnO-MB nanocomposite matrix. Electrochemical measurements were employed to study biosensing response of the GOx/ZnO-MB/ITO bioelectrode as a function of glucose concentration. The low oxidation potential (−0.23 V of the hybrid bioelectrode, in a mediatorless electrolyte, makes it resistant against interference from other bio-molecules. The low value of Michaelis-Menten constant (2.65 mM indicates that immobilized GOx retains its enzymatic activity significantly on the surface of nanocomposite hybrid matrix that results in an enhanced affinity towards its substrate (glucose. The ZnO-MB nanocomposite hybrid matrix, exhibiting enhanced sensing response (0.2 μAmM−1cm−2 with long shelf-life (>10 weeks, has potential for the realization of an integrated biosensing device.

Technetium 99m methylene diphosphonate bone scanning in osteoarthritic hands

International Nuclear Information System (INIS)

Buckland-Wright, J.C.; Lynch, J.A.; Macfarlane, D.G.; Homoeopathic Hospital, Tunbridge; Fogelman, I.; Emery, P.

1991-01-01

In this prospective study, the radiological features characteristic of osteoarthritis of the hand were compared with the radionuclide bone scan images. A total of 32 patients was assessed at 6-monthly intervals for 18 months. Microfocal radiographs were taken at each visit. The high magnification and resolution of this technique permitted direct measurement of joint space width, subchondral sclerosis, osteophyte number and area and juxta-articular radiolucency area for each joint in the hand. Four-hour technetium 99m methylene diphosphonate bone scans were taken at 0 and 12 months and the activity of tracer uptake at each joint scored. The latter was compared with each X-radiographic feature at every visit and the changes between visits analysed. The scan scores did not correlate with any of the X-radiographic features other than osteophyte size. During the study the size of growing and remodelling osteophytes increased significantly at joints with raised or increased isotope uptake. (orig.)

Technetium 99m methylene diphosphonate bone scanning in osteoarthritic hands

Energy Technology Data Exchange (ETDEWEB)

Buckland-Wright, J.C.; Lynch, J.A. (United Medical and Dental Schools of Guy' s and Saint Thomas' , London (UK). Dept. of Anatomy); Macfarlane, D.G. (United Medical and Dental Schools of Guy' s and Saint Thomas' , London (UK). Dept. of Anatomy Homoeopathic Hospital, Tunbridge (UK). Dept. of Rheumatology); Fogelman, I. (United Medical and Dental Schools of Guy' s and Saint Thomas' , London (UK). Dept. of Nuclear Medicine); Emery, P. (United Medical and Dental Schools of Guy' s and Saint Thomas' , London (UK). Dept. of Rheumatology)

1991-01-01

In this prospective study, the radiological features characteristic of osteoarthritis of the hand were compared with the radionuclide bone scan images. A total of 32 patients was assessed at 6-monthly intervals for 18 months. Microfocal radiographs were taken at each visit. The high magnification and resolution of this technique permitted direct measurement of joint space width, subchondral sclerosis, osteophyte number and area and juxta-articular radiolucency area for each joint in the hand. Four-hour technetium 99m methylene diphosphonate bone scans were taken at 0 and 12 months and the activity of tracer uptake at each joint scored. The latter was compared with each X-radiographic feature at every visit and the changes between visits analysed. The scan scores did not correlate with any of the X-radiographic features other than osteophyte size. During the study the size of growing and remodelling osteophytes increased significantly at joints with raised or increased isotope uptake. (orig.).

Photocatalytic degradation of methylene blue by C 3 N 4 /ZnO

Indian Academy of Sciences (India)

The photocatalytic activities of prepared samples were investigated under the illumination of blacklight and fluorescent lamps as the low wattage light source. The C 3 N 4 /ZnO showed a better photocatalytic activity than ZnO to degrade a methylene blue (MB) dye solution using blacklight lamps, but there is no significant ...

Total Synthesis of Bryostatins. Development of Methodology for Atom-Economic and Stereoselective Synthesis of the C-ring Subunit

Science.gov (United States)

Trost, Barry M.; Frontier, Alison J.; Thiel, Oliver R.; Yang, Hanbiao; Dong, Guangbin

2012-01-01

Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for stereoselective assembly of the C-ring subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the C-ring subunit of bryostatins. PMID:21793057

Intraoperative use of fibrin glue dyed with methylene blue in surgery for branchial cleft anomalies.

Science.gov (United States)

Piccioni, Michela; Bottazzoli, Marco; Nassif, Nader; Stefini, Stefania; Nicolai, Piero

2016-09-01

We present a new method of optimizing the results of surgery for branchial cleft anomalies based on the intraoperative injection of fibrin glue combined with methylene blue dye. Retrospective single-center cohort study. The method was applied in 17 patients suffering from branchial anomalies. Six (35.29%) had a preauricular lesion; three (17.65%) had lesions derived from the first arch/pouch/groove (type I), four (23.53%) had lesions derived from the first (type II), one (5.88%) had lesions derived from the second, one (5.88%) had lesions derived from the third, and two (11.76%) had lesions derived from the fourth. The median and mean age at surgery were 10 and 10.6 years, respectively. All patients were followed by periodic clinical and ultrasonographic examination. The combination of fibrin glue with methylene blue facilitated the correct assessment of the extension of the lesions and their intraoperative manipulation. After a mean follow-up of 47.8 months, all patients were free of disease. Intraoperative injection of branchial fistulae and cysts by a mixture of fibrin glue and methylene blue is an effective, easy, and safe tool to track lesions and achieve radical resection. The technique requires a definitive validation on a large cohort with adequate stratification of patients. 4 Laryngoscope, 126:2147-2150, 2016. © 2015 The American Laryngological, Rhinological and Otological Society, Inc.

Synergistic effect of pulsed corona discharges and ozonation on decolourization of methylene blue in water

Energy Technology Data Exchange (ETDEWEB)

Malik, Muhammad Arif [Applied Chemistry Division, PINSTECH, PO Nilore, Islamabad (Pakistan); Ubaid-ur-Rehman [Applied Chemistry Division, PINSTECH, PO Nilore, Islamabad (Pakistan); Ghaffar, Abdul; Ahmed, Kurshid [Electronics Division, PINSTECH, PO Nilore, Islamabad (Pakistan)

2002-08-01

The effect of O{sub 2} and O{sub 3} bubbling on decolourization of methylene blue by pulsed corona discharges in water was studied. The pulsed corona discharges were produced by charging an 80 pF capacitor with a 40 kV DC source, through a 100 M{omega} resistor, and discharging it into a needle-plate type reactor at 60 Hz through a rotating spark gap switch. A 20 ml sample of 13.25 mg l{sup -1} methylene blue in distilled water was decolourized in 120 min. Bubbling O{sub 2} at 10 ml min{sup -1} through the discharge region reduced the decolourization time to 25 min. Bubbling O{sub 2} containing 1500 {mu}mol O{sub 3} l{sup -1} at 10 ml min{sup -1} reduced the decolourization time to 8 min. The O{sub 3} was produced by fractionating input energy between a water treatment reactor and a O{sub 3} generator, i.e. no additional energy was consumed for O{sub 3} production. Under the same experimental conditions methylene blue solution in tap water was decolourized in >210 min by corona discharge in solution, in 30 min by corona discharge with O{sub 2} bubbling, and in 11 min by corona discharge with bubbling of O{sub 2} containing 1500 {mu}mol O{sub 3} l{sup -1}.

Kinetics and equilibrium studies on removal of methylene blue and methyl orange by adsorption onto activated carbon prepared from date pits-A comparative study

International Nuclear Information System (INIS)

Mahmoudi, Khaled; Hosni, Khaled; Hamdi, Noureddine; Srasra, Ezzeddine

2015-01-01

The adsorption of Methylene blue and Methyl orange by date pits carbon was carried out by varying parameters such as agitation time, pH and dye concentration. Equilibrium adsorption data followed both Langmuir and Freundlich isotherms. Adsorption followed second-order rate kinetics. The adsorption capacity was found to be 434 and 455mg of methyl orange and methylene blue, respectively, per g of the date pits carbon. Acidic pH is favorable for the adsorption of methyl orange against a basic medium which is favorable for the adsorption of MB. An opposite result was found for the methylene blue adsorption

Facile preparation of poly(methylene blue) modified carbon paste electrode for the detection and quantification of catechin

Energy Technology Data Exchange (ETDEWEB)

Manasa, G [Electrochemistry Research Group, Department of Chemistry, St. Joseph' s College, Lalbagh Road, Bangalore, 560027, Karnataka (India); Mascarenhas, Ronald J, E-mail: ronaldmasc2311@yahoo.co.in [Electrochemistry Research Group, Department of Chemistry, St. Joseph' s College, Lalbagh Road, Bangalore, 560027, Karnataka (India); Satpati, Ashis K [Analytical Chemistry Division, Bhabha Atomic Research Centre, Anushakthi Nagar, Trombay, Mumbai 400094, Maharashtra (India); D' Souza, Ozma J [Electrochemistry Research Group, Department of Chemistry, St. Joseph' s College, Lalbagh Road, Bangalore, 560027, Karnataka (India); Dhason, A [Soft Condensed Matter, Raman Research Institute, Sadashivnagar, Bangalore 560080, Karnataka (India)

2017-04-01

Free radicals are formed as byproducts of metabolism, and are highly unstable due to the presence of unpaired electrons. They readily react with other important cellular components such as DNA causing them damage. Antioxidants such as (+)-catechin (CAT), neutralize free radicals in the blood stream. Hence there is a need for detection and quantification of catechin concentration in various food sources and beverages. Electro-oxidative properties of catechin were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). A carbon paste working electrode modified by electropolymerizing methylene blue (MB) was fabricated. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) techniques were used to study the surface morphology of the electrode. Quasi-reversible electron transfer reaction occurred at + 0.260 V through a diffusion controlled process. In comparison to the bare carbon paste electrode (CPE), there was a significant 5.3 times increment in anodic current sensitivity at the modified electrode at physiological pH. Our findings indicate that for the electro-oxidation of CAT, CPE is a better base material for electropolymerization of MB compared to glassy carbon electrode (GCE). Nyquist plot followed the theoretical shape, indicating low interfacial charge transfer resistance of 0.095 kΩ at the modified electrode. Calibration plots obtained by DPV were linear in two ranges of 1.0 × 10{sup −3} to 1.0 × 10{sup −6} and 1.0 × 10{sup −7} to 0.1 × 10{sup −8} M. The limit of detection (LOD) and limit of quantification (LOQ) was 4.9 nM and 14 nM respectively. Application of the developed electrode was demonstrated by detecting catechin in green tea and spiked fruit juice with satisfactory recoveries. The sensor was stable, sensitive, selective and reproducible. - Highlights: • Remarkable electrocatalytic oxidation of Catechin at poly(methylene blue) modified CPE • Complete elimination of signal

Fabrication of magnetic carbon composites from peanut shells and its application as a heterogeneous Fenton catalyst in removal of methylene blue

Energy Technology Data Exchange (ETDEWEB)

Zhou, Lincheng, E-mail: zhoulc@lzu.edu.cn; Ma, Junjun; Zhang, He; Shao, Yanming; Li, Yanfeng

2015-01-01

Graphical abstract: Peanut shell magnetic carbon (PMC) were fabricated by carbonized the mixture of peanut shells and (NH{sub 4}){sub 3}Fe(C{sub 2}O{sub 4}){sub 3}. The obtained PMC exhibit high efficiency in catalysis oxidation methylene blue with the help of K{sub 2}S{sub 2}O{sub 8} and it can be easily separated from aqueous by external magnetic field. Meanwhile, the catalyst can be reused for seven times almost without decreased of activity. - Highlights: • Novel peanut shell magnetic carbon (PMC) catalysts were successfully synthesized. • PMC exhibited superior activity as a heterogeneous Fenton-like catalyst. • A high efficient Fenton-like system was set up for removal MB. • PMC posed excellent catalysis oxidation quality, stability and good reusability. - Abstract: Magnetic carbons were prepared from agricultural waste peanut shells and Ferric ammonium oxalate via a simple impregnation and carbonization process. The obtained composites were characterized by element analysis, MÖssbauer spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, X-ray diffraction, vibrating sample magnetometry and the Brunauer-Emmett-Teller surface area method, respectively. The magnetic carbon material was used as catalyst of heterogeneous Fenton reaction to remove methylene blue with the help of persulfate in waste water. The results indicated that both the removal rate and removal efficiency of this catalytic system are very excellent. The degradation efficiency was best (90% within 30 min) using initial concentrations of 0.5 g L{sup −1} persulfate and 40 mg L{sup −1} methylene blue. The removal mechanism was investigated by LC-MS. The catalyst retained its activity after seven reuses, indicating its good stability and reusability. It is inexpensive because it consists mainly of agricultural waste. Its porosity contributed to its high activity, which was achieved without any additional activation process. These indicating that the catalyst is

Palladium Hydride Promoted Stereoselective Isomerization of Unactivated Di(exo)methylenes to Endocyclic Dienes

OpenAIRE

Jung, Michael E.; Lee, Gloria S.; Pham, Hung V.; Houk, K. N.

2014-01-01

The exomethylenes of 2,6-disubstituted bicyclo[3.3.1]nonan-9-ones 2 are readily isomerized over a palladium catalyst under an atmosphere of hydrogen to predominantly form the isomer 3 with C 2 symmetry with very little formation of the analogous product with C s symmetry. A hydrogen source is essential to effect the rearrangement.

An electrochemical aptasensor for chiral peptide detection using layer-by-layer assembly of polyelectrolyte-methylene blue/polyelectrolyte-graphene multilayer

International Nuclear Information System (INIS)

Qin Haixia; Liu Jiyang; Chen Chaogui; Wang Jiahi; Wang Erkang

2012-01-01

Highlights: ► An electrochemical aptasensor for selective detection of peptide is constructed. ► This aptasensor is based on grapheme multilayer via layer-by-layer assembly. ► Such multilayer facilitates electron transfer and provides more adsorption sites. - Abstract: Here we demonstrate for the first time that by physically adsorbing aptamer onto conductive film assembled via alternate adsorption of graphene/polyelectrolyte and methylene blue/polyelectrolyte, a label-free electrochemical aptasensor with high sensitivity and selectivity for peptide detection is constructed. Graphene multilayer derived from layer-by-layer assembly has played significant roles in this sensing strategy: allowing accumulation of methylene blue, facilitating electron transfer and providing much more adsorption site. As compared to previous electrochemical aptasensors, the current sensor based on graphene multilayer alternated with electroactive molecule layer offers extremely high capability for sensitive detection of target without interference of environmental surrounding. This electroactive probe-confined graphene multilayer confers great flexibility to combine with differential pulse voltammetry (DPV) together. In the presence of target D entiomer of arginine vasopressin (D-VP), the binding of peptide to aptamer block the electron transfer process of MB, leading to decreased current peak of DPV. By this way, this electrochemical aptasensor based on electroactive molecule-intercalated graphene multilayer provide highly sensitive and specific detection of D-VP with the lowest detectable concentration of 1 ng mL −1 and a wide detection range from 1 to 265 ng mL −1 .

Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols for the Stereoselective Construction of C(20) in Steroid Side Chains: Scope and Topological Diversification.

Science.gov (United States)

Li, Houhua; Mazet, Clément

2015-08-26

The stereoselective construction of C20 in steroidal derivatives by a highly diastereoselective Ir-catalyzed isomerization of primary allylic alcohols is reported. A key aspect of this strategy is a straightforward access to geometrically pure steroidal enol tosylate and enol triflate intermediates for subsequent high yielding stereoretentive Negishi cross-coupling reactions to allow structural diversity to be introduced. A range of allylic alcohols participates in the diastereoselective isomerization under the optimized reaction conditions. Electron-rich and electron-poor aryl or heteroaryl substituents are particularly well-tolerated, and the stereospecific nature of the reaction provides indifferently access to the natural C20-(R) and unnatural C20-(S) configurations. Alkyl containing substrates are more challenging as they affect regioselectivity of iridium-hydride insertion. A rationale for the high diastereoselectivities observed is proposed for aryl containing precursors. The scope of our method is further highlighted through topological diversification in the side chain and within the polycyclic domain of advanced and complex steroidal architectures. These findings have the potential to greatly simplify access to epimeric structural analogues of important steroid scaffolds for applications in biological, pharmaceutical, and medical sciences.

Stereoselective Synthesis of(Z)-4-(2-Bromovinyl)benzenesulfonyl Azide and Its Synthetic Utility for the Transformation to(2)-N-[4-(2-Bromovinyl)benzenesulfonyl]imidates

Institute of Scientific and Technical Information of China (English)

ZHANG Wensheng; KUANG Chunxiang; YANG Qing

2009-01-01

A novel method for the stereoselective synthesis of(Z)-4-(2-bromovinyl)benzenesulfonyl azide by simultaneous azidation and debrorninative decarboxylation of anti-2,3-dibromo-3-(4-chlorosulfonylphenyl)propanoic acid using NaN3 only was developed.Facile transformation of(Z)-4-(2-bromovinyl)benzenesulfonyl azide to(Z)-N-[4(2-bromovinyl)benzenesulfonyl]imidates was also achieved by Cu-catalyzed three-component coulping of (Z)-4-(2-bromovinyi)benzenesulfonyl azide,terminal alkynes and alcohols/phenols.

Application of a genetic algorithm in the conformational analysis of methylene-acetal-linked thymine dimers in DNA: Comparison with distance geometry calculations

International Nuclear Information System (INIS)

Beckers, Mischa L.M.; Buydens, Lutgarde M.C.; Pikkemaat, Jeroen A.; Altona, Cornelis

1997-01-01

The three-dimensional spatial structure of a methylene-acetal-linked thymine dimer present in a 10 base-pair (bp) sense-antisense DNA duplex was studied with a genetic algorithm designed to interpret NOE distance restraints. Trial solutions were represented by torsion angles. This means that bond angles for the dimer trial structures are kept fixed during the genetic algorithm optimization. Bond angle values were extracted from a 10 bp sense-antisense duplex model that was subjected to energy minimization by means of a modified AMBER force field. A set of 63 proton-proton distance restraints defining the methylene-acetal-linked thymine dimer was available. The genetic algorithm minimizes the difference between distances in the trial structures and distance restraints. A large conformational search space could be covered in the genetic algorithm optimization by allowing a wide range of torsion angles. The genetic algorithm optimization in all cases led to one family of structures. This family of the methylene-acetal-linked thymine dimer in the duplex differs from the family that was suggested from distance geometry calculations. It is demonstrated that the bond angle geometry around the methylene-acetal linkage plays an important role in the optimization

Pyrite-enhanced methylene blue degradation in non-thermal plasma water treatment reactor

Energy Technology Data Exchange (ETDEWEB)

Benetoli, Luis Otavio de Brito, E-mail: luskywalcker@yahoo.com.br [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil); Cadorin, Bruno Mena; Baldissarelli, Vanessa Zanon [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil); Geremias, Reginaldo [Departamento de Ciencias Rurais, Universidade Federal de Santa Catarina (UFSC), Curitibanos, SC (Brazil); Goncalvez de Souza, Ivan [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil); Debacher, Nito Angelo, E-mail: debacher@qmc.ufsc.br [Departamento de Quimica, Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil)

2012-10-30

Highlights: Black-Right-Pointing-Pointer We use O{sub 2} as the feed gas and pyrite was added to the non-thermal plasma reactor. Black-Right-Pointing-Pointer The methylene blue removal by NTP increased in the presence of pyrite. Black-Right-Pointing-Pointer The total organic carbon content decreased substantially. Black-Right-Pointing-Pointer The acute toxicity test showed that the treated solution is not toxic. Black-Right-Pointing-Pointer The dye degradation occurs via electron impact as well as successive hydroxylation. - Abstract: In this study, methylene blue (MB) removal from an aqueous phase by electrical discharge non-thermal plasma (NTP) over water was investigated using three different feed gases: N{sub 2}, Ar, and O{sub 2}. The results showed that the dye removal rate was not strongly dependent on the feed gas when the electrical current was kept the same for all gases. The hydrogen peroxide generation in the water varied according to the feed gas (N{sub 2} < Ar < O{sub 2}). Using O{sub 2} as the feed gas, pyrite was added to the reactor in acid medium resulting in an accentuated increase in the dye removal, which suggests that pyrite acts as a Fenton-like catalyst. The total organic carbon (TOC) content of the dye solution decreased slightly as the plasma treatment time increased, but in the presence of the pyrite catalyst the TOC removal increased substantially. The acute toxicity test using Artemia sp. microcrustaceans showed that the treated solution is not toxic when Ar, O{sub 2} or O{sub 2}-pyrite is employed. Electrospray ionization mass spectrometry analysis (ESI-MS) of the treated samples indicated that the dye degradation occurs via high energy electron impact as well as successive hydroxylation in the benzene rings of the dye molecules.

3D Oxidized Graphene Frameworks: An Efficient Adsorbent for Methylene Blue

Science.gov (United States)

Pandey, Abhishek; Deb, Madhurima; Tiwari, Shreya; Pawar, Pranav Bhagwan; Saxena, Sumit; Shukla, Shobha

2018-04-01

Extraordinary properties of graphene and its derivatives have found application in varied areas such as energy, electronics, optical devices and sensors, to name a few. Large surface area along with specialized functional groups make these materials attractive for removal of dye molecules in solution via adsorption. Industrial effluents contain large amounts of toxic chemicals resulting in pollution of water bodies, which pose environmental hazards in general. Here we report application of 3D oxidized graphene frameworks in the efficient removal of cationic dye molecules such as methylene blue via adsorption. Systematic parametric studies investigating the effect of the initial dye concentration, pH and contact time have been performed. Spectroscopic analysis of the filtrate suggests that tortuous paths in 3D oxidized graphene frameworks result in efficient removal of dye molecules due to enhanced interaction. The hydroxyl groups retained in these 3D oxidized graphene frameworks facilitate adsorption of the dye molecules while passing through the adsorbent. pH studies suggest that maximum removal efficiency for methylene blue was achieved at pH value of 9. The results suggest that these 3D oxidized graphene frameworks can be used for purification of large volumes of contaminated water from cationic dyes in waste water treatment plants.

Sulfonamide antibiotic removal and nitrogen recovery from synthetic urine by the combination of rotating advanced oxidation contactor and methylene urea synthesis process

OpenAIRE

Fukahori, S.; Fujiwara, T.; Ito, R.; Funamizu, N.

2015-01-01

The combination of nitrogen recovery and pharmaceutical removal processes for livestock urine treatment were investigated to suppress the discharge of pollutants and recover nitrogen as resources. We combined methylene urea synthesis from urea and adsorption and photocatalytic decomposition of sulfonamide antibiotic using rotating advanced oxidation contactor (RAOC) contained for obtaining both safe fertilizer and reclaimed water. The methylene urea synthesis could recover urea in synthetic u...

Stereoselective synthesis of an iodinated resveratrol analog: Preliminary bioevaluation studies of the radioiodinated species

Energy Technology Data Exchange (ETDEWEB)

Dhyani, Manish V.; Kameswaran, Mythili; Korde, Aruna G.; Pandey, Usha [Radiopharmaceuticals Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Chattopadhyay, Subrata [Bio-Organic Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Banerjee, Sharmila, E-mail: sharmila@barc.gov.i [Radiopharmaceuticals Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2011-07-15

Stereoselective synthesis of an E-hydroxystilbene has been carried out using the McMurry reaction. Synthesis of a monoiodinated hydroxystilbene has been carried out by a McMurry cross-coupling reaction. For the purpose of biological evaluation, the facile electrophilic substitution route has been attempted to radioiodinate it with {sup 125}I. The HPLC pattern of the radioiodinated hydroxystilbene, which could be obtained in >90% radiochemical purity, was found to be identical to that of its non-radioactive analog that has been independently prepared using the McMurry cross-coupling route. In vitro cell uptake studies were carried out in breast cancer cells MCF7, overexpressing estrogen receptors. In vivo biodistribution studies in female Swiss mice show a uterine uptake of 0.85{+-}0.4% ID/g at 3 h.p.i. with a uterus to muscle ratio of 2.83. Uptake in the thyroid was insignificant indicating good in vivo stability of the radioiodinated hydroxystilbene.

Stereoselectivity of the demethylation of nicotine piperidine homologues by Nicotiana plumbaginifolia cell suspension cultures.

Science.gov (United States)

Bartholomeusz, Trixie Ann; Molinié, Roland; Roscher, Albrecht; Felpin, François-Xavier; Gillet, Françoise; Lebreton, Jacques; Mesnard, François; Robins, Richard J

2005-08-01

The metabolism of (R,S)-N-methylanabasine and (R,S)-N-methylanatabine has been studied in a cell suspension culture of Nicotiana plumbaginifolia. Both substrates are effectively demethylated, anabasine or anatabine, respectively, accumulating in the medium. Similarly, there is strong stereoselectivity for the (R)-isomers of both substrates. The kinetics of metabolism of (R,S)-N-methylanabasine differ significantly from those of nicotine in that no further degradation of the initial demethylation product occurs. (R,S)-N-Methylanatabine, however, shows kinetics closer to those of nicotine, with loss of alkaloid from the system. Further more, (R,S)-N-methylanabasine does not diminish (S)-nicotine demethylation, indicating a lack of competition. However, the metabolism of (S)-nicotine is affected by the presence of (R,S)-N-methylanabasine. Hence, the demethylation of the piperidine homologues of nicotine is seen to be similar but not identical to that of the pyridine analogues. The implications of these different metabolic profiles in relation to the demethylation activity are discussed.

Rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes with substituted allenes: stereoselective construction of tri- and tetrasubstituted exocyclic olefins.

Science.gov (United States)

Evans, P Andrew; Negru, Daniela E; Shang, Deju

2015-04-13

The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hybrid Monolith of Graphene/TEMPO-Oxidized Cellulose Nanofiber as Mechanically Robust, Highly Functional, and Recyclable Adsorbent of Methylene Blue Dye

Directory of Open Access Journals (Sweden)

Asif Hussain

2018-01-01

Full Text Available Herein we demonstrate first report on fabrication, characterization, and adsorptive appraisal of graphene/cellulose nanofibers (GO/CNFs monolith for methylene blue (MB dye. Series of hybrid monolith (GO/CNFs were assembled via urea assisted self-assembly method. Hybrid materials were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction patterns, Raman spectroscopy, elemental analysis, thermogravimetric curve analysis, specific surface area, surface charge density measurement, and compressional mechanical analysis. It was proposed that strong chemical interaction (mainly hydrogen bonding was responsible for the formation of hybrid assembly. GO/CNFs monolith showed mechanically robust architecture with tunable pore structure and surface properties. GO/CNFs adsorbent could completely remove trace to moderate concentrations of MB dye and follow pseudo-second-order kinetics model. Adsorption isotherm behaviors were found in the following order: Langmuir isotherm > Freundlich isotherm > Temkin isotherm model. Maximum adsorption capacity of 227.27 mg g−1 was achieved which is much higher than reported graphene based monoliths and magnetic adsorbent. Incorporation of nanocellulose follows exponential relationship with dye uptake capacities. High surface charge density and specific surface area were main dye adsorptive mechanism. Regeneration and recycling efficiency was achieved up to four consecutive cycles with cost-effective recollection and zero recontamination of treated water.

Microwave atmospheric pressure plasma jets for wastewater treatment: Degradation of methylene blue as a model dye.

Science.gov (United States)

García, María C; Mora, Manuel; Esquivel, Dolores; Foster, John E; Rodero, Antonio; Jiménez-Sanchidrián, César; Romero-Salguero, Francisco J

2017-08-01

The degradation of methylene blue in aqueous solution as a model dye using a non thermal microwave (2.45 GHz) plasma jet at atmospheric pressure has been investigated. Argon has been used as feed gas and aqueous solutions with different concentrations of the dye were treated using the effluent from plasma jet in a remote exposure. The removal efficiency increased as the dye concentration decreased from 250 to 5 ppm. Methylene blue degrades after different treatment times, depending on the experimental plasma conditions. Thus, kinetic constants up to 0.177 min -1 were obtained. The higher the Ar flow, the faster the degradation rate. Optical emission spectroscopy (OES) was used to gather information about the species present in the gas phase, specifically excited argon atoms. Argon excited species and hydrogen peroxide play an important role in the degradation of the dye. In fact, the conversion of methylene blue was directly related to the density of argon excited species in the gas phase and the concentration of hydrogen peroxide in the aqueous liquid phase. Values of energy yield at 50% dye conversion of 0.296 g/kWh were achieved. Also, the use of two plasma applicators in parallel has been proven to improve energy efficiency. Copyright © 2017 Elsevier Ltd. All rights reserved.

Combination photodynamic therapy of human breast cancer using salicylic acid and methylene blue

Science.gov (United States)

Hosseinzadeh, Reza; Khorsandi, Khatereh; Jahanshiri, Maryam

2017-09-01

The objective of this study was to evaluate the effects of combination therapy with methylene blue (MB) assisted photodynamic therapy (PDT) and salicylic acid (SA) as chemo-therapy anticancer agent. The binding of salicylic acid to methylene blue was studied using spectrophotometric method. The results show the 1:2 complex formation between SA and MB. The binding constants and related Gibbs free energies o are obtained (Kb1 = 183.74, Kb2 = 38.13 and ∆ Gb1° = 12.92 kJ·mol- 1, ∆ Gb2° =9.02 kJ·mol- 1). The spectrophotometric results show the improvement in solubilization and reduction prevention for SA and MB in the complex form. These results are in agreements with cellular experiments. The dark toxicity measurements represent the improve efficacy of chemotherapy using combination of SA and MB. The photodynamic therapy results (using red LED as light source (630 nm; power density: 30 mW cm- 2)) show that the cancer cell killing efficiency of MB increases in the combination with SA due to reduction prevention and stabilization of monomeric form of MB.

Removal of methylene blue from aqueous solution by adsorption onto pineapple leaf powder

International Nuclear Information System (INIS)

Weng, Chih-Huang; Lin, Yao-Tung; Tzeng, Tai-Wei

2009-01-01

The ability of an unconventional bio-adsorbent, pineapple leaf powder (PLP) for the adsorption of methylene blue (MB) from aqueous solution was studied. It was observed that intra-particle diffusion was involved in the adsorption process and that the kinetic data fitted well with a pseudo-second-order equation. Fitting parameters revealed that the rate of adsorption increased with decrease in dye concentration and decrease in ionic strength while the mixing speed did not have a significant effect on adsorption. The adsorption was favorable at higher pH and lower temperature, and the equilibrium data were well fitted by the Langmuir isotherm. The maximum adsorption capacity varied from 4.68 x 10 -4 to 9.28 x 10 -4 mol/g when pH increases from 3.5 to 9.5. Thermodynamic parameters suggest that the adsorption is a typical physical process, spontaneous, and exothermic in nature. The results revealed that this agricultural waste has potential to be used as an economical adsorbent for the removal of methylene blue from aqueous solution.

Removal of methylene blue from aqueous solution by adsorption onto pineapple leaf powder

Energy Technology Data Exchange (ETDEWEB)

Weng, Chih-Huang, E-mail: chweng@isu.edu.tw [Department of Civil and Ecological Engineering, I-Shou University, Da-Hsu Township, Kaohsiung 84008, Taiwan (China); Lin, Yao-Tung; Tzeng, Tai-Wei [Department of Soil and Environmental Sciences, National Chung Hsing University, TaiChung 40227, Taiwan (China)

2009-10-15

The ability of an unconventional bio-adsorbent, pineapple leaf powder (PLP) for the adsorption of methylene blue (MB) from aqueous solution was studied. It was observed that intra-particle diffusion was involved in the adsorption process and that the kinetic data fitted well with a pseudo-second-order equation. Fitting parameters revealed that the rate of adsorption increased with decrease in dye concentration and decrease in ionic strength while the mixing speed did not have a significant effect on adsorption. The adsorption was favorable at higher pH and lower temperature, and the equilibrium data were well fitted by the Langmuir isotherm. The maximum adsorption capacity varied from 4.68 x 10{sup -4} to 9.28 x 10{sup -4} mol/g when pH increases from 3.5 to 9.5. Thermodynamic parameters suggest that the adsorption is a typical physical process, spontaneous, and exothermic in nature. The results revealed that this agricultural waste has potential to be used as an economical adsorbent for the removal of methylene blue from aqueous solution.

Use of ZnO:Mn particles for degradation of methylene blue by photocatalysis process

International Nuclear Information System (INIS)

Giraldi, T. R.; Swerts, J. P.; Vicente, M. A.; Paris, E.C.; Ribeiro, C.

2016-01-01

The management of water use in the agricultural environment is a key factor to build new environmentally sustainable productive methods. Photocatalysis is a promising method for water decontamination. This research paper aimed to evaluate the photocatalytic potential of pure and Mn-doped ZnO particles. The materials were obtained by the polymeric precursor method, and characterized by X-ray diffraction, N_2 adsorption in low temperature, infrared and ultraviolet spectroscopy, and photoluminescence. In order to evaluate ZnO:Mn particles photo efficiency, experiments were carried out by applying the methylene blue dye solution to photodegradation under UVC exposure. The particles had ZnO single-phase, but low specific surface area. The sample ZnO:0.25% Mn presented higher efficiency in the methylene blue photocatalytic degradation test. This efficiency was related to a higher band gap energy value and a lower rate of electron recombination, which allows greater formation of hydroxyl radicals, which are responsible for dye degradation. (author)

L-allo-threonine aldolase with an H128Y/S292R mutation from Aeromonas jandaei DK-39 reveals the structural basis of changes in substrate stereoselectivity.

Science.gov (United States)

Qin, Hui-Min; Imai, Fabiana Lica; Miyakawa, Takuya; Kataoka, Michihiko; Kitamura, Nahoko; Urano, Nobuyuki; Mori, Koji; Kawabata, Hiroshi; Okai, Masahiko; Ohtsuka, Jun; Hou, Feng; Nagata, Koji; Shimizu, Sakayu; Tanokura, Masaru

2014-06-01

L-allo-Threonine aldolase (LATA), a pyridoxal-5'-phosphate-dependent enzyme from Aeromonas jandaei DK-39, stereospecifically catalyzes the reversible interconversion of L-allo-threonine to glycine and acetaldehyde. Here, the crystal structures of LATA and its mutant LATA_H128Y/S292R were determined at 2.59 and 2.50 Å resolution, respectively. Their structures implied that conformational changes in the loop consisting of residues Ala123-Pro131, where His128 moved 4.2 Å outwards from the active site on mutation to a tyrosine residue, regulate the substrate specificity for L-allo-threonine versus L-threonine. Saturation mutagenesis of His128 led to diverse stereoselectivity towards L-allo-threonine and L-threonine. Moreover, the H128Y mutant showed the highest activity towards the two substrates, with an 8.4-fold increase towards L-threonine and a 2.0-fold increase towards L-allo-threonine compared with the wild-type enzyme. The crystal structures of LATA and its mutant LATA_H128Y/S292R reported here will provide further insights into the regulation of the stereoselectivity of threonine aldolases targeted for the catalysis of L-allo-threonine/L-threonine synthesis.

Ionic imbalance and lack of effect of adjuvant treatment with methylene blue in the hamster model of leptospirosis

Directory of Open Access Journals (Sweden)

Cleiton Silva Santos

2013-06-01

Full Text Available Leptospirosis in humans usually involves hypokalaemia and hypomagnesaemia and the putative mechanism underlying such ionic imbalances may be related to nitric oxide (NO production. We previously demonstrated the correlation between serum levels of NO and the severity of renal disease in patients with severe leptospirosis. Methylene blue inhibits soluble guanylyl cyclase (downstream of the action of any NO synthase isoforms and was recently reported to have beneficial effects on clinical and experimental sepsis. We investigated the occurrence of serum ionic changes in experimental leptospirosis at various time points (4, 8, 16 and 28 days in a hamster model. We also determined the effect of methylene blue treatment when administered as an adjuvant therapy, combined with late initiation of standard antibiotic (ampicillin treatment. Hypokalaemia was not reproduced in this model: all of the groups developed increased levels of serum potassium (K. Furthermore, hypermagnesaemia, rather than magnesium (Mg depletion, was observed in this hamster model of acute infection. These findings may be associated with an accelerated progression to acute renal failure. Adjuvant treatment with methylene blue had no effect on survival or serum Mg and K levels during acute-phase leptospirosis in hamsters.

Photocatalytic Degradation of Methylene Blue Using TiO2 Impregnated Diatomite

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Ranfang Zuo

2014-01-01

Full Text Available Nano-TiO2 showed a good catalytic activity, but it is easy to agglomerate, resulting in the reduction or even complete loss of photocatalytic activity. The dispersion of TiO2 particles on porous materials was a potential solution to this problem. Diatomite has high specific surface and absorbability because of its particular shell structure. Thus, TiO2/diatomite composite, prepared by loading TiO2 on the surface of diatomite, was a good photocatalyst, through absorbing organic compounds with diatomite and degrading them with TiO2. Scanning electron microscopy (SEM, energy dispersive spectrum (EDS, X-ray diffraction (XRD, chemical analysis, and Fourier transform infrared spectrometry (FTIR indicated that TiO2 was impregnated well on the surface of diatomite. Furthermore, TiO2/diatomite was more active than nano-TiO2 for the degradation of methylene blue (MB in solution. MB at concentrations of 15 and 35 ppm can be completely degraded in 20 and 40 min, respectively.

Quantitative evaluation of plasma after methylene blue and white light treatment in four Chinese blood centers.

Science.gov (United States)

Chunhui, Yang; Guohui, Bian; Hong, Yang; Xiaopu, Xiao; Zherong, Bai; Mingyuan, Wang; Xinsheng, Zhang; Juanjuan, Wang; Changqing, Li; Wuping, Li

2013-12-01

Pathogen reduction technology is an important process in the blood safety system, including solvent/detergent treatment, filtration and methylene blue-photochemical technology (MB-PCT). To investigate the quality of MB-PCT-treated plasma, plasma samples from four Chinese blood centers were analyzed over 12 months of storage to determine the recovery of activities and levels of various plasma proteins. Ten plasma units each from the Suzhou, Yancheng, Chongqing and Shandong blood centers were divided into two aliquots. One was subjected to treatment with one of two methylene blue-photochemical technology instruments and the other was used as control. The treated and untreated sample pairs were stored at -30°C. The recovery rates of coagulation factors, inhibitor proteins, total protein, immunoglobulins, and complement proteins were measured at different time points after storage. The mean recovery of most proteins exceeded 80% after MB treatment. The exceptions were factor XI and fibrinogen, of which only 71.3-74% and 69.0-92.3% were retained during storage. The two equipment types differed in terms of residual MB concentration in the plasma samples (0.18 μM and 0.29 μM, respectively). They had similar protein recovery rates at 0.5 month but differed at later time points. The four blood centers differed significantly with regard to factor II, V, VIII and fibrinogen activities. Only the samples from the Shandong blood center met the methylene blue treated fresh frozen plasma requirement. The major factor that influenced the quality of the MB-FFP samples was the time taken between blood collection and storage. Methylene blue treated plasma showed reduced coagulation factor (CF) activity and protein levels. The MB treatment-induced damage to the proteins was acceptable at the four Chinese blood centers, but the quality of the MB-treated plasma in general was not satisfactory. The main factor affecting plasma quality may be the duration of the collection and

Improved photocatalytic activity of highly ordered TiO{sub 2} nanowire arrays for methylene blue degradation

Energy Technology Data Exchange (ETDEWEB)

Lv, Xiaojun, E-mail: xjlv@mail.ipc.ac.cn [Technical Institute of Physics and Chemistry, Key Laboratory of Photochemical Conversion and Optoelectronic Materials and HKU-CAS Joint Laboratory on New Materials, Chinese Academy of Sciences, Beijing 100190 (China); Zhang, Hao; Chang, Haixin [WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8578 (Japan)

2012-10-15

Although many efforts have been done on the photocatalytic properties of anodic TiO{sub 2} nanotubes, much less work is done on the photocatalytic performance of TiO{sub 2} nanowires. Self-organized anodic TiO{sub 2} nanowire arrays have been fabricated using a simple electrochemical approach and used as photocatalysts in photodegradation of methylene blue (MB) dyes. Here we found for the first time TiO{sub 2} nanowires have better photocatalytic properties and incident photon-to-current efficiency (IPCE) than TiO{sub 2} nanotubes. N doped TiO{sub 2} nanowires showed further enhancement in photodegradation activity and photocurrent response in the visible region. Such TiO{sub 2} nanowires are expected to have great potential in photodegradation of pollutants, photovoltaic solar energy conversion and water splitting for hydrogen generation as well. -- Highlights: Black-Right-Pointing-Pointer TiO{sub 2} nanowire arrays electrode fabricated via anodizing Ti foil. Black-Right-Pointing-Pointer TiO{sub 2} nanowire arrays have higher photodegradation activity. Black-Right-Pointing-Pointer N doped TiO{sub 2} nanowires enhanced visible-light photocatalytic activity.

Visible-Light Photocatalytic Decarboxylation of α,β-Unsaturated Carboxylic Acids: Facile Access to Stereoselective Difluoromethylated Styrenes in Batch and Flow

Science.gov (United States)

2017-01-01

The development of synthetic methodologies which provide access to both stereoisomers of α,β-disubstituted olefins is a challenging undertaking. Herein, we describe the development of an operationally simple and stereoselective synthesis of difluoromethylated styrenes via a visible-light photocatalytic decarboxylation strategy using fac-Ir(ppy)3 as the photocatalyst. Meta- and para-substituted cinnamic acids provide the expected E-isomer. In contrast, ortho-substituted cinnamic acids yield selectively the less stable Z-product, whereas the E-isomer can be obtained via continuous-flow processing through accurate control of the reaction time. Furthermore, our protocol is amenable to the decarboxylative difluoromethylation of aryl propiolic acids. PMID:29109904

A Novel of Buton Asphalt and Methylene Blue as Dye-Sensitized Solar Cell using TiO2/Ti Nanotubes Electrode

Science.gov (United States)

Nurhidayani; Muzakkar, M. Z.; Maulidiyah; Wibowo, D.; Nurdin, M.

2017-11-01

A study of TiO2/Ti nanotubes arrays (NTAs) based on Dye-Sensitized Solar Cell (DSSC) used Asphalt Buton (Asbuton) extract and methylene blue (MB) as a photosensitizer dye has been conducted. The aim of this research is that the Asbuton extract and Methylene Blue (MB) performance as a dye on DSSC solar cells is able to obtain the voltage-currents produced by visible light irradiation. Electrode TiO2/Ti NTAs have been successfully synthesized by anodizing methods, then characterized by using XRD showed that the anatase crystals formed. Subsequently, the morphology showed that the nanotubes formed which has coated by Asbuton extract. The DSSC system was formed by a sandwich structure and tested by using Multimeter Digital with Potentiostat instrument. The characteristics of current (I) and potential (V) versus time indicated that the Asbuton was obtained in a high-performance in 30s of 14,000µV 0.844µA, meanwhile MB dyes were 8,000µV0.573µA. Based on this research, the Asbuton extract from Buton Island-Southeast Sulawesi-Indonesia was potential for natural dyes in DSSC system.

Extraosseous uptake of sup(99m)technetium methylene diphosphonate: Neuroblastoma or radiation therapy

Energy Technology Data Exchange (ETDEWEB)

Sty, J R; Kun, L; Casper, J; Babbitt, D P [Wisconsin Univ., Milwaukee (USA). Dept. of Radiology

1980-01-01

A child with a ganglioneuroblastoma and tumor uptake of sup(99m)technetium methylene diphosphonate (sup(99m)Tc-MDP) is presented. After surgical removal of an encapsulated tumor and radiation therapy, an interval bone scan demonstrated the same presurgical abnormality. Awareness of abnormal uptake of sup(99m)Tc-MDP in irradiated renal tissue prevents interpreting radiation nephritis as recurrent tumor.

Hydrothermal synthesis of graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite for removal of Cu (II) and methylene blue

Science.gov (United States)

Long, Zhihang; Zhan, Yingqing; Li, Fei; Wan, Xinyi; He, Yi; Hou, Chunyan; Hu, Hai

2017-09-01

In this work, highly activated graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite adsorbent was prepared from a simple hydrothermal route by using ferrous sulfate as precursor. For this purpose, the graphene oxide/multiwalled carbon nanotube architectures were formed through the π-π attractions between them, followed by attaching Fe3O4 nanoparticles onto their surface. The structure and composition of as-prepared ternary nanocomposite were characterized by XRD, FTIR, XPS, SEM, TEM, Raman, TGA, and BET. It was found that the resultant porous graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite with large surface area could effectively prevent the π-π stacking interactions between graphene oxide nanosheets and greatly improve sorption sites on the surfaces. Thus, owing to the unique ternary nanocomposite architecture and synergistic effect among various components, as-prepared ternary nanocomposite exhibited high separation efficiency when they were used to remove the Cu (II) and methylene blue from aqueous solutions. Furthermore, the adsorption isotherms of ternary nanocomposite structures for Cu (II) and methylene blue removal fitted the Langmuir isotherm model. This work demonstrated that the graphene oxide/multiwalled carbon nanotube/Fe3O4 ternary nanocomposite was promising as an efficient adsorbent for heavy metal ions and organic dye removal from wastewater in low concentration.

Phospholyl(borane) Amino Acids and Peptides: Stereoselective Synthesis and Fluorescent Properties with Large Stokes Shift.

Science.gov (United States)

Arribat, Mathieu; Rémond, Emmanuelle; Clément, Sébastien; Lee, Arie Van Der; Cavelier, Florine

2018-01-24

The synthesis of phospholyl(borane) amino acids was stereoselectively achieved by reaction of phospholide anion with iodo α-amino ester derived from l-aspartic acid or l-serine, followed by in situ complexation with borane. Phospholyl(borane) amino acids are easy to store and can be subjected to direct transformation into the corresponding free phospholyl, gold complex, oxide or sulfur derivatives as well as phospholinium salts, thus offering a variety of side chains. After selective deprotection of carboxylic function or amine, C- or N- peptide coupling with an alanine moiety proved the possible incorporation into peptides. Such phospholyl amino acid and peptide derivatives exhibit fluorescent properties with a large Stokes shift (160 nm) and fluorescence up to 535 nm, depending on the phosphole aromaticity and the chemical environment. These phospholyl(borane) amino acids constitute a new class of unnatural amino acids useful for structure-activities relationship studies and appear to be promising fluorophores for the development of labeled peptides.

Methylene Blue-Aided In Vivo Staining of Central Airways during Flexible Bronchoscopy

Directory of Open Access Journals (Sweden)

Sabine Zirlik

2012-01-01

Full Text Available Background. The early diagnosis of malignant and premalignant changes of the bronchial mucosa remains a major challenge during bronchoscopy. Intravital staining techniques are not new. Previous small case series suggested that analysis of the bronchial mucosal surface using chromoendoscopy allows a prediction between neoplastic and nonneoplastic lesions. Objectives. The aim of the present study was to evaluate chromobronchoscopy as a method to identify malignant and premalignant lesions in the central airways in a prospective manner. Methods. In 26 patients we performed chromoendoscopy with 0.1% methylene blue during ongoing flexible white light bronchoscopy. Circumscribed lesions in central airways were further analyzed by biopsies and histopathologic examination. Results. In the majority of cases neither flat nor polypoid lesions in the central airways were stained by methylene blue. In particular, exophytic growth of lung cancer did not show any specific pattern in chromobronchoscopy. However, a specific dye staining was detected in one case where exophytic growth of metastatic colorectal cancer was present in the right upper lobe. In two other cases, a circumscribed staining was noted in unsuspicious mucosa. But histology revealed inflammation only. Conclusions. In contrast to previous studies, the present findings clearly indicate that chromobronchoscopy is not useful for early detection of malignant or premalignant lesions of the central airways.

Nanostructure CdS/ZnO heterojunction configuration for photocatalytic degradation of Methylene blue

Science.gov (United States)

Velanganni, S.; Pravinraj, S.; Immanuel, P.; Thiruneelakandan, R.

2018-04-01

In the present manuscript, thin films of Zinc Oxide (ZnO) have been deposited on a FTO substrate using a simple successive ionic layer adsorption and reaction (SILAR) and chemical bath deposition (CBD) method. Cadmium Sulphide (CdS) nanoparticles are sensitized over ZnO thin films using SILAR method. The synthesized nanostructured CdS/ZnO heterojunction thin films was characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), High resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), UV-Vis spectroscopy and Raman spectroscopy techniques. The band gap of CdS nanoparticles over ZnO nanostructure was found to be about 3.20 eV. The photocatalytic activities of the deposited CdS/ZnO thin films were evaluated by the degradation of methylene blue (MB) in an aqueous solution under sun light irradiation.

Stereoselective synthesis of the Halaven C14-C26 fragment from D-quinic acid: crystallization-induced diastereoselective transformation of an α-methyl nitrile.

Science.gov (United States)

Belanger, Francis; Chase, Charles E; Endo, Atsushi; Fang, Francis G; Li, Jing; Mathieu, Steven R; Wilcoxen, Annie Z; Zhang, Huiming

2015-04-20

Crystallization-induced diastereoselective transformation (CIDT) of an α-methyl nitrile completes an entirely non-chromatographic synthesis of the halichondrin B C14-C26 stereochemical array. The requisite α-methyl nitrile substrate is derived from D-quinic acid through a series of substrate-controlled stereoselective reactions via a number of crystalline intermediates that benefit from a rigid polycyclic template. Therefore, all four stereogenic centers in the Halaven C14-C26 fragment were derived from the single chiral source D-quinic acid. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Permeation of lysosomal membranes in the course of photo-sensitization with methylene blue and hematoporphyrin: study by cellular microspectrofluorometry

International Nuclear Information System (INIS)

Santus, R.; Kohen, C.; Kohen, E.; Morliere, P.; Dubertret, L.; Tocci, P.M.

1983-01-01

The photodynamically-induced liberation of lysosomal enzymes using β-galactosidase as marker for the lysosomal enzymes has been studied by microspectrofluorometry on mouse L cells. Similar studies have been carried out using N-acetyl-β-glucosaminidase as marker for the lysosomal enzymes of human fibroblasts. The high sensitivity of the fluorescence detection makes it possible to use 4-methylumbelliferyl substrates for the enzymes contained in a single cell. Methylene blue and hematoporphyrin readily incorporate into both cells and upon excitation, sensitize lysosomal membrane damages, leading to enzyme release accompanying strong morphological changes. (author)

Large-scale synthesis of tert-butyl (3R,5S)-6-chloro-3,5-dihydroxyhexanoate by a stereoselective carbonyl reductase with high substrate concentration and product yield.

Science.gov (United States)

Liu, Zhi-Qiang; Hu, Zhong-Liang; Zhang, Xiao-Jian; Tang, Xiao-Ling; Cheng, Feng; Xue, Ya-Ping; Wang, Ya-Jun; Wu, Lin; Yao, Dan-Kai; Zhou, Yi-Teng; Zheng, Yu-Guo

2017-05-01

To biosynthesize the (3R,5S)-CDHH in an industrial scale, a newly synthesized stereoselective short chain carbonyl reductase (SCR) was successfully cloned and expressed in Escherichia coli. The fermentation of recombinant E. coli harboring SCR was carried out in 500 L and 5000 L fermenters, with biomass and specific activity of 9.7 g DCW/L, 15749.95 U/g DCW, and 10.97 g DCW/L, 19210.12 U/g DCW, respectively. The recombinant SCR was successfully applied for efficient production of (3R,5S)-CDHH. The scale-up synthesis of (3R,5S)-CDHH was performed in 5000 L bioreactor with 400 g/L of (S)-CHOH at 30°C, resulting in a space-time yield of 13.7 mM/h/g DCW, which was the highest ever reported. After isolation and purification, the yield and d.e. of (3R,5S)-CDHH reached 97.5% and 99.5%, respectively. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:612-620, 2017. © 2017 American Institute of Chemical Engineers.

Reagentless D-sorbitol biosensor based on D-sorbitol dehydrogenase immobilized in a sol-gel carbon nanotubes-poly(methylene green) composite.

Science.gov (United States)

Wang, Zhijie; Etienne, Mathieu; Urbanova, Veronika; Kohring, Gert-Wieland; Walcarius, Alain

2013-04-01

A reagentless D-sorbitol biosensor based on NAD-dependent D-sorbitol dehydrogenase (DSDH) immobilized in a sol-gel carbon nanotubes-poly(methylene green) composite has been developed. It was prepared by durably immobilizing the NAD(+) cofactor with DSDH in a sol-gel thin film on the surface of carbon nanotubes functionalized with poly(methylene green). This device enables selective determination of D-sorbitol at 0.2 V with a sensitivity of 8.7 μA mmol(-1) L cm(-2) and a detection limit of 0.11 mmol L(-1). Moreover, this biosensor has excellent operational stability upon continuous use in hydrodynamic conditions.

Stereoselective toxicity of etoxazole to MCF-7 cells and its dissipation behavior in citrus and soil.

Science.gov (United States)

Sun, Dali; Pang, Junxiao; Fang, Qi; Zhou, Zhiqin; Jiao, Bining

2016-12-01

The stereoselective cytotoxicity of new chiral acaricide etoxazole and its dissipation in citrus and soil were investigated for the first time. Enantioselective toxicity and oxidative stress of etoxazole toward MCF-7 cells was conducted. The phenomenon of dose- and form-dependent cytotoxicity was demonstrated by MTT and LDH assays, ROS generation, and SOD and CAT activity alternation. Cytotoxicity ranks were found to be consistent with oxidative damage as (R)- > Rac- > (S)-etoxazole. Moreover, the results of enantioselective degradation showed that (S)-etoxazole degraded faster than its antipode (R)-etoxazole. The gradual raise of EF values indicated the achievement of enantioselective degradation in citrus and soil, leaving the enrichment of (R)-etoxazole isomer. Significant differences of environmental behavior and cytotoxicity of etoxazole enantiomers were found in this study which provided valuable insight into the mechanism of potential toxicity and warranted more careful assessment of this pesticide before its agricultural application.

Is Cytox 3522 (10% methylene-bis-thiocyanate) a human skin sensitizer?

DEFF Research Database (Denmark)

Andersen, Klaus Ejner; Hamann, K

1983-01-01

Methylene-bis-thiocyanate is an antimicrobial agent in Cytox 3522 (American Cyanamid Corporation) and Nalco 206 (Nalco Chemical Company). Both are wide-spectrum industrial biocides. Cytox 3522 showed a strong sensitization potential in guineau pigs using the Guinea Pig Maximization Test and the O...... and the Open Epicutaneous Test procedures. In spite of this, human sensitization has not been reported. This may be explained by several factors such as limited exposure, low-use concentration and a lack of diagnostic patch tests in selected patients....

Extraosseous uptake of sup(99m)technetium methylene diphosphonate: Neuroblastoma or radiation therapy

International Nuclear Information System (INIS)

Sty, J.R.; Kun, L.; Casper, J.; Babbitt, D.P.

1980-01-01

A child with a ganglioneuroblastoma and tumor uptake of sup(99m)technetium methylene diphosphonate (sup(99m)Tc-MDP) is presented. After surgical removal of an encapsulated tumor and radiation therapy, an interval bone scan demonstrated the same presurgical abnormality. Awareness of abnormal uptake of sup(99m)Tc-MDP in irradiated renal tissue prevents interpreting radiation nephritis as recurrent tumor. (orig.) [de

Oxygen Vacancy-Mediated ZnO Nanoparticle Photocatalyst for Degradation of Methylene Blue

Directory of Open Access Journals (Sweden)

Qiuping Zhang

2018-02-01

Full Text Available ZnO nanoparticles (NPs are synthesized by deoxidizing ZnO powder in a vacuum drying process. This process reduces the size of the NPs and increases the concentration of oxygen vacancies on their surfaces. ZnO NPs with sufficient oxygen vacancies are highly effective for the photodecomposition of methylene blue (MB dye in water under ultraviolet irradiation. The MB degradation efficiency exceeds 99 percent after 50 min of light irradiation, and the catalytic property of the NPs remains stable over several complete degradation cycles. It is revealed that the concentration of oxygen vacancies on the surface, and the photocatalytic activity, are both higher for smaller NPs. Oxygen vacancies reduce the recombination rate of photo-generated charge carriers by capturing the electrons and hence, improve the efficiency of redox reactions. In addition, a smaller particle size leads to a larger specific surface area and a higher photonic efficiency for the ZnO NPs.

Regenerable, innovative porous silicon-based polymer-derived ceramics for removal of methylene blue and rhodamine B from textile and environmental waters.

Science.gov (United States)

Bruzzoniti, Maria Concetta; Appendini, Marta; Onida, Barbara; Castiglioni, Michele; Del Bubba, Massimo; Vanzetti, Lia; Jana, Prasanta; Sorarù, Gian Domenico; Rivoira, Luca

2018-04-01

The presence of residual color in treated textile wastewater above the regulation limits is still a critical issue in many textile districts. Innovative, polymer-derived ceramics of the Si-C-O system were here synthesized in order to obtain porous nanocomposite materials where a free carbon phase is dispersed into a silicon carbide/silicon oxycarbide network. The sorbents were comprehensively characterized for the removal of two model water-soluble dyes (i.e., the cation methylene blue and the zwitterion rhodamine B). Adsorption is very rapid and controlled by intra-particle and/or film diffusion, depending on dye concentration. Among the nanocomposites studied, the SiOC aerogel (total capacity about 45 mg/g, is easily regenerated under mild treatment (250 °C, 2 h). Adsorption of dyes is not affected by the matrix composition: removals of 150 mg/L methylene blue from river water and simulated textile wastewater with high content of metal ions (2-50 mg/L) and chemical oxygen demand (800 mg/L) were higher than 92% and quantitative for a dye concentration of 1 mg/L.

Role of methylene spacer in the excitation energy transfer in europium 1- and 2- naphthylcarboxylates

Energy Technology Data Exchange (ETDEWEB)

Zhuravlev, K. [V.A. Kotelnikov Institute of Radioengineering and Electronics of RAS, 1 Vvedenskii sq., Fryazino Moscow reg. 141190 (Russian Federation); Tsaryuk, V., E-mail: vit225@ire216.msk.s [V.A. Kotelnikov Institute of Radioengineering and Electronics of RAS, 1 Vvedenskii sq., Fryazino Moscow reg. 141190 (Russian Federation); Kudryashova, V.; Pekareva, I. [V.A. Kotelnikov Institute of Radioengineering and Electronics of RAS, 1 Vvedenskii sq., Fryazino Moscow reg. 141190 (Russian Federation); Sokolnicki, J. [Faculty of Chemistry, University of WrocLaw, 14 F. Joliot-Curie str., WrocLaw 50-383 (Poland); Yakovlev, Yu. [V.A. Kotelnikov Institute of Radioengineering and Electronics of RAS, 1 Vvedenskii sq., Fryazino Moscow reg. 141190 (Russian Federation)

2010-08-15

A series of compounds Ln(RCOO){sub 3}.Phen (Ln=Eu, Gd, Tb; RCOO{sup -}-1- and 2-naphthoate, 1- and 2-naphthylacetate, 1- and 2-naphthoxyacetate anions, Phen-1,10-phenanthroline) was investigated by methods of optical spectroscopy. Compounds of composition Ln(RCOO){sub 3}.nH{sub 2}O with the same carboxylate ligands are also considered. Results of studies of the effects of methylene spacer decoupling the {pi}-{pi}- or p-{pi}-conjugation in the naphthylcarboxylate ligand on the structure of Eu{sup 3+} coordination centre, on the lifetime of {sup 5}D{sub 0} (Eu{sup 3+}) state, and on processes of the excitation energy transfer to Eu{sup 3+} or Tb{sup 3+} ions are presented. Introduction of the methylene bridge in the ligand weakens the influence of the steric hindrances in forming of a crystal lattice and results in lowering the distortion of the Eu{sup 3+} luminescence centre, and in elongation of the observed {sup 5}D{sub 0} lifetime {tau}{sub obs}. The latter is caused by decrease in contribution of the radiative processes rate 1/{tau}{sub r}. This is confirmed by the correlation between the lifetimes {tau}{sub obs} and the quantities '{tau}{sub r}.const' inversely proportional to the total integral intensities of Eu(RCOO){sub 3}.Phen luminescence spectra. The methylene spacer performs a role of regulator of sensitization of the Ln{sup 3+} luminescence efficiency by means of an influence on mutual location of lowest triplet states of the ligands, the ligand-metal charge transfer (LMCT) states, and the emitting states of Ln{sup 3+} ions. The lowest triplet state in lanthanide naphthylcarboxylate adducts with Phen is related to carboxylate anion. A presence of the methylene spacer in naphthylcarboxylate ligand increases the triplet state energy. At the same time, the energy of 'carboxylic group-Eu{sup 3+} ion' charge transfer states falls, which can promote the degradation of excitation energy. In naphthylcarboxylates investigated a range of the

The antimalarial activities of methylene blue and the 1,4-naphthoquinone 3-[4-(trifluoromethyl)benzyl]-menadione are not due to inhibition of the mitochondrial electron transport chain.

Science.gov (United States)

Ehrhardt, Katharina; Davioud-Charvet, Elisabeth; Ke, Hangjun; Vaidya, Akhil B; Lanzer, Michael; Deponte, Marcel

2013-05-01

Methylene blue and a series of recently developed 1,4-naphthoquinones, including 3-[4-(substituted)benzyl]-menadiones, are potent antimalarial agents in vitro and in vivo. The activity of these structurally diverse compounds against the human malaria parasite Plasmodium falciparum might involve their peculiar redox properties. According to the current theory, redox-active methylene blue and 3-[4-(trifluoromethyl)benzyl]-menadione are "subversive substrates." These agents are thought to shuttle electrons from reduced flavoproteins to acceptors such as hemoglobin-associated or free Fe(III)-protoporphyrin IX. The reduction of Fe(III)-protoporphyrin IX could subsequently prevent essential hemoglobin digestion and heme detoxification in the parasite. Alternatively, owing to their structures and redox properties, methylene blue and 1,4-naphthoquinones might also affect the mitochondrial electron transport chain. Here, we tested the latter hypothesis using an established system of transgenic P. falciparum cell lines and the antimalarial agents atovaquone and chloroquine as controls. In contrast to atovaquone, methylene blue and 3-[4-(trifluoromethyl)benzyl]-menadione do not inhibit the mitochondrial electron transport chain. A systematic comparison of the morphologies of drug-treated parasites furthermore suggests that the three drugs do not share a mechanism of action. Our findings support the idea that methylene blue and 3-[4-(trifluoromethyl)benzyl]-menadione exert their antimalarial activity as redox-active subversive substrates.

Liver metastases of breast carcinoma detected on /sup 99m/Tc-methylene diphosphonate bone scan

International Nuclear Information System (INIS)

Baumert, J.E.; Lantieri, R.L.; Horning, S.; McDougall, I.R.

1980-01-01

The accumulation of bone-seeking radiopharmaceuticals has been reported in liver metastases from colon carcinoma and oat cell carcinoma of the lung. Two patients with breast carcinoma in whom hepatic metastases were visualized on /sup 99m/Tc-methylene diphosphonate bone images are described. This has not been previously reported

Stereoselective Synthesis of 8,12-Furanoeudesmanes from Santonin. Absolute Stereochemistry of Natural Furanoeudesma-1,3-diene and Tubipofurane.

Science.gov (United States)

Blay, Gonzalo; Cardona, Luz; García, Begoña; Pedro, José R.; Sánchez, Juan J.

1996-05-31

Ketobutenolide 3, easily obtained from santonin (1), has been transformed into two natural furanoeudesmanes 4 and 5, isolated from Commiphora molmol and Tubipora musica, respectively. trans- And cis-decalin systems were obtained by stereoselective reduction of the C(4)-C(5) double bond in 3 in the following way: hydrogenation of 3 over Pd/C followed by acidic treatment gave the cis isomer 10 as the major product; selective hydrogenation of the C(1)-C(2) double bond with the Wilkinson's catalyst followed by reduction with NaTeH yielded mainly the trans isomer 9. Compounds 9 and 10 were transformed into 4 and 5 in parallel sequences. Optical rotation and CD measurements of the synthetic products revealed that the stereochemistry of both natural products should be revised to their enantiomeric form.

P25-graphene hydrogels: room-temperature synthesis and application for removal of methylene blue from aqueous solution.

Science.gov (United States)

Hou, Chengyi; Zhang, Qinghong; Li, Yaogang; Wang, Hongzhi

2012-02-29

Herein we report a room-temperature synthesis of chemically bonded TiO2 (P25)-graphene composite hydrogels and their use as high performance visible light photocatalysts. The three-dimensional (3D) TiO2-carbon composite exhibits a significant enhancement in the reaction rate in the decontamination of methylene blue, compared to the bare P25. The 3D P25-graphene hydrogel is much easier to prepare and apply as a macroscopic device, compared to the 2D P25-graphene sheets. This work could provide new insights into the room-temperature synthesis of graphene-based materials. As a kind of the novel 3D graphene-based composite, the obtained high performance P25-graphene gel could be widely used in the environmental protection issues. Copyright © 2012. Published by Elsevier B.V.

Breakdown of methylene blue and methyl orange by pulsed corona discharge

Science.gov (United States)

Grabowski, L. R.; van Veldhuizen, E. M.; Pemen, A. J. M.; Rutgers, W. R.

2007-05-01

The recently developed corona above water technique is applied to water containing 10 mg l-1 methylene blue (MB) or methyl orange (MO). The corona discharge pulses are created with a spark gap switched capacitor followed by a transmission line transformer. The pulse amplitude is 40 kV; its duration is 50 ns. At a pulse repetition rate of 10 Hz this leads to an average power of 0.6 W into the discharge. MB and MO are completely decolourized in ~20 min. This corresponds to a yield of ~4.5 gr kW-1h-1, which is much higher than obtained with other discharge techniques or sonoluminescence. The high yield is reflected in the observed temperature increase of only ~1 K. Tests with additional chemicals show that the initial speed of the conversion can be influenced but the total time required for total decolourization is constant. Further, it follows that the main oxidation path of the dyes is by direct ozone attack and the conversion products are strong acids.

Breakdown of methylene blue and methyl orange by pulsed corona discharge

Energy Technology Data Exchange (ETDEWEB)

Grabowski, L R [Department of Applied Physics, Technische Universiteit Eindhoven (Netherlands); Veldhuizen, E M van [Department of Applied Physics, Technische Universiteit Eindhoven (Netherlands); Pemen, A J M [Department of Electrical Engineering, Technische Universiteit Eindhoven (Netherlands); Rutgers, W R [Department of Applied Physics, Technische Universiteit Eindhoven (Netherlands)

2007-05-15

The recently developed corona above water technique is applied to water containing 10 mg l{sup -1} methylene blue (MB) or methyl orange (MO). The corona discharge pulses are created with a spark gap switched capacitor followed by a transmission line transformer. The pulse amplitude is 40 kV; its duration is 50 ns. At a pulse repetition rate of 10 Hz this leads to an average power of 0.6 W into the discharge. MB and MO are completely decolourized in {approx}20 min. This corresponds to a yield of {approx}4.5 gr kW{sup -1}h{sup -1}, which is much higher than obtained with other discharge techniques or sonoluminescence. The high yield is reflected in the observed temperature increase of only {approx}1 K. Tests with additional chemicals show that the initial speed of the conversion can be influenced but the total time required for total decolourization is constant. Further, it follows that the main oxidation path of the dyes is by direct ozone attack and the conversion products are strong acids.

Breakdown of methylene blue and methyl orange by pulsed corona discharge

International Nuclear Information System (INIS)

Grabowski, L R; Veldhuizen, E M van; Pemen, A J M; Rutgers, W R

2007-01-01

The recently developed corona above water technique is applied to water containing 10 mg l -1 methylene blue (MB) or methyl orange (MO). The corona discharge pulses are created with a spark gap switched capacitor followed by a transmission line transformer. The pulse amplitude is 40 kV; its duration is 50 ns. At a pulse repetition rate of 10 Hz this leads to an average power of 0.6 W into the discharge. MB and MO are completely decolourized in ∼20 min. This corresponds to a yield of ∼4.5 gr kW -1 h -1 , which is much higher than obtained with other discharge techniques or sonoluminescence. The high yield is reflected in the observed temperature increase of only ∼1 K. Tests with additional chemicals show that the initial speed of the conversion can be influenced but the total time required for total decolourization is constant. Further, it follows that the main oxidation path of the dyes is by direct ozone attack and the conversion products are strong acids

Total synthesis of bryostatins: the development of methodology for the atom-economic and stereoselective synthesis of the ring C subunit.

Science.gov (United States)

Trost, Barry M; Frontier, Alison J; Thiel, Oliver R; Yang, Hanbiao; Dong, Guangbin

2011-08-22

Bryostatins, a family of structurally complicated macrolides, exhibit an exceptional range of biological activities. The limited availability and structural complexity of these molecules makes development of an efficient total synthesis particularly important. This article describes our initial efforts towards the total synthesis of bryostatins, in which chemoselective and atom-economical methods for the stereoselective assembly of the ring C subunit were developed. A Pd-catalyzed tandem alkyne-alkyne coupling/6-endo-dig cyclization sequence was explored and successfully pursued in the synthesis of a dihydropyran ring system. Elaboration of this methodology ultimately led to a concise synthesis of the ring C subunit of bryostatins. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Post-operative outcomes following the excision of dorsal wrist ganglions with/without the use of Methylene Blue

Directory of Open Access Journals (Sweden)

Suleyman Tas

2016-04-01

Conclusions: The recurrence of cysts is rare after complete excision, particularly when rupture is prevented. Methylene blue injection is useful for ensuring complete excision and, therefore, to prevent recurrence. [Hand Microsurg 2016; 5(1.000: 1-6

SU-E-I-64: Transverse Relaxation Time in Methylene Protons of Non-Alcoholic Fatty Liver Disease Rats

Energy Technology Data Exchange (ETDEWEB)

Song, K-H; Lee, D-W; Choe, B-Y [Department of Biomedical Engineering, Research Institute of Biomedical Engineering, College of Medicine, The Catholic University of Korea, Seoul, Seoul (Korea, Republic of)

2015-06-15

Purpose: The aim of this study was to evaluate transverse relaxation time of methylene resonance compared to other lipid resonances. Methods: The examinations were performed using a 3.0 T scanner with a point — resolved spectroscopy (PRESS) sequence. Lipid relaxation time in a lipid phantom filled with canola oil was estimated considering repetition time (TR) as 6000 msec and echo time (TE) as 40 — 550 msec. For in vivo proton magnetic resonance spectroscopy ({sup 1}H — MRS), eight male Sprague — Dawley rats were given free access to a normal - chow (NC) and eight other male Sprague-Dawley rats were given free access to a high — fat (HF) diet. Both groups drank water ad libitum. T{sub 2} measurements in the rats’ livers were conducted at a fixed TR of 6000 msec and TE of 40 – 220 msec. Exponential curve fitting quality was calculated through the coefficients of determination (R{sup 2}). Results: A chemical analysis of phantom and liver was not performed but a T{sub 2} decay curve was acquired. The T{sub 2} relaxation time of methylene resonance was estimated as follows: NC rats, 37.07 ± 4.32 msec; HF rats, 31.43 ± 1.81 msec (p < 0.05). The extrapolated M0 values were higher in HF rats than in NC rats (p < 0.005). Conclusion: This study of {sup 1}H-MRS led to sufficient spectral resolution and signal — to — noise ratio differences to characterize all observable resonances for yielding T{sub 2} relaxation times of methylene resonance. {sup 1}H — MRS relaxation times may be useful for quantitative characterization of various liver diseases, including fatty liver disease. This study was supported by grant (2012-007883 and 2014R1A2A1A10050270) from the Mid-career Researcher Program through the NRF funded by Ministry of Science. In addition, this study was supported by the Industrial R&D of MOTIE/KEIT (10048997, Development of the core technology for integrated therapy devices based on real-time MRI-guided tumor tracking)

Complexing Methylene Blue with Phosphorus Dendrimers to Increase Photodynamic Activity

Directory of Open Access Journals (Sweden)

Monika Dabrzalska

2017-02-01

Full Text Available The efficiency of photodynamic therapy is limited mainly due to low selectivity, unfavorable biodistribution of photosensitizers, and long-lasting skin sensitivity to light. However, drug delivery systems based on nanoparticles may overcome the limitations mentioned above. Among others, dendrimers are particularly attractive as carriers, because of their globular architecture and high loading capacity. The goal of the study was to check whether an anionic phosphorus dendrimer is suitable as a carrier of a photosensitizer—methylene blue (MB. As a biological model, basal cell carcinoma cell lines were used. We checked the influence of the MB complexation on its singlet oxygen production ability using a commercial fluorescence probe. Next, cellular uptake, phototoxicity, reactive oxygen species (ROS generation, and cell death were investigated. The MB-anionic dendrimer complex (MB-1an was found to generate less singlet oxygen; however, the complex showed higher cellular uptake and phototoxicity against basal cell carcinoma cell lines, which was accompanied with enhanced ROS production. Owing to the obtained results, we conclude that the photodynamic activity of MB complexed with an anionic dendrimer is higher than free MB against basal cell carcinoma cell lines.

Highly efficient Fenton and enzyme-mimetic activities of NH2-MIL-88B(Fe) metal organic framework for methylene blue degradation.

Science.gov (United States)

He, Jianchuan; Zhang, Yao; Zhang, Xiaodan; Huang, Yuming

2018-03-26

Here, we show that NH 2 -MIL-88B(Fe) can be used as a peroxidase-like catalyst for Fenton-like degradation of methylene blue (MB) in water. The iron-based NH 2 -MIL-88B(Fe) metal organic framework (MOF) was synthesized by a facile and rapid microwave heating method. It was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, powder X-ray diffraction, and the Brunauer-Emmett-Teller method. The NH 2 -MIL-88B(Fe) MOF possesses intrinsic oxidase-like and peroxidase-like activities. The reaction parameters that affect MB degradation were investigated, including the solution pH, NH 2 -MIL-88B(Fe) MOF and H 2 O 2 concentrations, and temperature. The results show that the NH 2 -MIL-88B(Fe) MOF exhibits a wide working pH range (pH 3.0-11.0), temperature tolerance, and good recyclability for MB removal. Under the optimal conditions, complete removal of MB was achieved within 45 min. In addition, removal of MB was above 80% after five cycles, showing the good recyclability of NH 2 -MIL-88B(Fe). The NH 2 -MIL-88B(Fe) MOF has the features of easy preparation, high efficiency, and good recyclability for MB removal in a wide pH range. Electron spin resonance and fluorescence probe results suggest the involvement of hydroxyl radicals in MB degradation. These findings provide new insight into the application of high-efficient MOF-based Fenton-like catalysts for water purification.

SOURCE CHARACTERIZATION AND CONTROL TECHNOLOGY ASSESSMENT OF METHYLENE CHLORIDE EMISSIONS FROM EASTMAN KODAK COMPANY, ROCHESTER, NY

Science.gov (United States)

The report gives results of an assessment of potential control technologies for methylene chloride (also known as dichloromethane or DCM) emission sources at Eastman Kodak Company's Kodak Park facility in Rochester, NY. DCM is a solvent used by Kodak in the manufacture of cellulo...

Photocatalytic degradation of methylene blue dye by zinc oxide nanoparticles obtained from precipitation and sol-gel methods.

Science.gov (United States)

Balcha, Abebe; Yadav, Om Prakash; Dey, Tania

2016-12-01

Zinc oxide (ZnO) nanoparticles were synthesized by precipitation and sol-gel methods. The aim of this study was to understand how different synthetic methods can affect the photocatalytic activity of ZnO nanoparticles. As-synthesized ZnO nanoparticles were characterized by X-ray diffraction (XRD) and UV-Visible spectroscopic techniques. XRD patterns of ZnO powders synthesized by precipitation and sol-gel methods revealed their hexagonal wurtzite structure with crystallite sizes of 30 and 28 nm, respectively. Their photocatalytic activities were evaluated by photocatalytic degradation of methylene blue, a common water pollutant, under UV radiation. The effects of operational parameters such as photocatalyst load and initial concentration of the dye on photocatalytic degradation of methylene blue were investigated. While the degradation of dye decreased over the studied dye concentration range of 20 to 100 mg/L, an optimum photocatalyst load of 250 mg/L was needed to achieve dye degradation as high as 81 and 92.5 % for ZnO prepared by precipitation and sol-gel methods, respectively. Assuming pseudo first-order reaction kinetics, this corresponded to rate constants of 8.4 × 10 -3 and 12.4 × 10 -3  min -1 , respectively. Hence, sol-gel method is preferred over precipitation method in order to achieve higher photocatalytic activity of ZnO nanostructures. Photocatalytic activity is further augmented by better choice of capping ligand for colloidal stabilization, starch being more effective than polyethylene glycol (PEG).

Direct, enantioselective α-alkylation of aldehydes using simple olefins.

Science.gov (United States)

Capacci, Andrew G; Malinowski, Justin T; McAlpine, Neil J; Kuhne, Jerome; MacMillan, David W C

2017-11-01

Although the α-alkylation of ketones has already been established, the analogous reaction using aldehyde substrates has proven surprisingly elusive. Despite the structural similarities between the two classes of compounds, the sensitivity and unique reactivity of the aldehyde functionality has typically required activated substrates or specialized additives. Here, we show that the synergistic merger of three catalytic processes-photoredox, enamine and hydrogen-atom transfer (HAT) catalysis-enables an enantioselective α-aldehyde alkylation reaction that employs simple olefins as coupling partners. Chiral imidazolidinones or prolinols, in combination with a thiophenol, iridium photoredox catalyst and visible light, have been successfully used in a triple catalytic process that is temporally sequenced to deliver a new hydrogen and electron-borrowing mechanism. This multicatalytic process enables both intra- and intermolecular aldehyde α-methylene coupling with olefins to construct both cyclic and acyclic products, respectively. With respect to atom and step-economy ideals, this stereoselective process allows the production of high-value molecules from feedstock chemicals in one step while consuming only photons.

Sol–gel synthesis of SnO2–MgO nanoparticles and their photocatalytic activity towards methylene blue degradation

International Nuclear Information System (INIS)

Bayal, Nisha; Jeevanandam, P.

2013-01-01

Graphical abstract: - Highlights: • A simple sol–gel method for the synthesis of SnO 2 –MgO nanoparticles is reported. • Band gap of SnO 2 can be tuned by varying the magnesium content in SnO 2 –MgO. • SnO 2 –MgO shows good photocatalytic activity towards degradation of methylene blue. - Abstract: SnO 2 –MgO mixed metal oxide nanoparticles were prepared by a simple sol–gel method. The nanoparticles were characterized by power X-ray diffraction, scanning electron microscopy coupled with energy dispersive X-ray analysis, transmission electron microscopy and UV–vis diffuse reflectance spectroscopy. The XRD results indicate the formation of mixed metal oxide nanoparticles and also a decrease of SnO 2 crystallite size in the mixed metal oxide nanoparticles with increasing magnesium oxide content. The reflectance spectroscopy results show a blue shift of the band gap of SnO 2 in the mixed metal oxide nanoparticles. The photocatalytic activity of the SnO 2 –MgO nanoparticles was tested using the photodegradation of aqueous methylene blue in the presence of sunlight. The results indicate that the mixed metal oxide nanoparticles possess higher efficiency for the photodegradation of methylene blue compared to pure SnO 2 nanoparticles

Synthesis of /sup 14/C-labeled felbamate from phenylacetic-(methylene-/sup 14/C) acid

Energy Technology Data Exchange (ETDEWEB)

Choi, Y.M.; Kucharczyk, N.; Sofia, R.D.

1986-05-01

A synthetic procedure for the preparation of 2-phenyl-1,3-propanediol-2-/sup 14/C dicarbamate, starting with phenylacetic-(methylene-/sup 14/C) acid was developed. The procedure from phenylacetic acid to 2-phenyl-1,3-propanediol dicarbamate has four steps via phenylmalonic acid and 2-phenyl-1,3-propanediol. The overall yield of all four steps was 28%.

Review of Extraskeletal Activity on Tc-99m Methylene Diphosphonate Bone Scintigraphy and Value of Cross-Sectional and SPECT-CT Imaging Correlation.

Science.gov (United States)

Bermo, Mohammed; Behnia, Sanaz; Fair, Joanna; Miyaoka, Robert S; Elojeimy, Saeed

2017-07-31

Recognizing the different mechanisms and imaging appearance of extraskeletal Tc-99m methylene diphosphonate uptake enhances the diagnostic value of bone scan interpretation. In this article, we present a pictorial review of the different mechanisms of extraskeletal Tc-99m methylene diphosphonate uptake on bone scintigraphy including neoplastic, inflammatory, ischemic, traumatic, excretory, and iatrogenic. We also illustrate through case examples the added value of correlation with cross-sectional and single photon emission computed tomography and computed tomography imaging in localizing and characterizing challenging cases of extraskeletal uptake. Copyright © 2017 Elsevier Inc. All rights reserved.

Methylene blue MMX® tablets for chromoendoscopy. Bioavailability, colon staining and safety in healthy volunteers undergoing a full colonoscopy.

Science.gov (United States)

Di Stefano, A F D; Radicioni, M M; Vaccani, A; Fransioli, A; Longo, L; Moro, L; Repici, A

2018-06-01

Methylene blue-MMX® tablets are proposed as an aid for detection and visualisation of adenomas and carcinomas in patients undergoing colonoscopy, by improving their detection rate and highlighting the presence of the intestinal dysplastic lesions. Single total doses of 100 and 200 mg were administered to healthy volunteers undergoing a bowel cleansing preparation and a full colonoscopy to investigate the colonic staining. The pharmacokinetics of methylene blue and the safety after exposure to the tablets were also investigated. With 200 mg, the best staining, assessed as the sum of acceptable and good staining, was achieved in the ascending colon and rectosigmoid (75% subjects each), the transverse and the descending colon (approximately 63% each). Absence of staining or overstaining were reported for no colonic region of interest in any subject. Similar results were observed in the 100 mg dose group. Methylene blue blood concentrations reached a peak (C max ) in a median time (T max ) of 12 h with 100 mg and 16 h with 200 mg. AUC 0-t was 10.7 ± 6.7 μg/mLxh after 100 mg and 25.2 ± 7.4 μg/mLxh after 200 mg. Half-life ranged between 9 and 22 h after the lower dose and between 6 and 26 h after the higher dose. The cumulative excretion was about 28% after 100 mg and about 39% after 200 mg. The overall frequency of adverse events was 39%, but only one was related to the product: abnormal transaminases. The most frequent adverse event was a transient polyuria (17%). One serious adverse event (gastrointestinal haemorrhage) led the subject to study discontinuation and hospitalisation and another subject withdrew the study due to one adverse event (haematemesis). Either event was not related to methylene blue. Copyright © 2017. Published by Elsevier Inc.

Stereoselective and regiospecific hydroxylation of ketamine and norketamine.

Science.gov (United States)

Desta, Zeruesenay; Moaddel, Ruin; Ogburn, Evan T; Xu, Cong; Ramamoorthy, Anuradha; Venkata, Swarajya Lakshmi Vattem; Sanghvi, Mitesh; Goldberg, Michael E; Torjman, Marc C; Wainer, Irving W

2012-11-01

The objective was to determine the cytochrome P450s (CYPs) responsible for the stereoselective and regiospecific hydroxylation of ketamine [(R,S)-Ket] to diastereomeric hydroxyketamines, (2S,6S;2R,6R)-HK (5a) and (2S,6R;2R,6S)-HK (5b) and norketamine [(R,S)-norKet] to hydroxynorketamines, (2S,6S;2R,6R)-HNK (4a), (2S,6R;2R,6S)-HNK (4b), (2S,5S;2R,5R)-HNK (4c), (2S,4S;2R,4R)-HNK (4d), (2S,4R;2R,4S)-HNK (4e), (2S,5R;2R,5S)-HNK (4f). The enantiomers of Ket and norKet were incubated with characterized human liver microsomes (HLMs) and expressed CYPs. Metabolites were identified and quantified using LC/MS/MS and apparent kinetic constants estimated using single-site Michaelis-Menten, Hill or substrate inhibition equation. 5a was predominantly formed from (S)-Ket by CYP2A6 and N-demethylated to 4a by CYP2B6. 5b was formed from (R)- and (S)-Ket by CYP3A4/3A5 and N-demethylated to 4b by multiple enzymes. norKet incubation produced 4a, 4c and 4f and minor amounts of 4d and 4e. CYP2A6 and CYP2B6 were the major enzymes responsible for the formation of 4a, 4d and 4f, and CYP3A4/3A5 for the formation of 4e. The 4b metabolite was not detected in the norKet incubates. 5a and 4b were detected in plasma samples from patients receiving (R,S)-Ket, indicating that 5a and 5b are significant Ket metabolites. Large variations in HNK concentrations were observed suggesting that pharmacogenetics and/or metabolic drug interactions may play a role in therapeutic response.

Photocatalytic decolorization of methylene blue over Zn1-xCoxO under visible light irradiation

International Nuclear Information System (INIS)

Xiao Qi; Zhang Jiang; Xiao Chong; Tan Xiaoke

2007-01-01

Co-doped ZnO photocatalysts were prepared by hydrothermal method. The obtained Co-doped ZnO powders were characterized by X-ray diffraction, UV-vis diffuse reflectance spectroscopy and photoluminescence (PL) spectra. The prepared Co-doped ZnO photocatalysts showed high photocatalytic activities for methylene blue decolorization at pH 10.5 under visible light irradiation. It was found that there were certain relationships between PL spectra and photocatalytic activity, namely, the stronger the PL intensity, the larger the content of oxygen vacancies and defects, the higher the photocatalytic activity. Therefore, in this study 3.0 mol% was the most suitable content of Co 2+ in ZnO, at which the recombination of photoinduced electrons and holes could be effectively inhibited and thereby the highest photocatalytic activity was formed

DNA Electrochemistry with Tethered Methylene Blue

Science.gov (United States)

Pheeney, Catrina G.

2012-01-01

Methylene blue (MB′), covalently attached to DNA through a flexible C12 alkyl linker, provides a sensitive redox reporter in DNA electrochemistry measurements. Tethered, intercalated MB′ is reduced through DNA-mediated charge transport; the incorporation of a single base mismatch at position 3, 10, or 14 of a 17-mer causes an attenuation of the signal to 62 ± 3% of the well-matched DNA, irrespective of position in the duplex. The redox signal intensity for MB′–DNA is found to be least 3-fold larger than that of Nile blue (NB)–DNA, indicating that MB′ is even more strongly coupled to the π-stack. The signal attenuation due to an intervening mismatch does, however, depend on DNA film density and the backfilling agent used to passivate the surface. These results highlight two mechanisms for reduction of MB′ on the DNA-modified electrode: reduction mediated by the DNA base pair stack and direct surface reduction of MB′ at the electrode. These two mechanisms are distinguished by their rates of electron transfer that differ by 20-fold. The extent of direct reduction at the surface can be controlled by assembly and buffer conditions. PMID:22512327

Green synthesis of silver nanoparticle-reduced graphene oxide using Psidium guajava and its application in SERS for the detection of methylene blue

Science.gov (United States)

Chettri, Prajwal; Vendamani, V. S.; Tripathi, Ajay; Singh, Manish Kumar; Pathak, Anand P.; Tiwari, Archana

2017-06-01

Here we present the synthesis of reduced graphene oxide and silver nanoparticle-reduced graphene oxide composites using aqueous extract of dry leaves of Psidium guajava by one pot reflux method. Psidium guajava extract simultaneously reduces silver nitrate and graphene oxide in the reaction mixture which is confirmed by various spectroscopic techniques. Variable concentrations of silver nitrate solution are used to obtain reduced graphene oxide with different dosage of silver nanoparticles and the resultant composites are examined using surface enhanced Raman scattering measurements. Considering methylene blue as a probe molecule, it is found that the surface enhanced Raman scattering activity increases with the increase in the dose of silver nanoparticles. Our as-synthesised silver nanoparticle-reduced graphene oxide composite shows remarkable performance in detecting methylene blue with concentration as low as 10-8 M for which the enhancement factor is 4.6 × 105. In addition, we report that the reduced graphene oxide quenches the photoluminescence of methylene blue more efficiently than silver nanoparticle-reduced graphene oxide composite. The charge transfer states have been extracted which are mainly responsible for the quenching processes.

Highly enantio- and diastereoselective synthesis of β-methyl-γ- monofluoromethyl-substituted alcohols

KAUST Repository

Yang, Wenguo

2011-06-07

Enanatiopure β-methyl-γ-monofluoromethyl alcohols were prepared from the allylic alkylation between fluorobis(phenylsulfonyl)methane with Morita-Baylis-Hillman carbonates. The reaction was catalyzed by using the Cinchona alkaloid derivative, (DHQD)2AQN. The origin of the stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed stereoselectivity. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraosseous uptake of /sup 99/sup(m)technetium methylene diphosphonate. Neuroblastoma or radiation therapy

Energy Technology Data Exchange (ETDEWEB)

Sty, J R; Kun, L; Casper, J; Babbitt, D P

1980-01-01

A child with a ganglioneuroblastoma and tumor uptake of /sup 99/sup(m)technetium methylene diphosphate (/sup 99/sup(m)Tc-MDP) is presented. After surgical removal of an encapsulated tumor and radiation therapy, an interval bone scan demonstrated the same presurgical abnormality. Awareness of abnormal uptake of /sup 99/sup(m)Tc-MDP in irradiated renal tissue prevents interpreting radiation nephritis as recurrent tumor.

Increased uptake of technetium-99m methylene diphosphonate in muscles in the course of polymyositis

International Nuclear Information System (INIS)

Niemir, Z.; Oleksa, R.; Czepczynski, R.; Sowinski, J.

2005-01-01

A case of a woman aged 46 years with signs of rhabdomyolysis and acute renal failure is presented. Coxsackie serum test was positive. Increased uptake of Technetium-99m methylene diphosphonate ( 99mT c-MDP) by muscles of thighs and calves was observed. After 1 year no increased accumulation of radiotracer in the muscles was found

Adsorption of methylene blue on raw and MTZ/imogolite hybrid surfaces: Effect of concentration and calorimetric investigation

Energy Technology Data Exchange (ETDEWEB)

Guerra, Denis L., E-mail: dlguerra@pq.cnpq.br [Universidade Federal de Mato Grosso, DRM, UFMT, Mato Grosso 78060 900 (Brazil); Batista, Adriano C. [Universidade Estadual do Norte Fluminense, UENF, Rio de Janeiro 28013 02 (Brazil); Viana, Rubia R. [Universidade Federal de Mato Grosso, DRM, UFMT, Mato Grosso 78060 900 (Brazil); Airoldi, Claudio [Chemistry Institute, State University of Campinas, PO Box 6154, 13084-971 Campinas, Sao Paulo (Brazil)

2010-11-15

The synthetic imogolite sample was used for organofunctionalization process with 2-mercaptothiazoline (MTZ). The compound 2-mercaptothiazoline was anchored onto imogolite surface by heterogeneous route. Due to the increment of basic centers attached to the pendant chains the dye adsorption capability of the final chelating material, was found to be higher than is precursor. The ability of these materials to remove methylene blue from aqueous solution was followed by a series of adsorption isotherms at room temperature and pH 4.0. The maximum number of moles adsorbed was determined to be 40.32 x 10{sup -2} and 65.13 x 10{sup -2} mmol g{sup -1} for IMO and IMO{sub MTZ}, respectively. The energetic effects caused by dye cations adsorption were determined through calorimetric titrations. Thermodynamics indicated the existence of favorable conditions for such methylene blue-nitrogen and sulfur interactions.

Stereoselective hydrogenation of olefins using rhodium-substituted carbonic anhydrase--a new reductase.

Science.gov (United States)

Jing, Qing; Okrasa, Krzysztof; Kazlauskas, Romas J

2009-01-01

One useful synthetic reaction missing from nature's toolbox is the direct hydrogenation of substrates using hydrogen. Instead nature uses cofactors like NADH to reduce organic substrates, which adds complexity and cost to these reductions. To create an enzyme that can directly reduce organic substrates with hydrogen, researchers have combined metal hydrogenation catalysts with proteins. One approach is an indirect link where a ligand is linked to a protein and the metal binds to the ligand. Another approach is direct linking of the metal to protein, but nonspecific binding of the metal limits this approach. Herein, we report a direct hydrogenation of olefins catalyzed by rhodium(I) bound to carbonic anhydrase (CA-[Rh]). We minimized nonspecific binding of rhodium by replacing histidine residues on the protein surface using site-directed mutagenesis or by chemically modifying the histidine residues. Hydrogenation catalyzed by CA-[Rh] is slightly slower than for uncomplexed rhodium(I), but the protein environment induces stereoselectivity favoring cis- over trans-stilbene by about 20:1. This enzyme is the first cofactor-independent reductase that reduces organic molecules using hydrogen. This catalyst is a good starting point to create variants with tailored reactivity and selectivity. This strategy to insert transition metals in the active site of metalloenzymes opens opportunities to a wider range of enzyme-catalyzed reactions.

Reversal by methylene blue of tetanic fade induced in cats by nitric oxide

Directory of Open Access Journals (Sweden)

C.R. Ambiel

1998-03-01

Full Text Available Previous data from our laboratory have indicated that nitric oxide (NO acting at the presynaptic level increases the amplitude of muscular contraction (AMC of the phrenic-diaphragm preparations isolated from indirectly stimulated rats, but, by acting at the postsynaptic level, it reduces the AMC when the preparations are directly stimulated. In the present study we investigated the effects induced by NO when tetanic frequencies of stimulation were applied to in vivo preparations (sciatic nerve-anterior tibial muscle of the cat. Intra-arterial injection of NO (0.75-1.5 mg/kg induced a dose-dependent increase in the Wedensky inhibition produced by high frequencies of stimulation applied to the motor nerve. Intra-arterial administration of 7.2 µg/kg methylene blue did not produce any change in AMC at low frequencies of nerve stimulation (0.2 Hz, but antagonized the NO-induced Wedensky inhibition. The experimental data suggest that NO-induced Wedensky inhibition may be mediated by the guanylate cyclase-cGMP pathway

Homogeneous photosensitized degradation of pharmaceuticals by using red light LED as light source and methylene blue as photosensitizer

NARCIS (Netherlands)

Ye, Y.; Bruning, H.; Yntema, D.; Mayer, M.; Rijnaarts, H.

2017-01-01

Research on employing advanced oxidation processes (AOPs) for pharmaceuticals removal is gaining interests. However, detrimental effects of background water constituents in complex water matrices are limiting their implementation. In this study, we report red light induced methylene blue

MO-G-18C-07: Improving T2 Determination and Quantification of Lipid Methylene Protons in Proton Magnetic Resonance Spectroscopy at 3 T

Energy Technology Data Exchange (ETDEWEB)

Breitkreutz, D. [of Oncology, University of Alberta, Edmonton, AB (Canada); Fallone, B. G.; Yahya, A. [of Oncology, University of Alberta, Edmonton, AB (Canada); Department of Medical Physics, Cross Cancer Institute, Edmonton, AB (Canada)

2014-06-15

Purpose: To improve proton magnetic resonance spectroscopy (MRS) transverse relaxation (T{sub 2}) determination and quantification of lipid methylene chain (1.3 ppm) protons by rewinding their J-coupling evolution. Methods: MRS experiments were performed on four lipid phantoms, namely, almond, corn, sunflower and oleic acid, using a 3 T Philips MRI scanner with a transmit/receive birdcage head coil. Two PRESS (Point RESolved Spectroscopy) pulse sequences were used. The first PRESS sequence employed standard bandwidth (BW) (∼550 Hz) RF (radiofrequency) refocussing pulses, while the second used refocussing pulses of narrow BW (∼50 Hz) designed to rewind J-coupling evolution of the methylene protons in the voxel of interest. Signal was acquired with each sequence from a 5×5×5 mm{sup 3} voxel, with a repetition time (TR) of 3000 ms, and with echo times (TE) of 100 to 200 ms in steps of 20 ms. 2048 sample points were measured with a 2000 Hz sampling bandwidth. Additionally, 30 mm outer volume suppression slabs were used to suppress signal outside the voxel of interest. The frequency of the RF pulses was set to that of the methylene resonance. Methylene peak areas were calculated and fitted in MATLAB to a monexponentially decaying function of the form M{sub 0}exp(-TE/T{sub 2}), where M{sub 0} is the extrapolated area when TE = 0 ms and yields a measure of concentration. Results: The determined values of M{sub 0} and T{sub 2} increased for all fatty acids when using the PRESS sequence with narrow BW refocussing pulses. M{sub 0} and T{sub 2} values increased by an average amount (over all the phantoms) of 31% and 14%, respectively. Conclusion: This investigation has demonstrated that J-coupling interactions of lipid methylene protons causes non-negligible signal losses which, if not accounted for, Result in underestimations of their levels and T{sub 2} values when performing MRS measurements. Funded by the Natural Sciences and Engineering Research Council of Canada

Wiring of heme enzymes by methylene-blue labeled dendrimers

DEFF Research Database (Denmark)

Álvarez-Martos, Isabel; Shahdost-fard, Faezeh; Ferapontova, Elena

2017-01-01

Redox-modified branched 3D dendrimeric nanostructures may be considered as perspective wires for electrical connection between redox enzymes and electrodes. Here, we studied electron transfer (ET) reactions and bioelectrocatalysis of heme-containing horseradish peroxidase (HRP) and heme- and moli......Redox-modified branched 3D dendrimeric nanostructures may be considered as perspective wires for electrical connection between redox enzymes and electrodes. Here, we studied electron transfer (ET) reactions and bioelectrocatalysis of heme-containing horseradish peroxidase (HRP) and heme......- and molibdopterin-containing sulfite oxidase (SOx), wired to gold by the methylene blue (MB)-labeled polyamidoamine (PAMAM) dendrimers. The enzymes’ electrochemical transformation and bioelectrocatalytic function could be followed at both unlabeled and MB-labeled dendrimer-modified electrodes with the formal redox......, optimization of bioelectrocatalysis of complex intermembrane and, possibly, membrane enzymes....

Performance Evaluation of Hap-Free Paint Strippers vs. Methylene-Chloride-Based Strippers for Removing Army Chemical Agent Resistant Coatings (CARC)

National Research Council Canada - National Science Library

Kelley, John; Considine, Thomas

2006-01-01

...). The purpose of this effort is to investigate HAP-free alternative chemical paint strippers as potential replacements for the methylene-chloride- based chemical strippers currently used in both processes...

A supramolecular photosensitizer system based on the host-guest complexation between water-soluble pillar[6]arene and methylene blue for durable photodynamic therapy.

Science.gov (United States)

Yang, Kui; Wen, Jia; Chao, Shuang; Liu, Jing; Yang, Ke; Pei, Yuxin; Pei, Zhichao

2018-06-05

A supramolecular photosensitizer system WP6-MB was synthesized based on water-soluble pillar[6]arene and the photosensitizer methylene blue (MB) via host-guest interaction. MB can complex with WP6 directly with a high complex constant without further modification. In particular, WP6-MB can reduce the dark toxicity of MB remarkably. Furthermore, it can efficiently overcome photobleaching and extend the time for singlet oxygen production of MB upon light irradiation, which is significant for durable photodynamic therapy.

Methylene Blue Dye-Induced Skin Necrosis in Immediate Breast Reconstruction: Evaluation and Management

Directory of Open Access Journals (Sweden)

Ji Hwan Lee

2014-05-01

Full Text Available Background For early breast cancer patients, skin-sparing mastectomy or nipple-sparing mastectomy with sentinel lymph node biopsy has become the mainstream treatment for immediate breast reconstruction in possible cases. However, a few cases of skin necrosis caused by methylene blue dye (MBD used for sentinel lymph node localization have been reported. Methods Immediate breast reconstruction using a silicone implant was performed on 35 breasts of 34 patients after mastectomy. For sentinel lymph node localization, 1% MBD (3 mL was injected into the subareolar area. The operation site was inspected in the postoperative evaluation. Results Six cases of immediate breast reconstruction using implants were complicated by methylene blue dye. One case of local infection was improved by conservative treatment. In two cases, partial necrosis and wound dehiscence of the incision areas were observed; thus, debridement and closure were performed. Of the three cases of wide skin necrosis, two cases underwent removal of the dead tissue and implants, followed by primary closure. In the other case, the breast implant was salvaged using latissimus dorsi musculocutaneous flap reconstruction. Conclusions The complications were caused by MBD toxicity, which aggravated blood disturbance and skin tension after implant insertion. When planning immediate breast reconstruction using silicone implants, complications of MBD should be discussed in detail prior to surgery, and appropriate management in the event of complications is required.

Optimization of microwave-assisted durian seed based activated carbon preparation conditions for methylene blue dye removal

Science.gov (United States)

Ahmad, Mohd Azmier; Hamid, Siti Ruqayyah Ab.; Yusop, Mohamad Firdaus Mohamad; Aziz, Hamidi Abdul

2017-10-01

Due to easy access and relatively high fixed carbon content of 26.13% in its raw form, durian seed based activated carbon (DSAC) was produced via microwave heating. For activation stage, physiochemical approach consist of carbon dioxide (CO2) gasification and potassium hydroxide (KOH) as chemical activator were employed. Three most influential preparation variables on adsorption performance and yield of activated carbon (AC), which is radiation power, radiation time and KOH impregnation ratio (IR) were optimized with the help of response surface methodology (RSM). The optimization result revealed that 440W, 4.0 minutes and 0.55 of radiation power, radiation time and IR respectively, were needed to remove 80.23% of methylene blue (MB) dye and to obtain 25.77% of DSAC's yield. High Brunauer-Emmet-Teller (BET) surface area, total pore volume and average pore size of 852.30m2/g, 0.465cm3/g and 3.74nm respectively, were obtained on optimized DSAC.

Well-ordered structure of methylene blue monolayers on Au(111) surface: electrochemical scanning tunneling microscopy studies.

Science.gov (United States)

Song, Yonghai; Wang, Li

2009-02-01

Well-ordered structure of methylene blue (MB) monolayers on Au(111) surface has been successfully obtained by controlling the substrate potential. Electrochemical scanning tunneling microscopy (ECSTM) examined the monolayers of MB on Au(111) in 0.1 M HClO(4) and showed long-range ordered, interweaved arrays of MB with quadratic symmetry on the substrate in the potential range of double-layer charging. High-resolution ECSTM image further revealed the details of the MB monolayers structure of c(5 x 5 radical 3)rect and the flat-lying orientation of ad-molecules. The dependence of molecular organization on the substrate potential and the formation mechanism of well-ordered structure on Au(111) surface were investigated in detail. The obtained well-ordered structure at the interface between a metal and an aqueous electrolyte might possibly be used as high-density device for signal memory and templates for the advanced nanopatterning of surfaces. (c) 2008 Wiley-Liss, Inc.

The stereoselective sulfate conjugation of 4'-methoxyfenoterol stereoisomers by sulfotransferase enzymes.

Science.gov (United States)

Iyer, Lalitha V; Ramamoorthy, Anuradha; Rutkowska, Ewelina; Furimsky, Anna M; Tang, Liang; Catz, Paul; Green, Carol E; Jozwiak, Krzysztof; Wainer, Irving W

2012-10-01

The presystemic sulfate conjugation of the stereoisomers of 4'-methoxyfenoterol, (R,R')-MF, (S,S')-MF, (R,S')-MF, and (S,R')-MF, was investigated using commercially available human intestinal S9 fractions, a mixture of sulfotransferase (SULT) enzymes. The results indicate that the sulfation was stereospecific and that an S-configuration at the β-OH carbon of the MF molecule enhanced the maximal formation rates with (S,R')-MF  (S,S')-MF  (R,S')-MF ≈ (R,R')-MF, and competition studies demonstrated that (S,R')-MF is an effective inhibitor of (R,R')-MF sulfation (IC(50) = 60 μM). In addition, the results from a cDNA-expressed human SULT isoform screen indicated that SULT1A1, SULT1A3, and SULT1E1 can mediate the sulfation of all four MF stereoisomers. Previously published molecular models of SULT1A3 and SULT1A1 were used in docking simulations of the MF stereoisomers using Molegro Virtual Docker. The models of the MF-SULT1A3 and MF-SULT1A1 complexes indicate that each of the two chiral centers of MF molecule plays a role in the observed relative stabilities. The observed stereoselectivity is the result of multiple hydrogen bonding interactions and induced conformational changes within the substrate-enzyme complex. In conclusion, the results suggest that a formulation developed from a mixture of (R,R')-MF and (S,R')-MF may increase the oral bioavailability of (R,R')-MF. Copyright © 2012 Wiley Periodicals, Inc.

Photochemistry and stereoselectivity of cellular retinaldehyde-binding protein from bovine retina

International Nuclear Information System (INIS)

Saari, J.C.; Bredberg, D.L.

1987-01-01

11-cis-Retinaldehyde bound to cellular retinaldehyde-binding protein (CRALBP) is unaffected in bovine eyecup preparations by illumination that bleaches approximately 70% of the rhodopsin. Illumination of retinal homogenates to which CRALBP X [ 3 H]11-cis-retinaldehyde had been added did not result in a reduction of the specific activity of recovered 11-cis-retinaldehyde, ruling out a bleaching regeneration cycle. The quantum efficiency of photoisomerization for CRALBP X 11-cis-retinaldehyde was determined by comparing the rate of photoisomerization of 11-cis-retinaldehyde bound to purified CRALBP and opsin. The low value obtained (0.07), coupled with a low molar extinction coefficient (15,400 M-1 cm-1), results in a photosensitivity only about 4% that of rhodopsin. CRALBP binds 9-cis- and 11-cis-retinaldehyde, producing complexes with absorption maxima at 405 and 425 nm, respectively. No complexes were detected with 13-cis- and all-trans-retinaldehyde. Following incubation of CRALBP X 11-cis-retinol with an equimolar mixture of 9-, 11-, 13-cis-, and all-trans-retinaldehydes, only 11-cis-retinaldehyde and residual 11-cis-retinol are present on the protein following separation from excess retinoids. A similar result is obtained following incubation of CRALBP X 11-cis-retinol with mixtures of 9- and 11-cis-retinaldehyde ranging in composition from 9:1 to 1:9 (9-cis-:11-cis-,mol/mol). The results indicate that CRALBP X 11-cis-retinol is sufficiently stereoselective in its binding properties to warrant consideration as a component of the mechanism for the generation of 11-cis-retinaldehyde in the dark

Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate

Directory of Open Access Journals (Sweden)

Makoto Nakajima

2011-06-01

Full Text Available Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner.

Methylene blue degradation by NaTaO3 sol-gel doped with Sm and La

International Nuclear Information System (INIS)

Torres-Martinez, Leticia M.; Cruz-Lopez, Arquimedes; Juarez-Ramirez, Isaias; Meza-de la Rosa, Ma. Elena

2009-01-01

In this work, NaTaO 3 compounds doped with 1 M% of La and Sm, were prepared by the sol-gel (SG) method and solid state (SS) reaction; and tested as photocatalysts on the degradation of methylene blue (MB) under UV light. The structural characterization by X-ray powder diffraction revealed that the crystallization of the NaTaO 3 phase prepared by the sol-gel method started at 600 deg. C, reaching maximum crystallization at 800 deg. C. It was determined that the presence of Sm and La retard the crystallization of the NaTaO 3 phase. On the other hand, the compounds synthesized in this work showed particle sizes in the nanometric scale, as it was observed by scanning electron microscopy (SEM). The specific surface area of the compounds synthesized by the sol-gel method, showed values 4 times higher than those obtained by the solid state reaction, favoring their functional and photocatalytic performance in the methylene blue degradation. In addition, the best photocatalytic performance was shown by the NaTaO 3 doped with Sm and heated at 600 deg. C, having a half-life time of 65 min.

Reactive oxygen species generation in aqueous solutions containing GdVO4:Eu3+ nanoparticles and their complexes with methylene blue

Science.gov (United States)

Hubenko, Kateryna; Yefimova, Svetlana; Tkacheva, Tatyana; Maksimchuk, Pavel; Borovoy, Igor; Klochkov, Vladimir; Kavok, Nataliya; Opolonin, Oleksander; Malyukin, Yuri

2018-04-01

It this letter, we report the study of free radicals and reactive oxygen species (ROS) generation in water solutions containing gadolinium orthovanadate GdVO4:Eu3+ nanoparticles (VNPs) and their complexes with methylene blue (MB) photosensitizer. The catalytic activity was studied under UV-Vis and X-ray irradiation by three methods (conjugated dienes test, OH· radical, and singlet oxygen detection). It has been shown that the VNPs-MB complexes reveal high efficiency of ROS generation under UV-Vis irradiation associated with both high efficiency of OH· radicals generation by VNPs and singlet oxygen generation by MB due to nonradiative excitation energy transfer from VNPs to MB molecules. Contrary to that under X-ray irradiation, the strong OH . radicals scavenging by VNPs has been observed.

Methylene blue as a lignin surrogate in manganese peroxidase reaction systems.

Science.gov (United States)

Goby, Jeffrey D; Penner, Michael H; Lajoie, Curtis A; Kelly, Christine J

2017-11-15

Manganese peroxidase (MnP) is associated with lignin degradation and is thus relevant to lignocellulosic-utilization technologies. Technological applications require reaction mixture optimization. A surrogate substrate can facilitate this if its susceptibility to degradation is easily monitored and mirrors that of lignin. The dye methylene blue (MB) was evaluated in these respects as a surrogate substrate by testing its reactivity in reaction mixtures containing relevant redox mediators (dicarboxylic acids, fatty acids). Relative rates of MB degradation were compared to available literature reports of lignin degradation under similar conditions, and suggest that MB can be a useful lignin surrogate in MnP systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Investigation of in vivo toxicity of hydroxylamine sulfate and the efficiency of intoxication treatment by α-tocopherol acetate and methylene blue.

Science.gov (United States)

Prodanchuk, Mykola G; Tsatsakis, Aristidis M; Prodanchuk, Georgiy M; Tsakalof, Andreas K

2013-11-01

Investigation of hydroxylamine sulfate toxicity mechanism in vivo and estimation of α-tocopherol acetate and methylene blue efficiency in poisoning treatments. In vivo experiments were conducted on 102 Wistar Han rats. The experiments investigated the hematotoxic and oxidative stress effects of hydroxylamine sulfate in acute and subacute toxicity treatment of animals. Electron Spin Resonance was used for quantitative determination of blood and liver tissue parameters alterations after intoxication. The osmotic fragility of erythrocytes, lipid peroxidation intensity and level of SH-groups in liver of rats were determined by established biochemical assays. Hydroxylamine sulfate cause an acute hematotoxicity and oxidative stress in vivo as demonstrated by the appearance of free oxidized iron in blood, reduced glutathione content and increased lipid peroxidation in liver. The experimental studies showed the formation of Hb-NO, MetHb in erythrocytes and as well of stable complex of reduced iron (Fe(2+)) with hydroxylamine sulfate. Methylene blue treatment does not reduce the Hb-NO or MetHb levels in intoxicated animals while administration of α-tocopherol acetate reduces substantially lipid peroxidation. Oxidative stress is a key mechanism of acute hematotoxicity caused by hydroxylamine sulfate. Methylene blue is not suitable antidote in case of hydroxylamine intoxication. Copyright © 2013 Elsevier Ltd. All rights reserved.

A New Property of Conjugated Polymer PFP: Catalytic Degradation of Methylene Blue Aqueous Solution

Institute of Scientific and Technical Information of China (English)

无

2005-01-01

A new property of conjugated polymer poly(furancarbinol-co-phenol)(PFP) was studied.The target copolymer was used as a catalyst after proper heating treatment. And dye methylene blue (MB) could be fully degraded and largely mineralized on PFP, under natural light or even in dark, in a few minutes. Furthermore, the catalytic activity could be preserved after several runs and the catalyst was readily separated. The effect of calcination temperature was also observed.

Stereoselectivity in ene reactions with 1O2: matrix effects in polymer supports, photo-oxygenation of organic salts and asymmetric synthesis.

Science.gov (United States)

Griesbeck, Axel G; Bartoschek, Anna; Neudörfl, Jörg; Miara, Claus

2006-01-01

The ene reaction of chiral allylic alcohols is applied as a tool for the investigation of intrapolymer effects by means of the stereoselectivity of the singlet-oxygen addition. The diastereo selectivity strongly depends on the structure of the polymer, the substrate loading degree and also on the degree of conversion demonstrating additional supramolecular effects evolving during the reaction. The efficiency and the stability of polymer-bound sensitizers were evaluated by the ene reaction of singlet oxygen with citronellol. The ene reaction with chiral ammonium salts of tiglic acid was conducted under solution phase conditions or in polystyrene beads under chiral contact ion-pair conditions. The products thus obtained precipitate during the photoreaction as ammonium salts. Moderate asymmetric induction was observed for this procedure for the first time.

Stereoselective Behavior of the Chiral Herbicides Diclofop-Methyl and Diclofop During the Soy Sauce Brewing Process.

Science.gov (United States)

Lu, Yuele; Zhang, Dong; Liao, Yahui; Diao, Jinling; Chen, Xiaolong

2016-01-01

Chiral pesticides are now receiving more and more attention in the food-making process. This experiment studied the enantioselective behavior of diclofop-methyl (DM) and its main metabolite, diclofop (DC), during the soy sauce brewing process. Two kinds of commonly used strains, Aspergillus oryzae and Saccharomyces rouxii, were investigated. However, they showed a different degradation ability to the enantiomers of DM and DC. It was observed that (-)-(S)-DM was degraded much faster than (+)-(R)-DM by Saccharomyces rouxii, while no stereoselective degradation was found by Aspergillus oryzae. DC represented a relatively long residue period in this fermentation process and both strains showed a weak degradation ability to DC, especially Saccharomyces rouxii. There was little DC detected in the final product, while most of the DC residues persisted in the lees, which were usually used as animal feeds or discarded into the environment directly as waste. Therefore, more attention should be paid to the soy sauce brewing process concerning pesticide residues both in the final product and byproducts. © 2015 Wiley Periodicals, Inc.

Hammond Postulate Mirroring Enables Enantiomeric Enrichment of Phosphorus Compounds via Two Thermodynamically Interconnected Sequential Stereoselective Processes.

Science.gov (United States)

Rajendran, Kamalraj V; Nikitin, Kirill V; Gilheany, Declan G

2015-07-29

The dynamic resolution of tertiary phosphines and phosphine oxides was monitored by NMR spectroscopy. It was found that the stereoselectivity is set during the formation of the diastereomeric alkoxyphosphonium salts (DAPS), such that their initial diastereomeric excess (de) limits the final enantiomeric excess (ee) of any phosphorus products derived from them. However, (31)P NMR monitoring of the spontaneous thermal decomposition of the DAPS shows consistent diastereomeric self-enrichment, indicating a higher rate constant for decomposition of the minor diastereomer. This crucial observation was confirmed by reductive trapping of the unreacted enriched DAPS with lithium tri-sec-butylborohydride (commercially distributed as L-Selectride reagent) at different time intervals after the start of reaction, which gives progressively higher ee of the phosphine product with time. It is proposed that the Hammond postulate operates for both formation and decomposition of DAPS intermediate so that the lower rate of formation and faster subsequent collapse of the minor isomer are thermodynamically linked. This kinetic enhancement of kinetic resolution furnishes up to 97% ee product.

Sol–gel synthesis of SnO{sub 2}–MgO nanoparticles and their photocatalytic activity towards methylene blue degradation

Energy Technology Data Exchange (ETDEWEB)

Bayal, Nisha; Jeevanandam, P., E-mail: jeevafcy@iitr.ernet.in

2013-10-15

Graphical abstract: - Highlights: • A simple sol–gel method for the synthesis of SnO{sub 2}–MgO nanoparticles is reported. • Band gap of SnO{sub 2} can be tuned by varying the magnesium content in SnO{sub 2}–MgO. • SnO{sub 2}–MgO shows good photocatalytic activity towards degradation of methylene blue. - Abstract: SnO{sub 2}–MgO mixed metal oxide nanoparticles were prepared by a simple sol–gel method. The nanoparticles were characterized by power X-ray diffraction, scanning electron microscopy coupled with energy dispersive X-ray analysis, transmission electron microscopy and UV–vis diffuse reflectance spectroscopy. The XRD results indicate the formation of mixed metal oxide nanoparticles and also a decrease of SnO{sub 2} crystallite size in the mixed metal oxide nanoparticles with increasing magnesium oxide content. The reflectance spectroscopy results show a blue shift of the band gap of SnO{sub 2} in the mixed metal oxide nanoparticles. The photocatalytic activity of the SnO{sub 2}–MgO nanoparticles was tested using the photodegradation of aqueous methylene blue in the presence of sunlight. The results indicate that the mixed metal oxide nanoparticles possess higher efficiency for the photodegradation of methylene blue compared to pure SnO{sub 2} nanoparticles.

A study on the adsorption of methylene blue onto gum ghatti/TiO2nanoparticles-based hydrogel nanocomposite

CSIR Research Space (South Africa)

Mittal, Hemant

2016-07-01

Full Text Available The objective of this work was to study the isotherm and kinetic models for the adsorption of methylene blue (MB) onto a TiO(sub2) nanoparticle (TiO(sub2)NP)-containing hydrogel nanocomposite (HNC) of polyacrylamide-grafted gum ghatti (PAAm...

Pseudopeptide-Based Hydrogels Trapping Methylene Blue and Eosin Y.

Science.gov (United States)

Milli, Lorenzo; Zanna, Nicola; Merlettini, Andrea; Di Giosia, Matteo; Calvaresi, Matteo; Focarete, Maria Letizia; Tomasini, Claudia

2016-08-16

We present herein the preparation of four different hydrogels based on the pseudopeptide gelator Fmoc-l-Phe-d-Oxd-OH (Fmoc=fluorenylmethyloxycarbonyl), either by changing the gelator concentration or adding graphene oxide (GO) to the water solution. The hydrogels have been analysed by rheological studies that demonstrated that pure hydrogels are slightly stronger compared to GO-loaded hydrogels. Then the hydrogels efficiency to trap the cationic methylene blue (MB) and anionic eosin Y (EY) dyes has been analyzed. MB is efficiently trapped by both the pure hydrogel and the GO-loaded hydrogel through π-π interactions and electrostatic interactions. In contrast, the removal of the anionic EY is achieved in less satisfactory yields, due to the unfavourable electrostatic interactions between the dye, the gelator and GO. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Immediate renal imaging and renography with /sup 99m/Tc methylene diphosphonate to assess renal blood flow, excretory function, and anatomy

International Nuclear Information System (INIS)

Glass, E.C.; DeNardo, G.L.; Hines, H.H.

1980-01-01

/sup 99m/Tc methylene diphosphonate (/sup 99m/Tc MDP) was evaluated as a clinical renal imaging agent in 20 patients referred for bone scintigraphy. Sequential scintigraphy, which was started immediately after injection, yielded blood flow studies of high quality, and subsequent images accurately delineated renal anatomy and excretion in nonazotemic patients. In comparison with delayed images, early images were vastly superior in quality and demonstrated improved target-to-nontarget activity ratios (p < 0.001) and improved lesion detectability (p < 0.01). Renal imaging performed incidental to bone scintigraphy with MDP can be greatly enhanced by initiating sequential scintigraphy immediately after injection

Utilization of zeolites synthesized from coal ash for methylene blue removal from water

Directory of Open Access Journals (Sweden)

Denise Alves Fungaro

2008-12-01

Full Text Available The adsorption of methylene blue from aqueous solution was carried out using zeolites synthesized from coal ash as low-cost adsorbents. The coal ash sample was converted to zeolites by hydrothermal treatment using different synthesis parameters. The materials were characterized by physical-chemical analysis, XRD and SEM studies. The adsorption isotherms can be fitted by Freundlich model. The values of the adsorption capacity of adsorbents were similar for adsorbents. Kinetic studies indicate that the adsorption follows pseudo-second-order kinetic model.

Olefination reactions of phosphorus-stabilized carbon nucleophiles.

Science.gov (United States)

Gu, Yonghong; Tian, Shi-Kai

2012-01-01

A range of phosphorus-stabilized carbon nucleophiles have been employed for alkene synthesis with high chemo-, regio-, and stereoselectivity. The Wittig, Horner-Wadsworth-Emmons, Horner-Wittig, and Evans-Akiba reactions utilize phosphonium-, phosphonate-, phosphine oxide-, and pentacoordinated phosphorane-stabilized carbanions as nucleophiles, respectively, to undergo olefination with aldehydes or ketones, and each of these transformations has its own advantages and limitations. Modifying the structures of these nucleophiles along with optimizing reaction conditions results in the formation of a wide variety of polysubstituted alkenes in a highly stereoselective manner. The olefination of imines with phosphonium ylides has recently emerged as a useful approach to tune the stereoselectivity for alkene synthesis. This review focuses on recent advances in the stereoselective olefination of phosphorus-stabilized carbon nucleophiles.

Stereoselective synthesis of an active metabolite of the potent PI3 kinase inhibitor PKI-179.

Science.gov (United States)

Chen, Zecheng; Venkatesan, Aranapakam M; Dos Santos, Osvaldo; Delos Santos, Efren; Dehnhardt, Christoph M; Ayral-Kaloustian, Semiramis; Ashcroft, Joseph; McDonald, Leonard A; Mansour, Tarek S

2010-03-05

The synthesis and stereochemical determination of 1-(4-(4-((1R,5R,6R)-6-hydroxy-3-oxa-8-azabicyclo[3.2.1]octan-8-yl)-6-morpholino-1,3,5-triazin-2-yl)phenyl)-3-(pyridin-4-yl)urea (2), an active metabolite of the potent PI3 kinase inhibitor PKI-179 (1), is described. Stereospecific hydroboration of the double bond of 2,5-dihydro-1H-pyrrole 8 gave the 2,3-trans alcohol 9 exclusively. The configuration of the 3-hydroxyl group in 9 was inverted by an oxidation and stereoselective reduction sequence to give the corresponding 2,3-cis isomer 23. Both exo (21) and endo (27) isomers of the metabolite 2 were prepared via a practical synthetic route from 9 and 23, respectively, and the stereochemistry of 2 was determined to be endo. The endo isomer (27) was separated into two enantiomers 28 and 29 by chiral HPLC. Compound 2 was found to be enantiomerically pure and identical to the enantiomer 28. The absolute stereochemistry of the enantiomer 28 was determined by Mosher's method, thus establishing the stereochemistry of the active metabolite 2.

"Heart-cut" bidimensional achiral-chiral liquid chromatography applied to the evaluation of stereoselective metabolism, in vivo biological activity and brain response to chiral drug candidates targeting the central nervous system.

Science.gov (United States)

Battisti, Umberto M; Citti, Cinzia; Larini, Martina; Ciccarella, Giuseppe; Stasiak, Natalia; Troisi, Luigino; Braghiroli, Daniela; Parenti, Carlo; Zoli, Michele; Cannazza, Giuseppe

2016-04-22

A "heart-cut" two-dimensional achiral-chiral liquid chromatography triple-quadrupole mass spectrometry method (LC-LC-MS/MS) was developed and coupled to in vivo cerebral microdialysis to evaluate the brain response to the chiral compound (±)-7-chloro-5-(3-furanyl)-3-methyl-3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxide ((±)-1), a potent positive allosteric modulator (PAM) of AMPA receptor. The method was successfully employed to evaluate also its stereoselective metabolism and in vitro biological activity. In particular, the LC achiral method developed, employs a pentafluorinated silica based column (Discovery HS-F5) to separate dopamine, acetylcholine, serotonin, (±)-1 and its two hepatic metabolites. In the "heart-cut" two-dimension achiral-chiral configuration, (±)-1 and (±)-1-d4 eluted from the achiral column (1st dimension), were transferred to a polysaccharide-based chiral column (2nd dimension, Chiralcel OD-RH) by using an automatic six-port valve. Single enantiomers of (±)-1 were separated and detected using electrospray positive ionization mode and quantified in selected reaction monitoring mode. The method was validated and showed good performance in terms of linearity, accuracy and precision. The new method employed showed several possible applications in the evaluation of: (a) brain response to neuroactive compounds by measuring variations in the brain extracellular levels of selected neurotransmitters and other biomarkers; (b) blood brain barrier penetration of drug candidates by measuring the free concentration of the drug in selected brain areas; (c) the presence of drug metabolites in the brain extracellular fluid that could prove very useful during drug discovery; (d) a possible stereoselective metabolization or blood brain barrier stereoselective crossing of chiral drugs. Finally, compared to the methods reported in the literature, this technique avoids the necessity of euthanizing an animal at each time point to measure drug

Stereoselective biodegradation of tricyclic terpanes in heavy oils from the Bolivar Coastal Fields, Venezuela

Energy Technology Data Exchange (ETDEWEB)

Alberdi, M. [Stanford University (United States). Dept. of Geological and Environmental Sciences; PDVSA-Intevep, Caracas (Venezuela); Moldowan, J.M.; Dahl, J.E. [Stanford University (United States). Dept. of Geological and Environmental Sciences; Peters, K.E. [Mobil Technology Co., Dallas, TX (United States)

2001-07-01

Gas chromatography-mass spectrometry (GC-MS) and GC-MS-MS analyses of heavy oils from Bolivar Coastal Fields (Lagunillas Field) show a complete set of demethylated tricyclic terpanes. As is the case for the 25-norhopanes, the demethylated tricyclics are probably formed in reservoirs by microbially-mediated removal of the methyl group from the C-10 position, generating putative 17-nor-tricyclic terpanes. Diastereomeric pairs of tricyclic terpanes are resolved above C{sub 24} due to resolution of 22S and 22R epimers, but the elution order of the 22S and 22R epimers is unknown. Early-eluting diastereomers (EE) predominate over late-eluting diastereomers (LE) (C{sub 25}-C{sub 29}) in the heavily degraded oils, indicating a stereoselective preference for the LE stereoisomers during biodegradation. Conversely, the LE diastereomers predominate over the EE diastereomers in the 17-nor tricyclic series (C{sub 24}-C{sub 28}), indicating that tricyclic terpanes and 17-nor-tricyclic terpanes are directly linked as precursors and products, respectively. A good correlation exists between the destruction of steranes and the demethylation of hopanes and tricyclic terpanes. This suggests that terpane demethylation occurs during sterane destruction and hopane demethylation, although the rate is slower, indicating that tricyclic terpanes are more resistant to biodegradation. (Author)

Photo-, sono- and sonophotocatalytic degradation of methylene blue using Fe3O4/ZrO2 composites catalysts

Science.gov (United States)

Kristianto, Y.; Taufik, A.; Saleh, R.

2017-07-01

In the present work, magnetite material Fe3O4/ZrO2 with various molar ratios was prepared by the two-step method (sol-gel followed by the ultrasonic-assisted method). The as-prepared samples were fairly characterized by various characterization methods, such as X-ray Diffraction (XRD), Vibrating Sample Magnetometer (VSM), Fourier Transform Infrared (FT-IR) and Thermal Gravimetric Analysis (TGA). The catalytic performance of the as-prepared samples was evaluated based on the degradation of methylene blue under UV light, ultrasound and combination of UV and ultrasound irradiation. The results revealed that the sample with Fe3O4:ZrO2 molar ratio of 0.5:1 showed the best catalytic performance under UV, ultrasound and UV + ultrasound irradiation. The degradation of methylene blue follows the order: sonophotocatalytic > sonocatalytic > photocatalytic. In addition, the effect of various scavengers has also been studied. Furthermore, all prepared samples could be used as a convenient recyclable catalyst.

An improved synthesis of 2,2−-((4-substituted phenyl methylene difurans by Ultrasound irradiation

Directory of Open Access Journals (Sweden)

Naween M. Yonis

2016-09-01

Full Text Available A new series of 2,2−((4-substituted phenyl methylene difuran was synthesized by one-pot cyclocondensation of aldehyde with excess furan at room temperature using trifluoro acetic acid as a catalyst under ultrasound irradiation in the absence of solvent. The products were compared with the classical condensation reactions. This method consistently enjoys the advantages of mild reaction conditions, excellent yields, easy work up and short time.

Studies on the Model Synthesis of the Brassinolide and Dolicholide Side Chains

Institute of Scientific and Technical Information of China (English)

Li Zeng PENG; Feng Zhi ZHANG; Tian Sheng MEI; Yu Lin LI

2003-01-01

A stereoselective synthesis of brassinolide and dolicholide, which involves constructionof the side chain enantiomers by a highly stereoselective aldol reaction of aldehyde 5 with theanion of α-silyloxy ketone 6 is described.

Stereoselective aminoacylation of a dinucleoside monophosphate by the imidazolides of DL-alanine and N-(tert-butoxycarbonyl)-DL-alanine

Science.gov (United States)

Profy, A. T.; Usher, D. A.

1984-01-01

The aminoacylation of diinosine monophosphate was studied experimentally. When the acylating agent was the imidazolide of N-(tert-butoxycarbonyl)-DL-alanine, a 40 percent enantiomeric excess of the isomer was incorporated at the 2' site and the positions of equilibrium for the reversible 2'-3' migration reaction differed for the D and L enantiomers. The reactivity of the nucleoside hydroxyl groups was found to decrease on the order 2'(3') less than internal 2' and less than 5', and the extent of the reaction was affected by the concentration of the imidazole buffer. Reaction of IpI with imidazolide of unprotected DL-alanine, by contrast, led to an excess of the D isomer at the internal 2' site. Finally, reaction with the N-carboxy anhydride of DL-alanine occurred without stereoselection. These results are found to be relevant to the study of the evolution of optical chemical activity and the origin of genetically directed protein synthesis.

Viability of the Fricke dosemeter doped with methylene blue; Viabilidade do dosimetro Fricke dopado com azul de metileno

Energy Technology Data Exchange (ETDEWEB)

Souza, V.L.B.; Santos, C.D.A.; Rodrigues, K.R.G.; Cunha, M.S.; Figueiredo, M.D.C.; Melo, R.T. [Centro Regional de Ciencias Nucleares do Nordeste (CRCN-NE/CNEN-PE), Recife, PE (Brazil)

2009-07-01

This work aims to find the possible utilization of the Fricke dosemeter doped with methylene blue (FMB) for the dosimetry of photodynamic therapy. The FMB was irradiated wit X rays and light emitted diodes demonstrating positive answers to the stimulus, being probably to be used for dosimetric objectives

The use of chemical modified chitosan with succinic anhydride in the methylene blue adsorption

International Nuclear Information System (INIS)

Lima, Ilauro S.; Ribeiro, Emerson S.; Airoldi, Claudio

2006-01-01

The adsorption capacity of a-chitosan and its modified form with succinic anhydride was compared with the traditional adsorbent active carbon by using the dye methylene blue, employed in the textile industry. The isotherms for both biopolymers were classified as SSA systems in the Giles model, more specifically in L class and subgroup 3. The dye concentration in the supernatant in the adsorption assay was determined through electronic spectroscopy. By calorimetric titration thermodynamic data of the interaction between methylene blue and the chemically modified chitosan at the solid/liquid interface were obtained. The enthalpy of the dye/chitosan interaction gave 2.47 ± 0.02 kJ mol-1 with an equilibrium constant of 7350 ± 10 and for the carbon/dye interaction this constant gave 5951 ± 8. The spontaneity of these adsorptions are reflected by the free Gibbs energies of -22.1 ± 0.4 and -21.5 ± 0.2 kJ mol-1, respectively, found for these systems. This new adsorbent derived from a natural polysaccharide is as efficient as activated carbon. However 97% of the bonded dye can be eluted by sodium chloride solution, while this same operation elutes only 42% from carbon. Chitosan is efficient in dye removal with the additional advantage of being cheap, non-toxic, biocompatible and biodegradable. (author)

Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

Science.gov (United States)

Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.

2016-01-01

An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification. PMID:26110812

Photocatalytic dechlorination of PCB 138 using leuco-methylene blue and visible light; reaction conditions and mechanisms

International Nuclear Information System (INIS)

Izadifard, Maryam; Langford, Cooper H.; Achari, Gopal

2010-01-01

A study of dechlorination of PCB 138, under visible light employing methylene blue (MB) and triethylamine (TEA) in acetonitrile/water has been conducted to investigate the details of the mechanism of dechlorination and to determine the efficiency of the process for this representative congener. Two other amines, N-methyldiethanolamine (MEDA) and (triethanolamine) TEOA also replaced TEA and two other solvents, methanol and ethanol replacing acetonitrile were examined for effects on reaction rates. The results show that PCB 138 can be dechlorinated efficiently in this photocatalytic reaction. Clarifying ambiguities in several previous reports, the reduced form of MB, leuco-methylene blue (LMB) was identified as responsible for the photoreaction with its excited state transferring an electron to PCBs; oxidized LMB (i.e. MB) is reduced back to LMB by the excess amine present. The reaction depends on a cycle driven by the amine as a sacrificial electron donor. MEDA proved to be the most efficient electron donor; apparently in consequence of the most favourable steady state concentration of LMB. Methanol and ethanol may be used to replace acetonitrile with little change in the efficiency of the reaction.

Potential Biosorbent Derived from Calligonum polygonoides for Removal of Methylene Blue Dye from Aqueous Solution

Science.gov (United States)

Nasrullah, Asma; Khan, Hizbullah; Khan, Amir Sada; Man, Zakaria; Muhammad, Nawshad; Khan, Muhammad Irfan; Abd El-Salam, Naser M.

2015-01-01

The ash of C. polygonoides (locally called balanza) was collected from Lakki Marwat, Khyber Pakhtunkhwa, Pakistan, and was utilized as biosorbent for methylene blue (MB) removal from aqueous solution. The ash was used as biosorbent without any physical or chemical treatment. The biosorbent was characterized by using various techniques such as Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The particle size and surface area were measured using particle size analyzer and Brunauer-Emmett-Teller equation (BET), respectively. The SEM and BET results expressed that the adsorbent has porous nature. Effects of various conditions such as initial concentration of methylene blue (MB), initial pH, contact time, dosage of biosorbent, and stirring rate were also investigated for the adsorption process. The rate of the adsorption of MB on biomass sample was fast, and equilibrium has been achieved within 1 hour. The kinetics of MB adsorption on biosorbent was studied by pseudo-first- and pseudo-second-order kinetic models and the pseudo-second-order has better mathematical fit with correlation coefficient value (R 2) of 0.999. The study revealed that C. polygonoides ash proved to be an effective, alternative, inexpensive, and environmentally benign biosorbent for MB removal from aqueous solution. PMID:25705714

Electrochemical behavior of an anticancer drug 5-fluorouracil at methylene blue modified carbon paste electrode

International Nuclear Information System (INIS)

Bukkitgar, Shikandar D.; Shetti, Nagaraj P.

2016-01-01

A novel sensor for the determination of 5-fluorouracil was constructed by electrochemical deposition of methylene blue on surface of carbon paste electrode. The electrode surface morphology was studied using Atomic force microscopy and XRD. The electrochemical activity of modified electrode was characterized using cyclic voltammetry and differential pulse method. The developed sensor shows impressive enlargement in sensitivity of 5-fluorouracil determination. The peak currents obtained from differential pulse voltammetry was linear with concentration of 5-fluorouracil in the range 4 × 10 −5 –1 × 10 −7 M and detection limit and quantification limit were calculated to be 2.04 nM and 6.18 nM respectively. Further, the sensor was successfully applied in pharmaceutical and biological fluid sample analysis. - Highlights: • Electrochemical oxidation of 5-fluorouracil has been investigated for first time at methylene blue modified carbon paste electrode • The electrode process was irreversible and diffusion controlled • Probable electrochemical mechanism was proposed which involved two proton and two electron transfer reaction • The LOD and LOQ values were calculated to be 2.04 nM and 6.18 nM, respectively, with good selectivity and sensitivity. • Proposed method was applied to 5-Fluorouracil determination in pharmaceutical and spiked human urine samples

New diphosphonate compounds for skeletal imaging: comparison with methylene diphosphonate

International Nuclear Information System (INIS)

Subramanian, G.; McAfee, J.G.; Thomas, F.D.; Feld, T.A.; Zapf-Longo, C.; Palladino, E.

1983-01-01

Three-hour biodistribution of Tc-99m complexes of six diphosphonates was compared in rabbits with tibial lesions to determine which was best for detection of focal bone lesions. Sr-85 was used as a standard. N,N-dimethylaminomethylene diphosphonate (DMAD) was the only agent with a higher lesion/normal bone ratio than methylene diphosphonate (MDP), attributable to lower concentration in normal bone. Hydroxymethane diphosphonate (HDP) and 2,3-dicarboxypropane-1, 1-diphosphonate (DPD) demonstrated higher concentration than MDP in normal bone without improving lesion contrast. They also exhibited much higher uptake in the liver and kidney, as well as muscle and red marrow in the case of DPD. None was superior to MDP as an all-purpose skeletal agent, though others may be better for specific applications

Facile synthesis of bird's nest-like TiO2 microstructure with exposed (001) facets for photocatalytic degradation of methylene blue

Science.gov (United States)

Zhang, Guozhong; Zhang, Shuqu; Wang, Longlu; Liu, Ran; Zeng, Yunxiong; Xia, Xinnian; Liu, Yutang; Luo, Shenglian

2017-01-01

The scrupulous design of hierarchical structure and highly active crystal facets exposure is essential for the creation of photocatalytic system. However, it is still a big challenge for scrupulous design of TiO2 architectures. In this paper, bird's nest-like anatase TiO2 microstructure with exposed highly active (001) surface has been successfully synthesized by a facile one-step solvothermal method. Methylene blue (MB) is chosen as a model pollutant to evaluate photocatalytic activity of as-obtained TiO2 samples. The results show that the photocatalytic activity of the bird's nest-like sample is more excellent than P25 in the degradation of MB due to high specific surface area and highly active (001) crystal facets exposure when tested under simulated solar light. Besides, it can be readily separated from the photocatalytic system by sedimentation after photocatalytic reaction, which is a significant advantage against conventional powder photocatalyst. The bird's nest-like microspheres with novel structure may have potential application in photocatalysis and other fields.

Facile decolorization of methylene blue by morphology-dependence δ-MnO2 nanosheets -modified diatomite

Science.gov (United States)

Yu, Ting Ting; Li, Kai Lin; Guo, Xiao Long; Li, Fei; Huang, Jia Mu; Zhang, Yu Xin

2015-12-01

In this work, coscinodiscus-diatomite and melosira-diatomite have been decorated by ultrathin birnessite MnO2 (δ-MnO2) nanosheets through a one-pot hydrothermal method without using any surfactants. The δ-MnO2 nanosheets are observed to grow vertically on the purified melosira-diatomite as well as coscinodiscus-diatomite. Moreover, the two composites exhibit high efficiency for decomposing methylene blue (MB) in the presence of H2O2. The coscinodiscus-diatmite@MnO2 achieves a removal rate of 81.8% (2 h), and yet melosira-diatomite@MnO2 reaches a higher degradation rate of 91.3% in 2 h. Additionally, the effects of catalyst amount, catalysis reaction temperature, preparing time have also been investigated. In principle, the diverse diatomite@MnO2 nanostructures not only present an environmentally friendly and low cost with a good cycling stability, but also offer a simple way for the catalytic degradation of dye waste water in practical applications.

The stereochemistry of the addition of chlorotitanium enolates of N-acyl oxazolidin-2-ones to 5- and 6- membered N-acyliminium ions

Directory of Open Access Journals (Sweden)

Pilli Ronaldo A.

2001-01-01

Full Text Available The stereoselective addition of chiral and achiral titanium enolates derived from the corresponding N-acyl oxazolidin-2-ones to 5- and 6- membered N-acyliminium ions afforded 2-substituted pyrrolidines in moderate to good diastereoisomeric ratio (5:1 to 14:1 while lower diastereoselection was generally observed in the formation of the corresponding 2-substituted piperidines. The stereochemical outcome was found to be modulated by the nature of the cyclic N-acyliminium ion (5- or 6-membered and of its carbamate and by the N-acyl group in the enolate precursor. The preferential lk approach seems to be dictated mainly by the minimization of non-bonding interactions between the N-acyl group in the chlorotitanium (IV enolate and the carbamate and methylene groups in the cyclic N-acyliminium ion.

A prospective randomized trial comparing patent blue and methylene blue for the detection of the sentinel lymph node in breast cancer patients

Directory of Open Access Journals (Sweden)

Régis Resende Paulinelli

Full Text Available Summary Introduction: Methylene blue is more widely available and less expensive than patent blue, with an apparently lower risk of anaphylaxis. Objective: The two dyes were compared regarding detection of the sentinel lymph node (SLN. Method: A prospective, randomized trial involved 142 patients with invasive breast carcinoma. Sixty-nine (49.3% assigned to patent blue (group A and 71 (50.70% to methylene blue (group B. Thirty-five patients (25.0% were clinical stage III or IV; 55 (38.7% had axillary lymph nodes affected; and 69 (49.3% underwent neoadjuvant chemotherapy. Two patients were excluded because the dye type was not recorded. Results: Patients and tumor characteristics were similar in both groups. SLNs were identified in 47 women (68.1% in group A and 43 (60.6% in group B (p=0.35. SLNs were affected in 22 cases (51.2% in group A and 21 (48.8% in group B (p=0.62. The SLN was the only node affected in 12 cases (54.5% in group A and six (33.3% in group B (p=0.18. The time and degree of difficulty involved in identifying the SLN were similar in both groups. There were no complications or allergies. Conclusion: Methylene blue performed as well as patent blue in identifying the SLN in breast cancer patients.

Acid-base-controlled stereoselective metalation of overhanging carboxylic acid porphyrins: consequences for the formation of heterobimetallic complexes.

Science.gov (United States)

Le Gac, Stéphane; Najjari, Btissam; Dorcet, Vincent; Roisnel, Thierry; Fusaro, Luca; Luhmer, Michel; Furet, Eric; Halet, Jean-François; Boitrel, Bernard

2013-08-12

Overhanging carboxylic acid porphyrins have revealed promising ditopic ligands offering a new entry in the field of supramolecular coordination chemistry of porphyrinoids. Notably, the adjunction of a so-called hanging-atop (HAT) Pb(II) cation to regular Pb(II) porphyrin complexes allowed a stereoselective incorporation of the N-core bound cation, and an allosterically controlled Newton's cradle-like motion of the two Pb(II) ions also emerged from such bimetallic complexes. In this contribution, we have extended this work to other ligands and metal ions, aiming at understanding the parameters that control the HAT Pb(II) coordination. The nature of the N-core bound metal ion (Zn(II), Cd(II)), the influence of the deprotonation state of the overhanging COOH group and the presence of a neutral ligand on the opposite side (exogenous or intramolecular), have been examined through (1)H NMR spectroscopic experiments with the help of radiocrystallographic structures and DFT calculations. Single and bis-strap ligands have been considered. They all incorporate a COOH group hung over the N-core on one side. For the bis-strap ligands, either an ester or an amide group has been introduced on the other side. In the presence of a base, the mononuclear Zn(II) or Cd(II) complexes incorporate the carbonyl of the overhanging carboxylate as apical ligand, decreasing its availability for the binding of a HAT Pb(II). An allosteric effector (e.g., 4-dimethylaminopyridine (DMAP), in the case of a single-strap ligand) or an intramolecular ligand (e.g., an amide group), strong enough to compete with the carbonyl of the hung COO(-), is required to switch the N-core bound cation to the opposite side with concomitant release of the COO(-), thereby allowing HAT Pb(II) complexation. In the absence of a base, Zn(II) or Cd(II) binds preferentially the carbonyl of the intramolecular ester or amide groups in apical position rather than that of the COOH. This better preorganization, with the

Stereoselective synthesis and spectral studies of some benzotriazolylacetyl hydrazones of 3-alkyl-2,6-diarylpiperidin-4-ones

Science.gov (United States)

Pillai, M. Velayutham; Rajeswari, K.; Kumar, C. Udhaya; Krishnan, K. Gokula; Mahendran, S.; Ramalingan, C.; Nagarajan, E. R.; Vidhyasagar, T.

2017-12-01

An effort to include biologically potent benzotriazole nucleus into piperidine ring is achieved through hydrazone formation. The characterization of the synthesized compounds was carried out using FT-IR, 1H &13C NMR, 1H-1H COSY, 1H-13C COSY, NOESY spectral techniques and GC-Mass spectrum. The spectral assignments were done without ambiguity using 2D-NMR techniques. The conformational preference of the piperidine ring deduced from the spectral studies is 'chair'. The diastereotopic nature of the methylene protons/methyl groups present in the molecules is revealed clearly in their spectral pattern observed.

Decolorization of Methylene Blue with TiO2 Sol via UV Irradiation Photocatalytic Degradation

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Jun Yao

2010-01-01

Full Text Available TiO2 sol was prepared for the degradation of methylene blue (MB solution under ultraviolet (UV irradiation. The absorption spectra of MB indicated that the maximum wavelength, 663 nm, almost kept the same. The performance of 92.3% for color removal was reached after 160 min. The particle size of TiO2 sol was about 22.5 nm. X-ray diffraction showed that TiO2 consisted of a single anatase phase. The small size and anatase phase probably resulted in high photocatalytic activity of TiO2 sol. The degradation ratio decreased as the initial concentration of MB increased. The photodegradation efficiency decreased in the order of pH 2>pH 9>pH 7. Regarding catalyst load, the degradation increased with the mass of catalyst up to an amount of 1.5 g⋅L−1 then decreased as the mass continued to increase. The addition of H2O2 to TiO2 sol resulted in an increase on the degradation ratio.

Characterizing the discoloration of methylene blue in Fe0/H2O systems.

Science.gov (United States)

Noubactep, C

2009-07-15

Methylene blue (MB) was used as a model molecule to characterize the aqueous reactivity of metallic iron in Fe(0)/H(2)O systems. Likely discoloration mechanisms under used experimental conditions are: (i) adsorption onto Fe(0) and Fe(0) corrosion products (CP), (ii) co-precipitation with in situ generated iron CP, (iii) reduction to colorless leukomethylene blue (LMB). MB mineralization (oxidation to CO(2)) is not expected. The kinetics of MB discoloration by Fe(0), Fe(2)O(3), Fe(3)O(4), MnO(2), and granular activated carbon were investigated in assay tubes under mechanically non-disturbed conditions. The evolution of MB discoloration was monitored spectrophotometrically. The effect of availability of CP, Fe(0) source, shaking rate, initial pH value, and chemical properties of the solution were studied. The results present evidence supporting co-precipitation of MB with in situ generated iron CP as main discoloration mechanism. Under high shaking intensities (>150 min(-1)), increased CP generation yields a brownish solution which disturbed MB determination, showing that a too high shear stress induced the suspension of in situ generated corrosion products. The present study clearly demonstrates that comparing results from various sources is difficult even when the results are achieved under seemingly similar conditions. The appeal for an unified experimental procedure for the investigation of processes in Fe(0)/H(2)O systems is reiterated.

Methylene Blue in Ventilator-Induced Lung Injury after Pneumonectomy: an Experimental Study

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Ye. V Suborov

2007-01-01

Full Text Available Objective: to study the expediency and efficiency of using methylene blue (MB on a model of pneumectomy (PE and subsequent ventilator-induced lung injury (VILI in sheep. Materials and methods. The study was conducted at the Research Laboratory of University of Tromse. The experiment included 23 sheep weighing 41.0±4.9 kg. Thoracotomy and right-sided pneumonectomy were performed in the animals under general anesthesia and controlled artificial ventilation. After measurement of the parameters of systemic hemodynamics and extravascular water of the lung (EVWL, the animals were divided into 3 groups: 1 a control group (CG, n=7 with a tidal volume (TV of 6 ml/kg and an end-expiratory positive pressure (PEEP of 2 cm H2O; 2 a VILI group (n=9 with a TV of 12 ml/kg and a PEEP of 0 cm H2O; 3 a group of MB (n=7 that was given in parallel with a damaging ventilation mode. The thermodilution technique (using a Cold Z-021 monitor, (Pulsion, Germany was employed to measure volumetric parameters and EVWL. The parameters of pulmonary hemodynamics, respiratory mechanics, and blood gas composition were recorded. Results: After its reduction at PE, EVWL index increased during damaging ventilation in the VILI and MB groups. In addition, there was an increase in pulmonary artery wedge pressure after PE in the MB and VILI groups. In the latter group, arterial hypoxemia was observed at the end of the experiment. Along with this, after PE pulmonary compliance decreased and airway pressure elevated in the VILI and MB groups. Conclusion: In the presented model of VILI, MB does not prevent the development of postp-neumectomic edema of the lung. Key words: thermochromodilution, acute lung injury, pneumectomy, ventilator-induced lung injury, postpneumectomic edema of the lung, methylene blue.

Potential biosorbent, Haloxylon recurvum plant stems, for the removal of methylene blue dye

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Warda Hassan

2017-05-01

Full Text Available Conventional technologies for the removal of dyes from the waste water are proving expensive due to non-regenerable materials used and their high costs. The use of dried biomass from Haloxylon recurvum plant stems (HRS was studied for the removal of methylene blue, a textile dye, from its aqueous solution. FTIR studies revealed a variety of functional groups on the plant surface including carboxyl and amino groups. The pH at the point of zero charge (pHpzc was found to be 6.3. The dye uptake by the plant increased with increasing pH, time of contact and dye concentration. Lagergren Pseudo first order and the Ho’s pseudo second order models were used to study the kinetics. The Langmuir and Freundlich equilibrium models were studied and the qmax was 22.93 mg/g. The changes in the values of free energy (ΔGo and enthalpy (ΔHo indicated the spontaneous, feasible and exothermic nature of the sorption process. H. recurvum plant is locally available in large quantities, so the powdered stems can act as a cost-effective and ecofriendly biosorbent for the removal of the dye from its aqueous solutions.

A novel bio-degradable polymer stabilized Ag/TiO2 nanocomposites and their catalytic activity on reduction of methylene blue under natural sun light.

Science.gov (United States)

Geetha, D; Kavitha, S; Ramesh, P S

2015-11-01

In the present work we defined a novel method of TiO2 doped silver nanocomposite synthesis and stabilization using bio-degradable polymers viz., chitosan (Cts) and polyethylene glycol (PEG). These polymers are used as reducing agents. The instant formation of AgNPs was analyzed by visual observation and UV-visible spectrophotometer. TiO2 nanoparticles doped at different concentrations viz., 0.03, 0.06 and 0.09mM on PEG/Cts stabilized silver (0.04wt%) were successfully synthesized. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the nanomaterial, producing ternary hybrid inorganic-organic nanomaterials. The results reveal that they have higher photocatalytic efficiencies under natural sun light. The synthesized TiO2 doped Ag nanocomposites (NCs) were characterized by SEM/EDS, TEM, XRD, FTIR and DLS with zeta potential. The stability of Ag/TiO2 nanocomposite is due to the high negative values of zeta potential and capping of constituents present in the biodegradable polymer which is evident from zeta potential and FT-IR studies. The XRD and EDS pattern of synthesized Ag/TiO2 NCs showed their crystalline structure, with face centered cubic geometry oriented in (111) plane. AFM and DLS studies revealed that the diameter of stable Ag/TiO2 NCs was approximately 35nm. Moreover the catalytic activity of synthesize Ag/TiO2 NCs in the reduction of methylene blue was studied by UV-visible spectrophotometer. The synthesized Ag/TiO2 NCs are observed to have a good catalytic activity on the reduction of methylene blue by bio-degradable which is confirmed by the decrease in absorbance maximum value of methylene blue with respect to time using UV-vis spectrophotometer. The significant enhancement in the photocatalytic activity of Ag/TiO2 nanocomposites under sun light irradiation can be ascribed to the effect of noble metal Ag by acting as electron traps in TiO2 band gap. Copyright © 2015. Published by Elsevier Inc.

Effect of CO2 Flow Rate on the Pinang Frond-Based Activated Carbon for Methylene Blue Removal

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S. G. Herawan

2013-01-01

Full Text Available Activated carbons are regularly used the treatment of dye wastewater. They can be produced from various organics materials having high level of carbon content. In this study, a novel Pinang frond activated carbon (PFAC was produced at various CO2 flow rates in the range of 150–600 mL/min at activation temperature of 800°C for 3 hours. The optimum PFAC sample is found on CO2 flow rate of 300 mL/min which gives the highest BET surface area and pore volume of 958 m2/g and 0.5469 mL/g, respectively. This sample shows well-developed pore structure with high fixed carbon content of 79.74%. The removal of methylene blue (MB by 95.8% for initial MB concentration of 50 mg/L and 72.6% for 500 mg/L is achieved via this sample. The PFAC is thus identified to be a suitable adsorbent for removing MB from aqueous solution.

Studies on the Total Synthesis of Amphidinolide O (II): A Stereoselective Synthesis of C1-C11 Fragment

Energy Technology Data Exchange (ETDEWEB)

Jang, Mi Yeon; Kim, Jong Woo; Lee, Duck Hyung [Sogang University, Seoul (Korea, Republic of)

2005-10-15

Two ketones and, the C1-C11 fragment of Amphidinolide O, were prepared stereoselectively via 14 and 16 step sequences in 8.7% and 2.0% overall yield, respectively. The amphidinolides were isolated from the marine dinoflagellate Amphidinium sp., which produces a host of secondary metabolites endowed with potent cytotoxicity against various cancer cell lines. Amphidinolide O displayed potent in vitro cytotoxicity against L1210 marine leukemia cells and human epidermoid carcinoma KB cells with 1.7 and 3.6 μg/mL of IC50s, respectively. In addition to our recent reports regarding to the synthesis of C12-C17 and C3-C11 fragments of amphidinolide O, we describe herein a new route to diastereoselective synthesis of C1-C11 fragment of. The retrosynthetic analysis of led to the C1-C11 fragment and C12-C17 fragment. The hemiketal was expected from acyclic precursor 4 which, in turn, would be derived by diastereoselective aldol reaction between ketone and aldehyde.

2-(Hetero(aryl)methylene)hydrazine-1-carbothioamides as potent urease inhibitors.

Science.gov (United States)

Saeed, Aamer; Imran, Aqeel; Channar, Pervaiz A; Shahid, Mohammad; Mahmood, Wajahat; Iqbal, Jamshed

2015-02-01

A small series of 2-(hetero(aryl)methylene) hydrazine-1-carbothioamides including two aryl derivatives was synthesized and tested for their inhibitory activity against urease. Compound (E)-2-(Furan-2-ylmethylene) hydrazine-1-carbothioamide (3f), having a furan ring, was the most potent inhibitor of urease with an IC50 value of 0.58 μM. Molecular modeling was carried out through docking the designed compounds into the urease binding site to predict whether these derivatives have analogous binding mode to the urease inhibitors. The study revealed that all of the tested compounds bind with both metal atoms at the active site of the enzyme. The aromatic ring of the compounds forms ionic interactions with the residues, Ala(440), Asp(494), Ala(636), and Met(637). © 2014 John Wiley & Sons A/S.

The determination of boron in aluminium of high purity

International Nuclear Information System (INIS)

Cook, E.B.T.; Holan, H.

1977-01-01

A description is given of the investigations that led to the development of chemical methods for the determination of boron within the range 0,25 to 1,0 p.p.m. in aluminium of high purity. Methods were developed that incorporated fluorimetry, directly in solutions containing aluminium and after separation of boron by liquid-liquid extraction into 2-ethyl-1,3 hexanediol. A published spectrophotometric method, involving extraction of the BF 4 sup(-) complex with methylene blue into dichloroethane, was modified for application to alluminium samples. Details of this modified procedure and the fluorimetric-extraction procedure are appended. The precision of the methylene-blue method is about 6 percent relative and is recommended for precision and speed in preference to others. Separation of boron by distillation and spectrophotometric determination with curcumin gave low values in comparison with those obtained by the other methods. Agreement between the boron values obtained on the samples tested was good for the fluorimetric and methylene-blue spectrophotometric methods

Modified solvothermal synthesis of cobalt ferrite (CoFe2O4) magnetic nanoparticles photocatalysts for degradation of methylene blue with H2O2/visible light

Science.gov (United States)

Kalam, Abul; Al-Sehemi, Abdullah G.; Assiri, Mohammed; Du, Gaohui; Ahmad, Tokeer; Ahmad, Irfan; Pannipara, M.

2018-03-01

Different grads of magnetic nano-scaled cobalt ferrites (CoFe2O4) photocatalysts were synthesized by modified Solvothermal (MST) process with and without polysaccharide. The indigenously synthesized photocatalysts were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), thermo gravimetric analysis (TGA), Fourier transform infrared (FT-IR), UV-visible (UV-vis) spectroscopy and N2 adsorption-desorption isotherm method. The Fourier transform infrared spectroscopy study showed the Fe-O stretching vibration 590-619 cm-1, confirming the formation of metal oxide. The crystallite size of the synthesized photocatalysts was found in the range between 20.0 and 30.0 nm. The surface area of obtained magnetic nanoparticles is found to be reasonably high in the range of 63.0-76.0 m2/g. The results shown that only MST-2 is the most active catalyst for photo-Fenton like scheme for fast photodegradation action of methylene blue dye, this is possible due to optical band gap estimated of 2.65 eV. Captivatingly the percentage of degradation efficiency increases up to 80% after 140 min by using MST-2 photocatalyst. Photocatalytic degradation of methylene blue (MB) dye under visible light irradiation with cobalt ferrite magnetic nanoparticles followed first order kinetic constant and rate constant of MST-2 is almost 2.0 times greater than MST-1 photocatalyst.

Photocatalytic degradation of methylene blue dye using Fe{sub 2}O{sub 3}/TiO{sub 2} nanoparticles prepared by sol–gel method

Energy Technology Data Exchange (ETDEWEB)

Ahmed, M.A., E-mail: abdelhay71@hotmail.com [Chemistry Department, Faculty of Science, Ain-Shams University (Egypt); El-Katori, Emad E.; Gharni, Zarha H. [Chemistry Department, Faculty of Science, King Khaled University (Saudi Arabia)

2013-03-15

Graphical abstract: Photocatalytic degradation of methylene blue dye was successfully carried over Fe{sub 2}O{sub 3}/TiO{sub 2} nanorods embedded various proportion of Fe{sub 2}O{sub 3} (0–20) wt.%. Highlights: ► Fe{sub 2}O{sub 3}/TiO{sub 2} nano mixed oxide samples were successfully synthesized by sol–gel method. ► Manipulation of particle size and structure were achieved by micelle template approach. ► Both adsorption and photocatalytic reactivity are the main reasons for exceptional decolorization of methylene blue dye. ► A new mechanism for electronic transition between TiO{sub 2} and Fe{sub 2}O{sub 3} was proposed. -- Abstract: The photocatalytic degradation of methylene blue dye was successfully carried under UV irradiation over Fe{sub 2}O{sub 3}/TiO{sub 2} nanoparticles embedded various composition of Fe{sub 2}O{sub 3} (0–20) wt.% synthesized by sol–gel process. Structural and textural features of the mixed oxide samples were investigated by X-ray diffraction [XRD], Fourier transformer infra-red [FTIR], Energy dispersive X-ray [EDX], Field emission electron microscope [FESEM] and transmission electron microscope [TEM]. However, the optical features were estimated using UV–Vis spectrophotometer. The results reveal that the incorporation of various Fe{sub 2}O{sub 3} up to 7% is associated by remarkable increase in surface area, reduction of particle size, stabilization of anatase phase, shifting the photoexcitation response of the sample to visible region and exceptional degradation of methylene blue dye. On the other hand, increasing Fe{sub 2}O{sub 3} contents up to 20 wt.% is associated by anatase–rutile transformation, increasing in particle size and remarkable decrease in surface area which are prime factors in reducing the degradation process. The experimental results indicate that Fe{sub 2}O{sub 3}/TiO{sub 2} nanoparticles having both the advantages of photodegradation–adsorption process which considered a promising new

Scientific Basis for Paint Stripping: Elucidated Combinatorial Mechanism of Methylene Chloride and Phenol Based Paint Removers

Science.gov (United States)

2014-01-22

TiO2 9.5 Isobutyl ketone 0.1 Iron oxide hydrate 2.5 n-Butyl acid phosphate 0.1 Carbazole dioxazine violet ɘ.1 Bentone 0.5 Table 3: MIL-PRF-85285...partial formulation films, with pigments and no fillers, and full formulation films of current military polyurethane coatings were analyzed in this...time of the solvents. 22-01-2014 Memorandum Report Paint stripper Methylene chloride Phenol Polyurethane 7 June 2012 – 6 June 2013 SERDP WP-2244

Novel silicone-based polymer containing active methylene designed for the removal of indoor formaldehyde

Energy Technology Data Exchange (ETDEWEB)

Niu, Song, E-mail: niusong84@163.com; Yan, Hongxia, E-mail: hongxiayan@nwpu.edu.cn

2015-04-28

Highlights: • A novel silicone-based polymer with active methylene was explored. • Surface tension of liquid paints could be lowered using the polymer. • The polymer was easy to migrate toward the air-coating interface. • Free HCHO could effectively be removed using the polymer. • A lights on HCHO reduction without complicated preparation procedure was shielded. - Abstract: Indoor air pollution is caused inevitably due to complicated home decoration, in which formaldehyde is one of the most typical pollutants. It will be a convenient, economical and effective strategy to remove indoor formaldehyde if imparting a feature of formaldehyde removal to decorative coatings. We have successfully explored a novel silicone-based polymer containing active methylene used as a formaldehyde absorbent in coatings via a straightforward transesterification process using inexpensive and easily available chemicals. The polymer has been characterized by {sup 13}C NMR, FTIR, GC and GPC. Formaldehyde removal capacity of the coating films containing different contents of the polymer has been investigated. The results indicated that coatings incorporating 4 wt% of the polymer could make the coating films exhibit significant improvement on formaldehyde removal including purificatory performance (>85%) and durability of purificatory effect (>60%), compared to those consisting of absorbents without any silicon, and improve yellowing resistance performance, while other properties, such as gloss, adhesion, pencil hardness, flexibility and impact resistance, were kept almost unaffected. The chemical absorption process of the silicone-based polymer filled in interior decorative coatings is demonstrated as a promising technology to purify indoor formaldehyde and thus can reduce the harm to individuals.

SrTiO3 Nanocube-Doped Polyaniline Nanocomposites with Enhanced Photocatalytic Degradation of Methylene Blue under Visible Light

Directory of Open Access Journals (Sweden)

Syed Shahabuddin

2016-02-01

Full Text Available The present study highlights the facile synthesis of polyaniline (PANI-based nanocomposites doped with SrTiO3 nanocubes synthesized via the in situ oxidative polymerization technique using ammonium persulfate (APS as an oxidant in acidic medium for the photocatalytic degradation of methylene blue dye. Field emission scanning electron microscopy (FESEM, transmission electron microscopy (TEM, thermogravimetric analysis (TGA, X-ray diffraction (XRD, UV–Vis spectroscopy, Brunauer–Emmett–Teller analysis (BET and Fourier transform infrared spectroscopy (FTIR measurements were used to characterize the prepared nanocomposite photocatalysts. The photocatalytic efficiencies of the photocatalysts were examined by degrading methylene blue (MB under visible light irradiation. The results showed that the degradation efficiency of the composite photocatalysts that were doped with SrTiO3 nanocubes was higher than that of the undoped polyaniline. In this study, the effects of the weight ratio of polyaniline to SrTiO3 on the photocatalytic activities were investigated. The results revealed that the nanocomposite P-Sr500 was found to be an optimum photocatalyst, with a 97% degradation efficiency after 90 min of irradiation under solar light.

Stereoselective in vitro metabolism of rhynchophylline and isorhynchophylline epimers of Uncaria rhynchophylla in rat liver microsomes.

Science.gov (United States)

Wang, Xin; Qiao, Zhou; Liu, Jia; Zheng, Mei; Liu, Wenyuan; Wu, Chunyong

2017-11-10

1. The objective was to investigate the underlying mechanism of the stereoselectivity in the metabolism of rhynchophylline (RIN) and isorhynchophylline (IRN) epimers in rat liver microsomes (RLM). 2. After incubation, eight metabolites of RIN (M1-5) and IRN (M6-8) reacted at A- and C-ring were identified using LC-Q-TOF/MS. Metabolic pathways included oxidation, hydroxylation, N-oxidation and dehydrogenation. In addition, hydroxylation at A-ring was the major metabolic pathway for RIN whereas the oxidation at C-ring was the major one for IRN. 3. Enzyme kinetics showed that the intrinsic clearance (CL int ) for IRN elimination was 1.9-fold higher than RIN and the degradation half-life (T 1/2 ) of RIN was 4.7-fold higher than that of IRN, indicating IRN was more favorable to be metabolized than RIN in RLM. 4. Data from chemical inhibition study demonstrated CYP3A was the predominant isoform involved in the metabolic elimination of both epimers, as well as the formation of M1-8. 5. In conclusion, data revealed that due to the spatial configurations at C-7 position, RIN and IRN epimers possessed different hepatic metabolic pathways and elimination rates which were mainly mediated by CYP3A.

Preparation and characterization of poly(AA co PVP)/PGS composite and its application for methylene blue adsorption.

Science.gov (United States)

Yang, Cai-xia; Lei, Lei; Zhou, Peng-xin; Zhang, Zhe; Lei, Zi-qiang

2015-04-01

Poly (AA co PVP)/PGS (PAPP) composite adsorbent was prepared by radical polymerization from Acrylic acid (AA), Polyvinylpyrrolidone (PVP) and Palygorskite (PGS), using N,N-methylenebisacrylamide (MBA) as cross-linker and potassium persulfate (KPS) as initiator. The PAPP was characterized with Fourier transform infrared (FT-IR), thermogravimetric analysis (TG), scanning electron microscope (SEM) and transmission electron microscopy (TEM). PAPP was used as adsorbent for the removal of methylene blue from aqueous solutions. The influences of pH, adsorption temperature and adsorption time on the adsorption properties of the composite to the dye were also investigated. Meanwhile, the adsorption rate data and adsorption equilibrium date were analyzed based on the pseudo-first-order and pseudo-second-order kinetic model, Langmuir and Freundlich isotherm models, respectively. The results indicating that the kinetic behavior better fit with the pseudo-second-order kinetic model. The maximum equilibrium adsorption capacity (q(m)) is 1815 mg/g at 289 K. The isotherm behavior can be explained by the Langmuir isotherm models. The activation energy was also evaluated for the removal of methylene blue onto PAPP. These results demonstrate that this composite material could be used as a good adsorbent for the removal of cationic dyes from wastewater. Copyright © 2014 Elsevier Inc. All rights reserved.

Comparing Different Strategies in Directed Evolution of Enzyme Stereoselectivity: Single- versus Double-Code Saturation Mutagenesis.

Science.gov (United States)

Sun, Zhoutong; Lonsdale, Richard; Li, Guangyue; Reetz, Manfred T

2016-10-04

Saturation mutagenesis at sites lining the binding pockets of enzymes constitutes a viable protein engineering technique for enhancing or inverting stereoselectivity. Statistical analysis shows that oversampling in the screening step (the bottleneck) increases astronomically as the number of residues in the randomization site increases, which is the reason why reduced amino acid alphabets have been employed, in addition to splitting large sites into smaller ones. Limonene epoxide hydrolase (LEH) has previously served as the experimental platform in these methodological efforts, enabling comparisons between single-code saturation mutagenesis (SCSM) and triple-code saturation mutagenesis (TCSM); these employ either only one or three amino acids, respectively, as building blocks. In this study the comparative platform is extended by exploring the efficacy of double-code saturation mutagenesis (DCSM), in which the reduced amino acid alphabet consists of two members, chosen according to the principles of rational design on the basis of structural information. The hydrolytic desymmetrization of cyclohexene oxide is used as the model reaction, with formation of either (R,R)- or (S,S)-cyclohexane-1,2-diol. DCSM proves to be clearly superior to the likewise tested SCSM, affording both R,R- and S,S-selective mutants. These variants are also good catalysts in reactions of further substrates. Docking computations reveal the basis of enantioselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stereoselectivity in the disposition and metabolism of the uricosuric-diuretic agent, indacrinone, in Rhesus monkeys

Energy Technology Data Exchange (ETDEWEB)

Zacchei, A.G.; Dobrinska, M.R.; Wishousky, T.I.; Kwan, K.C.; White, S.D.

The physiological disposition following intravenous dosing of the separate enantiomers of indacrinone-/sup 14/C (I), and of their major metabolite, 4'-hydroxyindacrinone-/sup 14/C (M), was studied in the rhesus monkey. Pharmacokinetic analysis indicated that the disposition of I and M was stereoselective. In the case of the enantiomers of I, the areas under the curves of plasma concentration vs. time were about sevenfold greater for the (S)(+)- as compared to the (R)(-)-enantiomer. Renal and plasma clearances of (R)(-)-I were five to seven times greater than those of (S)(+)-I. Total urinary recovery of unchanged drug and metabolite accounted for 70% of the administered dose of either enantiomer. The systemic availability of (R)(-)-M from (R)(-)-I was approximately 21% of the dose, whereas that of (S)(+)-M from (S)(+)-I was only 4%. More pronounced differences were noted in the kinetics of metabolite disposition. The AUC values were about 27 times greater for (S)(+)-M than (R)(-)-M, and the renal and plasma clearances were approximately 25-fold higher for (R)(-)-M as compared to (S)(+)-M. The volume of distribution of (S)(+)-M was only 12% of that observed with (R)(+)-M. There was no evidence of glucuronide or sulfate conjugates of any of the enantiomers. These findings are consistent with the pharmacological activity attributed to the different enantiomers.

TiO₂ (rutile) embedded inulin--A versatile bio-nanocomposite for photocatalytic degradation of methylene blue.

Science.gov (United States)

Jayanthi Kalaivani, G; Suja, S K

2016-06-05

Inulin, a water soluble carbohydrate polymer, was extracted from Allium sativum L. by hot water diffusion method. A novel bio-nanocomposite was prepared by embedding TiO2 (rutile) onto the inulin matrix. The extracted inulin and the prepared bio-nanocomposite were characterized using UV-vis, FT-IR, XRD, SEM, TEM and TGA techniques. The photocatalytic activity of the bio-nanocomposite for the degradation of methylene blue was studied under UV illumination in batch mode experiment and was found to be twice as high as that of pristine TiO2. The kapp for inulin-TiO2 (0.0449 min(-1)) was higher than that for TiO2 (0.0325 min(-1)) which may be due to the synergistic action of inulin and TiO2. The stabilization of photo excited electron suppressed the electron-hole pair recombination thereby inducing the electrons and the holes to participate in the photo reduction and oxidation processes, respectively and enhancing the photocatalytic activity. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetics, Equilibrium, and Thermodynamic Studies on Adsorption of Methylene Blue by Carbonized Plant Leaf Powder

Directory of Open Access Journals (Sweden)

V. Gunasekar

2013-01-01

Full Text Available Carbon synthesized from plant leaf powder was employed for the adsorption of methylene blue from aqueous effluent. Effects of pH (2, 4, 6, 8, and 9, dye concentration (50, 100, 150, and 200 mg/dm3, adsorbent dosage (0.5, 1.0, 1.5, and 2.0 g/dm3, and temperature (303, 313, and 323 K were studied. The process followed pseudo-second-order kinetics. Equilibrium data was examined with Langmuir and Freundlich isotherm models and Langmuir model was found to be the best fitting model with high R2 and low chi2 values. Langmuir monolayer adsorption capacity of the adsorbent was found to be 61.22 mg/g. From the thermodynamic analysis, ΔH, ΔG, and ΔS values for the adsorption of MB onto the plant leaf carbon were found out. From the values of free energy change, the process was found out to be feasible process. From the magnitude of ΔH, the process was found to be endothermic physisorption.

Antibacterial activity of berberine-NorA pump inhibitor hybrids with a methylene ether linking group.

Science.gov (United States)

Samosorn, Siritron; Tanwirat, Bongkot; Muhamad, Nussara; Casadei, Gabriele; Tomkiewicz, Danuta; Lewis, Kim; Suksamrarn, Apichart; Prammananan, Therdsak; Gornall, Karina C; Beck, Jennifer L; Bremner, John B

2009-06-01

Conjugation of the NorA substrate berberine and the NorA inhibitor 5-nitro-2-phenyl-1H-indole via a methylene ether linking group gave the 13-substituted berberine-NorA inhibitor hybrid, 3. A series of simpler arylmethyl ether hybrid structures were also synthesized. The hybrid 3 showed excellent antibacterial activity (MIC Staphylococcus aureus, 1.7 microM), which was over 382-fold more active than the parent antibacterial berberine, against this bacterium. This compound was also shown to block the NorA efflux pump in S. aureus.

Novel methylene bridged ethylenediamine-type ligands: Synthesis and spectral characterization

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Mihajlović-Lalić Ljiljana E.

2014-01-01

Full Text Available Herein we report the synthesis of two new organic compounds, diisobutyl- and diisopentyl N,N′-methylene-(S,S-ethylenediamine-N,N′-di-2-(3-cyclohexylpropanoate. A one-pot procedure was carried out by adding the reducing agent and carbonyl compound into the methanol solution of the parent compounds (iso-butyl and iso-pentyl esters of (S,S-ethylenediamine-N,N′-di-2-(3-cyclohexylpropanoic acid in appropriate stoichiometric ratios. The compounds were fully characterized by infrared, ESI-MS, 1D (1H, 13C and 2D (COSY, HSQC, HMBC NMR spectroscopy and elemental analysis. The spectral data confirm the presence of -CH2- group introduced between nitrogen atoms of the ethylenediamine moiety revealing neutral form of potential bidentate ligand. [Projekat Ministarstva nauke Republike Srbije, br. 172035. The authors also acknowledge the support of the FP7 RegPot project FCUB ERA GA No. 256716. The EC does not share responsibility for the content of the article

Wiring of Glucose Oxidizing Flavin Adenine Dinucleotide-Dependent Enzymes by Methylene Blue-Modified Third Generation Poly(amidoamine) Dendrimers Attached to Spectroscopic Graphite Electrodes

International Nuclear Information System (INIS)

Castaing, Victor; Álvarez-Martos, Isabel; Ferapontova, Elena E.

2016-01-01

Highlights: • Methylene blue(MB)-labelled 3 G dendrimers electronically wire flavoenzymes to graphite electrodes. • Dendrimer-templated organization of MB improves electron transfer efficiency. • Covalent attachment of dendrimers to graphite provides stability of binding superior to S-Au. • Sugar-oxidizing hexose oxidase can be wired with no loss of FAD and electrocatalytic activity. - Abstract: Electro-enzymatic biotransformation requires an efficient and robust electronic communication between the biomolecules and electrodes, often performed by the relevant electron transfer (ET) mediating systems. Of those, redox-labeled dendrimeric structures, biocompatible and bearing spatially ordered multiple redox centers, represent an advanced alternative to the existing approaches. Here we show that methylene blue (MB)-labeled G3 PAMAM dendrimers covalently attached to the high-surface area spectroscopic graphite (Gr) electrodes form stable and spatially resolved electronic wires, characterized by the heterogeneous ET rate constant of 7.1 ± 0.1 s"−"1; they can be used for electronic wiring of glucose-oxidizing FAD-containing enzymes, such as hexose oxidase (HOX), and further bioelectrocatalysis of glucose oxidation, starting, at pH 7, from -100 mV vs. Ag/AgCl. Thus, dendrimer-templated electronic wires, comprising MB molecules conjugated to the periphery of the PAMAM and anchored to the surface of cost-effective Gr electrodes represent an efficient and robust tool for protein wiring to electrodes for their perspective bioelectronic applications in biosensors and biofuel cells.

Preparation and characterization of intrinsically coloured polymers using high energy radiation induced processes

International Nuclear Information System (INIS)

Guthrie, J.T.

1978-07-01

Information on the development in research is given in the utilization of high energy radiation sources in polymerizations and on polymer characterization in the following three areas: studies on the nitrile-styrene system, studies on the radiation induced polymerization of 2-vinyl anthraquinone and the graft polymerization of vinyl monomers onto cellulose in the DMSO/HCHO/cellulose system. Within the framework of research in radiation induced polymerization, samples of 2-vinyl anthraquinone were subjected to X-ray diffraction and e.s.r. examinations and the kinetics and mechanism of γ-ray induced solution polymerization of 2-vinyl anthraquinone in methylene chloride and dimethyl sulfoxide was investigated. Methylene chloride was found to be an efficient solvent for poly(2-vinyl anthraquinone). The rate of polymerization in methylene chloride was 10 3 times greater than that obtained using dimethyl sulfoxide as solvent

Laccase immobilized on methylene blue modified mesoporous silica MCM-41/PVA

International Nuclear Information System (INIS)

Xu Xinhua; Lu Ping; Zhou Yumei; Zhao Zhenzhen; Guo Meiqing

2009-01-01

The mesoporous silica sieve MCM-41 containing methylene blue (MB) provides a suitable immobilization of biomolecule matrix due to its uniform pore structure, high surface areas, good biocompatibility and nice conductivity. Based on this, a facilely fabricated amperometric biosensor by entrapping laccase into the MB modified MCM-41/PVA composite film has been developed. Laccase from Trametes versicolor is assembled on a composite film of MCM-41 containing MB/PVA modified Au electrode and the electrode is characterized with respect to transmission electron microscopy (TEM) and scanning electron microscopic (SEM), Cyclic voltammetry (CV), response time, detection limit, linear range and activity of laccase. The laccase modified electrode remains good redox behavior in pH 4.95 acetate buffer solution, at room temperature in present of 0.1 mM catechol. The response time (t 90% ) of the modified electrode is less than 4 s for catechol. The detection limit is 0.331 μM and the linear detect range is about from 4.0 μM to 87.98 μM for catechol with a correlation coefficient of 0.99913(S/N = 3). The apparent Michaelis-Menten (K M app ) is estimated using the Lineweaver-Burk equation and the K M app value is about 0.256 mM. This work demonstrated that the mesoporous silica MCM-41 containing MB provides a novel support for laccase immobilization and the construction of biosensors with a faster response and better bioactivity.

Enhanced photocatalytic degradation of methylene blue by ZnO-reduced graphene oxide composite synthesized via microwave-assisted reaction

Energy Technology Data Exchange (ETDEWEB)

Lv Tian [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Pan Likun, E-mail: lkpan@phy.ecnu.edu.cn [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China); Liu Xinjuan; Lu Ting; Zhu Guang; Sun Zhuo [Engineering Research Center for Nanophotonics and Advanced Instrument, Ministry of Education, Department of Physics, East China Normal University, Shanghai, 200062 (China)

2011-10-13

Highlights: > ZnO-reduced graphene oxide composite is synthesized via microwave assisted reaction. > The method allows a facile, safe and rapid reaction in aqueous media. > A high dye degradation efficiency is achieved under UV light irradiation. - Abstract: A quick and facile microwave-assisted reaction is used to synthesize ZnO-reduced graphene oxide (RGO) hybrid composites by reducing graphite oxide dispersion with zinc nitrate using a microwave synthesis system. Their photocatalytic performance in degradation of methylene blue is investigated and the results show that the RGO plays an important role in the enhancement of photocatalytic performance and the ZnO-RGO composite with 1.1 wt. % RGO achieves a maximum degradation efficiency of 88% in a neutral solution under UV light irradiation for 260 min as compared with pure ZnO (68%) due to the increased light absorption, the reduced charge recombination with the introduction of RGO.

Modified solvothermal synthesis of cobalt ferrite (CoFe2O4 magnetic nanoparticles photocatalysts for degradation of methylene blue with H2O2/visible light

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Abul Kalam

2018-03-01

Full Text Available Different grads of magnetic nano-scaled cobalt ferrites (CoFe2O4 photocatalysts were synthesized by modified Solvothermal (MST process with and without polysaccharide. The indigenously synthesized photocatalysts were characterized by means of X-ray diffraction (XRD, scanning electron microscopy (SEM, transmission electron microscopy (TEM, high-resolution transmission electron microscopy (HRTEM, thermo gravimetric analysis (TGA, Fourier transform infrared (FT-IR, UV–visible (UV–vis spectroscopy and N2 adsorption–desorption isotherm method. The Fourier transform infrared spectroscopy study showed the Fe-O stretching vibration 590–619 cm−1, confirming the formation of metal oxide. The crystallite size of the synthesized photocatalysts was found in the range between 20.0 and 30.0 nm. The surface area of obtained magnetic nanoparticles is found to be reasonably high in the range of 63.0–76.0 m2/g. The results shown that only MST-2 is the most active catalyst for photo-Fenton like scheme for fast photodegradation action of methylene blue dye, this is possible due to optical band gap estimated of 2.65 eV. Captivatingly the percentage of degradation efficiency increases up to 80% after 140 min by using MST-2 photocatalyst. Photocatalytic degradation of methylene blue (MB dye under visible light irradiation with cobalt ferrite magnetic nanoparticles followed first order kinetic constant and rate constant of MST-2 is almost 2.0 times greater than MST-1 photocatalyst. Keywords: Cobalt ferrite, Photocatalysis, Kinetics, Optical properties, Surface area studies

The use of intravenous hydroxocobalamin as a rescue in methylene blue-resistant vasoplegic syndrome in cardiac surgery

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Yi Cai

2017-01-01

Full Text Available Vasoplegic syndrome is a well-recognized complication during cardiopulmonary bypass (CPB and is associated with increased morbidity and mortality, especially when refractory to conventional vasoconstrictor therapy. This is the first reported case of vasoplegia on CPB unresponsive to methylene blue whereas responsive to hydroxocobalamin, which indicates that the effect of hydroxocobalamin outside of the nitric oxide system is significant or that the two drugs have a synergistic effect in one or multiple mechanisms.

Insight into highly efficient removal of cadmium and methylene blue by eco-friendly magnesium silicate-hydrothermal carbon composite

Science.gov (United States)

Xiong, Ting; Yuan, Xingzhong; Chen, Xiaohong; Wu, Zhibin; Wang, Hou; Leng, Lijian; Wang, Hui; Jiang, Longbo; Zeng, Guangming

2018-01-01

Water pollution is one of the forefront environmental problems. Due to the simplification, flexibility and low cost, the adsorption becomes one of the most fashionable technology and the exploitation of adsorbents has drawn greatly attention. In this study, a novel magnesium silicate-hydrothermal carbon composite (MS-C) was synthesized by facile hydrothermal carbonization and used to remove the cadmium (Cd(II)) and methylene blue (MB) from wastewater. It was shown that the porous and lump-like magnesium silicate (MS) was decorated with multiple hydrothermal carbon (HC) via the Csbnd Osbnd Si covalent bonding. Further, the adsorption behavior of Cd(II) and MB based on the MS, HC, and MS-C were systematically investigated. The equilibrium data of both Cd(II) and MB were fitted well with Langmuir model. Compared to pure MS and HC, the adsorption capacity of composite was significantly improved, accompanied by the maximum adsorption capacity of 108 mg/g for Cd(II) and 418 mg/g for MB, respectively. In the Cd(II)-MB binary system, the adsorption of Cd(II) was favored in comparison with that of MB. The removal of Cd(II) was mainly ascribed to electrostatic attraction and the ion exchange interaction. Meanwhile, the adsorption of MB onto adsorbent was driven by the electrostatic attraction, π-π interaction and hydrogen bond. In view of these empirical results and real water treatment, the environmental friendly and low-cost MS-C holds a potential for separate or simultaneous removal of Cd(II) and MB in practical applications.

Modification of bamboo-based activated carbon using microwave radiation and its effects on the adsorption of methylene blue

International Nuclear Information System (INIS)

Liu Qingsong; Zheng Tong; Li Nan; Wang Peng; Abulikemu, Gulizhaer

2010-01-01

Modification of bamboo-based activated carbon was carried out in a microwave oven under N 2 atmosphere. The virgin and modified activated carbons were characterized by means of low temperature N 2 adsorption, acid-base titration, point of zero charge (pH pzc ) measurement, FTIR and XPS spectra. A gradual decrease in the surface acidic groups was observed during the modification, while the surface basicity was enhanced to some extent, which gave rise to an increase in the pH pzc value. The species of the functional groups and relative content of various elements and groups were given further analysis using FTIR and XPS spectra. An increase in the micropores was found at the start, and the micropores were then extended into larger ones, resulting in an increase in the pore volume and average pore size. Adsorption studies showed enhanced adsorption of methylene blue on the modified activated carbons, caused mainly by the enlargement of the micropores. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable for the virgin and modified activated carbons, respectively. Kinetic studies exhibited faster adsorption rate of methylene blue on the modified activated carbons, and the pseudo-second-order model fitted well for all of the activated carbons.

Modification of bamboo-based activated carbon using microwave radiation and its effects on the adsorption of methylene blue

Energy Technology Data Exchange (ETDEWEB)

Liu Qingsong; Zheng Tong; Li Nan [State Key Laboratory of Urban Water Resource and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090 (China); Wang Peng, E-mail: pwang73@vip.sina.com [State Key Laboratory of Urban Water Resource and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090 (China); Abulikemu, Gulizhaer [State Key Laboratory of Urban Water Resource and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin 150090 (China)

2010-03-01

Modification of bamboo-based activated carbon was carried out in a microwave oven under N{sub 2} atmosphere. The virgin and modified activated carbons were characterized by means of low temperature N{sub 2} adsorption, acid-base titration, point of zero charge (pH{sub pzc}) measurement, FTIR and XPS spectra. A gradual decrease in the surface acidic groups was observed during the modification, while the surface basicity was enhanced to some extent, which gave rise to an increase in the pH{sub pzc} value. The species of the functional groups and relative content of various elements and groups were given further analysis using FTIR and XPS spectra. An increase in the micropores was found at the start, and the micropores were then extended into larger ones, resulting in an increase in the pore volume and average pore size. Adsorption studies showed enhanced adsorption of methylene blue on the modified activated carbons, caused mainly by the enlargement of the micropores. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable for the virgin and modified activated carbons, respectively. Kinetic studies exhibited faster adsorption rate of methylene blue on the modified activated carbons, and the pseudo-second-order model fitted well for all of the activated carbons.

Modification of bamboo-based activated carbon using microwave radiation and its effects on the adsorption of methylene blue

Science.gov (United States)

Liu, Qing-Song; Zheng, Tong; Li, Nan; Wang, Peng; Abulikemu, Gulizhaer

2010-03-01

Modification of bamboo-based activated carbon was carried out in a microwave oven under N 2 atmosphere. The virgin and modified activated carbons were characterized by means of low temperature N 2 adsorption, acid-base titration, point of zero charge (pH pzc) measurement, FTIR and XPS spectra. A gradual decrease in the surface acidic groups was observed during the modification, while the surface basicity was enhanced to some extent, which gave rise to an increase in the pH pzc value. The species of the functional groups and relative content of various elements and groups were given further analysis using FTIR and XPS spectra. An increase in the micropores was found at the start, and the micropores were then extended into larger ones, resulting in an increase in the pore volume and average pore size. Adsorption studies showed enhanced adsorption of methylene blue on the modified activated carbons, caused mainly by the enlargement of the micropores. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable for the virgin and modified activated carbons, respectively. Kinetic studies exhibited faster adsorption rate of methylene blue on the modified activated carbons, and the pseudo-second-order model fitted well for all of the activated carbons.

Spinal meningeal uptake of technetium-99m methylene diphosphonate in meningeal seeding by malignant lymphoma

International Nuclear Information System (INIS)

Siegal, T.; Or, R.; Matzner, Y.; Samuels, L.D.

1980-01-01

Definite diagnosis of meningeal seeding by systemic cancer relies on the presence of malignant cells in the cerebrospinal fluid (CSF). In the absence of such cells in the CSF, only two other tests strongly suggest the diagnosis - a CT scan and a myelogram. This paper reports a case in which the diagnosis was strongly suggested by an unusual uptake of Tc-99m methylene diphosphonate by the leptomeninges during a skeletal scan and later established by the presence of malignant cells in the CSF. The radionuclide scan may be an additional diagnostic test in some cases with meningeal seeding by systemic cancer

Fe(III/TiO2-Montmorillonite Photocatalyst in Photo-Fenton-Like Degradation of Methylene Blue

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Is Fatimah

2015-01-01

Full Text Available A photodegradation process of methylene blue (MB in aqueous solution using Fe(III/TiO2-montmorillonite photocatalyst is presented. The photocatalyst material was prepared using Indonesian natural montmorillonite in TiO2 pillarization process followed by Fe(III ion exchange. Kinetic study on MB degradation was conducted and evaluated by three kinetic models: the pseudo-first- and second-order equations and the Elovich equation. From the results, it is concluded that the degradation under the photo-Fenton-like process utilizing Fe(III/TiO2-montmorillonite photocatalyst conformed to the Elovich kinetic model.

Analysis of chiral non-steroidal anti-inflammatory drugs flurbiprofen, ketoprofen and etodolac binding with HSA

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Chang-Chuan Guo

2011-08-01

Full Text Available The protein binding of non-steroidal anti-inflammatory drugs flurbiprofen, ketoprofen and etodolac with human serum albumin (HSA was investigated using indirect chiral high performance liquid chromatography (HPLC and ultrafiltration techniques. S-(–-1-(1-naphthyl-ethylamine (S-NEA was utilized as chiral derivatization reagent and pre-column derivatization RP-HPLC method was established for the separation and assay of the three pairs of enantiomer. The method had good linear relationship over the investigated concentration range without interference. The average extraction efficiency was higher than 85% in different systems, and the intra-day and inter-day precisions were less than 15%. In serum albumin, the protein binding of etodolac enantiomers showed significant stereoselectivity that the affinity of S-enantiomer was stronger than R-enantiomer, and the stereoselectivity ratio reached 6.06; Flurbiprofen had only weak stereoselectivity in HSA, and ketoprofen had no stereoselectivity at all. Scatchard curves showed that all the three chiral drugs had two types of binding sites in HSA. Keywords: Protein binding, Non-steroidal anti-inflammatory drugs, Enantiomer, Stereoselectivity, Human serum albumin

Epoxidation of the methamphetamine pyrolysis product, trans-phenylpropene, to trans-phenylpropylene oxide by CYP enzymes and stereoselective glutathione adduct formation

International Nuclear Information System (INIS)

Sanga, Madhu; Younis, Islam R.; Tirumalai, Padma S.; Bland, Tina M.; Banaszewska, Monica; Konat, Gregory W.; Tracy, Timothy S.; Gannett, Peter M.; Callery, Patrick S.

2006-01-01

Pyrolytic products of smoked methamphetamine hydrochloride are well established. Among the various degradation products formed, trans-phenylpropene (trans-β-methylstyrene) is structurally similar to styrene analogues known to be bioactivated by CYP enzymes. In human liver microsomes, trans-phenylpropene was converted to the epoxide trans-phenylpropylene oxide (trans-2-methyl-3-phenyloxirane) and cinnamyl alcohol. Incubation of trans-phenylpropene with microsomes in the presence of enzyme-specific P450 enzyme inhibitors indicated the involvement of CYP2E1, CYP1A2, and CYP3A4 enzymes. Both (R,R)-phenylpropylene oxide and (S,S)-phenylpropylene oxide were formed in human liver microsomal preparations. Enantiomers of trans-phenylpropylene oxide were stereoselectively and regioselectively conjugated in a Phase II drug metabolism reaction catalyzed by human liver cytosolic enzymes consisting of conjugation with glutathione. The structure of the phenylpropylene oxide-glutathione adduct is consistent with nucleophilic ring-opening by attack at the benzylic carbon. Exposure of cultured C6 glial cells to (S,S)-phenylpropylene oxide produced a cytotoxic response in a concentration-dependent manner based on cell degeneration and death

Blood schizontocidal activity of methylene blue in combination with antimalarials against Plasmodium falciparum

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Garavito G.

2007-06-01

Full Text Available Methylene blue (MB is the oldest synthetic antimalarial. It is not used anymore as antimalarial but should be reconsidered. For this purpose we have measured its impact on both chloroquine sensitive and resistant Plasmodium strains. We showed that around 5 nM of MB were able to inhibit 50% of the parasite growth in vitro and that late rings and early trophozoites were the most sensitive stages; while early rings, late trophozoites and schizonts were less sensitive. Drug interaction study following fractional inhibitory concentrations (FIC method showed antagonism with amodiaquine, atovaquone, doxycycline, pyrimethamine; additivity with artemether, chloroquine, mefloquine, primaquine and synergy with quinine. These results confirmed the interest of MB that could be integrated in a new low cost antimalarial combination therapy.

Enhanced removal of Methylene Blue by electrocoagulation using iron electrodes

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Mohamed S. Mahmoud

2013-06-01

Full Text Available The removal of pollutants from effluents by electrocoagulation has become an attractive method in recent years. The study deals with the enhancement of removal of Methylene Blue dye by using an electromagnetic field during the electrocoagulation process. Effects of electrolyte concentration, dye concentration, intensity and the direction of the electromagnet on the decolorization efficiency have been investigated. The formed ferric hydroxide flocs trap colloidal particles and make solid–liquid separation easier during the next stage. The electrocoagulation stages must be optimized in order to design an economically feasible process. The results showed that the optimum electrolysis was 10–20 min at a current density of 8 mA/cm2, while the optimum concentration of the electrolyte (NaOH was found to be 2 wt.% when the dye concentration was 50 mg/L. The utilization of an electromagnetic field enhanced the dye removal due to the induced motion of paramagnetic ions inside the solution. The power consumption required to remove the dye was reduced by 45% in the case of applying an electromagnetic field.

Uptake and localization of sup(99m)technetium-methylene-diphosphonate in bone

International Nuclear Information System (INIS)

Savelkoul, T.J.F.

1984-01-01

The author investigated the uptake and localization of 99m-technetium-methylene-diphosphonate (99m-Tc-MDP) in bone, to develop a sensitive mean for the detection of early osseous disease. In an electrolysis procedure without the presence of contaminating reductants a 99m-Tc-MDP complex is formed with clear bone-seeking properties. The scans performed in experimental animals are comparable in quality with 99m-Tc(Sn)-MDP scans. The uptake of 99m-Tc-MDP is faster and higher than the uptake of reduced hydrolyzed 99m-Tc. Uptake of 99m-Tc(Sn)-MDP in bone can only take place after decomposition of the complex. As 99m-Tc-MDP is taken up as a unit, this may be a better agent to evaluate the osteoblastic activity in the skeleton. (Auth./R.B.)

Sacrococcygeal chordoma: increased 99mTc methylene diphosphonate uptake on single photon emission computed tomography/computed tomography bone scintigraphy

International Nuclear Information System (INIS)

Kamaleshwaran, Koramadai Karuppuswamy; Bhattacharya, Anish; Harisankar, Chidambaram Natarajan Balasubramaniam; Mittal, Bhagwant Rai; Goni, Vijay

2012-01-01

Chordoma is a malignant tumor arising from the remnants of the notochord, and is the most frequent primitive tumor of the sacrum. While most sacral tumors show increased concentration of bone-seeking radiopharmaceuticals, chordomas usually exhibit decreased uptake. The authors present an image of a sacrococcygeal chordoma with osteolysis and increased uptake of 99m Tc methylene diphosphonate on planar and single photon emission computed tomography/computed tomography bone scintigraphy. (author)

Crystal Violet and Methylene Green as Low-Dose Liquid Dosimetry Systems

International Nuclear Information System (INIS)

Ebraheem, S.; Beshir, W.B.; Hassan, H.M.

2008-01-01

The ultimate aim of the present work is studying of the possibility of using some organic solutions for gamma radiation monitors and to evaluate and characterize the dosimetric properties of these compounds. Crystal violet (CV) and methylene green (MG) aqueous solutions with different concentrations have been prepared and irradiated to different absorbed doses. The solutions were readout using absorption spectrophotometry technique at λ m ax 592 nm and 614 nm for CV and MG respectively. The maximum useful dose range was investigated and found to be concentration dependent. It was found that the useful dose range was from 10-160 Gy for CV and from 10-200 Gy for MG. The radiation chemical yield, G-value, was calculated for the studied solutions. The ph effect and the effect of different additives, chloral hydrate and ethanol have been also investigated. The pre- and post- irradiation stabilities of these solutions under different storage conditions were studied and the results showed different significant dependence on the storage condition

Acid-base catalysis of N-[(morpholine)methylene]daunorubicin.

Science.gov (United States)

Krause, Anna; Jelińska, Anna; Cielecka-Piontek, Judyta; Klawitter, Maria; Zalewski, Przemysław; Oszczapowicz, Irena; Wąsowska, Małgorzata

2012-08-01

The stability of N-[(morpholine)methylene]-daunorubicin hydrochloride (MMD) was investigated in the pH range 0.44-13.54, at 313, 308, 303 and 298 K. The degradation of MMD as a result of hydrolysis is a pseudo-first-order reaction described by the following equation: ln c = ln c(0) - k(obs)• t. In the solutions of hydrochloric acid, sodium hydroxide, borate, acetate and phosphate buffers, k(obs) = k(pH) because general acid-base catalysis was not observed. Specific acid-base catalysis of MMD comprises the following reactions: hydrolysis of the protonated molecules of MMD catalyzed by hydrogen ions (k(1)) and spontaneous hydrolysis of MMD molecules other than the protonated ones (k(2)) under the influence of water. The total rate of the reaction is equal to the sum of partial reactions: k(pH) = k(1) • a(H)+ • f(1) + k(2) • f(2) where: k(1) is the second-order rate constant (mol(-1) l s(-1)) of the specific hydrogen ion-catalyzed degradation of the protonated molecules of MMD; k(2) is the pseudo-first-order rate constant (s(-1)) of the water-catalyzed degradation of MMD molecules other than the protonated ones, f(1) - f(2) are fractions of the compound. MMD is the most stable at approx. pH 2.5.

Highly stereocontrolled synthesis of trans-enediynes via carbocupration of fluoroalkylated diynes

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Tsutomu Konno

2012-12-01

Full Text Available Treatment of readily prepared (Z-6-benzyloxy-1,1,1,2-tetrafluoro-6-methyl-2-hepten-4-yne with 1.5 equiv of LHMDS in −78 °C for 1 h gave the corresponding trifluoromethylated diyne in an excellent yield. This diyne was found to be a good substrate for the carbocupration with various higher-ordered cyanocuprates to give the corresponding vinylcuprates in a highly regio- and stereoselective manner. The in situ generated vinylcuprates could react very smoothly with an excess amount of iodine, the vinyl iodides being obtained in high yields. Thus-obtained iodides underwent a very smooth Sonogashira cross-coupling reaction to afford various trans-enediynes in high yields.

Kinetic and Thermodynamics of Methylene Blue Adsorption onto Zero Valent Iron Supported on Mesoporous Silica

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Atyaf Khalid Hameed

2016-08-01

Full Text Available Zero valent iron supported on mesoporous silicanano particles (NZVI/MSNs was prepared by the aqueous phase borohydride reduction methods. Prior to the reduction, mesoporous silica nanoparticles (MSNs were prepared through the activation of fumed silica with concentrated HCl by refluxing at 90 °C. FTIR, XRD, FESEM, EDX and BET were used to characterize theadsorbents prepared. BET surface areas of MSNs, NZVI, and NZVI/MSNs were 126, 41, and 72 m2/g for, respectively. The performance of NZVI/MSNs as adsorbent was examined by adsorption of methylene blue (MB, performed in series of batch experiments. In the kinetic studies, pseudo first order and pseudo second order kinetic models were examined. The pseudo second order equation provided the best fit with the experimental data. Thermodynamic studies indicated that the adsorption process is endothermic with ΔH° was 90.53 kJ/mol. Positive ΔS° (300 J/mol and negative ΔG° (-6.42 kJ/mol was recorded, indicating the spontaneous of the adsorption process and naturally favorable. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th March 2016; Revised: 18th March 2016; Accepted: 18th March 2016 How to Cite: Hameed, A.K., Dewayanto, N., Dongyun, D., Nordin, M.R., Mohd Hasbi Ab. Rahim, M.H.A. (2016. Kinetic and Thermodynamics of Methylene Blue Adsorption onto Zero Valent Iron Supported on Mesoporous Silica. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (2: 250-261 (doi:10.9767/bcrec.11.2.443.250-261 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.2.443.250-261

Preparation, characterization and application of N-methylene phosphonic acid chitosan grafted magnesia–zirconia stationary phase

Energy Technology Data Exchange (ETDEWEB)

Wang, Qing; Chen, Jie; Huang, Kun; Zhang, Xin; Xu, Li [Tongji School of Pharmacy, Huazhong University of Science and Technology, Wuhan 430030 (China); Shi, Zhi-guo, E-mail: shizg@whu.edu.cn [Department of Chemistry, Wuhan University, Wuhan 430072 (China)

2015-01-07

Highlights: • N-methylene phosphonic acid chitosan grafted MgO–ZrO{sub 2} was prepared. • It exhibited superior HILIC chromatographic performance to the bare MgO–ZrO{sub 2}. • Monosaccharides, phospholipids and peptides were successfully separated. • It was a promising HILIC stationary phase. - Abstract: A hydrophilic stationary phase (SP) was prepared through grafting N-methylene phosphonic acid chitosan on magnesia–zirconia particles (P-CTS-MgO–ZrO{sub 2}) via Lewis acid–base interaction. The resulting material was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy, scanning electron microscope and nitrogen adsorption analysis. The chromatographic performance of P-CTS-MgO–ZrO{sub 2} was systemically evaluated by studying effect of acetonitrile content, pH and buffer concentration in the mobile phase. The results demonstrated that the novel SP provided hydrophilic, electrostatic-repulsion and ion-exchange interactions. Compared to the bare MgO–ZrO{sub 2}, P-CTS-MgO–ZrO{sub 2} exhibited superior peak shape, reasonable resolution and reduced analysis time in separation of basic analytes. Besides, remarkable resolving power of acids, i.e. six non-steroidal anti-inflammatory drugs which failed to be eluted from the bare MgO–ZrO{sub 2}, was obtained with the theoretical plate number (N/m) of 4653–31313, asymmetry factor <1.21 and the resolution of 1.6–3.4. Finally, P-CTS-MgO–ZrO{sub 2} SP was applied to separate monosaccharides, phospholipids and peptides. P-CTS-MgO–ZrO{sub 2} was a promising hydrophilic SP for wide applications.

Cytochrome P-450 dependent ethanol oxidation. Kinetic isotope effects and absence of stereoselectivity

International Nuclear Information System (INIS)

Ekstroem, G.; Norsten, C.; Cronholm, T.; Ingelman-Sundberg, M.

1987-01-01

Deuterium isotope effects [/sup D/(V/K)] and stereoselectivity of ethanol oxidation in cytochrome P-450 containing systems and in the xanthine-xanthine oxidase system were compared with those of yeast alcohol dehydrogenase. The isotope effects were determined by using both a noncompetitive method, including incubation of unlabeled of [1,1- 2 H 2 ] ethanol at various concentrations, and a competitive method, where 1:1 mixtures of [1- 13 C]- and [ 2 H 6 ] ethanol or [2,2,2- 2 H 3 ]- and [1,1- 2 H 2 ] ethanol were incubated and the acetaldehyde formed was analyzed by gas chromatography/mass spectrometry. The /sup D/(V/K) isotope effects of the cytochrome P-450 dependent ethanol oxidation were about 4 with liver microsomes from imidazole-, phenobarbital- or acetone-treated rabbits or with microsomes from acetone- or ethanol-treated rats. Similar isotope effects were reached with reconstituted membranes containing the rabbit ethanol-inducible cytochrome P-450 (LMeb), whereas control rat microsomes and membranes containing rabbit phenobarbital-inducible P-450 LM 2 oxidized the alcohol with /sup D/(V/K) of about 2.8 and 1.8, respectively. Addition of Fe/sup III/EDTA either to microsomes from phenobarbital-treated rabbits or to membranes containing P-450 LMeb significantly lowered the isotope effect. Incubations of all cytochrome P-450 containing systems of the xanthine-xanthine oxidase systems with (1R)- and (1S)-[1- 2 H] ethanol, revealed, taking the isotope effects into account, that 44-66% of the ethanol oxidized had lost the 1-pro-R hydrogen. The data indicate that cytochrome P-450 dependent ethanol oxidation is not stereospecific and that cleavage of the C 1 -H bond appears to be a rate-determining step in the catalysis by the ethanol-inducible form of P-450. The contribution of hydroxyl radicals in ethanol oxidation by the various enzymic systems is discussed

Methylene blue adsorption of GMZ bentonite and the effect of hyper-alkaline solution erosion

International Nuclear Information System (INIS)

Chen Bao; Zhang Huixin; Zhu Chunming; Chen Ping

2012-01-01

The method of combining the halo method with the spectrometer method, was used to study on the Methylene blue (MB) adsorption of Gaomiaozi (GMZ) bentonite, which had been eroded by hyper-alkaline solution, to investigate the mechanism of the effect of hyper-alkaline pore water on the buffer/backfill properties of GMZ bentonite. Results present, method employed in this article is brief and feasible, and high accuracy; The total specific surface area calculated by the test of MB adsorption is more accurate than the method of ethylene glycol monomethyl ether (EGIVIE). The MB adsorption of samples, which had been eroded by hyper-alkaline solution, decreases with the increase of the concentration of hyper-alkaline solution, and the change law agrees with the variation of the mass percentage of montmorillonite in bentonite tested by X- Ray diffraction (XRD). Therefore, the erosion of hyper-alkaline pore water might dissolve montmorillonite, which is the effective composition of bentonite, and destroy the tetrahedron- octahedron-tetrahedron (T-O-T) structure of montmorillonite, then lead to the decrease of cation exchange capability and the specific surface area of montmorillonite, and the the macroscopic expressions are the decrease of MB adsorption, the swelling potential and the increase of permeability. (authors)

Green synthesis of halloysite nanotubes supported Ag nanoparticles for photocatalytic decomposition of methylene blue

International Nuclear Information System (INIS)

Zou Meiling; Zhu Han; Xu Congsheng; Du Mingliang; Fu Yaqin

2012-01-01

Using tea polyphenols (TPs) as a reductant, Ag nanoparticles (AgNPs) supported on halloysite nanotubes (HNTs) were simply and greenly synthesized for the photocatalytic decomposition of methylene blue (MB). HNTs were initially functionalized by N-β-aminoethyl-γ-aminopropyl trimethoxysilane (AEAPTMS) to introduce amino groups to form N-HNTs to fasten the AgNPs; then AgNPs were synthesized and ‘anchored’ on the surface of the HNTs. Fourier transform infrared spectroscopy was employed to testify the amino groups on the surface of the HNTs. Transmission electron microscopy, field-emission scanning electron microscopy and x-ray diffraction were utilized to characterize the structure and morphology of the synthesized HNTs supported by the AgNPs (AgNPs-N-HNTs). The results showed that the AgNPs had been synthesized and ‘anchored’ onto the surface of the HNTs with a diameter of about 20-30 nm. X-ray photoelectron spectroscopy analysis revealed the chelating interaction between the AgNPs and N atoms together with the TP molecular. The photocatalytic activity of the as-prepared AgNPs-N-HNTs catalyst was evaluated by decomposition of MB; the results showed that the prepared catalyst exhibited excellent catalytic activity and high adsorption capability to MB. (paper)

Synthesis of Spiroisoxazolines by 1,3-Dipolar Cycloaddition

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Peter Ertl

1997-04-01

Full Text Available The cycloaddition of the chiral nitrile oxide 1 to 1-R-substituted 3,3-methylene-5,5-dimethyl-2-pyrrolidinones 2 (where R is H, n-butyl-, 1,1-dimethylethoxycarbonyl-, 1-methylethenyl- and acetyl- proceeds regioselectively under the formation of spiroisoxazolines, namely 7-R-substituted-6-oxo-8,8-dimethyl-1-oxa-2,7-diazaspiro[4,4]non-2-enes 5 and 6. The asymmetric induction expected by the a-chiral centre of the nitrile oxide 1 was not very effective, diastereoisomers 5 and 6 were formed in an approximate 50:50 ratio. The stereoselectivity of the 1,3-dipolar cycloaddition of the arylnitrile oxide 7 with the chiral lactam 3 and the achiral lactone 4 are investigated. The attack of the 1,3-dipole occurred from the less hindered face of the dipolarophile 3 and 4, giving the major isomer 8 and 10, respectively.

Remote stereocontrol by sulfinyl groups: reduction of delta-ketosulfoxides.

Science.gov (United States)

García Ruano, José L; Fernández-Ibáñez, M Angeles; Maestro, M Carmen; Rodríguez-Fernández, M Mercedes

2005-03-04

The reduction of delta-ketosulfoxides constitutes the first evidence of the efficiency of the sulfinyl group to control the stereoselectivity of 1,5-asymmetric induction processes. The use of DIBAL/Yb(OTf)3 or L-Selectride as the reducing agents provides delta-hydroxysulfoxides with the opposite configuration at the hydroxylic carbon in a highly stereoselective way.

Caulerpa racemosa: a marine green alga for eco-friendly synthesis of silver nanoparticles and its catalytic degradation of methylene blue.

Science.gov (United States)

Edison, Thomas Nesakumar Jebakumar Immanuel; Atchudan, Raji; Kamal, Chennappan; Lee, Yong Rok

2016-09-01

In this study, a simple and green method has been demonstrated for the synthesis of highly stable silver nanoparticles (AgNPs) using aqueous extract of Caulerpa racemosa (C. racemosa) as a reducing and capping agent. The formation and stability of AgNPs were studied using visual observation and UV-Visible (UV-Vis) spectroscopy. The stable AgNPs were further characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy and high resolution transmission electron microscopy (HR-TEM) with energy dispersive spectroscopic (EDS) methods. The biosynthesized AgNPs showed a sharp surface plasmon resonance peak at 441 nm in the visible region and they have extended stability which has been confirmed by the UV-Vis spectroscopic results. XRD result revealed the crystalline nature of synthesized AgNPs and they are mainly oriented in (111) plane. FT-IR studies proved that the phytoconstituents of C. racemosa protect the AgNPs from aggregation and also which are responsible for the high stability. The size of synthesized AgNPs was approximately 25 nm with distorted spherical shape, identified from the HR-TEM images. The synthesized AgNPs showed excellent catalytic activity towards degradation of methylene blue.

Analytical determination of specific 4,4'-methylene diphenyl diisocyanate hemoglobin adducts in human blood.

Science.gov (United States)

Gries, Wolfgang; Leng, Gabriele

2013-09-01

4,4'-Methylene diphenyl diisocyanate (MDI) is one of the most important isocyanates in the industrial production of polyurethane and other MDI-based synthetics. Because of its high reactivity, it is known as a sensitizing agent, caused by protein adducts. Analysis of MDI is routinely done by determination of the nonspecific 4,4'-methylenedianiline as a marker for MDI exposure in urine and blood. Since several publications have reported specific adducts of MDI and albumin or hemoglobin, more information about their existence in humans is necessary. Specific adducts of MDI and hemoglobin were only reported in rats after high-dose MDI inhalation. The aim of this investigation was to detect the hemoglobin adduct 5-isopropyl-3-[4-(4-aminobenzyl)phenyl]hydantoin (ABP-Val-Hyd) in human blood for the first time. We found values up to 5.2 ng ABP-Val-Hyd/g globin (16 pmol/g) in blood samples of workers exposed to MDI. Because there was no information available about possible amounts of this specific MDI marker, the analytical method focused on optimal sensitivity and selectivity. Using gas chromatography-high-resolution mass spectrometry with negative chemical ionization, we achieved a detection limit of 0.02 ng ABP-Val-Hyd/g globin (0.062 pmol/g). The robustness of the method was confirmed by relative standard deviations between 3.0 and 9.8 %. Combined with a linear detection range up to 10 ng ABP-Val-Hyd/g globin (31 pmol/g), the enhanced precision parameter demonstrates that the method described is optimized for screening studies of the human population.

A comparative study of the DG-OMEGA (DG Omega), DGII, and GAT method for the structure elucidation of a methylene-acetal linked thymine dinucleotide

NARCIS (Netherlands)

van Kampen, A. H. C.; Beckers, M. L. M.; Buydens, L. M. C.

1997-01-01

This research continues the investigation of the properties of the recently developed structure elucidation method DG-OMEGA (DG Omega). Towards this end it was applied for the structure determination of a methylene-acetal linked thymine dinucleotide. The performance of DG Omega was compared to the

THE DEGRADATION OF METHYLENE BLUE OVER M2TiO4 SPINEL PHOTOCATALYST

Directory of Open Access Journals (Sweden)

N FODIL CHERIF

2014-06-01

Full Text Available Heterogeneous photocatalysis is an advanced oxidation process (AOP which has been widely studied by numerous researchers in the world and is used to degrade or remove a wide range of pollutants in water and air. In this study, the photocatalytic oxidation and mineralization of methylene blue in aqueous catalyst suspensions of coprecipitated cobalt titanium oxide has been carried out in a helical reactor. The photodegradation was investigated using two kinds of irradiation lamps one emitting at 254 nm and the other emitting at 365 nm. Results showed that photodegradation is an effective method for the removal of MB from wastewaters. The efficiency of the process depends strongly on the experimental conditions of synthesis. We observed that 40 % of pollutant was degraded after 3 hours of UV irradiation.

Solubility limit of methyl red and methylene blue in microemulsions and liquid crystals of water, sds and pentanol systems

OpenAIRE

Beri, D.; Pratami, A.; Gobah, P. L.; Dwimala, P.; Amran, A.

2017-01-01

Solubility of dyes in amphiphilic association structures of water, SDS and penthanol system (i.e. in the phases of microemulsions and liquid crystals) was attracted much interest due to its wide industrial and technological applications. This research was focused on understanding the solubility limitation of methyl red and methylene blue in microemulsion and liquid crystal phases. Experimental results showed that the highest solubility of methyl red was in LLC, followed by w/o microemulsion a...

Valorization of two waste streams into activated carbon and studying its adsorption kinetics, equilibrium isotherms and thermodynamics for methylene blue removal

Directory of Open Access Journals (Sweden)

Zeid Abdullah AlOthman

2014-12-01

Full Text Available Wastes must be managed properly to avoid negative impacts that may result. Open burning of waste causes air pollution which is particularly hazardous. Flies, mosquitoes and rats are major problems in poorly managed surroundings. Uncollected wastes often cause unsanitary conditions and hinder the efforts to keep streets and open spaces in a clean and attractive condition. During final disposal methane is generated, it is much more effective than carbon dioxide as a greenhouse gas, leading to climate change. Therefore, this study describes the possible valorization of two waste streams into activated carbon (AC with added value due to copyrolysis. High efficiency activated carbon was prepared by the copyrolysis of palm stem waste and lubricating oil waste. The effects of the lubricating oil waste to palm stem ratio and the carbonization temperature on the yield and adsorption capacity of the activated carbon were investigated. The results indicated that the carbon yield depended strongly on both the carbonization temperature and the lubricating oil to palm stem ratio. The efficiency of the adsorption of methylene blue (MB onto the prepared carbons increased when the lubricating oil to palm stem ratio increased due to synergistic effect. The effects of pH, contact time, and the initial adsorbate concentration on the adsorption of methylene blue were investigated. The maximum adsorption capacity (128.89 mg/g of MB occurred at pH 8.0. The MB adsorption kinetics were analyzed using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models. The results indicated that the adsorption of MB onto activated carbon is best described using a second order kinetic model. Adsorption data are well fitted with Langmuir and Freundlich isotherms. The thermodynamic parameters; ΔG°, ΔH° and ΔS° indicate that the adsorption is spontaneous and endothermic.

Safety and performance analysis of acriflavine and methylene blue for in vivo imaging of precancerous lesions using fibered confocal fluorescence microscopy (FCFM): an experimental study.

Science.gov (United States)

Obstoy, Bérengère; Salaun, Mathieu; Veresezan, Liana; Sesboüé, Richard; Bohn, Pierre; Boland, François-Xavier; Thiberville, Luc

2015-03-31

Fibered confocal fluorescence microscopy (FCFM) allows in vivo investigation of pulmonary microstructures. However, the bronchial epithelium can only be imaged using exogenous fluorophores. The objective of this study is to compare methylene blue (MB) and acriflavine genotoxicity and to assess FCFM performance for in vivo imaging of precancerous lesions. Genotoxicity was assessed using the comet assay on both cultured human lymphocytes and NCI-H460 cells, which had been exposed to MB or acriflavine before being illuminated at 660 or 488 nm, respectively. FCFM was performed on precancerous lesions in the hamster cheek pouch model, following topical application of the fluorophores. FCFM data were analyzed according to histology. No genotoxicity was found using 0.01% (w/v) MB after illumination at 660 nm for 2 and 15 min (5 mW). Acriflavine exposure (0.025%) led to DNA damages, increasing from 2 to 15 min of light exposure at 448 nm in both lymphocytes (83.4 to 88%, p = 0.021) and NCI H460 cell populations (79.9 to 84.6%, p = 0.045). In total, 11 invasive carcinoma, 24 reserve cell hyperplasia, and 17 dysplasia lesions were imaged using FCFM in vivo. With both fluorophores, the cellular density increased from hyperplasia to high-grade dysplasia (p < 0.05). With MB, the cellular diameter significantly decreased (48.9 to 13.9 μm) from hyperplasia to carcinoma (p < 0.05). In this model, a cut-off diameter of 30 μm enabled the diagnosis of high-grade lesions with a sensitivity of 94.7% and a specificity of 97%. Methylene blue can be used safely to image precancerous lesions in vivo. This study does not support the use of acriflavine in humans.

Kinetics of pyridine degradation along with toluene and methylene chloride with Bacillus sp. in packed bed reactor

Energy Technology Data Exchange (ETDEWEB)

Uma, B.; Sandhya, S. [National Environmental Engineering Research Institute, CSIR-Complex, Madras (India)

1998-04-01

Bacillus coagulans strain isolated from contaminated soil was immobilised on activated carbon for degradation of pyridine, toluene and methylene chloride containing synthetic wastewaters. Pyridine was supplied as the only source of nitrogen in the wastewaters. Continuous runs in a packed bed laboratory reactor showed that immobilized B. coagulans can degrade pyridine along with other organics rapidly and the effluent ammonia is also controlled in presence of ``organic carbon``. About 644 mg/l of influent TOC was efficiently degraded (82.85%) at 64.05 mg/l/hr loading. (orig.) With 2 figs., 4 tabs., 15 refs.

Photocatalysis of methylene blue contaminated water using titania fiber doped with silicon

International Nuclear Information System (INIS)

Ugarteche, C.V.; Alves, A.K.; Berutti, F.A.; Bergmann, C.P.

2009-01-01

In this work, titania fibers doped with silicon were synthesized by electro spinning methodology, using titanium propoxide, silicon tetra propoxide and a solution of polyvinylpyrrolidone as precursors. The non-tissue material obtained was characterized by X-ray diffraction to determine the phase and crystallite size, BET method to determine the surface and SEM to analyze the microstructure of the fibers. The photo catalytic activity of the fibers in comparison with the standard TiO 2 Degussa P25 was evaluated using a 20ppm methylene blue solution. The composition containing 30% of silicon kept the anatase phase stable until the heat treatment temperature of 800 deg C. In the other compositions there was a formation of the rutile phase, which is less photoactive. The compositions containing silicon were photo catalytic efficient and some of them were more active that the standard P25. (author)

Stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements from proton magnetic relaxation data

International Nuclear Information System (INIS)

Sal'nikov, Yu.I.; Chevela, V.V.

1987-01-01

A new approach to identification of stereoselective and stereospecific effects in the formation of heteronuclear tartrate complexes of 3d- and 4f-elements according to proton magnetic relaxation data is developed. At the first stage comparison of experimental dependences of the property measured (relaxation efficiency coefficient, Bjerrum function etc.) on the consentrational parameters is conducted. Their different course in systems with dH 4 L (d-tartaric acid) and dlH 4 L (dl-tartaric acid) points out to the presence of stereoeffects. Then, using mathematical simulation the most true stoichiometry of complex particles is determined as well as optimized values of their stability constants and intensity factors. The method is used when investigating the following systems: Fe 3+ -dH 4 L(dlH 4 L), Ln 3+ -dH 4 L(dlH 4 L), Fe 3+ -Ln 3+ -dH 4 L(dlH 4 L)(Ln 3+ -Gd 3+ , Ho 3+ , Er 3+ , Tm 3+ )

Selective C-H Halogenation with a Highly Fluorinated Manganese Porphyrin.

Science.gov (United States)

Li, Gang; Dilger, Andrew K; Cheng, Peter T; Ewing, William R; Groves, John T

2018-01-26

The selective C-H functionalization of aliphatic molecules remains a challenge in organic synthesis. While radical chain halogenation reactions provide efficient access to many halogenated molecules, the use of typical protocols for the selective halogenation of electron-deficient and strained aliphatic molecules is rare. Herein, we report selective C-H chlorination and fluorination reactions promoted by an electron-deficient manganese pentafluorophenyl porphyrin catalyst, Mn(TPFPP)Cl. This catalyst displays superior properties for the aliphatic halogenation of recalcitrant, electron-deficient, and strained substrates with unique regio- and stereoselectivity. UV/Vis analysis during the course of the reaction indicated that an oxo-Mn V species is responsible for hydrogen-atom abstraction. The observed stereoselectivity results from steric interactions between the bulky porphyrin ligand and the intermediate substrate radical in the halogen rebound step. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Au and AuCu Nanoparticles Supported on SBA-15 Ordered Mesoporous Titania-Silica as Catalysts for Methylene Blue Photodegradation

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Isabel Barroso-Martín

2018-05-01

Full Text Available The photocatalytic degradation of methylene blue (MB dye has been performed under UV irradiation in aqueous suspension, employing photocatalysts based on Au (1.5 wt % and AuCu (Au/Cu = 1, 2.0 wt %, and supported on SBA-15-ordered mesoporous silica, with and without titania (Si/Ti = 3, in order to evaluate the versatility of this mesoporous support in this type of reaction of great impact from the environmental point of view. Samples were characterized by X-ray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption-desorption at −196 °C, and X-ray photoelectron spectroscopy (XPS, so as to study their structural, optical, and chemical properties. All the prepared catalysts were found to be active in the test reaction. The bimetallic AuCu-based catalysts attained very high MB degradation values, in particular AuCu/SBA-15 titania-silica sample reached 100% of dye oxidation after the monitored reaction period (120 min.

Evaluation of La-Doped Mesoporous Bioactive Glass as Adsorbent and Photocatalyst for Removal of Methylene Blue from Aqueous Solution

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Liying Li

2015-01-01

Full Text Available A series of La-doped mesoporous bioactive glass (BG-La materials with excellent biosafety and hypotoxicity have been prepared and tested as adsorbent. The study was aimed to evaluate the possibility of utilizing BG-La for the adsorptive removal of methylene blue (MB from aqueous solution and test the adsorption and desorption behavior of this new material. The process parameters affecting adsorption behaviors such as pH, contact time, and initial concentration and the photocatalytic degradation of MB were systematically investigated. The result showed that BG-La had excellent removal rate (R of MB, and BG-La showed better photocatalytic effect than undoped mesoporous bioactive glass (BG. Furthermore, the MB loaded BG-La was easily desorbed with acid solution due to its electronegativity and mesoporous structure. The result indicated that these materials can be employed as candidates for removal of dye pollutant owing to their high removal rate, excellent photocatalytic effect, desorption performance, and their reusability.

Complexation between carrageenan and methylene blue for sensor design

Science.gov (United States)

Ling, Yew Pei; Heng, Lee Yook

2013-11-01

Theoretical studies on the methylene blue (MB)-carrageenans complexation at solution and solid states have been carried out via ultraviolet spectrophotoscopy and reflectometry methods. The equilibrium constant (Ka) of the MBcarrageenans complexation follows the order of Iota > Lambda > Kappa carrageenans, which indicated Iota-carrageenan forms a stable complex. MB-carrageenan complexation reaction showed decrease in Ka value from 210.71 ppm-1 to 114.57 ppm-1 when the reaction temperature increased from 298 K to 323 K. Le Chatelier's principle and mass action law explained that the MB-carrageenan complexation was an exothermic reaction (ΔH=-18.54 kJmol-1) that release heat. Thus MB-carrageenan complex was less stable at high temperature and tend to dissociate into free MB and carrageenan molecules. It was also supported by the van't Hoff equation. The reaction is a spontaneous process (ΔG=-13.23 kJmol-1) where the randomness of the molecules reduced (ΔS=-17.83 Jmol-1K-1) due to complexation. Besides, linear regression of the concentration and absorption of the MB-carrageenan reaction obeys the Beer Lambert law, which elucidated that the complexation process was not affected by any concentration dependent factors such as aggregation and self-quenching. Moreover, linear Benesi Hilderbrend plot revealed that the interaction between MB and carrageenan was a reversible and stoichiometric reaction with 1:1 ratio. However, the molar extinction coefficient (ɛ) and molar adsorption coefficient (μa) of the MB-carrageenan complex were lower compared to free MB, described that the complex was less adsorptive. The sensor constructed based on these theoretical investigations showed response behavior that was similar with solution test as both have attraction for carrageenans in the sequence of Iota-, Lambda-, Kappa- carrageenans. Likewise, carrageenan sensor was more selective towards Iota-carrageenan than to Lambda- and Kappa-carrageenans, and no response observed when

Nitrile ylides: diastereoselective cycloadditions using chiral oxazolidinones without Lewis acid.

Science.gov (United States)

Sibi, Mukund P; Soeta, Takahiro; Jasperse, Craig P

2009-12-03

Lewis acid complexation is generally required for chiral-auxiliary-controlled stereoselectivity, and chiral Lewis acid catalysis is frequently optimal for introducing asymmetry. In this work, we show that nitrile ylide cycloadditions to electron-poor acceptors attached to chiral auxiliaries proceed in high yield and stereoselectivity in the absence of Lewis acids. In contrast, chiral Lewis acids are inferior in these cycloadditions.

High stereoselective cyclopropanation reaction of 3-acylcoumarins ...

Indian Academy of Sciences (India)

Wintec

bromoketones at room temperature ..... Qin Zhao et al. 394. Table 2. Scope of reaction.a. Entry. R1. R2. Product. Time/h. Yieldb/%. 1. OC2H5. H. 3a. 2. 68. 2. OCH3. H. 3b. 2. 64. 3. CH3. H. 3c. 2. 40. 4. Ph. H. 3d. 3. 25c. 5. OC2H5. CH3. 3e. 2. 50. 6.

Methylene chloride exposure and carboxyhemoglobin levels in cabinetmakers

Science.gov (United States)

Banjoko, Sunny O.; Sridhar Mynapelli, K. C.; Ogunkola, Isiah O.; Masheyi, Olatunde O.

2007-01-01

Methylene chloride (MeCl2) is a clear colorless volatile sweet smelling lipophilic solvent used as a constituent of wood vanishes and paints. Human exposure is mainly due to inhalation and its biotransformation by the hepatic mixed function oxidases (MFO) leads to formation of carbon monoxide (CO). Simultaneous exposure to MeCl2 and increased ambient CO results in undesirably increased carboxyhemoglobin (COHb) formation, which predisposes to carboxyhemoglobinaemia with the central nervous system as the primary target organ of toxicity. In this study, ambient CO levels were determined using a CO personal monitor in different pasts of Ibadan Nigeria and work place microenvironment of 50 Cabinet makers (test group) and 50 volunteer (control) in non-furniture making occupations. Mann Whitney U and Kruskaal Wallis were the statistical methods of analysis used. Questionnaires were administered to both groups carboxyhaemoglobin levels were determined in venous blood drawn from individuals in the two groups by differential spectrophotometric method. Ambient CO levels in Ibadan were observed to be between 4 and 52 ppm with a mean of 20 ppm. Work environment CO levels were significantly higher in test subjects than controls at 5.2 ± 1.08 ppm and 2.08 ± 0.91 ppm respectively (P 0.05). It is therefore imperative to substitute MeCl2 for safer chemicals in wood vanish and paints and the use of protective gas masks and adequate ventilation should be mandatory whenever MeCl2 is used. PMID:21938216

Cytologic and radiosensibilizer action of the methylene blue

International Nuclear Information System (INIS)

Teixeira, P.C.N.

1989-01-01

This work was designed with the aim of studying the use of Methylene Blue as a possible cellular sensitizer to heat and X-rays effects. We were able to show that MB can sensitize bacteria to these two agents. This sensitization is dependent on factors that can interfere with the penetration of the dye through the cellular membrane, like temperature, concentration and permeability. On the other hand, the sensitization is dependent on repair systems. In this work, we show that damages induced by heat and MB are repaired chiefly by the excision repair system, since mutants deficient in UVR ABC endonuclease or in DNA polimerase I are very sensitive to this treatment. This was confirmed by measuring the excision of sup(3)H labeled thymidine from the DNA after treatment of bacteria with heat and MB. Repair of damage produced by X-rays depends on the DNA polimerase I enzyme. It seems that MB can interfere with this enzyme inhibiting the repair of X-rays produced lesions. It is shown too that MB alone, in alkaline conditions, can induce single-strand-breaks in DNA. This means that in the cells, MB probably induces alkali labilizations that become SSB in alkaline conditions. Since X rays are used in cancer therapy, and MB penetrates preferably in malignant cells, our aim was to determine the possibility of using these two agents to improve the discrimination of the lethal effects of X-rays between malignant and normal cells. (author)

Nanomolar determination of 4-nitrophenol based on a poly(methylene blue)-modified glassy carbon electrode.

Science.gov (United States)

Giribabu, Krishnamoorthy; Suresh, Ranganathan; Manigandan, Ramadoss; Munusamy, Settu; Kumar, Sivakumar Praveen; Muthamizh, Selvamani; Narayanan, Vengidusamy

2013-10-07

A poly(methylene blue)-modified glassy carbon electrode (PMB/GCE) was fabricated by electropolymerisation of methylene blue on a GCE and further utilized to investigate the electrochemical determination of 4-nitrophenol (4-NP) by cyclic voltammetry (CV), differential pulse voltammetry and chronocoulometry. The morphology of the PMB on GCE was examined using a scanning electron microscope (SEM). An oxidation peak of 4-NP at the PMB modified electrode was observed at 0.28 V, and in the case of bare GCE, no oxidation peak was observed, which indicates that PMB/GCE exhibits a remarkable effect on the electrochemical determination of 4-NP. Due to this remarkable effect of PMB/GCE, a sensitive and simple electrochemical method was proposed for the determination of 4-NP. The effect of the scan rate and pH was investigated to determine the optimum conditions at which the PMB/GCE exhibits a higher sensitivity with a lower detection limit. Moreover, kinetic parameters such as the electron transfer number, proton transfer number and standard heterogeneous rate constant were calculated. Under optimum conditions, the oxidation current of 4-NP is proportional to its concentration in the range of 15-250 nM with a correlation coefficient of 0.9963. The detection limit was found to be 90 nM (S/N = 3). The proposed method based on PMB/GCE is simple, easy and cost effective. To further confirm its possible application, the proposed method was successfully used for the determination of 4-NP in real water samples with recoveries ranging from 97% to 101.6%. The interference due to sodium, potassium, calcium, magnesium, copper, zinc, iron, sulphate, carbonate, chloride, nitrate and phosphate was found to be almost negligible.

Methylene-bis[(aminomethyl)phosphinic acids]: synthesis, acid-base and coordination properties.

Science.gov (United States)

David, Tomáš; Procházková, Soňa; Havlíčková, Jana; Kotek, Jan; Kubíček, Vojtěch; Hermann, Petr; Lukeš, Ivan

2013-02-21

Three symmetrical methylene-bis[(aminomethyl)phosphinic acids] bearing different substituents on the central carbon atom, (NH(2)CH(2))PO(2)H-C(R(1))(R(2))-PO(2)H(CH(2)NH(2)) where R(1) = OH, R(2) = Me (H(2)L(1)), R(1) = OH, R(2) = Ph (H(2)L(2)) and R(1),R(2) = H (H(2)L(3)), were synthesized. Acid-base and complexing properties of the ligands were studied in solution as well as in the solid state. The ligands show unusually high basicity of the nitrogen atoms (log K(1) = 9.5-10, log K(2) = 8.5-9) if compared with simple (aminomethyl)phosphinic acids and, consequently, high stability constants of the complexes with studied divalent metal ions. The study showed the important role of the hydroxo group attached to the central carbon atom of the geminal bis(phosphinate) moiety. Deprotonation of the hydroxo group yields the alcoholate anion which tends to play the role of a bridging ligand and induces formation of polynuclear complexes. Solid-state structures of complexes [H(2)N=C(NH(2))(2)][Cu(2)(H(-1)L(2))(2)]CO(3)·10H(2)O and Li(2)[Co(4)(H(-1)L(1))(3)(OH)]·17.5H(2)O were determined by X-ray diffraction. The complexes show unexpected geometries forming dinuclear and cubane-like structures, respectively. The dinuclear copper(II) complex contains a bridging μ(2)-alcoholate group with the (-)O-P(=O)-CH(2)-NH(2) fragments of each ligand molecule chelated to the different central ion. In the cubane cobalt(II) complex, one μ(3)-hydroxide and three μ(3)-alcoholate anions are located in the cube vertices and both phosphinate groups of one ligand molecule are chelating the same cobalt(II) ion while each of its amino groups are bound to different neighbouring metal ions. All such three metal ions are bridged by the alcoholate group of a given ligand.

Kinetics of tissue distribution and elimination of 4,4'-methylene bis(2-chloroaniline) in rats

International Nuclear Information System (INIS)

Tobes, M.C.; Brown, L.E.; Chin, B.; Marsh, D.D.

1983-01-01

The tissue distribution kinetics and elimination of 4,4'-methylene bis(2-chloroaniline) (MBOCA) in rats was studied after a single dose of [ 14 C]MBOCA (0.49 mg/kg body weight, i.v.). The highest concentrations of radioactivity were in the small intestine, liver, adipose, lung, kidney, skin, and adrenals. For most tissues, a rapid decrease in radioactivity was followed by a slower decrease except for the small intestine, adipose and skin which demonstrated transient increases. Subcellular distribution in liver at 1 h showed radioactivity in all cell fractions. Although very lipophilic, [ 14 C]MBOCA was completely eliminated within 48 h with the major route via the feces (73.4%). (Auth.)

Equilibrium models and kinetic for the adsorption of methylene blue on Co-hectorites

International Nuclear Information System (INIS)

Ma Jun; Jia Yongzhong; Jing Yan; Sun Jinhe; Yao Ying; Wang Xiaohua

2010-01-01

The adsorption of methylene blue (MB) onto the surface of cobalt doping hectorite (Co-hectorite) was systematically studied. The physical properties of Co-hectorites were investigated, where characterizations were carried out by X-ray diffraction (XRD) and Electron Diffraction Spectrum (EDS) techniques, and morphology was examined by nitrogen adsorption. The sample with a Co content 5% (m/m) had a higher specific surface area than other Co-hectorites. The pore diameters were distributed between 2.5 and 5.0 nm. The adsorption results revealed that Co-hectorite surfaces possessed effective interactions with MB and bases, and greatest adsorption capacity achieved with Co content 5%, where the best-fit isotherm model was the Langmuir adsorption model. Kinetic studies were fitted to the pseudo-second-order kinetic model. The intraparticle diffusion was not the rate-limiting step for the whole reaction.

Decolorization of methylene blue in aqueous suspensions of gold nanoparticles using parallel nanosecond pulsed laser.

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Zong, Yan P; Liu, Xian H; Du, Xi W; Lu, Yi R; Wang, Mei Y; Wang, Guang Y

2013-01-01

Using 532 nm parallel nanosecond pulsed laser, the decolorization of methylene blue (MB) in aqueous suspensions of gold nanoparticles (GNPs) was studied. The effects of various experimental parameters, such as irradiation time, laser energy, and initial MB concentration on the decolorization rate were investigated. Experiments using real samples of textile dyeing wastewater were also carried out to examine the effectiveness of the method in more complex samples. From the results, the following conclusions may be drawn: (i) Under the optimum conditions (pH 7.19, 135 mJ laser energy, 4 mg/L MB concentration, and 11.6 mg/L GNP concentration), the rate of MB decolorization could reach 94% in 15 min. The decolorization follows pseudo-first-order kinetics; (ii) The amount of MB decreased rapidly during the decolorization. No intermediates of the decolorization could be detected by high-performance liquid chromatography. These observations indicate that MB was decolorized through a very rapid degradation mechanism; (iii) The rate of MB decolorization increased with the increase in laser energy (at laser energies of 0 to 135 mJ); and, (iv) The efficient decolorization of MB in real samples of textile dyeing wastewater was achieved at a decolorization rate of about 85% in 15 min.

The hybrid methylene blue-zeolite system: a higher efficient photo catalyst for photo inactivation of pathogenic microorganisms

International Nuclear Information System (INIS)

Smolinska, M.; Cik, G.; Sersen, F.; Caplovicova, M.; Takacova, A.; Kopani, M.

2015-01-01

The composite system can be prepared by incorporation of methylene blue into the channels of zeolite and by adsorption on the surface of the crystals. The composite photo sensitizer effectively absorbs the red light (kmax = 648 nm) and upon illumination with light-emitting diode at a fluence rate of 1.02 mW cm-2 generates effectively reactive singlet oxygen in aqueous solution, which was proved by EPR spectroscopy. To test efficiency for inactivation of pathogenic microorganisms, we measured photo killing of bacteria Escherichia coli and Staphylococcus aureus and yeasts Candida albicans. We found out that after the microorganisms have been adsorbed at the surface of such modified zeolite, the photo generated singlet oxygen quickly penetrates their cell walls, bringing about their effective photo inactivation. The growth inhibition reached almost 50 % at 200 and 400 mg modified zeolite in 1 ml of medium in E. coli and C. albicans, respectively. On the other hand, the growth inhibition of S. aureus reached 50 % at far smaller amount of photo catalyst (30 lg per 1 ml of medium). These results demonstrate differences in sensitivities of bacteria and yeast growth. The comparison revealed that concentration required for IC50 was in case of C. albicans several orders of magnitude lower for a zeolite-immobilized dye than it was for a freely dissolved dye. In S. aureus, this concentration was even lower by four orders of magnitude. Thus, our work suggested a new possibility to exploitation of zeolite and methylene blue in the protection of biologically contaminated environment, and in photodynamic therapy.

Effect of vanillin on methylene blue plus light-induced single-strand breaks in plasmid pBR322 DNA.

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Kumar, S S; Ghosh, A; Devasagayam, T P; Chauhan, P S

2000-09-20

The ability of vanillin (4-hydroxy-3-methoxybenzaldehyde), a naturally occurring food flavouring agent, in inhibiting photosensitization-induced single-strand breaks (ssbs) in plasmid pBR322 DNA has been examined in an in vitro system, independent of DNA repair/replication processes. Photosensitization of DNA with methylene blue, visible light and oxygen, induced ssbs resulting in the production of open circular form (OC form) in a concentration-dependent manner. The yield of OC form induced by photosensitization was increased several-fold by deuteration of the buffer and was found to be inhibited by sodium azide, a scavenger of singlet oxygen (1O(2)). Vanillin, per se, did not induce but inhibited photosensitization-induced ssbs in plasmid DNA, at millimolar concentrations. The inhibitory effect of vanillin was both concentration- and time-dependent. On a molar basis, vanillin was, however, less effective than trolox, a water-soluble analogue of alpha-tocopherol. Photosensitization by methylene blue system generates singlet oxygen, as one of the major components of ROS. Therefore, interaction of singlet oxygen with vanillin was investigated. The rate constant of vanillin with 1O(2) was estimated to be 5.93x10(7)M(-1)s(-1) and that of sodium azide as 2. 7x10(8)M(-1)s(-1). The present investigations show that vanillin can protect against photosensitization-induced ssbs in the plasmid pBR322 DNA, and this effect may partly be due to its ability to scavenge 1O(2).

Stereoselective synthesis of 5-alkoxycarbonyl-4 alkyl-2-anino-3-cyano-6-methyl-4H-pyranes 3 via asymmetric Michael addition to aceptors-gamma-stereogenics; Sintesis esteroselective de 5-alcoxicarbonil-4-alquil-2-amino-3-ciano-6-metil-4H-piranos via adicion Michael sobre aceptores-gama-esterogenicos

Energy Technology Data Exchange (ETDEWEB)

Martinez-Grau, A.; Jimenez, B.; Martin, N.; Seoane, C.; Marco, J.L. [Departamento de Quimica Organica, Facultad de Quimica, Universidad Complutense, Madrid (Spain)

1994-12-31

The stereoselective synthesis of 5-alkoxycarbonyl-4-alkyl-2-amino-3-cyano-6-methyl-4H-pyrans 3 via asymmetric Michael addition of malononitrile to gamma-stereogenic alpha-acetylacrylates 2 obtained by Knoevenagel reaction of acetylacetates to quiral alpha-hydroxyaldehydes 1 is described. The resulting 2-amino-4H-pyrans 3 have been obtained in moderate yield and good diastereoselectivity. 15 refs.

Performance of zeolite ceramic membrane synthesized by wet mixing method as methylene blue dye wastewater filter

Science.gov (United States)

Masturi; Widodo, R. D.; Edie, S. S.; Amri, U.; Sidiq, A. L.; Alighiri, D.; Wulandari, N. A.; Susilawati; Amanah, S. N.

2018-03-01

Problem of pollution in water continues in Indonesia, with its manufacturing sector as biggest contributor to economic growth. One out of many technological solutions is post-treating industrial wastewater by membrane filtering technology. We presented a result of our fabrication of ceramic membrane made from zeolite with simple mixing and he. At 5% of (poring agent):(total weight), its permeability stays around 2.8 mD (10‑14m2) with slight variance around it, attributed to the mixture being in far below percolating threshold. All our membranes achieve remarkable above 90% rejection rate of methylene blue as solute waste in water solvent.

Use of rice husk for the removal of methylene blue in fixed-bed columns

Directory of Open Access Journals (Sweden)

Yurany A. Villada-Villada

2014-08-01

Full Text Available This work shows the use of rice husk in the removal of cationic dye methylene blue on continuous system. A factorial design 23 with center points and random distribution was implemented to evaluate the correlation of the experimental factors in the adsorption process. The considered variables were pH, particle size, salt presence, flow rate, dye initial concentration, and bed depth. The samples were analyzed in defined time intervals. The amount of removed dye was quantified by UV spectroscopy - Visible. Adams-Bohart, Thomas and BDST (Bed-depht/service time analysis models were used to predict the breakthrough curves using non-linear regression and establish the characteristic parameters of the process. It was found that the transference of dye toward the adsorbent is favored by a basic pH, a small particle size, low flow rate and dye concentration, and high bed depth. The design of experiments established that the initial dye concentration and the bed depth were the most significant factors. Regarding the models, the Thomas provided the best fit to describe the breakthrough curves in experimental conditions and Adams-Bohart was found suitable for dynamic behavior limited to the initial part. Finally, BDST model exhibited a good correlation and allowed to establish that bed depth is a determinant factor for scaling process.

Phosphorus dendrimers and photodynamic therapy. Spectroscopic studies on two dendrimer-photosensitizer complexes: Cationic phosphorus dendrimer with rose bengal and anionic phosphorus dendrimer with methylene blue.

Science.gov (United States)

Dabrzalska, Monika; Zablocka, Maria; Mignani, Serge; Majoral, Jean Pierre; Klajnert-Maculewicz, Barbara

2015-08-15

Dendrimers due to their unique architecture may play an important role in drug delivery systems including chemotherapy, gene therapy and recently, photodynamic therapy as well. We investigated two dendrimer-photosensitizer systems in context of potential use of these systems in photodynamic therapy. The mixtures of an anionic phosphorus dendrimer of the second generation and methylene blue were studied by UV-vis spectroscopy while that of a cationic phosphorus dendrimer (third generation) and rose bengal were investigated by spectrofluorimetric methods. Spectroscopic analysis of these two systems revealed the formation of dendrimer-photosensitizer complexes via electrostatic interactions as well as π stacking. The stoichiometry of the rose bengal-cationic dendrimer complex was estimated to be 7:1 and 9:1 for the methylene blue-anionic dendrimer complex. The results suggest that these polyanionic or polycationic phosphorus dendrimers can be promising candidates as carriers in photodynamic therapy. Copyright © 2015 Elsevier B.V. All rights reserved.

Biodegradation of Methylene Blue Dye by Sequential Treatment Using Anaerobic Hybrid Reactor and Submerged Aerobic Fixed Film Bioreactor

Science.gov (United States)

Farooqi, Izharul H.; Basheer, Farrukh; Tiwari, Pradeepika

2017-12-01

Laboratory scale experiments were carried out to access the feasibility of sequential anaerobic/aerobic biological treatment for the biodegradation of Methylene Blue (MB) dye. Anaerobic studies were performed using anaerobic hybrid reactor (consisting of UASB and Anaerobic filter) whereas submerged aerobic fixed film reactor was used as aerobic reactor. Degradation of MB dye was attempted using neutralized acetic acid (1000 mg/L) as co-substrate. MB dye concentration was stepwise increased from 10 to 70 mg/L after reaching steady state in each dye concentration. Such a gradual increase in the dye concentration helps in the proper acclimatization of the sludge to dyes thereby avoiding the possible inhibitory effects to biological activities at high dye concentrations. The overall treatment efficiency of MB through sequential anaerobic-aerobic reactor operation was 90% at maximum attempted dye concentration of 70 mg/L. The effluent from anaerobic reactor was analysed for intermediate biodegradation products through HPLC. It was observed that catechol, quinone, amino pyrine, 1,4 diamino benzene were present. However they were absent in final effluent.

The interactions of azure B, a metabolite of methylene blue, with acetylcholinesterase and butyrylcholinesterase

International Nuclear Information System (INIS)

Petzer, Anél; Harvey, Brian H.; Petzer, Jacobus P.

2014-01-01

Methylene blue (MB) is reported to possess diverse pharmacological actions and is attracting increasing attention for the treatment of neurodegenerative disorders such as Alzheimer's disease. Among the pharmacological actions of MB, is the significant inhibition of acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE). These activities may, at least in part, underlie MB's beneficial effects in Alzheimer's disease. MB is metabolized to yield N-demethylated products of which azure B, the monodemethyl metabolite, is the predominant species. Azure B has been shown to be pharmacologically active and also possesses a variety of biological actions. Azure B therefore may contribute to the pharmacological profile of MB. Based on these considerations, the present study investigates the possibility that azure B may, similar to MB, act as an inhibitor of human AChE and BuChE. The results document that azure B inhibits AChE and BuChE with IC 50 values of 0.486 μM and 1.99 μM, respectively. The results further show that azure B inhibits AChE and BuChE reversibly, and that the modes of inhibition are most likely competitive. Although the AChE and BuChE inhibitory activities of azure B are twofold and fivefold, respectively, less potent than those recorded for MB [IC 50 (AChE) = 0.214 μM; IC 50 (BuChE) = 0.389 μM] under identical conditions, azure B may be a contributor to MB's in vivo activation of the cholinergic system and beneficial effects in Alzheimer's disease. - Highlights: • Methylene blue (MB) is a known inhibitor of AChE and BuChE. • Azure B, the major metabolite of MB, also is an inhibitor of AChE and BuChE. • Azure B may be a contributor to MB's in vivo activation of the cholinergic system. • Azure B may contribute to MB's potential in Alzheimer's disease therapy

Stereo-selectivity and regio-selectivity in the metabolism of 7,8-dihydrobenzo[a]pyrene by cytochrome P450, epoxide hydrolase and hepatic microsomes from 3-methylcholanthrene-treated rats.

Science.gov (United States)

Adams, J D; Yagi, H; Levin, W; Jerina, D M

1995-03-30

The active site of cytochrome P450 1A1 has been probed with the substrate 7,8-dihydrobenzo[a]pyrene using a purified, reconstituted system composed of cytochrome P450 1A1, NADPH-cytochrome c reductase and lipid in the presence or absence of epoxide hydrolase. The turnover of the substrate was found to be 38 nmol/nmol of cytochrome P450/min. The metabolic products that were identified are: a phenolic 7,8-dihydrobenzo[a]pyrene (20-29%); 9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (17-28%); benzo[a]pyrene (12-19%); 7-hydroxy-7,8-dihydrobenzo[a]pyrene (13-16%); 8-hydroxy-7,8-dihydrobenzo[a]pyrene (7-15%); 3-hydroxybenzo[a]pyrene (7-15%); 4,5-epoxy-4,5,7,8-tetrahydrobenzo[a]pyrene (0-4%); and a triol of 7,8,9,10-tetrahydrobenzo[a]pyrene (0-4%). 9,10-Epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene undergoes rapid hydrolysis to cis- and trans-9,10-dihydroxy-dihydroxy-7,8,9,10-tetrahydrobenzo[a]pyrene (2:1) by benzylic attack of water at C-10. Approximately 71% of the trans diols are derived from (+)-(9S,10R)-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene, indicating that cytochrome P450 1A1 has more than a 2:1 preference for selective epoxidation of an enantiotopic face of 7,8-dihydrobenzo[a]pyrene. This stereo-selectivity agrees with the postulated stereo-selectivity predicted by a previously described active site model for cytochrome P450 1A1. Epoxide hydrolase in pure form or in hepatic microsomes catalyzes the hydrolysis of 9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene, which is inhibited by 1,1,1-trichloropropane 2,3-oxide. The (+)-(9S,10R)-isomer of the epoxide is slightly preferred as a substrate over its enantiomer and is cleaved by benzylic and nonbenzylic attack. Only benzylic attack was found with (-)-(9R,10S)-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene.

Removal of methylene blue by adsorption onto activated carbon developed from Ficus carica bast

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Deepak Pathania

2017-02-01

Full Text Available In this study, activated carbon was developed from Ficus carica bast (FCBAC. The experiments were carried out to explore methylene blue (MB uptake by FCBAC. The influence of various experimental factors such as contact time, initial dye concentration, adsorbent dosage, temperature and pH of dye solution was investigated. The adsorption equilibrium was represented with Langmuir, Freundlich and Temkin isotherm models. Langmuir and Tempkin equations were found to have the correlation coefficient value in good agreement. Adsorption of MB onto FCBAC followed pseudo second order kinetics. The calculated values of ΔH°, ΔS° and ΔG° were found to be 21.55 kJ/mol, 76.24 J/mol K and −1.55 kJ/mol, respectably. Adsorption process was spontaneous and endothermic in nature.

Visible-light photocatalytic degradation of methylene blue with laser-induced Ag/ZnO nanoparticles

International Nuclear Information System (INIS)

Whang, Thou-Jen; Hsieh, Mu-Tao; Chen, Huang-Han

2012-01-01

The preparation of Ag doped ZnO nanoparticles conducted through the method of laser-induction is presented in this work. The Ag/ZnO nanoparticles attained from various weight percentages of added AgNO 3 relative to ZnO were applied under visible-light irradiation for evaluating the heterogeneous photocatalytic degradations of methylene blue (MB) solutions. It was shown that the catalytic behavior of Ag/ZnO nanoparticles in the visible-light range is notably improved through the Ag deposition onto ZnO nanoparticles by the method of laser-induction with a maximum effectiveness of 92% degradation. The properties of the nanoparticles were characterized by the employments of UV-vis spectroscopy (UV-vis), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), and selected-area electron diffraction (SAED).

Complexes between lanthanide (III) and yttrium (III) picrates and tetra methylene sulfoxide as ligand

International Nuclear Information System (INIS)

Silva, M.A.A. da.

1991-01-01

The preparation and characterization of addition compounds between lanthanide (III) and yttrium (III) picrates and tetra methylene sulfoxide as ligand were described. The adducts were prepared in the molar relation 1 (salt): 3(ligand) in ethanol. They are microcrystalline with more intense color than those of their respective hydrated salts. At room temperature conditions they are non hygroscopic and do not present perceptible alterations. They became slightly opalescent, when heated between 363 and 423 K. At higher temperatures under several heating ratios, the behavior shown is the same: melting between 439 and 472 K. The characterization of the compounds was made by elemental analysis, electrolytic conductance measurements, X-ray powder patterns, infrared spectroscopy, visible electronic absorption and emission spectra of the neodymium (III) and europium (III), respectively. (author). 116 refs., 17 tabs., 11 figs

Methylene blue adsorption in clay mineral dealt with organic cation; Sorcao de azul de metileno em argila esmectitica tratada com cation organico

Energy Technology Data Exchange (ETDEWEB)

Silva, T.L. [Universidade Federal do Para (UFPA), Maraba, PA (Brazil). Faculdade de Engenharia de Materiais; Lemos, V.P., E-mail: tls1981@hotmail.com [Universidade Federal do Para (UFPA), Belem, PA (Brazil). Centro de Geociencias

2011-07-01

The interaction among organic cations, as the methylene blue (AM) and benzyltrimethylammonium (BTMA), and clay minerals of the group of the smectite they result in the formation of applied materials in the adsorption of organic pollutant presents in waters, soils and you cultivate. In this work they were prepared the adsorbents (organic-clays) smectite - AM and smectite-BTMA. The precursory sample of smectite was collected in Rio Branco-Acre. We were also used an smectite sample collected in Sena Madureira (SM)-Acre already characterized in previous work and a sample of standard smectite Swy-2-Na-Montmorillonite (SWy-2) of Wymong - USA. The organic agents selected for this study they were: Blue of Methylene, denominated AM and Benzyltrimethylammonium, denominated BTMA. They were appraised the capacities adsorptive of the treated samples with BTMA being used AM as adsorbate. The results of these evaluations detected that ran total adsorption of AM (concentrations varying from 1 to 10 ppm) for the treated samples with BTMA. The organic cation, BTMA, interacting with the surfaces of the natural clay was more efficient in the adsorption of AM than the clay without the previous treatment with this salt. (author)

Methylene Blue for Vasoplegic Syndrome Postcardiac Surgery

Science.gov (United States)

Habib, Aly Makram; Elsherbeny, Ahmed Galal; Almehizia, Rayd Abdelaziz

2018-01-01

Objectives: cardiopulmonary bypass (CPB) can be complicated by vasoplegia that is refractory to vasopressors. Methylene blue (MB) represents an alternative in such cases. Patients and Methods: Retrospective observational historical control-matched study. From 2010 to 2015, all patients who received MB for vasoplegia post-CPB were included in this study. Historical controls from the period of 2004 to 2009 were matched. End-points were the time till improvement of vasoplegia (Ti), 30-day mortality, cardiac surgical Intensive Care Unit (CSICU) morbidity, and length of stay (LOS). Results: Twenty-eight patients were matched in both groups. There were no statistically significant differences between the two groups in demographic, laboratory data on admission, or hemodynamic profile before use of MB. Ti and time to complete discontinuation of vasopressors were statistically significant less in MB group (8.2 ± 2.6 vs. 29.7 ± 6.4, P = 0.00 and 22.6 ± 5.2 vs. 55.3 ± 9.4, P = 0.00) respectively. Mortality at day 30 was significantly higher in controls compared to MB (1 patient [3.6%] vs. 6 patients [21.4%], long rank P = 0.04). CSICU, hospital LOS, and incidence of renal failure was significantly higher in control group (12.4 ± 3.7 vs. 7 ± 1.4, P = 0.03), (19.5 ± 2.4 vs. 10.9 ± 3.2, P = 0.05) and (9 patients [32.1%] vs. 2 patients [7.1%], P = 0.04), respectively. Duration of mechanical ventilation was less in MB patients; however, did not reach statistical significance. Conclusions: the use of MB for vasoplegia postcardiac surgery was associated with rapid recovery of hemodynamics, shorter need for vasopressors, less ICU mortality, less incidence of renal failure, and shorter LOS. PMID:29657374

Enantiomeric profiling of a chemically diverse mixture of chiral pharmaceuticals in urban water

International Nuclear Information System (INIS)

Evans, S.; Bagnall, J.; Kasprzyk-Hordern, B.

2017-01-01

. - Highlights: • Chiral drugs present in wastewater and receiving waters enriched with one enantiomeric form. • Stereoselective microbial degradation observed in receiving water and activated sludge microcosms. • Preferential degradation of S(+)-, R(+)- & S(+)- amphetamines, beta-blockers & antidepressants respectively. • Desmethyl metabolites showed higher degradation rate and stereoselectivity. • Metabolites enriched with enantiomers of opposite configuration to their parent compounds. - Enantiomeric profiling of chemically diverse mixtures of chiral pharmaceuticals in urban water shows high stereoselectivity of environmental processes.

Utilization of visible to NIR light energy by Yb"+"3, Er"+"3 and Tm"+"3 doped BiVO_4 for the photocatalytic degradation of methylene blue

International Nuclear Information System (INIS)

Regmi, Chhabilal; Kshetri, Yuwaraj K.; Ray, Schindra Kumar; Pandey, Ramesh Prasad; Lee, Soo Wohn

2017-01-01

Highlights: • Lanthanide doped BiVO_4 as highly efficient upconversion and photocatalytic material. • Well defined beads like morphology for better photocatalytic activity. • Effective utilization of NIR and visible light for efficient photocatalytic degradation of methylene blue. • Nontoxic to human cells, potential for application in biological fields. - Abstract: Lanthanide-doped BiVO_4 semiconductors with efficient photocatalytic activities over a broad range of the solar light spectrum have been synthesized by the microwave hydrothermal method using ethylenediaminetetraacetic acid (EDTA). The structural, morphological, and optical properties of the as-synthesized samples were evaluated by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray powder diffraction (XRD), Raman spectroscopy, FT-IR spectroscopy, UV–vis diffuse reflectance spectroscopy (DRS), and photoluminescence spectroscopy (PL). The chemical compositions were analyzed by X-ray photoelectron spectroscopy (XPS). The toxicity of the samples was measured using Mus musculus skin melanoma cells (B16-F10 (ATCC"® CRL-6475™)) and were found to be nontoxic for human cells. The photocatalytic efficiency of the prepared samples was evaluated by methylene blue (MB) degradation. The best photocatalytic activity was shown by BiVO_4 with 6:3:3 mol percentage of Yb"+"3:Er"+"3:Tm"+"3 in all solar light spectrum. The synthesized samples possess low band gap energy and a hollow structure suitable for the better photocatalytic activity. The observed NIR photoactivity supports that the upconversion mechanism is involved in the overall photocatalytic process. Therefore, this approach provides a better alternative upconversion material for integral solar light absorption.

Computer-Assisted Design and Synthetic Applications of Chiral Enol Borinates: Novel, Highly Enantioselective Aldol Reagents

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Gennari Cesare

1998-01-01

Full Text Available We have recently described the development of a quantitative transition state model for the prediction of stereoselectivity in the boron-mediated aldol reaction. This model provides qualitative insights into the factors contributing to the stereochemical outcome of a variety of reactions of synthetic importance. The force field model was used to assist the design and preparation of new chiral boron ligands derived from menthone. The chiral boron enolates were employed in various stereoselective processes, including the addition to chiral aldehydes and the reagent-controlled total synthesis of (3S,4S-statine. The chiral enolates derived from alpha-halo and alpha-oxysubstituted thioacetates were added to aldehydes and imines. Addition to imines leads to the enantioselective synthesis of chiral aziridines, a formal total synthesis of (+-thiamphenicol, and a new highly efficient synthesis of the paclitaxel (taxol® C-13 side-chain and taxol semisynthesis from baccatin III. The stereochemical outcome of the addition to imines was rationalised with the aid of computational studies. Enantioselective addition reactions of the chiral boron enolate derived from thioacetate have successfully been applied to solid phase bound aldehydes to give aldol products in comparable yields and enantioselectivities to the usual solution conditions.

Synthesis of 4-Methylene-2-cyclohexenones and Their Aromatization Reaction toward para-Methoxylmethyl Anisole Derivatives

International Nuclear Information System (INIS)

Lee, Jeong Mi; Lee, Ka Young; Kim, Jae Nyoung

2004-01-01

We and other groups have reported the selective introduction of nucleophiles at the secondary benzylic position of the Baylis-Hillman acetates via the corresponding DABCO salts. Thus, we envisioned that we could prepare 4-methylene- 2-cyclohexenone skeleton and para-methoxymethyl anisoles by combining the DABCO salt concept and the aromatization reaction with iodine in methanol. Suitably substituted anisoles are useful as the starting materials for the fragrances, dyes and pesticides, as antioxidants in oils and fats, or as stabilizers of plastics. Moreover, paramethoxymethyl anisoles have been used for the kinetic acetalization of diol or amino alcohol systems in the presence of DDQ5 during the synthesis of (+)-FR900482, taxotere side chain,5c cyclopropyl lactone oxylipins, and erythromycin A.

Sensitive flotation-spectrophotometric determination of gold, based on the gold(I)-iodide-methylene blue system.

Science.gov (United States)

Marczenko, Z; Jankowski, K

1985-04-01

The gold(I)-iodide-Methylene Blue (MB) system is suitable for flotation separation and spectrophotometric determination of gold. Under the optimum conditions [(MB(+))(AuI(2)(-))].3[(MB(+))(I(3)(-))] is formed, and floated with cyclohexane. The product is dissolved in methanol and its absorbance measured. The molar absorptivity is 3.4 x 10(5)1.mole(-1).cm(-1) at 655 nm. The proposed method is more than three times as sensitive as the Rhodamine B method. Pt, Pd, Ag and Hg interfere seriously, and Ir, Rh, Bi and Cd to a smaller extent. Preliminary separation of gold by precipitation with tellurium as a collector is recommended. The method has been applied to determination of gold traces (about 1 x 10(-4)%) in a copper sample.

Kinetics of tissue distribution and elimination of 4,4'-methylene bis(2-chloroaniline) in rats

Energy Technology Data Exchange (ETDEWEB)

Tobes, M.C.; Brown, L.E.; Chin, B.; Marsh, D.D. (Michigan Univ., Ann Arbor (USA). Medical Center)

1983-06-01

The tissue distribution kinetics and elimination of 4,4'-methylene bis(2-chloroaniline) (MBOCA) in rats was studied after a single dose of (/sup 14/C)MBOCA (0.49 mg/kg body weight, i.v.). The highest concentrations of radioactivity were in the small intestine, liver, adipose, lung, kidney, skin, and adrenals. For most tissues, a rapid decrease in radioactivity was followed by a slower decrease except for the small intestine, adipose and skin which demonstrated transient increases. Subcellular distribution in liver at 1 h showed radioactivity in all cell fractions. Although very lipophilic, (/sup 14/C)MBOCA was completely eliminated within 48 h with the major route via the feces (73.4%).

Highly solvatochromic emission of electron donor-acceptor compounds containing propanedioato boron electron acceptors

NARCIS (Netherlands)

Brouwer, A.M.; Bakker, N.A.C.; Wiering, P.G.; Verhoeven, J.W.

1991-01-01

Light-induced electron transfer occurs in bifunctional compounds consisting of 1,3-diphenylpropanedioato boron oxalate or fluoride electron acceptors and simple aromatic electron-donor groups, linked by a methylene bridge; fluorescence from the highly polar charge-transfer excited state is

Synthesis of CdS Sensitized TiO2 Photocatalysts: Methylene Blue Adsorption and Enhanced Photocatalytic Activities

Directory of Open Access Journals (Sweden)

A. B. Makama

2016-01-01

Full Text Available A series of CdS/TiO2 nanocomposites with different Cd to Ti molar ratio were synthesized from P25-TiO2 nanopowder using microwave-assisted hydrothermal method. The as-produced powders were characterized by XRD, electron microscopy, EDX, and UV-Vis diffuse reflectance spectroscopy. The adsorption capacity and photocatalytic activity of the samples were investigated using methylene blue as a model pollutant. Sorption tests revealed that the adsorption of MB onto the samples obeys the Freundlich-Langmuir isotherm model. The sorption capacity decreased as follows: TiO2>TCd2>TCd1>TCd3>TCd4. The results of the photocatalytic tests under high-intensity discharge (HID lamp revealed that CdS/TiO2 powders with low Cd to Ti molar ratios exhibited much higher activities than P25-TiO2. The CdS/TiO2 sample with 20% CdS/(TCd2 showed the most activity among all these samples. The results also show that the Cd to Ti molar ratio of the nanocomposite has a significant effect on the photodegradation of MB and the enhanced activities exhibited by the nanocomposites are because of the low rate of electron-hole recombination.

Investigation on effect of methylene spacer in holographic grating formation in eosin containing polymethacrylates

Energy Technology Data Exchange (ETDEWEB)

Manickasundaram, S. [Department of Chemistry, Anna University, Sardar Vallabai Patel Road, Chennai 600025 (India); Kannan, P. [Department of Chemistry, Anna University, Sardar Vallabai Patel Road, Chennai 600025 (India)]. E-mail: pakannan@annauniv.edu; Deepa, S. [Centre for Laser Technology, Department of Physics, Anna University, Chennai 600025 (India); Palanisamy, P.K. [Centre for Laser Technology, Department of Physics, Anna University, Chennai 600025 (India)

2007-01-15

A new series of eosin dye based poly(alkyloxymethacrylate)s was synthesized with an even number of side-chain methylene spacers by a free radical addition polymerization method for holographic optical data storage applications. These polymers were characterized by UV, IR and {sup 1}H NMR spectroscopy. The glass transition temperature and thermal stability of the polymers were investigated by DSC and TGA, respectively. As the spacer length increases in the side-chain, Tg, Tm and thermal stability of the polymers decrease, while a reverse trend was observed with film forming ability of the polymers. The optical characterization of the polymers was investigated by forming holographic grating using an Argon ion laser. The grating diffraction efficiency was found to depend not only on the concentration of polymeric film but also on the spacer length of the polymers.

Investigation on effect of methylene spacer in holographic grating formation in eosin containing polymethacrylates

International Nuclear Information System (INIS)

Manickasundaram, S.; Kannan, P.; Deepa, S.; Palanisamy, P.K.

2007-01-01

A new series of eosin dye based poly(alkyloxymethacrylate)s was synthesized with an even number of side-chain methylene spacers by a free radical addition polymerization method for holographic optical data storage applications. These polymers were characterized by UV, IR and 1 H NMR spectroscopy. The glass transition temperature and thermal stability of the polymers were investigated by DSC and TGA, respectively. As the spacer length increases in the side-chain, Tg, Tm and thermal stability of the polymers decrease, while a reverse trend was observed with film forming ability of the polymers. The optical characterization of the polymers was investigated by forming holographic grating using an Argon ion laser. The grating diffraction efficiency was found to depend not only on the concentration of polymeric film but also on the spacer length of the polymers

3,3′-Di-tert-butyl-1,1′-[1,3-phenylenebis(methylene]diurea

Directory of Open Access Journals (Sweden)

Md. Alamgir Hossain

2010-03-01

Full Text Available The title compound, C18H30N4O2, contains two tert-butyl urea groups, each connected to a benzene ring though a methylene group. One of the groups occupies a position almost normal to the aromatic plane with a C—N—C—C torsion angle of −94.4 (4°, while the other is considerably twisted from the ring with a C—N—C—C torsion angle of −136.1 (4°. In the crystal, pairs of molecules are connected to each other, forming centrosymmetric dimers in which two NH groups of one molecule act as hydrogen-bond donors to one carbonyl O atom of the other molecule. The dimers are linked into sheets parallel to (100 by N—H...O hydrogen bonds involving the remaining N—H and C=O groups.

Life-threatening intoxication with methylene bis(thiocyanate: clinical picture and pitfalls. A case report

Directory of Open Access Journals (Sweden)

Schnuelle Peter

2006-04-01

Full Text Available Abstract Background Methylene bis(thiocyanate (MBT is a microbiocidal agent mainly used in industrial water cooling systems and paper mills as an inhibitor of algae, fungi, and bacteria. Case presentation We describe the first case of severe intoxication following inhalation of powder in an industrial worker. Profound cyanosis and respiratory failure caused by severe methemoglobinemia developed within several minutes. Despite immediate admission to the intensive care unit, where mechanical ventilation and hemodialysis for toxin elimination were initiated, multi-organ failure involving liver, kidneys, and lungs developed. While liver failure was leading, the patient was successfully treated with the MARS (molecular adsorbent recirculating system procedure. Conclusion Intoxication with MBT is a potentially life-threatening intoxication causing severe methemoglobinemia and multi-organ failure. Extracorporeal liver albumin dialysis (MARS appears to be an effective treatment to allow recovery of hepatic function.

Technetium-99m methylene diphosphonate scintimammography for evaluation of palpable breast masses

International Nuclear Information System (INIS)

Shah, S.; Khan, M.M.; Khan, A.U.; Khan, S.M.; Khan, A.A.

2002-01-01

Objective:To evaluate technetium-99m methylene diphosphonate (/sup 99m/Tc-MDP) as a noninvasive tumor-localizing agent in patients with palpable breast masses and to differentiate malignant from benign breast lesions. Design: It was an observational and experimental study. Place and Duration of Study: the study was conducted at the Institute of Radiotherapy and Nuclear Medicine (IRNUM), Peshawar during a six-month period (June to November, 1995). Subjects and Methods: 99m Tc-MDP scintimammography (SMM) was performed in thirty patients with palpable breast masses (Group A). Ten patients with no palpable breast abnormality (Group B) also underwent /sup 99m/Tc-MDP breast study; they served as controls. Upright anterior, lateral and oblique lateral images of the breasts were acquired 10-30 minutes after intravenous injection of 740 MBq of /sup 99m/Tc-MDP. This was performed during routine bone scanning. SMM was followed by surgical and /or needle biopsy. Results: breast cancer was histologically diagnosed in twenty two (73%), and benign disease found in eight patients (27%). Of the twenty two breast carcinomas, twenty (91%) were detected using /sup 99m/Tc-MDP SMM, while no uptake was seen in two (9%). Of the eight patients with pathologically proven benign breast lesions, seven (88%) either did not show any uptake or showed faint bilateral accumulation. Focal /sup 99m/Tc-MDP uptake was observed in one fibroadenoma. Conclusion: The study showed that SMM with /sup 99m/Tc-MDP is positive in a high percentage of patients with carcinoma of the breast and may differentiate malignant from benign masses. (author)

Obtaining multifunctional composites using styrofoam recycling: methylene blue adsorption; Obtencao de compositos multifuncionais utilizando reciclagem de isopor: adsorcao de azul de metileno

Energy Technology Data Exchange (ETDEWEB)

Silva, T.H. da; Ferreira, B.F.; Faria, E.H. de; Ciuffi, K.J.; Calefi, P.S., E-mail: tiagohonoratosilva@hotmail.com [Universidade de Franca, SP (Brazil)

2011-07-01

There is high risk of environmental contamination by the textile industry if the generated waste is disposed into water streams and rivers. Another sector responsible for the generation of large amounts of waste is the styrofoam industry, since styrofoam is employed in various areas for packaging production. Therefore, today there is constant search for sustainable economic growth by means of materials recycling and reduction of residual pollutants. In this context, the present work aims to promote styrofoam recycling with its further utilization in the production of a kaolin-styrofoam composite for application as adsorbent of methylene blue originated from textile industry effluents. This adsorption is investigated in a column system, by exploiting the adsorptive properties of kaolin, such as large surface area and chemical and structural characteristics. The obtained materials were characterized by thermogravimetric analysis, X-ray diffraction, and UV-visible absorption spectroscopy. (author)

Graphene hydrogels with embedded metal nanoparticles as efficient catalysts in 4-nitrophenol reduction and methylene blue decolorization

Directory of Open Access Journals (Sweden)

Żelechowska Kamila

2016-12-01

Full Text Available Synthesis and characterization of the graphene hydrogels with three different metallic nanoparticles, that is Au, Ag and Cu, respectively is presented. Synthesized in a one-pot approach graphene hydrogels with embedded metallic nanoparticles were tested as heterogeneous catalysts in a model reaction of 4-nitrophenol reduction. The highest activity was obtained for graphene hydrogel with Cu nanoparticles and additional reaction of methylene blued degradation was evaluated using this system. The obtained outstanding catalytic activity arises from the synergistic effect of graphene and metallic nanoparticles. The hydrogel form of the catalyst benefits in the easiness in separation from the reaction mixture (for example using tweezers and reusability.

New stereoselective intramolecular

Science.gov (United States)

Alajarin; Vidal; Tovar; Ramirez De Arellano MC; Cossio; Arrieta; Lecea

2000-11-03

Efficient 1,4-asymmetric induction has been achieved in the highly stereocontrolled intramolecular [2 + 2] cycloadditions between ketenimines and imines, leading to 1,2-dihydroazeto[2, 1-b]quinazolines. The chiral methine carbon adjacent to the iminic nitrogen controls the exclusive formation of the cycloadducts with relative trans configuration at C2 and C8. The stepwise mechanistic model, based on theoretical calculations, fully supports the stereochemical outcome of these cycloadditions.

The correlation between structural properties, geometrical features, and photoactivity of freestanding TiO2 nanotubes in comparative degradation of 2,4-dichlorophenol and methylene blue

Science.gov (United States)

Vahabzadeh Pasikhani, Javad; Gilani, Neda; Ebrahimian Pirbazari, Azadeh

2018-02-01

Freestanding TiO2 nanotubes (FSNTs) with various physical dimensions were fabricated by two-step anodization process with different voltages and anodization times. The detachment method employed in this study involved voltage reduction at the end of the second step and ultrasonic chemical treatment. The results demonstrated that this detachment method is a beneficial technique to create thin open-mouthed and closed-end FSNTs (with lengths of 6-14 μm). Moreover, the influences of anodization conditions on photocatalytic activity, structural properties and geometrical features of FSNTs in comparative degradation of two non-colored (2,4-dichlorophenol) and colored (methylene blue) pollutants were investigated. Findings revealed that the quantity of the photocatalyst utilized is an effective parameter and using the optimum weight (10 mg/100 ml of 2,4-dichlorophenol) could increase the efficiency of the process up to 21%. Further, the results demonstrated that if equal optimum weights of FSNTs are chosen, decreases in voltage and anodization time significantly influence the structural properties, geometrical features, and photodegradation efficiency. The enhancement achieved in the degradation of both 2,4-dichlorophenol and methylene blue using the nanotubes with the shortest diameter (54 nm) and length (6.5 μm), which possess the lowest porosity (0.5) and also the highest surface area (0.53 m2 g-1), nanotubes’ density (19 cm2 cm-2) and wall thickness to length ratio (2). In addition, the results obtained indicated that the degradation reactions follow first-order kinetics in the degradation of the both pollutants. The apparent degradation rate constant of methylene blue was approximately 1.2 times greater than of the 2,4-dichlorophenol due to the negative charge of the nanotubes’ surface and electrostatic adsorptions.

Removal of methylene blue and rhodamine B from water by zirconium oxide/graphene

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Sumita Rani

2016-04-01

Full Text Available Methylene blue (MB and rhodamine B dyes (RB were degraded from water using zirconium oxide (ZrO2 and zirconium oxide/graphene composites (ZrO2/GR as photocatalyst. The photocatalytic efficiency was calculated from absorption spectra obtained using UV–visible spectroscopy. It has been observed that photodegradation time as well as photocatalytic efficiency increase with the concentration of catalyst up to a certain limit after which effect was reversed. The degradation was studied as a function of pH also. It was found that photocatalytic efficiency was more in alkaline medium than acidic medium. Degradation of RB takes place at higher value of pH as compared to MB. The degradation time for MB was 1 h using ZrO2 which get reduced to 32 min using ZrO2/GR composite and for RB it reduced to 40 min (using ZrO2/GR from 80 min (ZrO2.